ICSM Full Programme (Synt Met)

P ROG RAMME
www.conferencepartners.ie/icsm
Welcome Letter Committees Acknowledgements General Information Academy Phone Number Social Programme Accompanying Persons Programme Map of Exhibition and Poster Presentations Programme at a glance Oral Programme Alphabetical List of Poster Presenters Poster Information & Poster Programme Abstracts Notes Map of Trinity
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TA B L E O F C O N T E N T S
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Welcome to Dublin,Irelands capital city,steeped in history and youthful energy. Medieval, Georgian and modern architecture provide a magnicent backdrop to a safe and friendly bustling port,where the cosmopolitan and charming converge in the delightful diversity that is Dublin. Trinity College Dublin is honoured to be your host for ICSM 2006.We extend a warm welcome to our Nobel Laureates,the Plenary, Keynote and Invited Speakers and all other participants and guests. The International Conference on Science and Technology of Synthetic Metals(ICSM) brings together leading scientists and engineers to discuss the latestadvances in Synthetic Metals (such as conducting polymers and carbonnanotubes). These materials are nding applications in areas as diverse as articial muscles, electronic noses, plastic solar cells, corrosion inhibition, biosensors, electronic textiles and nerve cell communications. The ability to manipulate matter on the nanometer scale (nanotechnology) presents the possibility of making materials more suitable for current engineering needs (eg: smaller, lighter) and to make new materials which open up new engineering and medical possibilities. Consequently, a synergy between synthetic metals, information technology, biotechnology and nanotechnology has emerged and is providing ground breaking and exciting scientic and industrial challenges. Plenary lectures from eminent international scientists will be among the highlights of the scientic program.These will include talks from several Nobel Laureates in a special opening session. As part of ICSM 2006, we will run special events aiming to communicate directly with businesses about potential partnerships and collaborations that are an integral part of modern R & D and which make possible the commercialisation of cutting-edge technology. ICSM has previously been held in Siofok (1976), New York (1977), Dubrovnik(1978), Helsingor (1980), Boulder (1981), Les Arcs (1982), Abano Terme (1984), Kyoto (1986), Santa Fe (1988), Tubingen (1990), Goteborg (1992), Seoul(1994), Snowbird (1996), Montpellier (1998), Bad Gastein (2000), Shanghai(2002) and Wollongong (2004). Ireland has many scenic, cultural and natural attractions, and is an excellent country to visit. As tourism is a major Irish industry, tourists are well-catered for, with quality accommodation, attractions and activities throughout the country. The hospitality is legendary- why not extend your visit and explore our island? Werner Blau, Trinity College Dublin
WELCOME LETTER
LOCAL ORGANISING COMMITTEE Werner Blau, TCD, Dublin Hugh James Byrne, DIT, Dublin Les Carpenter, Dow Corning, TCD, Dublin Jonathan Coleman, TCD, Dublin Dermot Diamond, DCU, Dublin Mauro Ferreira, TCD, Dublin John M. Kelly, TCD, Dublin Mary McNamara, DIT, Dublin SCIENTIFIC COMMITTEE Valerie Barron, NUI Galway Carmel Breslin, NUI Maynooth David Corr, NTERA Ltd. Dublin Paul Dawson, QUB Belfast Donald Fitzmaurice, UCD Dublin Edmond Magner, Univ. Limerick Michael Mulloy, HP Ireland Brian Norton, DIT Dublin Pagona Papakonstantinou, U Ulster Jenny Patterson, Intel Ireland Gareth Redmond, Tyndall NI, Cork Gordon Wallace, DCU and Universityof Wollongong
INTERNATIONAL ADVISORY BOARD 1. Z.Valy Vardeny, Salt Lake City, UT, 32. John R. Reynolds, Gainsville, FL, USA USA 33. Joel S. Miller, Salt Lake City,UT, 2.Yung W. Park, Seoul, KR USA 3. Xin Sun, Fudan, CN 4. William R. Salaneck, Linkoping, SE 34. Jean-Paul Pouget, Orsay, FR 35. Jean-Luc Bredas,Atlanta, GA, USA 5. Tokio Yamabe, Nagasaki,JP 36. Jaume Veciana, Barcelona, ES 6. Takehiko Ishiguro, Kyoto, JP 37. Hidetoshi Fukuyama, Sendai, JP 7. Silvia Tomic, Zagreb, CRO 38. Helmut Neugebauer, Linz,AT 8. Siegmar Roth, Stuttgart, DE 39. Hans. Kuzmany,Vienna,AT 9. Shaojun Dong, Beijing, CN 40. Giuseppe Zerbi, Milan, IT 10. Serguei Brazovskii, Orsay, FR 41. Guenther Leising, Graz,AT 11. Serge Lefrant, Nantes, FR 42. Gerard Bidan, Grenoble, FR 12. Seiichi Kagoshima, Tokyo, JP 43. Fred Wudl, Los Angeles, CA, USA 13. Sedar Sariciftci, Linz,AT 14. Ronald L. Elsenbaumer, Arlington, 44. Francis Garnier, Paris, FR TX, USA 45. Esther Conwell, Rochester, NY, USA 15. Roland Resel, Graz,AT 16. Robert M. Metzger, Tuscaloosa, AL, 46. Eitan Ehrenfreund, Haifa, IL USA 47. Egbert W. Meijer, Eindhoven, NL 17. Rimma P. Shibaeva, 48. Donal D. C. Bradley, London, UK Chernogolovka, RU 49. Denis Jerome, Paris, FR 18. Richard H. Friend, Cambridge, UK 50. Daoben Zhu, Beijing, CN 19. Renato Bozio, Padua, IT 51. Claude Bourbonnais, Sherbrooke, 20. Reghu Menon, Bangalore, IN CA 21. Ray Baughman, Dallas, TX, USA 52. Chang-qin Wu, Fudan, CN 22. Peter Baeuerle, Ulm, DE 53. Celso P. de Melo, Recife, BR 23. Paul M. Chaikin, New York, NY, 54. Carlo Taliani, Bologna, IT USA 55. Bernhard Wessling,Ammersbek, 24. Patrick Bernier, CNRS, FR DE 25. Michael Hanack, Tubingen, DE 56. Arthur Epstein, Columbus, OH 26. Luis Alcacer, Lisbona, PT 57. Anvar Zakhidov, Dallas, TX, USA 27. Long Y.Chiang, Lowell, MA, 58. Andrew Holmes, Melbourne,AUS 28. Libero Zuppiroli, Lausanne, CH 59. Andras Janossy, Budapest, HU 29. Lewis Rothberg, Rochester, NY, 60. Alan R. Bishop, Los Alamos, NM, USA USA 30. Klaus Muellen, Mainz, DE 61. Alan Kaiser,Wellington, NZ 31. Katsumi Yoshino, Osaka, Jp 62. Adam Pron, Grenoble, FR
COMMITTEES
ACKNOWLEDGEMENTS The organisers and delegates of ICSM 2206 are very appreciative of the support and help given by the following sponsors and exhibitors: SFI Forfas Discovery Science & Engineering Enterprise Ireland Hewlett Packard Failte Ireland Intel SGL Carbon Renishaw eDAQ / Red Box Direct Ltd Nanocyl CRANN CREST SCIENCE FOUNDATION IRELAND (SFI) The National Foundation for Excellence in Scientic Research On behalf of the Irish government, SFI is investing in academic researchers and research teams who are most likely to generate new knowledge, leading-edge technologies, and competitive enterprises in the elds underpinning two broad areas, Biotechnology (BioT) and Information and Communications Technology (ICT). SFI makes awards based upon the merit review of distinguished scientists. SFI also advances co-operative efforts among education, government, and industry that support its elds of emphasis. www.s.ie FORFS Forfs is Irelands national board responsible for providing policy advice to Government on enterprise, trade, science, technology and innovation in Ireland. Among Forfs functions are: industrial policy development and co-ordination of State bodies such as IDA Ireland and Enterprise Ireland; the promotion of scientic research and innovation in close association with Science Foundation Ireland and the Advisory Council on Science, Technology and Innovation; and research, analysis and policy advice on competitiveness and economic development, through the National Competitiveness Council and the Expert Group on Future Skills Needs. http:// www.forfas.ie DISCOVER SCIENCE & ENGINEERING (DSE) Discover Science & Engineering (DSE) aims to increase interest in science, technology, innovation and engineering among students, teachers and members of the public. DSEs mission is to contribute to Irelands continued growth and development as a society that has an active and informed interest and involvement in science, engineering and technology. Its overall objectives are to increase the numbers of students studying the physical sciences, promote a positive attitude to careers in science, engineering and technology and to foster a greater understanding of science and its value to Irish society. The DSE programme was developed in response to a key recommendation of the Task Force on the Physical Sciences. This called for a coordinated effort to increase interest in science and encourage young people to consider science as a viable career option. DSE brings together many science, engineering, technology and innovation awareness activities that were previously managed by different bodies, public and private. DSE aims to build and expand on these activities and to deliver a more focused, strategic and quantiable awareness campaign.
ACKNOWLEDGEMENTS
ENTERPRISE IRELAND Enterprise Ireland is the Irish state development agency focused on accelerating the development of worldclass Irish companies. Our vision is to transform Irish companies into businesses that are Market focused and Innovation driven. Our focus is on ve main areas of activity; Achieving export sales; Investing in research and innovation; Competing through productivity; Starting up and scaling up; Driving regional enterprise. Through our extensive network of 13 Irish ofces and 33 International ofces, we work with our clients to assist them to compete and to grow. HEWLETT PACKARD HPs Dublin Inkjet Manufacturing Operation (DIMO) is the nucleus of HPs operation in Liffey Park technology campus and a critical business in HPs Imaging and Printing Group (IPG), built in 1995 its primary function is to manufacture inkjet print cartridges for HP inkjet printers. Being the only HP inkjet print manufacturing site in Europe, a variety of different types of original HP cartridges are produced at DIMO.Latest technologies and a high- tech environment assure the outstanding quality and reliability which customers expect from the HP trademark and have seen the site progress from solely manufacturing to R&D today. FILTE IRELAND Filte Ireland is the National Tourism Development Authority, established by the Irish Government in May 2003 to guide and promote the evolution of tourism as a leading indigenous component of the Irish economy. To this end, Filte Ireland, working in partnership with the tourism industry, provides an extensive range of support services and business solutions designed specically to develop and sustain Ireland as a high-quality and competitive tourism destination. INTEL Ireland is Intels manufacturing and technology centre for Europe. The Intel Ireland campus, at Collinstown Industrial Park, Leixlip, County Kildare, is Intels fourth largest manufacturing site overall, and the largest outside the United States. Intel is also engaged in a range of research collaborations with third level institutions in Ireland including DCU, TCD, NUI Maynooth, UCC, UCD, UL, DIT and QUB. Intel is the major industrial partner in CRANN (Centre for Research in Adaptive Nanostructures and Nanodevices) a consortium of industry and university research groups. SGL CARBON GROUP We are one of the leading suppliers of graphite specialties world-wide and the only one that masters all methods of production. We supply a wide range of products made of isostatically pressed, extruded, die- and vibration-molded graphite, carbon/carbon, felt, graphite foils and laminated sheets, carbon and graphite yarns for a variety of applications in todays key industries. Our strength lies in the tailoring of material properties and in the precision of our processing, oriented towards the requirements of our customers. We offer all customers worldwide highest quality solutions to all their graphite specialty needs. We focus our efforts towards ; customer orientation; strengthening our market and technology position by continuously improving our materials and production facilities, as well as the products themselves; ongoing improvement of our efciency in all business processes; new business development to identify and realize new carbon/graphite applications; global business approach In order to breed a culture of continuous improvement we have started a long term initiative under the title of SGL EXCELLENCE, a further evolution of our Total Quality Management (TQM) approach using SIX SIGMA as a key tool.
ACKNOWLEDGEMENTS
RENISHAW PLC Renishaw plc manufactures a wide range of spectroscopy products, including Raman microscopes, compact process monitoring spectrometers, laser diodes, and state-of-the-art cooled CCD detectors, for end-user and OEM applications. Also available from Renishaw, combined with Raman spectroscopy, are infrared, scanning probe, scanning electron, and confocal laser scanning microscopes. These integrated systems enable users to perform two or more analytical techniques on the same sample region, under the same conditions, in a single instrument. eDAQ - RED BOX DIRECT eDAQ electrochemistry systems are ideal for studies of conducting polymers and nano particles, and are used for cyclic voltametry, electroplomerisation, chronoamperometry/potentiometry and other electrochemical techniques. eDAQ data acquisition systems can also be used for recording the output from solar cells, as well as signals from force and displacement transducers used for articial muscle studies. See our new 4-channel potentiostat for sensor monitoring! NANOCYL - CARBON NANOTUBE LEADER Nanocyl was founded in 2002 with the goal to become the leading global manufacturer of specialty and industrial carbon nanotubes. Today, as one of the largest producers of industrial and research-grade nanotubes, Nanocyl has batch and continuous reactors with a production capacity in excess of 5 tonnes per year and the ability to quickly increase production to meet customer demand. Work is in progress to bring a high-capacity industrial reactor on stream in 2007.. Nanocyl produces high-quality carbon nanotubes using the catalytic carbon vapour deposition (CCVD) process. Nanocyl has developed signicant expertise and intellectual property around this technology. This method is the basis for producing all grades of Nanocyls product line, from single-wall research grades to multi-wall industrial grade carbon nanotubes. Nanocyl is continually developing new, value-added products, such as the in-situ polymerized NC9000 series - a high-concentration nanotube polymer blend. CRANN The Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin (TCD), is an internationally recognised centre of excellence in nanoscience, funded by Science Foundation Ireland (SFI). CRANNs mission encompasses three research themes: Magnetic nanostructures and devices Bottom-up Fabrication and Testing of Nanoscale Integrated Devices Nano-biology of cell surface interactions and involves extensive collaborations with industry partners, including Intel and Hewlett Packard and a number of Irish high-tech companies. CRANN, afliated with the Schools of Physics, Chemistry and the Life Sciences, provides a unique collaborative and interdisciplinary environment in which innovative research is carried out by teams of internationally renowned experts and leading industry gures to address the big challenges faced by the Information and Communication Technologies and Biotechnology sectors. http://www.crann.tcd.ie/ CENTRE FOR RESEARCH IN ENGINEERING SURFACE TECHNOLOGY - CREST The Centre for Research in Engineering Surface Technology (CREST) is a platform for applied research in surface science that contributes to academic and industrial growth on this island. CREST has assembled a team of highly trained scientists to focus on academic research and on helping companies in Ireland research and develop innovative new materials. It is the premier surface coating consultancy service in Ireland and a national approval laboratory that has been used by many Irish government agencies (e.g. An Post, NRA, NSAI) to give advice on public and private projects. The Centre offers services ranging from material surface characterisation and corrosion control to the development of nano-coatings and additives. In 2005, CREST received the DIT Faculty of Engineering Award for contribution to industry.
ACKNOWLEDGEMENTS
GENERAL INFORMATION
Contact Number: 01- 608 1648 Enquiries for the following should be made at the registration desk: General information regarding the conference Social events Daily excursions Accompanying persons programme Accommodation changes Book a taxi Internet access
White Badge Pink Badge White Badge with Blue Ribbon White Badge with Red Ribbon White Badge with Green Ribbon White Badge with Blue Ribbon
Full Delegate Accompanying Person Exhibitor Local Organising Committee Keynote Speaker Invited Speaker
G E N E R A L I N F O R M AT I O N
SERVICES IN THE ARTS BUILDING The following services are available in the Arts Building: DUBLIN Internet Facilities - a password to gain access to Dublin, the capital of the Republic of Ireland, is the TCD network is available at the registration increasingly the venue for a variety of international desk. The passwords are 10.00. One password conferences. Today, it is a city of ne Georgian is valid for the full week of the conference. Buildings, excellent stores and shops, pubs and Public Telephone (telephone cards are sold in restaurants, museums and antique shops, all commachines beside telephone) bining to make it one of the most enjoyable cities Coffee Shop in Europe. Photocopying (photocopying ticket is required) Cloakroom (luggage storage on Friday) During the course of the conference you will have the opportunity to visit one of the most historic LUNCH buildings in the city. The State Apartments of Dub- Lunch will be served in the Dining Hall, Buttery and lin Castle will host the State Reception. Bar (please see point 3 on Map) each day except Friday 7th July. To cater for large numbers, lunch will be availVENUE TRINITY COLLEGE DUBLIN able from 13.00hrs 14.30hrs. There will be queuing, so Trinity College Dublin, founded in 1952, is situated please be patient! Your badge is your ticket, so please right in the heart of Dublin city, the city campus ensure that you wear it at all times. occupies some 47 acres (including the Trinity College Enterprise Centre). This 16th century campus, SPEAKER PREVIEW ROOM surrounded by attractive gardens, is an ideal locaThe speaker preview room is located in Room 2026 on tion for conferences with well-equipped lecture the Upper Concourse of the Arts Building. All presentatheatres, accommodation, banking, travel agency, tions must be handed in 24hrs advance. shopping and tourist attractions. The main conference building is the Arts Building. All conference POSTER PRESENTATIONS hotels except UCD are within walking distance Poster boards are located in the Samuel Beckett of Trinity Conference Centre, situated in the Arts Theatre, the Lower Concourse and the Upper Block (please see point 2 on Map) Concourse of the Arts Building (please see poster map layout page 14 & 15). REGISTRATION DESK Opening times: BADGES Sunday 2nd July 14.00hrs 18.00hrs Your badge must be worn at all time as it is your ticket Monday 19th to all sessions, tea/coffee, lunches, Welcome Reception Thursday 6th July 08.00hrs 18.00hrs and State Reception. Loss of your badge will incur a Friday 7th July 08.00hrs 13.00hrs replacement charge of 10.00
LIST OF DELEGATES A list of delegates will be available at the registration desk on request. This list is also on the abstract CD ROM. MESSAGES Urgent messages may be left on the message board at the registration desk. BANK There is a bank outside the University for foreign exchange on Monday to Friday only. There are automatic teller machines on site, which can be accessed 24 hours a day. SHOPPING Dublin has a busy city centre shopping area around Grafton street and across the river. There is a huge range of products to bring home; from traditional Irish handmade crafts to international designer labels. Things to buy; woollen knits, tweeds, crystal, Claddagh rings, pottery, silver and music. Shopping hours are from 9.00am to 6.00pm, Monday to Saturday, with shops open until 8.00pm on Thursdays, and most shops open from 12.00 noon to 6.00pm on Sundays.
LOST AND FOUND Articles found should be taken to the Registration Desk in the Arts Building. INSURANCE The Conference Organising Committee or its agents, will not be responsible for any medical expenses, loss or accidents incurred during the conference. Delegates are strongly advised to arrange their own personal insurance to cover medical and other expenses including accident or loss. Where a delegate has to cancel for medical reasons, the normal cancellation fee will apply. It is recommended that citizens from EU countries bring with them a current EHIC card. TRANSPORT TO EVENING EVENTS A conference coach service will be provided for the following evening functions: Sunday 2nd July Opening Ceremony and Welcome Reception Monday 3rd July Irish Night (Optional ticket required) Coaches on Sunday 2nd July will pick up and return delegates to Nassau Street. Coaches on Monday 3rd July to the Irish Night will depart from the main square in Dublin Castle at 19.45hrs and return delegates to the conference hotels after the Irish Night. (Please refer to Social Programme on page 10 for times of coaches for each social function) TAXIS In Dublin taxis are available at designated taxi ranks and can also be hailed down. Alternatively, you can book a taxi with the registration desk. Please see listed below recommended contact taxi companies for outside ofce hours: Taxi 2000 - 6775555 NCR Taxi 836 5555 POSTER #: 1-88 are located in The Beckett Theatre 89-145 are located in The Lower Concourse 146-200 are located in The Upper Concourse eg. 1-M is Poster#1 on Monday
EATING OUT Dublin has wonderful restaurants in the city centre. A list of restaurants will be available at the registration desk. TIPPING Tipping is at your discretion, in some hotels and restaurants a service charge of 10-15% is added to your bill. A small tip is appreciated for good service. Tipping is not unusual in pubs and bars. Tip cabs 10% and porters 65cent per bag. SMOKING POLICY Smoking is not permitted in any building in Trinity College. Since 29th March 2004 the Irish Government has implemented a smoking ban in the workplace in Ireland. This means smoking is forbidden in enclosed places of work in Ireland. This includes ofce blocks, various buildings, public houses/bars, restaurants and company vehicles (cars and vans).
POSTERS M- Poster to be displayed on Monday TU- Poster to be displayed on Tuesday W- Poster to be displayed on Wednesday TH- Poster to be displayed on Thursday F- Poster to be displayed on Friday
COFERENCE HOTELS: Westbury Hotel Davenport Hotel Alexander Hotel Mont Clare Hotel Clarion Hotel IFSC Brooks Hotel Quality Hotel Paramount Hotel Buswells Hotel Jurys Custom House Jurys Christchurch Academy Hotel Mercer Court Accommodation Isaacs Jacobs Inn Youth Hostel
Tel: Tel: Tel: Tel: Tel: Tel: Tel: Tel: Tel: Tel: Tel: Tel: Tel: Tel:
00-353-1-6791122 00-353-1-6073500 00-353-1-6073700 00-353-1-6073800 00-353-1-4338826 00-353-1-6704000 00-353-1-6439500 00-353-1-4179900 00-353-1-6146500 00-353-1-6075000 00-353-1-4540000 00-353-1-8780666 00-353-1-4744120 00-353-1-8555660
MEDICAL EMERGENCY CONTACT NUMBER: Doctors on Duty: 00353 1 453 9333
SOCIAL PROGRAMME Tickets for the Irish Night and Dublin Literary Pub Crawl can be purchased at the social & excursion section of the registration desk in the Upper Concourse of the Arts Building. SUNDAY, 2ND JULY - OPENING CEREMONY AND WELCOME RECEPTION Venue: OReilly Hall, UCD Coach: Depart 18:00 from Nassau Street and leave UCD at 21:30 for Nassau Street Time: 18:30-21:30 hours Dress: Casual This evening will provide an opportunity for delegates to meet in a relaxed environment and catch up with old friends. Return transportation will be provided. Cost included in Registration Fee MONDAY, 3RD JULY - STATE RECEPTION Venue: Dublin Castle Time: 18:30-20:00 hours Dress: Smart Casual A Minister will host a reception in the historic State Apartments of Dublin Castle. Delegates must make their own way there (6 minutes walking distance from Trinity College). Cost included in Registration Fee MONDAY, 3RD JULY - IRISH NIGHT (OPTIONAL NIGHT -TICKET REQUIRED) Venue: Taylors 3 Rock Coach: Depart 19.45hrs fron the Main Square in Dublin Castle. Time: 19:45-23:00 hours Dress: Casual This relaxed evening includes Irish music and craic and also contemporary Riverdance style dancing, paired with a delicious meal and drinks with dinner. Return transport will be available at the end of the evening to Nassau Street. Cost: 79.00
SOCIAL PROGRAMME
TUESDAY, 4TH JULY - DUBLIN LITERARY PUB CRAWL & DINNER IN TEMPLE BAR (OPTIONAL NIGHT -TICKET REQUIRED) Venue: Luigi Malones Time: 18:50-22:30 hours Dress: Casual Delegates are to meet at the main entrance to Trinity College at 18:50pm, marked number 1 on the map. Dinner and drinks will be served in Luigi Malones in the famous Temple Bar followed by a literary walk of famous Dublin Pubs. This will give you the opportunity to discover Dublin and its pubs through the eyes of famous Dublin Street Poets who will bring alive Dublins writers such as Swift,Yeats, Joyce, Wilde and Beckett. There will be a cash bar in each pub. Cost: 69.00 TUESDAY, 4TH JULY - ADVISORY BOARD DINNER (INVITATION REQUIRED) Venue: Alexander Hotel Time: 20:00-23:00 hours Dress: Casual A dinner for the Advisory Board will take place in the Annesly Suite of the Alexander Hotel. This evening will include dinner and drinks with dinner. Advisory Board Members are to make their own way their (5 minutes walking distance from Trinity College).
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WEDNESDAY, 5TH JULY - GALA DINNER (OPTIONAL NIGHT -TICKET REQUIRED) Venue: Trinity Dining Hall Time: 19:30-23:00 hours Dress: Smart The evening begins with drinks on arrival, followed by dinner and entertainment. Delegates are to make their own way to the Dining Hall marked number 5 on the map. Cost: 95.00 THURSDAY, 6TH JULY - CONCERT WITH THE GOETHE INSTITUT CHOIR DUBLIN AND W.J. BLAU, ORGAN IN ST.FINIANS CHURCH (OPTIONAL NIGHT TICKET REQUIRED) Venue: St.Finians Church, 24 Adelaide Road , Dublin 2 (15 minutes walking distance from Trinity through St. Stephens Green) Time: 20:00-21:30 hours Dress: Casual A program of classical music by Bach, Mozart, Palestrina, Lasso and others in the historical surroundings of St.Finians Church. Doors open at 19.45hrs Due to limited seating available in the church, attendance will be by pre-booked free tickets only and this event is now booked out. OPTIONAL TOURS Tickets for any of the following tours can be purchased at the Social/Excursion section at the conference registration desk in the Upper Concourse of Trinity College. Dublin City Tour (Hop On, Hop Off ) This fully guided tour gives you an overall avour of our historic and ancient city. You will see examples of Dublins superb architecture in the Georgian Streets and Squares. This hop-on-hop-off tour will allow you to visit St. Patricks Cathedral and Christchurch Cathedral, the Guinness Storehouse and the Old Jameson Distillery. Tour duration is approximately 90 minutes Details: This tour runs daily, with the rst tour departing at 09.30hrs. Cost: 15.00 per person Tour departs from: Stop 1, Outside Dublin Tourism, 14 Upper OConnell St, Dublin 1 Newgrange (Half Day Tour) In the heart of the Boyne Valley, Co. Meath. You will visit the Bru na Boinne Visitor Centre, which will interpret the archaeological heritage of the Boyne Valley, which includes the megalithic passage tombs of Newgrange & Knowth. You will be taken on a guided tour in the tombs the oldest and largest Neolithic burial chamber in Europe (3000BC), which predates the Egyptian Pyramids. Lunch in not included, although a lunch venue will be available on the day. Details: This tour runs on Monday 3rd July, Tuesday 4th July, Friday 7th July and Saturday 8th July. Times: Tour departs at 10.00hrs and returns to Dublin at 15.45hrs approx. Cost: 32.00 per person. Tour departs from: Gray line desk 1, Dublin Tourism Ofce, Suffolk St, Dublin 2 Please be at the meeting point 20 minutes before the tours departure.
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SOCIAL PROGRAMME
Wicklow Mountains, Valleys, Lakes, Glendalough & Avoca Tour (Full Day Tour) Sit back, relax and let us take you through some of the loveliest countryside in Ireland. This tour takes you rst throught the Wicklow Gap and the Blessington lakes, including a photo stop en route. The tour continues to the pretty village of Avoca (home to the famous drama Ballykissangle), with time to enjoy the famous Avoca Handweaver, reputed to be the oldest mill in Ireland. Then onto the highlight of the tour, Glendalough glen of the two lakes a truly spell binding place and home to the impressive 10th century Round Towers Details: This tour departs daily at 9.45hrs and returns to Dublin at 17.00hrs approx. Cost: 32.00 per person. Tour departs from: Stop 1, Outside Dublin Tourism, 14 Upper OConnell St, Dublin 1 Please be at the meeting point 20 minutes before the tours departure. The North Coast Tour / The Dublin Bay & Castle Tour After a brief introduction to Dublin City, you will visit the pretty coastal village of Malahide and the 14th century Malahide Castle, where you will enjoy a guided tour and have time to wander in the craft shops and gardens. The tour then trails past the pretty shing village of Howth towards Howth Summit where there will be a 10 minute stop to enjoy the breathtaking views of Dublin Bay. The tour then coninutes back into Dublin via the northern coastline. Details: This tour runs daily. Times: Tour departs at 14.15hrs and returns to Dublin at 17.30hrs approx. Cost: 22.00 per person Tour departs from: Stop 1, Outside Dublin Tourism, 14 Upper OConnell Street, Dublin 1 Please be at the meeting point 20 minutes before the tours departure.
Please note that you must make your own way to all departure destinations
SOCIAL PROGRAMME
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ACCOMMPANYING PERSONS PROGRAMME SUNDAY, 2ND JULY 18:00 Coaches depart Nassau Street for UCD 18:30 Opening Ceremony and Welcome Reception in OReilly Hall UCD 21:30 Coaches depart UCD for Nassau Street MONDAY, 3RD JULY 9:30am Meet in Trinity College Dining Hall for tea, coffee and scones 10:15 Tour of Trinity including book of Kells Dublin 12:00 A walking tour of Dublin and its elegant Georgian buildings Dublin Hop On Hop Off Tour
THURSDAY, 6TH JULY 9:30 Gather at The registration desk 9:45 Tour departs, visit Powerscourt Estate and Glendalough 17:15 Coach arrives back to Dublin
* Lunch is not included, although a lunch venue will be available on Monday and Thursday * Please ask at the registration desk for your Memnto. * Please note that accompanying persons may not attend scientic sessions or lunch in Trinity
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AC C O M PA N Y I N G P E R S O N S P RO G R A M M E
MONDAY, 3RD JULY 18:30 State Reception in Dublin Castle, Please make your own way there. (6 mins walking distance)
M A P O F E X H I B I T I O N A N D P O S T E R P R E S E N TAT I O N S
Upper Concourse
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ICSM REGISTRATION
1-M = Monday Poster #1 1-TU = Tuesday Poster #1 1-W = Wednaesday Poster #1 1-TH = Thursday Poster #1 1- FR = Friday Poster #1
Information Stands
Beckett Theatre
M A P O F E X H I B I T I O N A N D P O S T E R P R E S E N TAT I O N S
Lower Concourse
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SUNDAY 2ND JULY 18.00 18:30 20:00 20:00 21:30 21:30 MONDAY 3RD JULY 08:30 10:30 10:30 11:00 11:00 13:00 13:00 14:30 14:30 16:30 16:30 18:00 18:30 20:00 19:45 22:30 TUESDAY 4TH JULY 08:30 10:30 10:30 11:00 11:00 13:00 13:00 14:30 14:30 16:30 16:30 18:00 18:50 22:30 Parallel Sessions Tea/Coffee Break and Poster Session 2 Keynotes Speakers Lunch in Dining Hall, Buttery and Bar Parallel Sessions Tea/Coffee and Poster Session 2 Meet at Main entrance Trinity College at 18:50 for optional Dublin Literary Pub Crawl and Dinner (ticket required) Parallel Sessions Tea/Coffee Break and Poster Session 1 Keynotes Speakers Lunch in Dining Hall, Buttery and Bar Parallel Sessions Tea/Coffee and Poster Session 1 State Reception in Dublin Castle Coaches depart for optional Irish Night (ticket required) Coaches depart Nassau Street for OReilly Hall, UCD Opening Ceremony in OReilly Hall Welcome Reception in OReilly Hall Coaches depart for Nassau Street
P RO G R A M M E AT A G L A N C E
WEDNESDAY 5TH JULY 08:30 10:30 10:30 11:00 11:00 13:00 13:00 14:30 14:30 16:30 16:30 18:00 19:30 20:00 20.00 23.00 Parallel Sessions Tea/Coffee Break and Poster Session 3 Keynotes Speakers Lunch in Dining Hall, Buttery and Bar Industry Sessions and Parallel Sessions Tea/Coffee and Poster Session 3 Drinks Reception in Trinity Atrium Gala Dinner in Trinity Dining Hall (ticket required)
THURSDAY 6TH JULY 08:30 10:30 10:30 11:00 11:00 13:00 13:00 14:30 14:30 16:30 16:30 18:00 20:00 21:30 FRIDAY 7TH JULY 08:30 10:30 10:30 11:00 11:00 12:00 12:00 13:00 13:00 Parallel Sessions Tea/Coffee Break and Poster Session 4 Keynotes Speakers Closing Ceremony and Prize Giving Conference Closes Parallel Sessions Tea/Coffee Break and Poster Session 4 Keynotes Speakers Lunch in Dining Hall, Buttery and Bar Parallel Sessions Tea/Coffee and Poster Session 4 Organ and Choir in St.Finians Church, 24 Adelaide Road , Dublin 2
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SUNDAY, 2ND JULY
OPENING SESSION , CHAIR: M DEVANE, LUCENT AND NANOIRELAND

TIME 18:00 18:30 -20:00 TITLE PRESENTER ABSTRACT # VENUE Coaches depart Nassau Street for OReilly Hall, UCD Alan Heeger Alan G. MacDiarmid S1 S2 OReilly Hall, UCD
Keynote - Plastic Electronics and Opto-electronics: Whats New?? Keynote - The Azanes: A Class of Material Incorporating Nano/Micro Self-Assembled Hollow Spheres Obtained by Aqueous Oxidative Polymerization of Aniline 20:00 21:30 Welcome Reception in OReilly Hall 21:30 Coaches depart UCD for Nassau Street MONDAY, 3RD JULY
ORGANIC CONDUCTORS & SUPERCONDUCTORS 1, CHAIR: T TAKAHASHI

TIME 8:30 9:00 TITLE Invited - TTF derivatives for electronic devices New Charge Transfer Salts of BEDT-TTF and perylene with paramagnetic Re(IV) complexes Crystal Growth and Conduction Property Measurement of Micro/Nano-size Molecular Conductors on SiO2/Si Substrates Metastable phases and quantum transitions in an organic CT salt. Stripe pattern formation probed by local infrared spectroscopy in current injected KTCNQ Strong Magnetoresistance Anomaly Directly Associated with Spin Flop in the p-d system, (EDT-DSDTFVSDS)2FeBr4 X-ray diffraction for q-(BEDTTTF)2CsZn(SCN)4 in electric elds- current dependence on the structure-property relation Structural And Electromagnetic Properties Of The Incommensurate Organic Superconductor (MDT-TS)(AuI2)0.441 PRESENTER Concepci Rovira Carlos GimnezSaiz Hiroshi M.Yamamoto Anna Painelli T. Sasaki ABSTRACT # M1 M2 VENUE Ed Burke
9:15
M3
9:45
M5
10:00
T. Fujimoto
M6
10:15
Masashi Watanabe
M7
10:30
Tadashi Kawamoto
M8
17
ORAL PROGRAMME
9:30
M4
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES 1, CHAIR: A DALTON

TIME 8:30 9:00 TITLE Invited - Super-Growth-The Highly Efcient Synthesis of SWNTs: From Forests to Solids Bromination of Expanded Graphite Improves the Electrical Conductivity of Graphite-Polymer Nanocomposites Characterising Functionalised Carbon Nanotubes Chirality Specic Measurements Of Nanotube Magnetism Field Emission from Carbon Nanotubes: From Isolated Nanotubes to Polymer Matrix Cathodes Invited - Carbon Nanotubes: Optics And Dynamics In Low Dimensional Systems PRESENTER Don Futaba Gad Marom ABSTRACT # M9 M10 VENUE Swift
9:15 9:30 9:45
Peter Fearon Omar N. Torrens David Carey
M11 M12 M13
10:00
Tobias Hertel
M14
MOLECULAR, POLYMER & NANO-ELECTRONICS 1, CHAIR: S PEKKER

TIME 8:30 TITLE Invited - Photoinduced Electron Transfer In Molecular Complexes Of Fullerenes In Solid State Resonant Magnetization Tunnelings in a One-Dimensional Iron(II)-containing Oxalate Chain Structure Air-Stable N-Channel Organic Transistors Based on a Soluble C84 Fullerene Derivative Inkjet Printing of 40 cm Organic Field-Effect Transistor Active Matrices for the Application to Electronic Articial Skins Dynamics of bipolaron in a polymer chain: Formation and dissociation Air-Stable N-Channel Organic Field-Effect Transistors Based On N,N-Bis(4-Flurobenzyl) -3, 4, 9, 10 - Perlene Tetra carboxylic Diimide Tuning Hole-Injection Barriers at OrganicMetal Interfaces with Electron Accepting Molecules High Electron Mobility C60 Molecule based Organic Field Effect Transistor PRESENTER Rimma Lyubovskaya ABSTRACT # M15 VENUE Ui Chadain
9:00
Kuan-Jiuh Lin
M16
9:15
T.D. Anthopoulos Tsuyoshi Sekitani
M17 M18
ORAL PROGRAMME
9:30
9:45 10:00
Chang-Qin Wu Yoshinobu Hosoi
M19 M20
10:15
Steffen Duhm
M21
10:30
Nir Tessler
M78
18
ELECTROCHEMICAL APPLICATIONS, ACTUATORS & SENSORS 1,CHAIR: C BRESLIN

TIME 8:30 TITLE Invited - Adaptive Materials - Foundations for the Next Generation of Chemo/Bio Sensing Devices An Ionic Polymer-Metal Composite Sensor For Bending Curvature Measurements Thermodynamic Interpretations To Taste Sensor Characteristics Of Polyacrylic Acid Grafted Cellulose Membrane Simultaneous sensing and actuating articial muscles: tactile muscles and conscious devices. Entrapment of Peroxidase into Polypyrrole for NADH Sensing Highly Sensitive Immunodetection of Cancer Biomarkers using Carbon Nanotube Amplication Schemes Conducting IPN Pastille-Shaped Actuators: From The Polymer Chemistry To The Device PRESENTER Dermot Diamond ABSTRACT # M22 VENUE Emmett
9:00 9:15
D.M.G. Preethichandra Sharmistha Mitra
M23 M24
9:30
TF Otero
M25
9:45 10:00
Takeshi Yamauchi Fotios Papadimitrakopoulos C. Chevrot
M26 M27
10:15
M28
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 1, CHAIR: D L CARROLL
TIME 8:30 9:00 9:15 9:30 TITLE Invited - Developing OLED Technology for Lighting Effects of active area scaling on white OLED performances White Polymer light emitting diodes High-Efciency White-Light-Emitting Devices from a Single Polymer by Mixing Singlet and Triplet Emission Bright White Light-Emitting Device from Ternary Nanocrystal Composites Synthesis and Secondary Structure of Various Poly(N-propargylamides) Spin Mixing At Conjugated Polymer Heterojunctions PRESENTER Anil Duggal Claudia Piliego Junbiao Peng Wei Yang ABSTRACT # M29 M30 M31 M32 VENUE Walton
9:45 10:00 10:15
Giuseppe Gigli Toshio Masuda N. C. Greenham
M33 M34 M35
TEA/COFFEE BREAK
10:30 - 11:00
19
ORAL PROGRAMME
KEYNOTE MON 1 , CHAIR: W J BLAU

11:00 Architecture in NanoSpace Sir Harald Kroto M36 Ed Burke, linked with Walton & Emmett
KEYNOTE MON 2
12:00 Physical Aspects of the Origin of Life Problem Albert J. Libchaber M37
LUNCH
13:00 - 14:00 Dining Hall, Buttery and Bar
INHERENTLY CONDUCTIVE POLYMERS 1, CHAIR:J JOO

TIME 14:30 15:00 15:15 15:30 TITLE Invited - Functionalised Polythiophene Films and Fibres Effect of Molecular Weight on the Structure and Crystallinity of Poly(3-hexylthiophene) Conducting Polymers As Acceptor Materials In situ ESR-UV/vis/NIR Spectroelectrochemical Study of the Oligomer Formation: Thiophene-Thiophene versus Phenyl-Phenyl Coupling in 2-(Diphenylamino)-Thiophenes Electrochemical Polymerization and Spectroscopic Characterization of Poly(paraphenylene) in Ionic Liquids Free Radical Scavenging and Antioxidant Properties of Conducting Polymers Invited - Self-Assembly and Synthesis of Highly Conductive Organic Polymers and Oligomers PRESENTER David Ofcer A. Zen Carita Kvarnstrm Lothar Dunscha ABSTRACT # M38 M39 M40 M41 VENUE Emmett
15:45
P. Damlin
M42
ORAL PROGRAMME
16:00 16:15
Paul A. Kilmartin Richard D. McCullough
M43 M44
MOLECULAR, POLYMER & NANO-ELECTRONICS 2, CHAIR: R LYUBOVSKAYA

TIME 14:30 TITLE PRESENTER ABSTRACT # M45 VENUE Invited - Rotor-Stator Crystals Of Fullerenes S. Pekker With Cubane: Molecular Recognition And Topochemistry Nanostructuration Of Organic Semi-ConG. Wantz ductors For Optoelectronic Devices Ui Chadain
15:00
M46
20
15:15
15:30 15:45
16:00 16:15
Strong electron-phonon interactions and electron pairing in the photoinduced excited electronic states in p-conjugated molecular systems Optoelectronic properties of large area liquid crystalline monodomains Syntheses and Properties of Photochromic Molecules and Photochromic Conducting Polymers Selftrapped electronic states at junctions of organic semiconductors. High mobility terthiophene polymer eld-effect transistors
Takashi Kato
M47
W.J. Grzegorczyk Tsuyoshi Kawai
M48 M49
Natasha Kirova M.N. Shkunov
M50 M51
MOLECULAR MAGNETS & SPINTRONICS 1, CHAIR: M WOHLGENANNT

TIME 14:30 15:00 TITLE Invited - Spin Dynamics In Organic Light Emitting Diodes And Spin-Valves Magnetic exchange interactions and spin density distribution in oxamato-type single molecule magnets Coordination complexes as a tool for multifunctional molecular materials. Muon-spin relaxation studies of molecular magnets showing reduced dimensionality Giant Magnetoresistive Effect at Room Temperature of Photoconductive Poly(N-vinylcarbazole) Film Invited - Towards Molecular Spintronics PRESENTER Valy Vardeny Bjrn Bruer ABSTRACT # M52 M53 VENUE Room 3126
15:15 15:30 15:45
Lahcne Ouahab T. Lancaster Tadaaki Ikoma
M54 M55 M56
16:00
Stefano Sanvito
M57
ENERGY STORAGE & CONVERSION MATERIALS 1, CHAIR: B KIPPELEN

TIME 14:30 15:00 TITLE Invited - Charge Transport In Polymer Based Solar Cells Current-voltage characteristics under illumination comparison to absorption and external quantum efciency spectra of organic solar cells High-Efciency Polymer Solar Cells Using Solution-Based Titanium Oxide Optical Spacer Solar Cells of Low-Bandgap Polyuorenes PRESENTER Paul W.M. Blom Andr Moliton ABSTRACT # M58 M59 VENUE Ed Burke
15:15 15:30
Kwanghee Lee Mats R Andersson
M60 M61
21
ORAL PROGRAMME
15:45
16:00
Efcient vacuum deposited organic solar cells Peter Buerle with high photovoltage based on a new lowband-gap oligothiophene and fullerene C60 Invited - How to build and model efcient Jean Michel Nunzi nanostructured organic solar cells
M62
M63
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 2, CHAIR:A DUGGAL
TIME 14:30 TITLE Structural Modication Of Single Wall Carbon Nanotube With 2-(2-Thienyl)Ethanol And Its Application In Polymer Solar Cells Ultrafast photoinduced insulator-to-metal switching and coherent phonon in 1/4 lling BEDT-TTF based salts. An ultrafast and steady-state emission study of styryl-substituted terthiophenes: tuning from a p,p* to a charge-transfer emitting state Voltage-Induced Infrared Absorption From The Field-Effect Transistor Based On Tcnq Interacting Polar Chromophores: Standard and Unconventional Excitonic Effects Multicoloured Micro- And Nano-Pixels Obtained By Planar Localization Of Colloidal Nanocrystals Invited- High Efciency Organic Photovoltaics: From Materials To Device Design PRESENTER Ana F. Nogueira ABSTRACT # M64 VENUE Walton
14:45
Shinichiro Iwai
M65
15:00
Tracey M. Clarke
M66
15:15 15:30 15:45
Yukio Furukawa Francesca Terenziani Luigi Martiradonna
M67 M68 M69
16:00
David L. Carroll
M70
ORAL PROGRAMME
ADVANCED FIBERS, TEXTILES & COATINGS, CHAIR: R BAUGHMAN

TIME 14:30 TITLE Invited - Conjugated Polymers for Corrosion Control: Scanning Probe Investigations of Polypyrrole-Al alloy Interactions Electrospinning of polyconjugated Polymers Based on Polythiophene Conducting Polymer and Metallized Composites of Cellulose Fibres and Wood, and their Potential Applications Conducting Polymer Fibers Processed from Precursor Polymer Electrospun nanobers of conjugated polymers: morphology, optical and structural properties PRESENTER Dennis E. Tallman ABSTRACT # M71 VENUE Swift
15:00 15:15
G. Iardino James H. Johnston
M72 M73
15:30 15:45
Gregory A. Sotzing Francesca Di Benedetto
M74 M75
22
16:00 16:15
Development of Textile Batteries for Embed- Richard Helmer ded Electronic Garments. Invited - Processable Polyaniline Nanobers Richard B. Kaner for Flash Welding, Sensors and Actuators
M76 M77
TEA/COFFEE AND POSTER SESSION 1

16:30 - 18:30 SOCIAL EVENTS 18:30 20:00 State Reception in Dublin Castle 19:45 23:00 Coaches depart for optional Irish Night (ticket required)
23
ORAL PROGRAMME
TUESDAY, 4TH JULY
ORGANIC CONDUCTORS & SUPERCONDUCTORS 2, CHAIR: C ROVIRA

TIME 8:30 9:00 9:15 9:30 9:45 TITLE Invited - Charge Disproportionation in Organic Molecular Conductors Peierls coupling and neutral-ionic transition in TTFCA Spin-Glass Behavior in the t-type Organic Conductor Electron Transport In Linked Ferrocenes Metallization of (TTM-TTP)I3 with a Highly One-Dimensional Half-Filled Band under Pressure beyond 7 GPa High magnetic eld studies of the fully gapped charge-density wave system (Per)2M(mnt)2 (where M = Au and Pt). Critical Points of Successive Transitions in Charge-Density-Wave State under Magnetic Fields A New Series of Conducting Anion Radical Salts, EtMe3Z[Pd(dmit)2]2 (Z=N, P, As, Sb) Various Mott-insulating States and their Release under Pressure PRESENTER Toshihiro Takahashi A. Girlando T. Nakanishi Laren M. Tolbert S.Yasuzuka ABSTRACT # TU1 TU2 TU3 TU4 TU5 VENUE Ed Burke
10:00
Ross D. McDonald
TU6
10:15
R.Yamaguchi
TU7
10:30
Reizo Kato
TU8
INHERENTLY CONDUCTIVE POLYMERS 2, CHAIR: D OFFICER

TIME TITLE Invited - Hybrid Nanotubes, Nanowires, and Nanojunctions Using p-Conjugated Polymers: Characteristics and Applications Synthesis Of Low Band Gap Poly (PThienylenvinylene) Ptv Via A Soluble Precursor Route, The Dithiocarbamate Precursor Route Application of Polypyrrole to Flexible Substrates Towards intelligent materials applications of polymer composites: reinforcement, optical activity and electrical conductivity Highly Ordered Crystalline Thin Film of Pentacene Fabricated by Controlled Solution Process Invited - Nanostructured Conductive Polymers for Sensing and Machinery Applications PRESENTER J. Joo ABSTRACT # TU9 VENUE Emmett
ORAL PROGRAMME
8:30
9:00
Fateme Banishoeib
TU11
9:15 9:30
Noel Clark Marc in het Panhuis
TU12 TU13
9:45
Takashi Minakata
TU14
10:00
Itamar Willner
TU15
24
MOLECULAR, POLYMER & NANO-ELECTRONICS 3, CHAIR: D VUILLAUME

TIME 8:30 9:00 TITLE Invited - Light-Emitting And Charge Transport In Organic Solids And Molecular Electronics Electrical Bistability of Substituted Bithiophenes: New Systems for Molecular Memories Molecular design of hopping transport in self-organized oligosilanes: Anisotropy of carrier hopping parallel/perpendicular to the molecular axis Electrical Control of Frster Energy Transfer to a Single Molecule Fullerene-based memory devices: structural and morphological studies Invited - Mapping Chemical Bond Formation between a Metallic Probe and a Single Molecule PRESENTER Zhigang Shuai A. Bianco ABSTRACT # TU16 TU17 VENUE Ui Chadain
9:15
H. Okumoto
TU18
9:30 9:45 10:00
K. Becker Himadri S. Majumdar John J. Boland
TU19 TU20 TU21
INORGANIC NANOSTRUCTURES & NANOTUBES, CHAIR: J N COLEMAN

TIME 8:30 9:00 9:15 9:30 TITLE Invited - Structural Studies of Crystalline Materials Inside the Wall of Carbon Nanotubes Spontaneously-formed SiC nanobers: characterization and applications Simulated Lattice Relaxation Of Photoexcited Platinum-Halide Chains An unexpected crystallographic structure of Mo6S3I6 nanowires determined using aberration-corrected electron microscopy Electron Transport In Nb4.77te4 Single Crystals Invited -Functionality of MoSIx molecular nanowires from molecular connectors to composites. PRESENTER Malcolm L.H. Green A. Huczko Jun Ohara Valeria Nicolosi ABSTRACT # TU22 TU23 TU24 TU25 VENUE Room 3126
9:45 10:00
A. Stolovits Dragan Mihailovich
TU26 TU27
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 3, CHAIR: S CURRAN
TIME 8:30 9:00 TITLE PRESENTER ABSTRACT # TU28 TU29 VENUE Walton Invited - Light-emitting diode fabricated from Hiroyuki Tajima heme proteins and related compounds Photophysics of Blue Phosphorescent Ir Ruth E. Harding Complexes for OLED Applications
25
ORAL PROGRAMME
9:15
9:30
9:45 10:00 10:15
Ab initio MO-CI based quantum master equation approach to exciton dynamics of double fan-shaped dendrimers Anthracene-cored dendrimers for solutionprocessible blue emitters: syntheses, characterizations, photoluminescence and electroluminescence[1] Energy Transfer Processes In Organic-Inorganic Semiconductor Nanostructures Synthesis and properties of dendritic oligothiophenes (DOTs) Electrical and optical characterization of organic light-emitting diodes using different hole transport layers.
Ryohei Kishi
TU30
Xu-hui Zhu
TU31
S. Blumstengel Chang-Qi Ma Adriano R.V. Benvenho
TU32 TU33 TU34
ENERGY STORAGE & CONVERSION MATERIALS 2, CHAIR: S SARICIFTCI

TIME 8:30 9:00 TITLE Invited - Controlling the nanostructure of polymer-based solar cells Fabrication of Asymmetric Microdisk Based on -Conjugated Polymer and Its Unidirectional Laser Emission Properties Variable Band-Gap Polymer Based Solar Cell: Effect of Energy Transfer on Photoconversion Efciency Charge Transport In Thin Photocells - The Mobility Spatial-Distribution Function Photocatalytic Properties Of Perylene/ Phthalocyanine Bilayer Responsive To A Widespread Visible Light Of <750 nm Functionalized Poly(phenylene vinylene) Diblock Copolymers and Electrospun Blends for Polymeric Photovoltaic Cells Hybrid Solar Cells with Inorganic Nanoparticles and Organic Conjugated Polymers PRESENTER Dieter Neher A. Fujii ABSTRACT # TU35 TU36 VENUE Swift
9:15
D. Gupta
TU37
9:30
Noam Rappaport Keiji Nagai
TU38 TU39
ORAL PROGRAMME
9:45
10:00
John P. Ferraris
TU40
10:15
Helmut Neugebauer
TU41
TEA/COFFEE BREAK
10:30 - 11:00
KEYNOTE TUE 1 , CHAIR: J M KELLY

11:00 Magneto transport of synthetic nanostructures and their device applicability: conducting polymer nanobers and carbon nanotubes Yung Woo Park TU42 Ed Burke, linked with Walton & Emmett
26
KEYNOTE TUE 2
12:00 Charges and excitons at interfaces in polymeric semiconductor structure Sir Richard Friend TU43
LUNCH
ORGANIC CONDUCTORS & SUPERCONDUCTORS 3, CHAIR:B KORIN-HAMZIC

TIME 14:30 14:45 TITLE Superconductivity In Ion-Beam Metal Mixed Polymers BEDT-TTF Derivatives With Metal Binding Centres: Substrates For Bifunctional Materials. Organic eld-effect transistors based on tetrathiafulvalene derivatives with fused aromatic rings Theory Views of New Experimental Observations of Solitons in Quasi 1D Conductors. Charge Ordering State of ET, BETS and [Pd(dmit)2] Salts by Temperature-Dependent Vibrational Spectroscopy Abnormal Enhancement of the Interlayer Electric Conduction with an In-Plane Magnetic Field Strong optical nonlinearity and its fast photoswitching in charge ordered ferroelectric a-(BEDT-TTF)2I3 Metal-Insulator Transition and p-d Interaction of Quasi-1D Organic Conductors (DMET)4(MCl4)(TCE)2 (M=Mn,Co,Cu,Zn) Mechanism of carrier photogeneration and carrier transport in molecular crystal tetracene PRESENTER Adam P Micolich John D. Wallis ABSTRACT # TU44 TU45 VENUE Ed Burke
15:00
Jun-ichi Nishida
TU46
15:15 15:30
Serguei Brazovskii Takashi Yamamoto
TU47 TU48
15:45
W. Kang
TU49
16:00
Kaoru Yamamoto
TU50
16:15
H. Ito
TU51
16:30
Daniel Moses
TU52
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES 2, CHAIR: D FUTABA

TIME 14:30 15:00 TITLE PRESENTER ABSTRACT # TU53 TU54 VENUE Swift Invited - Thermal and Electromechanical Alex Zettl Properties of Carbon and BN Nanotubes Raman Spectra Of (N,M)-Identied Individu- M. Pailleta al Single-Walled Carbon Nanotubes
27
ORAL PROGRAMME
15:15
15:30
15:45 16:00 16:15
Coherent Anti-Stokes Raman Scattering On Single-Walled Carbon Nanotubes Thin Films Excited Through The Surface Plasmons Fractionation of Single Wall Carbon Nanotubes According to Diameter and Metallicity based on Their Inherent Redox Differences Electronic uctuations in Multi-walled carbon Nanotubes Experimental and Theoretical Studies of Nano-scale Periodic Porous Carbon Invited - Universal Properties Of QuasiOne-Dimensional Excitons In Semiconducting Single-Walled Carbon Nanotubes And Pi-Conjugated Polymers
S.Lefrant
TU55
Fotios Papadimitrakopoulos B. Raquet Katsumi Yoshino Sumit Mazumdar
TU56
TU57 TU86 TU58
SELF ASSEMBLY, CHAIR: J M KELLY

TIME 14:30 15:00 15:15 15:30 TITLE PRESENTER ABSTRACT # TU59 TU60 TU61 TU62 VENUE Room 3126 Invited - Non-covalent Graphitic Nanostruc- Takuzo Aida tures by Programmed Self-Assembly 3D Self-assembly of organic semiconductors Elena Mena-Osteritz Self-assembly of fully conjugated TTF oligom- Masahiko Iyoda ers Crystal Structures and Magnetic ProperTomoyuki Akutaties of Electron-Rich Polyoxometalates with gawa Hydrogen-Bonding Cations Self-organisation and self-assembly in nano/ Toru Maekawa micro objects disperse systems Functionalised Carbon Nanotubes as Building J.M. Balach Blocks of Electronic Self-assembled Nanostructures Statistical mechanics of self-assembly: are John F. Maguire there applications in nanomaterials manufacturing?
15:45
TU63 TU64
ORAL PROGRAMME
16:00
16:15
TU65
ELECTROCHEMICAL APPLICATIONS, ACTUATORS & SENSORS 2, CHAIR: G WALLACE

TIME 14:30 TITLE PRESENTER ABSTRACT # TU66 VENUE Invited - The High Speed Production, Proper- Ray Baughman ties, and Applications of Carbon Nanotube Yarns and Transparent Sheets Carbon Nanotube Reinforcement of ConG. M. Spinks ducting Polymers and Hydrogels for High Strength Actuators Ui Chadain
15:00
TU67
28
15:15 15:30 15:45
16:00 16:15
Origami Actuators With Conducting Polymers Linear and Out-of-Plane Conducting Polymer Actuators Soft actuators based on conducting polymers, polypyrrole, - High performance and the energy conversion efciency Electrochemical Behavior of Ferritin/Carbon Nanotubes Complex Films Transparent and Flexible Carbon Nanotube / Polyaniline pH Sensors
Hidenori Okuzaki Jadranka TravasSejdic K. Kaneto
TU68 TU69 TU70
Kwang Min Shin Martti Kaempgen
TU71 TU86
BIO/ MEDICAL MATERIALS & BIONANOTECHNOLOGY 1, CHAIR:V BARRON

TIME 14:30 TITLE Invited - Ultrasensitive Optical Detection of DNA and Proteins Based on Cationic Polythiophene Conjugated Oligomers And Polymers Functionalized With Small Biomolecules For Sensing Organic Field Effect Transistors Structure-Property Relationships in Melanins - a Unique Class of Conducting Bio-macromolecule High sensitivity polymer photodetectors for portable medical applications Inherently Conducting Polymer for Microuidics Dielectric Spectroscopy of DNA Aqueous Solutions Bio-Organic Field-Effect Transistor Memory Element PRESENTER Mario Leclerc ABSTRACT # TU73 VENUE Emmett
15:00
G.M. Farinola
TU74
15:15
P. Meredith
TU75
15:30 15:45 16:00 16:15
Xuhua Wang Y.Z. Wu S.Tomi P. Stadler
TU76 TU77
TU79
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 4, CHAIR: K WALZER
TIME 14:30 TITLE PRESENTER ABSTRACT # TU80 VENUE Walton Invited - Design And Synthesis Of ConjuSeth Marder gated Materials For Photonic And Opto-Electronic Applications Polymer/PCBM blend photovoltaic device B.C. Duck response at the rst telecom window. Excited states two photon absorption of M. Meneghetti molecular systems
15:00 15:15
TU81 TU82
29
ORAL PROGRAMME
TU78
15:30
15:45
16:00
The Role Of Excitons Statistic Distribution In The Temperature Dependence Of The Poly(9,9-Dioctyluorene) -Phase Photoluminescence 3-Dimensional Energy Transport in Highly Luminescent Condensed Media: Quantitative Experimental and Theoretical Analysis Primary photoexcitations and their interconversion in oligophenylenevinylene nanocrystals: the role of excess energy studied with sub-30 fs resolution
M. Anni
TU83
Johannes Gierschner H.-J. Egelhaaf
TU84
TU85

16:30 - 18:00 SOCIAL EVENTS 18:50 22:30 Meet at Main entrance Trinity College for optional Dublin Literary Pub Crawl and Dinner (ticket required)
ORAL PROGRAMME
30
WEDNESDAY, 5TH JULY
ORGANIC CONDUCTORS & SUPERCONDUCTORS 4, CHAIR: D MOSES

TIME 8:30 TITLE Invited - Magneto-transport properties of Quasi-One-Dimensional Organic Conductors FT-IR and Raman spectroscopic study, aided by quantum chemical DFT calculations of the conducting salt (DOEO)4HgBr4TCE Mixed Order Parameters, Accidental Nodes And Broken Time Reversal Symmetry In Organic Superconductors: A Group Theoretical Analysis Exchange interaction between p conduction electrons and localized 3d spins on the eld induced superconductor, l-(BETS)2FeCl4; studied by 77Se NMR 13C NMR and X-ray Analyses of Charge Ordering Phenomena in (TMTTF)2X Polymorphism in organic semiconductors PRESENTER Bojana Korin-Hamzic A. apiski ABSTRACT # W1 VENUE Ed Burke
9:00
W2
9:15
B. J. Powell
W3
9:30
K. Hiraki
W4
9:45 10:00 10:15 10:30
Metallic and Mott-Hubbard Insulating States in Potassium Intercalated Pentacene Multimode Peierls Distortion and 2D Dimer- Yoshiyuki Ono ization
Toshikazu Nakamura Raffaele G. Della Valle Monica F. Craciun
W5 W6 W7 W8
INHERENTLY CONDUCTIVE POLYMERS 3, CHAIR: M IN HET PANHUIS

8:30 9:00 Invited - Synthesis Of Conducting Polymers In Ionic Liquids Computer Simulations Of The Structural Properties Of Conducting Polymers: The Review Of Some Recent Results Vapour phase polymerized poly(3,4-ethylenedioxythiophene) (VPP-PEDOT) Electron-Ion Interaction in Conducting Polymers Meta-Stable Polaronic Phase Induced By Background Illumination In MEH-PPV N-Functionalized Dithieno[3,2-b:2,3d]pyrroles: Monomers, Oligomers, and Polymers Jenny Pringle W. uny W9 W10 Emmett
9:15 9:30 9:45 10:00
Lichun Chen V.N. Prigodin E. Ehrenfreund Seth C. Rasmussen
W11 W12 W13 W14
31
ORAL PROGRAMME
TIME
TITLE
PRESENTER
ABSTRACT #
VENUE
10:15 10:30
Nanober Seeding: A General Synthetic Sanjeev K. Manohar Route to Conducting Polymer Nanobers Polyaniline Nanotubes Formed in Amino Acid Paul A. Kilmartin Solutions
W15 W16
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES 3, CHAIR: T HERTEL

TIME 8:30 9:00 9:15 TITLE Invited -Four-Point Resistance of Carbon Nanotubes Physical Properties of Novel Free-standing Polymer Nanotube Thin Films High Resolution Inkjet Printed Single-Walled Carbon Nanotube (SWNT) TFT for Macroelectronic Devices 2d Carbon Nanotube Networks: A New Material For Transparent Electronics A new interpretation of the G band of nanotubes Invited - Synthesis and Properties of Carbon Cluster Complexes PRESENTER Adrian Bachtold Emer Lahiff Gyoujin Cho ABSTRACT # W17 W18 W19 VENUE Swift
9:30 9:45 10:00
David Hecht Chiara Castiglioni Eiichi Nakamura
W20 W21 W22
MOLECULAR, POLYMER & NANO-ELECTRONICS 4, CHAIR: J PATTERSON

TIME 8:30 9:00 TITLE Invited - Electronic Properties Of Organic Monolayers And Nanowires Hexagonal Network Organization Of DyeLoaded Zeolite L Crystals By Surface Tension Driven Auto-Assembly Comparative Study on Field-Effect and Electrochemical Transistors of P3HT and SWNT Structure and Function: Probing the Role of Morphology in Organic Electronic Devices Acid Base Chemistry in Conjugated Materials The Effect of Polarization on Intermolecular Electronic Coupling and Charge Transport in Organic Semiconductors Voltage Induced Metal-Insulator Transition in Organic Field-Effect Transistors PRESENTER Dominique Vuillaume Sami Yunus ABSTRACT # W23 W24 VENUE Ui Chadain
ORAL PROGRAMME
9:15 9:30 9:45 10:00
H. Shimotani P.C. Dastoor Douglas S. Dudis Demetrio A. da Silva Filho Anoop S. Dhoot
W25 W26 W27 W28
10:15
W29
32
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 5, CHAIR: R MENON
TIME 8:30 TITLE Invited - Functional Nanocomposites Based On Semiconducting Polymers For Light-Emitting And Photovoltaic Applications Efcient white OLED for lighting application: combination of uorescent and phosphorescent light emitting materials Soluble and thermally stable molecules for Organic Light-Emitting Transistors Dynamics of bipolaron in a polymer chain: Formation and dissociation Phosphorescent Dendrimers With Charge Transporting Dendrons Saturable and reverse Saturable Absorption of Asymetric Push -Pull Porpymns PRESENTER Gitti Frey ABSTRACT # W30 VENUE Walton
9:00
Byung Doo Chin
W31
9:15 9:30 9:45 10:00
F.Cicoira Chang-Qin Wu Paul L. Burn Eleni G.A. Notaras
W32 W33 W34 W58
ENERGY STORAGE & CONVERSION MATERIALS 3, CHAIR: M SUMMERS

TIME 8:30 TITLE Invited - A Theoretical Insight Into Charge Generation And Recombination Rates In Organic Solar Cells High-Efciency Photovoltaic Devices Based on Regioregular 3-Alkoxythiophene Copolymers Conjugated Block Copolymers for Photovoltaics Using Proximal Probe Microscopy and Spectroscopy to develop and fabricate high efciency Organic Solar Cells Determination of the Electron dynamics in Blends of Conjugated Polymers and Fullerene Derivatives Polarized Emission Microspectroscopy of Thiophene/Phenylene Co-Oligomer Crystals Invited - Multilayer Organic Solar Cells Based On Polycrystalline Semiconductors PRESENTER Jerome Cornil ABSTRACT # W35 VENUE Room 3126
9:00
Qibing Pei
W36
9:15 9:30
Sam-Shajing Sun Seamus Curran
W37 W38
9:45
T.J. Savenije
W39
10:00 10:15
Takeshi Yamao Bernard Kippelen
W40 W41
TEA/COFFEE BREAK
10:30 - 11:00
33
ORAL PROGRAMME
KEYNOTE WED 1, CHAIR: J N COLEMAN

11:00 Taming carbon nanotubes for electronics Eleanor Campbell W42 Ed Burke, linked with Walton & Emmett
KEYNOTE WED 2
12:00 Fluorene-Based Polymer Gain Media Donal Bradley W43
LUNCH
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 6, CHAIR: T MATSUI
TIME 14:30 15:00 15:15 TITLE Invited - White Light From OLEDS A New Lighting Source Tunability Of The Optical Properties Of Nanostructured Composite Polymeric Materials A Theoretical Study On The Exciton Binding Energy In Coupled Poly(P-Phenylene Vinylene) Molecules p-Conjugated Organic Ionic Crystals for Terahertz-Wave Generation Polymer Matrix Based Phosphorescent Emitters Electrochemical And Spectroscopic Properties Of Photoluminescent Oligomers And Polymers With Mixed Electronic And Redox Conductivity Polymer Light-Emitting Electrochemical Cells with Multiple or Relaxed Homojunction PRESENTER Karsten Walzer A. Camposeo K. Gao ABSTRACT # W44 W45 W46 VENUE Walton
15:30 15:45 16:00
Shuji Okada Hartmut Krueger Mieczyslaw Lapkowski
W47 W48 W49
ORAL PROGRAMME
16:15
J. Gao
W50
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES 6, CHAIR: G LANZANI

TIME 14:30 15:00 TITLE PRESENTER ABSTRACT # W51 W52 VENUE Swift Invited - Protein Functionalisation of Carbon Alan Dalton Nanotubes Dispersion Of Single-Walled Carbon Nano- Silvia Giordani tubes
34
15:15
15:30 15:45
16:00
Electrochemical Devices Prepared from Conducting Polymer Film and Fibre. Utilizing Room Temperature Ionic Liquid Electrolyte High Optical Quality Carbon Nanotube-Polymer Composites For Photonics Applications Electroactive Polymer-Carbon Nanotube Composites: Smart Materials for Optoelectronic Applications Invited - Charge Transport In Doped SingleWalled Carbon Nanotubes
Benjamin R. Mattes
W53
V. Scardaci W.K. Maser
W54 W55
Vojislav Krstic
W57
DESYGN-IT WORKSHOP
14:30 - 16:30 Details of European Project Results on Nanotube Syunthesis and Apllications for Selected Industrial Technologies DESYGN-IT Team W59 Room 3126

16:30 - 18:00 SOCIAL EVENTS 19:30 20:00 Drinks Reception in Trinity Atrium 20.00 23.00 Gala Dinner in Trinity Dining Hall
35
ORAL PROGRAMME
THURSDAY, 6TH JULY
ORGANIC CONDUCTORS & SUPERCONDUCTORS 5, CHAIR: S ROTH

TIME 8:30 9:00 TITLE Invited - ET Compounds; Playground Of Spin And Charge With Frustration Superconductors, metals and semiconductors of BEDT-TTF with magnetic [Fe(C5O5)3]3- and [M(C2O4)3]3- complexes (M = Fe and Cr) The Coupling between Magnetic Transition and Conducting Properties in a Spin-Crossover Molecular Conductor High Pressure Optical Spectroscopy Of The Neutral-Ionic Phase Transition In TTF-CA Magnetic Torque in Superconducting State of l-(BETS)2FexGa1-xClO4 Structural Studies Of 2D Organic Conductors Having Charge Ordered And Superconducting Phases New complexes Based on Extended TTF Ligands: A Basis for New Single-Component Molecular Metals Magnetic Field Induced Connement In Layered Conductors PRESENTER Kazushi Kanoda Carlos J. GmezGarca Kazuyuki Takahashi ABSTRACT # TH1 TH2 VENUE Ed Burke
9:15
TH3
9:30 9:45 10:00
M. Masino S. Uji Ryusuke Kondo
TH4 TH5 TH6
10:15
M. Almeida
TH7
10:30
S. Haddad
TH8
INHERENTLY CONDUCTIVE POLYMERS 4, CHAIR: J PRINGLE

TIME TITLE Polyazulene and its Derivative: Electrosynthesis and Spectroelectrochemical Characterisation Nanoscale Composites Of Conducting Polymers: Characterisation And Possible Applications Helical Conjugated Polymers - Chiral Polymerization and Super Hierarchical Structure Hybrid Systems Of Conjugated Polymers And Platinum Group Metals Comparison Of Polaron Pairs And Bipolarons As Doubly Charged States Of Conjugated Polymers Evidence Of Effective Conjugated Segment Distribution In PPV And PPV-SWNT Composite Films: Role Of Precursor And Conversion Temperature PRESENTER B. Meana-Esteban ABSTRACT # TH9 VENUE Emmett 8:45
ORAL PROGRAMME
9:00
C.Visy
TH10
9:15 9:30 9:45
Kazuo Akagi Magdalena Hasik Gernot Paasch
TH11 TH12 TH13
10:00
E. Mulazzi
TH14
36
10:15
Effects Of Gold Nano-Particles On Optical And Transport Properties Of Conjugated Polymers
Daniel Moses
TH15
MOLECULAR, POLYMER & NANO-ELECTRONICS 5, CHAIR: P DASTOOR

TIME 9:00 9:15 TITLE Photophysical Properties Of Dyes Inserted In Nanostructured Organic Hosts Exciton Mobility, Static Disorder, And Lattice Phonon-Exciton Coupling In Oligothiophene Crystals Molecular Weight Effects on Phase Separation and Performance of Light-Emitting Diodes Fabricated with Polyuorene-Based Conjugated Polymer Blends Controlled Crystallization of Organic Semiconductors by Reticulate Doping and Zonecasting Techniques Controlling molecular level alignment and interface dipoles in self-assembled monolayers on noble metals: A theoretical study New polymers for organic electronics effect of molecular and supramolecular parameters on the performance of eld effect transistors and photovoltaic cells. PRESENTER C. Botta L. Raimondo ABSTRACT # TH16 TH17 VENUE Ui Chadain
9:30
Keng-Hoong Yim
TH18
9:45
Jacek Ulanski
TH19
10:00
Egbert Zojer
TH20
10:15
Adam Pron
TH21
8:30 8:45 9:00 9:15
9:30 9:45 10:00
Spin-Orbital Coupling Effects on Magnetoresistance in Organic Semiconducting Materials High Temperature Magnetoresistance in Thin Film Organic Semiconductors Advances in the structuring and patterning of single-molecule magnets on surfaces Photo-Induced Switchiing Between SingleChain Quantum Magnet And Paramagnet, And Conducting Single-Molecule Quantum Magnets And Single-Chain Quantum Magnets Giant magnetoresistance effect in C60-Co nano-composites Towards Controlled Magnetism in ElectronDoped Metal-Phthalocyanine Materials Large Magnetoresistance In OLEDS
Bin Hu Jeremy D. Bergeson J.Veciana Masahiro Yamashita
TH22 TH23 TH24 TH25
Room 3126
S. Miwa Monica F. Craciun M. Wohlgenannt
TH26 TH27 TH28
37
ORAL PROGRAMME
TIME
TITLE
PRESENTER
ABSTRACT #
VENUE
10:15
Reaction of iron with C60 at high temperaA.V.Talyzin ture high pressure conditions: formation of Fe3C and implications for magnetic carbon.
TH29
BIO/ MEDICAL MATERIALS & BIONANOTECHNOLOGY 2, CHAIR: E MAGNER

TIME 8:30 9:00 TITLE Invited - Materials and Applications for Medical Devices Amyloid-like protein brils for alignment and assembly of conjugated polyelectrolytes into nanowire geometries. Picosecond Infra-red Transient Absorption Studies of DNA in Different Conformations Photo-initiated Synergistic Processes in Bacteriorhodopsin-Conducting Polymer Systems Hierarchical Structure and EL Properties of Photopolymerized DNA/Polyaniline Complex A novel cationic conjugated polymer for DNA detection Invited - Organic Conductors and Medical Bionics: Current Status and Future Opportunities PRESENTER James McLaughlin Anna Herland ABSTRACT # TH30 TH31 VENUE Swift
9:15 9:30 9:45
John M. Kelly N. Arun Norihisa Kobayashi
TH32 TH33 TH34
10:00 10:15
Jadranka TravasSejdic Gordon Wallace
TH35 TH36
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 7, CHAIR: I SAMUEL
TIME TITLE Invited - Tunable Plasmonic Photonic Crystals Using Heavily-Doped Organic Conducting Polymers Thiophene-Based Dendritic Materials Energy Modulated Heterostructures For Charge Transfer And Connement Based On Conjugated Polymers Correlated Charge Transport through MottInsulator-Metal Interfaces Tetracene Light Emitting Transistors on unusual substrates Energy Transfer Processes In Hybrid Organic-Inorganic Nanocomposites Effects of different length-scale organicorganic heterojunctions on photophysical process. PRESENTER T. Matsui ABSTRACT # TH37 VENUE Walton 8:30
ORAL PROGRAMME
9:00 9:15
Amaresh Mishra F. E.G. Guimares
TH38 TH39
9:30 9:45 10:00 10:15
K.Yonemitsu C. Santato Carsten Dosche Annamaria Petrozza
TH40 TH41 TH42 TH43
38
TEA/COFFEE BREAK
10:30 - 11:00
KEYNOTE THU 1 , CHAIR: M MCNAMARA

11:00 Nanoshuttles and Force-Activated Nanoadhesives Viola Vogel TH44 Ed Burke, linked with Walton & Emmett
KEYNOTE THU 2
12:00 New Molecular and Supramolecular Motifs For the Construction of Organic Semiconductors Klaus Muellen TH45
LUNCH
13:00 - 14.30 Dining Hall, Buttery and Bar
ORGANIC CONDUCTORS & SUPERCONDUCTORS 6, CHAIR: AKIKO KOBAYASHI

TIME 14:30 15:00 15:15 TITLE Invited - Exploration of Charge Transfer Salts Based On Cytosine-TCNQ Derivatives The slow, hot death of interlayer coherence in k-phase BEDT-TTF superconductors Nature of Photo-induced Metallic Phase in (EDO-TTF)2PF6 Studied by Ultrafast IR Spectroscopy Ab Initio Electronic-Structure Calculations for Single-Component Molecular Conductors Charge Carrier Dynamics in the Vicinity of the Mott Transition in k-(BEDT-TTF)2X Unconventional Interlayer Magnetotransport in the Weakly Incoherent Regime PRESENTER Gunzi Saito Paul Goddard Ken Onda ABSTRACT # TH46 TH47 TH48 VENUE Ed Burke
15:45 16:00
Michael Dumm M.V. Kartsovnik
TH50 TH51
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES 4, CHAIR: A KAISER

TIME 14:30 15:00 TITLE Invited - Dispersions And Ordered Assemblies Of Carbon Nanotubes Control of Carrier Density by the Solution Method in Carbon Nanotube Transistors PRESENTER Philippe Poulin T. Takenobu ABSTRACT # TH52 TH53 VENUE Swift
39
ORAL PROGRAMME
15:30
Shoji Ishibashi
TH49
15:15
15:30
15:45 16:00
16:15
The role of the encaged species on fullerene stability: Dysprosium-based endohedral fullerenes Design, Synthesis, and Electrochemical Characteristics of Highly Near-Infrared Absorbing Emerald Green [60]Fullerene Acceptors Ultrashort pulse mode-locked laser based on nanotube saturable absorbers Sterically Hindered DiphenylaminouoreneC60 Dyads and Triads: Synthesis, Multiphoton Absorption and Energy-Transfer Studies Invited - Coherent Phonons In Carbon-Based Nanostructures: Probing Molecular Dynamics In The Time Domain
Lothar Dunsch
TH54
Long Y. Chiang
TH55
A.G. Rozhin Loon-Seng Tan
TH56 TH57
Gugliemo Lanzani
TH58
MOLECULAR, POLYMER & NANO-ELECTRONICS 6, CHAIR: P DAWSON

TIME 14:30 TITLE Invited - Aberration-Corrected Scanning Transmission Electron Microscopy For The Atomic And Electronic Structure Characterisation Of Nanomaterials Photoinduced Electron Transfer In DonorAcceptor Fullerene Based Compounds In Solid State Size-dependence of electronic coupling revealed by self-assembling oligothiophenes Electronic properties of helically-wrapped nanotubes Solution-processed Thin Film Transistors Using Random-network Carbon Nanotubes Disentangling electron and hole currents in bipolar devices From Conductive Polymer Composites with Controlled Morphology to Smart Materials PRESENTER Peter Nellist ABSTRACT # TH59 VENUE Ui Chadain
15:00
R.N. Lyubovskaya
TH60
15:15 15:30
Sebastian Westenhoff Andrew Wall M. Shiraishi M. Kemerink G. Boiteux
TH61 TH62 TH63 TH64 TH65
ORAL PROGRAMME
15:45 16:00 16:15
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 8, CHAIR: S MARDER
TIME 14:30 TITLE Enhancement of the Spontaneous Emission Rate of a Fluorescent Molecular Dye Imbedded in a Micro-Pillar Microcavity A High Work-Function Conducting Polymer for Enhanced OLED Performance PRESENTER A. M. Adawi ABSTRACT # TH66 VENUE Walton
14:45
C-H. Hsu
TH67
40
15:00 15:15
15:30
15:45
Inuence Of Doping On Spin Dependent Exciton Formation in Alq3 based OLEDs Exciton-Phonon Coupling In Tetrauoroacridine Single Crystals: Free And Self-Trapped Excitons Hybrid Metal/Organic Systems For Photonics: Polydiacetylenes Mono-Layers On Au Nanoparticles And Self-Assembled Films On Functionalized Surfaces Colour-Tuning Of Light-Emitting Devices Based On Polyuorine Derivatives Through The Maskless Dye-Diffusion Technique
Carlos F. O. Graeff S. Tavazzi
TH68 TH70
Marina Alloisio
TH71
Kazuya Tada
TH72
ENERGY STORAGE & CONVERSION MATERIALS 4, CHAIR: J CORNIL

TIME 14:30 TITLE Resonance energy transfer from organic chromophores to PCBM: a mechanism for improved exciton harvesting in organic photovoltaic cells? Flexible, Long Lived, Large Area Organic Solar Cells Solar Cells And OLEDs With Transparent Carbon Nanotube Electrodes Effect of Soluble Fullerene Addition in Polymer:Polymer Solar Cells Molecular Heterostructure Organic Solar Cells Light-Harvesting Host-Guest Antenna Materials for Photonic Devices The Inuence of Nanomorphology of Treated and Untreated Bulk-Heterojunction Solar Cells to the Charge Carrier Transport and Recombination PRESENTER Melissa A. Summers ABSTRACT # TH73 VENUE Room 3126
15:00 15:15 15:30 15:45 16:00 16:15
Christoph Lungenschmied Anvar A. Zakhidov Y. Kim F.Meghdadi Andr Devaux R. sterbacka
TH74 TH76 TH77 TH78
TH80
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 9, CHAIR:T KOBAYASHI
TIME 14:30 TITLE PRESENTER ABSTRACT # TH81 VENUE Emmett Invited - Intra- And Interchain Triplet DiffuAnna Khler sion In A Pt-Containing Polymer And Monomer Apparent Vibronics In P-Conjugated Systems; E. Ehrenfreund Coalesced Raman Modes
15:00
TH82
41
ORAL PROGRAMME
TH79
15:15
15:30 15:45 16:00
16:15
Unravelling Structure-Property Relations In Polyuorene-Based Organic Semiconductors Using Single Molecule Spectroscopy Multilayer Light-Emitting Diodes Based on Crosslinked Polyuorenes Efcient Frster Coupling between Inorganic and Organic Excitons Enhanced gain induced by Surface-PlasmonResonance in dyes-gold nano-particles in polymer Random Lasers -Electron Delocalization and Reversible Optical Switching in New Photochromic Oligomers and Polymers. From Molecules to Devices
K. Becker
TH83
Jorge Morgado C. Belton D.Davidov
TH84 TH85 TH86
G. Zerbi
TH87

16:30 - 18:00 SOCIAL EVENTS 20:00 21:30 Organ and Choir in Trinity Chapel (ticket required)
ORAL PROGRAMME
42
FRIDAY, 7TH JULY
ORGANIC CONDUCTORS & SUPERCONDUCTORS 7, CHAIR: G SAITO

TIME 8:30 TITLE Invited - Single-component Molecular Metals and Novel Monoanionic Metal Complexes with Extended-TTF Type Ligands. Annihilation of Magnetism due to Faint Molecular Displacements in (TPEDOT)3(Sb2F11)(benzene) Conduction Mechanism of Network Structures between Molecular-Assembly Nanowires and Nanoparticles Non-Linear Current-Voltage Characteristics of q-(BEDT-TTF)2MZn(SCN)4 (M=Cs, Rb) Trends in the superuid stiffness of molecular superconductors Direct Micro-Patterning of TTF-Based Organic Conductors on Flexible Substrates Electrical properties of conductive LangmuirBlodgett lms of dialkyldimethylammoniumAu(dmit)2 salt PRESENTER Akiko Kobayashi ABSTRACT # F1 VENUE Ed Burke
9:00
Hideki Yamochi
F2
9:15
F3
9:30 9:45 10:00 10:15
Yamaguchi Takahide Stephen J. Blundell Marta Mas-Torrent Yasuhiro F. Miura
F4 F5 F6 F7
INHERENTLY CONDUCTIVE POLYMERS 5, CHAIR: E. EHRENFREUND

TIME 8:30 TITLE Spatially Continuous Phase Of Highly Conductive Polypyrrole On Polyethylene Porous Films ESR, Raman and Conductivity and Studies on Fractionated Poly(2-methoxy-aniline-5-sulfonic acid) Conducting Polymer Photopolymerization: The Role of Nitrate ons Probing Electronic States Existing Outside Of p-Conjugated Polymer Surface Strong Effect Of The Diameter On The Electrical Properties Of Single PEDOT Nanowires Calcium Silicate Facilitated Polymerisation of MAS Induction Of Titanium Deposition Through Nucleation With Pyrrole In An Ionic Liquid Fabrication Of Conducting Polymer Nanowire Devices PRESENTER G.K.Elyashevich ABSTRACT # F8 VENUE Emmett
8:45
P.C. Innis
F9
9:00 9:15 9:30
W.M. de Azevedo X.T. Hao J.L. Duvail
F10 F11 F12
9:45 10:00 10:15
T. Borrmann William E. Price N.T. Kemp
F13 F14 F15
43
ORAL PROGRAMME
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES 5, CHAIR: P POULIN

TIME 8:30 9:00 9:15 TITLE Invited - Electronic Properties of Carbon Nanotubes and Other Materials Ultraviolet Photoelectron Spectroscopy of Multiple Atoms Encapsulated Fullerenes In Vitro Cytoxicity Testing Of Single Walled Carbon Nanotubes On Human A549 Lung Cells A Cellular And Spectroscopic Study Light Actuation of Polymer-Nanotube Composites Raman Analysis of Highly Conjugated Polypyrrole on Multiwalled Carbon Nanotube Nanotemplates Invited- Direct Spinning of Carbon Nanotube Fibres with Metallic Characteristics PRESENTER Alan B. Kaiser Shojun Hino Alan Casey ABSTRACT # F16 F17 F18 VENUE Swift
9:30 9:45
Samit Ahir Bin Chen
F20 F21
10:00
Alan Windle
F22
MOLECULAR, POLYMER & NANO-ELECTRONICS 7, CHAIR: C BOTTA

TIME 8:30 TITLE Invited - Organic and Hybrid Nanocomposites for Optoelectronic Devices and Bio-Organic Interface. Conduction In Disordered Semiconducting Polymers: New Theoretical Perspectives The Fabrication of Interdigitated Electrodes with low cost Nanoimprint Lithography and Electroplating for Photovoltaic Applications High-Performance Ambipolar Transistors And Schottky Diodes Based On Rubrene Single Crystals Temperature Dependence Of Electrical Characteristics Of Thin-Film Field-Effect Transistors Magnetic States and Peierls Instability in Polyacene Bloch Oscillations In A One-Dimensional Conducting Polymer PRESENTER Serdar Sariciftci ABSTRACT # F23 VENUE Ui Chadain
9:00 9:15
P.A. Bobbert Ravin Ginige
F24 F25
ORAL PROGRAMME
9:30
T. Takenobu
F26
9:45
P. Stallinga
F27
10:00 10:15
Maria Cristina dos Santos D. S. Liu
F28 F29
44
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS 10, CHAIR: A KHLER
TIME 8:30 9:00 9:15 9:30 9:45 TITLE Invited - Light-emitting dendrimers: tuneable optoelectronic materials Sub-Wavelength Structures For Polymer Lasers Contradictory Roles Of Excited State Absorption In Laser Materials Charge Transfer Rates, Quenching and NonAdiabaticity Waveguiding, Microcavity Effects and Optically Pumped Lasing in Single Polymer Nanowires Visible And Near-Infrared Optical Gain And Laser Emission In Photopumped Micro- And Nano-Structured Polymer Laser Cavities Fluorescence Up-Conversion And Lasing In Semiconducting Polymers PRESENTER Ifor Samuel Colin R. Belton Hacene Manaa Donal MacKernan Deirdre OCarroll ABSTRACT # F30 F31 F32 F33 F34 VENUE Walton
10:00
Takeyuki Kobayashi
F35
10:15
G. Tsiminis
F36
TEA/COFFEE BREAK
10:30 - 11:00
KEYNOTE FRI 1, CHAIR: H J BYRNE

11:00 Organic-Based Magnets and Spintronics Arthur Epstein F37 Ed Burke, linked with Walton & Emmett
CLOSING CEREMONY AND PRIZE GIVING

12:00 - 13:00
45
ORAL PROGRAMME
Each delegate will receive a CD Rom containing the abstracts for the poster presentations. Posters are located in the Beckett Theatre, the Lower Concourse and the Upper Concourse of the Arts Building. See map on page for location of posters. Surname, First Name Aarnio, H. Abbas, Gamal Abe, Shuji Abe, Masahiro Abrusci, Agnese Adawi, A. M. Agostinelli, T. Ahn, Sejung Ach, R. Ach, R. Ak, Metin Akagi, Kazuo Akima, N. Akimoto, Tatsuya Akutsu, Hiroki Akutsu-Sato, Akane Akutsu-Sato, Akane Alccer, Lus Alcock, Bernadette E. Aleshin, A. N. Alves, Helena Amarasinghe, D Ambrosch-Draxl, Claudia Analytis, James G. Andersson, Jens Antognazza, M.R. Antony, Rmi Aron, Denis Arima, Valentina Arlauskas, Kestutis sberg, Peter Ashizawa, Minoru slund, Andreas Athanasopoulos, Stavros Athanasopoulos, Stavros Poster & Abstract # 46-W 41-TH 163-TU 113-TH 101-M 103-W 112-W 156-TU 39-W 65-TH 69-M 101-TU 49-TH 7-TH 17-W 18-TU 13-TH 83-W 157-M 154-M 113-W 123-W 194-TH 30-W 47-TU 119-M 165-TH 37-TH 72-TU 61-TH 132-TH 8-W 36-TU 43-M 157-TU Atmeh, Muath Aubert, Pierre-Henri Azumi, Reiko Bcklund, T.G Bakulin, A. A. Ballantyne, Amy M. Bando, Yoshimasa Banks, Dylan Bar, Yehoram Baring, L.A. Barra, M. Baumgarten, Martin Beecher, P. Belcher, Warwick J. Bra Abrem, Mat Bergin, Shane D. Berlin, A. Bernasik, A. Bernasik, Andrzej Beverina, Luca Bergeson, Jeremy Bhatia, V. Biebersdorf, Andreas Biscaro, R. S. Bjrk, Per Blanchard, P. Blanco, Ral Blighe, Fiona M. Blinova, N.V. Blond, D. Blouin, Nicolas Bokria, Jayesh G. Bokria, Jayesh G. Borrmann, T. Boudiba, L. Boyukbayram, A.Elif Brennan, M. E. 65-TU 91-M 176-TU 97-W 73-TH 98-M 17-M 124-W 181-TU 116-M 84-W 122-TH 163-W 97-M 52-TU 51-M 116-TU 152-W 82-TH 51-TU 178-W 138-W 100-M 149-M 131-TH 103-M 169-W 183-W 144-M 42-TU 152-TU 154-W 95-TH 175-W 22-TH 45-TU 53-TU
ALPHABETICAL LIST OF POSTER PRESENTERS
46
Brown, Stuart Bruno, Mariano M. Buisson, J.P. Burridge, Kerstin A. Busi, M. Cabanillas-Gonzalez, J. Cadby, A. Cairns, Mathew J. Caironi, M. Campos, Milton Camposeo, A. Cano-Corts, Laura Crdenas, J. R. Cardone, Antonio Careem, M.A. Caruso, M. E. Cassinese, A. Cathcart, Helen Cava, Carlos Chakaroun, M. Chambon, S. Chang, Yi-Ming Chauvet, O. Chen, Junwu Chen, Yi Cheylan, S. Cheylan, S. Chiba, Ryo Chiba, Ryo Chien, Shu-Hua Choi, Jong-Ho Choi, Jong-Ho Choi, Hyun Chul Clark, Jenny Coldea, Amalia Compagnini, Giuseppe Cooney, Ralph P. Corr, Serena A. Cucchi, I. Cucchi, I.
27-TH 64-TH 46-TH 85-TU 62-TU 78-W 54-W 86-TU 86-M 143-M 115-W 14-W 63-W 184-TH 67-M 170-M 159-M 146-TH 38-M 174-M 95-M 141-M 41-TU 147-TH 179-TH 177-M 107-W 16-M 12-W 91-TU 146-M 89-W 133-W 96-TH 25-TU 80-TU 168-W 141-TH 4-TU 62-W
Cuia, HengBo Cunningham, A. Curran, Seamus Curreli, Simona Curreli, Simona Cury, Luiz, Alberto Danno, T. Davenas, J. Dawson, Paul de Albuquer, J.E. de Azevedo, W. M. de Castro Folgueras, Luiza de Jauregui , David Saez de Melo, Celso P. de Melo, C.P. de Oliveira Neto, Pedro Henrique de Oliveira Queiroz, Jos Rildo Deakin, Peter del Mercato, L. L. Dennany, Lynn Dettlaff-Weglikowska, Urszula Devi, Lekshmi, Sudha Dimitriev, O.P. Djiango, Martin Djurado, D. Djurado, David Dmitriev, I. Yu. dos Santos, M. C> Doyle, James J. Drury, Anna Dumm, Michael Dunstan, Dave E. Dvorsek, Damjna e Silva, Magela e Silva, Geraldo Magela Earley, Sean T. Eisenberg, David
121-M 90-M 50-TU 181-M 60-TH 150-TH 172-TU 157-TH 96-TU 84-TH 72-TH 37-M 166-M 117-TU 24-M 106-M 78-TU 121-TH 200-TH 173-W 188-M
47
83-TU 33-TH 42-M 9-M 12-TH 155-TH 80-M 49-W 51-TH 164-M 148-W 106-TH 29-TU 124-TU 121-W 154-TU
Elizarov, S.G. Endo, Daigoro Endo, Toshiyuki Eom, Jae-Hoon Ertas, Merve Faez, Roselena Faez, Roselena Fang, Chun Fedorko, P. Ferenczi, Toby A. M. Ferrer-Anglada, N. Finlayson, C.E. Flores, Jean-Charles Fogel, Yulia Foitzik, Richard C. Folgueras, L.C. Folgueras, Ana D. Fournet, P. Frail, Paul R. Fratiloiu, S. Friedlein, Rainer Fryczkowska, B. Fryczkowski, R. Fujii, Masaharu Fujii, Akihiko Fujinami, Hiroki Fukumoto, Hiroki Fumagalli, L. G.L, Pakhomov Gal, Yeong-Soon Gal, Yeong-Soon Gambhir, Sanjeev Geskin, Victor Getautis, Vytautas Giacometti , J. A. Gigli, Giuseppe Gimnez-Saiz, Carlos Goh, Chiatzun Goicoechea, J. Gomes, P.J.
93-M 130-M 171-TH 100-W 87-M 94-TU 156-W 128-TU 147-M 178-TU 177-W 189-TH 155-W 185-M 67-W 142-M 23-TH 66-W 164-W 70-TU 175-TU 57-W 68-W 112-TH 183-TH 123-TU 99-TU 82-W 159-TH 178-M 181-W 172-W 179-TU 174-TH 151-W 129-W 158-M 42-W 136-W 33-TU
Gomes, Henrique Leonel Gmez Garca, Carlos, J. Gomis, V. Gong, Doowon Gordon, Keith C. Gtz, Gnther Goubard, F.Goubard Graeff, C. F. O. Graef, Carlos F. O. Grazulevicius, Juozas Vidas Guimares, F. E. G Gupta, D. Guta, Arne Hkansson, Eva Hamedi, Mahiar Hannewald, Karsten Hansen, Thomas Steen Harada, Shiro Harashina, Yuko Harigaya, Kikuo Harley, Claire C. Hassanien, Abdou Hedderman, Theresa Hee Song, Jae Hendy, Gillian M. Hennebicq, E. Hernandez, Y. R. Herv, Katel Heth, Christopher L. Hiraoka, M. Hiratani, Narumi Hiromitsu, Ichiro Hodson, Ronan Holmes, Justin D Holzapfel, M. Hoppe, Harald Horner, Stephan Hosoda, Miyuki Huang, Wei
168-TU 125-TH 8-TU 131-TU 115-M 58-TU 45-W 188-TU 39-TU 167-M 140-TU 68-TH 179-W 59-W 68-M 139-TH 74-M 15-TH 71-W 44-M 57-M 30-M 53-TH 36-M 145-TH 139-TU 55-TH 118-TH 160-M 171-TU 17-TU 113-M 167-TH 182-W 78-M 70-TH 79-M 89-TU 74-TU
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Huang, Wei Huh, JaeHoon Hyun Lee, Seung Ichimura, Koichi Iguchi, Hiroaki Inokuchi, Makoto Inomata, Aoi Iraqi, Ahmed Ishikawa, Shigeru Ishikawa, M. Ishikawa, M. Isono, T. Ito, T. Ito, Takayoshi Ito, Hiroshi Ito, Hiroshi Ito, Mitsuhiro Ivanov, V.F. Iwahori, Fumiyasu Iwase, F. Iyoda, Masahiko Jadamiec, Malgorzata Jensen, Bjrn Winther Jeong, Seon-Hwa Jeong, Seon-Hwa Jeong, Seon Jhang, SungHo Jian, Lin Jin, Wusong Jin, Reina Joo, Jinsoo Jousselme, Bruno Jung, Minhoon Jung, Bo Ram Juka, Gytis Kageyama, Hiroshi Kahol, P.K. Kalbc, Martin Kane-Maguire, Leon Kang, H. S.
138-TH 186-M 50-M 4-M 87-TH 6-TU 188-TH 21-TH 94-M 13-TU 11-W 11-M 5-M 8-TH 11-TH 17-TH 123-TH 160-W 115-TH 15-W 151-TU 108-TH 118-TU 59-TU 31-W 134-TH 55-M 169-M 21-TU 69-TU 97-TH 36-TH 64-TU 70-W 78-TH 98-W 161-W 179-M 105-TH 131-W
Kang Gu, Bon Kano, Masataka Kaplan-Ashiri, I. Katagiri, Hideki Katayama, Shinya Katayama, Shinya Katsuhara, Mao Kavitha, B. Kawakami, Daisuke Kawamoto, Tadashi Kazantseva, Natalia Kearney, John Kee Lee, Chang Kelly, Fern M. Kemerink, M. Kpas, Anna Khan, Umar Kihara, Takumi Kihara, Takumi Kim, Nam Gwang Kim, D. W. Kim, Chul Am Kim, Hyunsuck Kim, Jun Ho Kim, Min Sup Kimata, M. Kimata, M. King, Sharon M. Kino, Hiori Kirkpatrick, James Kirwan, David Kishida, Hideo Kishine, Jun-Ichiro Kishine, J. Kiss, Takayuki Kitagawa, Y. Kitagawa, Hiroshi Kobayashi, Akito Kobayashi, Kensuke Kobayashi, Atsushi
38-TU 85-W 77-TU 98-TU 9-W 20-W 19-TH 37-W 161-M 26-TH 124-TH 9-TU 40-TU 60-W 85-M 116-W 59-TH 6-M 2-TH 172-M 16-TU 127-TU 134-W 137-W 128-TH 23-M 26-W 90-TU 27-W 170-TU 34-M 86-TH 136-M 1-W 6-TH 52-M 88-TH 12-M 25-M 156-M
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Kobayashi, Hayao Kobayashi, Kensuke Kobayashi, Hirokazu Kobayashi, T. Koizumi, Take-aki Koizumi, Kenichi Kojima, Masahiko Konoike, Takako Konyushenko, E.N. Kooistra, Floris B. Kosaka, Yosuke Kovts, va Krinichnyi, Victor I. Kufazvinei, C. Kulasi, Akbar Kulikov, A.V. Kulszewicz-Bajer, I. Kumagai, Akira Kumar, Anil Kun, Harismah Kuritka, I. Kuroda, S. Kwan Kim, Young Kwon, Young, Rock Lahiff, Emer Lai, C.C. Lattante, Sandro Laukhina,, E. Leahy, Rory Ledwith, Deirdre M. Lee, Y. Lee, Changhee Lee, Dong Su Lee, Hoosung Lee, Ju Yul Lee, G. J. Lee, Darren Lee, G. J. Lee, Haeseong Lee, Ha-Jin
1-TU 2-W 47-W 110-W 108-TU 119-TH 81-W 24-TH 120-TU 49-TU 32-TU 197-TH 172-TH 32-M 10-TU 140-M 134-M 114-TU 155-M 5-W 72-W 171-W 181-TH 109-TU 40-TH 40-W 168-TH 29-M 91-W 44-TU 76-M 104-M 107-M 112-M 20-TU 81-TU 95-TU 138-TU 149-TU 43-TH
Lee, Hyun, Jung Lee, Changhee Lei, Jie Lepage , Harding Lepnev, Leonid Li, Sheng-biao Li, Yanqin Lim, Kwon Taek Limo-Vieira, P Lindfors, Tom Lindgren, Lars Liu, D. S. Liu, Xiao-jing Liu, Jianwei Logakis, Emmanuel Lpez Navarrete, Juan Teodomiro Lucas, Bruno Ler, L. Lungenschmied, Christoph Lygaitis, R. Lynch, Patrick Lyubovskaya, R.N. Macchi, G. Maesato, Mitsuhiko Maeshima, N. Maia, Francisco C. B. Majumdar, Sayani Maki, K. Malik, Sharali Mallouki, M. Manaa, Hacene Manca, Michele Mangold, K.-M. Marabelli, F. Martin, Lee Massuyeau, F. Masuda, Toshio Matsuda, Masaki Matsunaga, Noriaki
90-TH 190-TH 74-W 71-M 151-TH 104-W 178-TH 149-W 87-W 75-M 62-TH 105-M 180-TU 47-TH 57-TH 99-TH 185-TH 117-M 43-W 163-TH 160-TH 4-TH 128-W 35-W 28-TU 198-TH 122-M 27-TU 54-M 107-TH 132-W 156-TH 139-M 136-TU 7-M 147-W 170-TH 11-TU 30-TH
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Mazumdar, S. Mc Carthy, Denis McCarthy, J. McEvoy, Niall, Patrick McGovern, David McNally, Andrea McNeill, C. R. Medina, Begoa Milian Medvedev, Vladislav Mele, Elisa Memminger, Karin Menaker, A. Menon, Reghu Menon, Reghu Meredith, P. Myk, J. Miuk, M. Milani, A. Minemawari, Hiromi Miranda, Paulo B. Mircea, Grigoras Mircea, Grigoras Misaki, Yohji Misaki, Yohji Mitsumi, Minoru Miyagawa, K. Miyashita, Satoshi Miyashita, Satoshi Miyazaki, Akira Mizoguchi, Kenji Moghal, Jonathan Molina, Mara, A. Moreno Oliva, Mara Moreno Oliva Mori, Seiichiro Mori, Taizo Mori, H. Mori, Keiko Morita, Hitoshi Morita, T
150-M 107-TU 24-W 80-W 48-W 96-W
192-TH 44-TH 79-W 27-M 14-TU 10-W 8-M 14-M 10-TH 16-TH 99-M 38-W 75-TH 2-TU 26-M 33-W 129-M 132-TU 66-TU 45-TH 92-W 115-TU 10-M
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2-M 79-TU 75-W 50-TH 43-TU 56-TU 67-TH 118-W 173-TH 142-TH 148-TU 111-TU 148-M 90-W 129-TH 165-M 64-W 80-TH 15-M 165-W 5-TU 3-TH 3-M 1-TH 26-TU 29-TH 21-M 5-TH 20-M 48-TU 142-TU 127-TH 114-M
Morrin, Aoife Mountrichas, Grigoris Mller, Harald Mller, Kevin Murata, Keizo Murphy, Robert Nagao, Hidemi Nagasawa, M. Naito, Masanobu Najari, Ahmed Nakamura, Takayoshi Nakano, Yoshiaki Nakano, Masayoshi Nardes, A.M. Neyshtadt, Shany Ni Mhuircheartaigh, Eimhin Nielsen, Christian B. Nishiakwa, Hiroyuki Nishida, Jun-ichi Nishikawa, Hiroyuki Nishio, Yutaka Nishio, Yutaka Nogami, Yoshio Nogami, Yoshio Nogami, Yoshio Nogami, Yoshio Nogueira, Ana F. Nogueira, Ana F. Nogueira , Ana, Flavia Noh, Dong-Youn Nomura, K. Noro, Shin-ichiro Noura, Benbellat Nowak, D. O.P.Dimitriev, Dimitriev OConnor, Ian Ogawa, Satoshi Ohlan, Anil Ohnuki, Hitoshi
37-TU 35-M 122-TU 101-TH 3-TU 72-M 84-TU 1-M 83-TH 35-TU 136-TH 14-TH 158-TH 112-TU 169-TH 38-TH
Ohnuki, Hitoshi Ohta, Koji Ohta, Koji Ohta, Suguru Oizumi, Hajime Ojima, M. Okada, Shuji Olivati, C.A. Olivier, Jean Omastov, Mria Onoda, Mitsuyoshi OReilly, Emmet J. Osada, T. Osuna, Reyes Malave Ota, Akira Otsubo, Kazuya Otsubo, Tetsuo Ottonelli, M. Ottonelli, Massimo Ozumi, Yoshinori Paasch, G. Padilla, J. Padmalekha, K.G. Padmanabhan, Sibu C.A266 Pagona, Georgia Painell, Anna Painelli, Anna Palma, Matteo Palma, Matteo Pan, Xiumei Pan, XiuMei Pandis, C. H. Papakonstantinou, P. Papavassiliou, G. C. Paraschuk, D. Park, Joonyoung Park, Jaehoon Park, Sang, Jun Park, D. H.
144-TU 145-TU 141-W 186-TH 22-TU 46-M 106-W 120-W 124-M 110-TH 70-M 184-M 31-TU 18-W 128-M 100-TH 148-TH 171-M 130-TU 152-M 199-TH 64-M 137-M 92-TU 42-TH 25-W 102-M 63-TU 68-TU 53-M 177-TH 180-W 130-TH 23-TU 76-TH 53-W 135-W 133-TH 195-TH
Passab, Alessandra Peeterbroeck, Sophie Peisert, H. Perissinotto, S. Persano, Luana Perzon, Erik Petrozza, Annamaria Phani, A.R. Pinto, N.J. Pirondini, Laura Pivrikas, Almantas Piwowarczyk, Konrad Plewa, Sylwia Plewa1, Sylwia Ploscaru, Mihaela Pokrop, Rafa Pompa, Pier, Paolo Posdorfer, Joerg Posdorfer, Joerg Potratz, Stefanie Powell, B. J. Pratt, Francis Preethichandra, D.M.G. Preezant, Yevgeni Priya, B. R. Proke, J. Proschek, Veronika Puigdollers, Joaquim Puschnig, P. Puzari, Amrit Qi, XiaoYing Qin, Chunsheng Qiu, Yongqing Qiu, Yongqing Rabaa, S. Ragni, Roberta Ramrez-Garca, Sonia Raposo, M. Redmond, Gareth Reinold, Egon
102-W 58-TH 110-M 142-W 153-TH 69-TH 187-TH 113-TU 65-W 61-TU 74-TH 103-TH 174-W 106-TU 88-TU 41-M 162-TH 77-M 98-TH 176-M 22-M 132-M 58-M 182-TU 35-TH 153-W 73-TU 79-TH 155-TU 81-TH 76-TU 193-TH 129-TU 180-TH 131-M 166-TH 73-M 118-M 126-W 133-TU
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Ren, J. F. Reynaud, Stphanie Reza Nateghi, Mohammad Ribeiro, P.A. Ribierre, J.C. Richardson, Michael J. Richardson, Scott Rickard, David Rizzo, Fabio Rizzo, Aurora Rocha, C. G. Roman, Lucimara Stolz Ruiz Delgado, Mari Carmen Rumyantsev, B. M. Russell-Hill, Paula Ryu, Gihan Sahin, Elif Sahmetlioglu, Ertugrul Saini, Parveen Saini, Raman Sakaguchi, Koichi Sakaguchi, Koichi Sako, Katsuya Sakurai, Yoko Salzmann, Ingo Sannino, Diana Santucci, S. Santucci, S. Sapurina, I. Sato, Masa-aki Sato, Daisuke Satsukawa, Hidetaka Schauer, F. Scheinert, Susanne Schikora, Martin Schillinger, Eva-Kathrin Schmidtke, Johanna P. Schppel, R. Scully, Shawn R.
55-W 161-TH 127-W 59-M 60-M 162-W 164-TH 45-M 140-W 18-TH 183-TU 162-M 40-M 49-M 83-M 150-W 150-TU 126-TH 20-TH 61-W 165-TU 111-TH 143-TH 147-TU 92-M 66-TH
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117-TH 105-TU 184-W 67-TU 125-TU 87-TU 146-W 180-M 134-TU 117-W 33-M 84-M 19-TU
Sedenkova, Ivana Segura, J. L. Seo, Hoon-Seok Seo, Hitoshi Seo, Hoon-Seok Seo, Ji Hoon Seo, Ji Hyun Servati, Peyman Sewell, Gavin Shan, Guangcun Shan, Guangcun Shaw, Paul Shi, Shaoqing Shi, Shaoqing Shibahara, Sota Shibao, Miho Shigematsu, Akihito Shimoi, Yukihiro Shimomura, Takeshi Shin, Hoon-Kyu Shin, Su Ryon Shin, Min, Kyoon Shkunov, M.N. Shusterman, O. Shusterman, Olga Shuttle, C. G. Sieval, Alexander Silvestri, Fabio Simmance, Timothy G. Simokaitiene, J. Simokaitien, J. Singh, Kuldeep Skkalov, Viera Skowroski, J. M. Small, Aaron C. Smyth, Ciarn Sooducho, Jadwiga Solomeshch, Olga Soreni-Harari, M. Soto-Oviedo, Mauro A.
91-TH 77-W 169-TU 21-W 29-W 185-W 182-M 187-TU 137-TU 126-M 133-M 89-M 162-TU 105-W 15-TU 86-W 186-TH 185-TU 69-W 146-TU 135-TH 140-TH 143-W 153-TU 173-TU 44-W 99-W 144-TH 12-TU 168-M 143-TU 104-TH 54-TH 51-W 56-W 56-M 63-M 144-W 120-M 104-TU
Sotzing, Gregory A. Stafstrm, S. Stafstrm, S. Stallinga, P. Stallinga, P. Stanculescu, A. Steinmetz, Johannes Stejskal, Jaroslav Stevenson, S.G. Strevens, Adam E. Subramanian, P. Sugano, Tadashi Sugawara, Shigeharu Sugiyama, Takuro Sundfors, Fredrik Surname, First Name Suzuki, Hiroki Suzuki, Seiko Suzumura,, Y. Syritski, V. Tada, Kazuya Taillepierre, P.Taillepierre Taillepierre, P.Taillepierre Takahashi, Hideaki Takaishi, Shinya Takamura, Mitsuhito Takano, Yoshiki Takashima, W. Takemura, Ichiro Takenobu, T. Takeoka, Yuko Takizawa, Shin-ya Tanaka, H. Tanaka, Senku Tanaka, Y. Tanaka, Hisashi Tanaka, Hisaaki Tang, Chao Terai, Akira Teramura, Masayasu
121-TU 158-TU 166-TU 174-TU 88-W 114-W 48-TH 94-TH 108-W 183-M 167-W 125-M 123-M 111-W 61-M Poster # 62-M 24-TU 3--TU 176-W 139-W 101-W 145-W 111-M 151-M 7-TU 13-M 81-M 116-TH 94-W 110-TU 175-M 102-TU 161-TU 3-W 9-TH 89-TH 126-TU 25-TH 31-TH
Terenziani, Francesca Thorn-Csnyi, E. Titus, Elby Todescato, Francesco Toffanind, Stefano Tokumoto, Madoka Tommasini, M. Toppare, Levent Tracy, Corey Trchov, M. Troisi, Luca Tsocheva, Dimitrinka Tsuchiizu, M. Tsunashima, Ryo Uda, Hiroshi Uemura, Sei Umemiya, Masamichi Uplaznik, Marko V.F., Ivanov Valadares, Marcelo Vandewal, Koen Vasdekis, A. E. Vzquez, Mercedes Venuti, Elisabetta Verlaak, Stijn Vigar, Nicholas A. Vilcakova, Jarmila Viola, Ilenia Viola, I. von Hauff, Elizabeth Wada, Yoshiki Wada, Hiroshi Wagner, Pawel Wall, Andrew Walmsley, Lygia Wang, Yunyun Wang, Leeyih Waskiewicz, Krzysztof Watanabe, N. Watanabe, Chiduru
135-TU 76-W 114-TH 85-TH 93-TU 23-W 39-M 66-M 122-W 158-W 154-TH 9-TU 4-W 48-M 141-TU 93-W 18-M 49-W 92-TH 109-TH 82-M 182-TH 157-W 16-W 164-TU 145-M 93-TH 163-M 34-TU 39-TH 184-TU 32-W 166-W 34-TH 120-TH 153-M 63-TH 149-TH 173-M 22-W
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Watt, Andrew A.R. Watt, Andrew A. R. Wei, J. H. Wei, Di Wei Huang, Zhun M. Weidlich, C. West, Keld Westenhoff, Sebastian Westgate, Thomas D. J. Wi Ong, Chi Williams, Jonny H. T. Wu, Hashen Wu, Chun-Guey Wu, Chang-Qin Xie, Ling-Hai Yabuuchi, Kazuhiro Yamada, Jun-ichi Yamamoto, Yohei Yamamoto, K. Yamao, Takeshi Yamashita, Yasufumi Yamato, K. Yamauchi, Miho Yang, Sze-Ming Yang, J.-P. Yano, Jun Yap, B.K. Yasuda, Takeshi Yasuzuka, Syuma Yazawa, Koji Yi, Hunan Yijie, Xia Yildiz, Hseyin Bekir Yin, L. Yoneyama, N. Yoshida, Yukihiro Yoshida, Yuki Yoshikawa, T. Yoshino, Harukazu Yoshino, Katsumi
31-M 36-W 109-M 77-TH 55-TU 58-W 138-M 160-TU 177-TU 57-TU 52-W 82-TU 119-TU 191-TH 152-TH 60-TU 32-TH 75-TU 5-W 71-TU 13-W 65-M 88-M 96-M 50-W 73-W 119-W 167-TU 28-TH 102-TH 7-W 176-TH 54-TU 28-W 34-W 127-M 71-TH 95-W 28-M 100-TU
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Yoshioka, Hideo Yu, Gui Yu. Sakharov, Ivan Zagorska, Malgorzata Zeysing, B. Zhang, Ning Zhang, Qinghua Zhang, Xuetong Zheng, Wei Zhong, G. Y. Zhuravleva, . S. Zojer, Egbert Zucolotto, Valtencir
19-W 130-W 46-TU 103-TU 187-M 19-M 52-TH 56-TH 175-TH 125-W 159-TU 108-M 137-TH
POSTER INFORMATION
Posters to be set-up between 08:00 9:00 each day Posters to be removed between and 17:45 18:00 hours each day Posters in place each day from 8:00 17:45 hours Authors in Attendance 10:30 11:00 hours and 16:30 18:00 hours Abstracts for poster presentations are on the CD Rom contained in the delegate pack. Poster #: 1-88 are located in the Beckett Theatre; 89-145 are located in the Lower Concourse; 146-200 are located in the Upper Concourse Poster # sufx:M: posters to be displayed on Monday TU: posters to be displayed on Tuesday W: posters to be displayed on Wednesday TH: posters to be displayed on Thursday
POSTER INFO & POSTER PROGRAMME
Examples: 1-M is poster board no. 1 on Monday, 139-TH is poster board no. 139 on Thursday
ORGANIC CONDUCTORS & SUPERCONDUCTORS P1

POSTER # & TITLE ABSTRACT # ON CD ROM 1-M Nonlinear electric conduction in the charge ordering phase of (TMTTF)2SbF6 2-M Temperature-dependent competition between charge-ordering and spin-Peierls transition in (TMTTF)2X: the role of quantum phonons 3-M Syntheses and Properties of Tetrakis- and Pentakis-Fused TTF-Type Donors 4-M STS on Partially deuterated k-(BEDT-TTF)2Cu[N(CN)2]Br 5-M Observation of Spin-Peierls Modulation in (TMTTF)2AsF6 by Synchrotron Radiation 6-M Magnetic Study of the Electronic States in b-(BEDT-TTF)(TCNQ) 7-M A new BEDT-TTF charge-transfer salt containing both and donor packing in the same lattice 8-M Low Temperature Structural Study of k-(BEDT-TTF)2Cu(NCS)2 9-M New radical salts based on BEDT-TTF and BEDT-TSeF with the polyanion [SMo12O40]n10-M Spontaneous Metallic Film Formation Of Bis(Ethylenedioxy)Tetraselen afulvalene (BEDO-TSEF) And Fatty Acid System 11-M Uniaxial Pressure Effect on Superconductivity of -(BDA-TTP)2I3 12-M Mechanism of Superconductivity in Quasi-Two-Dimensional Organic Conductor a-BEDT-TTF salt 13-M Charge-Ordered vs. Zero-Gap Semiconducting States of a-(BEDTTTF)2I3 14-M Low Temperature Structural Study of k-(BEDT-TTF)2Cu(NCS)2 15-M Novel ET salt with Unusual Stoichiometry : ET3(Br3)5 PRESENTER M. Nagasawa S. Mazumdar Yohji MISAKI Koichi Ichimura T. Ito Takumi Kihara Lee Martin Yoshio Nogami Simona Curreli Hitoshi Ohnuki T. Isono Akito Kobayashi Yoshiki Takano+D48 Yoshio Nogami Hiromi Minemawari
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16-M 17-M 18-M 19-M 20-M 21-M 22-M 23-M 24-M 25-M 26-M 27-M 28-M 29-M
Metal-insulator transition on (DCl-DCNQI)2Ag studied by 35, 37ClNQR and 13C-NMR An Incommensurate Organic Superconductor at Tc = 6.2 K; (MDTTS)IxBry TTF Based Charge Transfer Salts With Transition Metal Complex Anions [Cr(L)n(NCS)4]- (L = isoq, phen, 2-pico) The effect of delocalisation on the exchange energy in meta- and para-linked Pt-containing carbazole polymers and monomers Structure and Physical Properties of TTF-Squaric Acid Derivatives Charge Ordering in q-(BEDT-TTF)2 RbZn(SCN)4 : Cooperative Effects of Electron Correlations and Lattice Distortions Conformational Changes in BEDT-TTF Low Temperature Fermi Surface of b-(BEDT-TTF)2CsCd(SCN)4 Infrared and Raman Studies of Charge-Order in Quasi-1D (TMTTF)2X Salts Quantum Critical Behavior in the Quasi 2D Conductor, k-(MeDHTTP)2AsF6 Charge Localized State in (TMTTF)2Br: 13C NMR Insulating State of a Superconducting DODHT Salt under Pressure Transport Properties and Phase Transition of a Novel Two-Dimensional Organic Conductor (DOET)2Au(CN)2 Polymorphism and High Temperature Solid State Reactions in Molecular Conductors (BEDT-TTF)2BrxIyCl3-x-y
Ryo Chiba Yoshimasa Bando Masamichi Umemiya Ning Zhang Akira Miyazaki Satoshi Miyashita B. J. Powell M. Kimata Michael Dumm Kensuke Kobayashi K. Nomura Hiroyuki Nishikawa Harukazu Yoshino Laukhina, E.
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES P1

POSTER # & TITLE ABSTRACT # ON CD ROM 30-M Effective Low Temperature Encapsulation Of Fullerene Derivatives In Single Wall Carbon Nanotubes 31-M Atomic-Molecular Superlattices 32-M Carbon Nanotube Reinforcement Of Ceramic Materials 33-M Modelling The Effect Of Randomly Dispersed Doping Agents In Carbon Nanotubes 34-M Electronic Properties of Nanotubes in Contact with Magnetic Impurities 35-M Intramolecular Electronic Interactions On Soluble Carbon Nanotubes/Semiconductor Nanoparticles Ensembles 36-M Simple Separation of Semiconducting Single-Walled Carbon Nanotube (SWNT) using Surface Functionalization and Column Chromatography 37-M Ab initio study of the endohedral fullerene isomers N@C60 and C@ C59N 38-M Electrical Properties Of Carbon Nanotubes Filled With Iron And Iron Oxide: Device Application PRESENTER Abdou Hassanien Andrew A. R. Watt C. Kufazvinei C. G. Rocha David Kirwan Grigoris Mountrichas Jae Hee Song M. C. dos Santos Carlos Cava
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POSTER PROGRAMME
39-M 40-M 41-M 42-M 43-M 44-M 45-M 46-M 48-M 49-M 50-M 51-M 52-M 53-M 54-M 55-M
p-Electron Delocalization in Carbon Linear Chains Microwave Purication Of Multiwall Carbon Nanotubes Molecular Hybrid Systems Containing Carbon Nanotubes And Polythiophene Derivatives Composite Architectures Fabricated From Nanotubes And Polymers For Coatings Applications. Giant Magnetoresistance of Nickel-contacted Carbon Nanotubes Exciton Effects in Boron-Nitride Nanotubes: Theoretical Study Structural Study on Three Tm2@C82 Isomers Fabrication of Nanoscale Periodic Porous Carbon with Various Pore Sizes and Its Field Emission Characteristics Structure of the LB Films of a Fullerene Linked Low-MolecularWeight Organogerator Role Of Topography On Hydrophobicity Hall Effect and Magnetoresistance of SOCl2 treated Carbon Nanotube Films Effect Of Solvents On The Bundle Dissociation Of Single-Wall Carbon Nanotubes Theoretical Studies on the Mechanism of Ferromagnetism in Rh-C60 Theoretical Study On Double-Atom Molecular Insertion In Different Dimensional Single-Walled Carbon Nanotubes Characterisation Studies of Carbon Nanoscrolls Analysis of Giant Random Telegraph Signals in Semiconducting Singlewalled Carbon Nanotubes
M. Tommasini Diana Sannino Rafa Pokrop Seamus Curran Stavros Athanasopoulos Kikuo Harigaya Koichi Sakaguchi M. Ojima Ryo Tsunashima S. Santucci Seung Hyun Lee Shane D Bergin Y. Kitagawa Xiumei Pan Sharali Malik SungHo Jhang
POSTER PROGRAMME
ELECTROCHEMICAL APPLICATIONS, ACTUATORS & SENSORS P1

POSTER # & TITLE ABSTRACT # ON CD ROM 56-M Autonomous Sensing using Trilayer Polypyrrole Actuators 57-M Selective Determination Of Dopamine In Ascorbic Acid Using A Novel Electrochemical Sensor 58-M Polymer Actuators Synthesized Under A High Transverse Electric Field 59-M Electrochemically Synthesis and Characterization of Conducting Copolymer 60-M A New Conducting Copolymer : 1-Phenyl-2,5-di(2-thienyl)-1H-pyrrole-co-EDOT and its Electrochromic Properties 61-M Electrochemically Polymerized Thiophenes with Covalently Bound Ion-recognition Sites and Charge-compensating Ions 62-M Electrically Driven PEDOT/PSS Paper Actuator 63-M New Electrochemical Aspects of Novel Phenothiazine Derivatives 64-M Improving Optical And Electrochemical Performance In Dual Conjugated Polymer Electrochromic Devices PRESENTER Ciarn Smyth Claire C. Harley D.M.G. Preethichandra Elif Sahin Ertugrul Sahmetlioglu Fredrik Sundfors Hiroki Suzuki Jadwiga Sooducho J. Padilla
58
65-M 66-M 67-M 68-M 69-M 70-M 71-M 72-M 73-M 74-M 75-M 76-M 77-M 78-M 79-M 80-M 81-M
Tubular Linear Actuators Using Conducting Polymer, Polypyrrole Synthesis And Characterization Of A New Soluble Conducting Polymer And Its Electrochromic Devices Optical Absorption Studies On Polypyrrole/Dodecyl Benzene Sulphonate Films Prepared And Cycled At Different Conditions Electrochemical Organic Transistors On The Micrometer Scale Patterned With Soft Lithography Electrochromic Properties Of A Novel Polythiophene Derivative A Self-Organized Bending-Beam Electrochemical Actuator New Amplication Strategy for Electrochemical Detection of DNA Hybridisation Signal using Ferrocene-Functionalized Polymers Carbon Nanotube-Polymer Composite As A Flexible Transparent Conductor Biomimetic Soft Pumps Based On Electromechanical Actuators Design Of All Polymer Micropump From The Conductive Polymer Poly(3,4 Ethylenedioxythiophene Optical Flow Analysis Methods for pH Measurements with Water Dispersions of Polyaniline Nanoparticles New Type Solid Polymer Electrolyte And Actuator Based On PEDOT/ NBR/Ionic Liquid A Fully Organic Sensor Based On Polyaniline Electron Transfer in Redox Cascades based on Triarylamine Redox Centres Fluorene-Pyridines As Stimuli-Responsive Electroactive Materials Fluorescence Quenching of Poly(3-octylthiophene) upon Electrochemical Doping Field Induced Charges In Organic Semiconductor Using Liquid As Gate Dielectric
K.Yamato Levent Toppare M.A. Careem Mahiar Hamedi Metin Ak Mitsuyoshi Onoda Harding Lepage, P. Robert Murphy Sonia RamrezGarca Thomas Steen Hansen Tom Lindfors Y. Lee Joerg Posdorfer M. Holzapfel Stephan Horner T. Danno W. Takashima
ENERGY STORAGE & CONVERSION MATERIALS P1

POSTER # & TITLE ABSTRACT # ON CD ROM 82-M Integrated Approach To Study Very Low Absorption Coefcients Of Thin Film, Organic D/A Blends For Next Generation Solar Cells 83-M Electronic structure of CuPc-C60 co-evaporated lms 84-M Polythiophene Based Photovoltaic Devices 85-M 86-M 87-M PRESENTER Koen Vandewal
S. Santucci Lucimara Stolz Roman. Temperature Dependent Built-In Potential In Organic Semiconductor M. Kemerink Devices Quantum efciency versus charge carriers mobility in planar P3HT M.Caironi based photodetectors Application of Conjugated Polymers in Electrochemical SupercapacMerve Ertas itors
59
POSTER PROGRAMME
88-M 89-M 90-M 91-M 92-M 93-M 94-M 95-M 96-M 97-M 98-M 99-M 100-M
Hydrogen Absorption Properties of CuPd Nanoparticles Singlet Exciton Diffusion in Poly(3-hexylthiophene) and Dissociation at a TiO2 Interface Dendrimers for Organic Photovoltaics Random And Alternated Carbazole-Based Copolymers Associated With C60 Or Perylene Derivatives For P/N Bulk Heterojunction. Enhanced Intersystem Crossing In Oligothiophene:Fullerene Blends Optical Absorption And Scattering In Blends Of Meh-Ppv And Electronic Acceptors With Ground-State Interaction Ab initio Calculation of the Binding Energy of a H2 Molecule on Molecular Models of Li-doped Polyacetylene Ageing Of Organic Solar Cells: Photo-Degradation Of MDMO-PPV/ PCBM Blends Syntheses of Ordered Titania Nanorod and P3HT Film as Solar Cell Material The Characterisation of N-Functionalised poly(dithieno[3,2-b:2,3d]pyrrole)s in Ternary Blend Bulk Heterojunction Structured Organic Electronic Devices. Effect of poly(3-hexylthiophene) molecular weight on charge transport and photovoltaic performance of polymer/PCBM bulk heterojunction solar cells. Dye Sensitized Solar Cells Using Polyaniline Copolymers As Sensitizers Efcient photosensitization of C60 microcrystals with II-VI and III-V semiconductor nanocrystals
Miho Yamauchi Paul Shaw Peter Deakin Pierre-Henri Aubert R. Schppel S.G. Elizarov Shigeru Ishikawa S. Chambon Sze-Ming Yang Warwick J Belcher Amy M. Ballantyne Ana F. Nogueira Andreas Biebersdorf
MOLECULAR, POLYMER & NANO-ELECTRONICS P1

POSTER # & TITLE ABSTRACT # ON CD ROM 101-M Photoinduced Charge Transfer and Efcient Energy Conversion in a Blend of a Low Bandgap Polyuorene Copolymer and CdSe Nanoparticles 102-M Current-Induced Chemistry In Molecular Junctions 103-M Monolayers Based On Oligothiophenes: Effect Of The Mode Of Fixation On The Properties And Functionalization 104-M Electron Mobility And Contact Resistance Of An N-Type Organic Thin-Film Transistor 105-M Bloch Oscillations In A One-Dimensional Conducting Polymer 106-M Extensional Rheouorescence of MEHPPV 107-M Quantum Dot Manipulation In A Single-Walled Carbon Nanotube Using A Carbon Nanotube Gate 108-M Decreasing The Hole Injection Barrier From Au Into Organic Semiconductors By UV/Ozone Treatment. 109-M Bipolaron And Soliton Assisted Charge Transport In A Polymer Chain
POSTER PROGRAMME
PRESENTER Agnese Abrusci Anna Painelli P. Blanchard Changhee Lee D. S. Liu Dave E. Dunstan Dong Su Lee Egbert Zojer J. H. Wei
60
110-M 111-M 112-M 113-M 114-M 115-M 116-M 117-M 118-M 119-M 120-M 121-M
Initial Growth Of Phthalocyanine Molecules On Rough Substrates: Study Of The Change Of The Molecular Orientation Theoretical Study on the Polarizabilities of Molecules in Solution by the Real- Space Quantum Mechanical / Molecular Mechanical Approach Patterning of Perylenetetracarboxylic Diimide Film by Electro- or Photo-Crosslinking of Pyrrole Substituents Poor Hole Transport from Au to Phthalocyanine and Its Improvement by an Interface Modication Molecular And Electronic Structures Of Aromatic And Quinoidal S,S-Dioxide Terthiophenes. Complementary Systems For Organic Electronic Materials Spectroscopy of Intermediate Terthiophene Radical Cations Generated by Photochemical and Chemical Oxidation. Colossal Dielectric Constant In Partially Doped Poly(3-Methythiophene) Pellets Real-time Investigation of Elementary Steps for Photo-induced Phase Transition in a Model Dimer Characterization of Poly(o-Methoxyaniline) Layer-By-Layer Films by High-Resolution VUV Photo-Absorption Photoexcitation Dynamics In Long Chain Polyenes Tailoring the Interface between Quantum Dots and Polymer in Organic Devices Dynamics Of Solitons In Polyacetylene As Particle Machine
H. Peisert Hideaki Takahashi Hoosung Lee Ichiro Hiromitsu Mara Moreno Oliva Keith C. Gordon L.A. Baring L. Ler M. Raposo M.R. Antognazza M. Soreni-Harari Jos Rildo de Oliveira Queiroz
MOLECULAR MAGNETS & SPINTRONICS P 1

POSTER # & TITLE ABSTRACT # ON CD ROM 122-M Application of polythiophene in organic spintronic devices 123-M An Analytical formula expressing Out-of-Plane Resistance of QuasiOne and -Two-Dimensional Layered Metals under Transverse Magnetic Fields 124-M Synthesis Of A New Ligand Derived From BEDT-TTF Bearing A Pyridine Group. 125-M Magneto-structural correlation in the organic radical, 5-carboxy-2thienyl nitronyl nitroxide (2-CATNN) 126-M Spin Dynamics in Strongly Correlated Electron-spin System of SingleMolecule Magnets 127-M Functional Ionic Liquids Based on Imidazolium Cations; Magnetic and Luminescence Properties 128-M F4TCNQ complexes with magnetic transition metal ions including Fe3+ and Cu2+ 129-M Synthesis of TTF-BisCNBipy and its Fe(II) and Fe(III) complexes
Sayani Majumdar Shigeharu Sugawara Jean Olivier Tadashi Sugano Guangcun Shan Yukihiro Yoshida Akira Ota Benbellat Noura
61
POSTER PROGRAMME
PRESENTER
130-M 131-M 132-M 133-M 134-M 136-M
137-M 138-M 139-M 140-M 141-M 142-M 143-M 144-M 145-M 146-M 147-M 148-M 149-M 150-M 151-M 152-M 153-M 154-M 155-M 156-M 157-M
Crystal Structures and magnetic properties of Reduced Polyoxometalate-Supramolecular Cation Complexes Structural and Magnetic Characterization of Novel RR(BzPy)[Ni(4py-edt)2] L= 4-pyridyl-1,2-ethylenedithiolate A Molecular System as an Ideal S=1/2 Heisenberg Magnetic Chain Spin Dynamics in Strongly Correlated Electron-spin System of SingleMolecule Magnets High-Spin Radical Cations of Alternating Poly(m-p-anilines) Static And Dynamical Anomalies Caused By Global Spin Chirality In Molecular-Based Chiral Magnets Inherently Conductive Polymers P 1 Magnetotransport in Doped PEDOT Films Electronic conductivity of PEDT Polypyrrole/palladium-composites for electrocatalyzed Heck reaction Spin Crossover In Polyaniline Synthesis and Morphologies of Water Soluble Poly(3-hexylthiophene)graft-poly(4-styrenesulfonate) Comb-like Copolymer Characterization Of Microwave Absorbers Prepared By Impregnation Of PAN Flexible Substrates With Polyaniline/Polyamic Acid Blends Sensing Behavior In MIS Diode Structure Under Methane Atmosphere Polymerization Of Aniline On Polyaniline Membrane Structural Interpretation of the Raman Spectrum of Polypyrrole Characterization of a,w-dihexylsexithiophene-based OTFTs prepared by the spin coating method Insulator-Metal Transition in Plasticized Polyaniline Enhanced Chain Organization In Conducting Polymers By Solvent Interactions: Small-Angle X-Ray Scattering Study Blends of Polyaniline and Polyurethane with High Electrical and Dielectric Properties Dynamics of the quasiordered structure in the regioregulated -conjugated polymer poly(4-methylthiazole-2,5-diyl) Visualization of the Local Electronic States in Quasi-One-Dimensional Halogen-Bridged Ni-Pd Mixed Metal Compounds by STM. Conformational Control of Optically Active Polythiophenes Synthesis of Conjugated-carbohydrate block copolymer by Atom Transfer Radical Polymerization (ATRP) Charge Transport in Polymer Nanostructures Functional and Processable Conducting Polymers Based On Poly(3,4Propylenedioxythiophene)s Systematic control of the electronic state in new two-legged MX-ladder complexes [(PtBr-dien)2bpy]2Y4 Application of Polypyrrole Films in the Development of a Novel Drug Carrier for the Controlled Release of Drugs
Daigoro Endo S. Rabaa Francis Pratt Guangcun Shan I. Kulszewicz-Bajer Jun-Ichiro Kishine
K.G. Padmalekha Keld West K.-M. Mangold Kulikov A.V Yi-Ming Chang L.C. Folgueras Milton Campos N.V. Blinova Nicholas A.Vigar Jong-Ho Choi P. Fedorko Reghu Menon R. S. Biscaro Seiichiro Mori Shinya Takaishi Yoshinori Ozumi Yunyun Wang A. N. Aleshin Anil Kumar Atsushi Kobayashi Bernadette E. Alcock
POSTER PROGRAMME
62
158-M 159-M 160-M 161-M
Electrochemical Synthesis, Kinetics And Specic Charges Of Hybrid Materials Containing Polypyrrole And Keggin Polyoxometalates Transport Properties Of Regiorefular Doped And Undoped Poly-3-(4Alkoxyphenyl) Thiophenes Film Poly(alkylaminothiophene)s: Heteratomic analogues of polyalkoxythiophenes or an unique new class of polythiophenes? Syntheses, Structures and Optical Properties of Halogen-Bridged Two-Leg Ladder Platinum Comlexes
Carlos Gimnez-Saiz A. Cassinese Christopher L. Heth Daisuke Kawakami
162-M 163-M 164-M 165-M 166-M 167-M 168-M 169-M 170-M 171-M 172-M 173-M 174-M 175-M 176-M 177-M 178-M 179-M 180-M
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS P 1 Phase Separation In Pentacene/Pentacenequinone Co-Evaporated Ingo Salzmann Thin Films Arrays of Organic Light-Emitting-Diodes by a Surface-Tension-driven Ilenia Viola approach Study of thermal and optical properties of ion implanted PEEK lms J.E. de Albuquerque by photothermal spectroscopies Excitonic Interactions In Organic Electrophosphorescent Emitters J. Myk Examination of Nano-Structured Materials for Enhanced Nonlinear James J. Doyle Optical Response Organic Charge Transport Materials For Electrophotographic PhoJuozas Vidas Gratoreceptors zulevicius Glass Forming Electroactive Materials Containing Phenothiazinyl J. Simokaitiene Groups Study of hole blocking layer by means of EL spectra in an organic light Lin Jian emitting diode with two emitting centers Microscopic investigation of the poly(9,9-dioctyluorene) phase and M. E. Caruso real time analysis of its formation The Pseudocoordination Centre Method for the prediction of Anten- M. Ottonelli nae Structures in Lanthanide Complexes Polymeric Luminescent Materials containing Aluminophores Nam Gwang Kim Optical Properties Of Polysilane/Silica Nanoparticle Hybrid Thin Films N. Watanabe Organic Red Light Emitting Devices With Europium Complex In Vari- M.Chakaroun ous Multilayer Structures. Phosphorescence Colour Tuning of Iridium Complexes Based on Shin-ya Takizawa 2-Phenylimidazo[1,2-a]pyridine Ligands, and Application to Polymer Light-emitting Device Conjugated Thiophene-Triazole Co-Oligomers Via Click-Chemistry Stefanie Potratz Single layer organic light emitting diode based on a thiophene polyS. Cheylan mer with a cyano group Synthesis and Properties of Conjugated Polybetaine by the Polymeri- Yeong-Soon Gal zation of 2-Ethynylpyridine with the Ring-Opening of 1,4-Butanesultone Spectroelectrochemical study of pedot-swcnt composite Martin Kalbc Charge transfer and photovoltaic behaviour in organic polymer/inor- David Rickard ganic nanowire composite
63
POSTER PROGRAMME
181-M 182-M 183-M 184-M 185-M 186-M 187-M 188-M
The Inuence of Poly(2-methoxyaniline-5-sulfonic acid) on the Electrochemical and Photochemical Properties Of a Highly Luminescent Ruthenium Complex Pure-white organic light emitting diodes by adjusting the device structure Characterisation of Organic Light-Emitting Diodes with a Metal Nanodot Array Anode The electrochemical and photochemical reactions of a highly luminescent ruthenium complex when coupled to COOH functionalised single walled carbon nanotubes. New Synthetic Approach towards Giant Polycyclic Aromatic Hydrocarbon Electrical and Morphological Characterization of Polypyrrole-Polystyrenesulfonate Processing of Conductive Polymers by Dispersion Dynamic Electronic Properties and Structure in Bicorannulenyl and Its Anions
Lynn Dennany Ji Hyun Seo Adam E. Strevens Emmet J. OReilly Yulia Fogel JaeHoon Huh B. Zeysing David Eisenberg
ORGANIC CONDUCTORS & SUPERCONDUCTORS P 2

POSTER # & TITLE ABSTRACT # ON CD ROM 1-TU Organic Alloys of Superconductor and Field-Induced Superconductor, l-(BETS)2FexGa1-xCl4 2-TU Gold Nanoparticles Coated With Organic Donor Molecules: Synthesis And Properties 3-TU Spin-Glass Behavior in the t-type Organic Conductor 4-TU Processing Of Polyalkylthiophenes In Nanobers By Electrostatic Spinning. 5-TU Synthesis Of Hyperbranched Copolymers Containing Triphenylamine And Fluorene Or Thiophene Units 6-TU Chromism by Shear Stress of Spiropyrans 7-TU The Control Of Bandgap Energy Of Quasi-1D-Halogen-Bridged Pd Complexes By Introducing Long Alkyl Chained Sulfosuccinate 8-TU Temperature Dependence Of The ESR Linewidth In Conductive Polypirrole. 9-TU Development of New Regioregular Head to Tail Polythiophenes with Ferrocene Substituents and Hydrophilic Side Chains 10-TU Preparation And Properties Of 3,6-Linked Carbazole Main Chain Polymers With Triphenylamine Substituents. 11-TU Magnetic Torque Measurements of Molecular Conductors Based on Metal Phthalocyanines 12-TU Preparation and Properties of 3,6-dimethyl carbazole-9-alkyl-9H-carbazole/ 2,5-Diphenyl-[1,3,4]oxadiazole main chain copolymers. 13-TU Structure and Physical Properties of Dicyano(phthalocyaninato)Iron(II I) Conductor With 2-D Arrangement PRESENTER Hayao Kobayashi Dong-Youn Noh Keizo Murata I. Cucchi Grigoras Mircea Makoto Inokuchi Mitsuhito Takamura V. Gomis John Kearney Akbar Kulasi Masaki Matsuda Timothy G. Simmance M. Ishikawa
POSTER PROGRAMME
64
14-TU 15-TU 16-TU 17-TU 18-TU 19-TU 20-TU 21-TU 22-TU 23-TU 24-TU 25-TU 26-TU 27-TU 28-TU 29-TU 3--TU 31-TU 32-TU 33-TU
T. Osada Yosuke Kosaka P.J. Gomes
BIO/ MEDICAL MATERIALS & BIONANOTECHNOLOGY P 2

POSTER # & TITLE ABSTRACT # ON CD ROM 34-TU Geometry And Surface Energy Effects On Capillary-Driven Flow 35-TU DNA Arrays: selective, ultrasensitive and simple detection of DNA on responsive solid supports 36-TU Synthesis of amino acid oligo/poly thiophenes based molecular probes- Detection of protein bril formation PRESENTER I.Viola Ahmed Najari Andreas slund
65
POSTER PROGRAMME
An Ionic(I)-Ionic(II) Phase Transition in a Biferrocene-F1TCNQ Charge-Transfer Complex A Novel Charge-Transfer Complex [Ni(Hpydt)2]TNAP; Synthesis, Structure Carbon Nanotubes Based Methanol Sensor for Fuel Cells Application Similarities and Differences in the Structures and Electrical Conductivity of DHDA-TTP, DHOTA-TTP and OTDA-TTP Salts Structures and Properties of BEDT-TTF Salts Derived from Several Alkylsulfonates Peruorinated Tetracene: Synthesis, Electrochemistry, Raman Spectroscopic Analysis And Dft Theoretical Calculations The Anisotropic Field Effect Mobility of Pentacene Single Crystal Self-Assembled Graphitic Nanotues with One-Handed Helical Arrays The effect of the disorder induced by the deuterated molecule substitution on the superconductivity of k-(BEDT-TTF)2Cu(NCS)2 Single-Component Nickel-1,2-Dithiolene Complexes, Candidate 19 F-NMR studies of an exotic Bechgard salt, (TMTSF)2FSO3 Fermiology of the quarter-lled quasi-two dimensional organic metal b-(BEDT-TTF)4[(H3O)Ga(C2O4)3] CH2Cl2 Neutral Mixed-Valent Conducting Polymer Formed by Electron Transfer between Metal d and Ligand p Orbitals AMRO In Bechgaard salts Photoinduced Dynamics Of Dimerized One-Dimensional Mott Insulators Longitudinal And Transverse Diffusion Of Conduction Electron Spins On Arene Radical Cation Stacks Effect of Interchain Hopping on Magnetic Susceptibility of Q1D Organic Conductors Experimental Evidence for Local Origin of Angle-Dependent Magnetotransport Phenomena in Layered Conductors Antiferromagnetic Molecular Metal (Me-3,5-DIP)[Ni(dmit)2]2 (Me-3,5DIP = N-methyl-3,5-diiodopyridinium; dmit = 1,3-dithiole-2-thione4,5-dithiolate) Effect of the polycounterions on the electrical properties of Poly(oMethoxyaniline) Layer-By-Layer Films
Yutaka Nishio 1Sota SHIBAHARA D. W. Kim Narumi Hiratani Akane Akutsu-Sato Mari Carmen Ruiz Delgado Ju Yul Lee Wusong Jin Hajime Oizumi G. C. Papavassiliou Seiko Suzuki Amalia Coldea Minoru Mitsumi K.Maki N. Maeshima David Saez de Jauregui Y. Suzumura,
37-TU 38-TU 39-TU 40-TU 41-TU 42-TU 43-TU 44-TU 45-TU 46-TU 47-TU 48-TU 49-TU 50-TU 51-TU 52-TU
POSTER PROGRAMME
53-TU 54-TU
Investigation of Nanostructured Biomaterials for Novel Biosensor Fabrication Methodologies Adjustment of the Twist of Nanobers using a Controlled Relay Time Inuence of doping on spin dependent exciton formation in Alq3 based OLEDs Study of the Swelling and Bending Behavior of Chitosan Hydrogels with an Imidazolium-Based Ionic Liquid Elaboration and characterization of amylose/SWNT complexes Electrospinning Of Carbon Nanotube Based Scaffolds For Tissue Engineering. Picosecond Infrared Transient Absorption Studies of 5`-Guanosine Monphosphate in Aqueous Solutions Silver Nanoparticle Based Platform Technology For Diagnostics. Immobilization Of Invertase And Glucose Oxidase In Conducting Graft Copolymers Of Polypyrrole And Thiophene Capped Polytetrahydrofuran Determination Of Glucose In Orange Juices Enzymatic Synthesis Of Chiral And Conducting Polyaniline Conjugated Polyelectrolytes As Reporter Molecules; Biochip Constructed By Soft Lithography Methods Nature Of Natural Dna And A Possibility Of Charge Carrier Doping Fullerenes for Time Gated Holographic Imaging Elastic Properties And Nanomanipulation Of Self-Assembled AmyloidLike Fibrils New p-Extended Water Soluble Squaraines As Singlet Oxygen Generators Simple, Label Free and Ultrasensitive Protein Detecting Array Based on Cationic polythiophene / DNA Aptamer Silver Nanoparticle Biosensing Technology for the Detection of Cardio Vascular Disease Risk Factors Immobilization of Tyrosinase in Poly(ethyleneoxide) Electrodes and Determination of Phenolics in Red Wines
Aoife Morrin Bon Kang Gu Carlos F. O. Graeff1 Chang Kee Lee O. Chauvet D.Blond David McGovern Deirdre M. Ledwith A.Elif Boyukbayram Ivan Yu. Sakharov Jens Andersson Kenji Mizoguchi Floris B. Kooistra L. L. del Mercato Luca Beverina Mat Bra Abrem M. E. Brennan Hseyin Bekir YILDIZ
SELF ASSEMBLY P 2
POSTER # & TITLE ABSTRACT # ON CD ROM 55-TU STM studies of the inuences on self-assembly properties of poly(phenylene-ethylene)s 56-TU Spontaneous C60 Inclusion in Self-Assembled Cyclodextrin Monolayers on Polycrystalline Gold 57-TU Synthesis of Di and Tri-Functionalized Hexaazatrinaphthalene 58-TU Poly(2,3-dihexyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine) (PDHexEDOT) - Chiroptical Properties and Aggregation Behaviour 59-TU Effects Of Surface-Pretreatment On The Pentacene-Based Thin-Film Transistors Produced By The Neutral Cluster Beam Deposition Method PRESENTER Zhun MWei Huang, Shengbin Lei,ChenWang Andrea McNally Chi Wi Ong Gnther Gtz Seon-Hwa Jeong
66
INORGANIC NANOSTRUCTURES & NANOTUBES

POSTER # & TITLE ABSTRACT # ON CD ROM 76-TU Temperature Dependence Investigation of CdTe QDs Synthesis in Organic Media 77-TU Mechanical Properties of WS2 Nanotubes 78-TU Sensor applications based on MoSIx nanowires 79-TU Dispersion Properties and Applications of Mo6S3I6 Nanowires 80-TU Properties And Deposition Of Au/Si Cluster Beams 81-TU 82-TU Structural and Nonlinear Optical Properties of Mono-layered Silver Nanoparticles Structures and Control of the Electronic States of Quasi-One-Dimensional Halogen-Bridged NiIII Complexes PRESENTER XiaoYing Qi I. Kaplan-Ashiri Damjna Dvorsek Denis Mc Carthy Giuseppe Compagnini G. J. Lee Hashen Wu
67
POSTER PROGRAMME
Self-Assembly of Low Molecular Weight Gelators under Hydrostatic Pressure Self-Assembly of Dual-Coded Supramolecular Polymers Self-Assembly Of Nanoscale Coordination Cages On Surfaces: Moving From Gold To Silicon Nanoscale Structural And Electronic Properties Of Nanographene Based Mono- And Bi-Component Architectures: A Kelvin Probe Force Microscopy Study Biomimetic Control of 3-Dimensional Micro- and Nano-Structure of Polypyrrole Photoactive C60 bridged Tetrameric Osmium and Ruthenium g-Cyclodextrin assemblies; Assembly and Spectroscopy Effect Of The Applied Magnetic Field On Formation Of Polyaniline Films Salt Counterions on Poly(o-Methoxyaniline) Layer-By-Layer Films Supramolecular Dynamic Architectures From p-Conjugated Discotics: Nanoscale Structural And Electronic Properties Thin Films of Ring-Shaped Polyoxomolybdate Cluster Opto-Electronic Properties Of Self-Organizing Porphyrin Trimers Liquid-Phase Growth of Thiophene/Phenylene Co-Oligomer Crystal Films Collective Diffusion Of Organic Molecules On Surfaces: A Zinc Porphyrin On Thiol-Functionalized Au(111) Experimental and Theoretical Study of Chemically Sensitive Monolayers in Organic Thin Film Transistors Synthesis, Characterization And Fluorescent Emitting Property Of A Novel Chemical Sensor With Guanine Residue Photoconduction Of Self-Assembled Nanotubes Consisting Of HexabenzocoroneneTrinitrouorenone Dyads
Kazuhiro Yabuuchi Laura Pirondini M. Busi Matteo Palma Minhoon Jung Muath Atmeh O.P.Dimitriev P.A. Ribeiro Matteo Palma Reina Jin S. Fratiloiu Takeshi YAMAO Valentina Arima Veronika Proschek Wei Huang Yohei Yamamoto
83-TU 84-TU 85-TU 86-TU 87-TU 88-TU 89-TU 90-TU 91-TU 92-TU 187-TU
Development Of Porous Molecular Crystals Exhibiting Novel Dielectric Properties Theoretical Study on Phonon Properties of Intercalation Compound Related to MgB2 Novel Kaolinite Conducting Polymer Hybrid Materials and their Anti-microbial Functionality The use of Polyaniline-functionalised Nano-structured Calcium Silicate as a Sorbent for Rhenium Amine-assisted synthesis and stabilisation of nanocrystalline gold Force spectroscopy measurements of MoSIx nanowires with functionalized biological molecules Syntheses, Structures And Physical Properties Of The Novel HalogenBridged Platinum Nanowires With Asymmetric Units Optical Properties of Nanocrystal Embedded Silicon Nanowires Ag-containing Titania-nanotubes: Preparation and Catalytic NO Decomposition A Facile Low-Temperature Synthesis of Titania Nanotubes by SoftChemical Treatment Silicon Nanowire Nanocomposites for Scalable Vertical Photodiodes
HengBo Cuia Hidemi Nagao Kerstin A Burridge Mathew J. Cairns Michael J. Richardson Mihaela Ploscaru Miyuki Hosoda Sharon M. King Shu-Hua Chien Sibu C. Padmanabhan Peyman Serrati
INHERENTLY CONDUCTIVE POLYMERS P 2

POSTER # & TITLE ABSTRACT # ON CD ROM 93-TU 5-(2, 2-Bithiophene)yl-Branched Penta- and Sexy-2,5-Thiophenes: Synthesis, Electrochemical and Photophysical Properties 94-TU Polystyrene Sulfonic Acid As Polyaniline Dopant And Compatibilizer In Polyaniline/SBR Blends 95-TU Organized Conducting Polymer Nanowire Array 96-TU Structure, Dynamics And Conductivity Of Plastdoped Poly(Anilines) 9-TU ANILINE/O-METHOXYANILINE COPOLYMERS: DSC STUDIES 98-TU First-Principles Excited State Method For Polymers By Coupled-Cluster Theory 99-TU Optical And Electrochemical Properties Of p-Conjugated Regioregular Poly(6-alkylpyridine-2,5-diyl)s 100-TU Conducting Polymer in Liquids and Liquid Crystals Studied by Acoustic Shear Horizontal Wave 101-TU Synthesis of Liquid Crystalline Photoresponsive Conjugated Polymers and Control of Polarized Fluorescence 102-TU Alkyl-Chain Dependence of Quadrimolecular Recombination Kinetics of Photoinduced Charge Carriers in Regioregular Poly(3-Alkylthiophene)/C60 Composites Probed by Light-Induced ESR 103-TU Electrochemical and Spectroscopic Properties of Alternate Copolymers of 3,4-Dioctyloxythiophene and Thiophene Oligomers PRESENTER Stefano Toffanind Roselena Faez Darren Lee D. Djurado Dimitrinka Tsocheva Hideki Katagiri Hiroki Fukumoto Katsumi YOSHINO Kazuo Akagi H. Tanaka Malgorzata Zagorska
POSTER PROGRAMME
68
104-TU 105-TU 106-TU 107-TU 108-TU 109-TU 110-TU 111-TU 112-TU 113-TU 114-TU 115-TU 116-TU 117-TU 118-TU 119-TU 120-TU 121-TU 122-TU 123-TU
Microwave absorption properties of composites based in Polyethylene and PAni-DBSA/organoclay nanocomposites Conductive Composites: One Step Synthesis For Specic Applications. Electrochemical and Spectroelectrochemical Investigation of the Properties of Tertiophenes and Thienylenevinylenes Substituted by 1,3-Indandione Group Super-Hierarchical Structure And Control Of Helical Polyacetylene Synthesis And Properties Of New p-Conjugated Polymers Containing A Diazaborole Side Chain Poly(3,4-Ethylenedioxythiophene) (Pedot) Thin Film Prepared By InSitu Polymerization As Polymer Electrode In Redox Supercapacitor Creation of Organic-Inorganic Hybrid Materials Containing p-Conjugated Oligomers Enantioselective Properties Of Overoxidized Polypyrrole Films Imprinted With L-Aspartic Acid Studied By Eqcm Technique Quantitative Understanding Of The Conductivity of PEDOT:PSS Highly Hydrophobic Polyaniline And Polypyrole Nanobers Synthesised By Electrospinning-Sol-Gel Process Preparation And Characterization Of Novel Thiophene Oligomers Combined With Pyridine And Pyrimidine Unit Polyaniline-PEDOT Copolymer Composite containing Nano Size Barium Ferrite Particles Polypyrrole Self-Assembled Mono- And Multilayers For Molecular Junctions Fabrication and Characterisation of Silver/Polyaniline Composite Nanowires in Anodic Alumina Membranes PEDT: A High Current Polymer Electronic Material Synthesis and Characterization of Cyclopentadithiophene Based Low Band-gap Conjugated Polymers Polyaniline Nanotubes Conducting Polymers from Processable Precursors via Solid-State Conversion Tetrathiapentalenes: Building Blocks for New p-Conjugated, Conducting Polymers Synthesis And Electroluminescence Properties Of Optically Active Regioregular Polythiophene Molecular & Polymeric Materials for Photonics & Displays P 2 TITLE
Mauro A. SotoOviedo Stphanie Reynaud Sylwia Plewa1 Taizo MORI Take-aki Koizumi Young Rock Kwon Yuko Takeoka A. Menaker A.M. Nardes A.R. Phani Akira Kumagai Anil Ohlan A. Berlin Anna Drury Bjrn Winther Jensen Chun-Guey Wu E.N. Konyushenko Gregory A. Sotzing Harald Mller Hiroki Fujinami
POSTER # & ABSTRACT # ON CD ROM 124-TU Thermally Induced Electrical Properties of (Poly Vinyl Alcohol)(Methyl Orange) Composites 125-TU Triplet Energy Transfer In Phosphorescent Iridium (III)-Cored Dendrimers
PRESENTER Celso P. de Melo J.C. Ribierre
69
POSTER PROGRAMME
126-TU 127-TU 128-TU 129-TU 130-TU 131-TU 132-TU 133-TU 134-TU 135-TU 136-TU 137-TU 138-TU
POSTER PROGRAMME
139-TU 140-TU 141-TU 142-TU 143-TU
PyreneSubstituted Teruorenes: Highly PL Efcient and Stable Blue-Emitter with Improved Hole-injection Ability Optical Characterization of a Microencapsulated Multi-Colored Electrophoretic Display Panel utilizing Electrophoretic Color Pigment Particles Photoluminescence Recovery of Polymer in Water Soluble Conjugated polymer/Cadmium Selenide Quantum Dots Composites DFT Study on second-order nonlinear optical property of mono(salicylaldiminato) Nickel() Schiff base metal complexes New Erbium Complexes Emitting in Infra- red region based on Oligothiophene And Thiopheneuorene Carboxylate Red Organic Light-Emitting Diodes Based On New Iridium Complexes Electrochemical And Optical Properties Of A Highly Fluorescent Triarylborane-Substituted Polycarbazole 3,4-Ethylenedioxythiophene (EDOT) Oligomers: Synthesis, Characterisation and Protonation Experiments Intense Luminescence Of A New Class Of b-Diketone Lanthanide Complexes Essential Models For Multipolar Chromophores: Symmetry Breaking And Aggregation Effects Effect Of Pressure On The Optical Properties Of Highly Oriented PPV Photoinduced Energy Transfer in Zeolite-Y Scaffolded Ruthenium and Iron polypyridyl Donor-Acceptor systems Liquid Crystal Alignment by Femtosecond Laser-Induced Periodic Surface Structure Nature And Dynamics Of Electronic Excitations In Conjugated Polymers Control Of Excitation Transport And Emission In Conjugated Polymers Using Ph Modied Azochromophore Self Assembled Nanolayers Photoluminescence Properties of facial- and meridional-Ir(ppy)3 Thin Films Electroabsorption study of conjugated polymers of 2-methoxy-5-2ethyl-hexyloxy-1, 4-phenylenevinylene and Poly (2,6-bis- (n-octyloxy)-1,5-NaphthyleneVinylene). Phenothiazinyl- and carbazolyl-substituted ethylene molecular glasses for application in OLEDs
Chao Tang Chul Am Kim Chun Fang Yongqing Qiu Massimo Ottonelli Doowon Gong D. Nowak Egon Reinold Fabio Rizzo Francesca Terenziani F. Marabelli Gavin Sewell G. J. Lee E. Hennebicq F. E.G. Guimares Hiroshi Uda Jonathan Moghal
J. Simokaitien
MOLECULAR, POLYMER & NANO-ELECTRONICS P 2

POSTER # & TITLE ABSTRACT # ON CD ROM 144-TU Effects Of Interfacial Modication On The Performance Of Organic Transistor Based On TCNQ LB Films PRESENTER Hitoshi Ohnuki
70
145-TU 146-TU 147-TU 148-TU 149-TU 150-TU 151-TU 152-TU 153-TU 154-TU 155-TU 156-TU 157-TU 158-TU 159-TU 160-TU 161-TU 162-TU 163-TU 164-TU 165-TU 166-TU 167-TU 168-TU
Theoretical Study on Two-Photon Absorption Properties of Dipolar D-p-A Molecules Macromolecular Domain Morphology and Nanopatterning of Carbazole Terminated Poly(aryl ether) Dendrimers by CS-AFM Excitation Dynamics at Polymer Heterojunctions Probed by HighPressure Spectroscopy Cyclic and Linear Oligophenothiazines - Building Blocks for New Redox Active Materials A Raman Study On Charge Transfer Phenomena Between A Thin Film Of Tetracyanoquinodimethane And N-Si Charge Transfer In Methoxyoligothiophene With Ferrocenyl Groups Giant -Expanded Macrocyclic Oligothiophenes As Molecular Materials Soluble, Electroactive and Photoactive Polycarbazoles and Poly(di)indolocarbazoles Phases of Polydiacetylene And Their Electro-Optical Properties Photo-Generation of Polaron Pairs in Coupled Chains of Polyacetylene The Effects Of Dynamical Screening And The Tamm-Dancoff Approximation For The Calculation Of Excitons In Organic Semiconductors Molecular Ruler based on Molecular Device fabricated by Electrochemical Deposition of Platinum Electrode Multiscale Approach Of Charge Transport In pConjugated Polymers The Effects Of Disorder And Chain Twists On Intra-Chain Polaron Transport In Conjugated Polymers. Temperature Dependece Of The Electric Conductivity In Film Polyparaxylylene+CdS Ultrafast Conformational Dynamics Of Conjugated Polymers Effect of Lithium Phthalocyanine Doping on Poly(3-hexylthiophene) Density Functional Theory Study On The Inuence Of Donor And Acceptor On Second-Order Nonlinear Optical Properties Of Organoimide Derivatives Of Hexamolybdates Exciton Coupling In Molecular And Polymeric Nanostructures A Microscopic Description Of Pentacene Thin-Film Growth And Related Defects Inuence Of Source/Drain Contacts On The Characteristics Of Organic Field Effect Transistors Electronic Structure Calculations Of Phenalenyl Based Neutral Radical Conductors Charge Transport Properties Of Oligo-P-Phenylenevinylenes In Organic Field-Effect Transistors Bias-stress in organic transistors and water related trap states
Koji Ohta Hoon-Kyu Shin Johanna P. Schmidtke Karin Memminger Haeseong Lee Masa-aki Sato Masahiko Iyoda Nicolas Blouin O. Shusterman Pedro Henrique de Oliveira Neto P. Puschnig Sejung Ahn Stavros Athanasopoulos S. Stafstrm . S. Zhuravleva Sebastian Westenhoff Senku Tanaka Shaoqing Shi Shuji Abe Stijn Verlaak Susanne Scheinert S. Stafstrm Takeshi Yasuda Henrique Leonel Gomes
71
POSTER PROGRAMME
Characterization of ,-dihexylsexithiophene-based thin-lm transistors Modeling Charge transport parameters in conjugated polymers: Inuence of closest distance Inkjet printing of organic charge-transfer compounds as organic metal electrodes Luminescence of polyaniline nanoparticles Evidence for Butatrienic Repeating Unit in the Conjugated Backbone Metal contacts of thin-lm eld-effect transistors On the dynamics of valence holes in large physisorbed oligoacene molecules Syhtheses, Single-Crystal Structures and Field-Effect Transistor Characteristics of , Linked Unsubstitueted Oligothiophenes Donor-Acceptor Dendralenes Basis of Colour Variation in Polyuorenes During Degradation Clues to HOMO-LUMO Switching in STM Imaging of Physisorbed Aromatic Molecules from Coherent Transport Simulations Polaron dissociation in a conjugated polaron Many Particle Monte Carlo simulations of Transport in Thin Polymer Films Microscopic analysis of dissociation/recombination and transport in amorphous organic semiconductor devices Infrared reection-absorption spectroscopy of alkali-metal-doped Alq3 thin lms using synchrotron radiation Femtosecond two photon absorption study of quasi-one-dimensional MX-chain compounds DFT Theory for Polarons in Oligothiophenes: Intermolecular Interaction Monte Carlo wavefuction approach to the exctiton dynamics of three-dimensional molecular aggregates Solvent Effects on Radiation Dosimetry based on MEH-PPV Solutions
Hoon-Seok Seo James Kirkpatrick M. Hiraoka O.P.Dimitriev Olga Shusterman P. Stallinga Rainer Friedlein Reiko Azumi Thomas D J Westgate Toby A.M. Ferenczi Victor Geskin Xiao-jing Liu Yehoram Bar Yevgeni Preezant Yoko Sakurai Yoshiki Wada Yukihiro SHIMOI Suguru Ohta C.F.O. Graeff
POSTER PROGRAMME
185-TU 186-TH 188-TU

POSTER # & TITLE ABSTRACT # ON CD ROM 1-W Electron-Phonon Processes And The Resistivity Anomaly In QuasiOne Dimensional Electron System With An Open Fermi Surface 2-W Quantum Critical Behavior in the Quasi 2D Conductor, k-(MeDHTTP)2AsF6 3-W Quantum Monte Carlo Study Of Charge Ordering In Two-Dimensional Electron Systems 4-W Renormalization-Group Study on the Dimensionality Effect in QuasiOne-Dimensional 1:1 Organic Compound (TTM-TTP)I3 PRESENTER J. Kishine Kensuke Kobayashi Y. Tanaka M. Tsuchiizu
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5-W 5-W 7-W 8-W 9-W 10-W 11-W 12-W 13-W 14-W 15-W 16-W 17-W 18-W 19-W 20-W 21-W 22-W 23-W 24-W 25-W 26-W
Synchrotron radiation diffraction of CDW state in a ring shaped crystal Preparation and Properties of alternating main chain copolymers with 3,6-linked-9-alkyl -9H-carbazole units and 2,7-linked 3,6-dimethyl-9alkyl-9H-carbazole units Synthesis and Properties of 2,7-Linked 9-Alkyl-3,6-dimethyl-carbazole Alternating Copolymers with Phenylene Units with Varying Number of Fluorine Substituents Syntheses and Structures of Pyrene Derivatives Functionalized with Thienyl Groups Occurrence of the Zero-Gap Semiconducting State in Quasi-Two-Dimensional Organic Conductors Two Steps Phase Transition from Mott-State to Charge Ordered State in Et2Me2Sb[Pd(dmit)2]2: Thermo-Dynamical Study p - d Interaction in a Dicyano(Phthalocyaninato)Iron(III) Conductor with 2-D Arrangement Anion Dynamics in the Organic Metal with Multi-instability, (EDOTTF)2PF6 Quantum Paraelectricity near the Neutral-Ionic Critical Point Coulomb energies and photoemission in TTF-TCNQ organic molecular conductors 79 Br NQR study of DMTTF-2,6-QBr2Cl2 around a neutral-ionic quantum critical point Organic Semiconductors: Phase Purity Control by Lattice Phonon Confocal Raman Mapping Structures and Properties of a Monoanionic Weak Electron Acceptor, Chloranil-4-NHCH2SO3, and its BEDT-TTF Salt Raman Spectroscopic Analysis And Dft Calculations On Two Fused Thienoacenes With Five And Seven Rings Interchain Mean-Field Approach To Charge-Ordering Transition Of Quasi One-Dimensional Molecular Conductors At Quarter Filling Occurrence of the Zero-Gap Semiconducting State in Quasi-Two-Dimensional Organic Conductors Coexistences and Competitions of Symmetry Broken States in Quasi-One- Dimensional Molecular Conductors - a Finite Temprature Study Two Dimensional Multimode Peierls Transition in the Presence of Anisotropy Anomalous Pressure Effect on the Superconductivity in an Organic Molecular Conductor b-(BDA-TTP)2SbF6 Novel Electronic States by Utilizing Molecular Degree of Freedom; Organic Superconductor, b-(meso-DMBEDT-TTF)2X and Related Materials Metastable Phases And Quantum Transitions In An Organic CT salt. Low Temperature Fermi Surface of b-(BEDT-TTF)2CsCd(SCN)4
K.Yamamoto Harismah Kun Hunan Yi Minoru Ashizawa Shinya Katayama Yutaka Nishio M. Ishikawa Ryo Chiba Yasufumi Yamashita Laura Cano-Corts F. Iwase Elisabetta Venuti Hiroki Akutsu
Hideo Yoshioka Shinya Katayama Hitoshi Seo Chiduru Watanabe Madoka Tokumoto H. Mori Anna Painell M. Kimata
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POSTER PROGRAMME
Reyes Malav Osuna
27-W 28-W 29-W 30-W 31-W 32-W 33-W 34-W 35-W
Appearance Of Dirac Cone Dispersion And Uniaxial Strain Dependence In Electronic Structure of a-(BEDT-TTF)2I3 Observation of Vortex Transition by Interlayer Resistance Measurements in k-(BEDT-TTF)2Cu(NCS)2 Effects of surface pretreatment on DHSTh-based thin-lm transistors The Effect Of Irradiation-Induced Disorder On The Interlayer Conductivity And Critical Temperature Of The Organic Superconductor k-(BEDT-TTF2-Cu-(SCN)2 Correlation Between Surface Treatment And Performance Of Tetracene-Based Field-Effect Transistors Exploring air-stable n-type organic transistors based on nickel complexes Development of Ambipolar Metal-Organic Thin-Film Transistors (MOTFTs) Non-superconducting phase appearance in the surface vicinity of k(BEDT-TTF)2Cu[N(CN)2]Br by fast cooling Anomalous magnetotransport in the p-d conductor (DIETSe)2FeCl4
Hiori Kino L.Yin Hoon-Seok Seo James G. Analytis Seon-Hwa Jeong Hiroshi Wada Shin-ichiro Noro N.Yoneyama Mitsuhiko Maesato
ENERGY STORAGE & CONVERSION MATERIALS P 3

POSTER # & ABSTRACT # ON CD ROM 36-W 37-W 38-W 39-W TITLE Lead Sulphide Nanocrystals for Photovoltaics An another blooming absorbing material for solar cells Structural Modication Of Single Wall Carbon Nanotube With 2-(2Thienyl)Ethanol And Its Application In Polymer Solar Cells Hole-Transporting Molecular Glasses Based On Carbazole For Solid Dye Sensitizer Solar Cells Ru (II) complex black dyes for dye-sensitized solar cell Effects of Molecular Surface Modication on Recombination and Charge Transfer in Organic-Inorganic Photovoltaic Cells The Internal Electric Field in Conjugated Polymer and Polymer:Fullerene Based Diodes Studied by Electroabsorption Spectroscopy Transport And Recombination In Polythiophene:Fullerene Solar Cells Photochemical Elaboration Of Nanohybrid Material Based On Tio2 And Poly(3,4Ethylene-dioxythiophene) Without Applied Potential Charge Pair Formation and Recombination Dynamics in an Alternating Polyuorene Copolymer for Solar Cell Applications Hydrogen-storage properties of Pd/Pt and Pd/Ir bimetallic nanoparticles Hydrogen-Storage Properties of Pd-Rh Nanoparticles Electronic transport properties of MoSIx nanowire bundles and networks Energy resonance in photoinduced electron transfer from terthiophene to C60 PRESENTER Andrew A. R. Watt B.Kavitha Ana F. Nogueira R. Ach C.C. Lai Chiatzun Goh Christoph Lungenschmied C. G. Shuttle F.Goubard H. Aarnio Hirokazu Kobayashi Hitoshi Morita Marko Uplaznik J.-P.Yang
POSTER PROGRAMME
40-W 42-W 43-W 44-W 45-W 46-W 47-W 48-W 49-W 50-W
74
51-W 52-W 53-W 54-W 55-W
Electrosorption Of Hydrogen In Nickel Foam/Palladium/Carbon Nanobers Composite Electrodes Electro-optical Modelling of Blended Polymer Solar Cells Improvement Of Device Performances By Red Dyes In Conjugated Polymers/Methanofullerene Plastic Solar Cell Energy Transfer Studies Using Photoluminescence Lifetime Correlated Near Optical Microscopy of Photoconducting Heterostructures Based On Nanoparticles MoS2/ Polymer For Photovoltaics
J. M. Skowroski Jonny H. T. Williams Joonyoung Park A. Cadby B.M. Rumyantsev
ADVANCED FIBERS, TEXTILES & COATINGS

POSTER # & ABSTRACT # ON CD ROM 56-W 57-W 58-W 59-W 60-W 61-W 62-W 63-W 64-W 65-W 66-W 67-W 68-W 69-W 70-W 71-W 72-W 73-W TITLE Novel Hybrid Materials of Cellulose Fibres with Magnetic Properties of cellulose and polyaniline synthesized in situ blends Prevention of biofouling on membranes by conducting polymer layers Novel method to Determine Electromagnetic Shielding Properties of Conducting Textiles in 1-18 GHz Frequency Range:Validation Fibres of Wool and Possum Fur Functionalised by Conducting Polymers UV created weak and dangling bonds in aryl-substituted polysilylenes Conducting textiles and yarns: Natural Silk Coated with Polypyrrole Growth of High Purity Polyaniline Nano and Micro Fibers Using the Electrospinning Technique Preparation of conductive textiles using pyrrole functionalized vinylsilane Electrical characterization of an electropsun hybrid organic/inorganic Schottky nanodiode Novel Soluble Tin Oxide Thin Films And Their Application For MetalEnhanced Fluorescence Application of soluble poly(3-decanylpyrrole) on textiles Morphology of PET/PANI junctions in coatings Relation between chromism and whisker formation of conducting polymer in solution Electro Magnetic Interference Shielding Pet Fabric/Poly(3,4-Ethylenedioxithiophene) (Pedot) Composite Highly Conducting PEDOT/PSS Microbers Electron Beam and UV Light Induced Phenomena in Polysilanes for Nanostructured Information Storage Polyaniline-triazine composite for corrosion protection of iron PRESENTER Aaron C. Small B. Fryczkowska C. Weidlich Eva Hkansson Fern M. Kelly F. Schauer I. Cucchi J. R. Crdenas M. Miuk N.J. Pinto P. Fournet Richard. C. Foitzik R. Fryczkowski Takeshi Shimomura Bo Ram Jung Yuko Harashina I. Kuritka Jun Yano
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POSTER PROGRAMME

POSTER # & TITLE ABSTRACT # ON CD ROM 74-W Investigation on hysteresis loop in organic devices 75-W Qualitative Analysis of Ge p-n photodiode structures using TEM techniques 76-W Homologous series of end-functionalised oligomers of substituted p-phenylene vinylenes and their relevance for theory and practice 77-W Semi-Conducting Polymers Bearing Perylenebisimide Units as Pendant Groups. Novel Materials with Enhanced Absorption Cross-section 78-W Picosecond charge mobility measurements in organic semiconductors 79-W 80-W 81-W 82-W 83-W 84-W 85-W Organic Field-Effect Transistors using p-Extended Phenanthroline Derivatives Memory devices using organic materials Investigation of Mechanism of Memory Behaviour of Organic FET Fabricated with Polypeptide as a Gate Dielectric Effect of contact resistances in the modeling of organic Thin Film Transistor Pentacene and Polyuorene Based Field Effect Transistors with Organic and Inorganic Dielectrics DC and AC characterization of conductance switching phenomena in Rose Bengal based devices Effect of the self-assembled monolayer on carrier transport in Organic eld effect transistors using 5,5-octyl-2,2:5,2:2-quaterthiophene as an active layer Fabrication of all plastic transistors using poly(3-hexylthiophene) The electronic state spectroscopy of c-C4F8 by VUV photoabsorption and its role on the plasma processing industry Modeling Thin-lm eld-effect transistors Bottom-contact OTS-pretreated DHSTh transistors Equivalent Circuit For Organic Field-Effect Transistor From Impedance Measurements Under DC Bias Chemical Vapour Deposition grown carbon nanotubes for interconnect technology Origin of Carriers in Organic Field Effect Transistors Studied by Displacement Current Measurement Fabrication of Organic FET Memory with Polypeptide by a Printing Method Ambipolar organic eld-effect transistors using rubrene single crystals Analysis of time-of-ight transient photocurrent in organic semiconductors with coplanar-electrodes conguration Characteristics of organic FET using fullerene derivatives PRESENTER Jie Lei J. McCarthy E. Thorn-Csnyi J. L. Segura J. Cabanillas-Gonzalez Jun-ichi Nishida Keiko Mori Masahiko Kojima L. Fumagalli Lus Alccer M. Barra Masataka Kano Miho Shibao P Limo-Vieira P. Stallinga Jong-Ho Choi Reghu Menon Rory Leahy Satoshi Ogawa Sei Uemura T. Takenobu T.Yoshikawa T Morita
POSTER PROGRAMME
86-W 87-W 88-W 89-W 90-W 91-W 92-W 93-W 94-W 95-W 96-W
76
97-W 98-W 99-W
Operating Principle of Polymer Insulator Organic Thin-Film Transistor T.G Bcklund Exposed to Moisture Fabrication and Performance of Organic Field Effect Transistors Using Hiroshi Kageyama Amorphous Molecular Materials New PCBM analogues for organic electronics Alexander B. Sieval
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS P 3

POSTER # & TITLE ABSTRACT # ON CD ROM 100-W Synthesis and characterization of a new iridium complex with a benzothiazole derivative 101-W Improved lifetime of organic light-emitting diode with protective silver cathode prepared by ion beam assisted deposition 102-W Fabrication of electroluminescent micro-arrays by dry contact printing 103-W A Two Fold Increase in the Light Extraction Efciency of Polymeric Light Emitting Diodes using a 2-Dimensional Photonic Crystal Placed beneath the Anode 104-W Synthesis and Properties of Fluorine -Containing PPV Derivates 105-W Density functional theory study on the inuence of donor and acceptor on second-order nonlinear optical properties of organoimide derivatives of hexamolybdates 106-W Synthesis of Polydiacetylene Derivatives with Extended p-Conjugation Systems for Third-Order Nonlinear Optics 107-W The Use Of Triphenyldiamine As The Active Layer In Organic LightEmitting Diodes 108-W Luminescence efciences in solution processable electrophosphorescent dendrimers 110-W p-p* transition and metal-to-ligand charge transfer transition in Iridium-complexes 111-W Temperature Measurements Of The Organic Layers In A Polymer Light-Emitting Diode By Raman Spectroscopy 112-W Trapping Effects On Frequency Response Of Dithiolene-Based Nir Photodetectors 113-W Synthesis and Properties of New Crosslinkable Fluorene-alt-bithiophene Copolymers 114-W Electrical Properties Of Perylene Derivative Organic Semiconductor/ Metal Contact 115-W Tunability Of The Optical Properties Of Nanostructured Composite Polymeric Materials 116-W Correlations between UV-Vis and Raman spectroelectrochemistry 117-W Blue light emitting devices from magic size CdSe/ZnS nanocrystals 118-W Environmental Effects on the Absorption Proles of p-Conjugated Molecular Systems: a Theoretical and Experimental Approach. PRESENTER Jae-Hoon Eom P.Taillepierre Alessandra Passab A. M. Adawi Sheng-biao Li Shaoqing Shi Shuji Okada S. Cheylan
T. Kobayashi Takuro Sugiyama T.Agostinelli Helena Alves A. Stanculescu A. Camposeo Anna Kpas Aurora Rizzo Begoa Milin Medina
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POSTER PROGRAMME
S.G. Stevenson
119-W 120-W 121-W 122-W 123-W 124-W 125-W 126-W 127-W 128-W 129-W 130-W 131-W 132-W 133-W 134-W
135-W 136-W 137-W 138-W 139-W 140-W 141-W 142-W 143-W 144-W 145-W
Hole and electron transport properties of a family of blue light emitting uorene-phenylenediamine copolymers Optical and electrical properties of mixed Langmuir-Blodgett lms of OC1OC6-PPV a liquid crystal Effect of pH Variation on the Luminescence of Colloidal Au/Polyaniline Systems Polymer Bulk Homojunction Light-emitting and Photovoltaic Cells High Gain Optical Amplication in MEH-PPV Films The Role Of Shunt Resistance In The Amplication Of Organic Photodetectors By inserting a very thin layer of organic material into a device to study its carrier transportation behavior Waveguiding, Microcavity Effects and Optically Pumped Lasing in Single Polymer Nanowires Lasing characteristics of b-phase poly(9,9-dioctyluorene) (PFO) Molecular interactions at the organic/inorganic interface in dye-loaded zeolite nanochannels Fabrication of Multi-Colour Pixels from a Single Active Molecule by Surface-Tension-Driven Technique Organic light-emitting diodes based on electromers Characteristics of organic thin lm transistor (OTFT) using PEDOT electrodes and insulating polymer Time-resolved Z-scan measurements in Cr3+ -doped laser crystals Preparation of ITO Thin Films by Sol-Gel Process and Their Characterizations Performance Improvement of Organic Thin Film Transistors with SelfAssembled Monolayer Formed by ALD Characteristics of Organic Thin-Film Transistors with PMMA-co-MMA and TiO2 Nanocomposite Formed by Sol-Gel Process Study on Organic Light-Emitting Electrochemical Cells Using Imidazodium Salts as Ionic Transport Liquids Improvement of chromaticity in WOLEDs with three emissive layers Photogenerated Carrier Transport and Surface Ordering of Polyhexylthiophene in Vertical Structures Colour-tuning of light-emitting devices based on polyuorine derivatives through the maskless dye-diffusion technique Color-Variable Organic Light-Emitting Devices Theoretical Study on Chain Length Dependence of Two-Photon Absorption Properties in p-Conjugated Triple-Bond Systems Pulse formation dynamics and optical switching in polymer lasers Unusual light emission from polymer eld-effect transistors Efcient Photo-Patternable Electronic Formulations of Light-Emitting Polymers Improved lifetime of organic light-emitting diode with protective silver cathode prepared by ion beam assisted deposition
B.K.Yap C.A. Olivati C.P. de Melo Corey Tracy D Amarasinghe Dylan Banks G.Y. Zhong Gareth Redmond Gihan Ryu G. Macchi Giuseppe Gigli Gui Yu H. S. Kang Hacene Manaa Hyun Chul Choi Hyunsuck Kim Jaehoon Park J. Goicoechea Jun Ho Kim V. Bhatia Kazuya Tada Koichi Sakaguchi Koji Ohta S. Perissinotto M.N. Shkunov Olga Solomeshch P.Taillepierre
POSTER PROGRAMME
78
146-W
Improved Operational Lifetime of Semiconducting Polymer Lasers Through Encapsulation.
Scott Richardson

POSTER # & TITLE ABSTRACT # ON CD ROM 147-W Time-Resolved Photoluminescence Of Ppv Nanotubes Synthesized By The Wetting Template Method 148-W Conducting polymer Preparation under extreme or non classical conditions 149-W Preparation of Semi-Conducting Polymer Nano-Particles and NanoFibres by Supercritical CO2 RESOLV Process 150-W Polyaniline-Based Material With A Mixed Electron And Proton Conductivity For Electrocatalytic Application 151-W Electrical Characterization of in-situ polymerized polyaniline thin lms 152-W Humidity Effects In Spin-Casted Films Of Polytiophene-Polystyrene Blends 153-W Ageing-temperature transition in polyaniline lms 154-W Poly(3,4-ethylenedioxythiophene) (PEDOT) Obtained from Processable Precursors 155-W Functionalized poly-3-alkylthiophene for photovoltaic devices 156-W Conducting hybrid materials based on polyaniline, clay and SBR prepared by in situ polymerization 157-W Electrodeposition of silver on electrochemically polymerized poly(3,4-ethylenedioxythiophene) 158-W Evolution of nanotubular structure during aniline polymerization 160-W Interpolymer Complexes Of Polyaniline With Different Polysulfonic Acids For Various Applications 161-W Magneto-transport studies in conducting polyaniline 162-W Synthesis of Processable Polyanilines for Technological Applications 163-W Formation of nanowire/polymer composites for organic semiconductors devices 164-W Meso-Meso Ethyne Bridged Porphyrins: A New Class of Conjugated Electronic Materials 165-W Ultraviolet photoluminescence in a semiconducting polymer (MEHPPV) 166-W Explosive Polymerization of Alkoxybromothiophenes 167-W Chemical Polymerisation Of Pyrrole Using Iron (III) Salts Of Alkyl Benzene Sulfonic Acids As Oxidising Agents 168-W Spectroscopic Studies of Dopant Effects in Poly (3,4-Ethylenedioxythiophene) (PEDOT) PRESENTER F. Massuyeau W. M. de Azevedo Kwon Taek Lim I. Sapurina J. A. Giacometti A. Bernasik J. Proke Jayesh G. Bokria Jean-Charles Flores Roselena Faez Mercedes Vzquez M. Trchov V.F. Ivanov P.K. Kahol Parveen Saini P. Beecher Paul R. Frail Paulo B. Miranda Pawel Wagner P.Subramanian Ralph P. Cooney
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169-W 171-W 172-W 173-W 174-W 175-W 176-W 177-W 178-W 179-W 180-W 181-W 182-W 183-W
Efcient Synthesis of Novel 3,4-Ethylenedioxythiophene (EDOT) Derivatives Endowed with Acceptor Moieties and Hydrogen Bonding Receptors Electron Spin Resonance of Field-induced Polarons in MIS Diode Structures and Polaron-Bipolaron Transformation at High Doping Levels Modication of Amine-functionalized Polyterthiophene Films Remediation of Chromium(VI) in Acidic Conditions with Polypyrrole Coated Titanium Electrochemical and Spectroelectrochemical Investigation of the Properties of Tertiophenes and Thienylenevinylenes Substituted by 1,3-Indandione Group Calcium silicate facilitated polymerisation of MAS Molecularly Imprinted Conducting Polymers For Protein Assays Transparent and Flexible Carbon Nanotube / Polypyrole and Carbon Nanotube / Polyaniline pH Sensors Synthesis of Polyaniline Nanobers via Porous Membrane Controlled Polymerization Functionalised Thiophene- Macrocycles Electrical and Thermal Properties of Polypropylene Montmonillonite / Polypyrrole Nanocomposites Synthesis and Electro-Optical Properties of an Ionic Polyacetylene Carrying Thiophene Moieties
Ral Blanco S. Kuroda Sanjeev Gambhir Sean T. Earley Sylwia Plewa T. Borrmann V. Syritski N.Ferrer-Anglada Jeremy Bergeson Arne Guta Ch. Pandis Yeong-Soon Gal
Preparation of Oriented Mesoporous Carbon Nano-Filaments within Justin D. Holmes the Pores of Anodic Alumina Membranes Mechanical Reinforcement of Carbon Nanotube Papers by the Incorporation of Polystyrene. Electrochemical Slow Relaxation in Polyaniline Highly Efcient White Organic Light-Emitting Diodes from novel Fluorescent and Phosphorescent materials Fiona M. Blighe Mohammad Reza Nateghi Ji Hoon Seo
POSTER PROGRAMME
184-W 185-W

POSTER # & ABSTRACT # ON CD ROM 1-TH 2-TH 3-TH 4-TH 5-TH TITLE Syntheses and Properties of (DT-TTF)-C60 Hybrid Systems Magnetic Study of the Electronic States in (BEDT-TTF)(TCNQ) Synthesis of polyaniline in presence of macrocyclic compounds CRYSTAL sTRUCTURE oF ORGANIC superconductor b-(EDTTTF)4(Hg3I8)1-x AT 90 K Charge ordering in q-(BEDT-TTF)2 RbZn(SCN)4 : Cooperative effects of electron correlations and lattice distortions PRESENTER Yohji Misaki Takumi Kihara Grigoras Mircea R.N. Lyubovskaya Satoshi Miyashita
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6-TH 7-TH 8-TH 9-TH 10-TH 11-TH 12-TH 13-TH 14-TH 15-TH 16-TH 17-TH 18-TH 19-TH 20-TH 21-TH 22-TH 23-TH 24-TH 25-TH 26-TH 27-TH 28-TH 29-TH 30-TH
Photoemission Spectroscopy of Organic Superconductor k-(BEDTTTF)2X (X = Cu[N(CN)2]Br, Cu(NCS)2) Angle Resolved Photoemission Spectroscopy of Two-dimensional Organic Metal (BEDT-TTF)3Br(pBIB) Low temperature Structural Study of a-(BEDT-TTF)2MHg(SCN)4 [M=K and Rb] Resistivity measurement of small crystals growing on ne patterned electrodes Structural Study of a and b-(BEDT-TTF)2I3 Uniaxial Compression Effect on the Superconductivity of b-(BDATTP)2SbF6 New superconducting and paramagnetic salts derived from (BEDT-TTF)4[H3OM(C2O4)3].PhX (M = Cr and Fe; X = F, Cl and Br) Structures and Properties of BEDT-TTF Salts Drived from Several Alkylsulfonates Deuteration Effect in Cation Radical Salts of EDO-TTF having Multiinstability of Possible charge disproportionation in a-(BETS)2I3 and a-(BEDT-STF)2I3: studied Structural Study of a and b-(BEDT-TTF)2I3 Metal-Insulator Transition and p-d Interaction of Quasi-1D Organic Conductors (DMET)4(MCl4)(TCE)2 (M=Mn,Co,Cu,Zn) Synthesis and Properties of novel Donor-Acceptor Systems with TTF unit Design and Synthesis of TTF-based Materials with Electron Withdrawing Groups 1H-NMR analysis of the Antiferromagnetic state of (TMTTF)2SbF6 Preparation, Optical and Electrochemical Properties of 2,7-Linked3,6-Dimethyl-9-Alkyl-Carbazole Main Chain Polymers and Copolymers. Cu (II) complex anion and perchlorate radical salts of benzo-TTF and TCET-TTF Upper critical eld Hc2 in triplet superconductor in Bechgaard salts (TMTSF)2PF6 Magnetocaloric effect and specic heat in k-(BETS)2FeBr4 Quantum Monte Carlo study of spin-Peierls transition in quasi-onedimensional materials Structural and electromagnetic properties of the incommensurate organic superconductor (MDT-TS)(AuI2)0.441 NMR to probe of the SDW/normal metal two-phase coexistence Metallization of (TTM-TTP)I3 with a Highly One-Dimensional HalfFilled Band under Pressure beyond 7 GPa 1 H NMR studies on Au(tmdt)2 under high pressures Cooling rate dependence of the magnetic torque in the FISDW transition of (TMTSF)2Cl4
Takayuki Kiss Tatsuya Akimoto Takayoshi Ito Hisashi TANAKA Yoshio Nogami Hiroshi Ito Simona Curreli Akane Akutsu-Sato Yoshiaki Nakano Shiro Harada Yoshio Nogami Hiroshi Ito Katsuya Sako Mao Katsuhara Hidetaka Satsukawa Ahmed Iraqi L. Boudiba Ana Domnguez Folgueras Takako KONOIKE Akira TERAI Tadashi Kawamoto Stuart Brown Syuma Yasuzuka K. Miyagawa Noriaki Matsunaga
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POSTER PROGRAMME
31-TH 32-TH
Magnetoresistance Anomaly and Shubnikov-de Haas Oscillations in b-(EDO-TTFVO)2FeCl4 Physical and Structural Properties of b-(BDA-TTP)2X (X = BrI2, Br2I) and b-(OTADA-TTP)2I3
Masayasu Teramura Jun-ichi Yamada
FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES P 4

POSTER # & TITLE ABSTRACT # ON CD ROM 33-TH Spark light induced by eld electron emission from carbon nanotube forests 34-TH Electronic properties of helically-wrapped nanotubes 35-TH Investigation of Water Based Suspensions of Carbon Nanotubes Using Optical .. 36-TH New diazonium salts of metal complexes for electrochemical 37-TH Understanding of the cubic A4C60 fullerides phase diagram: evidences for the metallic phase in Li4C60 38-TH Linear and Nonlinear Optical Properties of Porphyrin- Carbon Nanotube Composite solutions 39-TH Investigations of electron injection processes in a methanofullerene thin lm transistor 40-TH Physical Properties of Novel Free-standing Polymer-Nanotube Thin lms 41-TH Enhanced Plasma Growth of High-Density Amorphous Carbon Nanostructures on 42-TH Carbon Nanohorn based Donor Acceptor Nanoensembles 43-TH Charge transfer phenomena between single-walled carbon nanotubes and tetrathiafulvalene 44-TH Development of C60-TTF dendrimers for the application to a photovoltaic device 45-TH New method for purication of carbon nanotubes and preparation of polymer-nanotubes composites 46-TH Photoluminescence with Near Infra Red Excitation in Single Wall Carbon Nanotubes 47-TH Aligned Carbon Nanotube/ZnO Heterojunction Arrays 48-TH Carbon nanotubes lled with conducting polymers via supercritical carbon dioxide 49-TH Absorption spectra from THz to visible region in highly oriented 50-TH Carbon Nanotube Growth on Co and Fe Nanoparticle Films 51-TH 52-TH Optics and Raman spectroscopy of vertically aligned carbon nanotubes Electronspun Carbon Nanotubes/ Polyacrylonitrile Nanobers with Uniaxially Aligned Arrays PRESENTER A. Cunningham Andrew Wall B.R.Priya Bruno Jousselme Denis Aron Eimhin Ni Mhuircheartaigh Elizabeth von Hauff Emer Lahiff Gamal Abbas Georgia Pagona Ha-Jin Lee Hiroyuki Nishiakwa Ian OConnor J.P. Buisson Jianwei Liu Johannes Steinmetz N. Akima Niall Patrick Mc Evoy Paul Dawson Qinghua Zhang
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53-TH 54-TH 55-TH 56-TH 57-TH 58-TH 59-TH 60-TH
Interactions of Polycyclic Aromatic Hydrocarbons and Single Walled Carbon Effect of ion irradiation on transport properties of transparent networks made of SWNT Percolation in Polyvinylalcohol - Carbon Nanotube composites: The role of the solvent Optically Active Polymer Carbon Nanotube Composite Nanostructures POLYPROPYLENE/MULTI-WALLED CARBON NANOTUBES NANOCOMPOSITES: STRUCTURE-PROPERTY RELATIONSHIPS A New Way to Disperse Carbon Nanotubes in EVA The effect of solvent choice on the mechanical and morphological properties of carbon nanotube-polymer composites. Conducting and transparent SWNT/polymer composites
Theresa Hedderman Viera Skkalov Y. R. Hernandez Xuetong Zhang Emmanuel Logakis Sophie Peeterbroeck Umar Khan Urszula Dettlaff-Weglikowska
ENERGY STORAGE & CONVERSION MATERIALS P 4

POSTER # & TITLE ABSTRACT # ON CD ROM 61-TH ELECTRIC AND PHOTOELECTRIC FEATURES OF VACUUM-DEPOSITED a-Si:H AND ORGANIC MATERIAL BLENDS 62-TH Synthesis and Properties of Alternating Fluorene-Based 63-TH Photoactive polybithiophene/titania hybrids prepared by electrochemical 64-TH Synthesis and Characterization of Nanostructured Carbon Materials for Energy Storage 65-TH P and n dopable carbazole/perylene alternated materials for organic photovoltaic devices 66-TH Exciton Diffusion and Energy Transfer in Organic Photovoltaics: Measurements and Novel Device Architectures 67-TH X-ray Microscopy of Polymer/Fullerene composites: Nanoscale Quantitative Chemical Imaging 68-TH Photocurrent Contrast Imaging of Semiconducting Polymer Based Structures 69-TH Synthesis and Properties of Low Band Gap Polyuorenes with Increased Molecular Weights for Photovoltaic Devices 70-TH Nanomorphology of Polymer/Fullerene Bulk Heterojunction Solar Cells 71-TH Photovoltaic Properties and Inner Electric Field of ZnO/Zn-phthalocyanine Hybrid Solar Cells 72-TH Polypyrrole Electrode Material For Piezoelectric Poly(Vinylidene Fluoride) Films 73-TH Charge Photogeneration in MEH-PPV/Pt0,75C60 Donore-Aaaeptor Blends PRESENTER Kestutis Arlauskas Lars Lindgren Leeyih Wang Mariano M. Bruno R. Ach Shawn R. Scully C. R. McNeill D. Gupta Erik Perzon Harald Hoppe Yuki Yoshida I.Yu. Dmitriev A.A. Bakulin
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74-TH 75-TH 76-TH 77-TH 78-TH 79-TH
Application of Novel Photo-electrical Techniques to Characterize Bulk-Heterojunction Solar Cells Bulk Hetrojunction Solar Cells Based on Conducting Ground-state charge-transfer complexes of MEH-PPV as low-bandgap absorbers for polymer solar cells High rectication organic diodes made of sulphonated polyaniline Recombination of Injected Plasma in Bulk-Heterojunction Solar Cells Air exposure stability of organic semiconductors from low-level optical absorption
Almantas Pivrikas Ana Flvia Nogueira D. Paraschuk Di Wei Gytis Juka Joaquim Puigdollers

POSTER # & TITLE ABSTRACT # ON CD ROM 80-TH Intermolecular interactions and p-electron delocalization in polyconjugated molecules 81-TH Ionically self-assembled and hierarchized poly(aniline)-dendrondopant supermolecules 82-TH Pattern Replication in Thin Films 83-TH Switching in Orientation of Macromolecular Silicon Nanorod on the Surfaces 84-TH Structure and electronic transport properties of stretched lms of plastdoped poly(aniline). 85-TH Inuence of the dielctric/organic interface on the hole mobility in light-emitting eld-effect transistors based on PPV derivatives 86-TH Manipulation of wavefunctions of photoexcited states for enhancement of third-order optical nonlinearity 87-TH Controlling the charge-ordering states of MMX chain compounds by the countercation 88-TH Mixed Conduction of Coordination Polymers 89-TH ESR Observations of Optically-Generated Solitons in Quasi-One-Dimensional Halogen-Bridged Diplatinum Complex, Pt2(n-pentylCS2)4I 90-TH Charge transport in quasi-one dimensional helical polyacetylene bers 91-TH The spectroscopic study of the molecular structure of polyaniline 92-TH Hyperconductivity In Polyaniline Films ? 93-TH Electric and dielectric behaviour of grate/polyaniline epoxy composites 94-TH Polyaniline-coated multi-wall carbon nanotubes containing a 95-TH p-Conjugated Polymers from New Polymer Precursors in the Solid State 96-TH Experimental determination of the nature of intermolecular interactions in regio-regular poly(3-hexylthiophene) 97-TH Hybrid Nanotubes, Nanowires, and Nanojunctions 98-TH Inuence of electrical eld on electrical and dielectrical properties 99-TH EXTENSIVE QUINOIDAL OLIGOTHIOPHENES: RAMAN AND THEORETICAL EVIDENCES OF PRESENTER A. Milani Amrit Puzari Andrzej Bernasik Masanobu Naito David Djurado Francesco Todescato Hideo Kishida Hiroaki Iguchi Hiroshi Kitagawa Hisaaki Tanaka Hyun Jung Lee Ivana Sedenkova Ivanov V.F. Jarmila VIilcakovs Jaroslav Stejskal Jayesh G. Bokria Jenny Clark Jinsoo Joo Joerg Posdorfer Juan Teodomiro Lpez Navarrete
POSTER PROGRAMME
84
100-TH 101-TH 102-TH 103-TH 104-TH 105-TH 106-TH 107-TH 108-TH 109-TH 110-TH 111-TH 112-TH 113-TH
Novel Pressure-Induced Metal-Insulator Synthesis of Polyacetylene and PEDOT Nanoparticles in Nonaqueous Emulsions Twist glass transition in regioregulated poly(3-alkylthiophene)s What do molecular simulations say about structure and dynamics of camphor-sulfonic acid doped polyaniline? Synthesis of Polyaniline in the presence of Aerosol OT and nano Induction of Chirality into Poly(2-methoxyaniline-5-sulfonic acid) via Binding with Amino Acids and Peptides Blends prepared from conducting polymer and precursor poly(acid amic) to be used as RAM Electrochemical storage of hybrid nanostructured conjugated materials in room temperature ionic liquid Electrochemical and Spectroelectrochemical Properties of Tertiophene and Thienylenevinylenes Substituted by Vinylphenyl Group Relaxation process studies in blends of conjugated polymers Electrical and surface properties of polypyrrole containing Head-to-tail coupled poly(thienylene-ethynylene)s for applications in photovoltaic devices Memory Effect of Composite Neuron-type Conducting Polymer Network Synthesis and Properties of 3,4-Dinitrothiophene Based
Kazuya Otsubo Kevin Mller Koji Yazawa Konrad Piwowarczyk Kuldeep Singh Leon Kane-Maguire Luiza de Castro Folgueras M. Mallouki Malgorzata Jadamiec Marcelo Valadares Mria Omastov Martin Schikora Masaharu Fujii Masahiro Abe
MOLECULAR MAGNETS & SPINTRONICS P 4

POSTER # & TITLE ABSTRACT # ON CD ROM 114-TH Ferromagnetic carbon nanotubes for magnetic data storage devices 115-TH Syntheses and Magnetic Properties of Organic Radical Containing Carborane Derivatives 116-TH Poly(thiaheterohelicene) : A Helical p-Conjugated Polymer 117-TH Spin polarization and magnetoresistance in ferromagnetic/organic semiconductor/ferromagnetic sandwiches 118-TH Two strategies to yield conducting - magnetic materials 119-TH Theoretical studies on the ferromagnetism of decamethyl ferrocenium 120-TH Room temperature ferromagnetic behavior in pellets of poly(3methyltiophene) 121-TH Polaron to Bipolaron Transition Dynamics in 122-TH Tuning the Exchange Interaction in High Spin Biradicals 123-TH Construction of a New Single Molecular Magnet (SMM) Family of a Mn4 Cluster 124-TH Magnetic spectra of ferrite/polyaniline composites 125-TH First Examples of Spin-Crossover Complexes Involving tcm- And tcnpOet- Polynitrile anions: Syntheses,Variable PRESENTER Elby Titus Fumiyasu Iwahori Ichiro Takemura J. F. Ren Katel Herv Kenichi Koizumi Lygia Walmsley Magela e Silva Martin Baumgarten Mitsuhiro Ito Natalia Kazantseva Carlos J. Gmez Garca
85
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126-TH
Rotor Structures of Allylammonium - ([18]crown-6) based Supramolecular Cations
Daisuke Sato
BIO/ MEDICAL MATERIALS & BIONANOTECHNOLOGY P 4

POSTER # & TITLE ABSTRACT # ON CD ROM 127-TH Smart Interpenetrated Networks of Hydrogels and Conducting Polymers 128-TH Fabrication and investigation of electromechanical behaviour of polymeric nanoactuator 129-TH Melanin: a Hybrid Protonic-Electronic Conductor 130-TH Direct DNA hybridization at disposable graphite electrodes modied with carbon nanotubes 131-TH Conjugated polyelectrolytes tools for biomolecular electronics and cell staining 132-TH Luminescent conjugated polyelectrolytes for biochip applications to decorate enzymes and as hydrogels in microchannels 133-TH Hydrogels Based on Chitosan as Bio-Actuators Responding to an External Stimulus 134-TH Synthesis and Characterization of PVA/PDADMAC EAP Hydrogels 135-TH Electropolymerization of a Conducting Polymer in a Biocompatible Hydrogel Matrix 136-TH Articial Molecular Rotors in Magnetic and Conducting Crystals 137-TH Immobilization of Antigen-containing liposomes in layer-by-layer lms: Molecular Recognition and Sensing Applications 138-TH Synthesis and characterization of a water-soluble zwitterionic poly(pphenyleneethynylene 139-TH Adsorption of Adenine on Graphite: Inuence of van der Waals Interaction 140-TH Oriented Polymeric Nanochannels on a Si Surface 141-TH Magnetic nanoparticle assemblies on DNA 142-TH Patterning hydrogels and proteins: smart emitting bio-circuits by microuidics 143-TH Novel biomaterials by conjugation of oligothiophenes and peptides 144-TH Enhancement of two-photon absorption cross section and singlet oxygen generation 145-TH Using the redox chemistry of polypyrrole to bind and release dopamine and epinephrine: applications in drug delivery 146-TH Understanding DNA Dispersed Single-Walled Carbon Nanotube Systems PRESENTER Mara A. Molina Min Sup Kim P. Meredith P. Papakonstantinou Per Bjrk Peter sberg Sang Jun Park Seon Jeong Kim Su Ryon Shin Takayoshi Nakamura Valtencir Zucolotto Wei Huang Karsten Hannewald Min Kyoon Shin Serena A. Corr Elisa Mele Eva-Kathrin Schillinger Fabio Silvestri Gillian M. Hendy Helen Cathcart
POSTER PROGRAMME
MOLECULAR & POLYMERIC MATERIALS FOR PHOTONICS & DISPLAYS P 4

147-TH Synthesis and Optoelectronic Properties of Conjugated Silole-Containing Polymers Junwu Chen
86
148-TH 149-TH 150-TH 151-TH 152-TH 153-TH 154-TH 155-TH 156-TH 157-TH 158-TH 159-TH 160-TH 161-TH 162-TH 163-TH 164-TH 165-TH 166-TH 167-TH 168-TH 169-TH 170-TH 171-TH 172-TH 173-TH 174-TH 175-TH
Tris(terphenylylpyridine)iridium complexes and tris(tritylphenylpyridin e)iridium complexes Electrochemical and spectroelectrochemical properties of electroluminescent polymers based on 1,4-dialkoxy-2,5-bis[2-(tien-2yl)ethenyl]benzene) Energy Transfer in Covalently Attached Host-Guest Systems Tandem Organic Light Amplier/Converter and Peculiarities Organic Semiconducting Antioxidant Based on Hindered Amine for Stable Blue Light-emitting Materials Monolithic polymer VCSELs tunable over the whole visible spectrum Multi wavelength emitters through hot embossing. Self-absorption effects as a tool to probe the vibronic relaxation processes Large Area Subicron-Sized OLEDs Array by Nanosphere Lithography Demonstration of Near Infrared Lasing in Dye-doped Polymeric Microrings Theoretical Study on the Third-Order Nonlinear Optical Chloranil doped phthalocyanine lms: structure and photoelectric properties A Systematic Study of the Effects of Naphthalene and Anthracence Substitution on the Properties of PPV Derivative Optical gain and lasing in micro- and nano-structured luminescent polymers Increasing the luminescence of colloidal semiconductor nanocrystals at nanoscale NEW electron-transporting naphtHalene diimide containing Synthesis of soluble -Conjugated poly p-phenylenes for OLEDs Application Organic red light emitting devices with europium complex in various NEW IRIDIUM COMPLEXES FOR PHOSPHORESCENT LIGHT EMITTING DEVICES Optical Effects in Materials Conned in Nanopores Optical gain and charge injection effects in single layer PFO waveguides with top and Hybrid mesostructered TiO2/conjugated polymer thin lms for photovoltaic applications Synthesis and Properties of Polyacetylenes Bearing Carbazole Moieties in The Sid A study of a- and b-phase poly(9,9-dioctyluorene) by electroabsorption spectroscopy Photoinduced Charge Transfer in Polymer/Fullerene System Polymer-nanocrystal composites active at Near-IR wavelengths Crosslinkable Molecular Glasses for Optoelectronics Theoretical Studies on the Structures and Absorption Spectra of Ph and t-Bu substituted 5-(2-pyridyl) Pyrazolate Boron
Tetsuo Otsubo Krzysztof Waskiewicz Lekshmi Sudha Devi Leonid Lepnev Ling-Hai Xie Luana Persano Luca Troisi Luiz Alberto Cury Manca Michele Martin Djiango Masayoshi Nakano Pakhomov G.L Patrick Lynch Paula Russell-Hill Pier Paolo Pompa R. Lygaitis Raman Saini Rmi Antony Roberta Ragni Ronan Hodson Sandro Lattante Shany Neyshtadt Toshio Masuda Toshiyuki Endo Victor I. Krinichnyi Vladislav Medvedev Vytautas Getautis Wei Zheng
87
POSTER PROGRAMME
176-TH 177-TH 178-TH 179-TH 180-TH 181-TH 182-TH 183-TH 184-TH 185-TH
Thickness dependence of 4,4,4-tris(N-carbazolyl)-triphenylamine (TCTA) layer Theoretical study on the electronic structure and optical properties of a uorine derivative First generation multifunctional platinum porphyrin dendrimers-based triplet emitters for OLED applications Synthesis, Characterization and Fluorescence Quenching of A Novel Fluorene-Based Anionic Water-Soluble Conjugated DFT study on the structure and second-order NLO properties of n Electrical Properties of Bottom-Contact Organic Thin-Film-Transistors Inserting a Polymeric Adhesion Layer Optimising the Performance of Nano Structured Polymer Lasers Fabrication of Asymmetric Microdisk Based on -Conjugated Polymer Synthesis of novel poly(arylenevinylene) polymers with uorinated double bonds Performances of a phototransistor based on organic materials
Xia Yijie XiuMei Pan Yanqin Li Yi Chen Yongqing Qiu Young Kwan Kim A. E.Vasdekis Akihiko Fujii Antonio Cardone Bruno Lucas

POSTER # & TITLE ABSTRACT # ON CD ROM 186-TH Syntheses and mixed conductivity of coordination polymers composed of 187-TH Control of rapid excimer formation in supramolecularly insulated semiconducting wires 188-TH Electrical Conductivity Measurements of Several Types of DNA Molecules on Pt Fine 189-TH Pentaphenylene All-in-One Materials 190-TH Degradation of the current-voltage characteristics and carrier mobility of a-NPD 191-TH A mechanism of photogenerated charged polaron in polymers 192-TH Discrete Reactive Conjugated Oligomers for Electronic Devices 193-TH Theoretical study on the second-order nonlinear optical properties 194-TH How to tailor excitonic effects in organic semiconductors? 195-TH Confocal Microscope Study of Single Strand of Light Emitting Polymer Nanotube 197-TH Formation and structure of higher fullerene-cubane crystals 198-TH Luminescence efciency enhancement through Frster migration suppression in conjugated polymers 199-TH Bipolaron mechanism for hysteresis in organic eld-effect devices 200-TH Polaron to Bipolaron Transition Dynamics in Conjugated Polymers PRESENTER Akihito Shigematsu Annamaria Petrozza Aoi Inomata C.E. Finlayson Changhee Lee Chang-Qin Wu Christian B. Nielsen Chunsheng Qin ClaudiaAmbrosch-Draxl D. H. Park va Kovts Francisco C. B. Maia G. Paasch Geraldo Magela e Silva
POSTER PROGRAMME
88
S1 PLASTIC ELECTRONICS AND OPTO-ELECTRONICS: WHATS NEW?? ALAN HEEGER Abstract: The past two years have demon strated that the eld of Semiconductoing and Metallic Polymers continues to be virbrant with exciting and important progress. I will summarize some of the highlights.
S2 THE AZANES: A CLASS OF MATERIAL INCORPORATING NANO/MICRO SELF-ASSEMBLED HOLLOW SPHERES OBTAINED BY AQUEOUS OXIDATIVE POLYMERIZATION OF ANILINE Alan G. MacDiarmida,b, Everaldo C. Venanciob and Pen-Cheng Wangb a Departments of Chemistry and Physics, University of Texas at Dallas, Richardson, TX, USA b Department of Chemistry, University of Pennsylvania, Philadelphia, PA, 19104, USA The nature of the product of the conventional aqueous oxidative polymerization of aniline by ammonium peroxydisulfate and HCl is extremely sensitive to the pH of the polymerization system. This is observed when the concentrations of reagents are sufciently dilute (at a pH of 3-4) to isolate the rst-formed product of the reaction which we believe is a member of the class of azanes, polymeric or oligomeric species containing a NN backbone in which each N atom is forming three covalent single bonds. The brown solid isolated has been characterized by its elemental analysis, UV-VIS, FTIR and 1H-NMR spectra. We believe, in the simplest case, it may be an organic-substituted hexa-azane. It is completely different in every way from any known form of polyaniline, in any oxidation state, of any degree of protonation. It is isolated as hollow microspheres (diameter, ~1.5 to 6 m) which have an essentially identical SEM appearance to hollow microspheres previously ascribed to conventional polyaniline. As the pH of the reactant system falls during the polymerization, polyaniline in its conventional forms begins to be formed; however, especially if the pH is held constant by a buffer solution, the pure azane can be isolated. We believe the azanes open up a new eld of self-assembled nano/micro particles of very considerable potential applicability to the emerging eld of nanoscience. Acknowledgements: Financially supported by University of Texas at Dallas; U.S. Dept. of Energy.
ABSTRACTS
M1 TTF DERIVATIVES FOR ELECTRONIC DEVICEs Concepci Rovira,a Marta Mas-Torrent,a Peter Hadley,b Elena Laukhina,a, N. Crivillers,a David Amabilino, a Elba Gomar,a Vladimir Laukhin,a,c Stuart Lindsdayd Stefan Bromley,e and Jaume Vecianaa,
a
Institut de Cincia de Materials de Barcelona (ICMAB-CSIC), Campus Universitari de Bellaterra, 08193 Cerdanyola, Spain. IKavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft, The Netherlands.. c Instituci Catalana de Recerca i Estudis Avanats (ICREA), Barcelona, Spain. d Department of Physics and Astronomy, Arizona State University, Tempe, AZ 85287, USA. e Faculty of Chemistry, University of Barcelona, Spain
b
Organic materials as synthetic metals and Field-effect transistors (OFETs) have attracted a great deal of interest in the last years due to their unique processing characteristics and performance levels achieved. However, in order to have devices suitable for low-cost integrated circuit technology, it is not only necessary to have materials with high carrier mobility but they also need to be solution-processed. Herein, we show our results in the preparations of single-crystal OFETs based on tetrathiafulvalene (TTF) derivatives prepared from solutions.[1] These crystals exhibit the highest mobility found for solution-processed materials, 2.5 cm2/Vs as well as a very good ON/OFF ratio (ON/OFF > 7105)and are also among the highest reported for OFETs. The crystals show good stability over weeks, even under measurement conditions including temperature changes and applied voltages. The off-current is stable and the mobility decreases only slightly. By changing the characteristics of the organic building blocks we are able to tune the OFETs mobility and a correlation between the crystal packing and the mobility can be stablished. Theoretical studies let us to demonstrate that the molecular packing is a key factor in assessing reorganizations energies and, thus, hopping mobility, an important characteristic in FETs.
S S S S S D T -T T F S S
Au elec trodes T T F c rys tal
(a)
S D B -T T F S S
(b)
(c)
Si S iO 2
Figure 1. (a) Molecular structure of tetrathiafulvalene (TTF) and dithiophene-tetrathiafulvalene (DT-TTF). (b) Device conguration used. (c) Optical microscope image of a DT-TTF single crystal lying on the gold electrodes. The results on the electrical properties of self-assembled monolayers of similar compounds on Au(111) will also be presented.[2] References 1. Mas-Torrent, M.; Durkut, M.; Hadley, P.; Ribas, X.; Rovira, C. J. Am. Chem. Soc, 2004, 126, 984; ibid. 6544; ibid. 8546; Mas-Torrent, M.; Hadley, P.; Ribas, X.; Rovira, C.; Synth. Metals, 2004, 146, 265; Appl. Phys.Lett. 86 , 2005 2. Gomar-Nadal, E.; Ramachandran, G. K.; Chen, F.; Burgin, T.; Rovira, C.; Amabilino, D. B.; Lindsay, S. M. J. Phys. Chem.B, 2004, 108, 7213.
M2 NEW CHARGE TRANSFER SALTS OF BEDT-TTF AND PERYLENE WITH PARAMAGNETIC RE(IV) COMPLEXES Carlos Gimnez-Saiz, Carola Rsser, Simona Curreli, Eugenia Martnez, Carlos J. Gmez-Garca, Jos R. Galn-Mascars, E. Coronado Instituto de Ciencia Molecular. Edicio de Institutos de Paterna. Apartado de correos(P.O. Box) 22085. 46071 Valencia, Spain. The design and synthesis of new molecular materials with unusual combination of physical properties as, for example, compounds coupling magnetic and conducting sublattices has become one of the most appealing challenges in the chemistry of materials.1 This class of multifunctional materials should provide a unique opportunity to study the physics arising from the competition and interplay of these properties. In this communication we will present the structural and physical characterization of four new radical salts containing paramagnetic complexes of Re(IV): (BEDT-TTF )8[ReCl4(C2O4)]22PhCN (1), (BEDT-TTF)[ReCl4(C2O4)] (2), per2[ReCl6]2H2O (3) and per3[ReCl6]2H2O (4). Compounds (2), (3) and (4) are all semiconducting paramagnets, while (1) shows a metallic behaviour with a metal to semiconducting transition at ca. 120 K.
S S
ET
Cl Cl
S S
S S
2
O O O
S S
per
Cl Cl Re Cl Cl Cl Cl
2
ABSTRACTS
Re Cl Cl O
[1] E. Coronado, P. Day, Chem. Rev. 2004, 104, 5419.
M3 CRYSTAL GROWTH AND CONDUCTION PROPERTY MEASUREMENT OF MICRO/NANO-SIZE MOLECULAR CONDUCTORS ON SIO2/SI SUBSTRATES Hiroshi M. Yamamoto, a,b Hiromi Ito, a,b Mutsumi Ikeda, a Toshiaki Suzuki, a Kazuhito Tsukagoshi, a and Reizo Kato a,b RIKEN, Wako-shi, Saitama 351-0198, Japan JST-CREST, Wako-shi, Saitama 351-0198, Japan E-mail; yhiroshi@riken.jp
a
We have recently developed two methods to grow moicro/nano-size crystalline molecular conductors from electrodes deposited on SiO2/Si substrates. The one is to grow the crystals by electrochemical reaction, and the other is to grow the crystals by chemical reaction between the Ag (or Cu) electrode and acceptor molecules. We have measured the conduction behaviors of these tiny crystalline molecular conductors, and compared them with those for bulk crystals. Here we report the conduction properties of micro/nano-size -(BEDT-TTF)2I3, (DMe-DCNQI)2Ag, (DMeDCNQI-d7)2Cu, (EDT-TTF)4BrI2(TIE)5, and so on. For example, micro-size -(BEDT-TTF)2I3, which shows a metal-insulator (M-I) transition at 135 K in bulk phase, on SiO2/Si substrate exhibited an M-I transition at 150 K. The difference in the transition temperature can be attributed to the crystal size and/or negative pressure effect based on the small thermal expansion coefcient of the substrate. This crystal also worked as an n-type eld effect transistor at 90 K. Another example is on the M-I transition of (DMe-DCNQI-d7)2Cu. This salt is known to show a sharp M-I transition at 80 K, but the sample of 100 nm thickness exhibited no transition or anomaly and kept metallic behavior down to 4 K. Rectifying behavior of (DMe-DCNQI)2Ag was achieved by exposing half side of the crystal to UV/vis light. Moreover, when it was embedded between Au and Ag electrodes, it showed bistable resistance behavior at room temperature in air as shown in the right gure below. This behavior is suitable for application use in electric circuits as resistive random access memory (RRAM).
Left gure: SEM image of the needle crystal of (DMe-DCNQI)2Ag embedded between two Ag/Au electrodes. Right gure: I-V characteristics of (DMe-DCNQI)2Ag attached to Ag/Au and Au electrodes at room temperature. The current is drawn in absolute value. The characters from a to d indicates the scan sequence of which rate is 0.4 V/sec.
M4 METASTABLE PHASES AND QUANTUM TRANSITIONS IN AN ORGANIC CT SALT. Anna Painelli1 and Zoltan Soos2
1) Dipartimento Chimica GIAF, Universita di Parma, 43100 Parma, Italy Department of Chemistry, Princeton University, Princeton NJ 08544 (USA)
2)
The neutral-ionic and dimerization (Peierls) transitions occur simultaneously at 81 K and 1 atm in the prototypical charge-transfer (CT) salt TTF-CA (tetrathiafulvalene-chloranil), whose spectra indicate -electron coupling to both molecular (e-mv) and lattice (e-ph) vibrations. The metallic point of the rigid lattice of rigid molecules separates a diamagnetic band insulator from a paramagnetic Mott insulator. Near the metallic point, competing instabilities driven by linear e-ph or e-mv coupling open a Peierls or charge-density-wave (CDW) gap in the band insulator and unconditionally lead to a dimerized ground state (GS) in the Mott insulator. We treat the instabilities of the band insulator exactly within a one-dimensional band of noninteracting fermions with alternating site energies . The GS is both charge ordered and dimerized only over a narrow range of parameters. The CDW regime is bistable over a narrow range of about = 0, with degenerate minima at = 0. CDWs of opposite sign resemble topological solitons between regions with opposite dimerization, as discussed in the Su-Schrieffer-Heeger model. In the bistable region with small 0, the energy E(N) for creating a bubble of N molecules in the metastable minumum increases linearly as N, where is the CDW amplitude. Metastable bubbles of N > 10 are thermally accessible at 300 K for small ~ 0.2 and typical band widths 4t < 1 eV. Since electron correlation is a prerequisite for Mott insulators, we use a Hubbard model for the ionic GS of TTF-CA with site energies and at most one electron per CA or one hole per TTF. The narrow bistable CDW regime of is about c = 0.666t and corresponds to a dimerized GS on the ionic side and an undimerized GS on the neutral side. Exact numerical solution for oligomers yields the energy of domain walls, similar to noninteracting case, and the N dependence for bubbles in the metastable minimum. Typical parameters for TTF-CA show that bubbles of N > 10 are thermally accessible at 300 K. A narrow bistable regime and thermally accessible metastable bubbles provide an attractive interpretation for the observation of two different ionicities with ~ 0.2 in infrared spectra of TTF-CA at 300 K over a pressure range of 0.9-1.2 GPa.
ABSTRACTS
M5 STRIPE PATTERN FORMATION PROBED BY LOCAL INFRARED SPECTROSCOPY IN CURRENT INJECTED K-TCNQ T. Sasaki1, N. Yoneyama1, N. Kobayashi1, Y. Ikemoto2 and H. Kimura2
1
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan 2 SPring-8, JASRI, Sayo, Hyogo 679-5198, Japan
Metal-Insulator transitions have attracted much attention recently in many kinds of strongly correlated electron systems. A charge transfer compound K-TCNQ is a typical Mott - Hubbard insulator with one-dimensional stacks of donor K+ and acceptor TCNQ. It has been revealed that the metallic or the low-resistance state can be achieved by applying an electric eld or current injection to the insulating state. In addition, a spatial periodic stripe pattern with m intervals has been observed in the current induced state.1 It has been considered that the stripes are composed of the alternated dimerized and less-dimerized domains of the TCNQ stacks. The purpose of this study is to clarify the origin of the macroscopic phase separation with a directional character in the current injected low resistance state of K-TCNQ. In the I-V characteristic measurements at room temperature, apparent negative resistance was observed in the current along the a-axis (TCNQ stacking direction). In the negative resistance region, visible stripe pattern appeared along the current direction (middle gure). The direction of the stripe pattern was different from the previous report1; the stripes came in perpendicular to the current (the a-axis) in Ref.[1] but parallel to the current in the present study. Scanning micro-region infrared reectance spectroscopy (SMIS) measurements using synchrotron radiation at BL43IR in SPring-8,2 was performed to know the space variation of the electronic states of the stripes. Although the present SMIS measurement could not obtain the specic electronic states of each stripes because of less optical resolution of 10 m than the stripe intervals of several m, a region where the stripe pattern appeared possessed the less-dimerized TCNQ stacks, which was proved by the reectance variation of the EMV coupled symmetric phonon mode at 2180 cm-1 of TCNQ. The difference of the stripe pattern may relate to the electrode conguration and the electronic eld distribution in the sample.
1 2
R. Kumai et al., Science 284, 1645 (1999). T. Sasaki et al., Phys. Rev. Lett. 92, 227001 (2004), J. Phys. Soc. Jpn. 74, 2351 (2005).
Figure (left): contour maps of the reectance in the region corresponding to the photograph of current injected K-TCNQ. Bright colour indicates high reectance of the EMV coupled TCNQ phonon mode (right gure), which corresponds to the insulating nature. (middle) Visible stripe pattern appears at 0.43mA (550V) but not at 0.37mA (500V). M6 STRONG MAGNETORESISTANCE ANOMALY DIRECTLY ASSOCIATED WITH SPIN FLOP IN THE -D SYSTEM, (EDT-DSDTFVSDS)2FEBR4 T. Fujimoto1, K. Yokogawa1, S. Yasuzuka1, H. Yoshino1, T. Hayashi2, T. Hiraoka2, H. Fujiwara2, 3, T. Sugimoto2, 3 and Keizo Murata 1 Dept. of Mat. Science, Grad. School of Science, Osaka City Univ.,Osaka 558-8585, Japan 2 Dept. of Chem., Grad. School of Science, Osaka Pref. Univ., Sakai 599-8570, Japan 3 CREST-JST, Saitama 332-0012, Japan Extremely large negative magnetoresistance (MR, 70 % reduction by 5 T, not shown here) is observed below 4.2 K in a new -d interaction system (EDT-DSDTFVSDS)2FeBr4, where EDT-DSDTFVSDS = ethylenedithiotetrathiafulvalenothioquinone-1,3-diselenolemethide, in which dspins are antiferromagnetically ordered at ~ 5 K. Moreover, a very deep dip (25 % reduction from background) in MR is also observed corresponding to spin op of d-spins in particular eld direction (see Figs. 1 and 2). This is the first servation of such a large reduction in MR associated with spin flop of neighboring d-spins, and is a strong evidence for the strong -d interaction. S S To compare with the result of FeBr4- salt, we also studied the nonmagnetic anion analogue (EDTS Se DSDTFVSDS)2GaBr4 based on the same bent TTF-type organic donor. Both salts featured by quasi-1D -electronic Se systems are metallic with metal-insulator transitions taking place at ~ 30 K. Energy gap estimated between 0.6 ~ 2 K S Se S of FeBr4- salt (~ 120 eV) is slightly larger than that of GaBr4- salt (~ 40 eV). This may be caused by -d interaction Se in FeBr4- salt.
0
1.5 T 2T 3T
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(EDT-DSDTFVSDS)2FeBr4 #0604
2 B (T) 3 4 5
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50 100
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0 (deg)
ABSTRACTS
Fig. 1. Magnetoresistance in (EDTDSDTFVSDS)2FeBr4, showing strong dip corresponding to spin op of d-spins. Denition of angle is the same as Fig. 2.
Fig. 2. Angular dependence of MR in (EDT-DSDTFVSDS)2FeBr4. Easy axis for antiferromagnetism is = 0. Magnetic eld is rotated in the conguration that eld is kept perpendicular to current for MR study.
M7 X-RAY DIFFRACTION FOR -(BEDT-TTF)2CSZN(SCN)4 IN ELECTRIC FIELDS - CURRENT DEPENDENCE ON THE STRUCTURE-PROPERTY RELATION Masashi Watanabe1, Takayoshi Ito2, Kenichiro Yamamoto2, Naoshi Ikeda2,3, Yoshio Nogami2,4, Hidenori Toyokawa3, Hiroyuki Ohsumi3, Yusaku Nakashima2, Shintaro Horita2, Yukio Noda1, Ichiro Terasaki5, Fumiaki Sawano5, Hatsumi Mori4,6 and Takehiko Mori7 1 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University 2 Department of Physics, Okayama University 3 Japan Synchrotron Radiation Research Institute 4CREST-JST 5 Department of Applied Physics, Waseda University 6 Institute for Solid State Physics, University of Tokyo 7 Department of Organic and Polymeric Materials, Tokyo Institute of Technology When two (or more) kinds of strongly competing nano-scale domains coexist in a material without an impurity or a defect, such an intrinsically inhomogeneous short-range-ordered structure can exhibit a giant nonlinear response by coupling with the corresponding external eld. Several years ago, we found one candidate for intrinsically inhomogeneous state in the organic charge transfer salt -(BEDT-TTF)2CsCo(SCN)4. 1 Below 120 K, two kinds of two-dimensional structure modulation of q1=(2/3 k 1/3) and q2=(0 k 1/2) were observed with a small structure correlation length of 10 nm. Among them, only the q2 modulation condenses into a three-dimensional short-range-ordered modulation of (0 0 1/2) below 50 K, 1 below which the system becomes an insulating state.2 Furthermore, no indication for thermodynamic phase transitions was observed down to liquid helium temperature, which also suggests the inhomogeneous state. Recently, a giant nonlinear conduction and DC-to-AC converting effect were observed around liquid helium temperature.3 Its isomorphic salt -(BEDT-TTF)2RbZn(SCN)4 undergoes a metal-insulator transition at 190 K, below which the charge ordered state with the same q2=(0 0 1/2) as shown in Fig.1 forms a long-range order. 4 Judging from the same wavevector, we think that the q2 modulation in the title compound corresponds to the charge disproportionated state with the same pattern. To understand the relationship between the structure modulations and the giant nonlinear conduction, we investigated the direct-current dependence on these short-range-ordered modulations. We used the 4-circled diffractometer at BL02B1 and synchrotron radiation of 15 keV from SPring-8. Figure 2 shows the electric current dependence of the diffuse scattering intensities at q2 at 12 K. The q2 intensity decreases with increasing current, while the q1 intensity shows no signicant change.3 To evaluate heating effects on the q2 intensity, we took X-ray photo under the current 0-10.5 mA. At 10.5 mA and 17 K the q2 intensity is nearly zero, which should not be ascribed to a simple joule heating effect by the following reason. The resistivity at 17 K and 10.5mA is about half of that at 85K and 0.4mA, whereas the q2 intensity at 17 K and 10.5 mA is similar to that at 85 K and 0.4 mA as shown in Fig. 3. 1 M. Watanabe, Y. Nogami, K. Oshima, H. Mori and S. Tanaka:
Fig. 1. Charge ordering pattern. Open and close ellipsoids represent hole-rich and holepoor molecules, respectively.
2
Fig. 2. Peak prole under the current of q2 at 12 K.
Fig. 3. q2 intensity with various currents at 17 K plotted as a function of the resistance. For comparison, q2 intensity without current at various temperatures is also plotted.
J. Phys. Soc. Japan, 68 (1999) 2654. H. Mori, S. Tanaka and T. Mori: Phys. Rev. B, 57 (1998) 12032. 3 F. Sawano, I. Terasaki, H. Mori, T. Mori, M. Watanabe, N. Ikeda, Y. Nogami and Y. Noda: Nature 437 (7058) (2005) 522-524. 4 M. Watanabe, Y. Noda, Y. Nogami and H. Mori: J. Phys. Soc. Jpn. 73(2004)116-122.
M8 STRUCTURAL AND ELECTROMAGNETIC PROPERTIES OF THE INCOMMENSURATE ORGANIC SUPERCONDUCTOR (MDTTS)(AUI2)0.441 Tadashi Kawamoto,1 Hisataka Endo,1 Yoshimasa Bando,1 Takehiko Mori,1 Toru Kakiuchi,2 Yusuke Wakabayashi,3 Hiroshi Sawa,2,3 Takako Konoike,4 Taichi Terashima,4 Shinya Uji,4 Kazuo Takimiya,5 and Tetsuo Otsubo5
1
Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-oakayama 2-12-1, Meguro-ku, Tokyo 152-8552, Japan 2 Department of Materials Structure Science, The Graduate University for Advanced Studies, Tsukuba, Ibaraki 305-0801, Japan 3 Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801, Japan 4 National Institute for Materials Science, Tsukuba, Ibaraki 305-0003, Japan 5 Department of Applied Chemistry, Hiroshima University, Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan
ABSTRACTS
The MDT-TSF (methylenedithio-tetraselenafulvalene) series salts are two dimensional incommensurate ambient pressure organic superconductors and the charge transfer degrees deviate from 0.5.1,2 (MDT-TS)(AuI2)0.441, where MDT-TS is 5H-2-(1,3-diselenol-2-ylidene)1,3,4,6-tetrathiapentalene, shows a metal-insulator transition at TMI = 50 K and the superconducting phase appears at Tc = 3.2 K above 10.5 kbar in spite of the basically same crystal structure as those of the MDT-TSF superconductors.3,4 Structural and electromagnetic properties of this organic superconductor have been investigated. The synchrotron radiation x-ray oscillation photographs show satellite spots with the wave vector q = 0.114(3)a* at room temperature, where a* is the reciprocal lattice vector of the donor cell (Fig. 1). The satellite spots at 1-q overlap with the anion h = 2 spots. The modulation
structure is commensurate to the anion lattice, but is incommensurate to the donor lattice. The energy spectra of the satellite reections do not include the scattering factor of Au atoms but include that of Se atoms; this indicates that the modulation is originated in the donor lattice. The lattice parameters smoothly decrease with decreasing temperature, and the wave vector q is independent of the temperature. The magnetic torque curves provide clear evidence that the ground state at ambient pressure is an antiferromagnetic insulating state with the high Nel temperature TN = 50 K and the high spin op eld 0Hsf = 6.9 T (Fig. 2). Our results indicate that the antiferromagnetic insulating state is not a simple charge ordered state. [1] K. Takimiya et al., Angew. Chem. Int. Ed. 40, 1122 (2001). [2] T. Kawamoto et al., Phys. Rev. B 65, 140508(R) (2002). [3] K. Takimiya et al., Chem. Mater. 16, 5120 (2004). [4] T. Kawamoto et al., Phys. Rev. B 71, 052501 (2005). Fig. 1 Peak proles. Fig. 2 Magnetic torque at 1.7 K.
M9 SUPER-GROWTH CARBON NANOTUBES -THE HIGHLY EFFICIENT SYNTHESIS: FROM FORESTS TO SOLIDSDon N. Futaba Research Center for Advanced Carbon Materials, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, 305-8565, Japan Water-assisted chemical vapor deposition (CVD), nicknamed Super-Growth [1], produces a massive growth of vertically aligned single-walled carbon nanotubes (SWNT), as tall as 2.5 millimeters and carbon purity over 99.9%. This dramatic enhancement in the synthesis of carbon nanotubes (CNT) by the addition of water into the growth ambient of a CVD system simultaneously addresses many critical obstacles, such as scalability, purity, and cost, and opens up innumerable opportunities ranging from fundamental research to real applications. This presentation will provide an overview of our recent progress in the synthesis and application of Super Growth SWNTs. First, I will provide a brief introduction to the Super-Growth concept. Second, I will present the results of our characterization studies of the growth dynamics, physical structure, surface area, etc., which highlights some of the strengths of the Super-growth forests. Third, I will present a new form of densely packed and aligned CNT material called the SWNT solid, with emphasis on its applications, such as energy and material storage. Lastly, challenges and future projects that are planned will be summarized. Figure 1: Photographs of a super-growth forest grown
(left) in a 10 minute growth time standing 2.5 mm in height and high density SWNT solid (right) with a density of 0.6 g/cm3.
M10 BROMINATION OF EXPANDED GRAPHITE IMPROVES THE ELECTRICAL CONDUCTIVITY OF GRAPHITE-POLYMER NANOCOMPOSITES Jing LI1, Linda VAISMAN2, Gad MAROM2 and Jang-Kyo KIM1 Hong Kong University of Science and Technology, Hong Kong; 2 Hebrew University of Jerusalem, Israel
ABSTRACTS
Graphite nanoplatelet (GNP) is a nanoscale conductive ller produced by exfoliating natural ake graphite, and has attracted signicant attention as the low cost alternative to metal- and carbon-based electrically conducting reinforcements for conducting polymer composites. Conducting polymer composites have many potential applications in electromagnetic interference shielding for electronic devices and electrostatic dissipation. In this study, the expanded graphite is brominated to improve its electrical conductivity while providing covalent functionality with the polymer matrix. The GNP was exposed to bromine vapor at room temperature for different durations. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and time-of-ight secondary ion mass spectrometry (ToF-SIMS) were employed to evaluate the intercalation of bromine atoms and quantitatively analyze the bonding types between the C and Br atoms. Nanocomposites were prepared from the brominated GNPs with epoxy resin based on the shear mixing and ultrasonication techniques. The electrical and mechanical properties of the nanocomposites were measured and compared with those without treatment. The intercalation of Br between graphene layers of GNP was conrmed by the XRD result, showing an increase in the interlayer spacing from 3.342 to 3.361 after the treatment. The level of intercalated bromine rose initially with the exposure duration, reaching saturation after about 10h exposure. The portion of ionic bonding reached the maximum after 3h exposure with the associated highest electrical conductivity of GNP, which coincided with the lowest covalent Br. Bromination increased the electrical conductivity of nanocomposites especially when the ller content was higher than the percolation threshold. Both the exural modulus and strength of nanocomposites showed upward trends after bromination due to the improved interfacial adhesion between the covalently functionalized GNPs and epoxy resin. The intensity of covalent Br (obtained from SIMS) was proportional to the concentration of covalently bonded bromine (obtained from XPS), which increased with bromination duration. The mechanism behind the ameliorating effect of bromination is that the intercalated Br atoms between the graphene planes act as an ionic acceptor, releasing holes into graphene layers and thus effectively increasing the electrical conductivity. However, if there are covalent bonds, the carrier mobility is degraded and the carrier concentration is depressed. This results in displacements of some of the carbon atoms from the highly planar structure of pristine graphite, decreasing the conductivity. These two mechanisms counterbalance each other, determining the nal conductivity value. By optimizing the exposure duration and thus the intensities of ionic and covalent Br, nanocomposites possessing balanced electrical and mechanical properties can be produced.
M11 CHARACTERISING FUNCTIONALISED CARBON NANOTUBES Peter Fearon, Raymond Whitby, Harry Kroto School of Life Sciences Arundel Building University of Sussex Brighton BN1 9QJ Much interest is currently focussed on utilising the mechanical and electronic properties of CNTs in a wide range of materials either as blends or via direct grafting of polymers onto CNT surfaces. Extensive functionalisation of the CNT is required prior to the later approach. Quantitative analysis of such chemistry is quite difcult due to the material type and the low concentrations of functional groups involved. FTIR and Raman are commonly used techniques. In this study standard TGA techniques have been coupled to FTIR spectroscopy and the emitted volatiles measured as an unambiguous record of the preceding chemistry. Figure one shows the preliminary data obtained when CNT functionalised with amide groups was subjected to TGA coupled to FTIR. The TGA prole (blue) shows the a stepped weight loss corresponding to 13% of the total Mass. The purple line is the 1st derivitive of this curve and denotes the points of maximum weight loss
5 5 10 10 15 15 20 20 25 25 30 30 35 35 40 40 45 45 50 50 55 55 60 60 65 65 70 70 75 75 80 80 85 min 85 min 26. 16 m g 0. 055 G ra m S c h m id t C N T 1 .8 D ia m i n o O c t a n e 0. 050 D T G A C N T 1 . 8 D ia m i no O c ta n e 0. 045 T G A C N T 1 .8 D i a m i n o O c t a n e
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50 0 5 100 10 150 15 200 20 250 25 300 30 350 35 400 40 450 45 500 50 550 55 600 60 650 65 700 70 750 75 800 80 850 C 85 mi n
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The Grams Schmidt prole (red) measures the total amount of evolved gases that reach the IR detector. This gas peaks at the points of max rate of weight loss and is thus a measure of the effectiveness of the collector. The study was applied to a range of functionalised CNTs and the excellent FTIR results compared to more standard techniques. In a parallel study novel mass spectrometry methods were applied to these materials. The results point to an interesting, unequivocal technique for characterisation of these.
M12 CHIRALITY SPECIFIC MEASUREMENTS OF NANOTUBE MAGNETISM Omar N. Torrens, Daniel E. Milkie, Han Y. Ban, James M. Kikkawa Department of Physics and Astronomy University of Pennsylvania Philadelphia, PA 19104 We use optical anisotropy to study the magnetism of SWNTs in suspension. Alignment of nanotubes in a magnetic eld is used to infer their intrinsic and extrinsic magnetic properties. First, a purely absorptive strategy uses a combination of Raman scattering and polarized absorbance to perform high-resolution studies of SWNT alignment in suspensions. The latter imply a magnetic anisotropy that reveals both linear orbital and ferromagnetic responses for HiPCO and laser-oven tubes even after standard purication routes. In contrast, we nd that DNA-wrapped SWNTs available from DuPont show essentially no FM impurity moment. Since the latter samples can be selectively enriched with single SWNT species, we are able to compare diamagnetic responses for different wrapping vectors (m,n) and to compare these with theoretical predictions. The latter studies rely on anisotropic absorbance AND photoluminescence to improve selectivity to specic tube species. HiPCO and laser oven work done in collaboration with Mohammad Islam and Arjun Yodh at the University of Pennsylvania Department of Physics. DNA-wrapped tube work done in collaboration with Ming Zheng, G. Bibiana Onoa and Timothy Gierke at Du Pont Central Research and Development. We thank the ONR/DARPA and NSF for grant support.
M13 FIELD EMISSION FROM CARBON NANOTUBES: FROM ISOLATED NANOTUBES TO POLYMER MATRIX CATHODES
Advanced Technology Institute, University of Surrey, Guildford GU2 7XH, United Kingdom Robert Murphy, Werner Blau and Jonathan Coleman School of Physics, Trinity College, Dublin 2, Ireland
ABSTRACTS
David Carey, Richard Smith and Ravi Silva
The high aspect ratio and current carrying ability of carbon nanotubes (CNTs) make them an attractive material for electron sources. Field screening effects are known to occur at high nanotube densities and most large area eld emission characteristics (FECs) reect ensemble averages of the sites with the lowest effective potential barriers. We have studied the FECs and the eld emission enhancement factor from isolated nanotubes mounted on high resolution manipulators within a scanning electron microscope. We have further developed an in-situ three terminal characterisation facility allowing estimates of the gate screening factor and gate transparency to be made. From isolated and individual nanotubes to a large area network of nanotubes, measurements of the FEC of carbon nanotube polymer spin cast composites cathodes have also been made. A range of composites with arc discharge nanotube mass fractions up to 7 % were prepared with electron emission at low applied electric elds observed. Emission characteristics, transport and emission mechanism of the electrons is discussed in terms of a polymer coating that surrounds the nanotube and acts as a tunnel barrier. This gives rise to uctuation induced tunnelling between the nanotubes which affects the eld emission. The effects of the disordered percolation control network on the eld emission along with prospects for applications are discussed. Comparison with emission from other carbon based materials system is also discussed.
M14 CARBON NANOTUBES: OPTICS AND DYNAMICS IN LOW DIMENSIONAL SYSTEMS Tobias Hertel Department of Physics and Astronomy, Vanderbilt University, Nashville, TN Semiconducting carbon nanotubes (s-CNTs) hold promise for application in a variety of optoelectronic devices and the last 5 years have witnessed breathtaking progress in our understanding of the underlying electronic and optical properties. Much of this progress has been initiated by recent advances with sample synthesis and processing. We have made use of such advances and combined them with a variety of spectroscopic techniques from photoluminescence excitation-, THz-, pump-probe- and time-resolved photoelectron-spectroscopy to time-correlated single photon counting, to explore the energetics and dynamics of carrier interactions in semiconducting and metallic CNTs. These studies shed new light onto the peculiar nature of the interaction between charge-carriers in low-dimensional systems. I will review recent progress in this exciting eld of research, which takes us on a journey through dimensionality, from the transition of the electronic structure from delocalized to one-dimensional in nanotube agglomerates and individual tubes respectively, over the unusual energetics of excited states, the ultrafast kinetics of intra- and interband scattering processes, the nature of e-ph and e-e interactions and nally to pathways for non-radiative decay. Apart from their benet for our understanding of nanotube optical properties at the fundamental level, these investigations also help to identify the challenges and unique opportunities that may be found in optical applications of these unique one-dimensional materials.
M15 PHOTOINDUCED ELECTRON TRANSFER IN DONOR-ACCEPTOR FULLERENE BASED COMPOUNDS IN SOLID STATE R.N. Lyubovskayaa*, D.V. Konareva, P.A. Troshina, R. Koeppeb, and N. S. Sariciftcib Institute of Problems of Chemical Physics RAS, hernogolovka, MD, 142432, Russia, E-mail: lyurn@icp.ac.ru b Linz Institute for Organic Solar Cells (LIOS), Johannes-Kepler-Universitt Linz, Austria
a
1. A series of molecular crystals of fullerenes with various organic donors with neutral ground state has been obtained. Electron transfer in these compounds induced by photoexcitation has been studied by light induced electron spin resonance (LESR)- and reaction yield detected magnetic resonance (RYDMR)- spectroscopy and the possibility of charge separation has been established [1-2]. 2. Photoconductivity and the effect of magnetic eld (B0<1 T) on photoconductivity have been studied for the rst time in single crystals of layered donor-acceptor complexes of fullerene 60 with tetrabenzyl-p-phenylenediamine (TBPDA(C60)2), tetrabenzo(1,2-bis[4H-thiopyran-4-ylidine]ethene) (Bz4BTPE60) [3], and metal dithiocarbamates, (M= Cu, Co [M(dedtc)2]260) [4]. Spin mechanism of free charge carrier generation in magnetic eld was established. It is shown that mainly direct charge transfer from donor molecules to acceptor C60 ones and photoexcitation of chromophore donor component contribute to the generation of free charge carriers in fullerene complexes. 3. An efcient method for the synthesis of a range of novel pyrrollidinofullerenes bearing pyridyl groups (PyPyF) have been developed [5]. These compounds became available in bulk and, therefore, very promising for material science applications. PyPyF are capable of axial coordination with the central metal atom in various metal porphyrins (ZnPor) and phthalocyanines (ZnPc); such complexation provides a facile route to non-covalently linked donor-acceptor dyads. The complex formation between a set of different PyPyF and macrocyclic donors was studied in solution and in solid state by means of UV-VIS and NMR spectroscopy, uorescence measurements, X-ray single crystal diffraction and LESR spectroscopy. The efcient charge separation was observed in solid donor-acceptor dyads by LESR measurements that revealed separate signals from PyPyF radical anions and ZnPor+ or ZnPc+ radical cations in the spectra. The activation energies for electron transfer in the studied dyads were estimated to be in the range16-50 meV. 4. Some PyPyFs have been utilized as acceptor materials in organic solar cells comprising zinc phthalocyanine ZnPc as a donor component [6]. High solubility of PyPyFs in organic solvents allowed their wet-processing and deposition on the sublimed ZnPc layer by spin-coating. The PyPyF-ZnPc photovoltaic devices exhibited advanced performance over reference PCBM-ZnPc solar cells. This effect was attributed to the coordination complex formation at the interphase between ZnPc and PyPyFs layers that improve charge separation under solar cell operation conditions. 1. 2. 3. D.V. Konarev, R.N. Lyubovskaya, G. Zerza, S.N. Sariciftci, Mol. Cryst Liq. Cryst, 2005, 427, 315-333. D.V. Lopatin, V.V. Rodaev, A.V. Umrikhin, D.V. Konarev, A.L. Litvinov, R.N. Lyubovskaya, J. Mat. Chem., 2005, 15, 657-660. D. V. Konarev, D. V. Lopatin, V. V. Rodaev, A. V. Umrikhin, S. S. Khasanov, G. Saito, K. Nakasuji, A. L. Litvinov, R. N. Lyubovskaya, J. Phys. Chem. Sold. 2005, 66, 711-715 D.V. Konarev, A.Y. Kovalevsky, D.V. Lopatin, V.V. Rodaev, A.V. Umrikhin, E.I. Yudanova, P. Coppens, R.N. Lyubovskaya, G. Saito, Dalton Trans., 2005, 1821-1825 P. A. Troshin, A. S. Peregudov, D. Muhlbauer, R. N. Lyubovskaya, Eur. J. Org. Chem. 2005, 3064-3074. R. Koeppe, N.S. Sariciftci, P.A. Troshin, R. N. Lyubovskaya, Appl. Phys. Lett. 2005, 87 (24), 244102
ABSTRACTS
4. 5. 6.
M16 RESONANT MAGNETIZATION TUNNELINGS IN A ONE-DIMENSIONAL IRON(II)-CONTAINING OXALATE CHAIN STRUCTURE Kuan-Jiuh Lin*a, Lu-Lin Li,a and Hung-Duen Yangb
a
Department of Chemistry, Center of Nanoscience and Nanotechnology, National Chung-Hsing University, Taichung 402,Taiwan (Republic of
China). E-mail: kjlin@dragon.nchu.edu.tw. b Department of Physics, National Sun Yat- Sen University, Kausiung 804, Taiwan (Republic of China). One-dimensional (1D) supramolecular materials possessing single-molecule magnets behavior have attracted a great deal of attention for data storage devices. We herein present the magnetization of an innite 1D oxalate chain structure that comprises alternating - and -iron(II) assemble building units, [FeII()FeII()(ox)2(Phen)2]n. The ac magnetic susceptibility for this chain structure is strongly frequency-dependent and characteristic of singlemolecule magnetic behavior. The hysteresis loop taken at 2.1 K shows a large coercive eld as great as 10000 Oe, which is signicantly larger than that reported for analogous oxalate-based magnetic compounds. Moreover, resonant tunneling steps between quantum spin-states are clearly seen in the magnetization hysteresis loops.
M17 AIR-STABLE N-CHANNEL ORGANIC TRANSISTORS BASED ON A SOLUBLE C84 FULLERENE DERIVATIVE T.D. Anthopoulos,a,b F.B. Kooistra,c H.J. Wondergem,a D. Kronholm,d J.C. Hummelen,c D.M. de Leeuw,a
[a]
Philips Research Laboratories, High Tech Campus 4 5656 AE Eindhoven,The Netherlands Department of Physics, Blackett Laboratory Imperial College London, London SW7 2BW, United Kingdom
[c] [b]
Molecular Electronics, Materials Science CentrePlus University of Groningen, Nijenborgh 4 9747 AG Groningen, The Netherlands Solenne B. V., Zernikerpark 12 9747 AN Groningen, The Netherlands
[d]
In recent years organic eld-effect transistors (OFETs) have demonstrated great potentials for use in low-end electronic applications.1-3 A key criterion for the successful utilisation of this technology is the ability to fabricate inexpensive, large-scale integrated circuits with high-yield. From silicon-based microelectronics it is known that a route, which satises this criterion is the use of complementary technology.3 Unlike in silicon-based microelectronics, however, where fabrication of discrete p- and n-channel transistors is a well-established process, fabrication of organic complementary circuits is still very challenging requiring separate deposition of two semiconductors i.e. a hole and an electron transporter, employing vacuum sublimation techniques3. An alternative and potentially cost-effective method for the processing of discrete p- and n-channel OFETs is by inkjet printing.4 Here, however, one must rely on soluble organic semiconductors with good environmental stability. Although for hole transporting materials this is not a major issue,2, 7 soluble and air-stable electron transporting molecules are scarce with very few exceptions.8,9 This distinct lack of electron transporting semiconductors has, to a degree, impaired progress towards solution processed organic complementary circuits. To this end a primary challenge is the discovery and/or development of air-stable n-type semiconductors with useful solubility. Herein, we report on a newly synthesized C84 fullerene derivative ([84]PCBM)6 and its applications in n-channel transistors and complementary circuits. Owing to the soluble nature of [84]PCBM, transistors and circuits can be fabricated using potentially cost-effective solution-processing methods. Most importantly [84]PCBM-based OFETs are air and light stable and fully functional even after exposure to ambient air for a period of six months. Despite the poor crystallinity of the [84]PCBM lms (determined by XRD), electron mobilities in the order of 10-3 - 10-2 cm/Vs are obtained. Additionally, hole transport is observed at low temperatures with the hole mobility in the range 10-5 10-4 cm2/Vs. To the best of our knowledge this is the rst report of an air-stable fullerene-based OFET and the rst ever observation of hole conduction in a C84-based molecule. To demonstrate the technological potentials of [84]PCBM transistors, quasistatic/dynamic characteristics of air-stable complementary circuits, fabricated and tested in air without encapsulation, will be presented. REFERENCES [1] D. M. de Leeuw, US Patent WO99/30432, 1999. [2] G. H. Gelinck, et al. Nat. Mater. 2004, 3, 106. [3] B. Crone, et al. Nature 2000, 403, 521. [4]M. M. Ling and Z. Bao, Chem. Mater. 2004, 16, 4824. [5] H. Sirringhaus et al. Science 1998, 280, 1741. [6] F. B. Kooistra, et al. (unpublished). [7] M. Heeney et al. J. Am. Chem. Soc. 2005, 127, 1078. [8] E. Katz, et al. Nature 2000, 404, 478. [9] B. A. Jones et al. Angew. Chem. Int. Ed. 2004, 43, 6363.
M18 AIR-STABLE N-CHANNEL ORGANIC TRANSISTORS BASED ON A SOLUBLE C84 FULLERENE DERIVATIVE T.D. Anthopoulos,a,b F.B. Kooistra,c H.J. Wondergem,a D. Kronholm,d J.C. Hummelen,c D.M. de Leeuw,a
[a]
Philips Research Laboratories, High Tech Campus 4 5656 AE Eindhoven, The Netherlands
[b]
Department of Physics, Blackett Laboratory
ABSTRACTS
Imperial College London, London SW7 2BW, United Kingdom

[c]
Molecular Electronics, Materials Science CentrePlus University of Groningen, Nijenborgh 4 9747 AG Groningen, The Netherlands Solenne B. V., Zernikerpark 12 9747 AN Groningen, The Netherlands
[d]
In recent years organic eld-effect transistors (OFETs) have demonstrated great potentials for use in low-end electronic applications.1-3 A key criterion for the successful utilisation of this technology is the ability to fabricate inexpensive, large-scale integrated circuits with high-yield. From silicon-based microelectronics it is known that a route, which satises this criterion is the use of complementary technology.3 Unlike in silicon-based microelectronics, however, where fabrication of discrete p- and n-channel transistors is a well-established process, fabrication of organic complementary circuits is still very challenging requiring separate deposition of two semiconductors i.e. a hole and an electron transporter, employing vacuum sublimation techniques3. An alternative and potentially cost-effective method for the processing of discrete p- and n-channel OFETs is by inkjet printing.4 Here, however, one must rely on soluble organic semiconductors with good environmental stability. Although for hole transporting materials this is not a major issue,2, 7 soluble and air-stable electron transporting molecules are scarce with very few exceptions.8,9 This distinct lack of electron transporting semiconductors has, to a degree, impaired progress towards solution processed organic complementary circuits. To this end a primary challenge is the discovery and/or development of air-stable n-type semiconductors with useful solubility. Herein, we report on a newly synthesized C84 fullerene derivative ([84]PCBM)6 and its applications in n-channel transistors and complementary circuits. Owing to the soluble nature of [84]PCBM, transistors and circuits can be fabricated using potentially cost-effective solution-processing methods. Most importantly [84]PCBM-based OFETs are air and light stable and fully functional even after exposure to ambient air for a period of six months. Despite the poor crystallinity of the [84]PCBM lms (determined by XRD), electron mobilities in the order of 10-3 - 10-2 cm/Vs are obtained. Additionally, hole transport is observed at low temperatures with the hole mobility in the range 10-5 10-4 cm2/Vs. To the best of our knowledge this is the rst report of an air-stable fullerene-based OFET and the rst ever observation of hole conduction in a C84-based molecule. To demonstrate the technological potentials of [84]PCBM transistors, quasistatic/dynamic characteristics of air-stable complementary circuits, fabricated and tested in air without encapsulation, will be presented. REFERENCES [1] D. M. de Leeuw, US Patent WO99/30432, 1999. [2] G. H. Gelinck, et al. Nat. Mater. 2004, 3, 106. [3] B. Crone, et al. Nature 2000, 403, 521. [4] M. M. Ling and Z. Bao, Chem. Mater. 2004, 16, 4824. [5] H. Sirringhaus et al. Science 1998, 280, 1741. [6] F. B. Kooistra, et al. (unpublished). [7] M. Heeney et al. J. Am. Chem. Soc. 2005, 127, 1078. [8] E. Katz, et al. Nature 2000, 404, 478. [9] B. A. Jones et al. Angew. Chem. Int. Ed. 2004, 43, 6363.
M19 DYNAMICS OF BIPOLARON IN A POLYMER CHAIN: FORMATION AND DISSOCIATION* Yong-Hong Yan and Chang-Qin Wu+ Department of Physics, Fudan University, Shanghai 200433, China Conducting polymers have attracted much interest for its commercial applications, e.g., organic light emitting diodes, solar cells, etc. Understanding mechanisms of the electron injection from metal electrodes into organic material is of great importance for improving the performance of these organicbased devices. Due to the strong electron-lattice interactions, it is well known that additional electrons or holes in conducting polymers will induce self-localized excitations, such as solitons (only in trans-polyacetylene), polarons and bipolarons. As a result, it has been generally accepted that the charge carriers in conjugated polymers are these excitations including both charge and lattice distortion. The formation and dissociation of bipolaron in non-degenerate polymers are investigated in this work by a non-adiabatic dynamical method, which allows the transition between instantaneous electronic states, through solving the time-dependent Schrdinger equations for electrons combined with the Newtonian equation of motion for lattices within the Su-Schrieffer-Heeger model with the hopping modied by an alternate Brazovskii-Kirova symmetry-breaking term (t). Bipolaron Formation: We consider the charge injection process from metal electrode to a non-degenerate polymer in a metal/polymer/metal structure. It is demonstrated that the dynamical formation of a bipolaron sensitively depends on the strength of applied electric eld, the work function of metal electrode, and the contact between the polymer and the electrode. For a given bias applied to one of the electrode (V0) and coupling between the electrode and the polymer (t), such as V0=0.79eV and t=1.0eV, the charge injection process depending on the electric eld can be divided into the following three cases: (1) in the absence of the electric eld, only one electron tunnels into the polymer to form a polaron near the middle of the polymer chain; (2) at low electric elds, two electrons transfer into the polymer chain to form a bipolaron; (3) at higher electric elds, bipolaron can not be formed in the polymer chain, electrons are transferred from the left electrode to right electrode through the polymer one by one accompanying with small irregular lattice deformations. Bipolaron Dissociation: We investigate the dynamics of a bipolaron in poly(p-phenylene vinylene) (PPV) at an external electric eld. At a high electric eld, a bipolaron is found to be dissociated as the case of a polaron due to the lattice being not responded simultaneously with the fast moving electrons but with a much high critical strength of order 106V/cm. This dissociation is regarded as the causation of a large increase in current in PPV at the eld observed in experiments. Furthermore, it is found that the bipolaron will not be formed in an electric eld with strength over 8x104V/cm. * Work supported by the National Natural Science Foundation of China and the State Ministry of Education of China. + Email address: cqw@fudan.edu.cn.
ABSTRACTS
M20 AIR-STABLE N-CHANNEL ORGANIC FIELD-EFFECT TRANSISTORS BASED ON N,N-BIS(4-FLUOROBENZYL)-3,4,9,10PERYLENE TETRACABOXYLIC DIIMIDE Yoshinobu Hosoi1, Daisuke Tsunami2, Hisao Ishii2, Yukio Furukawa1 Department of Chemistry, School of Science and Engineering, Waseda University,
Shinjuku-ku, Tokyo 169-8555, Japan. Research Institute of Electrical Communication, Tohoku University, Aoba-ku, 2-1-1 Kata-hira, Sendai, Miyagi 980-8577, Japan.
Air stable n-channel organic eld-effect transistors (OFETs) with high electron mobility are necessary for the fabrication of complementary circuits and bipolar transistors. Several materials such as C60 show high electron mobility (ca. 1 cm2/Vs) in vacuum. However, only few n-channel OFETs operate in air. It is expected that the OFETs based on the n-type materials with large electron afnity operate stably in air. Thus, we have synthesized N,N-bis(4-uorobenzyl)-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-PFB), because the electron-withdrawing 4-uorobenzyl group as an N-substituent at the imide may enlarge the electron afnity of the material. In this study, we have fabricated an OFET based on PTCDIPFB. An n-channel transistor operation in accumulation mode have been demonstrated in air. An electron mobility of 5.0 x 10-2 cm2/Vs and an on/off ratio of 106 have been obtained. Atomic force microscopy and infrared spectroscopy have been employed to investigate the lm growth of PTCDI-PFB. The lm morphology and molecular orientation drastically change as a function of the lm thickness.
M21 TUNING HOLE-INJECTION BARRIERS AT ORGANIC-METAL INTERFACES WITH ELECTRON ACCEPTING MOLECULES Steffen Duhm, Hendrik Glowatzki, Jrgen P. Rabe and Norbert Koch Humboldt-Universitt zu Berlin, Institut f. Physik, Newtonstr. 15, D-12489 Berlin, Germany Robert L. Johnson Universitt Hamburg, Institut f. Experimentalphysik, D-22761 Hamburg, Germany Jrgen Klankermayer RWTH-Aachen, Inst. f. Techn. u. Makromolekulare Chemie, D-52074 Aachen, Germany Antje Vollmer Berliner Elektronenspeicherring-Gesellschaft fr Synchrotronstrahlung m.b.H., D-12489 Berlin, Germany
There is an increasing demand for ne-tuning the energy level alignment between conjugated organic materials (COM) and metal electrodes in the rapidly developing eld of organic electronics. Interface energetics are determined fundamentally by the interaction between the COM and the electrode. We present a new approach to tune hole-injection barriers by adsorbing a (sub-) monolayer of an electron acceptor on the metal electrode. Partial charge transfer (CT) from the metal to the acceptor produces a chemisorbed layer, which reduces the hole-injection barrier (h) to the COM overlayer. We tested the acceptors tetracyano-anthraquinodimethane (TCAQ), octouoroanthraquinone (FAQ) and tetrauoro-tetracyanoquinodimethane (F4TCNQ). FAQ and F4-TCNQ undergo a CT reaction with the metals Ag and Au, but TCAQ reacts only with Ag. This was determined by ultraviolet and x-ray photoelectron spectroscopy (UPS and XPS). The energy level alignment of subsequently deposited molecules was investigated using sexithienyl (6T), N,N-bis-(1-naphthyl)-N,N-diphenyl-1,1-biphenyl-4,4-diamine (-NPD) and p-sexiphenyl (6P) as second layers. The UPS results show a reduction of the hole-injection barriers by up to 1.2 eV. In addition, by adjusting the acceptor pre-coverage, h could be varied systematically within this interval. By choosing different material combinations we have shown that the reduction of h is independent of the CT formation ability of the acceptor and the COM overlayer. Our results suggest that the hole-injection barriers at virtually any organic/metal interface can be optimized by employing (sub-) monolayer coverages of strong electron acceptors. M22 ADAPTIVE MATERIALS FOUNDATIONS FOR THE NEXT GENERATION OF CHEMICAL SENSORS Dermot Diamond, Adaptive Sensors Group, National Centre for Sensor Research, Dublin City University, Dublin 9, Ireland Wireless communications technologies are rapidly becoming completely pervasive, and the mobile phone is evolving into a personal portal between individual people and the digital world of communications and information access. However, the vast bulk of information stored and accessed on the web is either text, audio, or graphics (pictures and video) based. Increasingly, the focus is shifting towards other types of data, and in particular, data generated by sensors and other instruments. The availability of low power, compact platforms known as Motes for acquiring, storing and wirelessly transmitting sensor data, and the incorporation of ad-hoc networking capabilities, has provided the basic framework for the realisation of wireless sensor networks. Like analytical instruments, there is a hierarchy of complexity and capability in communications technologies, with the more complex and powerful technologies of each tending to pair off. Merging low cost, reliable chemical sensors and biosensors with mote platforms is conceptually very attractive, as this could lead to the realisation of widely deployed chemo/biosensor networks with applications in environmental sensing, food quality tracking, personal health monitoring, and security/threat detection. However, even the simplest chemical sensor is far too complex and costly to deploy in large numbers, and maintenance is an apparently insurmountable obstacle. In this paper, I will discuss the use of advanced functional materials for producing sensors that are to some extent self-maintaining,a nd self-regulating, and therefore potentially capable of continuous autonomous operation for extended periods of time.
M23 AN IONIC POLYMER-METAL COMPOSITE SENSOR FOR BENDING CURVATURE MEASUREMENTS. D.M.G. Preethichandra, A.K. Thakur, W. Takashima and K. Kaneto
ABSTRACTS
Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, 2-4, Hibikino, Wakamatusu-ku, Kitakyushu-Shi, 808-0196, Japan Bending curvature measurement is a very crucial issue in bio-mimetic robotics. Especially in human imitating robotic hands, where every single nger movement has to be tracked very accurately in order to imitate. Humanoid robotic hands are being developed around the world by many research teams. Most of them are equipped with high performance vision sensors for getting the real time information on nger movements and complex algorithms to generate the motor driving signals of the robot hand. The problem with vision is other body parts coming into the scene may cause a critical loss of information. Some of the human imitating hands use sensors made with conducting polymers or rubber and carbon mixtures1. They usually work on the change of intrinsic resistance of the polymer but the bending direction measurement is a problem unless it has multiple layers. Measuring a sharp bending angle is not much serious a problem with optical methods, but here we are dealing with human ngers where the bending can be measured only as a curvature. Therefore a exible and in situ sensor whish will not disturb the normal operations of the human hand is needed. Addressing this problem, we describe in this paper a novel sensor which can produce information not only on the bending curvature but also the bending direction. This is made using the well known proton exchange membrane Naon manufactured by Dupont. There are many methods to deposit electrodes on the Naon surface, but most of them are expensive and time consuming procedures2. Here in this paper, we explain a straight forward method of making ionic polymer-metal composite layer as the electrode and then develop the sensor using it. The developed sensor exhibits very good relationship between its output voltage and the bending curvature. Depending on the direction of bending, it outputs either a positive or a negative voltage so that the bending direction determination is straightforward. This is the most signicant feature of this sensor in contrast to the existing polymer based sensors where single layered polymer sensors can not provide the bending direction information. Though this was developed as a sensor, it works as a very powerful actuator compared to the ordinary polymer actuators of the same size. We are now investigating the ability of making the same device work on both the modes in a time sequential process in order to provide a feedback on bending curvature of an articial muscle made using this ionic polymer-metal composite. References 1. D. De Rossi et. al. IEEE Sensors, 2,1606 (2002) 2. K.J. Kim et. al.,Polymer,43, 797, (2002)
M24 THERMODYNAMIC INTERPRETATIONS TO TASTE SENSOR CHARACTERISTICS OF POLYACRYLIC ACID GRAFTED CELLULOSE MEMBRANE Sharmistha Mitra (Majumder), Alok Sen and Basudam Adhikari* Materials Science Centre, Indian Institute of Technology, Kharagpur-721302, India.
Previously, fabrication of taste sensors was done by incorporating lipids in PVC matrix 1 or adsorbing lipids into Millipore lter paper 2. We have taken an attempt to prepare taste sensor material by functionalizing some polymers. The sensor characteristics like temporal stability, response stability, response to different taste substances, and reproducibility of sensing performance were studied using polyacrylic acid (PAA) 3 grafted cellulose membrane. Sensor device prepared with this membrane has shown distinct response patterns for different taste substances in terms of membrane potential. Threshold concentrations of PAA grafted cellulose membrane for HCl, NaCl, quinine-hydrochloride (Q-HCl), sucrose and monosodium glutamate (MSG) are 0.001 mM, 0.01 mM, 0.08 mM, 0.08 mM and 0.01 mM, respectively. The threshold concentrations excepting that for Q-HCl are below human threshold concentrations 4, 5. Membranes also showed characteristic response patterns for organic acids like acetic acid, citric acid, formic acid etc., mineral acids like HCl, H2SO4 and HNO3, etc., salts, bitter substances, sweet substances and umami substances. Surface charge density of the membrane was estimated. Sensor device prepared with this membrane has excellent shelf life. In this paper some attempts have been made to explain thermodynamically the nature of the response patterns of the membrane to different taste substances with the help of Nernst equation. Keywords: taste sensor; taste substances; grafted membrane; functionalized polymer.
References 1. Hayashi K, Yamanaka M, Toko K, Yamafugi K. Multichannel taste sensor using lipid membranes. Sens Actuators B, Chem 1990; 2: 205-213. 2. Miyake M, Kamo N, Kurihara K, Kobatake Y. Physico-chemical studies of taste reception. J Membr Biol 1975; 22:197-209. 3. Majumdar S, Dey J and Adhikari B. Taste sensing with polyacrylic acid grafted cellulose membrane. Talanta 2006; 69: 131-139. 4. Pfaffmann C. The sense of taste. In: Field J, editor. Handbook of physiology. vol.1, section 1, Neurophysiology. Washington, DC: American Physiological Society; 1959. p.507. 5. Yamaguchi S. The synergistic effect of monosodium glutamate and disodium 5inosinate. J Food Sci 1967; 32: 473-8.
M25
ABSTRACTS
SIMULTANEOUS SENSING AND ACTUATING ARTIFICIAL MUSCLES: TACTILE MUSCLES AND CONSCIOUS DEVICES TF Otero, G Vzquez, M Caballero, J Lpez-Cascales, I Rodrguez, J Padilla and A Fernndez Universidad Politcnica de Cartagena Centre for Electrochemistry and Intelligent Materials
Carlos III, s/n, 30203 Cartagena, Spain The oversimplied electrochemical reaction for the oxidation/reduction of any prevailing anion interchange-conducting polymer, (pPy)s + n(Cl-)aq+ mH2O [(pPyn+)s(Cl-)n (H2O)m]gel + (n e-)metal includes electrochemical properties and electrochemical applications of those non-stoichiometric materials. The change of volume between (pPy)s and [(pPyn+)s(Cl-)n (H2O)m]gel originates articial muscles. According with the chemical equilibrium the muscle potential, working under constant current, must be inuenced by any chemical or physical variable acting on the equilibrium. As expected the evolution of any device (bilayer, triple layer or complex design) muscle potential changes: under different concentrations of the electrolyte, different temperatures, different weights attached to the bottom of the muscle, or different current owing through the device. Lineal evolutions are obtained for the electrical energy consumed by the articial muscle to cross over a constant angle, as a function of the studied experimental variable. Both signals, the actuating current and the muscle potential response, are included in the same two connecting wires opening a new paradigm for the robotic devices. Those results underline the simultaneous sensing and actuating capabilities of the device. The ability of the devices for sensing mechanical variables opens the way for exploring one of the most exciting possibilities that scientists are trying to reproduce: the tactile sense. Considering that trailing increasing weights by the muscle we obtain increasing muscle potentials, if a muscle moves freely and meets an obstacle opposing a mechanical resistance lower than the mechanical energy produced by the device, the device must touch, push and shift the obstacle. At the beginning of the movement the muscle moves freely until it touches the obstacle: the evolution of the muscle potential must be the same as that of the muscle moving without any hanging weight. When the muscle touches the obstacle it feels a mechanical resistance and, according to the above conclusion, the muscle produces an extra energy by raising their overpotential. Depending on how fast this evolution occurs we can obtain a response to the touching moment. Moreover, if we repeat the experiment using obstacles producing increasing resistances (increasing weight obstacles) increasing potential steps are produced, proportional to the obstacle weight at the moment of the contact: this is a touching sensor. The moving device indicates the moment of contact and the mechanical resistance opposed by the obstacle. When the mechanical resistance of the obstacle exceeds the mechanical energy produced by the device, the device is unable to shift the obstacle and the muscle potential steps to very high values at the moment of contact. So we have a muscle with tactile sense: quite simple response analysis software can transform the ensemble (computer, potentiostat and device) into a very primitive conscious system. The system indicates when a muscle, or the mechanical tool driven by the muscle, touches an obstacle and how much mechanical resistance the obstacle opposes.
M26 ENTRAPMENT OF PEROXIDASE INTO POLYPYRROLE FOR NADH SENSING Takeshi YAMAUCHI1, 3*, Takeshi Suzuki1, Hiroshi SAITO2, and Norio TSUBOKAWA2, 3 Graduate School of Science and Technology, Niigata University, 2Faculty of Engineering, Niigata University, 3Center for Trandisciplinary Research, Niigata University
Abstract In this paper, we described an electrochemical polymerization method for incorporating high density horseradish peroxidase into polypyrrole lm in a one-step process and applied it for various organic acids sensing electrodes. We also developed micro enzyme electrode using this peroxidase entrapping method using dialysis membrane. Obtained micro enzyme electrode was applied to biosensor for nicotinamide adenine dinucleotide (NADH) detection. Synthesis of enzyme immobilized polypyrrole lm onto Au wire surface was performed using a conventional three electrode system, containing an Au electrode as the working electrode and a platinum electrode as the counter electrode, a SCE (saturated calomel electrode) as the reference electrode. Au electrode was covered with dialysis membrane tube which lled. Polypyrrole lm was synthesized for 10 minutes under the constant potential of 2.0V supplied by a Hokuto Denko model HABF501 Potentiostat/Galvanostat. Application to amperometric NADH sensor was investigated by steadystate current measurements at pH 7.0, 37C. The one step preparation of enzyme electrode with dialysis membrane was succeeded by electrochemical polymerization method. The amount of enzyme immobilized in the polymer lm was estimated to be 8 X 10-6 g/cm2 by Lowry method. It was appeared that high density enzyme was entrapped into polypyrrole lm in a one-step process. Amperometric NADH sensing with the composite lms gave the result that response current increased linearly with substrate concentration. The relationship between enzyme activity of immobilized enzymes and conductivity of the lms was investigated. Amperometric NADH sensing ability of composite lms were related with enzyme activity of peroxidase. Micro enzyme electrode prepared by the same method also had NADH sensing characteristics. * Author for correspondence 8050 Ikarashi Ni-no-cho, Niigata 950-2181, Japan Tel/Fax +81252627790 E-mail yamauchi@gs.niigata-u.ac.jp
M27 HIGHLY SENSITIVE IMMUNODETECTION OF CANCER BIOMARKERS USING CARBON NANOTUBE AMPLIFICATION SCHEMES Fotios Papadimitrakopoulos, Xin Yu, Bernard Munge, Vyomesh Patel, Gary Jensen, Ashwin Bhirde, Joseph D. Gong, Sang-Nyon Kim, John Gillespie, J. Silvio Gutkind, and James F. Rusling Nanomaterials Optoelectronics Laboratory Dept. of Chemistry, Polymer Program, IMS University of Connecticut Storrs, Connecticut 06269-3136
Sensitive measurement of proteins is a critical need in many aspects of biomedical research and diagnosis. In particular, measurement of collections of cancer biomarkers is promising to obtain highly reliable predictions for early cancer detection. In this paper we describe highly sensitive electrochemical immunosensors based on single-wall carbon nanotube (SWNT) forests for the selective detection of cancer biomarkers in serum and tissue lysates. Bioconjugates featuring horseradish peroxidase (HRP) labels and secondary antibodies (Ab2) linked to carbon nanotubes (CNT)
ABSTRACTS
at high HRP/Ab2 ratio were used to replace singly-labeled secondary antibodies for greatly amplied sensitivity. Combining HRP-CNT-Ab2 bioconjugates with SWNT immunosensors resulted in a detection limit for prostate specic antigen (PSA) in 10 L of undiluted calf serum of 4 pg mL-1 (100 amol mL-1), a mass detection limit of 40 fg. Accurate detection of PSA in human serum samples was demonstrated by comparison to standard ELISA assays. PSA was quantitatively measured in prostate tissue samples for which PSA could not be differentiated by the gold standard immunohistochemical staining method. These easily fabricated SWNT immunosensors show excellent promise for clinical screening of cancer biomarkers and point-of-care diagnostics. Financial support from ARO is kindly appreciated.
M28 CONDUCTING IPN PASTILLE-SHAPED ACTUATORS: FROM THE POLYMER CHEMISTRY TO THE DEVICE F. Vidal1, C. Plesse1, A. Keddhar2, J. Citerin2, D. Teyssi1, C. Chevrot1
1
Laboratoire de Physicochimie des Polymres et des Interfaces (EA 2528), Universit de Cergy-Pontoise, 5 mail Gay Lussac, 95013 Cergy Pontois, France. 2 Laboratoire Systmes complexes -CNRS-UEVE, Universit dEvry, 40 rue du Pelvoux, CE 1455 Courcouronnes, 91020 Evry Cedex, France Among electroactive actuators, those based on electronic conducting polymers (ECPs) possess several advantages (softness, low actuation voltages, large deformations) but also some drawbacks (bending movements only, delamination). In order to overcome the delamination process observed in working three layered actuators, we have developed a new concept of actuators consisting in an interpenetrating polymer network (IPN) matrix in which 3, 4-ethylenedioxythiophene (EDOT) is chemically polymerized [1]. The typical IPN matrix we developed results from the association of the two following cross-linked polymers: the rst one, polyethylene oxide (PEO), will ensure the ionic conductivity of the system after salt incorporation while the second one, polybutadiene (PB), will allow to adjust the required mechanical properties. The chemical polymerization of EDOT within the IPN leads to the formation of a PEDOT gradient, its concentration decreasing from the outside faces towards the centre of the IPN. So, such a one piece actuator is equivalent to a three layered actuator except for the fact that the adhesion between layers is built in due to the synthetic procedure. Up to 106 bending deformations in open air can be observed after incorporation of a classical salt or better a room temperature ionic liquid applying a
low voltage at a frequency from 0.1 to 15 Hz [1]. However, linear deformations are more interesting for a number of applications than simple bending motions. Thus it will be presented in this paper how this challenge was successfully met. The description of the design of the open air working actuator will be presented as well as the transformation of this actuator into a pastille-shaped device which could lead to a promising tactile display [2]. [1] F. Vidal, C. Plesse, D. Teyssi, C. Chevrot, Synth. Met., 142, 2004, 287-291. [2] J. Citerin, A. Kheddar, F. Vidal, C. Chevrot, D. Teyssi, SPIEs annual international symposium on smart structures and materials, San Diego, USA, February 26-march 2 2006.
M29 INVITED DEVELOPING OLED TECHNOLOGY FOR LIGHTING ALAN DUGGAL
M30 EFFECTS OF ACTIVE AREA SCALING ON WHITE OLED PERFORMANCES Claudia Piliego, Marco Mazzeo,Marco Salerno and Giuseppe Gigli Nanotechnology Laboratory of CNR-INFM, Distretto Tecnologico ISUFI, Lecce University, Via Arnesano Km 5, I-73100, Lecce, Italy
The realization of a large area emitting panel is the target of several worldwide research and industrial activities, but until now an accurate study of the effect of the active area on device performances has not been reported. In this work the effects on OLED performances induced by scaling the active area are investigated by realizing different sized square OLEDs with an active region ranging from 0,25 cm2 to 9cm2. For the active layer we used 4,4-bis (2,2-diphenylvynil,1,1 biphenyl) DPVBi doped with Rubrene deposited through a coevaporation process on a plasma cleaned ITO substrate, which acts as an anode. White emission with CIE coordinates 0,36-0,42 and CRI50, was obtained for a Rubrene concentration of 8wt%. The nal OLED structure included 30nm DPVBi and 10nm Alq3 as an electron transporting layer (ETL) and a cathode consisting of 45 nm of thermally evaporated Calcium followed by 120 nm of Aluminum. All the devices were encapsulated in an inert atmosphere. Oled I-V- L characteristics were recorded from different regions of the active devices. We observed that the device performances such as, color emission, luminance, operating current etc., were strongly dependant on the distance from the contact point. This effect, mainly due to the voltage drop induced by the ITO resistivity, increases as the active area of the device increases. This strongly limits the possibility of fabricating large area devices with uniform emission and reduced dissipated power, due to Joule effect. In order to eliminate the non-uniformity induced by the drop in voltage along the ITO substrate we proposed different contact geometries as well as the insertion of a thin, transparent metal grid with properly spaced bars in the ITO anode. Effects of the area scaling on the proposed devices were analyzed and compared with conventional Oled devices.
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14000 12000 10000 8000 6000 4000 2000 0 0,5 1,0 1,5 2,0 2,5 3,0 6V 8V 10V 12V 14V 16V 18V
S ide (cm)
M31 POLYMER LIGHT EMITTING DIODES Yunhua Xua, Qiaoli Niua, Xiuju Zhanga,b, Jiaxing Jianga, Junbiao Penga,2, and Yong Caoa
a
Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, and Key Laboratory of Specially Functional Materials and Advanced Manufacturing Technology Ministry of Education Guangzhou, 510640, China b Department of Material Science and Engineering, Jinan University, Guangzhou, 510632, China
Corresponding author. Tel.: +86 20 87114535; fax: +86 20 87110606., E-mail address: psjbpeng@scut.edu.cn (J. Peng).
White polymer light-emitting diodes (WPLEDs) have strongly absorbed increasing research interest in the applications of a new generation of light sources for backlighting of liquid crystal displays (LCD) and lighting sources. The polymer-based devices, often consist of a single active layer easily made by wet processes, including spin-casting, screen printing, or ink-jet printing techniques [1,2], which are expected to reduce the cost in mass production, especially in the production of large-area panel displays. So far, the performances of WPLEDs do not meet the need of practical applications in lighting and backlight of LCD, such as the performances of efciency, stability of CIE coordinates with drive voltage and stress, long lifetime. In this presentation, we designed and synthesized several highly efcient triplet state compounds and polymers (Fig.2), optimized device structure, and realized efcient and CIE coordinates stable WPLEDs (Their characteristics are shown in the following table).
Name of device Device A Device B Device C Device structure Anode/PVK/Active layer /Cathode Anode / Active layer/ Cathode Anode/PVK/Active layer/ Cathode Turn on Voltage (V) 4.9 7.5 3.8 Efciency (cd/A) 7.6 5.6 9 CIE Coordinates (0.31, 0.37) (0.31,0.35) (0.33,0.33)
Anode: ITO/PEDOT; Cathode: Ba/Al; PVK: poly(N-vinylcarbazole) Active layer: Device A: poly(9,9-dioctyluorene) (PFO) blend with phenyl-substituted PPV derivative (P-PPV) and a copolymer of 9,9-diotyluorene-co4,7-dis3-hexyl-thien-2-yld-2,1,3-benzothiadiazole (PFO-DBT); Device B: poly(9,9-dioctyluorenyl-2,7-diyl) end capped with dimethylphenyl (PFO) doped by phosphorescent dye of Iridium(III) bis(2,4-diurophenyl-2-pyridine-4-phenyl-p-carbarzole) -5-(pyridin-2-yl)-1,2,4-triazole (CzBPFPZ); Device C: PFO-poss (Polyhedral oligomeric silsesquioxane-terminated poly(9,9-dioctyluorene)) blend with fac-tris(2-(4-ter-butyl)phenylpyridine) iridium (III) [Ir(Bu-ppy)3] and bis-(1-phenylisoquinolyl)iridium(III)(1-triuoro) acetylacetonate [(Piq)2Ir(acaF)].
[1] X. Gong, M. R. Robinson, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Mater. 14 (2002) 581. [2] Y. Xu, J. Peng, J. Jiang, W. Xu, W. Yang, Y. Cao, Appl. Phys. Lett. 87 (2005) 193502
M32 HIGH-EFFICIENCY WHITE-LIGHT-EMITTING DEVICES FROM A SINGLE POLYMER BY MIXING SINGLET AND TRIPLET EMISSION Wei Yang , Jiaxing Jiang, Yunhua Xu, Hongyu Zhen, and Yong Cao Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology; Guangzhou 510640, China We present current progress on realization of efcient white light emission from a single polymer, which simultaneously consists of uorescenceand phosphorescence-emitting species. By introducing a small amount of benzothiadiazole (BT) segments into the polyuorene backbone and attaching a small amount of iridium complexes to the side-chain of macromolecule, white light emission was obtained from three individual emission species. Large band gap uorene segment was used as the host for blue light-emitting species, the benzothiadiazole segment was selected as green emission. Ir complex was used as triplet red-light emission species because of its high quantum efciency owing to strong spin-orbital coupling of heavy-metal ions. By adjusting the content of benzothiadiazole or/and iridium complex, the energy transfer between the large and small band gap species can be controlled to realize the simultaneous emissions of three species and further combine to form white light. The emission of white light can be obtained by adjusting the content of comonomers. The white polymer light-emitting diode (WPLED) by means of polyuorene-based copolymer (PFBT5-Phq2) containing 0.05 mol% of green light-emitting BT and 0.2 mol% of red light-emitting iridium
ABSTRACTS
complex shows the highest luminous efciency of 6.1 cd/A at the current density of 2.2 mA/cm2 with the Commission Internationale de lEelairrage (CIE) coordinates of (0.33, 0.46). The maximum luminance of 10100 cd/m2 was achieved at the current density of 345 mA/cm2 with the CIE coordinates of (0.31, 0.41). The light color emitted from the devices of the copolymers is stable in white region at different applied voltages, and the EL efciencies remain still high at high current density, which indicates that the approach to incorporate singlet emission species into the polymer backbone and to graft triplet emission species onto the side-chain of polymer is promising for WPLEDs. The results of the white-light-emitting polymers grafted with iridium complex as side group will be discussed in comparison with that iridium complex on the polymer backbone.
O O
B H 17C8
B O O C8H 17
+ Br H17C8 C8H 17
Br
Br N S N
Br
Br + N
Br CF 3
2
SPC
O O Ir N 2
H17C8 C8H17 * N S N x m
H17C8
C8H17 * N y n O O Ir N 2 CF 3
Scheme 1 Synthetic routes for the copolymers.
M33 BRIGHT WHITE LIGHT-EMITTING DEVICE FROM TERNARY NANOCRYSTAL COMPOSITES Yanqin Li, Aurora Rizzo, Roberto Cingolani, and Giuseppe Gigli* NNL, National Nanotechnology Laboratory of CNR-INFM, Distretto Tecnologico ISUFI, Lecce University, Via Arnesano Km 5, I-73100, Lecce, Italy e-mail: liyanqin@mailing.unile.it LEDs based on colloidal inorganic semiconductor nanocrystals (QDs) represent a completely new technology platform for the development of atpanel displays and at-panel lighting systems[1-6]. Their major advantages are the easy tuning of the saturated color emission across the visible-NIR range and the high chemical and optical stability of the nanocrystal composites. These characteristics open the way to a new class of hybrid devices in which the low cost, exible technology of organic LEDs is combined with the long operating lifetime of inorganic semiconductor devices. Coe et al[4,5] have demonstrated a hybrid high efciency (1.6 cd A-1 at 2000 cd m-2) monochromic LED by exploiting phase segregation processes between CdSe quantum dots and an organic matrix. This resulted in the formation of a very thin layer of CdSe QDs sandwiched between the organic layers, which improved the electron injection in the inorganic active medium and, in turn, the LED performances. However, so far, few studies have been reported on white light-emitting devices based on QDs. Here, we demonstrate the rst efcient hybrid light-emitting device, with white emission from chemically and optically stable ternary nanocrystal composites dispersed in an organic matrix. White bright emission is obtained from homogenous blends, without phase segregation between the active ternary QDs composites and the organic matrix, exploiting the energy transfer and charge-trapping properties of the different species. The maximum brightness of the device is 1050 cd m-2 at 58 mA cm-2, which corresponds to a current efciency of 1.8 cd A-1, and a turn-on voltage of 6V are measured in air atmosphere. To our knowledge, this is the highest efciency hybrid device with white emission only from ternary QDs composites. The proposed approach is a new general method for the fabrication of potential long operating lifetime, high efciency white light-emitting devices.
ABSTRACTS
Figure. Electroluminescence and photoluminescence spectra and characteristics of the ternary QDs device. a, Electroluminescence spectrum for the device: ITO//PEDOT:PSS//CBP:QDs(B,G,R, c%=18:2:1)//Alq3//Ca/Al. b, Photoluminescence spectra corresponding to isolated lake blue, green and red quantum dots, which measured in solid state. c, V-I, V-L characteristics of the device. Inset: A photo taken from the working device. [1] J. L. Zhao, J. Y. Zhang, C. Y. Jiang, J. Bohnenberger, T. Basch, A. Mews, J. Appl. Phys. 2004, 96, 3206. [2] H. Yang, P. H. Holloway, J. Phys. Chem. B 2003, 107, 9705. [3] M. C. Schlamp, X. G. Peng, A. P. Alivisatos, J. Appl. Phys. 1997, 82, 5837. [4] S. Coe, W. K. Woo, M. Bawendi, V. Bulovi, Nature 2002, 420, 800. [5] S. Coe, W. K. Woo, J. S. Steckel, M. Bawendi, V. Bulovi, Org. Electron. 2003, 4, 123. [6] Y. Q. Li, A. Rizzo, M. Mazzeo, L. Carbone, L. Manna, R. Cingolani, G. Gigli, J. Appl. Phys. 2005, 97, 113501.
M34 SYNTHESIS AND SECONDARY STRUCTURE OFVARIOUS POLY(N-PROPARGYLAMIDES) Toshio MASUDA, Toru FUJII, Junichi TABEI, Masashi SHIOTSUKI, Fumio SANDA Department of Polymer Chemistry Graduate School of Engineering, Kyoto University Katsura Campus, Kyoto 615-8510, Japan Naturally occurring biomacromolecules including proteins and DNA commonly form a higher order structure such as helix. The three-dimensionally ordered structure signicantly contributes to specic functions that maintain living systems. Synthetic helical polymers have attracted much attention, because they possibly exhibit sophisticated features and functions based on the regulated structure similar to biomacromolecules [1]. Highly stereoregular polymers with moderate rigidity possibly take a helical structure. We have previously reported that N-propargylamides undergo polymerization with Rh catalysts to give cisstereoregular polyacetylene derivatives forming a helix, which is stabilized by Rh catalyst in THF or MeOH intramolecular hydrogen bonds between the pendant amide groups as well as by 1 : X = NH, R = steric repulsion [2]. 5 : X = NH, R = The present study deals with the polymerization of N-propargylamides bearing 2 : X = O, R = 6 : X = NH, R = alkyl (1), hydroxy (3 and 5), and ester (6 and 7) groups, along with propargyl esters (2 3 : X = NH, R = and 4), and examination of the effect of the pendant groups on the secondary structure of the formed polymers. 4 : X = O, R = 7 : X = NH, R =
n
OH
OH
Figure 1. CD spectra of poly(1) and poly(2) measured in CHCl3.
OH
Monomers 1 and 2 were polymerized with (nbd)Rh+[6-C6H5B(C6H5)3] as a catalyst in THF at 30 C for 1 h. Monomers 37 were polymerized with [(nbd)RhCl]2 as a catalyst in MeOH at 30 C for 24 h. After that, the solutions were poured into a large amount of MeOH or Et2O to precipitate the polymers. They were collected by ltration, and dried under reduced pressure. Poly(1)poly(7) with moderate molecular weights (Mn > 8,000) were obtained in 5875% yields. Poly(1) showed a Cotton effect based on the polyacetylene main chain in CHCl3 at 2055 C, indicating that it adopts a helical conformation with predominantly one-handed screw sense (Figure 1). On the other hand, poly(2) Figure 2. CD spectra of poly(5) did not show an obvious Cotton effect. It presumably takes a random coil structure in spite of bulky pendant measured in various solvents at 20 C groups. These results mean that hydrogen bonding between the pendant amide groups is important for stabilizing (c = 0.1 mM). the helical structure. Poly(3) showed a Cotton effect based on the main chain in DMF, indicating that it also adopts a helical conformation with predominantly one-handed screw sense. On the other hand, the poly(propargyl ester) counterpart, poly(4), only showed a weak Cotton effect. These results indicate that hydrogen bonding between not the hydroxy groups but amide groups is important for stabilizing the helical structure. Although poly(5) showed a strong Cotton effect in THF and DMF, it did not in CHCl3 (Figure 2). It seems that the hydroxy groups of the polymer largely interact with polar solvents in this case, and they do not interrupt the efcient hydrogen bonding between the amide groups, resulting in the formation of a helical structure. CD spectroscopic analysis indicated that poly(6) and poly(7) also form a helix. The absence of hydroxy groups is also operative for helix formation of these polymers. References [1] Nakano, T.; Okamoto, Y. Chem. Rev. 2001, 101, 40134038. [2] Nomura, R.; Tabei, J.; Masuda, T. J. Am. Chem. Soc. 2001, 123, 84308431.
M35 SPIN MIXING AT CONJUGATED POLYMER HETEROJUNCTIONS T. A. Ford1, H. Ohkita2,3, S. Cook2, J. R. Durrant2 and N. C. Greenham1 Cavendish Laboratory, J.J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom 3 Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan
2 1
ABSTRACTS
Excitons in polymer light-emitting diodes are formed by the capture of opposite charges to form inter-chain bound states (charge pairs) followed by further relaxation to form intrachain excitons. To achieve a yield of singlet excitons which differs from the statistical 25% requires two conditions to be satised: (a) the relaxation rate from triplet charge pairs to triplet excitons must be different to the relaxation rate from singlet charge pairs to singlet excitons; and (b) there must be a rapid mixing of the spin states of charge pairs. Here, we demonstrate that rapid spin-mixing does indeed occur in the charge-separated states formed at the interfaces in a blend of two polyuorenes. Steady-state photoinduced absorption measurements show a signicant increase in the yield of triplet excitons in the blend compared with the pure polymers. The singlet excitons produced by photoexcitation undergo charge separation at the interfaces, leading to charge pair and exciplex states with small exchange energies where intersystem crossing can occur to the triplet manifold, followed by relaxation to form intra-chain triplet excitons. Transient triplet-state absorption spectroscopy allows the timescales of the spin-mixing processes to be measured directly. Prompt triplet exciton generation takes place in the polaron pair states formed immediately after charge transfer from a photogenerated exciton, with a rate of at least 2 107 s1. Further delayed triplets are generated by intersystem crossing in long-lived exciplex states, with a rate of 5 106 s1. These
measurements suggest that it should be possible to achieve non-statistical singlet yields in polymer light-emitting diodes
M36 ARCHITECTURE IN NANOSPACE - SIR HARALD KROTO
M37 PHYSICAL ASPECTS OF THE ORIGIN OF LIFE PROBLEM Albert J. Libchaber Laboratory of Experimental Condensed Matter Physics The Rockefeller University, New York, USA - Temperature differences across porous rocks may feed accumulation and replication of evolving molecules. Such non-equilibrium conditions near porous thermal submarine vents are pieces in the fascinating puzzle of the origin of life. - Encapsulation of cells in a membrane is another step in this puzzle. Building an articial cell based on gene expression inside vesicles reveal the physical constraints to overcome, in particular energy exchange, osmotic pressure, sources and sinks for protein production.
M38 FUNCTIONALISED POLYTHIOPHENE FILMS AND FIBRES D. L. Ofcer, A. M. Ballantyne, R. Breukers, S. Gambhir and K. Wagner Nanomaterials Research Centre and MacDiarmid Institute for Advanced Materials and Nanotechnology, Massey University, Palmerston North, New Zealand . Email: D.Ofcer@massey.ac.nz There is intense interest in the application of inherently conducting polymers (ICPs) to a wide variety of areas such as photovoltaics, light emitting diodes, actuators and chemical sensing.1 The key challenge in utilizing ICPs is the ordered integration of functionalised polymers into devices at the nanoscale; better control of polymer structure and morphology could dramatically improve device performance.2 This requires both the introduction of functionality into the polymer as well as the formation of polymer nanostructures, without signicantly affecting the inherent properties of the ICP. One approach to this involves the introduction of the functionality after polymer nanostructure formation. There have been a number of approaches to the formation of ICP nanostructures.2 Polymer nanoparticles can be formed using steric stabilizers or micellar polymerisation and physical templates used to form nanostructured polymer lms. One of the simplest approaches is the use of electrostatic dispersion or electrospinning to produce ICP nanobres, which have application in photovoltaics, nanoelectronics, actuators and sensor development. Although discovered in the 1930s, electrospinning has only recently been applied to the preparation and processing of conducting polymer nanobres.3 Thus polyaniline (PANI)/polyethylene oxide (PEO) nanobres can be obtained from a PANI/PEO solution subjected to an electric eld of 20 kV. The nanobres form a nonoven mat with extremely high surface area (of the order of 1000 m2/g) on a metal substrate.4 Due to the high surface area, variation in shape and surface chemistry applications as diverse as membranes, tissue scaffolding and nanoelectronics to ltration and sensors have been proposed for these electrospun mats.5,6 The method is, however, dependant on the availability of a soluble form of the polymer and the vast majority of conducting polymers are insoluble. We have been investigating functionalised poly(terthiophene)s for a variety of applications such as photovoltaics7 and batteries.8 These applications require processable polymers and therefore, we have developed soluble poly(terthiophene)s with simple functional groups through chemical or electrochemical oxidative polymerization.9 Solutions of these functionalised polymers can be electrospun with up to 10% PEO to give a variety of micro- or nanobres. The functionalised polymers can be further elaborated in solution or as lms with bulky photoactive (e.g. porphyrins) or redox-active (e.g. ferrocene) functionality. This opens the way for the development of a variety of functionalised ICP nanostructures. References (1) Wallace, G. G.; Spinks, G. M.; Kane-Maguire, L. A. P.; Teasdale, P. R. Conductive Electroactive Polymers: Intelligent Material Systems; 2nd ed.; CRC Press: Boca Raton, 2003. (2) Wallace, G. G.; Innis, P. C. Journal of Nanoscience and Nanotechnology 2002, 2, 441-451. (3) Norris, I. D.; Shaker, M.; Ko, F. K.; MacDiarmid, A. G. Synthetic Metals 2000, 114, 109. (4) MacDiarmid, A. G. Synthetic Metals 2001, 125, 11-22. (5) Bognitzki, M.; Frese, T.; Steinhart, M.; Greiner, A.; Wendorff, J. H.; Schaper, A.; Hellwig, M. Polymer Engineering and Science 2001, 41, 982989. (6) Deitzel, J. M.; Kosik, W.; McKnight, S. H.; Beck Tan, N. C.; DeSimone, J. M.; Crette, S. Polymer 2001, 43, 1025-1029. (7) Chen, J.; Burrell, A. K.; Campbell, W. M.; Ofcer, D. L.; Too, C. O.; Wallace, G. G. Electrochimica Acta 2004, 49, 329-337. (8) Wang, C. Y.; Ballantyne, A. M.; Hall, S. B.; Too, C. O.; Ofcer, D. L.; Wallace, G. G. Journal of Power Sources 2006, 156, 610-614. (9) Gambhir, S.; Wagner, K.; Ofcer, D. L. Synthetic Metals 2005, 154, 117-120.
M39 EFFECT OF MOLECULAR WEIGHT ON THE STRUCTURE AND CRYSTALLINITY OF POLY(3-HEXYLTHIOPHENE)
ABSTRACTS
A. Zen, M. Saphiannikova, D. Neher Institute of Physics, University of Potsdam, Am Neuen Palais 10, D-14469 Potsdam, Germany Jrg Grenzer, Institute of Ion Beam Physics and Materials Research, Bautzner Landstrasse 128, D-01328 Dresden, Germany Souren Grigorian, Ullrich Pietsch,
Institute of Physics, University of Siegen, Walter Flex Strasse 3, D-57068 Siegen, Germany Udom Asawapirom, Silvia Janietz, Fraunhofer Institute for Applied Polymer Research, Geiselberg-Str.69, D-14476 Golm, Germany Ullrich Scherf, Macromolecular Chemistry, University of Wuppertal, Gauss-Str.20, D-42097 Wuppertal, Germany Ingo Lieberwirth, Gerhard Wegner Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz, Germany
Recently, two different groups have reported independently, that the mobility of eld-effect transistors made from regioregular poly(3-hexylthiophene) (P3HT) increases strongly with molecular weight. Two different models were presented, one proposing carrier trapping at grain boundaries and the second putting emphasis on the conformation and packing of the polymer chains in the thin layers for different molecular weights.1-3 Here, we present the results of detailed investigations of powders and thin lms of deuterated P3HT fractions with different molecular weight. For powder samples, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) were used to investigate the structure and crystallization behavior of the polymers. The GPC investigations show that all weight fractions possess a rather broad molecular weight distribution. DSC measurements revealed a strong decrease of the crystallization temperature and, most important, a signicant decrease of the degree of crystallinity with decreasing molecular weight. In order to study the structure of thin layers in lateral and vertical directions, both transmission electron microscopy (TEM) and X-ray grazing incidence diffraction (GID) were utilized. These methods show that thin layers of the low molecular weight fraction consist of well-dened crystalline domains embedded in a disordered matrix. We propose that the transport properties of layers prepared from fractions of poly(3-hexylthiophene) with different molecular weight is largely determined by the crystallinity of the samples and not by the perfection of the packing of the chains in the individual crystallites.4 1. R. J. Kline, M. D. McGehee, E. N. Kadnikova, J. Liu, J. M. J. Frechet, Adv. Mater. 2003, 15, 1519. 2. A. Zen, J. Paum, S. Hirschmann, W. Zhuang, F. Jaiser, U. Asawapirom, J. P. Rabe, U. Scherf, D. Neher Adv. Funct. Mater. 2004, 14, 757. 3. R. J. Kline, M. D. McGehee, E. N. Kadnikova, J. Liu, J. M. J. Frechet, M. F. Toney, Macromolecules 2005, 38, 3312. 4. A. Zen, M. Saphiannikova, D. Neher, J. Grenzer, S. Grigorian, U. Pietsch, U. Asawapirom, S. Janietz, U. Scherf, I. Lieberwirth, G. Wegner. Macromolecules 2006, 39, 2162.
M40 CONDUCTING POLYMERS AS ACCEPTOR MATERIALS Anna sterholm, Beatriz Meana Esteban, Henrik Gustafsson, Pia Damlin, Tom Lindfors, Carita Kvarnstrm and Ari Ivaska bo Akademi University, Process Chemistry Centre, c/o Laboratory of Analytical Chemistry, Biskopsgatan 8, FIN-20500 bo/Turku Finland
The selection of conducting polymers that are used as electron acceptors is by far not as wide as the range of polymers that are applied as hole transporting layers in different devices. A limiting factor for applying chemically produced conducting polymers with acceptor properties is the material insolubility. In this work we present the electrosynthesis of different n-dopable conjugated polymers on different substrates (Pt, Al). Poly(3,4-ethylenedioxy)thiophene, PEDOT, and Poly(paraphenylene vinylene), PPV, are polymers that both undergo a reversible reduction 1,2 . These polymers are polymerized on top of alumina and their properties as acceptor materials is studied. In order to improve the acceptor capacity of conducting polymers, different types of fused ring systems were investigated. Polymerization of azulene (1), binaphthyl (2) and 2methoxynaphthalene (3) was made in 0.1 M tetrabutylammonium- hexauorophosphate, TBAPF6 solutions of either acetonitrile or nitrobenzene. Electrosynthesis was made on both Pt and on Al-substrates. The charging characteristics were studied by cyclic voltammetry and by in situ Attenuated Total Reection-Fourier Transform Infrared Spectroscopy, ATR-FTIR.
OCH3
1 2
C. Kvarnstrm, H. Neugebauer, A. Ivaska, N.S. Sariciftci, J. Mol. Struct. 521 (2000) 271-277. P. Damlin, C. Kvarnstrm, H. Neugebauer, A. Ivaska, Synth. Met. 123 (2001) 141-148.
M41 IN SITU ESR-UV/VIS/NIR SPECTROELECTROCHEMICAL STUDY OF THE OLIGOMER FORMATION: THIOPHENETHIOPHENE VERSUS Phenyl-Phenyl Coupling in 2-(Diphenylamino)-Thiophenes
IFW Dresden, Institute of Solid State Research, Department of Electrochemistry and Conducting Polymers, D-01069 Dresden, Germany; b Slovak University of Technology, Faculty of Chemical and Food Technology, Department of Physical Chemistry, SK-812 37 Bratislava, Slovak Republic;
ABSTRACTS
Peter Raptaa,b, Olaf Zeikac,d, Dirk Rohdea, Horst Hartmannc and Lothar Dunscha
Dresden University of Technology, Institute of Applied Photophysics, D-01062 Dresden, Germany; d New address: Novaled GmbH, Tatzberg 49, D-01307 Dresden
It is of general importance in modern electrochemistry that in situ spectroelectrochemical studies are a prerequisite to get a well established mechanism for the formation of oligomers and polymers in a doped and conducting state. Here the oxidation of several 2-diphenylamino-substituted thiophenes and N,N-bis(2-diphenylamino-5-thienyl)-substituted phenylene-1,4-diamines with a different substitution pattern in the 5-position of their thiophene moieties has been studied by cyclovoltammetric and spectroelectrochemical measurements (ESR, UV/vis/NIR). These measurements reveal both the structure of the oligomeric products obtained and that of their cationic intermediates including the pathway of their formation and follow-up reactions. Thus, the formation of the radical cations in the rst electrochemical oxidation step of the target molecules has been demonstrated. Depending on the substitution pattern these radical cations give rise to several consecutive processes to a different extent. Thus radical dimers, dehydrodimers with a 2,2-bithiophene, 3,3-bithiophene, or benzidine structure as well as radical-monocationic and dicationic products can be formed. For N,N-bis(2diphenylamino-5-thienyl)-substituted phenylene-1,4-diamines rather stable radical cations and dications were primarily formed and unambiguously proved. These species were transformed into 2,2-bithiophene dimers and oligomers, as far as the 5-postion in the thiophene moieties are non-substituted. By in situ spectroelectrochemistry the inuence of the substituents on the type of the oligomer formed can be demonstrated and followed in detail.
M42 ELECTROCHEMICAL POLYMERIZATION AND SPECTROSCOPIC CHARACTERIZATION OF POLY(PARAPHENYLENE) IN IONIC LIQUIDS P. Damlin, C. Kvarnstrm, and A. Ivaska Process Chemistry Group, Laboratory of Analytical Chemistry, bo Akademi University, Biskopsgatan 8, 20500 bo-Turku pdamlin@abo.
Two different ionic liquids, 1-Butyl-3-methyl-imidazolium tetrauoroborate (BMIMBF4) and Butylmethylpyrrolidium bis(triuoromethylsulfonyl)i mide (MeBuPyrrBTA) have been used as electrolyte medium in the electrochemical polymerization of poly(paraphenylen) (PPP). This polymer has been studied in great detail in different aprotic organic media and in media with acidic character. The aim of this work was to determine the effect of the ionic liquids on the electropolymerization and charging-discharging processes of PPP. In order to obtain polymer formation from biphenyl water has to be strictly avoided. Ionic liquids show air and moisture stability which should be an advantageous media in the electropolymerization reaction of biphenyl. Cyclic voltammetry and in situ attenuated total reection Fourier transform infrared (ATR-FTIR) spectroscopy has been used as characterization techniques. M43 FREE RADICAL SCAVENGING AND ANTIOXIDANT PROPERTIES OF CONDUCTING POLYMERS Paul A. Kilmartin, Marija Gizdavic-Nikolaidis, Zoran Zujovic, Ralph P. Cooney, Jadranka Travas-Sejdic and Graham A. Bowmaker Polymer Electronics Research Centre, Department of Chemistry, The University of Auckland, Private Bag 92019, Auckland, New Zealand Conducting polymers are potentially useful for a range of applications in which they will come into contact with biological tissues. These applications include articial muscles, in drug release, nerve regeneration and as scaffolds for cell attachment. The radical scavenging properties of antioxidants consumed in the diet are often assessed by their ability to react with stable free radicals such as 1,1-diphenyl-2-picrylhydrazyl (DPPH). In the present study the free radical scavenging and antioxidant properties of several intrinsically conducting polymers has been monitored by electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopy. Commercially available soluble polyaniline and polypyrrole were found to be efcient and rapid scavengers of DPPH radicals in solution, as monitored by the time decay of the DPPH EPR signal after addition of the polymer to the DPPH solution. Further experiments using solid polyaniline samples, in the partially oxidized or fully reduced state, using solid-state 13C NMR (CP MAS = cross-polarization magic angle spinning; NQS = non-quaternary suppression; CPPI = cross-polarization phase inversion) NMR spectroscopy showed that the polyaniline was oxidized through its interaction with DPPH radicals. EPR measurements show that this is accompanied by a decrease in the polaron concentration in the polymer [1, 2]. A quantitative study of a 15N-labeled sample of polyaniline by 15N and 13C NMR spectroscopy showed that the imine content of the PANI was increased from 45 to 65% upon reaction with DPPH, and this was conrmed by N1s XPS analysis. The amount of DPPH radical scavenged is about 20 times greater than the amount required to increase the imine content by the amount determined by the spectroscopic analyses, so the identication of a further process is required to account for the high degree of radical scavenging observed [3]. Aniline monomer also reacts with DPPH radicals, but at a much slower rate than polyaniline [1]. EPR spectroscopy reveals the presence of aniline oligomers in the products of this reaction [4].
ABSTRACTS
[1] P.A.Kilmartin, M.Gizdavic-Nikolaidis, Z.Zujovic, J.Travas-Sejdic, G.A.Bowmaker and R.P.Cooney, Synth. Met., 153 (2005) 153-156. [2] Z.D.Zujovic, M.Gizdavic-Nikolaidis, P.A.Kilmartin, J.Travas-Sejdic, R.P.Cooney and G.A.Bowmaker, Appl. Magn. Reson., 28 (2005) 123-136. [3] Z.D.Zujovic, M.Gizdavic-Nikolaidis, P.A.Kilmartin, H.Idriss, S.D.Senanayake and G.A.Bowmaker, Polymer, 47 (2006) 1166-1171. [4] M.Gizdavic-Nikolaidis, P.A.Kilmartin, Z.D.Zujovic, J.Travas-Sejdic, R.P.Cooney and G.A.Bowmaker, Appl. Magn. Reson., 29 (2005) 729-739.
15 N CP/MAS NMR spectra of 15N labeled PANI (A) before, and (B) after reaction with DPPH.
M44 SELF-ASSEMBLY AND SYNTHESIS OF HIGHLY CONDUCTIVE POLYMERS AND OLIGOMERS Richard D. McCullough Carnegie Mellon University, Pittsburgh, Pennsylvania, USA Here will be presented progress on the synthesis and study of living, regioregular polythiophenes. We have developed a new method that gives a living polymerization system that produces extremely well-dened regioregular polythiophenes with precise molecular weights and very low polydispersities (1.2). This method allows for a plethora of new conducting polymer structures to be prepared including end-capped regioregular polythiophenes, block copolymers of different alkylthiophene units, block copolymers of regioregular polythiophenes and structural polymers such as polyacrylates, polyisoprenes, polystyrenes, polyethylene glycols, etc. A series of structural and devices studies will also be presented that show enhanced transistor performance, new trends in the mobility versus structure, new nanowire formation via new self-assembly patterns and trends, and overall improvements in the understanding of conductive polymers.
AFM Images of Self-Assembled Nanowires of Regioregular Polythiophenes of Precise Molecular Weights
AFM Images of Nanowires Formed From a Block Copolymer of Regioregular Polythiophe
M45 ROTOR-STATOR CRYSTALS OF FULLERENES WITH CUBANE: MOLECULAR RECOGNITION AND TOPOCHEMISTRY
S. Pekkera, . Kovtsa, G. Oszlnyia, G. Bortela, E. Jakabb, B. J. Nagyc, I. Jalsovszkyc, K. Kamarsa, G. Faigela Research Institute for Solid State Physics and Optics, HAS, Budapest, Hungary. bInstitute of Materials and Environmental Chemistry, CRC, HAS, Budapest, Hungary. cDepartment of Organic Chemistry, Etvs Lornd University, Budapest, Hungary.
[1] Pekker, S., Kovts, ., Oszlnyi, G., Bnyei, Gy., Klupp, G., Bortel, G., Jalsovszky, I. Jakab, E., Borondics F., Kamars, K., Bokor, M., Kriza, G.,
ABSTRACTS
Fullerenes and cubane form a new family of molecular crystals with rich phase diagrams, unusual dynamics and topochemical activity1. C60C8H8, the rst member of this family is the highest possible symmetry heteromolecular crystal. Its rocksalt lattice consists of octahedrally coordinated fullerene and cubane molecules. Fullerenes do not form a host framework so the structure is stabilized by the interaction between the alternating array of fullerene and cubane molecules: the match of the convex fullerene and concave cubane surfaces, i. e. molecular recognition, maximizes the attraction between these molecules. The increased attractive interaction keeps cubane in the equilibrium position, with the C4 axes oriented parallel to the cell edges. The orientation of fullerenes has no signicant inuence on the molecular recognition because of the incommensurate atomic arrangements of the matching surfaces. Thus, fullerenes can freely rotate in the molecular bearings of the nearest neighbor cubanes. The smooth rotation of fullerene molecules results in the lowest orientational ordering temperature in the family of fullerene-based materials. The alternation of static and rotating components distincts the new fullerene-cubane material from both the orientationally ordered and plastic crystals, and it may be the basis of future molecular motors. Cubane forms similar crystals of rotor-stator characteristics with the fullerenes in the range of C60-C84. The intermolecular interactions, simplied by the high symmetry structures, make possible an effective crystal engineering of this family of materials: the lattice parameters of the new crystals can be designed with high accuracy. Not all rotor-stator phases are cubic: the deviation of C70 and C76 molecules from the spherical shape gives rise to the formation of lower symmetry structures with anisotropic rotation of the fullerene molecules. Substituted cubanes may also form similar molecular crystals with fullerenes. In the rhombohedral crystal of C60-1,4-diethynyl-cubane the acetylene sidegroups are aligned parallel to the c axis and are inserted in the trigonal sites by enlarging their size. In the expanded lattice the inuence of molecular recognition is decreased, allowing uniaxial libration of the cubane units. The family of rotor-stator phases can also be extended to the derivatives of functionalized fullerenes. The unimolecular decomposition of cubane induces an unusual type of topochemical reactions: a thermal single phase copolymerization with the surrounding fullerenes in the crystal lattice. The resulting copolymers form interpenetrating networks, percolating in the primitive cubic sublattices of the precursor crystals. They are high stability polymers which decompose at temperatures above 400 C. Single crystals retain their shiny at faces in the polymerized materials, and even after the partial decomposition.
Tompa, K., Faigel, G., Nature Materials, 2005, 4, 764.
M46 NANOSTRUCTURATION OF ORGANIC SEMI-CONDUCTORS FOR OPTOELECTRONIC DEVICES G. Wantz (a), O.J. Dautel (b), L. Hirsch (a), L. Vignau (a), F. Serein-Spirau (b), J.P. Lre-Porte (b), J.J.E. Moreau (b) and J.P. Parneix (a) (a) Fdration de Recherche CNRS FR2648 Laboratoires PIOM & IXL, Ecole Nationale Suprieure de Chimie et de Physique de Bordeaux, 16 Av. Pey Berland 33607 Pessac Cedex, France (b) Htrochimie Molculaire et Macromolculaire, UMR 5076, Ecole Nationale Suprieure de Chimie de Montpellier, 8 rue de lEcole Normale 34296 Montpellier Cedex 05, France The design of highly ordered molecular materials represents a real challenge in organic electronics in order to match material properties and electronics requirements. Organic light emitting diodes (OLEDs), organic eld-effect transistors (OFETs) and photovoltaic solar cells are the main three promising devices under investigations around the world. This study reports on the use of bis-imido-phenylene vinylene derivatives 1,2 for these applications. Nanostructurations of the organic layers have been observed in several cases and correlated with electronic properties. A rst molecule, named ImPV, has been used in single layer OLEDs to produce greenish light with acceptable performances. The material is deposited by vacuum evaporation. The effect of the substrate temperature during the evaporation process of the light emitting material has been investigated. The substrate temperature have a great inuence on thin lm morphology since a non-amorphous growth is observed. Heating the substrate implies a more ordered lm. Using this technique, molecules of ImPV self-organized in an even layered lm with molecular layers of 1.7 nm-thick, i.e. a tilted single molecule. OLEDs based on heated substrates exhibit enhanced quantum and luminous efciencies and retarded dark-spots growth. Optimising the substrate temperature enabled to reach efciencies of 3.09 Cd/A and 0.7 lm/W which are very promising values for single layer OLEDs. We have also demonstrated that such a nanostructuration in a lamellar layer induces a broadening of the density of exciting states in the semiconductor. Other bis-imido-phenylene vinylene derivatives (ImPVSi), bifunctionalized with silsesquioxane, have also been studied. These compounds are solgel processable. Before the sol-gel process, the formation of a J-aggregation in the solid state of ImPVSi is observed, whereas a H-aggregation is demonstrated on sol-gel processed coatings. Such a nanostructuration induces different electronic behaviours. With the native precursor, high brighness OLEDs have been made. After the sol-gel process, almost no light output is obtained. If used as photovoltaic devices, the sol-gel processed layer, however, exhibit interesting properties.
G. Wantz, O.J. Dautel, R. Almairac, L. Hirsch, L. Vignau, F. Serein-Spirau, J.-P. Lere-Porte, J.J.E. Moreau and J.-P. Parneix, Organic Electronics 7, 38 (2006) O.J. Dautel, G. Wantz, R. Almairac, D. Flot, L. Hirsch, J.-P. Lere-Porte, J.-P. Parneix, F. Serein-Spirau, L. Vignau and J.J.E. Moreau, J. Am. Chem. Soc. In Press (2006)
M47 STRONG ELECTRON-PHONON INTERACTIONS AND ELECTRON PAIRING IN THE PHOTOINDUCED EXCITED ELECTRONIC STATES IN -CONJUGATED MOLECULAR SYSTEMS Takashi Kato and Tokio Yamabe Institute for Innovative Science and Technology, Graduate School of Engineering, Nagasaki Institute of Applied Science, 3-1, Shuku-machi, Nagasaki 851-0121, Japan
ABSTRACTS
Electron-phonon interactions play an essential role in various research elds such as electrical conductivity and superconductivity. In this work, we theoretically investigated the conditions under which the electron-phonon interactions become strong, in view of the phase patterns of the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO). We estimated electron-phonon coupling constants in the photoinduced excited electronic states1-3 (lHOMO-LUMO), in which one electron in the HOMO is promoted to the LUMO, as well as in the monoanions (lLUMO) and monocations (lHOMO) in various nano-sized molecular systems. The estimated lHOMO-LUMO values are much larger than the lLUMO and lHOMO values in molecular systems. For example, in phenanthrene (C14H10), the lHOMO-LUMO value (0.895eV) is much larger than the lLUMO (0.300 eV) and lHOMO (0.215 eV) values. This is because the atomic orbitals between two neighboring carbon atoms which are combined in phase (out of phase) in the HOMO are combined out of phase (in phase) in the LUMO in various -conjugated hydrocarbons. Our predicted characteristics of the electronphonon interactions in the monocations of acenes were recently conrmed experimentally.4,5 We also discussed the condition that the electron-electron interactions become attractive via electron-phonon interactions in the excited electronic states.1-3 We found that the attractive electron-electron interactions can be more easily realized in the excited electronic states than in the monoanions and monocations. This is because the lHOMO-LUMO values are much larger than the lLUMO and lHOMO values, and because the Coulomb pseudopotential * values between electrons are always positive in the monoanions and cations while the * values would be very small in the excited electronic states, in which the total charge is zero (neutral). We
also discussed the relationship between the normal conducting and hypothetical superconducting states in nanosized molecular crystals.1-3 Large lHOMO-LUMO values and small lLUMO and lHOMO values are suitable conditions for the excited electronic states in molecular systems to become metallic and superconducting states. For example, the lHOMO-LUMO value for naphthalene C10H8 (0.795 eV) is similar to that for uoro-naphthalene C10F8 (0.836 eV), however, the lLUMO (0.254 eV) and lHOMO (0.173 eV) values for C10H8 are much smaller than those (0.393 and 0.324 eV) for C10F8. In general, the lLUMO and lHOMO values for uoroacenes become much larger than those for acenes by H-F substitutions, on the other hand, the lHOMO-LUMO values hardly change by such substitutions. Therefore, hypothetical photoinduced superconductivity would be more easily realized in acenes than in uoroacenes. It may be very difcult for photoinduced excited electronic states of molecular systems to exhibit superconductivity because of unstable electronic structures of the excited electronic states and the technological difculties up to now. However, it is worth noting that, in principle, photoinduction can be more effective way for the molecular systems to exhibit high temperature superconductivity than electron and hole doping because the lHOMO-LUMO values are much larger than the lLUMO and lHOMO values and the * values for the excited electronic states are smaller than those for the monoanions and cations. [1] T. Kato and T. Yamabe, (Transworld Research Network, Kerala) Photochemistry and Photobiology; Photochemistry towards novel electronics, edited by Takashi Kato, in press. [2] T. Kato and T. Yamabe, J. Phys. Chem. A, 109, 4804 (2005). [3] T. Kato and T. Yamabe, J. Chem. Phys., 123, 024301 (2005). [4] V. Coropceanu, M. Malagoli, D. A. da Silva Filho, N. E. Gruhn, T. G. Bill, and J. L. Brdas, Phys. Rev. Lett. 89, 275503 (2002). [5] J. L. Brdas, D. Beljonne, V. Coropceanu, and J. Cornil, Chem. Rev. 104, 4971 (2004).
M48 Optoelectronic properties of large area liquid crystalline monodomains W.J. Grzegorczyka, T.J. Savenijea, J.J.P. Valetonb, D.M. de Leeuwc and L.D.A. Siebbelesa
a
Opto-electronic Materials Section, Delft University of Technology, Mekelweg 15, 2629 JB Delft, The Netherlands Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands c Philips Research Laboratories, Professor Holstlaan 4, 5656 AA Eindhoven, The Netherlands
b
Thin lms of 5,5-bis(5-hexyl-2-thienylethynyl)-2,2:5,2-terthiophene (TR5-C6) spin-coated on a rubbed polyimide layer (PI) self organize into large area (~15 cm in diameter) monodomains1. The high degree of structural alignment and the absence of grain boundaries make them particularly interesting for organic eld-effect transistor applications. In the present work we applied =355nm -2 polarized optical absorption (PAS) and electrodeless microwave photoconductivity 10 L- P 8 measurements (TRMC) on TR5-C6 lms with PI rubbed along the short and long side 6 L+ P of the sample (P- and P+, respectively) to reveal the optical and electrical anisotropy L+ P + 4 L-P+ within these layers.
2
From the PAS measurements on P- and P+ it was found that the magnitude of the TR5C6-characteristic absorption peak at 356 nm changes dramatically on varying the angle of the incident light with the substrate and on the light polarization. By analyzing the data we conclude that all TR5-C6 molecules are oriented in one direction and make a tilt-angle of 50 degrees with the substrate, which is in agreement with the X-Ray Diffraction results obtained by van Breemen et al.1
10
-3 8 6 4
L2
PL+
E-
P+ 10 By using the TRMC technique mobile charge carriers induced with a 355 nm laser pulse 8 are monitored on a nano- to mili-second timescale. Note that only mobile charge carriers 1ns 10ns 100ns 1s 10s 100s time (positive and negative) in the direction along the electric eld vector of the microwaves2 are probed. Figure 1 shows the photoconductivity transients for both samples normalized TRMC transients normalized to the optical attenuation to their optical attenuation using polarized laser light parallel or perpendicular to the Figure 1. for each of the four possible experimental congurations, rubbing direction. The results show that although optical absorption is found to be as shown in the insert. L+, L- denote laser polarization, P+, P- the polyimide rubbing direction and E- electric eld highly anisotropic, the measured photoconductivity is almost isotropic. This may be polarization of the microwaves. attributed to the herring-bone3 arrangement of TR5-C6 molecules, which yields similar molecular interactions in the two perpendicular directions in the plane of the sample.
-4
A. J. J. M. v. Breemen, Journal of American Chemical Society 128, 2336-2345 (2006).

2
F. C. Grozema, Advanced Materials 13, 1627+ (2001). H. Zhang, Advanced Materials 12, 1336 (2000).
M49 DESIGN, SYNTHESIS, AND ELECTROCHEMICAL CHARACTERISTICS OF HIGHLY NEAR-INFRARED ABSORBING EMERALD GREEN [60]FULLERENE ACCEPTORS
Long Y. Chiang,a Taizoon Canteenwala,a and Hsing-Ling Wangb

a
Department of Chemistry, University of Massachusetts Lowell, Lowell, MA 0185, USA (Emial: Long_Chiang@uml.edu)
ABSTRACTS
Bioscience Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA
We unexpectly found a new approach toward the synthesis of Emerald Green [60]Fullerene (EFn) compounds in gram-quantity by using hexaanionic C60 intermediate (C606), as a R reagent in one-pot reaction, for attaching 6 addends on one C60 cage. Ultra-high negative R charge density with repulsion among 6 same charges in a close vicinity on the spherical R R R surface of only 10 in diameter makes the chemistry versatile for new derivatives preparation. The nding led to synthesis of dodecaalkylated emerald green fullerenes C60[C(CH3)(CO2Et)2]6 (EF-6MC2) as a new class of C60 hexaadducts exhibiting nearinfrared absorption at 760 ( = 6,632 L/mol-cm) and 850 ( = 12,755 L/mol-cm) nm and named according to their intrinsic green color. X-ray diffraction data analysis of the R R R R heptad EF-6MC4t in a single crystal form allowed us to mark all sp3 cage carbon positions each bound with one di(t-butyl)--methylmalonate subunit. Structurally, formation of a double-triphenylene interconnected all-trans 18-trannulene electronic conguration on R R R : C(CH3)(CO2-t-Bu)2 the fullerene cage was proposed to be responsible for its near-IR absorption. Electrochemical characteristics of highly symmetrical EF-6MC2 molecules in solution substantiated high multielectron accepting capability with a low rst reduction potential in a similar value as that of pristine C60, indicating no reduction of electron accepting capability of the fullerene cage even after functionalization with 6 addends. Coupling of these near-IR optical properties with electron accepting characteristics of the C60 cage may allow the utility of EF-6MCn as n-type photosensitizers in conjunction with the devices addressing near-IR sensing and light energy harvesting, such as broadband photovoltaic cells,
R
(a) Front view
(b) Back view
over 700940 nm.
M50 SELFTRAPPED ELECTRONIC STATES AT JUNCTIONS OF ORGANIC SEMICONDUCTORS. N. Kirova, Laboratoire de Physique des Solides, Universit Paris-Sud, 91405 Orsay, France There is an increasing number of experimental studies of transport properties of unconventional semiconductors: dielectric oxides, molecular crystals, undoped polymers and other synthetic materials as active materials at high electric elds in the geometry of the eld effect transistors (FET). A new experimental dimension comes from the possibility to change carrier concentration under the applied gate electric eld near the junction interface. We consider the conditions to maintain a high volume concentration of the injected charge near the junction interface, the active role of the gate dielectrics, the effects of electron-phonon coupling at the junction. The interaction of the injected electron in the semiconducting layer with the surface phonon modes results in formation of a polaron, located near the interface between the semiconductor and the gate dielectrics. Such a long range interface polaron can exist already for non-polar semiconductors, like molecular crystals and it will be ultimately present in the traditional oxides like SrTiO3. The polaron formation results in substantial growth of the charge carrier effective mass, were diminishing their mobility. The effect is endorsed by the bias electric eld. The existence of polarons shows up in enhanced effective mass, mid-gap states and in pseudo-gap regime in tunnelling experiments. The mobility measured in organic FET is not only the property of specic organic molecule used, but it intrinsically depends on the organic/gate dielectric interface. The pronounced polaronic effects in conducting polymers change drastically the contact properties of these materials with respect to traditional semiconductors. Instead of the usual band banding near the contact interface, new allowed electronic bands appear inside the band gap. As a result the bias electric eld and the injected charge penetrate into the polymer via creation of a soliton lattice, which period changes with the distance from the contact surface. This results in the branching of the band structure. New narrow allowed bands grow inside the original gap, also expanding in their turn. The corresponding band structure is presented at Fig.2. Single electron carriers (polarons) are pulled to the contact area forming induced surface states. In time resolved experiments, e.g. in optically assistant junction formation, the charge injection goes via two steps: (i) fast dynamic process: charge injection and polaron formation; (ii) slow kinetic process: majority carriers - polarons collide and are absorbed into the ground state - providing one more period in the soliton lattice. The minority carriers (polarons of opposite sign) recombine with preexisting solitons reducing their number. The depletion layer is formed via reduction of soliton concentration.
20 15
Polymer
Conduction band Polaron Fermi level Soliton band
10 5
Valence band
5 10 15 20 25
Fig. 1. Single parameter t for the inuence of the gate dielectric on the mobility of the molecular crystal FET. Experimental points are taken from [1]
Fig. 2. Band structure near metal-polymer junction
ABSTRACTS
[1] A. F. Stassen, R. W. I. de Boer, N. N. Iosad, A. F. Morpurgo. Appl. Phys. Lett. 85 (2004) 3899.
M51 HIGH MOBILITY TERTHIOPHENE POLYMER FIELD-EFFECT TRANSISTORS M.N. Shkunov, R. Rawcliffe, D. Sparrowe, M. Heeney, S. Tierney, I. McCulloch Merck Chemicals, Chilworth Science Park, Southampton SO16 7QD, UK Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge carrier mobility, optimised through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. In this work we report the highest eld-effect mobility reported in polymer p-type transistors to date of up to 0.72 cm2/Vs. Devices were based on novel thieno[3,2-b]thiophene liquid crystalline polymer with excellent self-organisation properties conrmed by very strong X-ray diffraction patterns originating from a lamellar-type polymer chain arrangements on a transistor substrate. Optimum molecular packing was found to be in very good agreement with molecular mechanics modelling suggesting very close - stacking distances for conjugated backbones of 3.5. Moreover, the devices were very stable in dry air environment with mobility exceeding 0.1cm2/Vs and ON/Off ratio of 105 for a period of months.
(a)
1
(b)
10
-2
0.1 Vsd=-60V 0.08

1/2 1/2
Heat Flow [W/g]
0.5
10
H29 C14 S S * S S
n
-3
Isd [A]
0.06
-5
C14 H29
10 10
-6
-0.5 0 50 100 150 T [ C]

o
10
200 250 300
-7
0.02 0 -60
10
-8
40
20
-20 Vg (V)
-40
Fig.1 (a) Digital scanning calorimetry (DSC) plot of thieno[3,2-b]thiophene polymer (chemical structure shown in the insert). Phase transitions can be seen at 230 oC and 100 oC on cooling cycle. (b) Field effect transistor transfer characteristics in N2 atmosphere of a device with chanel width W=2000m and channel length L=5m exhibiting a charge carrier mobility of 0.72cm2/Vs. Isd transistor source-drain current, Vsd - source-drain voltage, Vg gate bias.
M52 SPIN DYNAMICS IN ORGANIC LIGHT EMITTING DIODES AND SPIN VALVES F. Wang1, C. G. Yang1, E. Ehrenfreund2 and Z. V. Vardeny1 Physics Department, University of Utah, Salt Lake City, UT 84112, USA 2 Physics Department, Technion-Israel Institute of Technology, Haifa 32000, ISRAEL
1
We have studied the spin dynamics of (i) photoexcited spin polarons in -conjugated polymer thin lms, and (ii) injected carriers into light emitting diodes (OLED); as well as (iii) spin polarized carriers injected from ferromagnetic (FM) electrodes into small molecule lms in spin-valve (SV) devices. (i) For spin polarons in -conjugated polymers we used the technique of cw and transient photoluminescence and photoinduced absorption detected magnetic resonance (PLDMR and PADMR, respectively). We found that the distant pair recombination is an excellent model for describing the spin dynamics at resonance conditions. From the frequency and microwave power dependencies of the spin resonance we inferred the polaron spin-lattice relaxation time and its dependence on the temperature. At moderate light excitation of ~ 500 mW/cm2 we found that the spin-lattice relaxation time in MEH-PPV is of the order of 10 sec; and is temperature independent up to ~250K. In contrast, the spin-lattice relaxation time for triplet excitons sharply decreases with the temperature, and actually is shorter than the triplet lifetime for temperature T > 40K. (ii) The electroluminescence-detected magnetic resonance (ELDMR) technique was employed to study spin dynamics of injected spin-1/2 polarons in OLEDs. We found that the spin lattice relaxation time depends on the injected current density. At low injected current density the spin ELDMR signal in MEH-PPV OLEDs dramatically increases and reach ~25%; consistent with the conclusions drawn previously about the singlet/triplet formation cross-section ratio in polymers using PADMR1,2 as well as OLEDs of Pt-polymers2,3. (iii) The spin dynamics of injected carriers was also studied in small molecule SV devices. We measured the giant magneto-resistance (GMR) in vertical spin valves of LSMO/OSEC/Co4, where LSMO stands for La1/3Sr2/3MnO3 and OSEC is an organic semiconductor such as Alq3 and -NPD. We found that the GMR decreases with the current density, and this can be explained by the phenomenon of Coulomb drag, which was recently advanced for 2D inorganic semiconductors. We also found that the GMR decreases with the temperature and disappears at ~ 200K regardless of the OSEC molecule. This indicates that the LSMO FM electrode is the culprit for the GMR decrease with the temperature5, and points to the direction we should follow for pursuing organic SV devices at room temperature. References
ABSTRACTS
1. M. Wohlgenannt et al., Nature 409, 494 (2001). 2. C. G. Yang et al., Phys. Rev. B 70 241202 (2004). 3. J. S. Wilson, et al., Nature 413, 828 (2001). 4. Z. H. Xiong et al., Nature 427, 821 (2004). 5. D. Wu, et al., Phys. Rev. Lett. 95, 016802 (2005). Supported by the NSF and DOE in the USA.
Isd
0.04
[A ]
10
-4
M53 MAGNETIC EXCHANGE INTERACTIONS AND SPIN DENSITY DISTRIBUTION IN OXAMATO-TYPE SINGLE MOLECULE MAGNETS
Bjrn Bruer1, Tobias Rffer2, Dietrich R. T. Zahn1, and Georgeta Salvan1 1Chemnitz University of Technology, Institute of Physics, Reichenhainer Strae 70, D-09126 Chemnitz; 2Chemnitz University of Technology, Institute of Chemistry, Strae der Nationen 62, D-09107 Chemnitz. Coordination complexes allow the step-wise incorporation of an increasing number of transition metal ions and thereby the variation of the total magnetic moment of the molecule. In this work a series of bis-oxamato type complexes containing three Cu atoms was synthesized to investigate the inuence of the N,N-bridge on the magnetic super exchange interaction within the molecule. As a measure of the magnetic interaction the magnetic coupling constants were determined using Superconducting Quantum Interference Device (SQUID) investigations. The interactions are antiferromagnetic and vary for different N,N-bridges. The magnetic interaction pathway within the molecule depends among others on the electron spin density and the charge density distribution around the paramagnetic centres. The former was determined using Electron Paramagnetic Resonance (EPR) spectroscopy on single crystals. (32 4) % of the spin density was found to be localized on the Cu-N bonds and less than (17 4) % on the Cu-O bonds in the central fragment. A similar trend was estimated for the charge density distribution by comparing the Raman frequencies of stretching vibrations around the central metal ion. The Raman spectra were acquired on powder of structurally isomorphic Cu and Ni complexes.
2+
O N N Cu N O
N Cu O
N O
N Cu N N O
2 BF4-
= N
N ,
N , N
In order to determine the inuence of the side group on the optical properties the molecules were deposited as thin lms onto Si(111) substrates using spin-coating. The Raman and IR spectra of the lms differ negligibly from that of the powders indicating that the molecular structure is preserved during the deposition process. The dielectric functions of the lms were determined using Variable Angle Spectroscopic Ellipsometry (VASE). The line shape and the intensity of the charge transfer transitions around 4 eV depend strongly on the N,N-bridge whereas the d-d transitions at 2 eV are almost not inuenced.
M54 COORDINATION COMPLEXES AS A TOOL FOR MULTIFUNCTIONAL MOLECULAR MATERIALS. Lahcne Ouahab, Kostyantyn S. Gavrylenko, Yann Legal, Olivier Cador, Stphane Golhen Equipe Organomtalliques et Matriaux Molculaires, UMR CNRS 6226 Sciences Chimiques de Rennes, Campus de Beaulieu, 35042 Rennes cedex, France. E-mail : ouahab@univ-rennes1.fr
Developpement of molecular electronics depends strongly on the developpement of functional molecules and molecule-based materials. Therefore, current trends in this last eld include nanoscience, functional single molecules such as single molecule magnets, single chain magnets and single molecule conductor, and multifunctional materials. In particular, designing molecule-based materials, which possess synergy or interplay between two or more properties such as electrical conductivity with magnetism or spin cross-over , is currently a challenging target and it has been attracting great interests from chemists and physicists for both application to devices or for fundamental science. Preparation of paramagnetic transition metal complexes where the redox active ligands such TTFs are coordinated to spin carrier is a very promising alternative to achieve conducting (or superconducting) magnets through interaction between d spins and mobile electrons.1
We present in this contribution a new route for the synthesis of homometallic and heterometallic polynuclear transition metal complexes as well as their crystal structures, cyclic voltametry and magnetic properties.2 The rst trinuclear complexes of this kind are shown in the gure and it constitutes a rst step towards high spin single molecules with redox active ligands 1. L. Ouahab, T. Enoki, Eur. J. Inorg. Chem., 931, (2004) 2. K.S. Gavrilenko, S.V. Punin, O. Cador, S. Golhen, L. Ouahab, V.V. Pavlishchuk, J. Am. Chem. Soc., 127, 12246 (2005).
M55
ABSTRACTS
MUON-SPIN RELAXATION STUDIES OF MOLECULAR MAGNETS SHOWING REDUCED DIMENSIONALITY T. Lancaster1, S.J. Blundell1, M.L. Brooks1, P.J. Baker1, F.L. Pratt2, J.L. Manson3
1
Clarendon Laboratory, Oxford University Department of Physics, Parks Road, Oxford, OX1 3PU, UK; ISIS Facility, Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX, UK 3 Department of Chemistry and Biochemistry, Eastern Washington University, Cheney, WA 99004, USA
2
We present the results of muon-spin relaxation (m+SR) studies of low-dimensional molecular magnets. These materials are self-assembled, polymeric compounds formed C + z n1 Cz 2 Cz n Cz 1 Cz 3 through bridging paramagnetic cation centres (such as Cu2+) with organic building k Hb k Hb k Hb k Hb carrier blocks (or ligands). Many materials of this kind possess low-dimensional (i.e. 2D, 1D h or even 0D) structural motifs and correspondingly display low-dimensional magnetic e-h p air k re(sing let) 0 n properties. The extent to which a material k re(triplet)=0 N represents an ideal low-dimensional system may be parameterised by the temperature A at which it undegoes a transitions to a state of 3D long range order (LRO), although PVC z Cz 1 an unambiguous experimental determination of the existence of LRO is often Figure 1 M olecular structure of poly( N - problematical. Recent theoretical studies using the stochastic series quantum Monte 1 vinylcarbazole) and a spin conservative hole hop s Carlo method show that for very anisotropic low-dimensional spin systems the entropy change at the critical temperature due to the onset of LRO is so small that it may make along a quasi -one dimen sional lattice mo del for an undetectable contribution to the measured specic heat. Other experimental methods photo carrie r ge nerat ion. are hampered by the reduced ordered moments displayed by many quasi-1D and 2D materials. In contrast, m+SR is uniquely sensitive to very small magnetic moments and provides unambiguous evidence for magnetic order in the form of a coherent precession of the muon-spin. We have therefore used the m+SR technique on a number of anisotropic materials to probe the crossover to a regime of 3D LRO which is invisible to other techniques. We present here results from m+SR measurements on examples of anisotropic molecular systems. We also discuss our measurements on novel uorinated molecular magnets where m+-F dipole-dipole coupling results in a distinctive m+SR signal. The existence of this coupling presents us with an inherently quantum mechanical process that allows the determination of the muon site and a singular insight into its local magnetic environment. These results demonstrate that muons may prove a particularly valuable tool for future studies in this eld.
A
-
site-1
site-2
site-3
site-n
k Hf
k Hf
k Hf
k Hf
k dis
P. Sengupta, A.W. Sandvik, and R.R.P. Singh, Phys. Rev. B, 68, 094423, 2003
M56 GIANT MAGNETORESISTIVE EFFECT AT ROOM TEMPERATURE OF PHOTOCONDUCTIVE POLY(N-VINYLCARBAZOLE) FILM Tadaaki Ikoma, Toshinari Ogiwara, Yutaka Takahashi, Kimio Akiyama and Shozo Tero-Kubota Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aobaku, Sendai 980-8577, Japan Electron spin is a subject of study that is attracting interest in the modern technology of organic electronics. It is recognized, for example, that the triplet state plays an important role in the efcient emission from electro-luminescent materials.1) Also, there has been a renewal of interest in the spin effect in photoconductors.2) Using time-resolved electron spin resonance3) and magnetic eld effect4) experiments, we have studied the carrier generation mechanism of electron acceptor (A)-doped poly(N-vinylcarbazole) (PVCz) thin lms. It has been concluded that the photocarrier is generated by stepwise hole hops on a quasi-one dimensional lattice model in which the hole transfers among the nearest carbazole (Cz) sites while holding the electron spin angular momentum as shown in Figure 1. From the comparison between the magnetic and electric eld effects on the carrier generation yield, it is pointed out that the magnetic eld can more effectively inuence the dynamics of short distance electron-hole (e-h) pairs than the electric eld.5) This property reminds us that the magnetic eld interacting with the spins of e-h pairs may effectively control the photoconductivity in aromatic polymer lms. Recently, for the rst time, the magnetic eld enhanced conductivity (decreasing magneto-resistance (MR)) has been observed in photoconduction via the triplet exciton while the photoconductivity via the singlet exciton was eliminated by the external magnetic eld.6) Based on these facts indicating that the photoinduced geminate e-h pair plays an important role for the carrier generation that determines the carrier number, in this paper, we investigated the dopant dependence of the MR of the PVCz amorphous lm and observed giant MR effects under atmospheric condition for the rst time.
ABSTRACTS
References [] M. A. Baldo, M. E. Thompson and S. R. Forrest, Nature, 403 (2000) 750; M. Wohlgenannt, K. Tandon, S. Mazumdar, S. Ramasesha and Z. V. Vardeny, Nature, 409 (2001) 494; J. Kalinowski, M. Cocchi, D. Virgili, V. Fattori and P. Di Marco, Phys. Rev. B, 70 (2004) 205303; . Mermer, G. Veeraraghavan, T. L. Francis, Y. Sheng. D. T. Nguyen, M. Wohlgenannt, A. Khler, M. K. Al-Suti and M. S. Khan, Phys. Rev. B, 73 (2005) 205202. [] K. Okamoto, N. Oda, A. Itaya and S. Kusabayashi, Chem. Phys. Lett., 35 (1975) 483; E. L. Frankevich, A. A. Lymarev, I. Sokolik, F. E. Karasz, S. Blumstengel, R. H. Baughman and H. H. Hrhold, Phys. Rev. B, 46 (1992) 9320; J. Kalinowski, J. Szmytkowski and W. Stampor, Chem. Phys. Lett., 378 (2003) 380. [] T. Ikoma, M. Nakai, K. Akiyama, S. Tero-Kubota and T. Ishii, Angew. Chem. Int. Ed., 40 (2001) 3234; T. Ikoma, K. Akiyama and S. Tero-Kubota, Phys. Rev. B, 71 (2005) 195206. [] F. Ito, T. Ikoma, K. Akiyama, Y. Kobori and S. Tero-Kubota, J. Am. Chem. Soc., 125 (2003) 4722; F. Ito, T. Ikoma, K. Akiyama, A. Watanabe, and S. Tero-Kubota, J. Phys. Chem. B, 109 (2005) 8707; ibid., 110 (2006) 5161; T. Ogiwara, T. Ikoma, K. Akiyama and S. Tero-Kubota, Chem. Phys. Lett., 411 (2005) 378. [] F. Ito, T. Ikoma, K. Akiyama and S. Tero-Kubota, J. Phys. Chem. B, 109 (2005) 7208; F. Ito, T. Ikoma and S. Tero-Kubota, Photochemistry, 36 (2005) 20. [] T. Ikoma, F. Ito, T. Ogiwara, K. Akiyama and S. Tero-Kubota, Chem. Lett., 34 (2005) 1424. Agranovich, V.M. et al., Excitons and optical nonlinearities in hybrid organic-inorganic nanostructures, J. Phys.: Condens. Matter 10, 9369-9399 (1998). S. Sadofev, S. Blumstengel, J. Cui, J. Puls, S. Rogaschewski, P. Schfer, Yu. G. Sadofyev, and F. Henneberger, Growth of high-quality ZnMgO epilayers and ZnO/ ZnMgO quantum well structures by radical-source molecular beam epitaxy on sapphire, Appl. Phys. Lett. 87 (2005) 091903.
M57 TOWARDS MOLECULAR SPINTRONICS Stefano Sanvito School of Physics, Trinity College, Dublin 2, Ireland The ability to manipulate electron spin in organic molecular materials offers a new and extremely tantalizing roadmap towards spin electronics, from both the fundamental and the technological point of view. This is mainly due to the unquestionable advantage of weak spin-orbit and hyperne interactions in organic molecules, which leads to the possibility of preserving spin-coherence over times and distances much longer than in conventional metals or semiconductors. Here we demonstrate theoretically that organic spin valves, obtained by sandwiching an organic molecule between magnetic contacts, can exhibit a large bias-dependent magnetoresistance and that this can be engineered by an appropriate choice of molecules and anchoring groups. Our results are obtained with a combination of state-of-the-art non-equilibrium transport methods and density functional theory, which we implement in the code Smeagol (http://www.smeagol.tcd.ie) We will show that although the magnitude of the effect varies with the details of the molecule, large magnetoresistance can be found both in the tunneling and in the metallic limit. Moreover the use of uneven current/voltage electrodes can open the possibility to correlate molecular rectication with spin-selectivity.
M58 CHARGE TRANSPORT IN POLYMER BASED SOLAR CELLS - PAUL W. M. BLOM
M59 CURRENT-VOLTAGE CHARACTERISTICS UNDER ILLUMINATION COMPARISON TO ABSORPTION AND EXTERNAL QUANTUM EFFICIENCY SPECTRA OF ORGANIC SOLAR CELLS Wassim Hojeij, Roshanak Radbeh, Bernard Ratier, Andr Moliton Universit de Limoges, Facult des Sciences et Techniques, CNRS, UMR 6172, Institut de Recherche XLIM, Dpartement MINACOM, 123 Av Albert Thomas, 87 060 Limoges Cedex, France Organic solar cells are intensively studied as an alternative to inorganic devices because of their potentially low coast and ease of fabrication. These organic solar cells are based on active layer with polymer or small molecule donor-acceptor couple in order to separate the photogenerated electronhole pairs. Planar and bulk heterojunction structures are commonly studied and recently 5 % power conversion efciency challenge has been reached both in the case of polymer3,4 or small molecule5 bulk heterojunction cells. In our laboratory organic solar cells based on small molecules are obtained by physical vapor deposition. Several studies have been already held in order to compare active layer morphology of planar, bulk and multilayer heterojunction6. We have shown in the case of phthalocyanine-C60 and phthalocyanine-perylene DA couples that bulk heterojunction structures can be obtained by evaporating subsequently very thin DA bilayers (multilayer structure) that give rise to an effective interpenetrated DA network provided evaporation parameters are observed. Nevertheless a mismatch between power conversion efciency extracted from I(V) curves under illumination and external quantum efciency (EQE) spectra can be noticed for the different structures. This might be due to the change of active layer absorption occurred by the vacuum evaporation experimental conditions (growth rate), which give rise to different molecular orientations. In this presentation , absorption and external quantum efciency spectra of the cells will be compared with the I(V) curves taken with different light intensities. In some examples studied it will be seen that high absorption correlated low EQE in the same spectral domain can be related to low shunt resistance in the resulting device, indicating electron-hole recombination in active layer.
M60 HIGH-EFFICIENCY POLYMER SOLAR CELLS USING SOLUTION-BASED Titanium Oxide Optical Spacer Kwanghee Lee1,2, Jin Young Kim1,2, Sun Hee Kim1, Alan J. Heeger2 Department of Physics, Pusan National University, Busan 609-735, Korea 2 Center for Polymers and Organic Solids, University of California at Santa Barbara, Santa Barbara, CA 93106, USA
1
Abstract Polymer solar cells are promising potential sources of renewable energy. Low cost plastic solar cells with high power conversion efciency would have major impact on the needs of our society.1 In this work, we report a new architecture for high efciency polymer solar cells introducing a new concept of optical spacer with new material.2 By implementing a novel solution-based titanium oxide (TiOx) layer between the active layer and the electron collecting Al electrode, we invented a way to increase ~50% in power conversion efciency compared to conventional polymer solar cells. The new devices exhibit ~6% power conversion efciency, which is the highest value reported to date for a polymer based photovoltaic
ABSTRACTS
cell. The TiOx layer increases the efciency by modifying the spatial distribution of the light intensity inside the device, thereby creating more photogenerated charge carriers in the bulk heterojunction layer.
1. W. Ma, C. Yang, X. Gong, K. Lee, A. J. Heeger, Adv. Func. Mater. 15, 1617 (2005). 2. J. Y. Kim, S. H. Kim, H.-H. Lee, K. Lee, W. Ma, X. Gong, A. J. Heeger, Adv. Mater. 18, 572 (2006).
M61 SOLAR CELLS OF LOW-BANDGAP POLYFLUORENES
Mats R Anderssona, Wendimagegn Mammoa, Lars Lindgrena, Erik Perzona, Johan Bijlevelda, Fengling Zhangb, Xiangjun Wangb, Abay Gadisab, Shimelis Admassieb and Olle Ingansb.
a b
Polymer Technology, Department of Chemical and Biological Engineering, Chalmers University of Technology, SE-412 96 Gothenburg, Sweden Biomolecular and Organic Electronics, (IFM), Linkping University , SE-581 83 Linkping, Sweden
In the search for high efciency polymer solar cells our efforts have, during several years, been concentrated on preparing and testing new lowbandgap materials. The polymers in question have been specically designed to be used in solar cells, something which require materials with high mobility of charges. In order to full this prerequisite, we have chosen to work with polyuorenes. However, the most common polyuorenes have relatively large bandgaps and we have therefore synthesized a number of different polyuorenes with extended absorption to cover the important parts of the solar emission. To decrease the bandgap, our strategy has been to prepare polymers based on planar conjugated segments with internal electron donor-acceptor-donor functions in between the uorene groups. One of the earlier prepared alternating polyuorene copolymers (APFO) has an onset of absorption at 980 nm (1.27 eV) and the obtained power conversion efciency for this polymer together with a fullerene derivative is 0.69% under simulated solar conditions. Several new polymers with increased molecular weight and tuned HOMO and LUMO position have been synthesized and evaluated. Preliminary results show a total power conversion efciency of 2.2% and an onset of photocurrent generation at 800 nm (1.55 eV) for one of the polymers in combination with PCBM, see Figure 1. The polymer synthesis, polymer properties, device structure, and device characteristics will be presented. Figure 1. Polymer structure and photocurrent action spectra at low light intensity.
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M62 EFFICIENT VACUUM DEPOSITED ORGANIC SOLAR CELLS WITH HIGH PHOTOVOLTAGE BASED ON A NEW LOW-BANDGAP OLIGOTHIOPHENE AND FULLERENE C60 Peter Buerle,*a Eduard Brier,a Egon Reinold,a
a
Kerstin Schulze,bChristian Uhrich,bRico Schppel,bKarl Leo,bMartin Pfeifferb Department of Organic Chemistry II, University of Ulm, Albert-Einstein-Allee 11, D-89081 Ulm, Germany; Email: peter.baeuerle@uni-ulm.de
b
Institute for Applied Photophysics, TU Dresden, D-01069 Dresden, Germany
Organic solar cells offer the possibility to produce solar cells on exible substrates such as plastic foils using exclusively cheap materials and lowtemperature processing technology. However, before they can be commercially used, it is necessary to increase their power efciency by developing materials with optimized absorption spectrum, energy levels and transport properties. Currently, the best efciencies of around 5% have been reported for heterojunction cells using either a phthalocyanine (e.g. CuPc1) or polythiophene (e.g. P3HT2) as donor (D) and a fullerene derivative as acceptor (A). In both cases, exciton separation at the heterointerface is very efcient, but the cells reach photovoltages below 0.6 V which is only around one third of the optical gap energy. The reason for this is in both cases a too low ionization energy of the donor leading to signicant energetic losses upon exciton separation. Here, we report the synthesis of a series of acceptor-capped oligothiophenes up to a heptamer leading to novel conjugated A-D-A systems. Investigation of the optical and electrochemical properties clearly revealed the inuence of the acceptor groups on the HOMO/LUMO levels.
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ABSTRACTS
Efcient organic solar cells based on a heterojunction between the acceptor-capped oligothiophene as donor (D) and fullerene C60 as acceptor (A) were fabricated by evaporation techniques. The cells reach photovoltages up to 1.0 V, which is due to the fact that in comparison to ordinary oligothiophenes the acceptor moieties lower the band gap and increase the ionization energy as determined by photoelectron spectroscopy. The most efcient solar cells reaching 4.3% power efciency at 118 mW/cm simulated sunlight are obtained when the photoactive heterojunction from the corresponding pentamer and C60 is embedded between a p-doped hole transport layer (HTL) on the anode side and a combination of a thin exciton blocking layer and Al on the cathode side. While the open circuit voltage is almost independent of the choice of the HTL material, the ll factor sensitively depends on the ionization energy and doping level of the HTL. 1. 2. J. Xue, B. P. Rand, S. Uchida, S. R. Forrest, Adv. Mater. 2005, 17, 66. F. Padinger, R. S. Rittberger, N. S. Sariciftci, Adv. Funct. Mater. 2003, 13, 85.
M63 HOW TO BUILD AND MODEL EFFICIENT NANOSTRUCTURED ORGANIC SOLAR CELLS BY JEAN MICHEL NUNZI
M64 STRUCTURAL MODIFICATION OF SINGLE WALL CARBON NANOTUBE WITH 2-(2-THIENYL)ETHANOL AND ITS APPLICATION IN POLYMER SOLAR CELLS
1
Bruno S. Lomba, 1Mauro A. Soto-Oviedo, 1Paulo R. R. Meira, 1Carlos R. D. Correia, 2F. N.Paschoal, 2A. P. Santos, 2Clascdia A. Furtado and 1Ana F. Nogueira E-mail: anaavia@iqm.unicamp.br Laboratrio de Nanotecnologia e Energia Solar - Instituto de Qumica Universidade Estadual de Campinas UNICAMP, CEP 13084-971, CP
6154, Campinas, Brazil. 2Laboratrio de Nanomateriais - Centro de Desenvolvimento da Tecnologia Nuclear - CDTN\CNEN, CEP 31270-901, Belo Horizonte, Brazil INTRODUCTION The search for chemical compatibility and solubility properties of single wall carbon nanotubes (SWNT) in polymer matrix has attracted much interest in developing modication or functionalization of their surfaces. Such modications have been concentrated in the open ends, exterior walls and interior cavity of the SWNT and are expected to play an important role in the mechanical and electronic properties of the nanotubes. The photovoltaic effect in organic solar cells based on conducting polymers can be signicantly improved by the introduction of SWNT, which act as an electron acceptor.1,2 The establishment of an internal electric eld in the composite promotes the exciton dissociation, contributing to the increase in the number of charge carriers, which are transported through the SWNT with minimal loss until the appropriated electrode. This work presents the structural modication of SWNT with 2-(2-thienyl)ethanol and its application with poly(3-octhylthiophene) (POT) in a bulk heterojunction organic solar cell. The modication of SWNT with the thiophene results in much more homogeneous lms and cells with improved performance. RESULTS AND DISCUSSION POT was successfully synthesized by the oxidation of the monomer with FeCl3 in chloroform. SWNT samples were modied by the introduction of carboxylic groups through the reaction with HNO3/H2SO4 (50/50 v/v) under stirring for 2 hours (SWNT-COOH). Afterwards, SWNT-COOH samples were treated with SOCl2 and in the sequence with 2-(2-thienyl)ethanol. The product (SWNT-TIOF) was washed with water to remove the excess of the thiophene and dry under vacuum. SWNT, SWNT-COOH, SWNT-TIOF and POT were characterized by UV-Vis, Infrared, Raman and uorescence spectroscopy and electrochemistry. According to the Raman spectra (Figure 1a), the pristine SWNT samples present a diameter of the 1.40 nm. The most important bands are the radial breathing mode in 160 cm-1, D band in 1310 cm-1, G band (graphitic) in 1575 cm-1 and G band in 2630 cm-1. The chemical modication with 2-(2thienylethanol) promotes a partial broken of the system, increasing the structural disorder of the SWNT veried by the raise in relative intensity of the D band in comparison to the G band. The presence of the thiophenic group was conrmed by the appearance of a new band in 1410 cm-1, assigned to the C=C stretching mode of the thiophene ring. The uorescence data shows the quenching of the excited singlet state of the POT after the introduction SWNT-TIOF (Figure 1b). The cyclic voltammetry of the nanocomposites also shows that after SWNT addition, a decrease in the POT oxidation potential is observed. Both data conrm an excited and ground state interaction between the SWNT and the conducting polymer.
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Figure 1: (a) SWNT-TIOF and SWNT Raman spectra (b) POT and POT/SWNT-TIOF uorescence spectra.
ABSTRACTS
Photovoltaic devices were assembled in the following conguration: Al|heterojunction|ITO; where the heterojunctions are the pristine polymer, SWNT/POT and SWNT-TIOF/POT. The devices fabricated with SWNT-TIOF/POT, presented a short circuit current (ISC) of 0.65A/cm2 and VOC > 0.6 V. The results are much higher than the devices using the pristine POT or SWNT/POT without modication. Although the photocurrent values are still low, efforts are in progress in our laboratory to improve device contacts, deposition conditions and SWNT content in the nanocomposite. ACKNOWLEDGEMENTS
Fapesp, Fapemig, CNEN ,CNPq and CAPES for nancial support. REFERENCES [1] Kymakis, E.; Amaratunga, A.G.J. Appl. Phys. Lett., 2002, 80, 113. [2] Guldi, D. M.; Rahman, G. M. A.; Zerbett, F.; Prato, M. Acc. Chem. Res., 2005, 38, 871.
M65 ULTRAFAST PHOTOINDUCED INSULATOR-TO-METAL SWITCHING AND COHERENT PHONON IN 1/4 FILLING BEDT-TTF BASED SALTS.
1,2 Shinichiro Iwai, 3Kaoru Yamamoto, 1Akimitsu Kashiwazaki, 1Fukiko Hiramatsu, Hideki Nakaya, 3Kyuya Yakushi, 4Hiroshi Okamoto, 5Hatsumi Mori. 1 Tohoku University, Sendai980, Japan, tel:+81-22-795-6423, Fax:+81-22-795-6425, s.iwai@sspp.phys.tohoku.ac.jp 2PRESTO-JST, 3University of Tokyo, 4Institute for molecular science, 5Institute for solid state physics, Tokyo University 1
Photo-induced insulator to metal (I-M) transition in 3d transition metal compounds have been a promising candidate for a new principle of ultrafast optical switching1). Another target of photoinduced I-M switching is an organic conductors with strong electron correlation (SCE)2). Realization of a sensitive / ultrafast response and a systematic study on a non-equilibrium dynamics in SCE materials are expected. In the present study, we have investigated a near- and mid-IR (0.1-1 eV) optical responses due to a photoinduced melting of a charge ordering (CO) in -(BEDT-TTF)2(RbZn)(SCN)4 (-Rb) and -(BEDT-TTF)2I3 (-I3) by femtosecond pump-probe spectroscopy. Fig. 1(a) show the polarized reectivity spectra of -I3 for normal (black curves) and perpendicular polarization (gray curves) to molecular stack (a axis). Figure (b) show differential spectra (RM-RI)/RI, where RM and RI respectively represent the reectivity of the metallic and the CO insulator phase. Transient reectivity (R/R) spectra at 20 K are shown in Fig.1 (c). Excitations were produced using a pump pulse (Eex= 0.89 eV) with polarization perpendicular to the molecular stack. It is noticed that the R/R spectra measured at 0.1 ps for both polarizations are analogous to (RM-RI)/RI for the respective polarizations. This demonstrates that an isotropic melting of CO occurs immediately after photoexcitation. Ultrafast optical responses and critical bahavior of photogenerated metallic state in -Rb and -I3 will be discussed. Hydrostatic pressure effect on the ultrafast dynamics will be also described. 1) S. Iwai et al. Phys. Rev. Lett. 91,057401(2003). 2) M .Chollet et al. Science 307, 87(2005).
Fig. 1
M66 AN ULTRAFAST AND STEADY-STATE EMISSION STUDY OF STYRYL-SUBSTITUTED TERTHIOPHENES: TUNING FROM A ,* TO A CHARGE-TRANSFER EMITTING STATE Tracey M. Clarke,1 Keith C. Gordon,1 Wing Sum Chan,2 David Lee Phillips,2 and David L. Ofcer.3
1. Department of Chemistry and MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, PO Box 56, Dunedin, New Zealand 2. Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong S. A. R.., P. R. China 3. Nanomaterials Research Centre and MacDiarmid Institute for Advanced Materials and Nanotechnology, Massey University, Private Bag 11222, Palmerston North, New Zealand
R
styryl-substituted terthiophenes studied.
The emission properties of a series of 3-[E-2-(4-R-phenyl) ethenyl]-2,2:5,2-terthiophene species (Figure
ABSTRACTS
Oligothiophenes have proven to be useful components in organic electronic devices such as organic light emitting diodes and photovoltaic cells. Advancing the understanding of organic semiconductors may allow a more rational design of these molecules, thereby enhancing the efciency of the resultant devices. The creation and behaviour of excitons is of particular importance in this regard. In order for efcient conductivity in photovoltaic cells to occur, charge separation of the excitons that form upon photoirradiation S S is necessary. It is therefore of interest to examine the excited state properties of oligothiophenes and, in S particular, oligothiophenes that have been substituted with groups possessing a strong electronic inuence, where the resultant spatial separation of the frontier molecular orbitals may aid charge separation of the Figure 1. Generalised structure of the excition.
1, where R = -H, -OMe, -NH2, -CN, -NMe2, -NO2) have been examined and compared to unsubstituted terthiophene. Picosecond time-resolved and solvent-dependent steady-state uorescence studies have been performed in conjunction with density functional theory (DFT) calculations in order to improve the understanding of their excited state structures. The emission studies revealed that alteration of the electronic nature of the para group on the phenyl ring from inert -H to the strongly electron donating -NMe2 causes signicant modications to the excited state properties, with a change in the emitting state from a ,* to a charge transfer state. This conclusion is supported by density functional theory calculations, which show that the nature of the frontier molecular orbitals also changes along the series. The frontier MOs are delocalised over both the styryl and terthiophene moieties for those molecules possessing ,* emitting states while spatially partitioned MOs are present for those molecules with charge transfer emitting states.
M67 VOLTAGE-INDUCED INFRARED ABSORPTION FROM THE FIELD-EFFECT TRANSISTOR BASED ON TCNQ Yukio Furukawa1, Junji Kawaguchi1, Yoshinobu Hosoi1, Ken Tsutsui2, Yasuo Wada2 Department of Chemistry, School of Science and Engineering, Waseda University, Shinjuku-ku, Tokyo 169-8555, Japan 2 Nanotechnology Research Laboratory, Waseda University, Shinjuku-ku, Tokyo 162-0041, Japan
1
Organic eld-effect transistors (OFETs) have made impressive progress over the past ten years because of their potential applications in exible devices. In the OFETs carriers induced by the application of a gate voltage are strongly associated with the electric properties of the devices. Thus, it is important to study carriers in the OFETs for the purpose of elucidating their working mechanism. It is well known that TCNQ exhibits mixed valence in molecular complexes. Infrared spectroscopy is very useful in studying carriers injected into the organic layer in OFETs. In this paper, we have observed voltage-induced infrared absorption from the OFET with n-Si, SiO2, and TCNQ as a gate electrode, an insulator, and a semiconductor, respectively, by infrared difference spectroscopy. The drain current voltage characteristics have indicated that TCNQ behaves as an n-type semiconductor. Saturation behaviours have been observed in the characteristics. From the observed saturation currents, the electron mobility has been obtained to be 1.4 104 cm2/Vs. Some positive bands have been observed in the gate-voltage induced FT-IR spectrum. These bands have been attributed to negative carriers. They have been formed by the application of the plus gate bias. The gate-voltage-induced 2157-cm1 band is attributable to the CN stretching vibration due to negative carriers, whereas TCNQ gives rise to the 2226-cm1 band. The wavenumber 2157 cm1 is almost the same as that of the radical anion of TCNQ in the literature. Thus, an electron injected is localized on one TCNQ molecule. The intensity of the 2157-cm1 band is proportional to the applied gate bias, which is consistent with the prediction based on a simple capacitor model. Infrared absorption induced by the application of a drain voltage has been also studied. The decreases in carrier number have been observed by the application of plus drain voltages. These decreases are associated with the saturation of the drain currents observed in the transistor characteristics. We have demonstrated that infrared spectroscopy is a powerful tool for studying carriers in OFETs.
M68 INTERACTING POLAR CHROMOPHORES: STANDARD AND UNCONVENTIONAL EXCITONIC EFFECTS Francesca Terenziani,a Mireille Blanchard-Desce b
b a Dipartimento di Chimica GIAF, Universit di Parma and INSTM-UdR Parma, Parco Area delle Scienze 17/a, I-43100 Parma, Italy Synthse et ElectroSynthse Organiques (CNRS, UMR 6510), Institut de Chimie, Universit de Rennes 1, Campus Scientique de Beaulieu, Bt 10A, F-35042 Rennes Cedex, France
Nonlinear optical properties of chromophoric dimers made up by polar and polarisable chromophores are investigated theoretically and experimentally, demonstrating strong unconventional excitonic effects, beyond the standard Heitler-London approximation. An example of theoretical predictions is shown in Figure 1, where the two-photon absorption (TPA) spectrum of chromophoric dimers is reported as a function of intermolecular distance and of relative orientation.
Figure 1
Figure 2
ABSTRACTS
Strong modulation of the TPA response (position, shape and intensity) is expected by changing the dimer geometry. In particular, the TPA band can be tuned over a range of more than 150 nm by means of the molecular geometry. Moreover, the response of a linear dimer is predicted to be twice as intense as the response of parallel or antiparallel dimers. This effect is remarkable also when compared to the reference monomer: a decrease or increase of the TPA cross section up to about 35% can be attained depending on the molecular arrangement. This suggests that electrostatic interchromophore interactions do affect the TPA response, and that they can be rationally exploited to optimise the desired response (both for TPA enhancement and spectral tuning).1 Theoretical predictions are conrmed by measurements of TPA cross sections of a few chromophoric dimers with respect to the monomeric analogue
(Figure 2). The model allows the observed trends to be explained and the origin of the strong non-additivity of the TPA response of dimers to be explicitly identied. In particular, strongly reduced TPA cross sections (by up to 40% per subchromophore) are observed for dimeric compounds relative to the reference monomeric chromophore. This strong decrease is heavily determined (up to one half) by excitonic effects beyond the Frenkel exciton model and the HeitlerLondon approximation. These effects, which stem from purely electrostatic interactions, lower the nonlinear optical response in the investigated cases, and are expected to enhance the TPA cross section for other supramolecular alignments (Figure 1).1 Electrostatic interactions cannot be overlooked when modelling or investigating highly concentrated and/or conned samples, as are usually needed in many applications. The correct knowledge of their effects can be exploited to guide engineering at the molecular and supramolecular level.
[1] F. Terenziani, M. Morone, S. Gmouh, M. Blanchard-Desce, ChemPhysChem 7 (2006) 685-696.
M69 MULTICOLOURED MICRO- AND NANO-PIXELS OBTAINED BY PLANAR LOCALIZATION OF COLLOIDAL NANOCRYSTALS Luigi Martiradonna*, Tiziana Stomeo*, Antonio Qualtieri*, Luigi Carbone*, Massimo De Vittorio* NNL, National Nanotechnology Laboratories of CNR * ISUFI, Istituto Superiore Universitario di Formazione Interdisciplinare, University of Lecce In this work we show the possibility to obtain fully-customable micro- and nano-pixels by localizing colloidal semiconductor nanocrystals (NCs) trough lithographic techniques. This positioning approach relies on the dispersion of CdSe/ZnS core/shell NCs into a layer of photo- or electrosensitive resist, which is subsequently patterned by means of photolithography or electron beam lithography (EBL), respectively. The demonstration of the effectiveness of this procedure in controlling the position of nanoemitters without modifying their optical properties has been achieved by a single lithographic procedure. Figure 1a shows the photoluminescence map collected on a pattern of a periodic arrays of nanopillars realized by ebeam lithography on a NCs/PMMA layer. Importantly, the possibility to re-align subsequent lithographic steps on the same substrate (as schematically shown in Figures 1b-1g) enables the localization of different colloidal nanoemitters in conning regions, with nanometer resolution. We have therefore positioned stripes of red, green and blue emitting colloidal nanocrystals on a GaAs substrate in subsequent lithographic processes, in order to obtain micrometer pixels. The overall photoluminescence of each pixel results in the sum of the intensities of these chromatic components (as schematically shown in Fig. 1h). By controlling the molar concentrations of the NCs and by varying the geometrical parameters of the localized patterns, we have nely tuned the PL spectrum of these pixels obtaining multicoloured and white emitters, as conrmed by optical analyses.
Fig 1: (a) Photoluminescence emission of PMMA/NCs pillars having a diameter equal to 800 nm and a period of 2 m, exposed to an e-beam lithography process; (b-g) schematic representation of two subsequent localization steps by means of photolithography; (h) scheme of white or multicoloured nanopixels obtained by merging the emission of green, blue and red NCs localized in conning regions.
This technique enables the fabrication of optically pumped coloured displays with very high image denition. Moreover, by using conductive photoresist as hosting matrix, also electrical injection can be explored. The possibility to localize low cost and highly photostable active materials recurring to cheap and wide area processes like photolithography opens the way to the industrial development of this approach.
M70 HIGH EFFICIENCY ORGANIC PHOTOVOLTAICS: FROM MATERIALS TO DEVICE DESIGN David L. Carroll Center for Nanotechnology and Molecular Materials, Wake Forest University, Winston-Salem, NC, USA Our recent reports of 5.2% efcient thin lm polymer solar cells have been based on meso-structured nanocomposite thin lm architectures. These nanocomposites are built with thiophene hosts and a series of nanomaterials organized within the host to provide charge mobility balance, enhanced optical coupling, and broader absorption bands for better spectral overlap with solar sources. In this talk, new data on the morphology of the nanophase and how it may affect the polymers crystal structure will be presented. We show meso-scale order is a result of nonequilibrium thermodynamic considerations and is intimately tied to device performance. Further, such mesostructured order within the nanophase can be created in a number of device architectures. We discuss on such bulk device architectures that capture the radiation more efciently and may allow
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external efciency numbers to greatly exceed current state-of-the-art.
M71 CONJUGATED POLYMERS FOR CORROSION CONTROL: SCANNING PROBE INVESTIGATIONS OF POLYPYRROLE-AL ALLOY INTERACTIONS Dennis E. Tallman,1,2 Jie He,1 Mark B. Jensen,3 Hosup Jung2 and Gordon P. Bierwagen2 Department of Chemistry and Molecular Biology, 2Department of Coatings and Polymeric Materials North Dakota State University, Fargo, ND, USA and, Concordia College, Moorhead, MN, USA
A common corrosion control strategy is to apply one or more layers of a coating to the metal to be protected. Such a coating may simply serve as a barrier between the metal and its environment, retarding the rate at which water, oxygen, and/or ions from the environment reach the metal surface. On the other hand, a coating may function as more than just a barrier, consisting of a material that can interact chemically and/or electrochemically with the metal, altering its corrosion behavior. Such a coating may be called an active coating. For example, coatings containing hexavalent chromium are often used to control the corrosion of aluminum alloys, whereas coatings containing Zn particles are commonly used on steel. Such coatings function through (often complex) electrochemical and/or chemical interactions of the active species (Cr(VI) or Zn) and their reaction products with the metal surface. By this denition, conducting polymer coatings are active coatings. This presentation will focus on the use of polypyrrole coatings for the protection of the Al alloy AA 2024-T3. The principal motivation for this work is the desire to develop active coatings free of Cr(VI), a corrosion inhibitor that likely will be banned due to its toxicity and issues related to safe handling and disposal. The inuence of electrodeposited polypyrrole (doped with 4,5-dihydroxy-1,3-benzenedisulfonate) on the corrosion behavior of AA 2024-T3 is being investigated by various scanning probe techniques, including the scanning vibrating electrode technique (SVET) for mapping local current density, the scanning ion electrode technique (SIET) for mapping local pH, and scanning electrochemical microscopy (SECM) for mapping oxygen distribution above coated substrates. The interaction between the active coating and the underlying metal substrate is (at least in part) based on electrical connectivity between these materials. Unlike iron and its alloys (where the oxide layer is electronically semiconducting), Al and its alloys form a high bandgap (electronically insulating) oxide. Thus, electron transfer through this oxide, either at defect sites or at surface heterogeneities (in the case of the alloys), must occur for these materials to electronically interact. SECM is currently being used to study electron transfer at Al alloy surfaces and the inuence of surface preparation on this important process. Additionally, atomic force microscopy (AFM), conductive AFM (C-AFM) and electric force microscopy (EFM) have been used to characterize the morphology, the surface potential and the conductivity of the polypyrrole coatings on the Al alloys. Selected results and conclusions from these studies will be presented, including an overview of the important issues surrounding the application of conjugated polymers as corrosion control coatings.
M72 ELECTROSPINNING OF POLYCONJUGATED POLYMERS BASED ON POLYTHIOPHENE G. Iardino, A. Bianco, C. Bertarelli, G. Zerbi Politecnico di Milano - Dip. di Chimica, Materiali ed Ingegneria Chimica G. Natta Piazza L. da Vinci 32 - 20133 Milano Among different polyconjugated materials, polythiophenes play an important role since they can reach good electrical properties after chemical doping; moreover they show a good physical and chemical stability and at the same time the level of free charges injected can be maintained for a long time. The possibility to process doped polythiophenes and transform them into brous morphology with submicrometric dimensions, paves the way to several applications in microelectronics (e.g. sensors) or in e-textiles production. In the last few years electrospinning1,2 has become an efcient technique to produce bers of different polymers (also polyconjugated3) with diameters ranging from few m down to 100 nm. We focused our efforts to produce bers of poly-alkylthiophene with electrospinning process4, from a solution at room temperature. In this case, a common polymer, such as poly-ethylenoxyde (PEO), was used as matrix in order to obtain bers with dimensional and geometrical homogeneity: the bers were electrospun from a chloroform solution and they have dimensions lower than one micron without morphological defects. The polymer matrix can be removed by a suitable washing procedure with acetonitrile. In order to increase the electrical conductivity, the bers have to be doped; it can be done at different stages of the production process. Normally after electrospinning, bers are doped with a solution of FeCl3 in acetonitrile, but it is also possible to bring polythiophene to the doped state by introducing FeCl3 doping solution in the polymer/solvent system before the electrospinning process. In a standard electrospinning setup the bers produced turn out to be randomly oriented on the metallic surface where they are collected. Unfortunately unaligned structures are not so useful for the use of bers in devices fabrications in such areas as microelectronics. However electrospinning is a versatile technique and bers could be highly oriented if a collecting system, made up of two parallel metallic surfaces, is used. The effective alignment of macromolecular chains in the bers, is determined by polarized infrared spectroscopy and an average degree of orientation is calculated from dichroic ratios of the characteristic absorption bands especially coming from the backbone vibrations. The results show that the polythiophenes chains are strongly aligned along the ber axis.
References 1. Z. Huanga, Y.-Z. Zhangb, M. Kotakic, S. Ramakrishnab, Comp. Sci. and Tech., 63, 2223 (2003) 2. 3. D. Li, Y. Xia, Adv. Mater., 16, 1151 (2004) N.J. Pinto, A.T. Johnson, A.G. MacDiarmid, et al., Appl. Phys. Lett. 83, 4244 (2003) Submitted
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4.
M73 CONDUCTING POLYMER AND METALLIZED COMPOSITES OF CELLULOSE FIBRES AND WOOD, AND THEIR POTENTIAL
APPLICATIONS James H. Johnston, Fern M. Kelly, Stefanie Neubauer and Thomas Borrmann School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington, New Zealand. Email: jim.johnston@vuw. ac.nz The development of polypyrrole and polyaniline intrinsically conducting polymer composites with the cellulose Kraft bres and wood (pinus radiata) in which the polymer fully coats the bre or wood surface, provide interesting novel hybrid materials that encompass the inherent properties of both precursor components. These include the electrical conductivity and chemical properties, notably redox, of the conducting polymer and the strength, exibility and macro properties of the cellulose bres and wood respectively. The redox properties of the polymer can be used to deposit silver nanoparticles onto the polymeribre or polymer -wood surfaces imparting effective anti-microbial properties to them. The electrically conducting surface facilitates electrochemical deposition of thin metal coatings which retain the underlying morphology of the bres or wood surface. As such, a range of novel products can be developed for new industry and consumer applications. Polymerisation was effected by treating the cellulose bres or wood surface with the pyrrole or polyaniline monomer followed be oxidation with ferric chloride or ammonium persulfate. Residual free polymer was removed by sonication and washing. SEM showed that the polypyrrole comprises nanosize spheres of 100-150nm that are fused together and fully coat the individual cellulose bres or wood surface (Fig. 1). The polyaniline coating is similar with spheres of 50-100nm. The surface morphology of the bres or wood is maintained. UV-Vis spectra show the polyaniline to be in the emeraldine salt form. Electrical conductivities of up to about 10-1 S.cm-1 for bre-polypyrrole composites and up to about 10-2 S.cm-1 for wood-polypyrrole composites were measured. The polyaniline analogues had conductivities about an order of magnitude less. The electrical conductivity facilitated the electrochemical deposition of metals, notably copper, onto the wood surface whilst retaining the surface morphology, thereby producing new metallized wood composite materials (Fig. 2). The chemical redox properties of the polymers enabled the recovery of metal ions, eg. silver, from solution as metal lms or nanoparticles directly onto the composite surface through redox coupling reactions. The silver nanoparticle surfaces exhibited signicant anti-microbial properties when tested against Staphlococcus aureus (Fig. 3).
Fig 1: Polypyrrole surface on a cellulose bre showing the spheres of polypyrrole fused into a coating.
Fig 2: Copper coating on woodpolypyrrole composite showing The morphology of the wood surface.
Fig 3: Anti-microbial effect (clear zones) of Ag nanoparticles.
M74 CONDUCTING POLYMER FIBERS PROCESSED FROM PRECURSOR POLYMER Gregory A. Sotzing,1 Chris Asemota, 1 Jia Choi1 and Manuel Marquez2 Department of Chemistry and Polymer Program,University of Connecticut, Storrs, CT-06269 2 INEST Group, New Technology Research Department, PMUSA, Richmond, VA 23298, USA and Los Alamos National Laboratory, Chemical Science & Technology Division, Los Alamos, New Mexico
1
Conducting polymers (CPs) are nding increasing research interests in areas such as electronic displays, smart sensors, actuators, tissue engineering, nanowires, capacitors, and a host of other current and emerging technologies. But they are generally insoluble and infusible which limits their applications. Among the several approaches attempted to improve their processability, the precursor polymer approach has been found to be very promising. Our group has demonstrated the solid-state oxidative conversion (SOC) of processable precursor polymers to conjugated polymers without compromising their redox function.1 CP bers are of special interest due to their higher surface area and can advance technologies where diffusion is a critical issue. Here, we report the preparation of conductive polymer ber in a controlled way via two different approaches, namely, electrospinning and melt drawing. The electrospinning method is a convenient, inexpensive way to generate bers with submicrometer to tens of nanometers diameter having lengths that can span a few kilometer. We have demonstrated the preparation of nanobers from precursor polymer via electrospinning and their solid-state conversion into welded nanobers exhibiting electrochromic function.2 The alignment of ber could be an important aspect for the construction of electro-optical devices. Here, we report the synthesis of precursor polymers for the preparation of aligned conductive polymer nanobers. These ber mats could nd application in membranes, capacitors, and actuators. Thus far, we have found that this technique is not limited to a specic surface in that we have prepared nanobers on aluminium, gold, glass, indium-doped tin oxide, and poly(ethyl eneterephthalate). Figure 1 is a eld emission scanning electron microscope (FESEM) picture obtained for aligned conductive polymer nanobers. We have further demonstrated the production of conductive polymer bers via melt drawing of the precursor polymer proceeded by conversion to conductive polymer in the solid-state. The precursor polymer demonstrates a Tm of ca. 210C and a decomposition at 400 C, in air.
Figure 1. FESEM image showing a collection of aligned bers in the sub micron diameter range.
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1. 2.
(a) Jang, S.Y.; Sotzing, G. A.; Marquez, M. Macromolecules 2002, 35, 7293. (b) Jang, S.Y.; Sotzing, G. A.; Marquez, M. Macromolecules 2004,37, 4351. Jang, S.; Seshadri, V.; Khil, M.; Kumar, A.; Marquez, M.; Mather, P. T.; Sotzing, G. A. Adv. Mater. 2005, 17, 2177.
M75 ELECTROSPUN NANOFIBERS OF CONJUGATED POLYMERS: MORPHOLOGY, OPTICAL AND STRUCTURAL PROPERTIES Francesca Di Benedetto1, Andrea Camposeo1, Roberto Cingolani1, Dario Pisignano1, Jennifer Atchinson2, Eric Gallo3, Bahram Nabet2,3, and Frank Ko2 NNL, National Nanotechnology Laboratory of INFM-CNR, Dipartimento di Ingegneria dellInnovazione, Universit di Lecce, via Arnesano, I73100 Lecce, Italy 2 Materials Science and Engineering Department, Drexel University, Philadelphia, PA 19104, USA 3 Electrical and Computer Engineering Department, Drexel University, Philadelphia, PA 19104, USA
The realization of one-dimensional (1D) nanostructures (lateral dimension of 1-100 nm) of conjugated polymers would allow interesting possibilities both for fundamental studies of the dependence of the structural and optoelectronic properties on the size and the one dimensional connement, and for applications in electromechanics and nano-optoelectronics. To date, 1D nanostructures of conducting polymers have been realized by polymerisation in nano-porous templates [1], dip-pen nano-lithography [2], self-assembly [3], and electrospinning [4]. Among these fabrication strategies, the last appears the most promising, being simple and inexpensive. The electrospinning process relies on the strong uniaxial deformation of the polymer materials taking place within milliseconds. In this work, we report on electrospun nanobers of different conjugated polymers and investigated the inuence of the spinning process on the morphological (SEM, AFM), optical (PL, Abs) and chemical properties (XRD, FTIR). The electrospun bers of poly[{2-methoxy-5-(2-ethylhexyloxy-,4-(1-cyanovinylenephenylene))-co-{2,5-bis(N,N-diphenylamino)-1,4phenylene}] have a diameter as low as 45 nm. In addition, the resultant bers exhibit a surface morphology with a porous structure characterized by nanoscale domains. This particular surface topography would further increase the surface area, thus strongly favouring applications such as catalysis, ltration, and solar cells. Special attention was paid to the internal structure within the resulting polymeric bers. The remarkable superposition of the FTIR spectra from the native polymer powder and from the electrospun bers indicate well-preserved chemical bonds. The XRD spectra from both samples only displayed an amorphous halo indicating no crystalline microstructure in the electrospun ber. The optical properties of the fabricated nanobers were also determined and compared to those of the native conjugated polymers. The integrated PL spectra did not show variations in either the linewidth or the emission peak wavelength (655 nm) with respect to the native polymers. These results indicate electrospinning as a very promising technique for the realisation of active uorescent polymeric nanobers.
Fig. 1 Scanning electron microscope picture of the electrospun conjugated polymer nanobers.
References [1] M. Steinhart, J. H. Wendorff, A. Greiner, R. B. Wehrspohn, K. Nielsch, J. Schilling, J. Choi and U. Gsele Science 2002 296: 1997 [2] R. D. Piner, J. Zhu, F. Xu, S. Hong and C. A. Mirkin Science 1999 283 661-663 [3] J. Liu, E. Sheina, T. Kowalewski, and R. D. McCullough Angew. Chem. Int. Ed. 2002, 41, 329 [4] D. Li and Y. Xia Adv Mat 2004, 16, 1151-1170
M76 DEVELOPMENT OF TEXTILE BATTERIES FOR EMBEDDED ELECTRONIC GARMENTS. Richard Helmer, Pam Petersen, Michael Mestrovic, Bill Humphries, Martin Prins and Louis Kyratzis. CSIRO Textile and Fibre Technology, PO Box 21, Belmont VIC 3216 Australia
Abstract Wearable energy sources are required to power electronic functionality in garments. The development of safe textile based power sources is explored for simple low powered electronic devices suited to common textile environments. A mechanically re-chargeable Aluminium-Air primary cell redox system was considered to be suitable for close human contact and not require complete sealing from the environment like many other exible power sources. Three sets of material classes suited to fabricating exible textile air cathodes and textile structures were investigated: inherently conducting polymer treated fabrics (CPF), inherently conducting polymer treated metallised fabric (CPMF), and metallised fabric (MF). The constant discharge potential and cell life were assessed as performance indicators for textile design optimisation arising from choice of materials, size, and textile construction. It was found that useful textile based Aluminium-air battery could be constructed from readily available materials: Aluminium (foil), a spacing material (e.g. non-woven scrim fabric), simple electrolyte (e.g. NaCl) and a textile cathode comprising yarns and fabrics, (including coated and/or treated yarns and fabrics). Conducting polymer treated fabric air cathodes gave the highest operational potential, see Figure 1. The conducting polymer electrodes degraded during discharge with possible changes in redox state and loss of dopant leading to increased electrode resistance (increased internal cell resistance), and lower over all cell redox potential. The metallised fabrics had the longest operational and shelf life and were more suited
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to repetitive mechanical recharging. www.conferencepartners.ie The 40x40mm Aluminium-air textile battery capacity was typically 15mAh and comparable to existing commercially prepared exible batteries.
1.0
0.8
CPMF CPF MF
Voltage (V)
0.6
0.4
0.2
0.0 0 100 200 300 Time (mins) 400 500 600
Figure 1. Continuous discharge performance in terms of cell potential with a 2 kOhm circuit of 40x40 mm Al-air textile batteries with three different air cathode fabrics: conducting polymer treated fabric (CPF), conducting polymer treated metallised fabric (CPMF), and metallised fabric (MF).
M77 PROCESSABLE POLYANILINE NANOFIBERS FOR FLASH WELDING, SENSORS AND ACTUATORS Richard B. Kaner Department of Chemistry and Biochemistry and California NanoSystems Institute, University of California, Los Angeles, Los Angeles, CA 90095-1569, USA By modifying the conventional chemical oxidation polymerization of aniline, we have developed two simple approaches to synthesize polyaniline nanobers with diameters tunable from 30 to 120 nm.[1,2,3] The key to producing pure nanobers is to suppress secondary growth that results in agglomerated particles. Both interfacial polymerization and rapidly mixing aniline, oxidant and acid produce pure nanobers.[1,2,3] These processes are template-free and readily scalable. Stable and processable colloids are now available.[4] Polyaniline nanobers exhibit an exceptional photothermal effect in which they instantaneously melt and cross-link upon exposure to a camera ash.[5] This novel ash welding technique can be used to form patterned nanober lms, create polymer based nanocomposites and make asymmetric polymer membranes. These asymmetric structures can act as mechanical actuators (articial muscles) when exposed to strong acids. Polyaniline nanobers are useful in many applications such as resistive-type sensors where their high surface area enable very rapid response times often less than two seconds.[6,7] Polyaniline nanobers can be modied to respond to many different vapors including toxic agents such as hydrogen sulde. The key is using a metal salt such as CuCl2 which reacts with H2S to produce CuS and HCl. This process converts a weak acid (H2S) into a strong acid (HCl), which in turn can be readily detected at very low concentrations. Polyaniline nanobers can be decorated with metal nanoparticles which not only can enhance sensor response but also leads to molecular memory devices.[8] References [1] Huang, J.; Virji, S.; Weiller, B.H.; Kaner, R.B. J. Am. Chem. Soc. 2003, 125, 314. [2] Huang, J.; Kaner, R.B. J. Am. Chem. Soc. 2004, 126, 851. [3] Huang, J.; Kaner R.B. Angew. Chem. Inter. Edition 2004, 43, 5817. [4] Li, D.; Kaner, R.B. Chem. Commun. 2005. 3286. [5] Huang, J.; Kaner, R.B. Nature Mater. 2004, 3, 783. [6] Virji, S.; Fowler, J.D.; Baker, C.O.; Huang, J.; Kaner, R.B.; Weiller, B.H.; Small 2005, 1, 624. [7] Virji, S.; Huang, J.; Kaner, R.B.; Weiller, B.H.; Nano Lett. 2004, 4, 491. [8] Tseng, R.J.; Haung, J.; Ouyang, J.; Kaner, R.B.; Yang, Y.; Nano Lett. 2005, 5, 1077.
M78 HIGH ELECTRON MOBILITY C60 MOLECULE BASED ORGANIC FIELD EFFECT TRANSISTOR Oded Globerman, Olga Solomesch, and Nir Tessler Microelecronic & Nanoelectronic Centers, Electrical Engineering Department, Technion Israel Institute of Technology, Haifa 32000, Israel
We report high mobility (1.5cm2/Vs) electron transporting organic eld effect transistor where the channel material is composed of the C60 molecule. Unlike other reports which utilizes UHV system or hot wall epitaxy to arrive at high electron mobility in C60 we employ standard vacuum sublimation system and rely on careful device preparation procedure. We report the effect of evaporation conditions, different insulator materials (SiO2 and organic polymers) as well as different contact metals.
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r r u 0.01 C
0.005 0 0
(a)
V G S =4V
1 2 3 4 5
Drain Source Voltage (V)
V G S =2V
Figure 1. Output characteristics of C60-FET with Ag Contacts.
Ag
Au
V DS =18V
Figure 2. The sqrt of the source-drain current as a function of gate bias. Note the extrapolated effective threshold voltage for Ag contacts is 1V and for Au contacts is 2.4V
y t i l i b ] o s M V2 / 2 e 1.5 v i t1
O rganic
S iO 2
Figure 3. The electron mobility as a function of gate voltage for two dielectric materials (sio2 and organic
polymer)
TU1 CHARGE DISPROPORTIONATION IN ORGANIC MOLECULAR CONDUCTORS Toshihiro Takahashi Department of Physics, Gakushuin University, Mejiro 1-5-1, Toshima-ku, Tokyo 171-8588, Japan Recently, it has been well established that a charge-ordered (CO) insulating state is one of the typical ground states of quarter-lled correlated electronic systems.1 This is a novel manifestation of Coulomb correlations. It seems almost the only possibility to stabilize an insulating state when a quarter-lled band has no or little dimerization. We will give a brief review of the CO phenomena experimentally conrmed in quarter-lled quasi1D conductors, such as (DI-DCNQI)2Ag and (TMTTF)2AsF6, and 2D-conductors, as the -phase and the -phase BEDT-TTF salts.1 We emphasize that a large charge disproportionation (CD) has already developed in the metallic state above transition; as observed in the -phase salts, (BEDT-TTF)2MZn(SCN)4 (M=Rb, Cs)2 and -(BEDT-TTF)2I3.3 This raises a serious question how such a large CD can be compatible with the metallic transport. Then we touch the recent progress in understanding the low temperature properties of -(BEDT-TTF)2I3. It is well known that this salt has anomalous physical properties exhibiting a variety of ground states; (1) CO metal-insulator transition at ambient pressure, 3,4 (2) narrow-gap semiconducting (NGS) state with extremely high mobility observed under pressure5 and (3) superconductivity under uniaxial strain along a-axis.6 A recent theoretical analysis7 has succeeded to explain all these phenomena on the basis of a unique band model, with band parameters determined experimentally under uniaxial strain.8 Especially, it was found that a noble dispersion of Dirac-cone type plays an essential role in this salt. Important and interesting issues are; whether this is a universal phenomena commonly observed in other similar materials and how the CO and the NGS state are correlated with each other. The iso-structural -I3 salts based on BETS and BEDT-STF molecule have been found to be quite similar to the BEDT-TTF based salt, as far as the transport properties are concerned. We found in these salts that a large CD develops in the metallic region well above the transition as in the BEDT-TTF salt. Finally, we show some more examples exhibiting CD in metallic states; (TMTSF)2FSO39 under pressure and -(BETS)2FeCl4.10 It is interesting to note that a superconductivity is observed in the vicinity of the CD state in these salts as in -(BEDT-TTF)2I3. 1) T. Takahashi, Y. Nogami and K. Yakushi, J. Phys. Soc. Jpn. 75 (2006) 051008-1. 2) R. Chiba, et al., Phys. Rev. Lett. 93 (2004) 216405. 3) S. Moroto, et al., J. Phys. IV France 114 (2004) 399. 4) Y. Takano, et al., J. Phys. Chem. Solids 62 (2001) 389. 5) N. Tajima, et al., J. Phys. Soc. Jpn. 69 (2000) 543. 6) N. Tajima, et al., J. Phys. Soc. Jpn. 71 (2002) 1832. 7) A. Kobayashi, et al., J. Phys. Soc. Jpn. 73 (2004) 3135. 8) R. Kondo and S. Kagoshima, J. Phys. IV France 114 (2004) 523. 9) H. Satsukawa, et al., Synth. Met. 153 (2005) 417. 10) K. Hiraki, et al., to be published
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TU2 PEIERLS COUPLING AND NEUTRAL-IONIC TRANSITION IN TTFCA A. Girlando, M. Masino, A. Painelli Dip. Chimica G.I.A.F. and INSTM-UdR Parma, Parma University, I-43100 Parma, Italy A. Brillante, R.G. Della Valle, E. Venuti Dip. Chimica Fisica ed Inorg. and INSTM-UdR Bologna, Bologna University, I-40136 Bologna, Italy N. Drichko, M. Dressel 1. Physikalisches Institut, Universitat Stuttgart, D-70550 Stuttgart, Germany
Mixed stacking (. . . DADA. . . ) is the main structural motif of 1:1 charge-transfer (CT) salts of organic -electron donors (D) and acceptors (A). In mixed stack crystals, the CT from D to A is along the stack, and yields the ground state ionicity . While CT crystals made by weak D and A yield a quasi-neutral (N, < 0.5) ground state, and generally crystallize in regular stacks with equal intermolecular spacing, strong D and A form ionic (I, > 0.5) stacks. In this case, the crystals are subject to the Peierls instability: the stacks dimerize, with alternating intermolecular spacing, yielding a potentially ferroelectric ground state. Of the highest interest are the few CT crystals at the N-I borderline, which they can cross under a change of temperature or pressure. The corresponding neutral-ionic transition (NIT) imply a complex interplay of both valence and dimerization instability. NIT are 1D collective charge transfers, and are associated to many intriguing phenomena, as the dramatic increase in conductivity and dielectric constant. It has been recently proposed that many of these phenomena can be due to charge oscillation induced by the vibration yielding the stack dimerization, namely, the Peierls mode.1 The Peierls mode is optically active, but its direct identication has been problematic, and only indirect evidence is available.2 We present an extensive investigation the lattice phonon dynamics of the prototype CT crystal undergoing NIT, TetrathiafulvaleneChloranil (TTFCA). A full interpretation of the low-frequency Raman spectra as a function of temperature, combined with Quasi Harmonic Lattice Dynamics (QHLD) calculations, allow us to identify the Peierls modes on the I phase. The direct identication of Peierls modes on the N side has been approached by measuring absolute reectance spectra in the 5-200 cm-1 region. However, the strong coupling with the electronic degrees of freedom prevents an easy interpretation of the spectra. We have calculated the Peierls coupling constants, by using the QHLD eigenvectors, and we have developed a model to calculate the infrared spectra, based on the Peierls-Hubbard Hamiltonian and the modern theory of polarizabity.1 The comparison between computation and experiment yields a full understanding of the role of the Peierls coupling into the peculiar properties displayed by TTF-CA at the N-I borderline. We believe the present approach is extensible to other CT crystals, and provides a signicant advance in the modeling of Peierls coupling in correlated systems. 1. Z. G. Soos, S. A. Bewick, A. Peri, A Painelli, J. Chem. Phys. 120 (2004) 6712. 2. M. Masino, A. Girlando, Z. G. Soos, Chem. Phys. Lett. 369 (2003) 428.
TU3 SPIN-GLASS BEHAVIOR IN THE -TYPE ORGANIC CONDUCTOR T. Nakanishi a, S. Yasuzuka a, H. Yoshino a, H. Fujiwara b,c, T. Sugimoto b,c, Y. Nishio d, K. Kajita d, G.A. Anyfantis e, G.C. Papavassiliou e, Keizo Murata a Department of Material Science, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka, 558-8585, Japan, E-mail : nakanisi@sci.osaka-cu.ac.jp, muratak@sci.osaka-cu.ac.jp b Department of chemistry, Graduate School of Science, Osaka Prefecture University, Osaka 559-8570, Japan c CREST-JST, Saitama 332-0012, Japan d Department of Physics, Toho University, Miyama, Funabashi, Chiba, 274-8510, Japan e Theor. and Phys., Chem. Inst., National Hellenic Res. Found., Athens, 116/35, Greece 5.2
a
-(EDO-S,S-DMEDT-TTF)2(AuCl2)1+y
ABSTRACTS
5.0 polycrystal (10.8 mg) H = 1 T The spin glass-like transition represented by the difference between ZFC (zero eld-cooled) and FC (eld-cooled) in the magnetic susceptibility () was observed in the Q2D organic conductor -(EDO4.8 S,S-DMEDT-TTF)2(AuCl2)1+ y (see Fig. 1(a)). What is remarkable is that the difference in resistivity 4.6 between ZFC and FC was also observed correspondingly to , which is the rst observation in organic FC 4.4 conductors (see Fig. 1(b)). The purpose of the present paper is to show this specic nature of this material (a) together with the data of specic heat, Hall effect, as well as SdH (Shubnikov de Haas) effects. 4.2 By decreasing temperature, the stepwise anomalies were observed in both a and c at TC = 20 ZFC 4.0 K without hysteresis. The step was suppressed by applying magnetic eld accompanied by a slight 9 increase in TC and vanished at 5 T. Since the step-height did not coincide with "TC", this change is not #0402 I // a H // c the transition described in the mean eld theory. We speculate that the lifetime () of itinerant electrons 8 0T becomes longer in magnetic Field. 7 (b) Temperature dependence of around 20 K corresponds to and MR data. Remanent magnetization ZFC is also observed below 20 K. However, it is remarkable that the 20 K transition was not detected in the 6 specic heat measurement. FC The contrasted behavior between FC and ZFC requires some kind of ferromagnetism (F). As 5 5T candidates, canted-antiferromagnetism (canted-AF) or spin-glass (SG) type ground states are discussed. 0.5 T 4 0.1 T Taking into account the result in the specic heat, which ignores the 20 K anomaly, we examined the model for the weakly canted-AF for the former case and diluted spin-glass for the latter case. Based on 0 5 10 15 20 25 30 detailed discussion, diluted spin-glass model is likely [1]. T (K) These conclusion is consistent with Fermi surface area of this salt is 0.23 % of FBZ (1st Brillouin zone) according to very small number of carrier (0.0023 carriers / donor site). This result also favors the view Fig. 1. Temperature dependences of (a) magnetization and (b) resistance. of small number of spins, if the magnetism is originated from itinerant electrons.
[1]
J.A. Mydosh, J. Magn. Magn. Mater. 20 (1978) 237.
TU4 ELECTRON TRANSPORT IN LINKED FERROCENES Laren M. Tolbert*, Yu Li, and Mira Josowicz School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400 (laren.tolbert@chemistry.gatech.edu)
Since the highest occupied molecular orbital in ferrocene is a metal-centered orbital, an examination of the redox potentials in binuclear ferrocene complexes linked by linear unsaturated bridges has emerged as a compelling motif for studying properties of molecular wires. However, the nature of the bridge in facilitating such communication is not a straightforward function of the oxidation potential of the bridge, but rather exhibits a more complex dependence on distance, oxidation potential, and orbital overlap. Since a number of chalcogens, heterocycles, and other moieties are proposed to intimately connect nanostructured materials electronically, an understanding of the nature of such communication is essential. Our approach is to place the redox mediator X between two ferrocenylvinyl groups such that the steric effects are comparable in all cases. We have uncovered some surprisingly effective linkers, as well as others which suppress communication in a counterintuitive fashion.
X
FeII FeIII
X = O, S, NR, PR, Se, O

Fe
II
, R
X
FeIII FeII
TU5 WITH A HIGHLY ONE-DIMENSIONAL Half-Filled Band under Pressure beyond 7 GPa METALLIZATION OF (TTM-TTP)I3
S. Yasuzuka1, Keizo Murata1, T. Fujimoto1, M. Shimotori1, T. Kawamoto2, T. Mori2, M. Hedo3, and Y. Uwatoko3 Department of Material Science, Graduate School of Science, Osaka City University, Osaka 558-8585, Japan Department of Organic and Polymeric Materials, Graduate School of Engineering, Tokyo Institute for Technology, Tokyo 152-8552, Japan 3 Institute for Solid State Physics, The University of Tokyo, Chiba 277-8585, Japan
4
It is theoretically predicted that the ground state of the 1D half-lled system is the Mott insulator at any positive on-site Coulomb interaction, U. In this conference, we demonstrate that the title compound (TTM-TTP)I3 with a highly one-dimensional half-lled band, where TTM-TTP stands for 2,5-bis[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-1,3,4,6-tetrathiapentalene, is almost metallized by the application of pressure beyond 7 GPa using the cubic anvil apparatus.1 Figure 1 shows the temperature dependence of resistivity in (TTM-TTP)I3 under various pressures. The insulating behavior is gradually suppressed with increasing pressure. At 5.7 GPa, the metallic temperature variation appears in the high-temperatures. At 8.0 GPa, the resistivity shows a slight upturn around 22 K. Above 5.7 GPa, the metallic behavior is expressed as ~ T with ~ 0.3 which is much smaller than the expected value of Fermi liquid theory, = 2. The obtained small exponent can correspond to the Tomonaga-Luttinger liquid exponent, K, of ~ 0.8 with the relation, ~ T4K3 . This value is consistent with the standard Hubbard Model, suggesting that (TTM-TTP)I3 is a best ideal material for the Hubbard Model.
2 1 8 6 4
1.7 GPa 2.0 GPa 2.9 GPa 4.2 GPa 5.7 GPa 7.0 GPa 8.0 GPa
2 4 6 8 2
ambient pressure
10
2 0 8 6 4
10
2 -1 8 6 4
10
10
6 8
100
300
[1] S. Yasuzuka et al., J. Phys. Soc. Jpn. 75 (2006) in press.
T (K)
ABSTRACTS
FIG. 1: Resistivity as a function of temperature under various pressures in (TTMTTP)I3.
TU6 HIGH MAGNETIC FIELD STUDIES OF THE FULLY GAPPED CHARGE-DENSITY WAVE SYSTEM (PER)2M(MNT)2 (WHERE M = AU AND PT). Ross D. McDonald,a , J. Singletona, P.A. Goddarda, N.Harrisona, A. Miglioria, E. Akhadovb, M.A Hoffbauerb A.P. Ramirezc and X. Chic. a National High Magnetic Field Laboratory, Los Alamos National Laboratory; b Chemistry Division, Los Alamos National Laboratory; c Bell Laboratories, Lucent Technologies;
In many quasi-one-dimensional organic metals a Fermi-surface instability results in a Charge Density Wave (CDW) state at low temperatures. The (Per)2M(mnt)2 salts, with M = Au and Pt, undergo a CDW transition at 12 K and 8 K respectively, although in the latter it is accompanied by the synchronous formation of a spin-Peierls phase. In both these materials the CDW formation fully gaps the Fermi surface. This combination of a low transition temperature and perfect nesting, provides unique opportunities for high magnetic eld investigation: these fully-gapped CDW systems provide scaled-down analogues of indirect-gap semiconductors, where the electronic bandwidth and bandgap are of the order of meV rather than eV. As a result, experimentally-available magnetic elds have a major effect on the bandstructure: the eld dependence of the thermodynamic gap results from a competition between Landau quantization attening the bands and opening the gap and Zeeman splitting closing it [1]. The zero eld CDW phase is thus destroyed at the Pauli paramagnetic limit, giving way to new ground states. Magnetization measurements, nonlinear charge transport corresponding to depinning of the CDW and narrow-band noise characteristic of the underlying CDW periodicity provide denitive evidence of a new CDW phase in this high eld regime. Finally, Field Effect Transistors (FET) that utilize a CDW material for the conducting channel, offer the promise of new device functionality, such as fast, coherent switching of the ground state [2]. Prototype FET devices fabricated from the (Per)2M(mnt)2 materials will be discussed and preliminary results in high elds presented. [1] Landau quantization effects in the charge-density-wave system (Per)2M(mnt)2 (where M = Au and Pt) R. D. McDonald, N. Harrison, J. Singleton, A. Bangura, P.A. Goddard, A. P. Ramirez and X. Chi Phys. Rev. Lett. 94, 106404 (2005) [2] Quantum coherent switch utilizing commensurate nanoelectrode and charge density periodicities, N. Harrison, J. Singleton and A. Migliori, US patent 60/485,370 (2003). Converted to full patent July 2004.
TU7 CRITICAL POINTS OF SUCCESSIVE TRANSITIONS IN CHARGE-DENSITY-WAVE STATE UNDER MAGNETIC FIELDS R. Yamaguchi, E. Ohmichi, and T. Osada Institute for Solid State Physics, the University of Tokyo Interplay of Zeeman effect and orbital effect of magnetic elds on charge density wave (CDW) state gives rise to rich and complicated phase diagram depending on the eld orientation. In order to clarify the detail of the phase diagram, we have performed surface impedance measurements of -(BEDT-TTF)2KHg(SCN)4 using the tunnel diode oscillator technique under pulsed magnetic elds up to 40T. The inset of Fig.1 shows the surface impedance traces against eld strength at several xed eld orientations. Each kink structure is considered to be a transition between different CDW subphases. From these data, we have constructed a phase diagram as shown in Fig.1. As the magnetic eld is tilted to the conducting plane, several transitions appear separating subphases, then they smear out merging subphases. Therefore, these successive transitions seem to have critical points in the phase diagram. Only a high-eld transition shows no critical point behaviour and can be observed even under the magnetic eld parallel to the conducting plane. To conrm the observed critical point behaviour, we have also studied the CDW instability of the highly anisotropic two-dimensional electron system under magnetic elds by evaluating the non-perturbed density response function (0)(q). As we have reported before, nesting imperfection stabilizes a semimetallic CDW state (CDWy) consisting of many subphases in the eld region between a zero eld CDW state (CDW0) and a high eld metallic CDW state (CDWx). Generally, (0)(q) has multiple peaks, each of which corresponds to a possible CDW subphase. In the CDWy region, when the highest peak switches from one peak to another, the system undergoes the transition into another subphase accompanying a discontinuous jump of the CDW wave vector. As the tilt angle of magnetic elds becomes closer to 90deg, the separation of these two peaks becomes smaller, and nally they merge into one peak (Fig.2). This causes the disappearance of the transition between two subphases, namely, the appearance of the critical point.
TU8 A NEW SERIES OF CONDUCTING ANION RADICAL SALTS, ETME3Z[PD(DMIT)2]2 (Z=N, P, AS, SB) Various Mott-insulating States and their Release under Pressure Reizo Kato1,2 Akiko Nakao,1,2 Akiko Tajima,1 Atsuko Fukaya,1 Jun-ya Eda,3 Masafumi Tamura1,2 1RIKEN, 2-1, Hirosawa, Wako-shi, Saitama 351-0198, Japan 2JST-CREST, 2-1, Hirosawa, Wako-shi, Saitama 351-0198, Japan 3Department of Physics, Toho University, Funabashi, Chiba 274-8510, Japan E-mail; reizo@riken.jp Five conducting EtMe3Z (Z=N, P, As, Sb) salts of the metal dithiolene complex Pd(dmit)2 (dmit = 1,3-dithiole-2-thione-4,5-dithiolate) have been prepared by the air-oxidation of the corresponding 2:1 salts. Their crystal data at room temperature are listed in Table 1. There are three structural types with the space groups, P21/m, P1, and C2/c, all of which are based on a strongly dimerized Pd(dmit)2 unit. The [Pd(dmit)2]2 dimers form a two-dimensional quasi triangular lattice. They belong to the strongly correlated system. At ambient pressure, all of them are Mott insulators where one electron is located on each dimer. The localized electrons exhibit various magnetic behaviors. The EtMe3Sb salt, where the deviation from the regular triangular lattice is small, shows frustrated paramagnetism down to the lowest temperature. The EtMe3As salt with larger deviation from the regular triangular lattice undergoes an antiferromagnetic transition at 23 K. The EtMe3P salt (P21/m) shows a spin-Peierls-like phase transition to a non-magnetic state at 25 K, which is the rst case in a two-dimensional spin system close to the triangular lattice. The EtMe3N salt shows a second-order phase transition to a non-
ABSTRACTS
magnetic state at 85 K and the EtMe3P (P1) salt also shows a second-order phase transition at 73 K. Mechanisms for these second-order transitions consistent with low-temperature crystal structures have not been found out. The application of hydrostatic pressure can release the Mott-insulating state and induce a metallic or superconducting state. The EtMe3P (P21/m) and EtMe3As salts exhibit the superconductivity at 5 K (3.3 kbar) and at 4 K (7 kbar), respectively. It is quite interesting that these two superconducting states would be associated with different types of Mott-insulating states: the spin Peierls-like non-magnetic state and the antiferromagnetic state.
Tabl e 1 Cryst al Dat a of EtMe 3 Z[Pd(dmit) 2 ]2 at roo m temperatu re.

Cation EtMe3N EtMe3P EtMe3P EtMe3As EtMe3Sb Space group P21/m P21/m P1 C2/c C2/c a/ 6.2650(4) 6.3960(3) 7.7810(5) 14.4690(6) 14.5220(5) b/ 36.520(2) 36.691(1) 18.621(1) 6.3790(3) 6.4080(2) c/ 7.7340(5) 7.9290(3) 6.3220(4) 37.328(2) 37.302(1) / 97.246(5) / 108.932(4) 114.302(2) 109.761(4) 96.987(4) 97.365(3) / 84.194(4) V / 3 1673.8(2) 1695.9(1) 853.5(1) 3419.7(3) 3442.6(2) Z 2 2 1 4 4 TU9 HYBRID NANOTUBES, NANOWIRES, AND NANOJUNCTIONS USING -CONJUGATED POLYMERS: CHARACTERISTICS AND APPLICATIONS* J. Jooa, D. H. Parka, S. H. Leea, S. H. Choia, Y. K. Honga, Y. B. Leea, H. J. Kimb, and C. Y. Kimb Korea University, Seoul, Korea and University of Incheon, Korea Hybrid double-walled nanotubes (HDWNTs) of light emitting polythiophene (PT), poly (3-methylthiophene) (P3MT) or poly (3-hexylthiophene) (P3HT), and conducting polypyrrole (PPy), enveloped by ferromagnetic nickel (Ni) or metallic copper (Cu) nanotubes were synthesized through electrochemical method by using nanoporous anodic aluminum oxide (Al2O3) template. From experiments of HR-TEM, SEM, and XRD, we observed the formation of the HDWNTs of the (semi) conducting polymers and Ni or Cu [Fig. 1 (a)]. The thickness of Ni and the PT layers of the PT/Ni HDWNTs was both ~10 nm. The variations of photoluminescence (PL) characteristics including UV/Vis absorption spectra and of the anisotropic remanent magnetization for the PT/Ni and P3MT/Ni HDWNTs were observed due to the hybrid-junction between the -conjugated polymers and the ferromagnetic Ni. Using confocal microscope, the PL of single strand of P3MT/Ni, P3MT, and P3HT nanotube are compared. We also observed the change of the PL peak of the single strand of P3MT/Ni HDWNT comparing with the pristine P3MT or P3HT nanotube [Fig. 1 (b)]. We present the applications of the HDWNTs based on PT and its derivatives to electrical and optical devices. The hetero-nanojunction of -conjugated polymers using poly(3,4-ethylenedioxythiophene) (PEDOT)PPy and PEDOT-PT were fabricated through sequential electrochemical polymerization method based on the Al2O3 template. To discern the formation, structure, and optical properties of the hetero-nanojunctions of the systems, we used SEM, TEM, FT-IR, and UV/Vis spectra. From the I-V characteristic curves, hetero-nanojunctions -conjugated polymer nanowires shows a rectication effect.
Figure 1 (a) HR-TEM image of P3MT/Ni HDWNT and (b) the PL spectrum of single strand of P3MT/Ni HDWNT by using confocal microscope.
TU10 COMBINATORIAL CHEMISTRY OF FUNCTIONALIZED CONDUCTING POLYMERS
ABSTRACTS
C.A. BARBERO, D.F. ACEVEDO, V.C. ORTIZ, J.M. BALACH, D.O. PERALTA, M.C. MIRAS, Depto de QumicaUniversidad Nacional de Rio Cuarto-5800- Argentina E-mail: cbarbero@exa.unrc.edu.ar Conductive polymers could have a variety of applications. The usual way to produce new ICP involves the synthesis or acquisition of a monomer, homopolymerization or copolimerization, followed for detailed study of the polymer properties. Another, less explored, route to produce materials
with varying properties involves post modication of already synthesized, and well characterized, conducting polymers. An alternative approach involves the combinatorial synthesis, coupled to high throughput screening of compounds. The method was initially developed to accelerate the discovery of pharmaceutical compounds [1], and has then been extended to the search of materials [2] and polymers [3]. Several compounds are produced through the reaction of several substrates with several reactants by the same reaction. The method will be illustrated using the reaction of combinatorially synthesized diazonium salts with polyaniline. The reaction for the synthesis of the azo dyes, its conversion into diazonium salts and subsequent reaction with polyaniline is given by Scheme 1:
NH 2 NO 2 /H NH 2 G1 G1
+
N G2 N G2
NH 2
NO 2 /H
N N G1 G2
N 2+ N N N G1 G2 N
P A NI
M odified P A NI
Scheme 1. Reaction pathway of diazonium coupling to polyaniline The effectiveness of the diazonium salts coupling to PANI was tested using FTIR spectroscopy on the products[3]. The optical absorption also changes due to polymer modication. While PANI is insoluble in common solvents, modication of the polymer by azo coupling renders the modied polymer soluble in some solvents, including water aqueous solutions, depending on the functional group incorporated. The conductivity of polymer lms deposited onto PE was also evaluated. It seems that the most important factor in the conductivity change is the size of the group, except for strongly electron withdrawing groups (e.g. NO2) that lower the conductivity by electronic effects. Given the fact that polyaniline is not soluble in common solvents, an important parameter is the polymer solubility. The modication reactions make the polymers soluble in common solvents, even in aqueous solutions [3]. Combinatorial synthesis is a powerful method to produce conductive polymers with novel properties. Using diazonium salt coupling with polyaniline, it is possible to produce modied polymers which are soluble in common solvents and have conductivities in the order of that of polyaniline. Acknowledgements The present work was nanced by SECYT-UNRC, CONICET, FONCYT and Fundacin Antorchas. D.F.A. and D.O.P thanks CONICET and FONCYT for graduate fellowships. V.C.O. and J.M.M thanks EDUMAT for undergraduate fellowships. C.A.B is a permanent research fellow of CONICET References [1] Wilson, S.R.; Czarnik, A.W.; Combinatorial Chemistry, J. Wiley & Sons, Inc., New York, (1997). [2] Jandeleit, B.; Schaefer,D.J.; Powers,T.S.; Turner, H.W. Weinberg, W.H.; Angew. Chem. Int. Ed., 38, 2494 (1999). [3] Brocchini, S.; James, K.; Tangpasuthadol, V.; Kohn, J.; J. Am. Chem. Soc.,119,4553(1997). [4] D.F. Acevedo, M.C. Miras, C. Barbero, J. Comb. Chem., 7,513 (2005).
TU11 SYNTHESIS OF LOW BAND GAP POLY (P-THIENYLENVINYLENE) PTV VIA A SOLUBLE PRECURSOR ROUTE, THE DITHIOCARBAMATE PRECURSOR ROUTE Fateme Banishoeib a, M. Breselge a, J. Manca a,b, T. Cleij a, L. Lutsen b, D. Vanderzande a,b a Hasselt University, Agoralaan Building D, IMO-Chemistry division, B-3590 Diepenbeek, Belgium b IMEC, IMOMEC division, Wetenschapspark 1, B-3590 Diepenbeek , Belgium
Conjugated conducting polymers have been a subject of much interest during the past three decades due to their variety of applications. Because of the presence of -conjugated bonds in the backbone, they have band structures (bandgap) similar to those inorganic semiconductors. Among all the conjugated polymers called PTV has attracted some attention because the electron rich thiophene ring has a positive effect on both conductivity and stability of the polymers. But PTVs poor processibility, insolubility and, non-fusibility due to the rigid backbone has restricted its practical utilization. The use of precursor routes to circumvent the insolubility problem is very common then, a soluble and easily processable, non conjugated precursor polymer is synthesised. We have synthesised PTV polymers via a new developed dithiocarbamate route in a good yield and satisfactory molecular weight. This new precursor route has some advantages: low value of the polymer polydispersity; high absorption maximum values of the conjugated PTV polymer max and therefore high average effective conjugation lengths. All these observations indicate that this new dithiocarbamete precursor route provides a solution for the synthesis of electron rich poly (p-arylene vinylene)s whose synthesis was problematic via the existing precursor routes.
TU12 APPLICATION OF POLYPYRROLE TO FLEXIBLE SUBSTRATES Bjrn Winther Jensena, Noel Clarkb, Priya Subramanianc, Richard J. N. Helmerd, Syed Ashrafa, Gordon G. Wallacef, Leone Spicciag and Douglas Macfarlaneh. aSenior Research Fellow, IPRI; fDirector, ARC Centre for Nanostructured Electromaterials Intelligent Polymer Research Institute, University of Wollongong, Northelds Avenue, Wollongong, 2522 bSenior Research Scientist dResearch Engineer, Ensis Papro, Private Bag 10, Clayton South, 3169 cPost Graduate Student, School of Chemistry, gProfessor, School of Chemistry hProfessor and Head of School, School of Chemistry Monash University, Wellington Road, Clayton 3800.
ABSTRACTS
Abstract Conducting polymers such as polypyrrole may be useful in smart packaging products, provided application methods can be developed that circumvent the insolubility and infusibility of these materials. Experiments were conducted in ve research areas, relevant to the application of polypyrrole to non-rigid substrates. The results suggested that application of polypyrrole from the liquid phase, either by deposition from depleted bulk solution or inkjet printing dispersions, are unlikely to give lms as regular as those produced by vapour phase polymerisation. Using the latter approach, two potential methods of applying patterned polypyrrole lms to non-rigid substrates were studied. The rst used hypochlorite to pattern a continuous lm of polypyrrole, previously applied by vapour phase polymerisation. The second used inkjet printing to apply an oxidant solution, whose pH had been raised by application of a volatile base, to non-rigid substrates. The higher pH reduced corrosion of the print head, increasing the lifetime of printers exposed to oxidative compounds. The base was subsequently evaporated by heating and the dried oxidant used as a template for vapour phase polymerization of polypyrrole. This method gave smooth, shiny and adherent polypyrrole lms on papers and polyester transparency, with high resolution. Using this application technology electrochromic devices with a planar geometry, based on polypyrrole and an ionic liquid, may be produced.
T13 TOWARDS INTELLIGENT MATERIALS APPLICATIONS OF POLYMER COMPOSITES: REINFORCEMENT, OPTICAL ACTIVITY AND ELECTRICAL CONDUCTIVITY Marc in het Panhuis Department of Physical Sciences, the University of Hull, Hull, United Kingdom E-mail: M.Panhuis@hull.ac.uk, Tel: +441482465220, Fax: +441482466410 Electroactive polymers can be engineered at the molecular level to recognise external stimuli, they are conductive and they are capable of localised processing. These are properties which makes them ideal building blocks for intelligent materials1. Carbon nanotubes share many of these characteristics, but are usually hampered by process-ability issues. In this presentation we demonstrate that the combination of polymers and carbon nanotubes into composite materials enhances their functionality, and investigate the suitability (of composites) as building blocks for intelligent materials. The mechanical properties of polymer carbon nanotube composites were enhanced 25 times by intercalation of a water soluble polymer into sheets of carbon nanotubes (Buckypaper)2. A completely soluble and optically active polymer carbon nanotube composite was obtained which could be easily processed into thin lms3. The conductivity of textiles was enhanced by four orders of magnitude using a polymer composite as template material4. In conclusion, polymer composites could aid the development of multifunctional materials useful as building blocks for intelligent materials. 1. G.G. Wallace, G.M. Spinks, L.A.P. Kane-Maguire and P.R. Teasdale, Conductive electroactive polymersIntelligent materials systems, CRC press, (2003). 2. C.J. Frizzell, M. in het Panhuis, D.H. Coutinho, K.J. Balkus, A.I. Minett, W.J. Blau and J.N. Coleman, Phys. Rev. B 72 (2005), 245420. 3. M. in het Panhuis, R. Sainz, P.C. Innis, L.A.P. Kane-Maguire, A.M. Benito, M.T. Martinez, S.E. Moulton, G.G. Wallace and W.K. Maser, J. Phys. Chem. B 109 (2005), 22725. 4. J. Wu, M. in het Panhuis, S.A. Ashraf and G.G. Wallace, in preparation
TU14 HIGHLY ORDERED CRYSTALLINE THIN FILM OF PENTACENE FABRICATED by Controlled Solution Process. Takashi Minakata 1),2), and Yutaka Natsume1),2) Asahi-KASEI Corporation, 2-1 Samejima, Fuji-shi, Shizuoka, 516-8501 Japan OITDA, Tsukuba Laboratory, AIST Central-4, 1-1-1, Higashi, Tshukuba, Ibaraki, 305-8565, Japan Considerable attention has been made for organic semiconductors to develop organic eld effect transistors (FET). Major interests have been focused on printing devices by organic semiconductors, because solution-processed and patterned thin lms have been prepared in an ambient atmosphere with a high production speed. Among many organic semiconductors presented so far, pentacene shows the reproducible largest carrier mobility. In general, thin lms of pentacene can be formed by vacuum deposition method, since the solubility of pentacene in organic solvent is extremely poor. Approach for fabricating thin lms of pentacene by solution process using soluble pentacene precursors has been presented. At the last conference at Woolongong, the authors presented solution-processed pentacene thin lms could be fabricated directly from pentacene solution without using precursor molecules 1). The solution-processed pentacene lms showed highly oriented and highly crystalline structure. It appeared that large platelet-crystals grown in the lms, and it was conrmed that crystalline size of solution-processed lms was larger than that of sublimed lms determined by grazing incidence X-ray diffraction. FETs formed with solution-processed lms exhibited good properties with the eld effect mobility of 0.5cm2/Vs. The authors have studied the both solution-processing conditions of thin lms by a simple drop casting method and the spreading ink in order to improve the lm quality. It turned out that defects such as deposited ne particulate aggregates and cracks in the lm inhibited carrier transport, and the defects could be reduced or eliminated by controlled fabrication conditions. These phenomena could be explained by crystal growth mechanism balanced between diffusion rate determined regime and crystal growth rate determined regime. FETs formed with high quality lms of solutionprocessed pentacene showed large eld effect mobilities above 1cm2/Vs even in bottom contact conguration. Inuences of impurities on both the morphology of the lm and FET performance were studied. Two kinds of coating methods, continuous lm coating and dotted patterned printing were performed. By continuous lm coating, dip-coating where the substrate was dipped perpendicularly to the solution surface, or one-directional coating on horizontally placed substrate, was made. Dotted patterns of pentacene thin lm and FET array of the isolated patterns were fabricated using a dispenser. Performance of the FETs formed with these methods has been studied. High quality pentacene thin lms by controlled solution-process with up-scalable fabrication methods are considered to be a useful tool for a large area lm coating or roll-to-roll processing in the future organic devices. Reference 1) T. Minakata, and Y. Natsume, Synthetic Metals, 153, 1 (2005)
ABSTRACTS
T15 NANOSTRUCTURED CONDUCTIVE POLYMERS FOR SENSING AND MACHINERY APPLICATIONS Itamar Willner Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel (willnea@vms.huji.ac.il)
The integration of Au nanoparticles (NPs)1 or carbon nanotubes (CNTs)2 with polyaniline (PAn) lms associated with electrodes control the redox properties of the polymer and improves the charge transport properties across the polymer. Upon the integration of Au NPs modied with a sulfonate capping layer or CNT functionalized with pyrene carboxylic acid units with PAn, the redox activity of the polymer is shifted to neutral pH values. This originates from the doping of the polymer with negative charges. Chronoamperometric experiments reveal that the Au NPs or CNT increase by 25-fold and 4-fold the rate of oxidation of the polymer lm, as compared to a polystyrene sulfonate doped PAn, respectively. The modied polymers were used as effective matrices for bioelectrocatalysis and electrocatalysis. The Au NP/PAn and CNT/PAn mediate the bioelectrocatalyzed oxidation of glucose by glucose oxidase (GOx). Also, the Au NP/PAn or CNT/PAn matrices were shaped in the form of microrods, and the high surface area of the composites enhanced the bioelectrocatalytic functions of the systems. Composite assemblies consisting of structurally aligned GOx or other enzymes in PAn lms yielded effective electrochemically-active matrices for bioelectrocatalysis.3 A new method for the electrochemically-ordered assembly of semiconductor NPs (CdS) capped with mercaptoaniline on a mercaptoaniline-functionalized monolayer electrodes was developed.4 The resulting aniline dimers, bridging the CdS NPs to the electrode, act as electron tunneling bridges that enhance photocurrent generation. Polyaniline lms associated with microcantilevers act as an electroactive material for the electrochemical activation of the mechanical motion of the cantilever.5 The electrochemical charging of the polymer, upon oxidation, yields a surface stress that stimulates the deection of the cantilever. The electrochemically-driven motion of the cantilever by PAn, together with electrical contacting of GOx by the PAn lm, pave the way to construct autonomous devices for the delivery of insulin. References 1. E. Granot, E. Katz, B. Basnar and I. Willner, Chem. Mater., 17, 4600-4609 (2005). 2. E. Granot, B. Basnar, Z. Cheglakov, E. Katz and I. Willner, Electroanalysis, 18, 26-34 (2006). 3. O.A. Raitman, E. Katz, A.F. Bckmann, I. Willner, J. Am. Chem. Soc., 124, 6487-6496 (2002). 4. E. Granot, F. Patolsky and I. Willner, J. Phys. Chem. B, 108, 5875-5881 (2004). 5. M. Lahav, C. Durkan, R. Gabai, E. Katz, I. Willner and M.E. Welland, Angew. Chem. Int. Ed., 40, 4095-4097 (2001).
TU16 LIGHT-EMITTING AND CHARGE TRANSPORT IN ORGANIC SOLIDS AND MOLECULAR DEVICES Zhigang Shuai, Qian Peng, Shiwei Yin, Hua Geng, Xiaodi Yang, Linjun Wang Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, 100080 Beijing, China zgshuai@iccas.ac.cn Modeling the transport phenomenon in organic materials and molecular devices are important for rational designs. In molecular electronic devices, the mechanism for negative differential resistance (NDR) is still unclear. In a well connected device, the self-energy contribution due to the molecule-electrode interaction would smear out the resonant peak. We show that (i) intermolecular interaction can play important role in the selfassembly monolayer devices [1], and (ii) through intermolecular charge transfer, the switching behavior of NDR can be obtained [2]. We also model the carrier transport in organic solids through Brownian motion coupled with Marcus electron transfer theory and rst-principles. The calculated hole mobility for the newly designed cyclic triphenylamine dimer FET device is 210-2 cm2/Vs, in good agreement with the experiment [3]. For the light-emitting siloles, we found that the electron and hole mobilities are very close each other, indicating the transport is balanced, which enhances the charge recombination rate [4]. Further, we found that for siloles, the aggregation can quench the internal conversion (IC) process, which can effectively enhance the luminescence, in contrast to the usual luminescence quenching [5]. The IC is generally modeled as in a displaced harmonic approximation, neglecting the difference in potential energy surface (PES) between the excited state and the ground state. Recently, we have developed a theory which can describe the IC process by taking into account the difference in PES of the initial and nal states at the Duschinskii rotation level. It is shown that the temperature dependence of IC is very sensitive to the difference in PES [6]. The implications to the electronic functional materials and devices will be discussed. References [1] Hua geng, et al., J. Phys. Chem. B 129, 12304 (2005). [2] Hua geng, et al. submitted. [3] Yabin Song, et al., submitted. [4] Shiwei Yin, et al., J. Phys. Chem. A. 110, 7138 (2006). [5] Gui Yu, Shiwei, Yin, et al., J. Am. Chem. Soc. 127, 6335 (2005) ; Shiwei Yi, et al., Phys. Rev. B 73, 205409 (2006) [6] Qian Peng, et al. submitted.
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TU17 ELECTRICAL BISTABILITY OF SUBSTITUTED BITHIOPHENES: NEW SYSTEMS FOR MOLECULAR MEMORIES A. Biancoa, A. Dundulachia, C. Bertarellia, M. Caironib, D. Natalib, M. Sampietrob, G. Zerbia a Dipartimento di Chimica, Materiali e Ingegneria Chimica b Dipartimento di Elettronica e Informazione Politecnico di Milano, P.za L. da Vinci, 32 - 20133 Milano Italy Organic conjugated materials showing electrical bistability have attracted signicant interest in fabricating memory devices that are able to switch reversibly between two or more states1-3. The two states can be controlled by voltage or current for organic materials to exhibit a high or low resistance state. In this framework we studied oligothiophenes capped with phenol groups (chemical structure in Fig. 1). They have an highly distorted aromatic system because of the large steric hindrance (conrmed by DFT calculations). The molecules can be converted to a less distorted and more conjugated quinoid stable state through a chemical oxidation with PbO2. Both aromatic and quinoid molecules were fully characterized by using electronic spectroscopy and, in particular, vibrational IR and Raman spectroscopy, which is highly sensitive to conjugated materials features. The capability of these molecules to have two stable forms with different electro-optical properties was the starting point to investigate their electrical bistability. 40
30 20 10 0 write -10 -20 -30 -40 -50 -4
erase
3 1 4 2
-2
VAl [V]
Figure 1 Chemical structure of the oligothiophenes studied on the left; a series of 10 consecutive I-V curves showing reversible bistability on the right. In the inset layout of the device structure. Simple vertical devices (Fig. 1) were built: lms (400 nm thick) were spin coated on an ITO substrate, then the Al electrode was evaporated on top. From the currentvoltage characteristics it is clear that the system shows an abrupt change from low to high conductivity when a suitable negative voltage is applied to Al electrode. The conductive state is maintained until a suitable positive voltage is applied. At this point the system turns back to a low conductive state. The two states are clearly discriminated by using a low probing voltage. The mechanism behind this bistability is investigated by using DFT (B3LYP, 6-31G**) calculations and in situ vibrational spectroscopy to trace back the conductivity switching to voltage induced modications of the molecule. 1. 2. 3. Bandyopadhyay, A. J. Pal, Appl. Phys. Lett. 84, 999 (2004). L. P. Ma, Q. F. Xu, Y. Yang, Appl. Phys. Lett., 84, 4908. 2004 J. He, L. P. Ma, J. H. Wu, Y. Yang, J. of Appl. Phys. 97 2005
(a) Type 1
~ 10
(b) T ype 2
TU18 MOLECULAR DESIGN OF HOPPING TRANSPORT IN SELF-ORGANIZED OLIGOSILANES: ANISOTROPY OF CARRIER HOPPING PARALLEL/PERPENDICULAR TO THE MOLECULAR AXIS
~4
H. Okumoto, C. Selvin, Y. Yoshida, M. Misaki, N. Tanigaki, A. Kaito, N. Minami National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 3058565, Japan An oligosilane R(SiMe2)nR (n:Si chain length, R:terminal group) molecule has a Si backbone with delocalized electrons (-conjugation). The molecules show unique carrier transport properties in a self-organized thin lm[1-3], which has a multi-layered structure of almost hexagonally packed molecules[4]. The long axes of capillary-lled molecules align normal to substrates (Fig. 1(a): Type1). Recently, we succeeded in aligning molecular long axes parallel to substrates (Fig. 1(b): Type 2) with a help of friction transferred poly-dimetylsilane thin lms[5]. For Type 1 alignment, a series of peaks in Fig. 2(a), observed by X-ray diffraction (XRD), yields an inter-layer distance that is the same as the molecular length, proving the molecular orientation depicted in Fig. 1 (a). On the other hand, an XRD pattern shown in Fig. 2(b) corresponds to the unit cell length of almost hexagonally packed molecules, proving the orientation of Type 2. Such high molecular orders enable us to measure carrier transport properties parallel [Type 1] and perpendicular [Type 2] to molecular long axes of oligosilanes. For both cases, non-dispersive time-of-ight (TOF) photocurrent waveforms were observed (insets in Fig. 2(a) and (b)). The mobility estimated from the clear transit time is displayed in Fig. 3. The mobility for Type 1 alignment (squares) shows a zigzag increase as increase of the number of Si atoms. This remarkable odd-even effect is explained by hopping distances and the number of highly ordered hopping sites located at the ends of molecules[2]. On the other hand, the mobility for Type 2 alignment (circles), lower than that for Type 1, has a simple linear relationship with the number of Si atoms. Although this dependence seems quite different from Type 1 alignment, we show that it also can be explained by highly ordered hopping sites as proposed for Type 1. The hopping transport in self-organized oligosilanes can be controlled by a molecular design of hopping sites, because molecular length (n) and terminal group (R) of oligosilanes systematically change the hopping distance and the number of hopping sites. In addition, the control of molecular orientation, which alters the hopping direction, can improve the versatility of this approach.
Fig.1: M olecu lar order of self-organ ized oligo silanes san dwich ed be tw een tw o su bstrates wi th e lectrod es: (a) O rient ation of mole cu lar long axe s p erpen dicu lar to su bstrates, (b) pa rallel to su bstrates. (a)T ype 1
(b) T ype 2
10 20 Diffraction angle 2
30
40
(degree)
Fig. 2: X -ray diffraction pa ttern s fo r selforgan ized oligo silanes (M e(SiM e 2)11 Me ) thin film s of Type 1 (a) an d Type 2 (b). Insets: a TO F photocu rren t w avefo rm for each typ e of molecu lar a lignm ent.
2.0 : Type 1 : Type 2 1.5
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1.0
0.5
0.0 9 10 Number of Si 11 12
Fig. 3: M ole cu lar len gth depen den ce o of hole m obil ity at 20 C. ( : Type 1, : Type 2)
References [1] H. Okumoto, et.al., Adv. Materials, 13, 72, (2001) [2] H. Okumoto et.al., Adv.Materials, 15,716, (2003) [3] H. Okumoto, et.al., Synthetic Metals, 153, 297, (2005) [4] T. Yatabe, et.al., Chem. Lett. 799, (1997) [5] N. Tanigaki, et.al., Thin Solid Films, 273, 263, (1996)
TU19 ELECTRICAL CONTROL OF FRSTER ENERGY TRANSFER TO A SINGLE MOLECULE K. Becker, J. M. Lupton, J. Mller, A. L. Rogach, J. Feldmann Photonics and Optoelectronics Group, Physics Department and Center for NanoScience, Ludwig-Maximilians-Universitt Mnchen, Munich, Germany D. V. Talapin, H. Weller Institute of Physical Chemistry, University of Hamburg, Hamburg, Germany
One of the key challenges in driving molecular electronics to the ultimate single molecule limit is the question of interfacing molecular logic circuits to the outside world. Whereas electrical interfacing is desirable in terms of scalability, it is extremely hard to perform reproducibly. In contrast, optical interfacing is comparatively facile and reproducible, but appears to be limited to dimensions of order the wavelength of light, orders of magnitude larger than single molecules. We present a nanoscale hybrid assembly resembling a single molecule eld effect transistor with an electrical gate combined with all-optical source and drain. This approach brings together the best of both worlds as the gate constitutes a large-area electrode, whereas source and drain are addressed optically using single absorbing and uorescent species. The device is based on the combination of two classes of materials, semiconductor nanorods and dye molecules, which join up in nanoscale assemblies whose functional properties arise as a hybrid of the physical nature of the two constituents. Efcient energy transfer from the strongly absorbing nanorods occurs to single dye molecules, providing an antenna pathway for excitation. The nanoparticles focus excitation energy directionally to adjacent single molecules analogous to molecular cascade structures. By introducing a small number of nanoparticles into a lm of dye acceptors we illustrate the feasibility of addressing single emitters in a large ensemble by resonant energy transfer. The approach breaks the diffraction limit in terms of spatial resolution of single molecule excitation, as photopumping of the molecules occurs only in the vicinity of the semiconductor nanoantennae. The efciency of energy transfer from the nanoantennae to the adjacent dye molecule depends on the degree of spectral overlap between nanocrystal emission and dye absorption. By applying an electric eld we employ the exceptional quantum conned Stark effect of rod-like heterostructure nanocrystals1,2 to drive the particle in and out of resonance with a single absorbing molecule. We can therefore use the electric gate to control the strength of energy transfer from the donor (source) to the acceptor (drain). Besides providing a universal route to designing highly efcient nanoscale light-harvesting units to mimic photosynthetic processes, this electrical control of energy transfer illustrates a novel single molecule switch or optical eld-effect transistor. Since the rate of energy transfer sensitively depends on electric eld, local changes in the dielectric environment can be monitored through modications of eld screening and thus energy transfer efciency. Finally, the feasibility of electrically tailoring energy cascade structures offers a route to improving the performance of synthetic light-harvesting complexes beyond that of natural systems. [1] J. Mller et al., Nano Lett. 5, 2044 (2005). [2] J. Mller et al., Phys. Rev. Lett. 93, 167402 (2004).
TU20 FULLERENE-BASED MEMORY DEVICES: STRUCTURAL AND MORPHOLOGICAL STUDIES Jayanta K. Baral1, Himadri S. Majumdar1, Ari Laiho2, J. Ruokolainen2, O. Ikkala2, and R. sterbacka1 1Department of Physics and Center for Functional Materials, bo Akademi, Turku, 20500, Finland. 2Optics and Molecular Materials, Helsinki University of Technology, Espoo, Helsinki, Finland. During past several years, organic memory devices have aroused considerable interest among researchers. Nowadays, paper and plastic based disposable printable memory attracts more attention for its robust device operation and few simple solution processing steps of organic and polymer materials. Since the beginning of this decade, there have been several reports of complicated sandwich structured organic devices showing memory1(a,b). Lately, a new type of organic bistable & multistable devices has been introduced that are simpler in structure and fabrication2. In these devices, the organic semiconductor fullerene (C60) nanoparticles were used as the active medium embedded in an inert polystyrene (PS) matrix and then sandwiched between two metal aluminium electrodes. Electrical bistability in form of switching and multistability in form of negative differential resistance (NDR) has been observed. Different device properties were observed for different concentration of C60 in PS. At lower concentration of C60, the devices showed bistability i.e. switching between ON-OFF states with current ratios more than 104 in some cases. At higher concentration of C60, bistability ceases, but NDR behaviour persisted. With the PS:C60 blend, it was quite difcult to fabricate a device thicker than 100nm without forming aggregates. Inhomogeneity and uncontrolled morphology of PS:C60 lm is the major problem for efcient device output. To overcome the solubility & thickness problem of fullerene, we fabricated similar devices from a fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) instead of C60. PCBM is soluble in most regular solvents. In our case we chose chloroform as the solvent that leads to lm thicknesses varying from 200nm to 750nm without forming aggregates. Film thickness decreased with decreasing concentration of PS for a xed weight ratio of PCBM and PS in the solutions. We observed regular NDR but inconsistent bistability in the devices with less than 500nm of lm thickness. Devices with lm thickness above 500nm showed low conductivity and NDR was absent. Furthermore, to obtain a better lm morphology in terms of controlled intermolecular distances between neighbouring C60 nanoparticles without forming aggregate, we looked into polystyrene-block-poly(4-vinyl pyridine) (PS-P4VP) block copolymer instead of the homopolymer PS. From Transmission Electron Microscopy (TEM) images of C60:PS-P4VP lms, it was revealed that due to phase separation of polystyrene block from the
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pyridine block, an ordered hexagonal arrangement of P4VP in PS and a well-controlled intermolecular distance for tunnelling purpose was observed. We expected similar electrical properties as the C60/homo-polystyrene in these new devices. The NDR was observed in the devices for all weight ratios of C60:PS-P4VP solution, but it was not consistent with varying concentration of C60 in PS-P4VP solution. This irregular NDR behaviour can be attributed to residual lithium ions from anionic vinyl polymerization of PS-P4VP. Memory in the form of bistability and multistability was studied in C60 based device. To fabricate a thicker (>100nm) lm of device fullerene derivative PCBM was used. NDR was observed in devices with wide range of PCBM thickness. PS-P4VP was chosen instead of PS to obtain well controlled lm morphology. Irregular NDR was observed due to lithium ions left during anionic polymerization of block co-polymer. References: 1 L. P. Ma et al, Appl. Phys. Lett, 80, 2297 (2002) (b) L. D. Bozano et al, Appl. Phys. Lett, 84, 607 (2004). 2 H. S. Majumdar et al, Organic Electronics, 6, 188 (2005).
TU21 MAPPING CHEMICAL BOND FORMATION BETWEEN A METALLIC PROBE AND A SINGLE MOLECULE John J. Boland School of Chemistry and the Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Ireland
There is enormous interest in contact formation at the nanoscale. In this talk I present a study that maps out chemical bond formation between a Pt-inked probe and a single 1,3-cyclohexadiene (1,3-CHD) molecule on Si(100). By dening an appropriate tunnelling energy window we separate the mechanical and electronic contributions to the current during the approach to contact and bond formation. I show that there are signicant forces between the probe and the C=C of the molecule and we track the relaxation of the molecule, the emergence of a chemical bond feature in the LDOS and the quenching of specic molecular vibrations during bond formation. Finally, I will discuss the application of this method to surface reaction dynamics.
TU22 STRUCTURAL STUDIES OF CRYSTALLINE MATERIALS INSIDE THE WALL OF CARBON NANOTUBES Malcolm L.H.Green Inorganic Chemistry Laboratory, Oxford University, Oxford OX1 3QR, UK Single wall carbon nanotubes (SWNTs) amay be regarded as atomically sized test tubes (diameter 2-4 nanometres). It has been established that a vast array of inorganic, organic and bioorganic compounds, can be placed inside the SWNT cavity. Enhanced image electron microscopy demonstrates that the nano encapsulated materials may have very different structures from those of the parent bulk materials. The remarkable chemical, physical and mechanical properties of SWNTs have generated proposals for many potential applications of materials containing SWNTs. For most of these systems the empty SWNTs could be replaced with lled SWNTs giving modied properties. The methods for lling emprty SWNTs and the characterization of the structures of materials inside the lled SWNTs using high resolution transmission electron microscopy will be presented. TU23 SPONTANEOUSLY-FORMED SIC NANOFIBERS: CHARACTERIZATION AND APPLICATIONS A. Huczko, H. Lange, M. Bystrzejewski, A. Fabianowska, S. Cudzio, M. Szala, A.T.S. Wee, K.C. Chin Department of Chemistry, Warsaw University, Warsaw, Poland Institute of Chemistry, Military University of Technology, Warsaw, Poland Department of Physics, National University of Singapore,Singapore Inorganic onedimensional nanostructures (carbides, nitrides) are spontaneously and efciently produced via a combustion synthesis carried out in a modied calorimetric bomb. The combustion technique is facile, safe, instantaneous and energy saving technology [1]. We found earlier [2-4] that the reductive dehalogenation of carbon halides with Sibearing reactants results in the formation of SiC nanobers, e.g., CaSi2(s) + (CF2)n(s) CaF2(s) + SiF4(g) + C(s) + SiC(s). Silicon carbide nanobres ca. 20100 nm in diameter with the aspect ratio higher than 1000 were isolated (and further puried) from the products (see gure) resulting from redox reaction between Sibearing compounds (mostly silicides) and perhalogenated hydrocarbons (e.g., Teon), and collected for further examination: XRD, Raman, and SEM/TEM. The optical limiting performance of the nanobres has been evaluated, in comparison to multi-walled carbon nanotubes. Single SiC nanobres have been also tried as a resonant mass sensor [5].
SEM image of SiC nanober-containing products (starting composition CaSi2/Teon) The formation mechanism of 1D SiC could be proposed as V-L-S gasphase reaction of radicals followed by the condensation and growth of nanowhiskers MeSi(s)+ (CF)n(s) SiFn(g)+ CF m(g) SiC(s)+ C(s)+ MeFn(s)+ SiF4(g). We succeeded in synthesizing SiC nanobers via a spontaneous deorination of uorinated carbon with Sicontaining reductants. 1D SiC nanocrystallites can be isolated and purield. Feasible applications of the produced nanostructures include mass sensors and optical limiters. REFERENCES 1. Xiu Z., Liu s., Lu M., Zhang H., Zhou G., Mat. Res. Bull., 2006, 41, 642-646.
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2. Huczko A., Lange H., Chojecki G., Cudzio S., Yan Qin Zhu, Kroto H. W., Walton D.R. M., J. Phys. Chem. B, 107, 2003, 2519-24 3. Cudzio S., Bystrzejewski M., Lange H., Huczko A., Carbon, 2005, 43, 1778-1782 4. A. Huczko, M. Bystrzejewski, H. Lange, A. Fabianowska, S. Cudzio, A. Panas, M. Szala, J. Phys. Chem. B 109, 2005, 16244-51 5. A. Huczko, H. Lange, M. Bystrzejewski, A. Fabianowska, S. Cudzio, M. Szala, A.T.S. Wee, K.C. Chin, A. Katan, A.V.Patil, E. Heeres, T.H. Oosterkamp, XXth IWEPNM, Kirchberg, Austria, 4-11.3.2006, Abstract Book, p. 56 ACKNOWLEDGEMENT This work was supported by the Ministry of Education and Science through the Department of Chemistry, Warsaw University, under Grant No. 3 TO8D 012 28.
TU24 SIMULATED LATTICE RELAXATION OF PHOTOEXCITED PLATINUM-HALIDE CHAINS Jun Ohara and Shoji Yamamoto Division of Physics, Hokkaido University, Sapporo 060-0810, Japan Quasi-one-dimensional halogen (X)-bridged transition-metal (M) complexes, referred to as MX chains, have been attracting much attention for several decades due to there unique properties originating from competing electron-electron and electron-lattice interactions. Substituting the metals, bridging halogens, surrounding ligands, and counter ions, we can widely tune their electronic structure and systematically investigate onedimensional electron-phonon cooperative phenomena. In recent years, binuclear metal analogs, referred to as MMX chains, have been synthesized and vigorously investigated. The direct metal-metal contact leads to various mixed-valent states. These states can be tuned thermally, optically, and by applying pressure. Some of MMX chains exhibit metallic conduction at room temperature. Hence we take more and more interest in solitons and polarons as charge and/or spin carriers. Thus motivated, we theoretically investigate dynamic features of photoproducts in MMX chains in comparison with those in conventional MX chains, calculating a relevant one-dimensional extended Peierls-Hubbard model within a time-dependent Hartree-Fock method. Figure 1 visualizes relaxation processes of a photogenerated excitons into a soliton pair or a polaron pair, where the system is photoexcited at t=0. A self-trapped exciton is dissociated into a charged or neutral soliton pair, while a higher-energy pumped electron-hole pair relaxes into polarons. Employing a variational method as well, we reveal a possible contrast between the soliton relaxation channels of MX and MMX chains.
Figure1: (a), (b), and (c) are respectively, nonlinear lattice relaxation channel connected to charged soliton, neutral soliton, and polaron pairs. In this gure, is frequency of optical phonons, while , and are respectively, bond order (1), net spin density (2), and net charge density (3) on the nth MMX unit at time t.
TU25 AN UNEXPECTED CRYSTALLOGRAPHIC STRUCTURE OF MO6S3I6 NANOWIRES DETERMINED USING ABERRATIONCORRECTED ELECTRON MICROSCOPY Valeria Nicolosi1, Eireann Cosgriff1, Peter D. Nellist1, Stefano Sanvito1, Satheesh Krishnamurthy1, Jeremy Sloan 2, Malcom Green2, Dragan Mihailovic3, Giuseppe Compagnini4, J. David Carey5, Werner J. Blau1 and Jonathan N. Coleman1
1School of Physics, Trinity College Dublin, University of Dublin, Dublin 2, Ireland. 2University of Oxford, Inorganic Chemistry Lab, S Parks Rd, Oxford, OX1 3QR England 3Jozef Stefan Institute, Ljubljana, 1000 Slovenia 4University Catania, Department of Chemistry, Catania, I-95125 Italy 5University of Surrey, Advanced Technology Institute, Guildford, Surrey GU2 7XH England
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Since their discovery MoSI nanowires have attracted a great deal of attention as they have signicant advantages over other one dimensional nanostructures. These include simple synthesis, strong dispersability and processability and uniform atomic structure and hence uniform electronic behaviour. However, very little is still known about these materials. In order to fully understand their properties it is imperative to conrm the atomic structure of those mono-dimensional objects as well as to understand the packing of the nanowires in bundles. Here we present a combined High Resolution Transmission Electron Microscopy (HRTEM) and Aberration Corrected Scanning Transmission Electron Microscopy (STEM) study of Mo6S3I6 nanowires, one of the most promising materials in the family of the MoSI compounds. This allows us to propose a structure for the isolated nanowires and a superlattice packing model for the nanowires in bundles. X-ray photoelectron spectroscopy (XPS) measurements conrm our ndings. Knowledge of the crystalline structure allows us to calculate the electronic structure, conrming the materials metallicity and the nature of their chemical bonds.
TU26 ELECTRON TRANSPORT IN NB4.77TE4 SINGLE CRYSTALS A. Stolovits1, R. K. Kremer2, Hj. Mattausch2, X.-M. Ren2, A. Sherman1, and A. Simon2 1 Tartu likooli Fsika Instituut, Riia 142, EE-51014 Tartu, Estonia 2 Max-Planck-Institut fr Festkrperforschung, Heisenbergstrae 1, D-70569 Stuttgart, Germany
Transition metal chalcogenides form various low-dimensional compounds which show superconductivity and transition to a charge density state.1 We present results of recent investigations on single crystals of Nb4.77Te4. The basic elements of the structure are compressed Nb6Te8 clusters which condense to form innite Nb5Te4 chains. These chains are linked through Nb-Te and Nb-Nb contacts. The compound undergoes a transition to superconductivity at Tc=0.60.9 K.2 Its electronic transport properties in the normal state are studied in the temperature range 1.3270 K and in magnetic elds up to 11 T. In the investigated temperature range the temperature variation of the resistivity is weak (<2%). Nonmonotonic behavior of the resistivity is observed which is characterized by two local maxima at T~2 and ~30 K. The temperature dependence of the resistivity is interpreted as an interplay of weak localization, weak antilocalization, and electron-electron interaction effects in the diffusion and the Cooper channel. The temperature dependence of the dephasing time extracted from the magnetoresistance data is determined by the electron-phonon interaction. The saturation of in the low-temperature limit correlates with Tc of the individual crystal and is ascribed to the scattering on magnetic impurities.2 The research is supported by the Estonian Science Foundation Grant No. 6655. 1 S. Roth and D. Carroll, One-Dimensional Metals (Wiley-VCH, Weinheim, 2004). 2 A. Stolovits,. A. Sherman, R. K. Kremer, Hj. Mattausch, H. Okudera, X-M. Ren, A. Simon, and J. R. OBrien, Phys. Rev. B 71, 144519 (2005).
TU27 FUNCTIONALITY OF MOSIX MOLECULAR NANOWIRES: FROM MAGNETIC MOLECULAR CONNECTORS TO COMPOSITES. Dragan Mihailovic Jozef Stefan Institute and Postgraduate School, Jamova 39, SI-1000 Ljubljana, Slovenia and Mo6 d.o.o. Teslova 30, SI-1000 Ljubljana, Slovenia. Fig.1 MoSIx nanowire structure. Inorganic molecular nanowires with the general formula MoxSyIz exhibit a variety of functional properties in which they display performance which is superior to other one-dimensional nanomaterials1-6. They are easiy to synthesise and purify, and particularly easy to disperse, so they have already been heralded as a serious alternative to carbon nanotubes in a number of applications. In this presentation we will give an overview of the basic properties of MoSIx nanowires, ranging from synthesis, fundamental electronic, mechanical, magnetic and chemical properties to emerging applications in nanoelectronics and biomedical nanodevices. The structure of the individual MoSIx nanowires (Fig.1) is shown to be best described in terms of a one-dimensional polymer Fig.1 MoSIx nanowire structure. composed of a string of rigid Mo-chalcogenide-halide clusters8 joined together by S brides. While their longitudinal Youngs modulus is very high3, these 1D chains are exceptionally weakly bound together into bundles, leading to easy dispersion in a variety of solvents. Unlike carbon nanotubes, the nanowires can be dispersed and functionalised in water and other polar solvents9. The stability of individual wires in air and in solution is conrmed by AFM measurements. The weak lateral bonds between nanowires lead to low sliding friction. This makes them of great potential interest for tribological applications10 and in combination with the exceptional dispersion characteristics useful components of self-lubricating composites. The functional properties relevant for nanoscale device fabrication will be discussed in more detail, particularly dispersion characteristics, functionalisation and attachment to gold particles and self-assembly upon synthesis. DFT calculations8,11 show that MoSIx nanowires are expected to be either metallic, semimetallic or semiconducting, depending on their stoichiometry. The basic stoichiometric compound Mo6S3I6 is calculated to have narrow electronic bands crossing the Fermi energy, with a large density of states at EF. Transport measurements on moly-paper, pressed pellets and single bundles all reveal similar variable-range-hopping behaviour, suggesting localisation of carriers occurs on undoped NWs. Calculations also suggest remarkable nonlinear mechanical, electronic and magnetic properties arising from the bistability of the S bridges11,12. Of particular interest is the coexistence of a local moments and metallic longitudinal conductivity. The S atoms at the ends are found to attach readily to gold nanoparticles and thiolated proteins, opening the way to high-yield self-assebly of comlex molecular circuits. We wish to acknowledge EU projects NANOTEMP and DESYN-IT. References 1 A. Remskar, M., Mrzel, A.; Skraba, Z.; Jesih, A.; Ceh, M.; Demsar, J.; Stadelmann, P.; Levy, F.; Mihailovic, D. Science, 292, 479-481. (2001) 2 Nemanic, V.; Zumer, M.; Zajec, B.; Pahor, J.; Remskar, M.; Mrzel, A.; Panjan, P.; Mihailovic, D. Applied Physics Letters, 82 , 25, 45734575, (2003) 3 Kis, A.; Mihailovic, D.; Remskar, M.; Mrzel, A.; Jesih, A.; Piwonski, I.; Kulik, A.J.; Benoit, W.; Forro, L. Advanced Materials,15, 9, 733736 (2003). 4 Nicolosi V., Vrbanic D., Mrzel A., McCauley J., O Flaherty S., Mihailovic D., Blau W.J., Coleman J.C., Chem.Phys Lett. 401, 13 (2004) 5 Dominko R., Arcon D., Mrzel A., Zorko A., Cevc P., Venturini P., Gaberscek M., Remskar M., Mihailovic D., Advanced Materials 14 (21),
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1531- (2002) 6 D.Mihailovic, Z.Jaglicic, D.Arcon, A.Mrzel, A. Zorko, M.Remskar and V.V.Kabanov, , R.Dominko, and C. J. Gmez-Garca. J. M. Martnez-Agudo. E. Coronado., Phys. Rev. Lett., 90, 146401 (2003) 7 Vrbanic, D.; Remskar, M.; Jesih, A.; Mrzel, A.; Umek, P.; Ponikvar, M.; Jancar, B.; Meden, A.; Novosel, B.; Pejovnik, S.; Venturini, P.; Coleman, J. C.; Mihailovic, D. Nanotechnology, 15, 635-638. (2004) 8 T.Meden et al (to be published, 2005) 9 V.Nicolosi et al Chem.Phys.Lett. (2005) 10 Joly Potuz L., Dassenoy F., Martin J.M., Vrbanic D., Mrzel A., Mihailovic D., Vogel W., Montagnac G., Tribology Letters (to be published) 11 I.Vilfan et al (to be published, 2005) 12 T.Yang et al., Phys. Rev.Lett 96, 125502 (2006)
TU28 LIGHT-EMITTING DIODE FABRICATED FROM HEME PROTEINS AND RELATED COMPOUNDS H. Tajima, T. Komino, K. Shimatani, S. Ikeda, M. Matsuda, Y. Ando, and H. Akiyama ISSP, The University of Tokyo, Japan An OLED is of interest not only for a practical purpose, but also for a basic research. By fabricating this device, we can measure the EL spectrum of an insulating compound, and can study electrical and optical properties simultaneously. We recently succeeded to obtain the EL spectra of cytochrome c1. This is the rst report on a biomolecular light-emitting diode (BIODE). Subsequently, we fabricated BIODE devices using other porphyrin-containing biomolecules myoglobin2 , chlorophyll a3). Interestingly, heme proteins (heme = iron porphyrin) do not or hardly exhibit PL, although chlorophyll a, which does not contain iron, exhibits PL. In this paper, we explain why heme exhibits EL but does not PL.4 We also report a drastic change of the EL spectra associated with the spin-state change in a compound containing heme.5 1. H. Tajima, et al, Solid Sates Commun. 2003, 126, 579. 2. H. Tajima et al, Synth. Met. 2005, 153, 29. 3. K. Shimatani et al, Chem. Lett. 2005, 34, 948. 4. S. Ikeda et al, Bull. Chem. Soc. Jpn. 2005, 78, 1608. 5. H. Tajima et al, Bull. Chem. Soc. Jpn., 2006, 79, 549.
TU29 PHOTOPHYSICS OF BLUE PHOSPHORESCENT IR COMPLEXES FOR OLED APPLICATIONS Ruth E. Harding, Raghu N Bera, Ifor D.W. Samuel Organic Semiconductor Centre, SUPA, School of Physics & Astronomy, University of St Andrews, North Haugh, St Andrews,Fife, KY16 9SS, UK Shih-Chun Lo, Christopher P. Shipley, Paul L. Burn Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Manseld Road, Oxford, OX1 3TA, UK Highly efcient electroluminescence (external quantum efciency >10%) has been reported by many groups for sky-blue, green and red materials. The development of and understanding of deep blue phosphorescent materials is a major challenge. We have developed new chromophores for this purpose based on the fac-tris(1-methyl-5-phenyl-3-propyl-[1,2,4]triazolyl]iridium(III) [Ir(ptz)3] complex. The basic complex and uorinated derivatives had 1931 Commission Internationale de lEclairage co-ordinates ranging between (0.16, 0.2) and (0.16, 0.12) at room temperature. Whilst successful in our aim of achieving deep blue phosphorescence at room temperature, the photoluminescence quantum yields in degassed toluene ranged between 74% and 2%, with the lowest value for the bluest compound. We have performed a range of photo-physical measurements on this family of materials to understand the factors controlling their photoluminescence quantum yield. The HuangRhys factor, a measure of the linear vibrational coupling strength of the excited state, was determined from photoluminescence spectra at 77K in frozen 2-methyltetrahydrofuran for the complexes (gure 1). It was found that the exponential energy gap law1 for non-radiative decay may not apply to the series of blue emissive complexes that included Ir(ptz)3, fac-tris{1-methyl-5-(4,6-diuorophenyl)-3propyl-[1,2,4]triazolyl}iridium(III) [Ir(f2ptz)3], and fac-tris{1-methyl-5-(6-uorophenyl)-3-propyl-[1,2,4]triazolyl}iridium(III) [Ir(fptz)3]. The measured temperature dependence of non-radiative decay showed Arrhenius behaviour around room temperature in 2-methyltetrahydrofuran (gure 2). The observed trends in non-radiative decay will be shown to be compatible with thermally activated vibrational decay between the lowest excited triplet (emissive) state and the ground state. 1 R Englman, J Jortner, Mol. Phys. 18 (1970) p.145
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Figure 1 Photon Energy (eV) PL s pectrum of Ir ( fptz) 3 a t 77 K in frozen meTH F . T he Huang R hys fa ctor was estima ted by usin g the equa tion S = -ln(I(0 0)/I(total) ) and estima ting a rea of I(0 -0) in two wa ys: twice area up to peak ma x (bl ue) or area to minimum (red).
Figure 2 Arrhe nius plot of non radi a tive decay ra te for Ir ( f2 ptz) 3 ( filled cir cles) and Ir ( fptz) 3 (open c ir cles). Linea r fits shown cor respond to activation energ ies of 0.67 and 0.27 eV res pectively.
TU30 AB INITIO MO-CI BASED QUANTUM MASTER EQUATION APPROACH TO EXCITON DYNAMICS OF DOUBLE FAN-SHAPED DENDRIMERS Ryohei Kishi, Suguru Ohta, Hideaki Takahashi, Shin-ichi Furukawa, Masayoshi Nakano Department of Materials Engineering Science,Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, JAPAN, E-mail: rkishi@cheng.es.osaka-u.ac.jp Dendrimers and dendritic aggregates have attracted much attention in the variety of elds of material science because they have unique functions originating in their tree-like and fractal architectures. There have been lots of studies on the relationships between energy migration process and unique structure of dendritic systems, clarifying that the efciency of energy migration is associated with the geometrical structure as well as the atomic/molecular species. Indeed, our previous study [1] has elucidated that slight changes in spatial symmetry of nanostar dendrimers signicantly inuence the energy migration efciency and rate. In this study, we examine whether the slight spatial changes caused by different substitution points of core monomer impact the energy migration rate and its pathway or not using double fan-shaped dendrimers shown in Fig. 1. The energy migration process of dendrimer is described by the exciton dynamics using the ab initio molecular orbital (MO) conguration interaction (CI) based quantum master equation (MOQME) approach [2]. In our MOQME formalism, the Hamiltonian of molecular system is assumed to be the ab initio electronic Hamiltonian, and the transition energies and moments between one-exciton states are calculated by the ab initio singly excitation CI (CIS) calculation. The time evolution of exciton density matrices are calculated by the quantum master equation including weak exciton-phonon coupling. The spatial distributions of a pair of hole and electron, exciton, are obtaind using those of occupied and virtual MOs, respectively, corresponding to the CIS congurations. Figure 1 shows the calculated double fan-shaped dendrimer models with different substitution points of core molecule, pentacene. The double fan-shaped parts are phenylacetylene nanostars (composed of two generations), which are linked with pentacene. It is noted that slight differences in substitution point of core molecule lead to the difference of entire spatial symmetry between them (see Fig.1). The MOQME approach is applied to these models in order to reveal the impact of spatial symmetry and the number of involved fan-shaped nanostars on the energy migration process. We further examine coherent exciton recurrence motions between double fan-shaped nanostars and pentacene, which stem from the superposition of the exciton states. From these results, we discuss a controllability of energy migration rate, pathway, efciency and the exciton recurrence motion form the viewpoint of a novel design for light harvesting and photon energy transportation as well as the generation of exciton superposition state in supermolecule based quantum devices.
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Figure 1 Models of double fan-shaped nanostar dendrimers with C2h (a), D2h (b) and C2v (c) spatial symmetries. References [1] M. Nakano, R. Kishi, M. Takahata, T. Nitta, K. Yamaguchi, J. Luminescence, 111, 359 (2005) [2] M. Nakano, M. Takahata, S. Yamada, R. Kishi, T. Nitta and K. Yamaguchi J. Chem. Phys., 120, 2359 (2004).
TU31 ANTHRACENE-CORED DENDRIMERS FOR SOLUTION-PROCESSIBLE BLUE EMITTERS: SYNTHESES, CHARACTERIZATIONS, PHOTOLUMINESCENCE AND ELECTROLUMINESCENCE Li Zhao, Chun Li, Yong Zhang, Xu-hui Zhu, Junbiao Peng and Yong Cao Institute of Polymer Optoelectronic Materials and Devices, Key Laboratory of Special Functional Materials and Advanced Manufacturing Technology, South China University of Technology (SCUT), Guangzhou 510640, China. A series of blue uorescent second-generation anthracene-cored dendrimer was readily synthesized and characterized. The perfect overlap of solution and solid emission spectra implied the absence of molecular aggregations in the solid lms, suppressed by the presence of rigid and bulky 1,3,5-phenylene based dendrons and 2-ethylhexyloxy solubilizing peripherial groups. The electroluminescent device [ITO/PEDOT:PSS/ PVK/dendrimer/Ba/Al] showed a peak emission at 422 nm with a narrow FWHI of merely ca. 42 nm and an attractive maximal external device efciency of 1.05%@184 cd/m2. The appealing solubility, photoluminescence and preliminary electroluminescence characteristics, as well as ease of syntheses, enable the anthracence-cored dendrimers to be a promising class of solution-processible blue emitters. References: 1. T.M Miller, T.X. Neenan, Chem. Mater. 1990, 2, 346. 2. M. Halim, J.N.G. Pillow, I.D.W. Samuel, P.L. Burn, Adv. Mater. 1999, 11, 371. 3. J.-Q. Qu, J.-Y. Zhang, A.C. Grimsdale, K. Mllen, F. Jaiser, X.-H. Yang, D. Neher, Macromolecules 2004, 37, 8297.
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Correspondence Associate Professor Dr. Xuhui Zhu
Email: xuhuizhu@scut.edu.cn Tel. (+) 86-20-87114346-15; Fax: (+) 86-20-87110606
TU32 ENERGY TRANSFER PROCESSES IN ORGANIC-INORGANIC SEMICONDUCTOR NANOSTRUCTURES S. Blumstengel, S. Sadofev, C. Xu, J. Puls, and F. Henneberger Institut fr Physik, Humboldt-Universitt zu Berlin, Newtonstr. 15, 12489 Berlin, Germany The exciton is the fundamental optical excitation of a dielectric solid. There are two types of excitons: In inorganic semiconductors, the relative motion of the electron and hole constituting the exciton encompasses hundreds of unit cells. Those spatially extended excitations are called WannierMott excitons. In contrast, for the small-size Frenkel excitons found in weakly bound molecular crystals, electron and hole are located on the same molecule. In the long history of excitons, these two cases have been always considered as being physically separate. However, the progress in material fabrication over the last years makes is feasibly to manufacture hybrid organic-inorganic semiconductor structures where Wannier- and Frenkel excitons are coupled to each other. It has been theoretically predicted that in such hybrid structures efcient electronic energy transfer between the inorganic semiconductor quantum well and the organic overlayer occurs which results in singular physical properties. Inspired by this work, we have studied energy transfer from a ZnO/ZnMgO quantum well to a thin overlayer of 2,2-p-phenylenebis(5-phenyloxazol) (POPOP). The inorganic heterostructure has been prepared by molecular beam epitaxy. POPOP was deposited on top of the structure by molecular beam deposition. Alternatively, the POPOP layer can be also produced from solution. ZnO has a band gap of 3.37 eV. Its high exciton binding energy of 60 meV gives rise to excitonic emission and laser action up to room temperature. It is currently an intensively studied material for ultraviolet and blue light-emitting devices. POPOP is a blue laser dye which maintains its high uorescence yield in the solid state. Moreover, its absorption bands overlap with the emission of the ZnO/ZnMgO quantum well, which is a prerequisite for resonant energy transfer. We have investigated the energy transfer process by means of photoluminescence excitation spectroscopy and its temporal evolution by time-resolved spectroscopy. The results of our investigations show, that efcient non-radiative energy transfer from the inorganic semiconductor quantum well to the POPOP layer takes place. The highest efciency in the tested hybrid structures is ET = 0.5. The coupling of Wannier and Frenkel excitons is of high practical relevance. Organic molecular crystals are efcient, versatile, and low-cost light emitters, however, low carrier mobilities limit device performance. In a hybrid structure, carrier injection can be achieved via the high-mobility inorganic part, while, after energy transfer, the radiative recombination takes place in the organic crystal. Agranovich, V.M. et al., Excitons and optical nonlinearities in hybrid organic-inorganic nanostructures, J. Phys.: Condens. Matter 10, 9369-9399 (1998). S. Sadofev, S. Blumstengel, J. Cui, J. Puls, S. Rogaschewski, P. Schfer, Yu. G. Sadofyev, and F. Henneberger, Growth of high-quality ZnMgO epilayers and ZnO/ ZnMgO quantum well structures by radical-source molecular beam epitaxy on sapphire, Appl. Phys. Lett. 87 (2005) 091903.
TU33 SYNTHESIS AND PROPERTIES OF DENDRITIC OLIGOTHIOPHENES (DOTS) Chang-Qi Ma, Elena Mena-Osteritz, Markus Wunderlin, Peter Buerle* Department of Organic Chemistry II, University of Ulm, Albert-Einstein-Allee 11, D-89081 Ulm, Germany Email: changqi.ma@uni-ulm.de As perfect monodisperse macromolecules with a special rigid hyperbranched and large -conjugated architecture, thiophene dendrimers have very interesting electrooptical and supramolecular assembly properties on surfaces and have shown great application pros-pects in organic and molecular electronics.1 In this contribution, we will present our recent results in the synthesis of novel dendri-tic oligothiophenes (DOTs) representing novel architectures for organic semiconductors. By a convergent approach, the synthesis up to 4th generation all-thiophene dendrons (dened 45-mer, 45T) has been realized. Due to the polarization ability of thiophene units and its high branched structure, 45T dissolves very well in organic solvents resulting in a promising processability in optoelectronic application. A single crystal structure analysis and theoretic calculations on the model compound 9T indicate shape persistence. For 45T, a band-gap of ca. 2.2 eV was conrmed by UV-vis spectra and cyclic voltammetry. Attempts to get the 4th generation dendrimer 90T, the dimer of 45T, are under way.
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TU34 ELECTRICAL AND OPTICAL CHARACTERIZATION OF ORGANIC LIGHT-EMITTING DIODES USING DIFFERENT HOLE TRANSPORT LAYERS. Adriano R. V. Benvenho1,2, Jos P. M. Serbena2, Rudolf Lessmann2, Ivo A. Hmmelgen2, Regina M. Q. de Mello3, Rosamaria W. C. Li 4, Jamille H. Cuvero 4, Jonas Gruber4 1 Universidade do Algarve, Faculdade de Cincias e Tecnologia, CEOT, Campus de Gambelas, 8005-139 Faro, Portugal (permanent adress), 2 Universidade Federal do Paran, Departamento de Fsica,81531-990, Curitiba, Paran, Brazil, 3Universidade Federal do Paran, Departamento de Qumica, 81531-990, Curitiba, Paran, Brazil. 4Universidade de So Paulo, Instituto de Qumica, 05513-970, So Paulo, SP, Brazil
Conjugated polymers and organic molecules are nowadays applied to a diversity of electronic and optoelectronic devices. One of the most important application of these materials is in light-emitting devices 1,2. In this work we propose the utilization of conjugated polymer and organic low weight molecular material like active layers, using different hole transport layers (HTLs). The devices were constructed in structure: FTO\ HTL\ PDO14FV\ Alq\Ca\Al, where HTLs are poly(3,4- ethylenedioxythiophene) : poly(4-styrenesulfonate) (PEDOT:PSS), poly(p-pheneylene) (PPP) and sulfonate polyaniline (SPAN). We use as active double layer a conjugated polymer poly(9,9-dioctyl-1,4-uorenilenevinylene) 3 (PDO14FV) and the low molecular weight material 8-hydroxiquinoline aluminium (Alq3). We used different HTL and optimize device thickness, PEDOT:PSS ( 100 nm), SPAN (40 nm), PPP (46 nm) , PDO14FV ( 23nm) and Alq3 ( 50 nm). Devices using electrodeposited conducting SPAN have better luminance if compare with PEDOT:PSS and PPP . In gure 1 we show the current density voltage for different devices and in gure 2 the luminescence voltage curves for the same devices. 600. 0
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References [1] Tang, C. W., VanSlyke, S. A. Organic electroluminescent diodes Applied Physics Letters 51(12): 913-915 1987. [2] Burroughes, J. H., Bradley, D. D. C., Brown, A. R., Marks, R. N., Mackay, K., Friend, R. H., Burns, P. L., Holmes, A. B. Light-emitting diodes based on conjugated polymers Nature 347(6293): 539-541 1990. [3] Gruber, J., Li, R. W. C., Aguiar L. H. J. M. C., Benvenho, A. R. V., Lessmann, R., Hmmelgen I. A. A novel soluble poly(uorenylenevinylene) conjugated polymer: synthesis, characterization and application to optoelectronic devices Journal of Materials Chemistry 15: 517-522 2005.
TU35 CONTROLING THE NANOSTRUCTURE OF POLYMER-BASED SOLAR CELLS Dieter Nehera and Thomas Kietzkea,b a Institute of Physics, University of Potsdam, Am Neuen Palais 10, D-14469 Potsdam b Institute of Materials Research and Engineering, 3 Research Link, 117602 Singapore e-mail: neher@rz.uni-potsdam.de Efcient photogeneration of charges in organic solar cells relies on the rapid dissociation of excitons at the interface between molecules of dissimilar electron afnity and ionization energy. A conclusive description of the elementary processes in these devices is generally aggravated by the complex morphology of such multicomponent layers. This presentation provides an overview of our recent advances in controlling the nanostructure of polymer-based solar cells. Using the miniemsulsion approach, ca. 50 nm nanoparticles, each containing electron-donating and electron-accepting polymers in a predictable amount, can be fabricated [1]. This approach allow us to separate solidication and layer formation and to study phase separation in a dened environment [2]. Detailed experiments with two well-known polyuorene copolymers, PFB and F8BT, showed that the blends which form within these nanoparticles consist of two phases, each containing a small fraction of the minority component. The dependence of the optical properties on particle composition could be accurately described in the framework of the Flory-Huggins theory. Studies on solar cells made from these particles showed that only one of the two phases dominates charge carrier generation. The second part of this talk discusses our recent result on solar cells based on derivatives of poly(p-phenylene-vinylene) (PPV). By combining a hardly-soluble electron-donating and a wellsoluble electron-accepting PPV, layers with a vertical composition gradient could be fabricated in a single step deposition process. These solar cells exhibited high external quantum efciencies (up to 32 %) and large open circuit voltages (up to 1.4 V), resulting an external energy conversion efciency of up to 1.7 % [3]. Time-resolved studies of the emission properties of these blend layers showed emission from both the donor intrachain exciton and from an interchain exciplex. Surprisingly, we found a strict correlation between the excimer emission intensity and the IPCE of the blend solar cells. Apparently, excimer emission is competing with the generation of free charges, in agreement with the results of earlier studies on PFderivatives [4]. References
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1. Th. Kietzke, D. Neher, K. Landfester, R. Montenegro, U. Scherf, R. Gntner, Novel approaches to polymer blends based on polymer nanoparticles, Nature Materials, 2 (2003) 408-412. 2. T. Kietzke, D. Neher, M. Kumke, R. Montenegro, K. Landfester, U. Scherf, A nanoparticle approach to control the phase separation in polyuorene photovoltaic devices, Macromolecules 37 (2004) 4882-4890. 3. Kietzke, H.H. Hrhold, D. Neher, Efcient polymer solar cells based on M3EH-PPV, Chem. Mater. 17 (2005) 6532-6537 4. A.C. Morteani, P. Sreearunothai, L.M. Herz, R.H. Friend, C. Silva, Exciton regeneration at polymeric semiconductor heterojunctions. Phys. Rev. Lett. 92 (2004) 247402
TU36 FABRICATION OF ASYMMETRIC MICRODISK BASED ON -CONJUGATED POLYMER AND ITS UNIDIRECTIONAL LASER EMISSION PROPERTIES A. Fujii, N. Tsujimoto, T. Nakao, T. Takashima, K. Yoshino* and M. Ozaki Division of Electrical, Electronic and Information Engineering, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan *Research Project Promotion Institute, Shimane University, Matsue 690-8504, Japan E-mail: afujii@eei.eng.osaka-u.ac.jp Conducting polymers with highly extended conjugated -electron systems in the main chains have attracted great interest from both fundamental and practical viewpoints, because they exhibit various novel properties. Among various conducting polymers, poly(p-phenylenevinylene) (PPV) and its derivatives are the most attractive materials for light-emitting diodes, because of their high solubility in common organic solvents and the high luminescence quantum efciency. Polymer lasers with microcylindrical structures, which are based on waveguide mode or whispering gallery mode, have attracted much attention as a novel type of lasers, because of the high Q factors and low threshold energy for the lasing. The laser emission from micro-cylindrical structures, such as microring and microdisk, however, radiates equally to each direction in plane from the cylindrical microcavity. Therefore, unidirectional laser beam is signicant for developing the device application in optical communication. The investigation of the spiral-shaped microdisk lasers utilizing luminescent -conjugated polymer, such as PPV derivatives, should be also important for the realization of a plastic laser diode. In this study, we report on the fabrication of asymmetry-shaped spiral microcavities consisting of a PPV derivative and the laser emission properties of the spiral microcavities of the PPV derivative. Figures 1 and 2 shows a SEM image of typical spiral-type microdisks and the multi-mode laser emission pattern from the spiral type microdisks when pulse-excitation was carried out by Nd: YAG laser. This laser demonstrated the obvious unidirectionality. 8000
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Fig.2 Emission spectrum of spiral microdisk
References [1] A. Fujii, T. Nishimura, Y. Yoshida, K. Yoshino and M. Ozaki, Jpn. J. Appl. Phys. 44 (2005) L1091. [2] A. Fujii, T. Nishimura, Y. Yoshida, Nishihara, M. Ozaki and K. Yoshino, Synth. Met., 153 (2005) 217. [3] Y. Yoshida, T. Nishimura, A. Fujii, M. Ozaki and K. Yoshino, Appl. Phys. Lett. 86 (2005) 141903. [4] Y. Yoshida, T. Nishimura, A. Fujii, M. Ozaki and K. Yoshino , Jpn. J. Appl. Phys. 44 (2005) L1056.
TU37 VARIABLE BAND-GAP POLYMER BASED SOLAR CELL: EFFECT OF ENERGY TRANSFER ON PHOTOCONVERSION EFFICIENCY. D. Guptaa, D. Kabraa, K. Nageshb, S. Ramakrishnanb, K.S. Narayana* a Chemistry and Physics of Materials Unit, Jawaharlal Nehru Center for Advanced Scientic Research, Jakkur, Bangalore560064, India b Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India
ABSTRACTS
We demonstrate that the energy transfer from low-conjugated (LC) poly[2-methoxy-5-(2ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) to high-conjugated (HC) MEHPPV, coupled with signicant electron transfer from HC to an acceptor species, offers a viable route for an efcient solar cell over a wide spectral range. An enhanced incident photon to current conversion efciency (IPCE) of 19% over a wide spectral range and power conversion efciency (P) of 1% was achieved in a ternary polymer blend lm consisting of HC (low band-gap), LC (high band-gap) and an acceptor polymer cyano-PPV (CNPPV), in an optimized ratio. A reasonable degree of control of the morphology which is a decisive factor for efcient solar cells can be achieved via thermal treatment procedures. The morphology that emerges from phase separation process in these polymer-blends is tracked by wide-eld photocurrent imaging. Our results point towards the
need of reducing LC-CNPPV interface and maximizing HC-CNPPV interface in these ternary blend photovoltaic devices. We also optimize these requirements by tailoring multilayer device structures. The ll factor aspect of the device is also addressed in more detail, taking recombination loss and space charge effects into account.
OEH OMe
1-X
LC
OEH
E g ~ 2.6 eV
HC
2.8 eV e
-
3.2 eV
OMe
Nonconjugated segment
* X
h
Conjugated
+
MeO
5 eV 5.4 eV CNPP V
X = 0.1 (Low conjugated), X = 1 (High conjugated).
TU38 CHARGE TRANSPORT IN THIN PHOTOCELLS - THE MOBILITY SPATIAL-DISTRIBUTION FUNCTION Noam Rappaport, Olga Solomesch, and Nir Tessler Microelecronic & Nanoelectronic Centers, Electrical Engineering Department, Technion Israel Institute of Technology, Haifa 32000, Israel
Using step-function excitation time of ight performed on thin lm devices (100-300nm) we observe what is commonly referred to as dispersive transport. We present a new physical explanation by which the dispersive nature is not due to non-equilibrium phenomena but is rather due to spatial inhomogeneity on the nanometer scale. We consider the semiconducting layer to be comprised of a distribution of parallel pathways (on the nm scale) each having a different, but well dened, mobility value. This new insight allows us to describe the measured curves using standard semiconductor equations and use them to analytically extract, for the rst time, a mobility distribution function. The mobility that we derive is of the slow charge specie which is the one limiting the efciency of solar cells, We present such measurements and analysis performed on both conjugated polymers and conjugated small molecules based lms. The results are compared, and found to be in good agreement with, power dependent quantum efciency measurements of photocells. 1 This new physical insight and experimental procedure are very useful in screening for long lived materials (in devices) and efcient solar cells.
i t 1.2 u 1 b i 0.8 r 0.6 t s 0.4 i 0.2 D

0 10-9
Mobility (cm 2v-1 s-1)
10-8
Figure 1. The mobility distribution function of electrons in a PPV polymer measured under short-circuit conditions (built in voltage was ~ 1V).
References 1. N. Rappaport, O. Solomesch, and N. Tessler, The interplay between space charge and recombination in conjugated polymer/molecule photocells, Journal of Applied Physics, vol. 98, pp. 033714, 2005
TU39 PHOTOCATALYTIC PROPERTIES OF PERYLENE/PHTHALOCYANINE BILAYER RESPONSIVE TO A WIDESPREAD VISIBLE LIGHT OF <750 NM
ABSTRACTS
Keiji NAGAI1 and Toshiyuki ABE2 1Institute of Laser Enginnering, Osaka University, Suita, Osaka 565-0871, Japan 2Department of Chemistry, Hirosaki University, Hirosaki, Aomori 036-8561, Japan E-mail: knagai@ile.osaka-u.ac.jp Organic bilayer, composed of a perylene derivative (3,4,9,10-perylenetetracarboxyl-bisbenzimidazole, PTCBI) and phthalocyanine (H2Pc), is known as typical photovoltaic material in dry system [1], and recently applied for tuning of high-power-laser ablation [2].
We have found the combination acts as a photoanode on ITO involving a catalytic oxidation of 2-mercaptoethanol in water [3]. Based on action spectrum for photocurrent, it was noted that the widespread visible light absorption (< 750 nm) by only the PTCBI can efciently induce the generation of photoanodic current at the interface of H2Pc/water coupled with a hole-conducting character of H2Pc. Oxygen evolution with small bias (> 0.4 V vs Ag/AgCl) happened under visible light illumination by adding IrO2 catalyst [4] or inserting cobult into phthalocyanine [5], both of the cases means the rst case of water splitting using organic semiconductor assisted by visible light and means stability of the bilayer under water and oxydation circumstance. In the case of reverse combination of H2Pc/PTCBI on ITO, the photoelectrode worked in water phase coexisting redox molecule (FeIII(CN)63(electron acceptor)) [6]. However, the action spectrum for the photocathodic current indicated that a broad visible-light absorption (400~750 nm) by only the PTCBI can also induce the photocurrent generation. This was supported by the case of the photoanodic combination that the PTCBI exciton can solely contribute to carrier generation through charge separation at the H2Pc/PTCBI interface. The photocathodic combination showed the novel photocathodic characteristics at the organic solid/water interface coupled with electron conduction through the n-type semiconductor, in addition to the ordinary characteristics at the p-type semiconductor/water interface.
Fig. 1 photoelectrocatalytic redox in water phase using visible light responsive perylene/phthalocyanine bilayer References [1] C. W. Tang, Appl. Phys. Lett. 1986, 48, 183 [2] K. Nagai, et al., Appl. Surf. Sci., 2002, 197, 808. [3] T. Abe, K. Nagai, et al., ChemPhysChem., 2004, 5, 716. [4] T. Abe, K. Nagai, et al., J. Electroanal.Chem., 2006, 587, 127. [5] T. Abe, K. Nagai, et al., Angew. Chem. Int ed., 2006, in press. [6] T. Abe, K. Nagai, et al., J. Electroanal.Chem, 2005, 583, 327.
TU40 FUNCTIONALIZED POLY(PHENYLENE VINYLENE) DIBLOCK COPOLYMERS AND ELECTROSPUN BLENDS FOR POLYMERIC PHOTOVOLTAIC CELLS John P. Ferraris, Danny Zepeda, Andrew L. Washington Jr., Kenneth J. Balkus, Jr. Department of Chemistry, University of Texas at Dallas, Richardson, Texas 75080 We report functionalized poly(phenylene vinylene) (PPV) diblock copolymers and blends with electron donating and withdrawing functionalities, which could enhance the photoinduced electron transfer (from donor to acceptor) in polymeric photovoltaic cells (PPVC). Although PPVCs present a promising alternative energy source, their power efciencies are low (1-5%) due to several factors such as charge recombination, limited exciton transport lengths and low charge carrier mobilities. Since photogenerated electrons/holes are largely conned to the electron donoracceptor interface, a well-dened polymeric donor-acceptor heterojunction proves to be a general strategy to more power efcient PPVCs. One approach is the use of thin lms comprising PPV-based block copolymers, which allow for the polymer chains to have dened electron donating and electron accepting segments (D-A). We report the synthesis of the PPV diblock copolymer of poly [1,4-bis-N,Nhexylaminomethyl]-2,5-phenylenevinylene (BAMH-PPV), poly [1,4-bis-2-ethylhexyloxy]-2,5-phenylenevinylene (BEH-PPV) and poly [1,4-bis(2-ethylhexylmercapto)]-2,5-phenylenevinylene (BEHM-PPV) as intermediates to D-A diblock copolymers of poly [1,4-bis-2-ethylhexyloxy]co-[1,4-bis-N,N,N-dimethylhexyl ammonium]-2,5-phenylenevinylene (BEH-co-QBAMH-PPV), poly [1,4-bis-2-ethylhexyloxy]-co-[1,4-bis-2ethylhexylsulnyl]-2,5-phenylenevinylene (BEH-co-BEHSO-PPV), and poly [1,4-bis-N,N-hexylaminomethyl]-co-[1,4-bis-(2-ethylhexylsulnyl)]2,5-phenylenevinylene (BAMH-co-BEHSO-PPV) diblock copolymers. The electron donating effects of the tertiary amine and oxygen, coupled with the electron withdrawing effects of the sulfoxide and the quaternary ammonium moieties present viable combinations for these D-A block systems. Another approach is electrospinning PPV-based donor-acceptor blends with the aid of surfactants. This process produces highly ordered polymer chains that increase the effective conjugation; possibly increasing the charge-carrier mobility that can enhance the overall efciency of photovoltaic devices. We report the electrospinning of poly (2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and poly(2dimethyloctylsilyl)-phenylenevinylene (DMOS-PPV) and MEH-PPV/DMOS-PPV blends. The optical properties and possible energy transfer from the donor (DMOS-PPV) to the acceptor (MEH-PPV) in the electrospun blend are also presented.
TU41 HYBRID SOLAR CELLS WITH INORGANIC NANOPARTICLES AND ORGANIC CONJUGATED POLYMERS Serap Gnes, Helmut Neugebauer, N. Serdar Sariciftci Linz Institute for Organic Solar Cells (LIOS), Physical Chemistry, Johannes Kepler University Linz, Altenbergerstrasse69, 4040 Linz, Austria Hybrid solar cells, consisting of conjugated polymeric organic and inorganic nanoparticle semiconductors, combine the electronic properties of nanoparticles with the lm forming properties of conjugated polymers. There are two concepts for making hybrid solar cells: The rst is the bulk heterojunction concept where charge transfer junctions are formed by mixing semiconductor nanocrystals with the conjugated polymers [1]. The second concept is based on the dye sensitized nanopourous titania solar cell concept [2], where dyes are used for sensitizing a nanoporous TiO2 lm which is acting as an electrode. In solid state dye sensitized solar cells the liquid electrolyte, which is used in the classical Grtzel type of solar
ABSTRACTS
cells, is replaced by a solid semiconductor like CuI [3] or CuSCN [4] or by conjugated polymers [5]. In similar solid state structures nanocrystals instead of dyes have been used for sensitizing the nanoporous electrodes [6]. Researchers also focus on replacing the TiO2 nanoporous electrodes with different inorganic materials such as ZnO, Nb2O5 and SnO2 [6]. An interesting strategy is also to replace TiO2 electrodes with other inorganic materials which have absorption in the visible part of the spectrum, such as CuInS2 [7]. In the presentation, an overview on the results of different concepts, studied in our group, will be discussed. One concept uses CuInS2, which acts as light absorbing material, as a p-type nanostructured electrode. We realized and investigated bilayer structures of nanoporous CuInS2 and PCBM (1(3-methoxycarbonyl)-propyl-1-1-phenyl-(6,6) C61) with or without using a dye complex of RuL2(NCS)/TBA(2:2) (where L= 2,2-bipyr idyl-4,4dicarboxylic acid; TBA= tetrabutylammonium) as sensitization interlayer. A signicant improvement in the device properties using the dye interlayer was obtained [7]. Another concept uses HgTe nanocrystals deposited on nanoporous TiO2 electrodes as well as blended into a hole transporting polymer [8]. Thus, we combine the solid state nanocrystals sensitized solar cell concept and the polymer/nanocystal blended solar cell concept. The device consists of TiO2 electrodes coated with water soluble HgTe nanocrystals in contact with a poly(3-hexylthiophene) matrix, mixed with organic solvent soluble HgTe nanocrystals. Both types of nanocrystals increase the photon harvesting efciency over a broad spectral range between 350 nm and 1500 nm. References: [1] E. Arici, N. S. Sariciftci, D. Meissner, Adv. Func. Mat. 2003, 13, 165 [2] M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Mller, R. Liska, N. Vlachopoulos, M. Grtzel, J. Am. Chem. Soc. 1993, 9, 439. [3] K. Tennakone, G. R. R. A. Kumara, I. R. M. Kottegada, K. G. U. Wijayantha, P. M. Sirimanne, Sci. Tech. 1995, 10, 1689. [4] B. O`Regan, D. T.Schwartz, S. M. Zakeeruddin, M. Graetzel, Adv. Mat. 2000, 12, 1263. [5] D. Gebeyehu, C. J. Brabec, N. S. Sariciftci, D. Vangenuegden, R. Kiebooms, D. Vanderzende, F. Kienberger, H. Schindler, Synth. Met. 2002, 125, 279. [6] R. Vogel, P. Hoyer, H. Weller, J. Phys. Chem. 1994, 98, 3183. [7]S. Gnes, R. Koeppe, E. Arici, N. S. Sariciftci, Proceedings of Turk. Phys. Soc., CD format, 02_SB18 [8]S. Gnes, H. Neugebauer, N. S. Sariciftci, J. Roither, M. Kovalenko, G. Pillwein, W. Heiss, in press, Adv. Func. Mat.
TU 42 MAGNETO TRANSPORT OF SYNTHETIC NANOSTRUCTURES AND THEIR DEVICE APPLICABILITY: CONDUCTING POLYMER NANOFIBERS AND CARBON NANOTUBES Y. W. Park School of Physics and Nano Systems Institute-National Core Research Center, Seoul National University, Seoul 151-747, Korea The low temperature magnetoresistance (MR) in quasi-one dimensional polymer nanobers and carbon nanotubes are reported for the magnetic eld up to 30 Tesla. Positive MR is observed in polymer nanobers [R(H=30T)/R(H=0) = +0.2 (+0.4) at T=1.5K for polyacetylene nanobers (polyaniline nanobers)] and the MR decreases as the applied electric eld increases. The details of applied voltage dependence of MR vary for different polymer nanobers. The low temperature MR of polymer nanobers is understood as tunneling conduction in an array of small conducting regions separated by nanoscale barriers. The spin-charge characteristics of the tunneling carriers are discussed. The low temperature MR of carbon nanotubes is negative up to 30 Tesla showing an upturn of MR toward positive at H>20 Tesla [R(H=20T)/R(H=0T) = -0.08 at T=1.5K]. The results are compared with the reported MR data measured by pulse magnetic eld up to H=50 Tesla. The prospects of nanoelectronic applications of polymer nanobers and carbon nanotubes are envisaged. References 1. N. Aleshin, H. J. Lee, S. H. Jhang, H. S. Kim, K. Akagi, Y. W. Park, Coulomb-blockade transport in quasi-one-dimensional polymer nanobers, Phys. Rev. B 72, 153202 (2005) 2. Hyun J. Lee, Zhao X. Jin, Andrey N. Aleshin, Ju Y. Lee, Mun J. Goh, Kazuo Akagi, Young S. Kim, Dong W. Kim, Yung W. Park, Dispersion and current-voltage characteristics of helical polyacetylene single ber, J. Am. Chem. Soc. 126, 16722 (2004) 3. A. N. Aleshin, H. J. Lee, Y. W. Park and K. Akagi, One-dimensional transport in polymer nanobers, Phys. Rev. Lett. 93, 196601 (2004)
TU 43 CHARGES AND EXCITONS AT INTERFACES IN POLYMERIC SEMICONDUCTOR STRUCTURE - Sir Richard Friend
TU44 SUPERCONDUCTIVITY IN ION-BEAM METAL MIXED POLYMERS Adam P Micolich,a Eric Tavenner,b Ben J. Powell,b Alex R. Hamilton,a Ross H. McKenzie,b Matthew T. Curry,c Ryan E. Giedd,c and Paul Meredithb aSchool of Physics, University of New South Wales, Sydney NSW 2052, Australia; email: mico@phys. unsw.edu.au; bDept. of Physics, University of Queensland, Brisbane QLD 4072, Australia; cCenter for Applied Science and Engineering, Missouri State University, Springeld MO 65804, U.S.A. Ion implantation of normally insulating polymers offers an alternative to depositing metals or conjugated organics onto plastic lms to make electronic circuits1. However, until very recently, all of these materials have shown insulating behaviour characterised by reduced conductivity with decreasing temperature. The use of metallic ion-beams was recently trialed,2 but resulted in a maximally implanted ion content insufcient for metallic conductivity due to a self-limiting sputtering process. One way to overcome this problem is to deposit a thin metal layer on the surface and use an ion-beam to mix this metal into the polymer a process known as metal mixing.3 This allows lower mass inert ions to be used, reducing the sputtering, while the metal layer ensures that sufcient metal atoms remain after implantation to allow metallic conductivity.
ABSTRACTS
Fig. 1: Four te rminal elec trica l res istance R 4T vs tem perature T demonst rating the pr esen ce of a zero resistanc e state belo w 3K. (In set) a photog raph of a typic al samp le demon strating tha t it retains its m echanical proper ties post imp lantation.
Following this approach, we have used a 50 keV N+ ion beam to mix a 100 thick Sn/Sb lm into a polyetheretherketone (PEEK) substrate. We will report the results of low-temperature electrical measurements of this Sn:Sb/PEEK metal mixed system4 where, in addition to observing metallic behaviour, we observe the onset of superconductivity at temperatures below 3K (see Fig. 1). Although superconducting-polymer blends displaying a partial Meissner effect have recently been developed,5 the present work is, to the best of our knowledge, the rst observation of superconductivity with a zero resistance state in plastic materials. We will also present our latest results demonstrating that the 5% Sb fraction is essential to the observed behaviour, and which provide strong indications that the observed superconductivity does not result from a residual thin-lm of alloy, but instead from a network of alloy grains coupled via a weakly conducting, ion-beam carbonized polymer matrix. 1. S.R. Forrest et al., Appl. Phys. Lett. 41, 708 (1982); J.A. Osaheni et al., Macromol. 25, 5828 (1992). 2. E. Tavenner et al., Synth. Met. 145, 183 (2004) 3. Y.Q. Wang et al., Nucl. Inst. Meth. Phys. Res. B 127/128, 710 (1997). 4. A.P. Micolich et al., Submitted to Appl. Phys. Lett., Cond-mat/0509278. 5. A. Tracz et al., Synth. Met. 120, 849 (2001).
TU45 BEDT-TTF DERIVATIVES WITH METAL BINDING CENTRES: SUBSTRATES FOR BIFUNCTIONAL MATERIALS. Qiang Wang, John D. Wallis School of Biomedical and Natural Sciences, Nottingham Trent University, Clifton Lane, Nottingham NG11 8NS, UK Peter Day Davy-Faraday Research Laboratory, The Royal Institution of Great Britain, 21 Abermarle St, London W1S 4 BS, UK
There has been considerable interest in preparing materials with new combinations of physical properties. Novel combinations of electrical and magnetic properties have been achieved utilising BEDT-TTF in Days paramagnetic superconductor1 and Coronados oxalate salts with independent conducting and ferromagnetic properties.2 Interplay between these properties has been observed in the Kobayashis salts of BETS with magnetic counterions.3 Building on our work on preparing functionalised BEDT-TTF derivatives,4,5 we will present progress in the preparation of new BEDT-TTF derivatives with metal binding centres, e.g. 1, 2 and 3, and outline their conversion to complexes with magnetic metal ions, as substrates for the preparation of bifunctional materials. Thus, 1 has been converted both to salts with M(hfac)2 (e.g. M = Ni(II), Co(II)) and has formed tris complexes with metal ions.
N S S S S S S S S S N S S S S S S S S S N N
1
N N S S S S S S S S S N
1. M. Kurmoo, A.W. Graham, P. Day, S.J. Coles, M.B. Hursthouse, J.L. Cauleld, J. Singleton, F.L. Pratt, W. Hayes, L. Ducassse, P. Guionneau, J. Amer. Chem. Soc., 1995, 117, 12209. 2. E. Coronado, J.R. Galen-Mascaros, C.J. Gomez-Garcia, V. Laukhin, Nature 2000, 408, 447. 3. S. Uji, H. Shinkawa, T. Terashima, T. Yakabe, Y. Terai, M. Tokumoto, A. Kobyashi, H. Tanaka, H. Kobayashi, Nature, 2001, 410, 908. 4. J.P. Grifths, J.D. Wallis, J. Mater. Chem., 2005, 15, 347. 5. J.-P. Grifths, R.J. Brown, B. Vital, P. Day, C.J. Matthews, J.D. Wallis, Tet. Lett., 2003, 44, 3127; .P. Grifths, N. Hui, R.J. Brown, P. Day, J. D. Wallis J. Org. Biomol. Chem., 2005, 3, 2155; J-P. Grifths, A. Arola Arnal, G. Appleby, J. D. Wallis, Tet. Lett. 2004, 45, 2813.
TU 46 Organic eld-effect transistors based on tetrathiafulvalene derivatives with fused aromatic rings Naraso,1 Jun-ich. Nishida,,1 Shizuo. Tokito,2 Yoshiro. Yamashita1 1Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8502, Japan, 2NHK Science and Technical Research Laboratories, Kinuta, Setagaya-ku, Tokyo 157-8510, Japan Much attention has been focused on organic eld effect transistors (OFET)s from viewpoints of application purposes for electronic devices as well as basic interest in charge transportation. Development of new semiconductors showing FET properties is particularly important to make progress in this eld. For this purpose, we have designed tetrathiafulvalene (TTF) derivatives and have investigated their FET characteristics. We have already reported TTF derivatives 1 as semiconductors for p-type FETs.1) Although usual TTF derivatives are labile to oxygen in thin lms, stabilization and strong - interactions were achieved by introducing fused aromatic rings to the TTF unit. The naphthalene derivative 1a has a herring-bone structure in the crystal and showed a high hole mobility of 0.42 cm2/Vs. On the other hand, the quinoxaline derivative 1b has a stacking structure owing to an intermolecular charge-transfer interaction and showed high stability to oxygen. The mobility was 0.2 cm2/Vs. We have now designed TTF derivatives 24 to improve the FET properties as well as to clarify the relationship between the structures and FET characteristics. The FET device of tetramethoxy derivative 2 showed a high on/off ratio of 107 which is much higher than that of 1a (103). Unsymmetrical TTF derivatives 3 were prepared by using a cross coupling reaction with triethyl phosphite. Selenium atoms were introduced
ABSTRACTS
to enhance intermolecular interactions. Both sulfur and selenium compounds of 3a take -stacking structures in contrast to the herring-bone structure of 2. The FET devices based on 3 showed low mobilities probably due to the disordered orientation on the substrate. On the other hand, bispyradino derivatives 4 showed higher hole mobilities, where clear XRD patterns were observed in the thin lms. Furthermore, we have found that introduction of electron-withdrawing groups to the quinoxaline derivative 1b resulted in n-type FET behavior, which is the rst example in the TTF derivatives.
X X S S S S X X MeO MeO S S 2 S S OMe OMe
1a: X = CH 1b: X = N
R R
N N
X X
S S
R R
N N
S S
S S
N N
3a: R = H, X = S, Se 3b: R, R = benzo, X = S, Se
4: X = H, F
Reference 1) Naraso, J. Nishida, S. Ando, J. Yamaguchi, K. Itaka, H. Koinuma, H. Tada, S. Tokito, and Y. Yamashita, J. Am. Chem. Soc., 2005, 127, 10142.
TU47 THEORY VIEWS OF NEW EXPERIMENTAL OBSERVATIONS OF SOLITONS IN QUASI 1D CONDUCTORS. Serguei Brazovskii*, Yu.I. Latyshev, S.I. Matveenko, P. Monceau *LPTMS-CNRS; bat 100, Univ. Paris-Sud, UMR 8626, ORSAY CEDEX, 91405, France. Physics of solitons in electronic processes was brought to the science of synthetic metals in 1970s through theories of charge density waves (CDW). It was boosted in the 1980s epoch of the polyacetylene and the SSH model. Solitons have reentered in 2000s through the discovery of the ferroelectric charge ordering in organic conductor1 and via new nano-scale experiments2,3 in CDW materials. Corresponding dynamical processes - instantons are responsible for subgap transitions leading to a pseudogap formation4. We are concerned with Electronic Crystals like Charge Disproportionation and CDWs, while their Wigner forms are also known in nano-wires and expected in doped polymers. Their common property is a deep selftrapping of electrons and their pairs into solitons, polarons, bipolarons. The theory tells1-4 that here the electronic processes (dynamic - optics, tunneling, kinetic - conductivity, static - doping, eld effect) goes on via discommensurations, dislocations, solitons. We shall demonstrate that all these effects appear in contemporary experiments. We shall recall experiments conrming solitons in organic metals, and particularly concentrate upon latest direct observations of microscopic solitons in processes of the coherent interlayer tunneling in inorganic CDWs2,3. We shall describe special nano-scale devices, fabricated from the chain compound NbSe3 using focused ion beams2,3. Tunneling spectra were drastically rened by working at high magnetic elds. Experiments2 prove that the internal quantum tunneling of electrons goes through channels of solitons, which might correspond to the long sought special quasiparticle - the spinon. The same experiments give access to reversible reconstruction of the junction via spontaneous creation of the solitonic lattice grid3. Its formation shows up through the staircase structure of the subgap tunneling spectrum. Most of tunneling takes place in the cores of the solitonic grid. The resolved tunneling in the normally forbidden subgap region recovers collective quantum processes like coherent phase slips4. 1 P.Monceau, F.Ya. Nad, S.Brazovskii, Phys. Rev. Lett., 86, 4080 (2001). 2 Yu.I. Latyshev, P. Monceau, S. Brazovskii, A.P. Orlov, T. Fournier, Phys. Rev. Lett. 95, 266402 (2005). 3 Yu.I. Latyshev, P. Monceau, S. Brazovskii, A.P. Orlov, T. Fournier, Phys. Rev. Lett., April 2006, to be bubl. 4 S. I. Matveenko and S. Brazovskii, Phys. Rev. B 72, 085120 (2005).
Tunneling conductance2 dI/dV of NbSe3 as a function of the reduced voltage V/ . The arrows: at 2 - single particle gap edge, at 2 /3 soliton peak, at Vt threshold for the field effect reconstruction.
TU48
ABSTRACTS
CHARGE ORDERING STATE OF ET, BETS AND [PD(DMIT)2] SALTS BY TEMPERATURE-DEPENDENT VIBRATIONAL SPECTROSCOPY Takashi Yamamoto, Reizo Kato, and Kyuya Yakushi Riken, 2-1 Hirosawa, Wako, 351-0198, Japan Institute for Molecular Science, Myodaiji, Okazaki, 444-8585, Japan
The charge ordering (CO) state has attracted considerable attention since inhomogeneous site charges are observed for the molecular conductors including highly conducting materials and the superconductor.1,2 The vibrational spectroscopy is a powerful method to investigate the structure and dynamics of the CO state along with the degree of charge transfer. In this symposium, we will present the vibrational spectra of ET, BETS and [Pd(dmit)2] salts, and discuss what dictates the CO state. i) ET5Te2I6 and BETS5Te2I6:3 As shown in Fig. 1, the charge sensitive mode, 2, splits into two bands. Therefore, both compounds are characterized as the CO state. Interestingly, the frequency of the structure sensitive (e-mv) mode, 3, of the ET-salt is almost equal to that of the BETS-salt, which indicates that the patterns of the CO state are identical to each other. This observation conrms that the CO state is mostly ascribed to the inter-site Coulomb interaction along the stacking direction.1 Inhomogeneous charges are robust above the metal-insulator transition temperature, TMI. It is likely that the highly conducting state is due to the competition between the most stable and secondary stable patterns.1 ii) Et2Me2Sb[Pd(dmit)2]2 and Cs[Pd(dmit)2]2:4 As shown in Fig. 2, the IR spectra of [Pd(dmit)2] salts often exhibit two bands around 1300 cm1. The higher frequency band denoted as A is assigned to the asymmetric C=C stretching mode and the lower frequency band denoted as B to the symmetric C=C stretching mode. The former is the charge sensitive mode, and the latter is the e-mv mode. Both salts undergo the CO phase transition because the band A discontinuously splits into two bands below TMI. Four e-mv modes exhibit a localized nature, and these modes are both IR and Raman active. This observation indicates that an organic layer consists of ionic and neutral dimers ([Pd(dmit)2]22- and [Pd(dmit)2]20).
Fig. 1. R aman sp ectra of ET 5 Te 2 I 6 and BETS 5 Te 2 I 6 .
Fig. 2. Conduc tivity (IR) spectra of Et 2 Me 2 Sb[Pd(dm it) 2 ] 2 .
[1] T. Yamamoto, et. al. Phys. Rev. B. in press. [2] A. F. Bangura, et. al. Phys. Rev. B. 72 (2005) 014543. [3] M. Fujiwara, et. al. J. Sol. Stat. Chem. 168 (2002) 396. [4] M. Tamura, et. al. Chem. Phys. Lett. 411 (2005) 133.
TU49 ABNORMAL ENHANCEMENT OF THE INTERLAYER ELECTRIC CONDUCTION WITH AN IN-PLANE MAGNETIC FIELD W. Kang1, Y. J. Jo1, H. Y. Kang1, T. Osada2 1Department of Physics, Ewha Womans University, Seoul 120-750, Korea 2Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba 277-8581, Japan Interlayer magnetotransport in layered conductors shows many kinds of dramatic oscillatory and resonance phenomena as a function of magnetic eld orientation. Numerous theoretical and experimental studies have been devoted to elucidate the underlying mechanism of the observed properties such as the Lebed resonances, the DannerChaikin Oscillations, the third angle effect. Recently, a new feature draws our attention. When the magnetic eld lies parallel to the conducting layers, the interlayer conductivity is abnormally enhanced, violating the simple argument of the Lorentz force picture. Within the framework of the semiclassical picture of the transport theory, the inuence of a magnetic eld should be the largest when the current ows perpendicular to the magnetic eld. In addition that the electrical conductivity is enhanced under in-plane eld, the enhanced conductivity is independent of the eld direction in the plane over a broad angular range around the intermediate conducting axis. We will present, in this paper, experimental results of the conductivity enhancement for three different compounds with various anion superlattice potentials and discuss the possible origin of this unusual feature. Fig. 1. Interlayer conductivity as a function of angle that the magnetic eld makes with the most conducting axis in the conducting plane. The sharp dips around 20 degree and 180 20 degree are the third angle effects. The atness of the Rzz around 90 degree deserves a special attention. Although the resistance increases about ve times from its minimum value at the third angle, it is still much smaller than that when there is a nite out of plane component of magnetic eld.
ABSTRACTS
TU50 STRONG OPTICAL NONLINEARITY AND ITS FAST PHOTO-SWITCHING IN CHARGE ORDERED FERROELECTRIC -(BEDTTTF)2I3 Kaoru YAMAMOTOa, Shinichiro IWAIb,c, Sergiy BOYKOd, Akimitsu KASHIWAZAKIb, Fukiko HIRAMATSUb, Chie OKABEa, Nobuyuki NISHIa, and Kyuya YAKUSHIa aInstitute for Molecular Science, Myodaiji, Okazaki, Aichi 444-8585, Japan; bTohoku University, Sendai, Miyagi, Japan; cPREST-JST; dUniversity of Ontario Institute of Technology, Oshawa, Ontario, Canada Recently, charge ordering (CO) has drawn growing attention as a newly recognized electronic phase in conductive CT complex with highly correlated electron. Formation of CO induces a local polarization. If the crystal symmetry allows survival of the polarization, macroscopic polarization appears as is seen in ferroelectrics. To nd such spontaneous polarization in charge ordered CT complex, we started to measure optical secondharmonic-generation (SHG). In the present paper, we report the experimental results performed on -(BEDT-TTF)2I3. This compound shows metal-to-insulator transition at 135 K due to CO. We measured SHG signal in transmission geometry using a very thin single crystal. Figure 1 displays the intensity of the SHG signal as a function of temperature. According to the plot, SHG signal rises at the phase transition temperature, and grows with lowing temperature. The emergence of second-order optical nonlinearity indicates that inversion symmetry existing in the metallic phase is broken by CO. Because the crystal system is triclinic, absence of the inversion means possible presence of Fig. 1 T em pe rature d epen den ce o f the SHG sig na l. spontaneous polarization. We estimated the nonlinear electric susceptibility of the compound, and Excitation light [ ex( =1400 nm , pulse width ~2 ps ] is found that it exceeded BBO, which is a typical nonlinear optical crystal. This fact strongly suggests pol arized in E //a-axis. SH light is collec ted wi thout that large spontaneous polarization is induced in the CO phase.
pol arizer.
While ferroelectricity of conventional ferroelectrics is governed by geometrical arrangement of ions, that of CO matters by electron arrangement. Therefore, the charge ordered ferroelectric is expected to show fast response against external perturbation. We demonstrated that the optical nonlinearity was suppressed instantaneously by photo excitation (100 fs) by pump-probe measurement. Noteworthy is the fact that the suppressed nonlinearity is recovered in 10 ps scale. The features of optical nonlinearity for the new ferroelectric will be presented.
TU51 METAL-INSULATOR TRANSITION AND -D INTERACTION OF QUASI-1D ORGANIC CONDUCTORS (DMET)4(MCL4)(TCE)2 (M=MN,CO,CU,ZN) H. Ito1, D. Suzuki1, H. Watanabe1, H. Tanaka1, S. Kuroda1, M. Umemiya2, S. Takaishi3, H. Miyasaka2, K.i. Sugiura2, M. Yamashita3,4, H. Tajima5, E. Ohmichi5, T. Osada5 1Department of Applied Physics, Nagoya University, Chikusa, Nagoya 464-8603, Japan 2Department of Chemistry, Tokyo Metropolitan University, Hachioji 192-0397, Japan 3Department of Chemistry, Tohoku University, Aoba, Sendai 980-8578, Japan 4CREST 5Institute of Solid State Physics, University of Tokyo, Kashiwa, Chiba 277-8581, Japan The asymmetrical donor of dimethyl(ethylenedithio)diselenadithiafulvalene (DMET) has produced a large number of quasi-one-dimensional (Q1D) conductors and superconductors to the latest member of (DMET)2CuCl2.1 In this paper we report the electronic state of the newly-synthesized DMET salts of (DMET)4MCl4(TCE)2 [M=Mn, Co, Cu, Zn] studied by resistivity, magnetoresistance, dc susceptibility and ESR measurements. Unlike the other Q1D DMET salts, the unit cell of these salts contains four molecules forming stacks along a+b direction, as shown in Fig.1. Then the Q1D Fermi surfaces are folded resulting in the semimetallic Fermi surfaces consisting of electron and hole pockets, as shown in Fig 2. With this background, the present salts with magnetic (Mn, Co, Cu) and nonmagnetic (Zn) ions may provide a new system for studying -d interactions. M=Mn, Co, Zn salts exhibit metal-insulator transitions at 25K, 15K, and 13 K, respectively. The M=Cu salt shows a semiconducting behaviour. Under pressure up to 7 kbar, no superconductivity is observed. In M=Mn, Co, and Cu, dc susceptibility and ESR signals from d-electrons are observed. In M=Mn, Cu, ESR signals with anomalous temperature dependence indicating -d interactions are observed. In M=Co,Zn a large magnetoresistance is observed with a hysteresis in magnetic eld sweep. In M=Co, a rapid-oscillation behaviour is observed above 30 T using pulsed high eld. These results indicate that the metal-insulator transition in the series of salts is caused by an SDW transition due to the imperfect nesting of the semimetallic Fermi surfaces, like (TMTSF)2NO3 under anion ordering.2 In M=Mn, Cu, the -d interaction affects the electronic state, suppressing the magneto-resistance in M=Mn and the metallic conduction in M=Cu salt. 1. H. Ito et al., Phys. Rev. B 71 (2005) 212503 2. T. Osada et al., Synth. Met. 55-57 (1993) 1795.
Fig.1
Fig. 2
ABSTRACTS
TU52 MECHANISM OF CARRIER PHOTOGENERATION AND CARRIER TRANSPORT IN MOLECULAR CRYSTAL TETRACENE Daniel Moses Institute for Polymers and Organic Solids, University of California, Santa Barbara, Santa Barbara CA 93106, USA Models for the carrier photoexcitation mechanism in molecular crystals have been established initially on the bases of measurements on oligo-acenes and later applied to conjugated polymers as well. These models emphasize the localized nature of photoexcitations and describe carrier generation as a secondary process involving exciton dissociation. We present the results of transient and steady-state photoconductivity measurements on single crystal tetracene that indicate a carrier photoexcitation mechanism that is at variance with these widely used models. We nd the transient photocurrent to increase as the sample temperature decreases, similarly to the behavior of the carrier mobility. Our studies indicate that the photocarrier quantum efciency in tetracene is independent of temperature, photon energy and light intensity, thus featuring the hallmarks of direct inter-band carrier photogeneration and coherent carrier transport at band states. We will discuss our nding in the context of the two transport mechanisms operating in molecular crystals and the way they are manifested in transient and steady-state photoconductivity measurements.
TU53 THERMAL AND ELECTROMECHANICAL PROPERTIES OF CARBON AND BORON NITRIDE NANOTUBES Alex Zettl 366 LeConte Hall, University of California at Berkeley, Berkeley, California 94720 U.S.A.
Carbon and boron nidride nanotubes have unusual geometrical, electronic, and vibrational structure. In this presentation I will explore the use of nanotubes as agents of mass transfer, heat transfer, and low-friction mechanical motion. Of particular interest is the coupling of high resoultion TEM imaging to transport and mechanical measurements. As such, electrical and thermal response changes are directly correlated to atomically-resolved structural changes.
TU54 RAMAN SPECTRA OF (N,M)-IDENTIFIED INDIVIDUAL SINGLE-WALLED CARBON NANOTUBES M. Pailleta, T. Michela , J.C. Meyerb , V. Popovc, L. Henrardc, and J.L Sauvajola a-LCVN (UMR 5587), Universit Montpellier II, 34 095 Montpellier France b-Max Planck Institute for Solid State Research, Stuttgart, Germany c-Facults Universitaires Notre Dame de la Paix, B-5000 Namur, Belgium
For long time, the resonance Raman responses of isolated SWCNTs were only measured on SWCNTs grown (deposited) on a substrate, and on SWCNTs wrapped in a surfactant. The responses have been mainly understood in the framework of different models of the electronic and mechanical properties. The goal of the complete experimental approach, that we have recently developed, was to relate the Raman response of an individual SWCNT to its (n,m) structure determined from an independent way. In this aim, a procedure including the preparation of substrates, the sample preparation, atomic force microscopy imaging (AFM), transmission electronic microscopy (TEM), Raman spectroscopy, and electron diffraction experiments has been developed. We demonstrate the determination of the structural indices (n,m) by electron diffraction and of the features of the phonon modes by Raman spectroscopy on the very same individual and isolated free-standing SWCNT 1. The precise and independent determinations of both structure and Raman features allow unambiguously answering at several important questions. 1-A relation between diameter (d) and the radial breathing mode (RBM) frequency is determined. We point out that these results are covering an unprecedented diameter range: from 1.3 nm to 3 nm. These results suggest that the RBM frequency is not simply inversely proportional to the nanotube diameter 2. The comparison with previous RBM frequency vs d relations obtained on SWCNTs grown on a substrate, or wrapped in a surfactant allows discussing the role of the environmental effect on the Raman response of SWCNT. 2-The proles of the tangential modes with respect to the structure of the tube are reported. The dependence of the frequency and line shape of the tangential modes are compared with the predictions of different models 3. 3- The comparison between the incident excitation energies for which an intense Raman signal is observed and the calculated transition energies allows us to determine precisely the values of the optical transition energies for SWCNTs in a broad diameter range 3. 4-In the debate concerning the dominant process at the origin of the rst-order Raman scattering in SWCNTs: single resonance process against double-resonance process, the ensemble of our results are well understood in the framework of a single resonance approach 3. [1] J. Meyer, M. Paillet, J.-L. Sauvajol, et al, AIP Conference proceedings, Kirchberg , page 512 (2005). [2] J.C. Meyer, M. Paillet et al, Phys. Rev. Lett. . 95 (2005) 217401 [3] M. Paillet, T. Michel, J.-L. Sauvajol et al, Phys. Rev. Lett. (Submitted, 2006)
S.Lefranta, I.Baltogb and M.Baibaracb aInstitut des Matriaux Jean Rouxel, B.P.32229, 44322 Nantes, France
ABSTRACTS
TU55 COHERENT ANTI-STOKES RAMAN SCATTERING ON SINGLE-WALLED CARBON NANOTUBES THIN FILMS EXCITED THROUGH THE SURFACE PLASMONS
bNational Institute of Materials Physics, Lab.Optics and Spectroscopy, Bucharest, P.O.Box MG-7, R-76900, Romania
We report experimental data which indicate that in nanometric thin lms of single-Walled Carbon Nanotubes, an anti-Stokes Raman emission, reminiscent of Coherent anti-Stokes Raman Scattering (CARS) is observed1. We demonstrate that under a tightfocusing of the excitation light, a CARS emission resulting from a wave mixing process between the incident laser light (l) and Stokes Raman light (s) generated by a Surface Enhanced Raman Scattering (SERS) mechanism is produced. Although the effect is observed on different materials, the work is restricted to the intense anti-Stokes emission of single-walled carbon nanotubes, copper phthalocyanine and poly(bithiophene). The results which corroborate the CARS emission are the following: i) a square relation between the CARS signal intensity and the lm thickness ; ii) a square relationship between the CARS signal intensity and the exciting laser intensity; iii) a dependence of the CARS intensity on the numerical aperture (NA) of the microscope objective used for the detection of the anti-Stokes emission, an abnormal anti-Stokes Raman signal being detected only using with a microscope objective of high NA, 0.95 and 0.55; iv) a polarization ratio in the anti-Stokes side always greater in comparison with that measured for a spontaneous Stokes Raman emission. On the basis of previous reports explaining the anti-Stokes spectra of SWNTs as being due to a double resonant Raman scattering effect produced by the excitation of different (n,m) nanotubes with the incident and Stokes scattered photons, the CARS process is another phenomenon which has to be taken into account, with potential applications for sensitive detection and identication of trace amounts of nanostructured materials. References: 1. I. Baltog, M. Baibarac, S. Lefrant, PRB 72, 245402 (2005).
TU56 FRACTIONATION OF SINGLE WALL CARBON NANOTUBES ACCORDING TO DIAMETER AND METALLICITY BASED ON THEIR INHERENT REDOX DIFFERENCE Fotios Papadimitrakopoulos Nanomaterials Optoelectronics Laboratory Dept. of Chemistry, Polymer Program, IMS University of Connecticut Storrs, Connecticut 06269-3136, USA Precise control of single wall carbon nanotubes (SWNTs) over length, diameter, type (or otherwise termed metallicity (metallic vs. semiconducting)) and chirality are of pivotal importance for their future involvement in high-end electronic and optoelectronic devices as well as in biosensory applications. From an electronics perspective, separation of SWNTs according to type and diameter (the latter of which controls the band-gap for semiconducting SWNTs) is of extreme importance. During the past three years a number of separation methodologies have been debuted and although large-scale enrichment remains a challenge, considerable progress have been achieved in this frontier. Our initial report on the preferential interaction of surfactant amines with sem-SWNTs, as opposed to met-SWNT fraction, provided the means to alter their respective solubility characteristics and afford separation.1 Until recently, very little was known on the underlying nature of this separation. In this contribution, the differential dedoping characteristics of SWNTs according to diameter and metallicity will be described as the fundamental cause that triggers this separation.2 This was deduced with the help of resonance Raman spectroscopy in conjunction with modeling of the Gibbs free energy and chargeloss as it pertains to the (n,m)-dependent SWNT integrated density of states (IDOS) across a redox jump. _________ 1. D. Chattopadhyay; I. Galeska; F. Papadimitrakopoulos, J. Am. Chem. Soc. 2003, 125(11), 3370-3375. 2. S. N. Kim; Z. Luo; F. Papadimitrakopoulos, Nano Letters, 2005, 5(12), 2500-2504. Financial support from ARO and AFOSR is kindly appreciated.
TU57 ELECTRONIC FLUCTUATIONS IN MULTI-WALLED CARBON NANOTUBES
B. Raquet, B. Lassagne, J.-M Broto Laboratoire National des Champs Magntiques pulss, LNCMP-UMR5147, CNRS-UPS-INSA, 143 av. de rangueil 31400 Toulouse, France J.-P Cleuziou, Th. Ondaruhu, M. Monthioux Centre dElaboration des Matriaux et dEtudes Structurales, CEMES-CNRS, UPR 8011, 29 rue Jeanne Marvig, 31055 Toulouse, Cedex 4 France
ABSTRACTS
The physics and application of Carbon Nanotubes (CNTs) in nano-electronics are currently under intense studies. Most of the striking characteristics of the electronic transport in CNTs have been expressed using the time average of the conductance. However, high order statistic conductance uctuations in nano-scale conductors are a powerful experimental tool to unveil the exceptional richness of charge carriers properties in a conned environment. The issue of the electronic noise experiments on CNTs has to be addressed in the very specic context of their unique electronic transport properties. This implies noise measurements as a function of the Fermi energy location to probe the interplay between the electronic uctuations and the band
structure. Up to now, the very few studies on individual CNTs display a low frequency 1/f-noise whose the magnitude ranges over four decades. The contribution of the tube alone to this noise and its structural quality dependence are opened questions. In this work [1], we bring evidence that gas, mainly oxygen surrounding the tube, signicantly contributes to the electronic uctuations at room temperature. Under controlled atmosphere, the excess noise level and its temperature dependence are also conditional on the conduction regimes of the tubes. We demonstrate that quasi-ballistic Multi-walled Carbon Nanotubes (MWCNTs) are low noise conductors at room temperature. The 1/fnoise behaves like a background noise independent on the number of conduction channels. In case of diffusive MWCNTs, we infer a distribution of the activation energies responsible for the intrinsic CNT noise. From multi-probes measurements, an estimate of the localized contact noise is proposed. Finally, we give evidence that low noise MWCNTs at room temperature may exhibit huge random telegraph noise at low temperature by tuning the Fermi energy location. From the spectroscopy of the RTN, we sketch the possible contribution of impurity scattering uctuations enhanced by quantum interferences.
[1] B. Lassagne & al., New J. Phys., accepted for publication 2006.
Presenting author for an oral contribution : Dr. Bertrand Raquet, Laboratoire National des Champs Magntiques pulss (LNCMP) -UMR5147, CNRS-UPS-INSA, 143 av. de rangueil 31400 Toulouse, France raquet@lncmp.org
TU 58 UNIVERSAL PROPERTIES OF QUASI-ONE-DIMENSIONAL EXCITONS IN SEMICONDUCTING SINGLE-WALLED CARBON NANOTUBES AND -CONJUGATED POLYMERS Sumit Mazumdar, Hongbo Zhao and Zhendong Wang University of Arizona -conjugation, quasi-one-dimensionality and Coulomb electron-electron interactions among the -electrons are common to both semiconducting single-walled carbon nanotubes (S-SWCNTs) and -conjugated polymers (PCPs). It is thus not surprising that there will exist strong similarities in the photophysics of these two classes of materials. In this talk we rst briey review the photophysics of PCPs, focusing on the theory of excitons and theoretical and experimental work on the nonlinear optical spectroscopy of these systems. Following this, we present the results of detailed calculations of the excitonic energy spectra of twenty-nine different S-SWCNTs with diameters ranging from 0.56 to 1.51 nm, nine of which are zigzag and the remaining chiral1,2. With Coulomb parameters that are identical to those that we had proposed earlier for the PCPs3, and a hopping integral that is smaller due to the characteristic curvature of S-SWCNTs, we are able to quantitatively t the energies of the rst and second longitudinal optical excitons in the S-SWCNTs. Our calculated exciton binding energies (some of which were predicted prior to the experiments1) are remarkably close to what are observed. Most importantly, we show that the essential states model of third-order optical nonlinearity, previously developed for PCPs3, applies also to the S-SWCNTs with minor modications4. Clear physical explanations of exciton formation, weak photoluminescence and nonlinear absorption in the S-SWCNTs will be presented. 1. H. Zhao and S. Mazumdar, Phys. Rev. Lett. 93, 157402 (2004). 2. Z.D. Wang, H. Zhao, and S. Mazumdar, to be published. 3. M. Chandross and S. Mazumdar, Phys. Rev. B 55, 1497 (1997). 4. H. Zhao, S. Mazumdar, C.-X. Sheng, M. Tong, and Z. V. Vardeny, Phys. Rev. B 73, 075403 (2006). TU59 NON-COVALENT GRAPHITIC NANOSTRUCTURES BY PROGRAMMED SELF-ASSEMBLY Takuzo AIDA1,2 and Takanori FUKUSHIMA2 1 Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan 2 ERATOSORST Nanospace Project, JST, National Museum of Emerging Science and Innovation, 2-41 Aomi, Koto-ku, Tokyo 135-0064, Japan E-mail: aida@macro.t.u-tokyo.ac.jp Self-assembly of -conjugated molecules has been recognized as a useful approach to the fabrication of electronic and optoelectronic soft materials with a nanometric structural precision. As the building block for programmed self-assembly, we took notice of hexa-peri-hexabenzocoronene, which is regarded as a molecular graphene and known to possess a strong tendency to stack together via -electronic interactions. In the present paper, we highlight our recent studies on a new family of discrete nanotubular graphites formed by self-assembly of amphiphilic HBC derivatives such as 1.[1] The nanotubes consist of a graphitic wall composed of a great number of -stacked hexabenzocoronene units. The wall is 3 nm thick, formed by helical arrays of the -stacked graphene molecules, where the exterior and interior surfaces of the nanotubes are both covered by hydrophilic triethylene glycol (TEG) chains. The graphitic nanotubes are redox active and electroconductive upon oxidation.[2] The use of amphiphilic hexabenzocoronenes with functional groups at the termini of the TEG chains results in the formation of graphitic nanotubes with various interesting properties.[35]
ABSTRACTS
References [1] Science 2004, 304, 1481. [2] Adv. Mater. 2006, 18, 1297. [3] Proc. Natl. Acad. Sci. USA 2005, 102, 10801. [4] J. Am. Chem. Soc. 2005, 127, 8284. [5] J. Am. Chem. Soc. 2006, 128, 4220.
TU 60 3D SELF-ASSEMBLY OF ORGANIC SEMICONDUCTORS Elena Mena-Osteritz Department of Organic Chemistry II, University of Ulm, Albert-Einstein-allee 11 89081-Ulm, Germany E-mail: elena.mena-osteritz@uni-ulm.de
Self-organized systems are in the focus of nanotechnology research because of their potential use in the bottom-up development of functional supramolecular structures. The construction of complex assemblies using molecular entities is a key point for the deve-lopment of novel functional materials.[1] However, the assembly of molecular materials in nanoscale architectures will be a crucial step for the future molecular scale electronics.[2] In this contribution the power of the scanning tunnelling microscopy and spectroscopy (STM and STS) to analyze interesting organic semiconductors, such as macrocyclic and linear oligothiophenes adsorbed on surfaces will be demonstrated. The measurements have been done at ambient temperature at the liquid-solid or air-solid interfaces. The specic molecular design allows the control of the intermolecular interactions [3] and 3D nanostructures can be grown based on an electron donor-acceptor concept (Fig. 1). Due to the high crystallinity of the non-covalent nanoarchitectures, dynamics, adsorption site and electronic properties can be analysed by means of high resolution STM images and scanning tunnelling spectroscopy.[4]
20
Figure 1: STM-Images of macrocyclic thiophene-C60 complexes with detailed image inserted (left) and linear quaterthiophene-C60 complexes (right). Insert: calculated models. [1] a) C.P. Collier, E.W. Wong, M. Belohradsky, F.M. Raymo, J.F.Stoddart, P.J. Kuekes, R.S. Williams, J.R. Heath, Science 1999, 285, 391. b) J.S. Tans, A.R.M. Verschueren, C. Dekker, Nature 1998, 393, 49. [2] H. Engelkamp, S. Middelbeek, R.J.M. Nolte, Science 1999, 284, 785. [3] E. Mena-Osteritz, Adv. Mater. 2002, 14, 609-616 [4] E. Mena-Osteritz and P. Buerle Adv. Mater. 2006, 18, 447- 451.
TU 61 SELF-ASSEMBLY OF FULLY CONJUGATED TTF OLIGOMERS Masahiko Iyoda, Hideo Enozawa, and Masashi Hasegawa Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
ABSTRACTS
Self-assembly of conjugated macrocycles and long helical molecules into complex, organized supramolecular structures via specic intermolecular interactions is a promising way to realize new molecular materials. Many intermolecular interactions such as hydrogen bonding, metal coordination, CT interaction, and stacking have been utilized recently to construct desired supramolecular architectures. Among these, cooperative S-S and stacking interactions of oligomeric TTFs can play an important part in preparing columnar aggregates with high charge carrier mobilities. In order to make self-assembled materials based on fully conjugated oligomeric TTFs with potential conducting and magnetic properties, we designed
R R S S S S S S S S
R R Bu nS S SBu n S S S S R S S R S Bu nS S
Bu nS S S S S S S S SBu n S
Bu nS Bu nS
S S
S S S S SBu n
2
S S
S S S
tris(tetrathiafulvaleno)dodecadehydro[18]annulene (1) and hexakis(tetrathia-fulvale nylethynyl)benzene (2) composed of large cores, TTF units, and peripheral alkyl chains. Compound 1 exhibits solvatochromic and thermochromic properties mainly SBu n caused by self-assembly of 1 in solution and forms molecular wire from an aqueous THF solution of 1. Similarly, 2 self-aggregates both in solution and in the solid state SBu n to form columnar structure and molecular wire. Interestingly, nanowire of 2 has a hexagonal arrangement of colums, whereas its lm on the glass surface forms an oblique columnar structure and exhibits a weak FET properties. Doping of 1 and 2 with iodine forms semi-conductors, reecting their columnar arrangements. SBun
1a : R = SBu n 1b: R = CO 2Bu n 1c : R = CO 2Octn
Bu nS
TU 62 CRYSTAL STRUCTURES AND MAGNETIC PROPERTIES OF ELECTRON-RICH POLYOXOMETALATES WITH HYDROGENBONDING CATIONS Tomoyuki Akutagawa,1, 2 Daigoro Endo,2 Hiroyuki Imai,1 Shin-ichiro Noro,1,2 Leroy Cronin3, Takayoshi Nakamura,1,2 1Research Institute for Electronic Science, Hokkaido University, 2Graduate School of Environmental Earth Science, Hokkaido University, 3Department of Chemistry, University of Glasgow. A variety of peculiar molecular structures such as Keggin-type Mo12 and gigantic Mo154-ring clusters have been reported in polyoxometalate (POM) system. The electrically active clusters have a potential to act as multi-electron reservoir by receiving electrons at MoVI sites. The reduced MoV sites have magnetic spins and thermally activated electrons, which migrates between structurally regulated Mo sites within the clusters. Here we present attempts to control the electronic structures, spin dynamics, and cluster arrangements within the crystals of Keggin-type Mo12 and gigantic Mo154-ring by using hydrogen-bonding p-phenylenediamine (PPD) derivatives (Fig. 1). The reduced Mo12 clusters were obtained by redox reaction between the electron-acceptor of H+3[PMo12O40]3- and the electron-donor of PPDs in CH3CN, which generated the S = 1/2 spin on the cluster. During the crystal formation, proton-transfer processes from the proton-donor of H+3[PMo12O40]3- to the proton-acceptor of PPDs in solution resulted in the hydrogen-bonding supramoleuclar system between PPD and Keggin clusters. Fig. 2 shows the crystal structure of (PPD)3[PMo12O40](CH3CN)6 (1). Each [PMo12O40] cluster arranged in a hexagonal packing through the N-H ~ O hydrogen bonding interactions between protonated PPD derivatives (4-aminoanilinium+ or p-phenylenedimmnoium2+) and the oxygen sites of [PMo12O40] cluster in the ab-plane. Along the c-axis, regular stack of [PMo12O40] clusters was Fig. 1. Molecular structures of Keggin-type observed. Between the hydrogen-bonding a) b) [XMo 12 O 40 ] and gigantic Mo 154 -ring clusters. PPD-[PMo12O40] network structures, one-dimensional channels were observed along the c-axis. The CH3CN molecules occupied the channel. Gigantic Mo154-ring clusters were prepared by the condensation reaction of b Na2[MoO4] in acidic solution. Instead of Na2[MoO4], transition metal salts of Co[MoO4] and Mn[MoO4] were employed for starting materials. In these crystals, both of Co and Mn were introduced as the counter cations of gigantic Mo154-ring a clusters, which showed the Curie-Weiss behaviour in temperature-dependent magnetic Fig. 2. Crystal structure of 1. a) Hydrogen-bonding susceptibility.
interaction between PP D and [PMo 12 O 40 ] . b) Unit c ell viewed along the c-axis.
TU63 SELF-ORGANISATION AND SELF-ASSEMBLY IN NANO/MICRO OBJECTS DISPERSE SYSTEMS Toru Maekawa1,*, Takahiro Fukuda1, Hisao Morimoto1, Yutaka Nagaoka1, Koji Ishii1, Raymond Whitby2 and Nicole Grobert3 1Bio-Nano Electronics Research Centre, Toyo University 2100 Kujirai, Kawagoe, Saitama 350-8585, Japan 2 Nanoscience and Nanotechnology Centre, University of Sussex Falmer, Brighton, BN1 9QJ, UK 3Department of Materials, University of Oxford Parks Road, Oxford OX1 3PH, UK We investigate self-organisation and self-assembly, which occur in (a) a ferromagnetic nanoparticles disperse system, (b) a paramagnetic microparticles disperse system, and (c) C60s disperse systems. (a) Ferromagnetic nanoparticles disperse system: We analyse the effect of the intensity of the dipole-dipole interactive energy and external magnetic eld, the system temperature and the number of particles on the cluster structures. We also show the effect of the cluster structures on the rheological characteristics of the particles disperse system. (b) Paramagnetic microparticles disperse system: We investigate the secondary structures created by chain clusters in a dc magnetic eld and the particles self-organisation and self-assembly process in a rotational magnetic eld. Based on the self-organisation mechanism, we demonstrate the manipulation of particles, clusters and cells using the rotational magnetic eld. (c) C60s dispersed in critical uids: We place C60 crystals in ethane, carbon dioxide and xenon and nd that clusters such as rods, helices and sheets, which are composed of C60s, are created when the uid systems are set so close to their critical points that critical opalescence occurs. We analyse the self-assembly process from the point of view of quantum molecular dynamics.
ABSTRACTS
TU64 FUNCTIONALISED CARBON NANOTUBES AS BUILDING BLOCKS OF ELECTRONIC SELF-ASSEMBLED NANOSTRUCTURES J.M. Balach, D.F. Acevedo, V.C. Ortiz, D.O. Peralta, M.C. Miras, C.A. Barbero Advanced Materials Programme, Universidad Nacional de Rio Cuarto, 5800- Rio Cuarto, Argentina, E-mail: cbarbero@exa.unrc.edu.ar Introduction Carbon nanotubes are interesting materials to be used as components of electronic devices such as transistors. While it is possible that some carbon nanotube devices could compete with silicon based devices (e.g. power transistors), it is more likely that wet processing of carbon nanotubes will allow producing simple devices of technological interest. Pristine carbon nanotubes have low solubility due to weak interaction with solvent molecules and strong and dispersive interaction between individual nanotubes. Therefore, the required solubility could be achieved by attachment of functional groups which interact efciently with solvents and, due to steric effects, decrease the interaction between neighbouring nanotubes. Results & Discussion In the present communication, different approaches of nanotube functionalisation are presented. Among them: covalent linking of functional groups and non covalent interaction with conducting polymers. The rst approach is made by reaction of the aromatic ring with aryl cations or formaction of acyl derivatives. The non covalent interaction is made by wrapping of the nanotubes with soluble conducting polyanilines. Those polyanilines are then produced by combinatorially selected chemical reactions on the polyaniline backbone . The functionalised nanotubes are then used to build electronic nanostructures, such as layer-by-layer self assembled multilayers made of functionalized nanotubes together with polyelectrolytes (including conducting polyelectrolytes). The mechanism of charge transfer between layers is probed by dynamic electrochemical techniques, uorescence, and electrocatalytic reactions. Conclusions It is possible to produce functionalized carbon nanotubes either by covalent functionalization or by wrapping with functionalized conducting polymers. Those soluble and functionalized materials could be used as building blocks of electronic nanostructures, such as layer-by-layer self assembled multilayers. Acknowledgements The present work was nanced by SECYT-UNRC, CONICET, FONCYT and Fundacin Antorchas. D.F.A. and D.O.P thanks CONICET and FONCYT for graduate fellowships. V.C.O. and J.M.M thanks EDUMAT for undergraduate fellowships. C.A.B is a permanent research fellow of CONICET. References S. Iijima,. Nature, 354(1991)56. C. A Dyke, .J.M. Tour, J. Am. Chem. Soc. 2003, 5, 1156; J.L. Bahr, J.M. Tour, Chem. Mater. 11(2001)3823. Diego F. Acevedo, Mara C. Miras, Cesar A. Barbero, Journal of Combinatorial Chemistry, 7(2005)513-516.
TU 65 STATISTICAL MECHANICS OF SELF-ASSEMBLY: ARE THERE APPLICATIONS IN NANOMATERIALS MANUFACTURING? John F. Maguire* Air Force Research Laboratory, Dayton, Ohio 45433-7746 *email: john.maguire@wpafb.af.mil The ability to predict and control the density, position and orientation of naononnanoparticles in polymer matrices and/or in thin lms and interfaces has far-reaching applications in nanoscience and technology. In particular, the control of colloidal phase transitions or so-called self-assembly may play an important role the development of viable manufacturing technologies for a wide range nanomaterials. However, statistical mechanics in the mesoscopic regime presents signicant challenges in both theory and computer simulation. In this talk I shall present a new method of conducting molecular dynamics (MD) simulations that uses an articial neural to increase computational speed by over three orders of magnitude. This technique enables dynamical simulation of large ensembles of hard objects of essentially arbitrarily complex geometry or size and is well suited to the simulation of granular or nanomaterials. The method will be illustrated using an MD study of an ensemble of 1800 hard smooth impenetrable equilateral triangles in two dimensions. At high packing fraction (0.6 < <0.9) this system exists as a liquid-crystalline-like phase (LCP) in which there is no long-range translational order but in which there is nearly perfect long-range orientational order. As the packing fraction decreases the LCP undergoes a transition to a uid state in which the long-range orientational correlation vanishes but short-range order is retained. Longlived clusters, notably hexamers, and chain-like structures are clearly apparent in the liquid phase and appear to be stabilized by a sort of internal orientational osmotic pressure. It is clearly seen that even at very low packing fraction the shape of purely repulsive nanoparticles gives rise to long-range structures that are not random. The ability to predict and control such structures has far reaching consequences in nanomaterials processing. These methods have the potential to bridge the distance and timescale gap in molecular dynamics simulation and open up possibility of rigorous simulation of large ensembles of nanoparticles. The extension to atomistic and colloidal systems will be discussed briey as well as recent applications in manufacturing technology.
TU66 SOLID-STATE FABRICATION, STRUCTURE, AND MULTIFUNCTIONAL APPLICATIONS OF CARBON NANOTUBE YARNS AND TRANSPARENT SHEETS
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R.H. Baughman, M. Zhang, S. Fang, A. A. Zakhidov, M. Kozlov, S. B. Lee, A. E. Aliev (University of Texas at Dallas), and K. R. Atkinson (CSIRO Textile & Fibre Technology, Belmont, Victoria, Australia) We describe novel methods for producing polymer-free carbon nanotube yarns and transparent sheets and describe their properties and applications as multifunctional materials. These fabrication methods start with a solid-state draw to produce a highly oriented aerogel, and involve twist, falsetwist, and/or liquid densication processes. The yarns are strong, highly resistant to creep and to knot or abrasion-induced failure and provide a giant
tunable Poissons ratio for stretch in the ber direction. The nanotube sheets have higher gravimetric strength than the strongest steel sheet or the polymers used for ultralight air vehicles and proposed for solar sails. Applications evaluations are described for articial muscles, thermal and light harvesting, energy storage, eld-emission electron sources, electrically conducting appliqus, three types of lamps and displays, and sensors.
TU 67 CARBON NANOTUBE REINFORCEMENT OF CONDUCTING POLYMERS AND HYDROGELS FOR HIGH STRENGTH ACTUATORS. G. M. Spinks1; V. Mottaghitalab1; B. Xi1; P. Whitten1; G. Wallace1; S. Kim2; S. Shin2; S. Kim2 1. ARC Centre for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northelds Ave, Wollongong, 2522, NSW, Australia. 2. Hanyang University, Seoul, South Korea.
Practical devices for electromechanical actuators will only be realised when the actuator materials can generate sufcient movement (stroke) and forces within a suitable time frame. Low voltage actuators based on conducting polymers appear attractive choices because of the relatively large strains and stresses that have been previously reported. However, the small size of the actuator materials used mean that the actual stroke (few mm) and forces (<1 N) are quite small. A serious limitation to the maximum force that can be generated by actuator materials is their breaking strength. The practical maximum stress for conducting polymer actuators is then only a few tens of MPa and is much less in some cases. The maximum stress that can be applied to hydrogels is also very small. In our recent work, we have considered the use of carbon nanotubes as strengthening reinforcement for conducting polymers and hydrogels. These high aspect ratio bers are capable of signicantly increasing the strength and stiffness of polymers when added in only small quantities. Although an increase in stiffness may reduce the amount of movement produced by the actuator, this deciency may be compensated by the increase in loadcarrying capacity. We report in this paper the effect of carbon nanotube additions on the actuation behaviour of both polyaniline and chitosan actuator materials. In both cases a signicant increase in actuation strength was observed. In addition, the effect of the carbon nanotubes on the modulus and, therefore, actuation strain was also considered. A small reduction in strain was noted for the polyaniline, but little change in actuation strain was observed for the chitosan hydrogels. The results are further analysed in terms of actuation mechanisms occurring in conducting polymers and hydrogels.
TU68 ORIGAMI ACTUATORS WITH CONDUCTING POLYMERS Hidenori Okuzaki and Tomooki Saido Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4-4-37 Takeda, Kofu 400-8511, Japan Conducting polymers have attracted considerable attention because dimensional changes resulting from electrochemical or chemical doping, characterized by the transportation of solvated ions between the inside of the polymer matrix and the surrounding electrolyte solution, electrostatic repulsion, and/or structural distortion through oxidation of polymers, can be applied to produce microactuators or articial muscles. Most of them exhibit dimensional changes in an electrolyte solution or in a swollen state, while few reports have been investigated on solid state polymers in a redox gas atmosphere or that employ a polyelectrolyte solid, gel, or ionic liquid. In the preceding papers, we have reported that electrochemically synthesized polypyrrole lms undergo quick and intensive bending in ambient air as a result of anisotropic dimensional change due to the sorption of water vapor from one side of the lm and have constructed polymer motors driving in air. Furthermore, we have found that polypyrrole lm exhibits contraction in air under application of an electric eld, where the electrically induced dimensional change of the polypyrrole lm is only 1-2%. To actuate a large strain under an electric eld, we fabricated an origami actuator as shown in Figure 1. In the manner of origami, two strips of polypyrrole lms are repeatedly folded so as to cross each other into the gure of a paper spring. When 2 V is applied through copper wires attached to top and bottom ends of the spring, the spring undergoes signicant elongation of over 30%. It is worth to note that the application of an electric eld causes contraction of the polypyrrole lm due to the desorption of water vapor but elongation of the spring. This can be explained by the modulation of elasticity: Upon application of an electric eld, the desorption of water vapor increases the elastic modulus of polypyrrole since water vapor molecules may behave as a plasticizer and enhance the motion of polymer chains. Thus, the polypyrrole becomes less deformative that tends to unfold the creases, leading to elongate the spring. Unlike in the conducting polymers based on the electrochemical doping, this system can serve as a new type of electrically driven muscle that works in air without using an electrolyte solution or counter and reference electrodes, where the applied voltage is capable of controlling the sorption equilibrium to desorb water vapor from the lm. Furthermore, this system can work at voltages one or two orders of magnitude lower than piezoelectric or electrostatic actuators because the dimensional change is owing to the electric current but the electric eld. Moreover, various conducting polymers or their derivatives that undergo dimensional changes due to the sorption of water vapor can be employed on the same principle.
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TU69 LINEAR AND OUT-OF-PLANE CONDUCTING POLYMER ACTUATORS Jadranka Travas-Sejdic, Rudolf Kiefer, Sreejith Valiavalappil, Shu Yi Chu, Paul A. Kilmartin, Graham A. Bowmaker, Ralph P. Cooney Polymer Electronics Research Centre, University of Auckland, Private Bag 92019, Auckland, New Zealand Intrinsically conducting polymers (ICP) are attractive materials for applications in actuators due to their low voltage operation, light weight, freedom in design of the polymeric matrix and ease of deposition in patterns 1. The actuation within ICPs results from the volume change arising from the movement of charge balancing solvated counterions in and out of the polymer matrix, along with changes in the conformation of the polymer backbone2. This property of volume change can be used to perform various modes of actuation, such as a bending beam3, linear actuation4 and outof-plane actuation5 which can be considered in the construction of various devices. Here we investigate the actuation properties of free standing polypyrrole (PPy) lms prepared from organic solutions of tetrabutylammonium triuoromethane- sulfonate (TBACF3SO3). The electrochemical and actuation properties of the 500 350 CV, 2mV/s lms are tested in a range of aqueous and non-aqueous electrolyte systems. Figure 1 presents 400 300 l the cyclic voltammogram and linear actuation obtained for a lm cycled in TBACF3SO3 (in 300 250 propylene carbonate (PC)). In this case, both anion and cation movement are observed during 200 200 lm oxidation, where the onset of anion movement occurs at the peak of the oxidation wave. 100 150 This is in contrast to the actuating behavior of PPy/CF3SO3 lms prepared in methyl benzoate 0 and cycled in NaPF6 (aq.) where only anion movement was reported6, and highlights the role 100 -100 the solvent system in actuator performance. 50
-200 -300 -1000 -500 0 500 1000
of
From the point of view of ICP applications in actuator devices, the important parameters are speed of actuation and durability. We will report on the effects of the variation of scan rate, electrolyte and solvent on the extent of linear actuation and the stability of cycling. The same polymer systems were tested for out-of-plane actuation with micro-sized PPy elements. The results, obtained by means of AFM, show that the out-of-plane actuation is signicantly larger than the in-plane actuation. Currently we are exploring the possibility of using both actuation modes in the construction of micro-uidic devices. 1 2 3 4 5 6
E / mV
Figur e 1. ECMD r esponse (dotted line ) a nd CV (solid line ) o f a free sta nd ing PP y/ CF 3 SO 3 film on cyc ling in 0.1 M TBA CF 3 SO 3 ( PC) . The actuati ng leng th of the f ilm w as 6 m m x 2 mm , and the thickness w as 15 m .
Smela, E. Adv. Mater. 2003, 15, 481-494. Baughman, R. H. Synth. Met. 1996, 78, 339-353. Maw, S.; Smela, E.; Yoshida, K.; Sommer-Larsen, P.; Stein, R. B. Sensors and Actuators, A: Physical 2001, A89, 175-184. Della Santa, A.; De Rossi, D.; Mazzoldi, A. Synth. Met. 1997, 90, 93-100. Smela, E.; Gadegaard, N. J.Phys.Chem.B 2001, 105, 9395-9405. Zama T., Hara S., Wataru T., Keneto K., Bull. Chem.Soc. Jpn., 2005, 78, 506-511.
TU70 SOFT ACTUATORS BASED ON CONDUCTING POLYMERS, POLYPYRROLE -High performance and the energy conversion efciencyK. Kaneto1, K. Yamato1, W. Takashima1, T. Zama1,2 and S. Hara2 1Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, 2-4 Hibikino, Wakamatsu-ku, Kitakyushu 808-0196, Japan. 2Eamex Co.,3-9-30 Tarumi-cho, Suita, Osaka 564-0062, Japan Corresponding author e-mail:kaneto@life.kyutech.ac.jp Soft actuators using electrochemomechanical deformation (ECMD) of a conducting polymer, polypyrrole (PPy) has been studied to attain better performance. The PPy lms were electrochemically prepared from methyl benzoate solution of tetra butyl ammonium (TBA) triuoromethansulf onate, TBACF3SO3 and TBA bis(peruoroalkylsufonil)imid, TBA(CnF2n+1SO2)2 N) (n = 1 - 4). The PPy lms prepared from TBACF3SO3 are tough and exible with the conductivity of more than 100 S/cm, and characterized as large force muscle with maximum stress of 49MPa1). On the other hand, the PPy lms obtained from TBA(CnF2n+1SO2)2 N were porous as shown in Fig.1 and gel in wet, and characterized as large contraction ratio muscle with the commonl strain of 26% and 39% at the maximum2). The maximum contraction ratio and force are more than those of natural muscles. The rate of deformation has been improved up to 12%/s by depositing Au electrode on the lm. Fig. 2 Surface morphologies of electrodeposited lms deposited by TBA(CF3SO2)2 N) and the photographs of left hand side are surfaces at electrode side and right hand side are solution side. The energy conversion efciency of the electrical input to mechanical output has been studied under the application of loads. It was found that with increasing the loads the both reduction and oxidation currents increased hence the input electrical energy increased as shown in Fib.2. The electrical input energy at free load is conjectured to charging the electrochemical cell. During contraction of the lm, 0.1-0.25 % of input electrical energy was utilized for the mechanical work3) as the energetical conversion efciency shown in Fig.3.
ABSTRACTS
Fig. 2 EEin for PPy lms consumed to lift weights. The base energy is associated with charging the cell.
Fig.3 Conversion energy efciency of PPy lm at various stress.
References 1) S. Hara, T. Zama, W. Takashima and K. Kaneto, Polym. J., 36 (2004) p. 933. 2) S. Hara, T. Zama, W. Takashima and K. Kaneto, Smart Mat. Struct., 14 (2005) p1502. 3) K. Kaneto, M. Kunifusa, K. Yamato and W. Takashima, to be published.
TU71 ELECTROCHEMICAL BEHAVIOR OF FERRITIN/CARBON NANOTUBES COMPLEX FILMS Kwang Min Shin, Sang Jun Park, Seoung Gil Yoon, Chang Kee Lee, Su Ryon Shin, Bon Gang Gu, Min Sup Kim, Min Kyoon Shin, and Seon Jeong Kim,* Dept. of Biomedical Engineering, Hanyang university, Seoul, Korea Ferritin is an iron storage protein founded in mammals and has a magnetic, electrochemical and assembly properties. Ferritin is remarkably stable and robust, and is able to withstand biologically high temperatures (up to 70) and a wide variation in pH 2.0 ~ 10.01. In the application of ferritin to biosensors and biofuel cells, a suitable immobilization method and the establishments of electron transfer between the electrodes are important factors. The natural afnity of CNTs to protein has been observed and documented in the literature 2,3. Because of the excellent electrical conductivity and protein afnity of carbon nanotubes, ferritin and carbon nanotubes complexes have great potentialitial in applications such as biosensor 4 and biofuel cells 5. Ferritin/CNT complex lms were prepared directly on the surface of an electrode, and the electrochemical analysis was carried out. The addition of ferritin stabilized the solution, and allowed the formation of a uniform lm of the complex to occur on the electrode. The lm was prepared by drop casting the solution of the complex on to the electrode. The effect of the composition of the ferritin/CNT complex was also analyzed electrochemically. The gure a) and b) showed that the electrochemical activity of ferritin remained after immobilization with the CNT in the complex lm, and that anodic and cathodic peaks were shifted because of conformational changes of ferritin in the complex. Ferritin showed an afnity with the CNTs, especially in the case of a 5 mg/ml aqueous ferritin complex with a 5 mg/ml SWNT (single wall carbon nanotubes), the ferritin redox peaks showed that the electrochemical activity of the complex was independent of the solvent and degree of dispersion of SWNT. In a case where a functionalized CNT was used instead of bare carbon nanotubes, the afnity between ferritin and the functionalized CNT allow for a uniform ferritin/CNT complex thin lm to be formed on the electrode and this also showed the characteristic redox reactions of ferritin. Because of the enhancement of the properties when ferritin and CNT were complexed, the ferritin/CNT complex lms can be used in applications such as biosensors and fuel cells.
References 1. T. Douglas, Biomimetic Approaches in Materials Science, Edited by S. Mann, pp91-115, VCH Publishers, New York, 1996 2. Y. Lin, L .F. Allard, and Y. Sun, J. Phys, Chem., B 108, 3760-3764, 2004 3. J. J. Davis, M. L. H. Green, H. A. O. Hill, Y. C. Leung, P. J. Sadler, J. Sloan, A. V. Xavior, and S. C. Tsang, Inorg. Chim. Acta. 272, 261-266, 1998
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(a) CV of CNT on an electrode
(b) CV of a CNT /ferritin complex lm
4. C. Zhi, Y. Bando, C. Tang and D. Goldberg, J. Am. Chem. Soc. 127, 17144-17145, 2005 5. J.W. Kim, S.H. Choi, P.H. Lillehei, G.C. King, G.D. Watt, S.H. Chu, Y. Park, and S. Thibeault, Proceedings of SPIEs Smart Structure and Materials, vol.5389, pp 453-461, 2004.
TU73 ULTRASENSITIVE OPTICAL DETECTION OF DNA AND PROTEINS BASED ON CATIONIC POLYTHIOPHENES Mario Leclerc Dpartement de chimie, Pavillon Alexandre Vachon, Universit Laval Quebec, Qc, CANADA, G1K 7P4
Conjugated polymers have received a lot of attention since they combine the best features of metals or inorganic materials with those of synthetic polymers. This synergy not only makes these materials useful in existing in electro-optical devices but also creates completely new opportunities. In this lecture, we will show how water-soluble luminescent polythiophenes can lead to the specic, rapid, and ultra-sensitive detection of unlabeled DNA, RNA, or proteins.1-3 This new optical detection mechanism is based on variable electrostatic interactions and conformational structures between a cationic polythiophene derivative and negatively-charged oligonucleotides.
Moreover, a signicant improvement of this strategy was recently reported through the efcient and fast energy transfer between the resulting uorescent polythiophene/double-stranded DNA and neighbouring uorophores attached to single-stranded DNA probes.4 This method makes now possible the rapid assessment of the identity of single nucleotide polymorphisms (SNPs), genes, and pathogens without the need for nucleic acid amplication. It is even possible to imagine the fabrication of reagentless, ultrasensitive, and specic biochips from this approach. Recent advances towards this goal will be described. 1) H. A. Ho et al., Angew. Chem. Int. Ed. 2002, 41, 1548. 2) K. Dor et al., J. Am. Chem. Soc. 2004, 126, 4240 3) H. A. Ho and M. Leclerc, J. Am. Chem. Soc. 2004, 126, 1384. 4) H. A. Ho et al., J. Am. Chem. Soc. 2005, 127, 12673.
TU74 CONJUGATED OLIGOMERS AND POLYMERS FUNCTIONALIZED WITH SMALL BIOMOLECULES FOR SENSING ORGANIC FIELD EFFECT TRANSISTORS G.M. Farinola,a L. Torsi,a M.C. Tanese,a O. Hassan Omar,b P. Iliade,a F. Babudri,a,b S. Casilli,c D. Colangiuli,a F. Naso,a,b L. Vallic aDipartimento di Chimica, Universit degli Studi di Bari - Bari (Italy) b CNR ICCOM, Dipartimento di Chimica, Universit degli Studi di Bari - Bari (Italy) c Dipartimento di Ingegneria dellInnovazione, Universit degli Studi di Lecce - Lecce (Italy) Conjugated oligomers and polymers functionalized with small biomolecules appear of special interest as active materials in resistor and transistor based sensors for chiral and/or biological analytes, since they can combine recognition capability of the substituents with electrical features of the conjugated backbones. In the frame of our studies dealing with novel organometallic strategies for the synthesis of polyconjugated materials,1 we obtained poly(aryleneethynylene)s (PAEs) functionalized with small biomolecules, such as glucose,2 amino acids, or nucleosides. Quartz crystal microbalance gravimetric sensors based on these PAEs demonstrated their ability to discriminate menthol enantiomers3. With the aim of synthesizing materials more suitable for transistor sensors, we moved to phenylene-thienylene oligomers, as good performances had been obtained in a resistive sensing device4 and in organic eld effect transistors (OFETs)5 based on Langmuir-Schfer (LS) thin lms of an alkoxysubstituted poly(phenylenethienylene). Therefore, we have set up a versatile synthetic strategy to obtain oligo(phenylenethienylene)s functionalized with protected amino acid or glucose units.
t
BO C H AcO AcO OAc O AcO S S O S S
O HN O
O S S S S
O
t
O O
OAc
BO C H NH O O
AcO
OAc O Ac
Multilayer LS structures made with the bio-substituted oligomers have shown good eld effect properties and have been used in OFET sensor devices for chiral discrimination. References: 1. Babudri F., Farinola G.M., Naso F. J. Mat. Chem. 2004, 14, 11. 2. Babudri F., Colangiuli D., Di Lorenzo P.A., Farinola G.M., Hassan Omar O., Naso F. Chem. Commun. 2003, 130. 3. Tanese M.C., Torsi L., Ciof N., Zotti L.A., Colangiuli D., Farinola G.M., Babudri F., Naso F., Giangregorio M.M., Sabbatini L., Zambonin P.G. Sens. Actuators B 2004, 100, 17. 4. Naso F., Babudri F., Colangiuli D., Farinola G.M., Quaranta F., Rella R., Tafuro R., Valli L. J. Am. Chem. Soc. 2003, 125, 9055. 5. Tanese M.C., Farinola G.M., Pignataro B., Valli L., Giotta L., Conoci S., Lang P., Colangiuli D., Babudri F., Naso F., Sabbatini L., Zambonin P.G.,
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Torsi L. Chem. Mater. 2006, 18, 778.
TU75 STRUCTURE-PROPERTY RELATIONSHIPS IN MELANINS - A UNIQUE CLASS OF CONDUCTING BIO-MACROMOLECULE 1P. Meredith, 1J. Riesz, 1S. Nighswander-Rempel, 2Ben J. Powell, 2J. Gilmore & 3Mark R. Pederson 1Soft Condensed Matter Physics Group, School of Physical Sciences, University of Queensland, Brisbane, QLD 4072, Australia 2Theory of Condensed Matter Physics Group, School of Physical Sciences, University of Queensland, Brisbane, QLD 4072, Australia 3Center for Computational Materials Science, Naval Research Laboratory, Washington, D.C. 20375, USA Abstract The melanins are a class of functional bio-macromolecules responsible for photoprotection and pigmentation in humans and many other species. They possess a unique collection of physico-chemical properties including condensed phase electrical conductivity and photoconductivity1, strong broad band monotonic UV and visible absorption (g.1)2, and very strong non-radiative conversion of photo-excited states3. Despite many decades of research activity in the melanin eld, signicant fundamental questions concerning their basic structure-property relationships still exist. One of the most important issues yet to resolve is that of the structure at the primary and secondary level. We have been studying eumelanin (the predominant form of the macromolecule in humans) for several years with a view to understanding how the molecular and supramolecular structures relate to observable macroscopic properties (optical and electrical properties in particular)4. Our motivations for this work are threefold: rstly, these systems may be the basis for a new class of bio-inspired functional materials; secondly, melanins represent a novel platform through which to study the condensed matter physics of conducting organics; and thirdly, these materials perform several important functions in biology (and indeed are implicated in disease states such as melanoma and Parkinsons) any advance in our knowledge of their basic physics and chemistry will have undoubted ow-on benets for human health. In our research we have applied a powerful multi-disciplinary strategy to the melanin structure problem. We have combined traditional experimental and theoretical condensed matter physics with directed organic synthesis, quantum-many-body and quantum chemistry calculations, molecular spectroscopy and molecular biophysical principles. In my paper I will describe our recent progress and highlight a new theory for describing the structure-property relationships of melanins4. This new theory is based upon extreme chemical disorder at the primary and secondary structural level, and we believe it explains the exotic physical and chemical properties of these systems. It is somewhat of a new paradigm in functional biomacromolecules, and I also speculate as to whether this may be specic to melanins or a more general feature of functional organics. References 1. M. A. Rosei, L. Mosca and F. Galluzzi, Syn. Met. 1996, 76, 331-335. 2. P. Meredith and J. Riesz, Photochem. Photobiol., 2004, 79(2), 211-216. 3. S. Nighswander-Rempel, J. Riesz, J. Gilmore and P. Meredith, J. Chem. Phys. 2005, 123, 194901. 4. P. Meredith, B. J. Powell, J. Riesz, S. Nighswander-Rempel, M. R. Pederson and E. Moore, Soft Matter, 2006, 2, 37-44 (2006).
Fig. 1 The broad band monotonic absorption prole of melanin a highly unusual feature amongst organic chromophores.
TU76 HIGH SENSITIVITY POLYMER PHOTODETECTORS FOR PORTABLE MEDICAL APPLICATIONS Xuhua Wang a,c, Edward M. Barrett a , Paul N Stavrinoua and Donal D. C. Bradley a,c* a Experimental Solid State physics Group, Blackett Laboratory, Imperial College London, London SW7 2AZ, United Kingdom Maliwan Amatatongchaib,d , Oliver Hofmann b,c, John C. de Mello b,c, Andrew J. de Mello b,c b Electronic Materials Group, Department of Chemistry, Imperial College London, London SW7 2AZ, United Kingdom c Molecular Vision Ltd, c/o Imperial College London, London SW7 2AZ, United Kingdom d Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, Thailand (Current address)
ABSTRACTS
A great many medical, industrial, and analytical applications require the sensitive detection of light originating for example from chemiluminescence, bioluminescence or uorescence. In such applications, the light is usually converted to an electrical signal with either a photomultiplier tube (PMT) or an inorganic semiconductor photodiode (ISPDs). The bulky nature and high voltage requirements of PMT detectors severely limit their use in portable, compact instrumentation, and ISPDs have consequently been making a very strong impact where portability is of primary concern. The advent of organic/polymer electronic devices that can be fabricated in cost-effective ways, for example by printing onto exible substrates, offers new prospects. The combination of organic photodiodes (OPDs) with microuidic chip structures, for instance, provides a promising route to disposable, compact and portable devices suited to markets in the bio-analytical, environmental and medical diagnostics sectors. Organic photodiodes (OPDs) have not, however, been widely used, in part due to perceived sensitivity problems. The work reported here demonstrates that readily processed OPDs with optimised congurations can be used as highly compact, high performance integrated detectors for portable medical diagnostic applications. Our OPDs were fabricated with blends of regioregular poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl C61 butyric-acid methyl-ester (PCBM). The devices have a broadband photoresponse from 350 nm to 650 nm with a peak quantum efciency of more than 60% at 550 nm. We report the effects of device geometry on the temporal response of the OPD, an important consideration for microscale detection due to the rapid reaction time within the microuidic environment. The signal rise and fall times are typically
found to be 0.3 s and 2 s for OPD areas of 1 mm2 and there is a linearity of photocurrent over at least ve orders of magnitude (up to the 1.26 mW maximum output from the 633 nm laser diode used in the test). In order to more fully explore the suitability of such OPDs portable detection we have used them to study antioxidant processes, with an on-chip assay based on peroxyoxalate chemiluminescence (CL) with 9,10-bis(phenylethylnyl)-anthracene (BPEA) as uorophore. The antioxidant capacity is determined by quantisation of the CL emission intensity. A sensitive PMT detector was used as a comparative standard to assess the sensitivity of our OPD and we found that the OPD provides a very comparable response to that of the PMT. The PMT was more sensitive at low light levels but the OPD was more sensitive at the light levels found during the CL assay measurements, most likely as a result of better spectral matching to the green emission from the BPEA uorophore. Further work aimed at improving the OPD performance is focused on reducing the dark current, enhancing the diode rectication ratio and providing long term stability. Our work demonstrates that OPDs, in combination with microuidic structures, offer a new approach to portable medical diagnostic devices.
TU77 INHERENTLY CONDUCTING POLYMER FOR MICROFLUIDICS Y.Z. Wu1, 2 (postgrad), K. Lau1, G. Spinks2, D. Diamond1, G.G. Wallace2 1SFI Adaptive Information Cluster, Adaptive Sensors Group,, Dublin City University, Dublin 9, Ireland 2ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute University of Wollongong, Northelds Avenue, Wollongong, NSW 2522, Australia Some recent work on the inherently conducting polymer based micro pumps and valves will be presented. The electromechanical actuation and controlled surface wetability of polypyrrole have been utilised in the design and development of low voltage microuidic devices. The TITAN micropump1 utilises a conned concentric arrangement of polypyrrole actuators to induce uid movement through an inner channel in a single unit. The innovative combination of the polymer electrical resistance, the electrochemical actuation and the appropriate electrical connection/ stimulation enables a novel peristaltic action to pump uids in a predetermined direction.
Direction of liquid movement Direction of liquid movement
contraction (1) -1.0 1 V, V the contraction initiated at inlet end initially starts from the inlet end contraction (2) -1.0 1 V, V contraction is progresses progressing duo to of the inherently along length tube resistance caused potential drop completefinally contraction (3) -1.0 1 V, V contraction along length of tube reaches another end
(4) W hen switched to +1 V, tube +1.0 V expansion initiated expansion starts at the inlet end at inlet end
(5) +1 V, expansion is progressing +1.0 V expansion progresses duo to the inherently resistance along length of tube caused potential drop
Open-ended glass pipette outlet To glass syringe

(b)
+1.0 V expansion finally reaches (6) +1 V, expansion finally reaches the the other The other end. Th eend. voltage is voltage switchedis toswitched 1 to 1.0 V again, and another V again, and another pumping circle pumping circle begins begins
(a) (b) Figure 1. Schematic view of (a) the TITAN assembly and (b) the sequence of valveless peristaltic actuation. The laminated micropump consists of two passive micro check valves and a polypyrrole ring-shaped actuator for the microuidic handling at a low ow rate and a relative high backpressure. The polypyrrole actuator functions as an electroactive piston that can be electrochemically switched to expand and contract to actuate the membrane and results in the outow and inow of liquid. A responsive micro valve was designed for use in wearable devices for the management of uid. Polypyrrole was coated onto a micro array of porous substrate, which can open / close and reversibly change its surface energy to induce the ow of liquid in response to the application of low voltages. Reference: [1] Wu, Y., D. Zhou, G.M. Spinks, P.C. Innis, and G.G. Wallace, TITAN: A Conducting Polymer Based Microuidic Pump. Smart Materials and Structures, (2005), 14(6), 1511-1516 TU78 DIELECTRIC SPECTROSCOPY OF DNA AQUEOUS SOLUTIONS
S.Tomi1*, S.Dolanski Babi1,2, T.Vuleti1, S.Kra3, D.Ivankovi3, L.Gripari4 and R.Podgornik5 1Institut za ziku, Zagreb, Croatia 2Dept. of Physics and Biophysics, Medical School, University of Zagreb, Zagreb, Croatia 3Rudjer Bokovi Institute, Zagreb, Croatia 4Dept. of Biological Chemistry, David Geffen School of Medicine, UCLA, Los Angeles, CA 5Dept.of Physics, University of Ljubljana and J .Stefan Institute, Ljubljana, Slovenia and Laboratory of Physical and Structural Biology NICHD, National Institute of Health, Bethesda, MD
ABSTRACTS
We demonstrate the power of low-frequency dielectric spectroscopy (40 Hz 110 MHz) as an highly-sensitive and non-destructive technique to detect dispersion of DNA aqueous solutions and give information on the fundamental length scales that determine the structure of these solutions composed of many DNA polymers1. Results for polydisperse genomic Na-DNA (most of fragments with 20 kbp) reveal two broad relaxation modes of strength 20<LF<100 and 5<HF<20, centered at 0.5 kHz<LF<70 kHz and 0.1 MHz<HF<15 MHz2. We discuss possible assignments for these relaxation modes inside the framework of the standard double layer model for polarization response of charged biopolymers in solution3. The results show that there are three fundamental length scales that determine the dielectric response of a semidilute DNA solution, each of them following the power law behavior with a distinct exponent. These are the average separation between the polyelectrolyte chains, or equivalently
the screening length of DNA acting as its own salt, the salt-dependent persistence length of a single polyelectrolyte chain and the mesh size of the polyelectrolyte solution.
References: 1. F. Bordi, C. Cametti and R.H. Colby, J.Phys.: Condens. Matter 16, R1423 (2004). 2. S.Tomic et al., submitted to Phys.Rev.Lett. (February 2006). 3. A.V.Dobrynin and M.Rubinstein, Prog.Polym.Sci. 30, 1049 (2005) and A.V.Dobrynin, R.H.Colby and M.Rubinstein, Macromolecules 28, 1859 (1995).
TU79 BIO-ORGANIC FIELD-EFFECT TRANSISTOR MEMORY ELEMENT P. Stadler, Th. Birendra Singh, N. S. Sariciftci Linz Institute of Organic Solar Cells, Physical Chemistry, Johannes Kepler University Linz, A4040, Austria James G. Grote Air Force Research Laboratory, Materials & Manufacturing Directorate, AFRL/MLPS, Wright-Patterson Air Force Base, Ohio 45433-7707 USA. R. Schwdiauer and S. Bauer Soft Matter Physics, Johannes Kepler University Linz, A4040, Austria Besides intrinsic material properties of the semiconductor, crucial factor for performance of Organic Field-Effect Transistors (OFETs) is the dielectric-semiconductor interface. First, Bio Organic Field-Effect Transistors (BioFETs) are realised with solution-processed methanofullerenes as semiconductor and deoxyribonucleic acid (DNA) and cyanoethylpullulane (CYEPL) as gate insulators. These transistors operate with gate voltage range below 10 V with a large hysteresis in its transfer characteristics (Figure 1). The large hysteresis observed is utilized for construction of memory element Organic Field-Effect Transistors (memOFETs)1. The origin of the large hysteresis is investigated using probing techniques such as capacitance measurements, transistor retention time, dynamic gate-voltage switching response and optical characterisation by second harmonic generation in metal-insulator-metal (MIM structure). These probing techniques qualitatively probe the origin of the hysteresis independently at the insulator alone and at the interface of insulator-semiconductor.
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Figure 1: Transfer chacteristics of an memOFET. References 1Th. B. Singh, N. Marjanovi, G. J. Matt, N. S. Sariciftci, R. Schwdiauer and S. Bauer, Appl. Phys. Lett., 85 5409 (2004). TU80 DESIGN AND SYNTHESIS OF CONJUGATED MATERIALS FOR PHOTONIC APPLICATIONS Seth R. Marder, Georgia Institute of Technology Molecules with large two-photon absorption cross-sections, , are in great demand for a variety of applications including two-photon-excited uorescence microscopy, optical-pulse supression, three-dimensional optical-data storage, and two-photon-induced biological release. These applications utilize two key features of two-photon absorption, namely, the ability to create excited states using photons of half the nominal excitation energy, which can provide improved penetration in absorbing or scattering media, and the I2 dependence of the process, which allows for excitation of chromophores with a high degree of spatial selectivity in three dimensions through using a tightly focused laser beam. A strategy for the design of molecules with large two-photon absorption cross sections, , has been developed, based on the concept that symmetric charge transfer upon excitation, either from the ends of a conjugated system to the center or vice versa, is correlated to enhanced values of . Properties of new squaraine and coordination complexes will also be reported upon. In addition the synthesis and characterization of materials with large third-order nonlinear susceptibility, (3), will be discussed.
TU81
ABSTRACTS
POLYMER/PCBM BLEND PHOTOVOLTAIC DEVICE RESPONSE AT THE FIRST TELECOM WINDOW. B.C. Duck, W.J. Belcher, J. Holdsworth and P.C. Dastoor Due to the rapid growth in demand for high speed large bandwidth communication in recent years, optical networks are being required to use a greater number of more densely packed wavelengths. Polymer based photodiodes would be suited for monitoring the health of these networks as they are a potentially inexpensive product that could be integrated into existing hardware. A blend device of poly[2-methoxy-5-(2-ethylhexyloxy)p-phenylene vinylene] (MEH-PPV) with [6,6]-phenyl C61-butyric acid methyl ester (PCBM) has been observed to produce photocurrent from wavelengths in the rst telecom window, centred at 850nm . Experimental data used to characterise and optimise polymer/PCBM blends towards photocurrent generation at these wavelengths will be presented.
TU82 EXCITED STATES TWO PHOTON ABSORPTION OF MOLECULAR SYSTEMS M. Meneghetti,1 V. Amendola,1 N. Schiccheri,1 M. Villano,1 M.P. Donzello,2 C. Ercolani,2 D. Dini,3 and M. Hanack3 1Dep. of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova (Italy) 2 Dep. of Chemistry, University of Rome La Sapienza, P.le A. Moro 5, 00185 Rome (Italy) 3Institut fr Organische Chemie,University of Tbingen, Auf der Morgenstelle 18, 72076 Tbingen (Germany)
F igure 1: T=18 K PL spectrum (bla ck li ne) an d 0 -0 li ne best fit cu rv es with our model(con tinuous gra y li ne) , with the model with the Bo ltzmann s tatistics with the exper imental abs orption FW H M ( das hed gr a y line), an d with a best fit, but unphysica l, 26 meV broa d absorption (bla ck dotted lin e).
Molecular systems have been considered for non linear optical applications because of their high polarizability. Highly delocalized -molecular structures, in particular, are very polarizable systems and are of primary interest for non linear optics. Delocalized electronic structures can be obtained within a single molecule or when radical molecules are associated like in organic conducting molecular crystals. The number of analysed molecules and structures is growing and there are evidences that it is not easy to obtain large and useful non linear responses although the systems have delocalized electrons. This is probably due to the low dimensional motion which the electrons can display in these systems. Some approaches can be followed to overcome this situation. One of these looks at higher polarizable states of the same molecular systems. In fact, usually, non linear optical properties are evaluated for systems in their ground state. We suggest, on the other hand, to use excited states of the same molecules since excited states are more polarizable than ground states and therefore, preparing a molecule in an excited state, will make it possible to have more polarizable states. We will report two photon absorptions from excited states (ES-TPA) in three molecular systems. The rst is a model system for organic conductors since it is obtained with dimers of TMTTF+ radicals, the second is based on a new hemiporphyrazine with a lower symmetry with respect to the parent phthalocyanines and the third is a pyrazinoporphyrazine complex in which a photoreduced state is active. The dimers absorb in the near infrared and we will show how nanoseconds pulses at 1064 nm can be efciently absorbed by two photon absorption from an excited state. Evaluation of the cross section for the two photon absorption is found to be 4 to 5 orders of magnitude larger than that found usually for the ground state. The second molecule shows a linear spectrum with a small absorption in the visible. Using nanosecond pulses at 532 nm we nd again two photon absorption from the rst excited state with a very large cross section. The third example reports a more complex situation in which a triplet state of the molecule is photoreduced and the produced monoanion shows, at 532 nm, a large two photon absorption from an excited state.
TU83 THE ROLE OF EXCITONS STATISTIC DISTRIBUTION IN THE TEMPERATURE DEPENDENCE OF THE POLY(9,9DIOCTYLFLUORENE) -PHASE PHOTOLUMINESCENCE M. Annia)*, M. E. Caruso a), S. Lattante b), R. Cingolani a) a)National Nanotechnology Laboratory (NNL) of CNR-INFM and Dipartimento di Ingegneria dellInnovazione, Universit degli Studi di Lecce, Via per Arnesano 73100 Lecce, Italy b) Dipartimento di Fisica and National Nanotechnology Laboratory (NNL) of CNR-INFM, Universit degli Studi di Lecce, Via per Arnesano 73100, Lecce, Italy Organic conjugated polymers have received great attention in the last decades, mainly due to their possible applications to low costs photonic, optoelectronic, and electronic devices. Quite interestingly, despite the wide interest in the emission properties of conjugated polymers, a complete understanding of basic features, like the photoluminescence (PL) spectra temperature dependence, is not yet available. In particular a PL peak energy shifts as the temperature increases has been often observed, but the origin of such shift is still matter of debate. Recent experimental results on MEH-PPV and Poly(9,9-dioctyluorene) (PF8), showed that the commonly used explanation in terms of a temperature dependent average conjugation length it is not always correct, as huge PL shifts can be observed even when the conjugation length is weakly temperature dependent. Another possible origin of the PL shift is the temperature dependence of the incoherent exciton migration among the inhomogeneously broadened excited states distribution. Concerning the PF8 phase emission two recent experiments indicate that both these arguments are not able to fully explain the experimental results. In particular it has been shown that the temperature dependence of the absorption spectra is much weaker than the PL one, while similar behaviours should be observed if the temperature induced energy shift were due to a variation of the conjugation length distribution. Moreover it has been demonstrated that the exciton energy migration becomes faster as the temperature increases but, in puzzling contrast with the PL experiments, this should lead to a red-shift with temperature, while a blue-shift is observed. In this paper we investigate the possible origin of the temperature dependence of the photoluminescence spectra of the PF8 phase. The 0-0 line emission energy shows a continuous blue-shift of about 29 meV as the temperature increases from T=18 K to T=300 K and an increase of the FWHM of about 49 meV. We show that these results can be quantitatively explained in the frame of a thermal quasi equilibrium distribution model
ABSTRACTS
of the excitons among an inhomogeneously broadened distribution of excited states. Our model includes an energy migration dependent statistic for the excitons, instead of a standard Boltzmann statistic. We show (see Fig. 1) that a model including a Boltzmann statistic is not able to reproduce even only the T=18 K PL spectrum with physically meaningful parameters, while good agreement is found with the modied statistics. We show that the PL blue-shift is mainly due to the interplay between the increase of the excitons quasi equilibrium temperature, which leads to a spectrum blueshift, and to an increase of the energy migration rate, which leads to a spectrum red-shift. Moreover we show that the energy shift of the absorption spectrum has negligible effects on the PL spectra lineshape and peak energy. We conclude that the temperature dependence of the PL spectra of the PF8 phase is not governed by a conjugation length variation of the emitting molecules, but by an interplay between the increasing exciton temperature and the increasing energy migration rate. Our explanation is expected to be suitable for other conjugated systems, and could stimulate further investigation of a more detailed relationship between the exciton migration rate and their statistical distribution among the excited states. * Corresponding authors e-mail:marco.anni@unile.it
TU84 3-DIMENSIONAL ENERGY TRANSPORT IN HIGHLY LUMINESCENT CONDENSED MEDIA: QUANTITATIVE EXPERIMENTAL AND THEORETICAL ANALYSIS Johannes Gierschner,1,2 Lars Poulsen,1 Hans-Joachim Egelhaaf, 1,3 Mikael Jazdzyk,4 Michael Hanack,4 Juan Carlos Sancho Garcia,2 Jrme Cornil,2 David Beljonnne,2 Jean-Edouard Communal,5 Andrea Mura,5 Giovanni Bongiovanni5 1 Institute of Physical & Theoretical Chemistry, University of Tbingen, Germany, 2 Laboratory for Chemistry of Novel Materials, University of Mons-Hainaut, Belgium, 3Dipartimento di Fisica, Politecnico di Milano, Italy, 4Institute of Organic Chemistry, University of Tbingen, Germany, 5Dipartimento di Fisica, Universit degli Studi di Cagliari, Italy. Highly luminescent chromophores included in the channels of well-ordered self-assembled nano-structured host-guest compounds offer unique properties, not only as highly attractive materials for opto-electronic applications, but also for a fundamental understanding of energy migration in condensed media: In the presence of rod-like chromophores, perhydrotriphenylene (PHTP) forms host-guest compounds (HGCs), where the active guest molecules are included in nano-channels between the PHTP stacks, so that the channels are completely lled (Fig. 1). The intra-channel distances between the dyes are given by their van-der-Waals lengths (2.0 nm), whereas the inter-channel distances (1.5 nm) are dened by the structure of the distorted pseudo-hexagonal host lattice (Fig. 2). The suppression of side-by-side interactions conserves the single molecule properties, in particular their high photoluminescence efciency of up to 90%, but at the same time offers tightly packed well-oriented systems with dye concentration as high as 0.48 M thus generating bright emissive samples. The highly ordered structure of the HGCs offers a unique possibility for an in-depth study of energy transfer (ET) processes in condensed media without the usual complications in solid-state samples, such as static & dynamic disorder, energy trapping and strongly changed optical properties by intermolecular interactions. Experimentally, the HGCs are investigated by steady-state and time-resolved uorescence (Fig. 3), where donor (D = distyrylbenzene, 2PV) and acceptor (A = quinquethiophenes, 5T) chromophores are co-included with D:A ratios in the range of 0.1% to 4%. At a theoretical level the energy transfer dynamics are calculated without any adjustable parameters by a Monte-Carlo approach with periodic boundary conditions, where the structure of the system is built from the output of MM/MD calculations. D-D and D-A singlet excitation ET steps are calculated beyond the Frster point-dipole limit in a full quantum-chemical approach. The calculated overall ET efciencies and the time traces for donors and acceptors are in excellent agreement with experiment (Fig. 4), suggesting our approach as a powerful tool in modelling ET dynamics in complex 3D systems. Fig. 1 Fig. 2 Fig. 3 Fig. 4
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TU85 PRIMARY PHOTOEXCITATIONS AND THEIR INTERCONVERSION IN OLIGOPHENYLENEVINYLENE NANOCRYSTALS: THE ROLE OF EXCESS ENERGY STUDIED WITH SUB-30 FS RESOLUTION L. Ler1,2, C. Manzoni1, H.-J. Egelhaaf 1,2, G. Cerullo1, D. Oelkrug2, G. Lanzani1 1ULTRAS-CNR-IFN, Politecnico di Milano, Pza Leonardo da Vinci 32, 20133 Milano, Italy 2Institut fr Physikalische und Theoretische Chemie, Universitt Tbingen, Auf der Morgenstelle 8, 72076 Tbingen, Germany
ABSTRACTS
The generation and recombination of charged states in polycrystalline lms of oligo(phenylenevinylene)s at high photoexcitation densities is investigated, using femtosecond pump-probe spectroscopy as a direct probe for the time-dependent density of photogenerated singlet, triplet, and doublet states. Exciting the lms with laser pulses of about 150 fs, singlet and triplet excited states as well as pairs of charged states are seen to form during the exciting pulse. Geminate recombination of the charge pairs is found in the rst picoseconds after formation, after which a nongeminate dispersive mechanism prevails. In the effort to identify the nature of the primary photoexcitations, the experiments were repeated with a temporal resolution of about 20 fs. When pumping with these pulses 0.9 eV above the absorption edge, predominantly charge carriers are formed as primary photoexcitations, whereas the
majority of the neutral singlet excited states are formed in a secondary process upon geminate charge recombination. The sublinear pump intensity dependence of singlet states concentration is explained by ultrafast annihilation involving hot singlet states. Upon pumping at the absorption edge, instantaneous stimulated emission is observed instead of charged states absorption, demonstrating that singlet states are the predominant primary photoexcitations at low excess energies.
TU86 TRANSPARENT AND FLEXIBLE CARBON NANOTUBE/POLYANILINE PH SENSOR M. Kaempgen, S. Roth Max-Planck-Institute for Solid State Research, Stuttgart, Germany Thin lm carbon nanotube networks are used as a conductive, transparent and exible backbone structure for electrochemically deposited polyaniline. Such a device is sensitive to pH allowing the potentiometric determination of pH values ranging from pH 1-13. The excellent performance in terms of linearity, selectivity, stability and fast response makes this device suitable for pH sensor applications. In addition, the extremely simple preparation technique allows the conversion of any user dened substrate into a pH sensor. Since this technique is not limited to polyaniline only, the deposition of various polymers on carbon nanotubes in general offers a great potential for demanding sensor applications.
W1 MAGNETO-TRANSPORT PROPERTIES OF QUASI-ONE-DIMENSIONAL ORGANIC CONDUCTORS Bojana Korin-Hamzi Institute of Physics, P.O.Box 304, HR-10001 Zagreb, Croatia
The quasi-1D character of the electronic structure of organic conductors and superconductors is based on the anisotropy of the tight-binding overlap integrals along the three crystallographic directions. The interactions between charge, spin and lattice degrees of freedom result in a very rich phase diagram with various ground states. By modication of the organic molecules and/or the counter ions the relevant physical parameters like overlap integrals, the Coulomb interactions or band lling can be varied allowing the exploration of the phenomena of one-dimensional physics. I will present our comparative study of the electric and galvanomagnetic properties of several organic conductors and superconductors with a focus on (TMTCF)2X (C= Se, S) compounds.1,2 Their phase diagram spanning from more anisotropic C = S to C = Se series shows the increasing interchain coupling that leads to the crossing-over of the dimensionality from 1D2D (3D). Our results on temperature and magnetic eld dependence of conductivity anisotropy, Hall effect and magnetoresistance (up to room temperature, and in magnetic elds up to 9T) enabled us to gain information about Fermi liquid or Luttinger liquid behavior at high temperatures, possible dimensional crossover, phase transitions, non-linear conductivity etc. The results are discussed in the framework of the existing theoretical models. The evidence that the 1D Luttinger liquid features appear in the transport properties at high temperatures in C=S series will be addressed as well as the strong evidence for charge ordering transition from transport measurements.2 1 B. Korin-Hamzi, E. Tafra, M. Basleti, A. Hamzi, G. Untereiner and M. Dressel, Phys. Rev. B 67, 014513 (2003) 2 B. Korin-Hamzi, E. Tafra, M. Basleti, A. Hamzi and M. Dressel, Phys. Rev. B 73, 115102 (2006)
W2 FT-IR AND RAMAN SPECTROSCOPIC STUDY, AIDED BY QUANTUM CHEMICAL DFT CALCULATIONS OF THE CONDUCTING SALT (DOEO)4HGBR4TCE A. apiski(a), A. Gsecka(a), A.I. Kotov(b) aInstitute of Molecular Physics, PAS, ul. Smoluchowskiego 17, 60-179 Pozna, Poland bInstitute of Problems of Chemical Physics, RAS, Chernogolovka, 142432, Russia Most of presently known organic conductors and superconductors were prepared using the [bis(ethylenedithio)tetrathiafulvalene] (BEDT-TTF or ET) and various acceptors. In the search for new interesting materials the chemical modication of ET is a way to new donors for highly conducting and even superconducting organic materials. Recently, two new derivatives of ET were synthesized where one or two ethylene groups are replaced by 1,4-dioxane rings: [(1,4-dioxane-diyl-2,3-ditio)ethylenedithiotetrathiafulvalene] (DOET) and [(1,4-dioxane-diyl-2,3-ditio)tetrathiafulvalene] (BDDT), respectively. In order to investigate the interaction in the stacking column, related to the size of the terminal ethylenedichalcogeno group, the new derivative [(1,4-dioxane-diyl-2,3-ditio)ethylenedioxytetrathiafulvalene] DOEO has been synthesized. Based on this unsymmetrical DOEO donor the new organic conductor (DOEO)4HgBr4.TCE was synthesized. The detailed crystallographic investigations of this salt were carried out by Bardin et al. [1] for two different temperatures: 293 and 30 K. The crystal structure consists of conducting donor layers of the -type packing alternating along the c-axis with insulating layers formed by [HgBr4]2- anions and solvent TCE molecules. In the conducting layers, parallel to the (ab) plane, the DOEO molecules are arranged in dimerized stacks parallel to the b-axis with head-to-tail packing mode. Close SS contacts, shorter than the sum of the van der Waals radii, are observed at room temperature inside a ribbon, whereas at 30 K are present between and inside the ribbons. At room temperature the [HgBr4]2- anions, solvent molecules, and ethylene groups in DOEO molecules are disordered. At low temperature, ethylene groups and [HgBr4]2- anions are ordered. The electrical behavior of (DOEO)4HgBr4.TCE showed a curious phenomenon [1]. The room temperature dc conductivity of a single crystal (DOEO)4HgBr4.TCE salt measured along the a direction within ab-plane was found to be RT = 5 S/cm, while perpendicular to this plane it was found to be almost ve orders of magnitude less. On cooling, in both experimentally measured directions, the resistivity increases until a maximum is reached around 140 K, become metallic in the lower temperature region, and nally undergo an insolating transition around 50 K. The anomaly observed at around 140 K can be caused by the impurity and/or the disorder of the counter anion and ethylene groups. However, the mechanism and the origin of this anomaly in the resistivity are still open to question.
ABSTRACTS
In the present work, we investigated absorption, polarized reectance, and Raman spectra and proposed the assignment of the fundamental vibrations of DOEO molecule. We simulated the dynamics of DOEO0, DOEO+, and TCE molecules using the commercial program Gaussian03. The calculations were carried out on an isolated molecule to determine the response of the molecular dynamics. The equilibrium geometry and vibrational transitions of the all investigated molecules were evaluated with a Becke-style 3-Parameter Density Functional Theory with the LeeYang-Parr correlation functional (B3LYP) using a basis set of 6-311++G(d,p). The starting point of the optimization process was the DOEO and TCE geometry taken from X-ray data. The mode description was performed using the GaussView program and Veda 4 program; with the help of the latter program we performed calculation of potential energy distribution (PED) of normal modes vibrations. The goal of these investigations is to obtain information on physical properties of investigated compound in the large spectral and temperature ranges and combine these results with the crystal structure and other physical properties of the investigated CT salt. [1] A.A. Bardin, A.I. Kotov, S.S. Hasanov, G.V. Shilow, L.I. Buravov, L. Ouahab, E.B. Yagubskii, Russian Journal of Coordination Chemistry, v.32 N2 (2006).
W3 MIXED ORDER PARAMETERS, ACCIDENTAL NODES AND BROKEN TIME REVERSAL SYMMETRY IN ORGANIC SUPERCONDUCTORS: A GROUP THEORETICAL ANALYSIS B. J. Powell Department of Physics, University of Queensland, Brisbane QLD 4072, Australia. powell@physics.uq.edu.au We present a group theoretic analysis of several classes of organic superconductors.1 We argue that highly frustrated half-lled layered organic superconductors, such as -(ET)2Cu2(CN)3 [where ET is BEDT-TTF or bis(ethylenedithio)tetrathiafulvalene] and -[Pd(dmit)2]2X, undergo two superconducting phase transitions, the rst from the normal state to a d-wave superconductor and the second to a d+id state (see Fig. below). We also show that the monoclinic distortion of -(ET)2Cu(NCS)2 means that the symmetry of its superconducting order parameter is different from that of orthorhombic -(ET)2Cu[N(CN)2]Br. We propose that quarter lled layered organic superconductors, e.g., -(ET)2I3, have dxy+s order parameters.
Fig: Sketch of the proposed phase diagram for superconductivity near the hexagonal lattice in -(ET)2Cu2(CN)3 and -[Pd(dmit)2]2X. is a symmetry breaking parameter which lowers the symmetry from C6v to C2h. Physically could represent uniaxial strain or pressure. 0 at ambient pressure in -(ET)2Cu2(CN)3 and -[Pd(dmit)2]2X due to the monoclinic crystal structures. T is the temperature. 1. B. J. Powell, cond-mat/0603057.
W4 EXCHANGE INTERACTION BETWEEN CONDUCTION ELECTRONS AND LOCALIZED 3D SPINS ON THE FIELD INDUCED SUPERCONDUCTOR, -(BETS)2FECL4; STUDIED BY 77SE NMR K. Hiraki1,6, H. Mayaffre1, M. Horvatic2, C. Berthier1,2, H. Tanaka3, A. Kobayashi4, H. Kobayashi5 and T. Takahashi6 1Laboratoire de Spectrometrie Physique, Universite Joseph Fourier, BP87, 38402 St. Martin dHeres, France; 2Grenoble High Magnetic Field Laboratory, BP166, 38042 Grenoble, France; 3Nanotechnology Research Institute, AIST, Tsukuba, Ibaraki 305-8568, Japan 4Department of Chemistry, University of Tokyo, Tokyo 103-0033, Japan; 5Institute for Molecular Science, Aichi 444-8585, Japan; 6Department of Physics, Gakushuin University, Tokyo 171-8588, Japan; -(BETS)2FeCl4 is a well-known material since a eld-induced superconductivity (FISC) has been discovered several years ago1. This salt is a charge transfer complex composed of organic BETS molecule and FeCl4 counter anion carrying magnetic Fe3+ (S=5/2). Two dimensional conducting sheets, consisting of a type arrangement of BETS molecules, are sandwiched by insulating FeCl4 layers2. The FISC state appears above 18 T when the magnetic eld is applied just parallel to the conducting plane. The maximum Tc, about 4 K, was observed around 33 T. The origin of this FISC was assumed to be the Jaccarino-Peter (JP) compensation effect; a negative exchange eld between the spins s of the band and the spins S of the Fe3+ (Js.S) is cancelled by the external eld at the BETS site. We have performed 77Se NMR measurements at high magnetic elds (13.5 T < H < 26 T) down to low temperatures (1.5 K) on a 77Se isotope enriched single crystal specimen. The spin polarization of the conducting electrons induced by the localized Fe3+ spins was measured through the Knight shift of 77Se and the exchange interaction, J was determined. From the extrapolation of the eld dependence of the shift, we obtained an exchange eld of -32 T; Knight shift should vanish at 32 T as shown in the
ABSTRACTS
Figure Field dependence of the NMR shift (f: squares) and linewidth (circles) at the several fields at 1.5 K. From the extrapolating the linear relation, the zero Knight shift is found at about 32 T.
gure, where the exchange eld cancels out the external eld. This value is in good agreement with that expected from transport measurements1. This result is the rst microscopic evidence of the cancellation of the external eld by the exchange eld seen by the electrons and clearly supports the model that the FISC state is due to the Jaccarino-Peter compensation effect3.
1 L. Balicas et al., Phys. Rev. Lett. 87, (2001) 067002 2 for example, H. Kobayashi et al., J. Am. Chem. Soc. 118, (1996) 368 3 V. Jaccarino and M. Peter, Phys. Rev. Lett. 9, (1962) 290
W5 13C NMR AND X-RAY ANALYSES OF CHARGE ORDERING PHENOMENA IN (TMTTF)2X Toshikazu Nakamura1,2, Ko Furukawa1,2 and Toshifumi Hara1 1 Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan 2 The Graduate University for Advanced Studies, Myodaiji, Okazaki 444-8585, Japan We performed magnetic resonance and X-ray measurements for a series of TMTTF salts to clarify the charge ordering phenomena of (TMTTF)2X. It is well known that the (TMTTF)2X salts show variations of the ground states. We showed that (TMTTF)2X salts were roughly divided into three groups: (Type I) ReO4, ClO4 (Td-symmetry), (Type II) SbF6, AsF6, PF6 (Oh-symmetry) and (Type III) Br and SCN salts. We proposed that the variation of ESR behaviors might have their origins in low-temperature variations of charge-ordering patterns such as -O-O-o-o- and -O-o-O-o- along the stacking axes. However, the charge ordering mechanisms in the TMTTF salts have not been claried yet, and it is an open question as to whether the charge ordering phenomena observed in TMTTF salts are universal for all types of salts. Hence we have performed 13C NMR measurements for one of the Type I salts with Td-symmetry counter anions, (TMTTF)2ReO4.We found an intermediate charge ordering phase for a Type I salt with a Tdsymmetry counter anion by the 13C NMR absorption line and spin-lattice relaxation rate, 13C T1-1. The 13C NMR spectra indicated two inequivalent molecules with unequal electron densities below 225 K. The absence of an associated magnetic anomaly at 225 K, as seen in Type II salts with Oh-symmetry counter anions, suggests the formation of -O-o-O-o- charge ordering. Moreover, we conrmed the spin-singlet transition associated with the ReO4 anion ordering at around 158 K. The marked change in the NMR lines at 158 K also indicates a redistribution of the electronic charge such as -O-O-o-o-. It is well known that deuteration often has a great inuence on the electronic states of organic conductors as a chemical pressure. We reported signicant enhancement by deuteration of the charge-order phase transition temperature, TCO, in ESR measurements for all (TMTTF)2X salts measured. It is advantageous to compare pristine and deuterated salts since they have most parts in common. Hence, in order to investigate the effect of deuteration on the charge ordering phenomena of (TMTTF)2X, we performed magnetic resonance (ESR, NMR) and X-ray measurements on (TMTTF-d12)2AsF6 and (TMTTF-d12)2SbF6 to clarify their low-temperature electronic and crystal structures. 19F NMR measurements for pristine and deuterated (TMTTF)2SbF6 indicates that no obvious relation between the SbF6 anion motion and the TMTTF charge-order. We also performed single crystal X-ray measurements to understand the deuteration effects and temperature dependence of the crystal structure. In general, a positive pressure effect is expected for deuteration, since the C-D bond length is shorter than that of C-H. In fact, in the case of (TMTTF)2SbF6, all lattice parameters decrease with deuteration at room temperature. Thus, a simple chemical pressure scenario can be ruled out. Hence we consider the dimerization effect. It is noted that chargeorder phases are not realized in simple Mott-Hubbard systems with large on-site Coulomb interactions. Temperature dependence of the inter-molecular distances and ratios of several TMTTF salts are shown. It seems likely a possible threshold value of B/A to stabilize the charge-ordering. We can explain the enhancement of TCO by deuteration within this framework. The possible origins of the charge ordering phenomena are discussed from a microscopy point of view. [1]T. Nakamura, J. Phys. Soc. Jpn. 72 (2003) 213-216. [2]F. Nad, P. Monceau, T. Nakamura and K. Furukawa, J. Phys.: Cond. Matter 17 (2005) L399-L406. [3]K. Furukawa, T. Hara and T. Nakamura, to be published in J. Phys. Soc. Jpn. 74 No.12 (2005). [4]T. Nakamura, K. Furukawa and T. Hara, to be published in J. Phys. Soc. Jpn. 75 No.1 (2006). [5]S. Fujiyama and T. Nakamura, to be published in J. Phys. Soc. Jpn. 75 No.1 (2006).
W6 POLYMORPHISM IN ORGANIC SEMICONDUCTORS Raffaele G. Della Valle, Elisabetta Venuti, Ivano Bilotti, Aldo Brillante Dip. Chimica Fisica e Inorganica and INSTM-UdR Bologna, University of Bologna, I-40136, Bologna, Italy Alberto Girlando and Matteo Masino Dip. Chimica GIAF and INSTM-UdR Parma, University of Parma, I-43100 Parma, Italy Organic semiconductors, such as oligoacenes, oligopolythiophenes and rubrene have the potential to challenge the silicon based semiconductors. While extremely high chemical purity is required for silicon, also good phase homogeneity is necessary for organics. In fact, coexistence of polymorphic phases, possibly on a micro scale, may be present even when the system is chemically pure. Although less appreciated than chemical contamination, phase inhomogeneities may be widespread, because the intrinsic molecular properties of the organic semiconductors seems to facilitate the occurrence of a large number of different polymorphs. The ideal organic semiconductor, in fact, is characterized by high conjugation and by extended transfer integrals, which are both required to lead from isolated molecules towards molecular wires or planes. These requirements favor higher electronic delocalization, quasi-planar structures, presence of functional groups, large and quite exible molecules. Large non spherical molecules, kept together by weak non-directional forces, are already expected to exhibit a variety of different crystalline arrangements. Furthermore, since these molecules are exible, the molecular geometry in the crystal may differ from that in the gas phase. The loss of intra-molecular energy induced by the geometrical deformation is easily compensated by packing energy gains, in the form of enhanced inter-molecular interactions.
ABSTRACTS
This situation seems to be ideal for the existence of many alternative packing arrangements, with small difference in structure and energy. Indeed, chemical purity and phase homogeneity (i.e. physical purity) are both required for optimal and reproducible device performance, effectively ensuring that the performance parameters are due to the intrinsic properties of the material. We tackle the problem of polymorphism in the organic semiconductors by combining experimental and theoretical methods. To shed some light on the origin of polymorphism, we have computed the possible crystal structures of mechanical equilibrium, either by starting from all the known xray structures or by generating thousands of random structures to sample the overall distribution of potential energy minima. The calculations were performed using molecules with geometry determined by ab initio methods, interacting through atom-atom potential models.1 For all compounds that we have studied, at least two different experimental polymorphs were known. In each case, these two polymorphs were indeed found to correspond to the two deepest minima identied by sampling. Hundreds of further minima, with a large variety of structural arrangements have also been predicted. Structurally similar, but distinct, polymorphs are found to exhibit very different computed vibrational frequencies and may therefore display different dynamical behaviors (vibrational density of states, electron-phonon couplings, etc.). This is expected to greatly affect the charge transport properties. For this reason, and since phase transitions may even occur within the operational temperature interval of the devices, the control of the crystalline phase of the material may be crucial. Experimentally we have found that different crystalline polymorphs may be easily distinguished by their Raman spectra in the region of the lattice phonons (usually below 150 cm1), whose frequencies probe the inter-molecular interactions and turn out to be very sensitive to differences in molecular packing. Therefore, micro-Raman and confocal Raman mapping in the phonon region, are most convenient diagnostic tools for in-situ and non destructive characterization of the phase purity. In pentacene, for instance, we have found out that the two polymorphs may coexist down to the m scale, and that inhomogeneities occur both at the surface and in the bulk of the crystals.2 In conclusion, phase homogeneity cannot be taken for granted, even for well formed single crystals. [1] R.G. Della Valle, E. Venuti, A. Brillante, A. Girlando, J. Chem. Phys. 118 (2003) 807. [2] A. Brillante, I. Bilotti, R.G. Della Valle, E. Venuti, M. Masino, A. Girlando, Adv. Mater. 17 (2005) 2549.
W7 METALLIC AND MOTT-HUBBARD INSULATING STATES IN POTASSIUM INTERCALATED PENTACENE Monica F. Craciun, Sven Rogge, and Alberto F. Morpurgo Kavli Institute of Nanoscience, Lorentzweg 1, 2628 CJ Delft, The Netherlands Pentacene (PEN) is a conjugated molecule very well known in the eld of plastic electronics for its use in high-mobility organic thin-lm, whose electronic properties are being investigated in great depth. One aspect that has attracted particular attention is the possibility to control the electrical conductivity by means of chemical doping. Doping is achieved through the inclusion of iodine1 and alkali atoms2, 3 that intercalate in between the planes of the molecular lms, and donate either holes (iodine) or electrons (alkali) to the molecules. For iodine doping1 earlier, and very recently also for rubidium doping4, it has been found that the conductivity of pentacene lms can become large (~100 S/cm) and exhibit metallic temperature dependence. However, very little is currently known about the doping dependence of the conductivity and the microscopic nature of electrical conduction in doped pentacene. Here, we report a systematic analysis of the doping and temperature dependence of the conductivity of pentacene thin lms intercalated with potassium. We nd that, upon potassium intercalation pentacene lms become metallic in a broad range of doping concentrations, up to one potassium atom per molecule. When the amount of potassium is increased beyond 1 K/PEN, a sharp drop of the conductivity is observed, concomitantly with a re-entrance into an insulating state. The analysis of the experimental data show that at high doping the conductivity cannot be described in terms of independent electrons lling the molecular band originating from the lowest unoccupied molecular orbital (LUMO). Rather, our observations indicates that the insulating behaviour is caused by the saturation of charge transfer from the potassium atoms to the pentacene molecules, so that, at high doping, the pentacene lms are left with one electron per molecule irrespective of the potassium concentration. One electron per molecule corresponds to a half lled LUMO, for which the occurrence of a Mott-Hubbard insulating state due to electron-electron interaction has been recently predicted theoretically5. Thus, the insulating state observed at high doping levels in our experiments is a manifestation of strong electronic correlations in molecular materials. References [1] Minakata T, Nagoya I, Ozaki M, JOURNAL OF APPLIED PHYSICS 69 (10), 7354-7356, 1991. [2] Minakata T, Ozaki M, Imai H, JOURNAL OF APPLIED PHYSICS 74 (2), 1079-1082, 1993. [3] Matsuo Y, Suzuki T, Yokoi, et al., JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS 65 (2-3), 619-621, 2004. [4] Kanedo Y, Suzuki T, Matsuo Y, et al., SYNTHETIC METALS 154 (1-3), 177-180, 2005. [5] Brocks G, van den Brink J, Morpurgo AF, PHYSICAL REVIEW LETTERS 93, 1464051-1464054, 2004.
W8 MULTIMODE PEIERLS DISTORTION AND 2D DIMERIZATION Shutaro Chibaa and Yoshiyuki Onoa,b aDepartment of Physics, Toho University, Miyama 2-2-1, Funabashi, Chiba 274-8510, Japan bResearch Center for Materials with Integrated Properties, Toho University, Miyama 2-2-1, Funabashi, Chiba 274-8510, Japan Generally, low dimensional electron-lattice systems with a half-lled electronic band exhibit the so-called Peierls transition where spontaneous lattice distortions are induced due to the coupling between the electrons and the lattice vibration modes. As is well-known, in one-dimensional systems, the 2kF-mode connecting two electronic states at the Fermi level constitutes the Peierls distortion. On the contrary, however, it has been found recently that the Peierls distortion in the 2D square lattice with a half-lled electronic band should involve not only the nesting vector (Q=(,), the lattice constant being assumed to be unity) component but also other various modes with wave vectors parallel to Q.1 We call this unusual Peierls state as the multimode Peierls state. In fact it has been argued that this multimode Peierls state has a lower energy than any other Peierls states considered so far for the 2D square lattice model.2 In the present work we discuss the spatial structure of the 2D multimode Peierls state for better understanding of the physical meaning of the multimode distortion. As a theoretical model, the standard 2D Peierls-Hubbard model is employed;
ABSTRACTS
H = [(t0 xi , j )( c i++1, j , s c i , j , s + h.c.) + (t0 y i , j )( c i+, j +1, s c i , j , s + h.c.)]

i , j ,s
K 2
(x
i, j
2 i, j
+ y i2, j ) + U ni , j , ni , j ,
i, j
where the rst term represents the electronic transfer term modied by the lattice distortions in respective directions, the second and the third terms describing the lattice potential energy and the electronic on-site repulsive interaction, respectively. The lattice distortions are determined so as to minimize the total energy of the system under the condition of the half-lling of the electronic band. In the case of weak U (U << t0), it has been found,3 within the Hartree-Fock approximation, that distortion pattern in the lowest energy state is not the one shown in Fig.1 (a), which is described in terms of a single wave vector Q, but the one depicted in Fig.1 (b), which involves not only Q but also other wave vectors parallel to Q. It is argued that the structure as shown in Fig. 1(b) is a natural extension of the dimerization in 1D systems, i.e. that any dimerized bond is isolated by longer bonds surrounding it. Fig. 1: The distortion patters in 2D Peierls-Hubbard system. The thick solid line represents a short bond, the thin dotted line being a long bond and the thin solid line the equidistant unchanged bond.
In the strong U region, we should project the model onto the antiferromagnetic Heisenberg model in which the exchange integral is modied by the lattice distortion, so-called spin-Peierls model.4 Even in this case, the multimode characteristics of the lattice distortion in the spin-Peierls state is fount to survive, though the spin-lattice coupling must exceeds a certain critical value in order to realize the spin-Peierls state. It is shown5 that the multimode spin-Peierls state as represented by Fig. 1(b) has the smallest critical coupling value compared to other distortion patterns so far considered,4 and therefore that the spin-Peierls state in 2D square lattice should have the multimode type distortion resulting in isolated spin-singlet pairs. Isolation of the dimers seems to be essential when we consider the Peierls state or the spin-Peierls state in the 2D square lattice. The multimode Peierls state was found to have a large degeneracy.1 From the consideration of the distortion patterns in real space as shown in Fig. 1(b), the degree of degeneracy can be straightforwardly understood. References 1. Y. Ono and T. Hamano: J. Phys. Soc. Jpn. 69 (2000) 1769, T. Hamano and Y. Ono: ibid 70 (2001)1849. 2. e.g. S. Tang and J.E. Hirsch: Phys. Rev. B 37 (1988) 9546. 3. S. Chiba and Y. Ono: J. Phys. Soc. Jpn. 73 (2004) 2777, cond-mat/0509634. 4. F.C. Zhang and P. Prelovsek: Phys. Rev. B 37 (1988) 1569, A.A. Omari: J. Phys. Soc. Jpn. 69 (2000)3387, J. Sirker, A. Klumper and K. Hamacher: Phys. Rev. B. 65 (2002) 134409. 5. S. Chiba, Y. Baba and Y. Ono: J. Phys. Soc. Jpn. 75 (2006) 034705.
W9 SYNTHESIS OF CONDUCTING POLYMERS IN IONIC LIQUIDS Jenny Pringle,*1 Orawan Ngamna,2 Jun Chen,2 Gordon G. Wallace,2 Maria Forsyth1 and Douglas R. MacFarlane3 1Department of Materials Engineering, 3 School of Chemistry, Monash University, Vic 3800, Australia. Jenny.Pringle@eng.monash.edu.au. 2Australian Centre of Excellence in Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northelds Avenue, Wollongong, NSW 2522, Australia. Ionic liquids are a relatively new class of solvent composed entirely of ions, which have a number of advantages over conventional solvents such as negligible vapour pressure and non-ammability. Ionic liquids can exhibit excellent oxidative and reductive stability, which allows access to potentials previously prohibited by the smaller electrochemical window of molecular solvent/electrolyte systems. We have investigated the use of ionic liquids for both the chemical and electrochemical synthesis of a range of conducting polymers.1 Ionic liquids can dissolve a wide range of organic and inorganic materials, which allows access to a plethora of oxidants and monomers for chemical polymerisation, some of which are either insoluble in, or outside the electrochemical stability of, molecular solvents. Here we report the rst use of an ionic liquid as a media for the chemical synthesis of poly(pyrrole), 5 m poly(thiophene) and poly(terthiophene) using a range of chemical oxidants, including gold chloride which results in the formation of conducting polymer nanoparticles, e.g. Fig 1, left.
Electrochemical synthesis of conducting polymers in ionic liquids can also produce particularly interesting morphological effects, including nano-dimensional features and directional growth (Fig 2, right), and SEM analysis provides valuable insight into the growth mechanisms of these materials.
ABSTRACTS
1. J. M. Pringle, M. Forsyth, D. R. MacFarlane, K. Wagner, S. B. Hall, D. L. Ofcer. The Inuence of the Monomer and the Ionic Liquid on the Electrochemical Preparation of Polythiophene. Polymer 2005, 47 (7), 2047-2058. 2. J. M. Pringle, J. Efthimiadis, P. C. Howlett, J. Efthimiadis, D. R. MacFarlane, A. B. Chaplin, S. B. Hall, D. L. Ofcer, G. G. Wallace, M. Forsyth, Electrochemical synthesis of polypyrrole in ionic liquids Polymer 2004, 45(5), 1447-1453.
W10 COMPUTER SIMULATIONS OF THE STRUCTURAL PROPERTIES OF CONDUCTING POLYMERS: THE REVIEW OF SOME RECENT RESULTS W. unya, D. Djuradob, M.R. Johnsonc , K. Piwowarczyka and M. niechowskia a Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, 30-059 Krakow, Al. Mickiewicza 30, Poland b Laboratoire dElectronique Molculaire Organique & Hybride, DRFMC/SPrAM/LEMOH, UMR (CEA, CNRS, UJF)5819, CEA Grenoble, 17 rue des Martyrs, , 38054 Grenoble, Cedex 9, France c Institut Laue Langevin, 6 rue Jules Horovitz, B.P. 156, 38042 Grenoble, Cedex 9, France The structure of conducting polymers has been intensively studied experimentally since their discovery, mainly by use of the X-ray diffraction techniques. A lot of very valuable and important results in this eld were published during last three decades. Nevertheless, due to the complex molecular structure, relatively low degree of crystallinity, and small average size of crystallites, the interpretation of experimental diffraction data is often very difcult. In such cases, the only tool to discover the reasonable structure model of studied conducting polymer is molecular modeling. In general, the main aim of molecular modeling procedure using computer is to propose a model, which exhibits reasonable chemical and physical parameters like density and rst of all the agreement of the calculated diffraction pattern with the crystalline component of the experimental data. Molecular modeling procedure is based usually on empirical force-eld methodology with conjunction of molecular dynamics method that was used by our team [1]. Our rst successful application of molecular dynamics simulation was related to plast-doped PANI system [2]. We were able to build the model system containing 9312 atoms, comprising two stacked bi-layers of PANI/dopant/dopant/PANI with 12 PANI segments of 8 benzene rings each. These molecular dynamics studies were performed mainly with the CERIUS2 package from Accelrys, using the condensed-phase, ab-initio optimized, second generation force eld COMPASS. Our results are in very good agreement both with experimental XRD and SAXS data, as well as the dynamical properties of the system that agree well with the results of quasi-elastic neutron scattering measurements. In another simulation project that was recently started, the super-cells of camphor-sulfonic acid doped polyaniline (PANI/CSA) were simulated in order to arbitrate between two different structure models for crystalline component of PANI/CSA system, proposed by Winokur [3] and Nandi [4]. Large sizes of simulated systems (ten thousands of atoms) allow studying the stability of proposed structures. We could also gather relevant statistics to see different binding patterns of CSA that is stabilized in polyaniline matrix by hydrogen bonds. Large sizes of simulated systems demanded usage of tools that perform better than CERIUS2. We adapted GROMACS package [5] - widely used for bio-molecular simulations as well as OPLS-AA force-eld [6]. References [1]. D. Frenkel and B. Smith, Understanding molecular simulation, Academic Press 2002 [2]. M. niechowski, D. Djurado, M. Bee, M.A. Gonzalez, M.R. Johnson, P. Rannou, B. Dufour, W. uny; Chem. Phys. 317, 289-300 (2005) [3]. M.J. Winokur, H. Guo, R.B. Kaner, Synt. Met., 119, 403 (2001) [4]. T. Jana, S. Roy, A.K. Nandi, Synth. Met.,132, 257-264 (2003) [5]. E. Lindahl, B. Hess, D. van der Spoel, J. Mol. Mod., 7, 306317 (2001) [6]. N. A. McDonald and W. L. Jorgensen, J. Phys. Chem. B, 102, 8049-8059 (1998)
W11 VAPOUR PHASE POLYMERIZED POLY(3,4-ETHYLENEDIOXYTHIOPHENE) (VPP-PEDOT)
Lichun Chen, Daniel Abler, Christian Schwemmer, Xuhua Wang, Donal Bradley Experimental Solid State Physics Group, Blackett Laboratory, Imperial College London, Prince Consort Road, London SW7 2AZ, UK E-mail: l.chen@imperial.ac.uk
Conducting polymer thin lms are a very attractive alternative to transparent conductive oxide electrodes for polymer light emitting diodes and solar cells. Here we report poly(3,4-ethylenedioxythiophene) (PEDOT) lms on glass and plastic substrates synthesised by an in vacuo vapour phase polymerization (VPP) method. The synthesised VPP-PEDOT lms obtained in our procedure have a surface roughness of less than 10 nm, a transparency around 80% and a conductivity > 800 S cm-1. The VPP-PEDOT synthesis comprises three key steps: oxidant deposition, monomer polymerization and residual oxidant removal. Oxidative doping of the PEDOT lm occurs concurrently with polymerization and the specics of the synthesis procedure have a signicant impact on the resulting VPP-PEDOT conductivity, transparency, and lm morphology. Raman and near infrared spectroscopy measurements show further that the PEDOT conjugation length is also synthesis procedure dependent.
W12 ELECTRON-ION INTERACTION IN CONDUCTING POLYMERS V.N. Prigodina,b, F.C. Hsua and A.J. Epsteina,c aDepartment of Physics, The Ohio State University, Columbus, Ohio 43210-1117 bIoffe Institute, 194021 St. Petersburg, Russia cDepartment of Chemistry, The Ohio State University, Columbus, Ohio 43210-1185
In last few years the electric eld effect in conducting polymers has attracted substantial fundamental and applied interest1. The effect already has been explored in a number of devices2 including transistors3,4. It is widely considered that electrochemical doping/dedoping is behind of the
ABSTRACTS
observable eld effect in conducting polymers5-6. The large free volume within the polymer network enables ions to easily move into and out of the polymers and to intensively interact with charged species inside the polymers. We develop the theory of ionic injection into conducting polymers. To describe electron-ion interaction the drift-diffusion approximation for electron and ion currents is used in combination with the Poisson equation to nd the common electric potential inside the polymers. The theory is consisted with the experimental data for ionic insertion into conducting polymers. But the predicted I(V) characteristics completely disagree with the experimental dependencies for conducting polymer based transistors. We suggest that the observable eld effect in conducting polymers rather is related to their structural peculiarities. The chain morphology of conducting polymers leads to the appearance of ordered grains with good conductivity separated by poorly conducting media of disordered chains7. The macroscopic conductivity is determined by electron coupling between the grains8. We propose that the main effect of ion insertion into the conducting polymers under application of gate voltage is breaking of the percolation network by removing critical hoping sites between highly conducting grains and, as a result, producing the conductor-nonconductor transition. For a low dimensional chain linked granular network the conductor-nonconductor transition can be induced by injecting a small fraction of ions. The present mechanism is supported by the dependence of electric eld effect on temperature, voltage, time, structural order and the level of ionic charging9. 1. 2. 3. 4. 5. 6. 7. 8. 9. J. Liu, N.J. Pinto, and A.G. MacDiarmid, J. Appl. Phys. 92, 6033-6038 (2002). L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, and J. R. Reynolds, Adv. Mat. 12, 481-494 (2000). A.J. Epstein, F.-C. Hsu, N.-R. Chiou, and V.N. Prigodin, Current Applied Physics 2, 339-343 (2002). H. Okuzaki, M. Ishihara, and S. Ashizawa, Synth. Met. 137, 947-948 (2003). M. Lapkowski and A. Pron, Synth. Met. 110, 79-83 (2000). Th. Johansson, L.A.A. Petersson, and O. Inganas, Synth. Met. 129, 269-274 (2002). J.P. Pouget, M.E. Jozefowicz, A.J. Epstein, X. Tang, and A.G. MacDiarmid, Macromolecules 24, 779-789 (1991). V.N. Prigodin and A.J. Epstein, Europhys. Lett. 60, 750-756 (2002). F.C. Hsu, et al., to be published.
W13 META-STABLE POLARONIC PHASE INDUCED BY BACKGROUND ILLUMINATION IN MEH-PPV T. Drori1,2, C.X. Sheng2, E. Gershman1, E. Ehrenfreund1, Y. Eichen1, Z.V. Vardeny1,2 1 Solid State Institute, Technion-Israel Institute of Technology, Haifa 32000, ISRAEL 2Physics Department, University of Utah, Salt Lake City, UT 84112, USA We report on a new meta-stable polaron supporting phase induced by UV illumination in both solid lms and diluted MEH-PPV pellets. The lms, which show no long lived photoexcited polarons while kept in the dark, are transformed reversibly to a state showing simultaneous reduced photoluminescence efciency and photoinduced polarons. Left in the dark at room temperature, the lms transform back to their original phase within 20--40 minutes. Fig. 1 illustrates this novel effect. While kept in vacuum in the dark for extended time, the photoinduced absorption (PIA) spectrum shows no signature of long lived photoexcited polarons (t, lower curve), namely: the characteristic electronic transition at ~0.3 eV and the infrared active vibrations (IRAV) below ~0.2 eV, which are the unique signatures of the polarons, are both missing. The absence of the photoexcited long lived polarons, indicates low defect concentration level. However, exposing the sample to background UV illumination for a long time, still under vacuum conditions, long lived polarons are observed (;, upper curve). The appearance of the long lived polarons is indicative for a bias-illumination induced polaron supporting phase. Unlike irreversible processes (e.g. oxidizing), this phase is metastable, reverting to the original non-polaron supporting phase when the sample is kept in the dark. We believe that the new phase is the result of an intra-chain defect, since the effect is observed even in very dilute MEH-PPV samples.
pure ME H-PPV
6
kept in the dark 200 min bias illum.
h 1 ; h 2
h 4;
h 3
0
H
0.1
0.2
0.3
0.4
0.5
E nergy (eV)
Fig.1 PIA of MEH-PPV. Fig. 2 Model
We propose a reversible intra-chain mechanism (Fig. 2) by which UV illumination can transform sections of the MEH-PPV species into a polaron supporting sections. In analogy to the well documented photocyclization of stilbene derivatives into dihydrophenanthrene derivatives, Z-diphenyl ethene conformer regions of the polymer are pre-organized to undergo a photochemically allowed cyclization into dihydro phenanthrene defects. These types of metastable species are normally characterized by very long lifetimes at room temperature. In the dark, and in the absence of oxygen, the dihydrophenanthrene skeleton undergoes a thermally induced ring opening, thus reverting to the Z-diphenyl ethane structure.
ABSTRACTS
W14 N-FUNCTIONALIZED DITHIENO[3,2-B:2,3-D]PYRROLES: MONOMERS, OLIGOMERS, AND POLYMERS Katsu Ogawa, Karla R. Radke, Hong Mo, Adam Wohl, and Seth C. Rasmussen Department of Chemistry and Molecular Biology North Dakota State University, Fargo, ND 58105 A potential advantage of utilizing conjugated polymers in technological applications is the ability to tune the properties of R the polymer at the molecular level. One such approach to tuning the polymer properties is the annulation of aromatic rings to N the repeat units, which has been found to be a powerful approach to the production of low band gap, conjugated polymers.1,2 However, the synthesis of such fused-ring precursors can be very laborious, especially if one wishes to incorporate side chains necessary for polymer solubility. We have recently developed a new general synthetic route to N-functionalized dithieno[3,2S S b:2,3-d]pyrroles (DTPs, Figure 1), which allows convenient access to the desired long-chain alkyl functionalized precursors needed for the production of soluble DTP-based materials.3 Synthesis of oligomeric and polymeric DTP-based materials via either oxidative coupling or catalytic Stille coupling will be presented. While electropolymerized polyDTPs are insoluble, soluble polymers can be produced via controlled chemical oxidative methods to produce materials with reduced bandgaps (~1.7 eV).4 Solution and solid-state characterization of the DTPbased materials will also be discussed, including electrochemical and photophysical studies, and these properties compared to related polythiophene materials.
(1) Pomerantz, M. In Handbook of Conducting Polymers, 2nd Ed.; Skotheim, T. A., Elsenbaumer, R. L., Reynolds, J. R., Eds.; Marcel Dekker, Inc.: New York, 1998, 277-309. (2) Roncali, J. Chem. Rev. 1997, 97, 173. (3) Ogawa, K.; Rasmussen, S. C. J. Org. Chem. 2003, 68, 2921. (4) Ogawa, K.; Stafford, J. A.; Rothstein, S. D. Tallman, D. E.; Rasmussen, S. C. Synth. Met. 2005, 152, 137.
W15 NANOFIBER SEEDING: A GENERAL SYNTHETIC ROUTE TO CONDUCTING POLYMER NANOFIBERS Xinyu Zhang, Aimei Wu, Harsha Kolla, Sumedh Surwade, Erling Beck, Rashmi D. Kulkarni, Alan G. MacDiarmid, Sanjeev K. Manohar Alan G. MacDiarmid Center for Innovation, Department of Chemistry, The University of Texas at Dallas, Richardson, Texas 75080 (USA) Fax: (+1)972-883-6586. Email: sanjeev.manohar@utdallas.edu We recently described a new synthetic approach called nanober seeding to synthesize bulk quantities of nanobers of polyaniline, in one step, without the need for large organic dopants, surfactants, or stochiometric amounts of insoluble templates.1 When a conventional chemical oxidative polymerization of aniline2 is carried out in the presence of 2-4 mg (seed quantities) of added nanobers of known chemical composition, the bulk morphology changes dramatically from granular to nano-brillar.1 This study extends the seeding method to all major classes of conducting polymers. For example, when the reaction is seeded by V2O5 nanobers, polyaniline, polypyrrole, polythiophene, and PEDOT nanobers can be obtained in bulk quantities, directly in their electronically conducting doped form (see Figure 1 b-d).3 The residual V2O5 nanobers dissolve readily in aq. 1.0M HCl (reaction mixture), eliminating cumbersome post-synthesis removal steps. We extend the general concept of seeding to also polyaniline nanobers synthesized at high dilution in the absence of seeds.4 We attribute brillar polymer growth under these dilute reaction conditions to large, rod-like, colorless aggregates formed during the induction period of the reaction (observed by light scattering). When the shape of these aggregates is altered Figure 1 . Bulk nanof ibe rs of do ped , co nducting po lyme rs s ynthes ized by nanofibe r seeding : (a) po lyaniline .HCl, (b) po lypy rrole.Cl, (c) PEDO T.CSA , (d) from rod-like to spherical (by increasing ionic strength), no nanobers are formed. In effect, po lythiophene .Cl. Inse t : po ly-3- p-flu orop heny l thiophene . Scal e: 200 nm . these rod-shaped aggregates could be viewed as soluble seeds that are formed in-situ during the polymerization. We postulate that at high concentrations, added nanober seeds promote brillar polymer growth by acting as nucleation sites for the formation of these aggregates on their surface. The authors gratefully acknowledge a sample of 3-p-uorophenylthiophene from Professor John P. Ferraris, and nancial support from The University of Texas at Dallas. References (1) Zhang, X.; Goux, W.J.; Manohar, S.K. J. Am. Chem. Soc., 2004, 126, 4502. (2) MacDiarmid, A.G. Angew. Chem. Int. Ed., 2001, 40, 2581. (3) Zhang, X.; Manohar, S.K. J. Am. Chem. Soc., 2004, 126, 12714. Zhang, X.; MacDiarmid, A.G.; Manohar, S.K. Chem. Commun., 2005, 42, 5328. Zhang, X.; Manohar, S.K. J. Am. Chem. Soc., 2005, 127, 14156. (4) Chiou, N.R.; Epstein, A.J. Adv. Mater. 2005, DOI 10.1002/adma.200401000.
W16
Lijuan Zhang, Hui Peng, Zoran D. Zujovic, Paul A. Kilmartin and Jadranka Travas-Sejdic Polymer Electronics Research Centre, Chemistry Department, The University of Auckland, Private Bag 92019, Auckland, New Zealand
ABSTRACTS
POLYANILINE NANOTUBES FORMED IN AMINO ACID SOLUTIONS
Nanotubes of the conducting polymer polyaniline have recently been observed to form through chemical polymerisation under specic experimental conditions.1-3 The high surface area of these low-dimensional organic conductors is of interest for the development of improved sensors and catalytic materials. Suggestions for the template for nanotube formation include micelles involving the dopant ions,1,2 or aniline oligomers formed in the early stages of polymerisation.3 Polyaniline nanotubes were prepared in solutions of six amino acids of different sizes via oxidative polymerisation using ammonium persulfate (Fig. 1). The external diameter of the nanotubes increased when larger amino acids were used, ranging from 191 ( 18) nm using glycine to 255 ( 43) nm with phenylalanine (n = 10) A role for the amino acid dopant in nanotube formation was therefore indicated, even though the nal product appeared to be largely anion exchanged with HSO3- formed from the persulfate oxidant. The tubular geometry was retained following dedoping with ammonium hydroxide, with nanotubes from glycine measuring 184 ( 29) nm and those from a phenylalanine solution 251 ( 33) nm in external diameter. The conductivity of compressed pellets was seen to fall from 2.2 3.6 x 10-2 S cm-1 for doped nanotubes to less than 10-6 S cm-1for undoped nanotubes. Structural features of doped and dedoped nanotubes were further conrmed using UV-visible, FTIR, Raman, XPS and solid state 13C CPMAS NMR spectroscopies, where new features unique to the polyaniline nanotube structure were observed. The lowering of N+ features above 400 eV in XPS core level spectra for N1s, along with a narrowing of peaks in 13C NMR, point to a lowering, but not complete loss, of conductive regions during dedeoping. Figure 1: SEM of polyaniline nanotubes formed from 0.4 M aniline and 0.1 M alanine.
[1] L.J. Zhang, Y.Z. Long, Z.J. Chen, M.X. Wan MX, The effect of hydrogen bonding on self-assembled polyaniline nanostructures. Adv. Funct. Mater. 14 (2004): 693-698. [2] L.J. Zhang, M.X. Wan, Chiral polyaniline nanotubes synthesized via a self-assembly process. Thin Solid Films 477 (2005): 24-31. [3] E.N. Konyushenko, J. Stejskal, I. Sedenkova, M. Trchova, I. Sapurina, M. Cieslar, J. Prokes, Polyaniline nanotubes: conditions of formation. Polym. Int. 55 (2006): 31-39.
W17 INVITED -FOUR-POINT RESISTANCE OF CARBON NANOTUBES Adrien Bachtold
W18 PHYSICAL PROPERTIES OF NOVEL FREE-STANDING POLYMER-NANOTUBE THIN FILMS Emer Lahiff, Jonathan N. Coleman, Werner J. Blau Department of Physics, University of Dublin, Trinity College, Dublin 2, Ireland The authors have previously demonstrated the fabrication of carbon nanotube-polymer composites whereby the nanotube dispersion can be controlled in a simple patented manner1,2. To achieve this, a polymeric material is introduced into the free volume contained in carbon nanotube (CNT) mats grown by chemical vapour deposition. The resulting composite material can then be peeled from the substrate to give a free standing lm (gure 1). Embedded carbon nanotubes provide a network of conduction pathways through an insulating polymer matrix. We demonstrate an increase in surface and bulk conductivities by factors of 107 and 108 respectively for a CNT loading of 0.4wt%. The presence of CNTs also causes the Youngs Modulus of the polymer lm to double3. It is shown that the presence of CNTs has no effect on the morphology of the polymer itself. We suggest that this technique is an efcient method of combining two materials in an inexpensive and scalable manner.
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Figure 1: SEM image of entangled NTs grown on SiO2. The tubes are then incorporated into a polymer matrix to produce a free-standing composite thin lm (inset). References [1] E. Lahiff, C.Y. Ryu, S. Curran, A.I. Minett, W.J. Blau, P.M. Ajayan, Nano Lett., 3, (10), 1333-1337, 2003. [2] Patent No. WO2004053464. Publication date 2004-06-24. [3] E. Lahiff, R. Leahy, J.N. Coleman, W.J. Blau, Carbon, In Press, Corrected Proof, Available online 20 January 2006
W19 HIGH RESOLUTION INKJET PRINTED SINGLE-WALLED CARBON NANOTUBE (SWNT) TFT FOR MACROELECTRONIC DEVICES Gyoujin Cho, Minhoon Jung, Jae Hee Song,1 James M. Tour2 Department of Chmical Engineering and 1Department of Chemistry, Sunchon National University, 315 Maegok Sunchon, Jeonnam 540-742 Korea, 2Department of Chemistry and Mechanical Engineering and Materials Science, and Center for Nanoscale Science and Technology, Rice University, MS 222, 6100 Main Street, Houston, Texas 77005 USA High resolution ink-jet printer has been employed to fabricate TFT on plastic lm. In this presentation, we would like to show the optimized printing conditions for printing gate, drain, source, dielectric layer, and active layer with 40 um of channel resolution. Silver-SWNT composite ink for printing electrodes, PMMA ink for dielectric layer and semiconducting SWNT ink for active layer are respectively used for printing TFT. The shape of droplets with the variation of viscosity, surface tension, and wetting has been investigated with the relation of printed quality of line patterns. The all printed resulting TFT has 150 cm2/Vs of eld effect mobility with on-off ratio of 200, a transconductance of 49 uS, and 300 mV/ decade of subthreshhold swing.
W20 2D CARBON NANOTUBE NETWORKS: A NEW MATERIAL FOR TRANSPARENT ELECTRONICS David Hecht, Liangbing Hu, Yangxin Zhou, George Grner Department of Physics and Astronomy and California NanoSystems Institute University of California, Los Angeles, CA 90095-1569, USA
This talk will focus on the electronic properties of two dimensional carbon nanotube networks, and on their application potential. Percolation issues1, together with the frequency dependent activity will be discussed. The network can be tuned from having semiconducting to metallic like behavior, and doping with electron withdrawing and donating species leads to networks with tailor-made electronic properties. The network is also highly transparent in the visible spectral range. This attribute -together with simple room temperature fabrication processes that include patternability -- opens up application opportunities in the area of electronics2, opto-electronics, photovoltaics, smart fabrics3, and sensors. Recent results on solar cells4, OLEDs5 and smart windows will be reviewed. Field effect transistors that incorporate nanotube network conducting channels together with complex functional molecules will also be discussed6. Finally a comparison will be made with conventional and emerging materials that compete in the area of disposable, exible, and printable electronics. References: 1. Hu, L; Hecht, D.S.; Grner, G. Percolation in Transparent and Conducting Carbon Nanotube Networks. Nano Letters, Vol. 4, No. 12 2513-2517 (2004). 2. Artukovic, E.; Kaempgen, M.; Hecht, D.S.; Roth, S.; Grner, G. Transparent and Flexible Carbon Nanotube Transistors. Nano Letters, Vol. 5, No. 4 757-760 (2005). 3. Hecht, D.S.; Hu, L.; Grner, G. Electronic Properties of Carbon Nanotube/Fabric Composites. Current Applied Physics, AIP, (2005). 4. J.F. Li, L. Hu, L. Wang, Y.X. Zhou, G. Grner, T.J. Marks, unpublished. 5. M. Rowell, M. McGehee, H.J. Prall, G. Dennler, N.S. Sariciftci, L. Hu, G. Grner, unpublished. 6. Hecht, D.S.; Ramirez, R.A.; Artukovic, E.; Briman, M. Chichak, K.; Stoddart, J.F.; Grner, G. Bio-inspired Detection of Light using Porphyrin Sensitised Carbon Nanotube FETs. Submitted to PNAS (2006).
W21 A NEW INTERPRETATION OF THE G BAND OF NANOTUBES Chiara Castiglioni, Eugenio Di Donato, Matteo Tommasini, Giuseppe Zerbi Dept. of Chemistry, Materials and Chemical Engineering Politecnico di Milano Piazza Leonardo da Vinci 32 20133 Milano and INSTM, UdR Milano, Italy The interpretation of the Raman spectra of carbon nanotubes presents still open questions. In particular, the G band of nanotubes samples shows a structured shape witch depends on the peculiar electronic structure of the tube and is due to the symmetry-breaking effects produced by the wrapping of the graphene sheet around a cylindrical surface. It is known that the higher frequency G peak practically is not diameter dependent (G+ = 1591 cm-1), while the lower-frequency G peak can be described according to the empirical t: G- = G+ - C/d2, with C being a different coefcient for metallic and semi conducting tubes (Cm > Cs) [1]. In this work we propose a general model that allows to calculate the phonon frequencies for any (n, m) nanotube based on a suitably developed force eld. The outcome of the model nally bring us to give a new interpretation of the G band in the Raman spectra of single walled carbon nanotubes (SWNTs). Our model is also able to predict the right linear dispersion of the radial breathing mode (RBM) with respect to the inverse diameter of the tube. Our approach is new in the eld inasmuch as we do not rely on rst principles calculations or zone folding of graphite, but merely extend the use of semi empirical valence force eld calculations derived from polyconjugated
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polymers [2-3] and graphite [4] to the domain of nanotubes. This choice is based on our previous experience in developing a semi empirical force eld for graphite and related molecular compounds [4]. Moreover, it is well known that for systems containing covalent bonds, a valence force eld is built upon parameters which are much closer to the chemical intuition than any Cartesian force constants. For this reason the transfer of these parameters is acceptable when one considers systems characterized by a similar chemical structure. In the proposed model we explicitly consider the curvature of the system and the effects of long range -conjugation. We show that the strength of the Electron Phonon Coupling (EPC) is directly related to the topology of the tube and is the main responsible of the different behavior between the Raman spectra of metallic and semi conducting tubes. On the basis of the vibrational force eld derived in this work we propose a new assignment of the G band. Moreover, based on symmetry selection rules, we can state that the LO modes of armchair tubes and the TO modes of zigzag tubes at 0 are silent in the Raman spectra. References [1] A. Jorio, A. G. Souza Filho, G. Dresselhaus, M.S. Dresselhaus, A.K. Swan, M.S. nl, B.B. Goldberg, M.A. Pimenta, J.H. Hafner, C.M. Lieber, and R. Saito, Phys. Rev. B, 65, 155412 (2002). [2] L. Piseri, R. Tubino, G. Dellepiane, Solid State Commun., 44, 1589 (1982). [3] L. Piseri, R. Tubino, L. Paltrinieri, G. Dellepiane, Solid State Commun., 46, 183 (1983). [4] C. Mapelli, C. Castiglioni, G. Zerbi, K. Mllen, Phys. Rev. B, 60, 12710 (1999)
W22 SYNTHESIS AND PROPERTIES OF CARBON CLUSTER COMPLEXES Prof. Eiichi Nakamura, The University of Tokyo
Carbon clusters remain to be the subject of thousands of papers every year. While a majority of these reports are concerned with intact entities, it is our belief that the future science of carbon clusters depends on chemically modied carbon cluster complexes and control of their nano architectures. Synthesis of metallofullerene derivatives and their electrochemical and photovoltaic properties will be discussed.
W23 ELECTRONIC PROPERTIES OF ORGANIC MONOLAYERS AND NANOWIRES D. Vuillaume Institut dElectronique, de Micro-electronique et de Nanotechnologie, CNRS Molecular Nanostructures & Devices group BP69, avenue Poincar, 59652 Villeneuve dAscq cedex, France.
I will review some of our recent experimental results on charge transport in organic nanostructures such as self-assembled monolayers, monolayers of organic semiconductors, organic nanowires and nanorings. We demonstrated [1] a molecular rectifying junction made from a sequential self-assembly on silicon. Our device features a simple synthesis with only one donor group and an alkyl spacer chain. These devices exhibit a marked current-voltage rectication behavior due to resonant transport between the Si conduction band and the molecule highest occupied molecular orbital. I will discuss the role of metal Fermi level pinning in the current-voltage behaviors of these molecular junctions [2]. I will also discuss some recent insights on the role of the metal/molecule interface in the electron tunnelling behavior of Si/alkyl chain/metal junctions [3]. Electrons and holes can be locally injected in a single pentacene monolayer island from the tip of an electrical force microscope [4]. The twodimensional distribution and concentration of the injected carriers are measured by EFM. I will discuss the relationship between the carrier distribution in the island and its molecular structure. In crystalline monolayer islands, both carriers are delocalized over the whole island. On the contrary, on disordered monolayer, carriers stay localized at their injection point. Charge and injection dynamics as well as spectroscopic information on the electronic structures of these organic nanostructures will be discussed. Electronic properties of some other molecular systems (SAM-FET, self-assembled nanowires and nanorings) will be also presented. [1] [2] [3] [4] S. Lenfant , C. Krzeminski, C. Delerue, G. Allan & D. Vuillaume. Nano Letters 3(6), 741-746 (2003). S. Lenfant, D. Guerin, C. Delerue & D. Vuillaume. Phys. Rev. Lett. (submitted). D.K. Aswal, S. Lenfant, D. Guerin, J.V. Yakhmi & D. Vuillaume. Small 1(7), 725-729 (2005). T. Heim, K. Lmimouni & D. Vuillaume. Nano Letters 4(11), 2145-2150 (2004)
W24 HEXAGONAL NETWORK ORGANIZATION OF DYE-LOADED ZEOLITE L CRYSTALS by surface tension driven auto-assembly Sami Yunusa, Fabrice Spanob, Alberto Bolognesib, Chiara Bottab, Dominik Brhwilerc, Arantzazu Zabala Ruizc, Gion Calzaferric aLaboratoire de Physico-Chimie et de Physique des matriaux, Universit catholique de Louvain, Place Croix du Sud 1, 1348 Louvain-la-Neuve, Belgium bIstituto per lo Studio delle Macromolecole, CNR Via E. Bassini 15, 20133 Milano, Italy c Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3000 Bern 9, Switzerland
ABSTRACTS
Hierarchically organized structures, presenting successive ordering from the molecular up to the millimetric scale are subject to great interest due to the direct relationship between the molecular arrangements (i.e. orientation of molecules) and the macroscopic geometry or properties. This is one aspect that makes nanotechnologies more appealing and promising in many technological elds as nano and microelectronics, nano and microbiology. Highly uorescent dye-loaded zeolite L crystals, measuring approximately 1.4 m in length and 650 nm in diameter, have been organized in a hexagonal network by a surface tension driven auto-assembly process. A self-assembled polydimethylsiloxane (PDMS) lm presenting a trigonal ordering of spherical protuberances, including a polystyrene (PS) hexagonal network occupying their interstices, was chosen as the basis for a surface tension driven auto-assembly. The overall wettability and the difference of surface tension between PDMS and PS surfaces were found to offer good conditions to order micrometric dye-loaded zeolite L crystals in a hexagonal network. The resulting lm displays a regular hexagonal pattern of polarized uorescence reecting the polarization properties of the dye molecules inserted in the parallel nanochannels of the zeolites.
W25 COMPARATIVE STUDY ON FIELD-EFFECT AND ELECTROCHEMICAL TRANSISTORS OF P3HT AND SWNT H. Shimotani,1 T. Kanbara,1 G. Diguet,2 K. Tsukagoshi,3 Y. Aoyagi,3,4 H. Kataura,5 Y. Iwasa1 1 Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan and JST-CREST, 4-1-8 Honcho, Kawaguchi-shi,Saitama 332-0012, Japan. 2 UFR SPM, University of Rennes 1,35042 Rennes, France. 3 RIKEN, 2-1, Hirosawa, Wako 351-0198, Japan. 4 Tokyo Institute of Technology, Yokohama 226-8502, Japan 5 AIST, Tsukuba 305-8562, Japan. Field-effect transistor (FET) is a powerful tool for studying electronic properties of organic materials by controllable, continuous, and reversible doping without any dopants. However, only a small amount of carriers can be usually accumulated by FETs. On the other hand, electrochemical transistor can accumulate a substantial amount of carriers employing an electrolyte as a gate electrode. We performed comparative study of these complimentary methods for regioregular poly(3-hexylthiophene) (RR-P3HT) and single-walled carbon nanotube (SWNT). Fig. 1 shows doping level dependency of mobility in FET and electrochemical transistor of a RR-P3HT lm on a SiO2 (400 nm) /n++-Si substrate with Au source and drain electrodes. The low mobility of electrochemical transistor at the low doping level is attributable to the inuence of the Coulomb potential of dopants by comparing with the FET.[1] Fig. 2 compares FET and electrochemical transistor characteristics of a SWNT bundle device made with e-beam lithography showing large carrier accumulation in the latter transistor. The electrochemical transistor of SWNT bundles showed stepwise increase of the conductivity by the increase of the electrochemical potential of the device. This is attributed to multi-subband transport, and revealed the comparable contributions of the geometrical and the chemical capacitance in SWNT electrochemical transistors.[2]
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[1] H. Shimotani et al., Appl. Phys. Lett., 86, 022104 (2005). [2] H. Shimotani et al., Appl. Phys. Lett., 88, 073104 (2006).
W26 STRUCTURE AND FUNCTION: PROBING THE ROLE OF MORPHOLOGY IN ORGANIC ELECTRONIC DEVICES C.R. McNeill1, B. Watts2, L. Thomsen2, W.J. Belcher2, N.C. Greenham1 and P.C. Dastoor2 1Cavendish Laboratory, J J Thomson Avenue, Cambridge CB3 0HE, United Kingdom 2School of Mathematical and Physical Sciences, University of Newcastle, Callaghan, NSW 2308, Australia Conjugated polymer blends have attracted great interest due to their application as the active layer in a variety of organic electronic devices such as solar cells and light emitting diodes. Although it is well-known that the performance of these devices depends critically upon the nano- and micro-scale morphology of these blends there are few techniques that can directly probe the structure and function of these materials. Near-eld Scanning Photocurrent Microscopy (NSPM) is a powerful new technique that allows for two-dimensional mapping of current in fully fabricated organic solar cells [1]. By rastering the light output from a near-eld scanning optical microscope tip through a semi-transparent electrode across the solar cell surface it is possible to simultaneously collect height and photocurrent images with a lateral resolution that is governed by the NSOM aperture. Scanning transmission X-ray microscopy (STXM) is an established synchrotron-based technique that is capable of providing chemical contrast in polymer blends with a lateral resolution of better than 50 nm. In this paper we present combined NSPM and STXM measurements probing the relationship between structure and function in photovoltaic devices based on p-xylene processed poly(9,9-dioctyluorene-co-bis-N,N(4,butylphenyl)-bis-N,N-phenyl-1,4-phenylene-diamine) [PFB] and poly(9,9-dioctyluorene-co-benzo-thiadiazole) [F8BT] blend lms. References
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1. McNeill, C.R.; Frohne, H.; Holdsworth, J.L.; Furst, J.E.; King, B.V.; Dastoor, P.C., Nano Letters 2004, 4, 219-223.
W27 ACID BASE CHEMISTRY IN CONJUGATED MATERIALS Douglas S. Dudis*, James A. Ryan and A. Todd Yeates Materials and Manufacturing Directorate Air Force Materials Laboratory Wright-Patterson AFB, OH 45433-7750 Acid-base chemistry is foundational to understanding many processes in nature. While oxidation-reduction processes in conjugated materials have been extensively investigated, acid-base properties have received relatively little attention by comparison. The Lewis-basicity of all trans-polyenes (CnHn+2, n = 4 - 24) have been determined by high level rst principles calculations and the basicity of all trans-polyacetylene determined by extrapolation of the oligomeric results. Surprisingly, polyacetylene is a rather strong base stronger than a number of common bases a result which appears to be unappreciated in the literature. The importance of this for understanding previously poorly understood synthetic processes, as well as for providing alternative paths for switching and enhancing optical properties, will be discussed. Protonation induces formation of solitons within the polyacetylene chain, the thermodynamics of which have been carefully mapped. The impacts of such chemical processes on the optical and nonlinear optical properties will be reported as will the inuences of solvent dielectric properties on the reaction thermodynamics. Variations in the position of protonation have been mapped, and the inuence of protonation upon IR, Raman and NMR spectral features will be reported.
W28 THE EFFECT OF POLARIZATION ON INTERMOLECULAR ELECTRONIC COUPLING AND CHARGE TRANSPORT IN ORGANIC SEMICONDUCTORS Demetrio A. da Silva Filho,1 Edward F. Valeev,1,2* Veaceslav Coropceanu,1 Seyhan Salman1 and Jean-Luc Brdas1 1School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400 2Computational Chemical Sciences Group, P.O. Box 2008 MS6367, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-63672
The performance of organics-based electronic devices depends to a large extent on the efciency of the charge-transport processes [1]. Theoretical investigations of charge transport in organic materials routinely assume that the parameters (site energies and transfer integrals) determined from monomer and dimer calculations can be reliably used to describe the extended system [2]. Here, we demonstrate that this transferability can fail even in molecular crystals with weak van der Waals intermolecular interactions, due to the substantial, but often ignored, electronic polarization. We show that failure to account for electronic polarization leads to qualitatively incorrect values and trends for the transfer integral computed with the popular energy splitting in dimer method in even simple prototypes such as ethylene and pentacene dimers. The polarization effect in these systems is largely electrostatic in nature, due (for instance in the case of a herringbone-type packing) to the positively charged hydrogen atoms of the edge molecule lowering the energy of the -orbitals of the face molecule. Most importantly, the net polarization effect can change dramatically upon transition from a dimer to an extended system. For example, the net level splitting in a prototypical face-to-edge one-dimensional stack of pentacene molecules is calculated to be 30% greater than the 0.47 eV splitting in the face-to-edge dimer; in contrast, the polarization-driven level splitting in the pentacene crystal is approximately one order of magnitude smaller due to the near-complete cancellation of several electrostatic contributions. We conclude that proper accounting for polarization effects is crucial to describe charge transport in many, if not most, organic semiconductors [3]. References [1] Newman, C. R.; Frisbie, C. D.; da Silva Filho, D. A.; Bredas, J. L.; Ewbank, P. C.; Mann, K. R. Chemistry of Materials 2004, 16, 44364451. [2] Bredas, J. L.; Calbert, J. P.; Da Silva Filho, D. A.; Cornil, J. Proceedings of the National Academy of Sciences of the United States of America 2002, 99, 5804-5809. [3] Edward F. Valeev, E. F.; Coropceanu, V.; da Silva Filho, D. A.; Salman, S.; Bredas, J. L. Journal of the American Chemical Society, to be published.
W29 VOLTAGE INDUCED METAL-INSULATOR TRANSITION IN ORGANIC FIELD-EFFECT TRANSISTORS Anoop S. Dhoot, Guangming Wang, Daniel Moses, and Alan J. Heeger Center for Polymers and Organic Solids and Mitsubishi Chemical Center for Advanced Materials, University of California, Santa Barbara, CA 93106, USA Both charge carrier density and temperature govern the carrier transport in organic eld-effect transistors (FETs). We have extensively studied the carrier transport in regio-regular polythiophene FETs from room temperature to 4.2 K. At low temperatures, Zabrodskii plots ( ) demonstrate that the gate voltage and source-drain voltage (Vsd) combine to induce the insulator-to-metal transition at a carrier density of 51012 cm-2. The carrier
ABSTRACTS
transport in the insulating regime is well described by phonon assisted hopping in a disordered Fermi Glass with Coulomb interaction between the hopping charge carrier and the opposite charge left behind, as described by Efros and Shklovskii. We nd the crossover to the metallic regime requires a signicant Vsd (20 kV/cm), which is assigned to electric eld assisted carrier tunnelling through randomly distributed potential barriers which further delocalizes occupied carrier states, driving the conductivity into the metallic regime. Analysis of the data indicates that a small fraction (<0.01) of the eld-induced charge carriers occupy delocalized states. We have also studied the carrier transport in solution processible, high performance conjugated small-molecule FETs ( > 0.1 cm2/Vs) and nd similar results as that found for the polymer devices, and examine the role of the contact resistance in the operation of the organic FETs. W30 FUNCTIONAL NANOCOMPOSITES BASED ON SEMICONDUCTING POLYMERS FOR LIGHT-EMITTING AND PHOTOVOLTAIC APPLICATIONS Gitti L Frey, Department of Materials Engineering, Technion - Israel Institute of Technology, Haifa 32000, Israel The unique combination of semiconducting properties with solution processability, provides the means to utilize conjugated polymers in exible, cheap, large area electronic applications. The fundamental process in polymer light-emitting diodes involve the injection of charge carriers from the electrodes into the emissive layer and their propagation along polymer chains to form electron-hole pairs (excitons) that can recombine through emission of a photon. In polymer photovoltaic devices, on the other hand, the excitons formed upon light absorption could dissociate into free electrons and holes propagating along polymer chains to form a current. The device performances, therefore, are strongly dependant on the dynamics and life-time of the excitons. Recently, we reported on the self-assembly of pre-formed semiconducting polymers and inorganic species into guest/host nanocomposites. Two types of host structures were used for polymer hosting: three-dimensional (3D) scaffolds such as mesoporous silica; and two-dimensional (2D) layered structures such as transition metal chalcogenides. The inorganic robust scaffold directs the conformation of individual polymer chains, chain-chain stacking and interfacial interactions with the scaffold walls; and hence the dynamics of the excitons. The optoelectronic processes are further modulated by the electronic interactions at the organic/inorganic interface. Therefore, judicious selection of the host matrix and polymer guest based on their structural, electronic and optical properties leads to improved device performances unattainable in pristine polymer lms.
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W31 BYUNG DOO CHIN, JAI KYEONG KIM, O OK PARK Optoelectronic Materials Research Center Korea Institute of Science and Technology PO Box 131, Cheongryang, Seoul, 130-650 Korea White organic light emitting devices (WOLEDs) are of considerable interest both for simple and efcient backlights of at-panel display and next generation light illumination devices. Among the several ways to obtain white light in OLED, we have investigated the combination of uorescent and phosphorescent dye-doped materials for high efciency and controllable white light broadband spectrum. First, WOLED with emitting layers of stacked small molecules and diluted dopant concentration were considered. Blue emission from 2,2,7,7-tetrakis-(2,2 -diphenyl-vinyl)- spiro9,9-biuorene (spiro-DPVBi : host) doped with 1.5~2.0% 1,4-bis[2-(3-N-ethylcarbazoryl) vinyl]benzene (BCzVB) and yellow-orange emission from rubrene were utilized to fabricate a uorescent white OLED, having additional green emission from 10-(2-benzothiazolyl)-1,1,7,7-tetramethyl2,3,6,7-tetrahydro-1H,5H,11H-benzo[l]pyrano [6,7,8-i j]quinolizin-11-one (C-545T) dopant for improved white broadband spectrum. Moreover, using phosphorescent orange-red dopant in a conventional triplet host material and identical uorescent blue light emitting layer, more efcient white OLED were produced. Dependence of dopant concentration, relative thickness of light emitting layer for each color, and their interplay were characterized. Second, we have shown the solution-processed, polymeric white OLEDs from the layered, uorescent blue polymeric materials and phosphorescent green/red dye-doped solutions. Although polymer OLEDs overall efciency and lifetime is still inferior to the small molecular devices by evaporation, polymeric white emission has advantages such as easily controllable color spectrum, suitability for large area coating, and feasibility on a exible application. Photophysical properties, energy transfer, and interfacial phenomena between uorescent polymeric light emitting materials and soluble phosphorescent dyes were characterized and optimized as a feasible study of next generation illumination and backlight devices with simplied fabrication process.
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W32 SOLUBLE AND THERMALLY STABLE MOLECULES FOR ORGANIC LIGHT-EMITTING TRANSISTORS F.Cicoira 1,2, C. Santato1, M. Melucci3, L. Favaretto3, M. Gazzano3, M. Muccini1, G. Barbarella3. [1] Consiglio Nazionale delle Ricerche Istituto per lo Studio dei Materiali Nanostrutturati, Via Gobetti 101, I-40129 Bologna (Italy) [2] INRS-EMT Universit du Qubec, 1650, Boulevard Lionel Boulet, Varennes, Qubec J3X 152, Canada. [3] Consiglio Nazionale delle Ricerche, Istituto per lo Studio della Sintesi Organica e la Fotoreattivit, Via Gobetti 101, I-40129 Bologna (Italy) We report on the design, synthesis, thin lm growth and optoelectronic properties of a newly synthesized dithienothiophene derivative.1 Very interestingly for future technological applications, Organic Light Emitting Transistors (OLETs) were successfully fabricated not only employing vacuum sublimation but also drop casting. Atomic Force Microscopy and Laser Scanning Confocal Microscopy show that both vacuum sublimed and drop cast DTT7Me lms have good SiO2 surface coverage. X-ray diffraction reveals that the lms have a highly ordered structure. This results introduce several novelties in organic optoelectronics: the demonstration of a novel multifunctional material able to conjugate good charge transport and electroluminescence in FET conguration and the rst solution processed OLET based on non polymeric systems. This last result paves the way towards all plastic, low temperature processed, large area organic optoelectronics. [1] F.Cicoira, C. Santato, M. Melucci, L. Favaretto, M. Gazzano, M. Muccini, G. Barbarella Organic Light-Emitting Transistors Based on SolutionCast and Vacuum-Sublimed Films of a Rigid Core Thiophene Oligomer, Advanced Materials 2006, 18, 169.
W33 DYNAMICS OF BIPOLARON IN A POLYMER CHAIN: FORMATION AND DISSOCIATION* Yong-Hong Yan, Zhong An, and Chang-Qin Wu+ Department of Physics, Fudan University, Shanghai 200433, China Conducting polymers have attracted much interest for its commercial applications, e.g., organic light emitting diodes, solar cells, etc. Understanding mechanisms of the electron injection from metal electrodes into organic material is of great importance for improving the performance of these organic-based devices. Due to the strong electron-lattice interactions, it is well known that additional electrons or holes in conducting polymers will induce self-localized excitations, such as solitons (only in trans-polyacetylene), polarons and bipolarons. As a result, it has been generally accepted that the charge carriers in conjugated polymers are these excitations including both charge and lattice distortion. The formation and dissociation of bipolaron in non-degenerate polymers are investigated in this work by a non-adiabatic dynamical method, which allows the transition between instantaneous electronic states, through solving the time-dependent Schrdinger equations for electrons combined with the Newtonian equation of motion for lattices within the Su-Schrieffer-Heeger model with the hopping modied by an alternate Brazovskii-Kirova symmetry-breaking term (t). Bipolaron Formation: We consider the charge injection process from metal electrode to a non-degenerate polymer in a metal/polymer/metal structure. It is demonstrated that the dynamical formation of a bipolaron sensitively depends on the strength of applied electric eld, the work function of metal electrode, and the contact between the polymer and the electrode. For a given bias applied to one of the electrode (V0) and coupling between the electrode and the polymer (t), such as V0=0.79eV and t=1.0eV, the charge injection process depending on the electric eld can be divided into the following three cases: (1) in the absence of the electric eld, only one electron tunnels into the polymer to form a polaron near the middle of the polymer chain; (2) at low electric elds, two electrons transfer into the polymer chain to form a bipolaron; (3) at higher electric elds, bipolaron can not be formed in the polymer chain, electrons are transferred from the left electrode to right electrode through the polymer one by one accompanying with small irregular lattice deformations. Bipolaron Dissociation: We investigate the dynamics of a bipolaron in poly(p-phenylene vinylene) (PPV) at an external electric eld. At a high electric eld, a bipolaron is found to be dissociated as the case of a polaron due to the lattice being not responded simultaneously with the fast moving electrons but with a much high critical strength of order 106V/cm. This dissociation is regarded as the causation of a large increase in current in PPV at the eld observed in experiments. Furthermore, it is found that the bipolaron will not be formed in an electric eld with strength over 8x104V/cm. * Work supported by the National Natural Science Foundation of China and the State Ministry of Education of China. + Email address: cqw@fudan.edu.cn.
W34 PHOSPHORESCENT DENDRIMERS WITH CHARGE TRANSPORTING DENDRONS Paul L. Burn, Kevin Knights, Christopher P. Shipley Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Manseld Road, Oxford, OX1 3TA, UK Stuart Stevenson, Ruth E. Harding, Jean-Charles Ribierre, Salvatore Gambino, Ifor D.W. Samuel Organic Semiconductor Centre, SUPA, School of Physics & Astronomy, University of St Andrews, North Haugh, St Andrews,Fife, KY16 9SS, UK
ABSTRACTS
Phosphorescent emitters have been used to give rise to highly efcient sky-blue, green and red organic light-emitting diodes. It is generally thought that phosphorescent emitters are particularly sensitive to concentration quenching of the emission. The main method for overcoming concentration quenching for small molecule phosphorescent emitters is to blend them into a host. The main hosts used contain carbazole moieties, e.g., 4,4bis(N-carbazolyl)biphenyl (CBP). The second approach to controlling the detrimental effects of intermolecular interactions is to incorporate the phosphorescent emitter as the core of a dendrimer. An advantage of the latter route is that the dendrimers are solution processible. The early work on dendrimers utilised fac-tris(2-phenylpyridyl)iridium(III) (Irppy3) cores, biphenyl based dendrons, and 2-ethylhexyloxy surface groups. Interactions that caused quenching of the luminescence were found to be controlled by either the generation and/or number of attached dendrons. However, the
biphenyl dendrons, which act as an intramolecular host for the emissive core, are electrical insulators. This in contrast to the host materials such as CBP, which are capable of transporting charge.
= N = = n-Pr n-Pr Irppy3
Figure 1: Schematic of a second generation dendrimer with Irppy3 core, carbazole dendrons, and uorenyl surface groups. We have therefore developed three generations of dendrimers with Irppy3 cores, carbazole containing dendrons, and new uorenyl surface groups (Figure 1). In this presentation we will describe the strategy for their preparation as well as their opto-electronic and device properties. We will illustrate the importance of the carbazole containing dendrons and show the effect of generation (number of carbazole units) on the properties of the dendrimers.
W35 THEORETICAL INSIGHT INTO CHARGE GENERATION AND RECOMBINATION RATES IN ORGANIC SOLAR CELLS Dr. Jrme Cornil University of Mons-Hainaut, Laboratory for Chemistry of Novel Materials Place du Parc 20, B-7000 Mons, Belgium Jerome@averell.umh.ac.be
Quantum-chemistry has now reached a stage where it can be exploited to estimate all the parameters entering into the Marcus expresssion for the rates of charge generation and recombination in blends used in organic solar cells [1]. This will be illustrated in this talk by focusing on various donor/acceptor complexes. We will demonstrate in particular that: (i) very specic geometric congurations can strongly limit the charge recombination process, highly detrimental for the devices, due to constraints imposed by the symmetry of the electronic levels involved in the process; this symmetry control can, however, be easily broken by slight geometric uctuations, thus pointing to the key role played by morphology [2]; (ii) two-dimensional molecules like phthalocyanines are very attractive compounds for solar cells. This originates from the fact that the twodimensional character induces a quasi-degeneracy of the lowest unoccupied electronic levels, which in turn promotes two pathways for exciton dissociation; this makes this process much less affected by positional disorder than in donor/acceptor blends incorporating rod-like molecules; (iii) a dissociation pathway involving an excited charge-separated state must be accounted for in some cases to rationalize the full dynamics of exciton dissociation [3]; and (iv) connecting covalently the donor and acceptor units by a bridge is required to promote sufciently fast dissociation rates when they are lying the same plane. [1] J.L. Brdas, D. Beljonne, S. Coropceanu, and J. Cornil, Chem. Rev. 104 (2004) 4971. [2] V. Lemaur, M.C. Steel, D. Beljonne, J.L. Brdas, and J. Cornil, J. Am. Chem. Soc. 127 (2005) 6077. [3] A. Burquel, V. Lemaur, D. Beljonne, R. Lazzaroni, and J. Cornil, J. Phys. Chem. 110 (2006) 3447.
W36 HIGH-EFFICIENCY PHOTOVOLTAIC DEVICES BASED ON REGIOREGULAR 3-ALKOXYTHIOPHENE COPOLYMERS Chenjun Shi, Yan Yao, Yang Yang, Qibing Pei Department of Materials Science and Engineering The Henry Samueli School of Engineering and Applied Science University of California, Los Angeles, CA 90095-1595 We report the synthesis and characterization of a series of regioregular copolymers that are based on 3-alkoxythiophene monomers. The alkoxy sidechains on the thiophene units are more effective than alkyl side-chains in reducing the bandgaps of the copolymers and enhancing charge transfer from the copolymers to electron-acceptors such as (6,6)-phenyl C61-butyric acid methyl ester (PCBM). Of the copolymers, poly(3-octylthiophene2,5-diyl-co-3-decyloxythiophene-2,5-diyl) (POT-co-DOT) and poly{(9,9-dioctyluorene)-2,7-diyl-alt-[4,7-bis(3-decyloxythien-2-yl)-2,1,3benzothiadiazole]-5,5-diyl} (PF-co-DTB) have been extensively investigated. Both copolymers are readily soluble in organic solvents and form high-quality thin lms. Electrochemical and photophysical studies revealed a bandgap of 1.64 eV for POT-co-DOT and 1.78 eV for PF-co-DTB. Bulk heterojunction photovoltaic devices were fabricated using blends of these copolymers and PCBM as the active layer, ITO-glass as the anode, and aluminum as the cathode. Power conversion efciency as high as 1.6% was achieved under simulated solar light AM 1.5G (100 mW/cm2) from preliminary solar cells with an active layer containing 20 wt% PF-co-DTB and 80 wt% PCBM. Substantial improvement in the solar cell performance is expected as the devices are being optimized. Regioregular poly(3-decyloxythiophene-2,5-diyl) will also be discussed as a suitable material for polymer solar cells.
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W37 CONJUGATED BLOCK COPOLYMERS FOR PHOTOVOLTAICS Sam-Shajing Sun, Cheng Zhang, Abram Ledbetter, Carl Bonner Center for Materials Research Norfolk State University 700 Park Avenue Norfolk, VA 23504, USA
Improvements of a novel class of light harvesting conjugated block copolymer, where electron-donating conjugated blocks (D) connected to electron-accepting conjugated blocks (A) via non conjugated and exible bridge chains (B), have been extensively investigated using donor and acceptor derivatized PPV analogs. The optical excitation energy gaps are 2.24 eV for the donor block (D), 2.33 eV and 2.45 eV for the two acceptor blocks (A1) and (A2) synthesized, with donor/acceptor LUMO energy offsets of 0.24 eV and 0.16 eV respectively. The GPC measured molecular weights match very well with theoretical predictions for the soluble blocks. For the less soluble blocks, the measured larger molecular weights are attributed to the PPV inter-molecular aggregation in THF. Conjugated block copolymer self assembly in solid state have been studied using AFM and XRD. In comparison to a simple D/A2 blend lm, the (DBA2B)n block copolymer lm exhibited very different thin lm morphology, stronger PL quenching, and much better light harvesting properties with a photovoltaic device open circuit voltages (Voc) improved from about 0.1 volt (D/A blend) to over 1.1 volt (DBA block) under identical conditions.
W38 USING PROXIMAL PROBE MICROSCOPY AND SPECTROSCOPY TO DEVELOP AND FABRICATE HIGH EFFICIENCY ORGANIC SOLAR CELLS Seamus Curran, James Dewald, David Carroll Physics Department New Mexico State University Las Cruces, NM 88001, USA In the last twenty years signicant advances have been made in proximal probe microscopy, where Atomic Force Microscopy (AFM) and Near Field Optical Microscopy (NSOM) can be used in developing a better understanding of nanoscale morphology. The use of these proximal probe techniques, coupled with spectroscopy can lead to invaluable information to developing high efciency nanoelectronics devices including Organic Solar Cells. From their use we can obtain important information about fabricating devices such as being able to relate components such as the open circuit voltage to morphological aspects of the devices using AFM. The NSOM can now be controlled in a similar manner to AFM in the non-contact mode. It enables us to look at the distribution of the molecular constituents in a nanocomposite that are used in the formation of the active layer in the photovoltaic. Using near eld optics, the thin lms fabricated are studied to gain an insight into the composition and dispersion of the nanomaterials within the composites. The use of spectroscopy coupled with the near eld effect can also enable us to see the precise performance of the devices in terms of spectral output at the nanoscale. This presentation will relate our ndings in terms of the morphological aspects and spectroscopic response to the actual architecture of the devices and how this information can be used in fabricating better performance and higher efciency organic solar cells which will enable us to go beyond our previously reported efciency of 5.2%.
W39 DETERMINATION OF THE ELECTRON DYNAMICS IN BLENDS OF CONJUGATED POLYMERS AND FULLERENE DERIVATIVES P.A.C. Quist, T.J. Savenije, J.M. Schins, J.E. Kroeze and L.D.A. Siebbeles Opto-Electronic Materials Section, Delft University of Technology,Julianalaan 134, 2628 BL Delft, The Netherlands For the development of photovoltaic devices based on blends of (low band-gap) conjugated polymers and soluble fullerene derivatives, knowledge of the parameters affecting the charge carrier dynamics is of prime importance. In this work we demonstrate a new electrodeless method to quantify the electron diffusion length within a blend consisting of poly[2-methoxy,5-(3,7dimethyl-octyloxy]-p-phenylene-vinylene (PPV) and 1-(3-methoxy carbonyl)propyl-1-phenyl-(6,6) C61 (PCBM). To this end, MDMO-PPV:PCBM blend lms with varying PCBM content were spin-coated on top of thin TiO2 lms on quartz substrates. The conductance of these hybrid systems on pulsed photo-excitation is measured using the Time-Resolved Microwave Conductivity technique (TRMC). On absorption of photons by the blend layer, ultrafast charge separation results in mobile electrons on the PCBM and holes on the polymer. Diffusion of the electrons in the blend lm occurs until the interface with TiO2 is reached, and injection into the conduction band takes place. These processes enhance the observed photo-conductance tremendously as compared to a blend spin-coated on an inert substrate, especially long after the laser pulse. By changing the side of excitation (via the quartz substrate: BS or directly exciting the blend: FS) or the wavelength different excitation proles can be generated within the blend layer. The resulting TRMC transients (see Fig. 1) could be tted using an analytical model yielding values for the diffusion constant (D) and the lifetime of the electron. The D values found for blends with weight fractions PCBM (WPCBM) of 0.11, 0.25, 0.50 are 310-13, 210-12, and 3.510-10 m2/s, respectively, in agreement with Literature data.1,2 The observed lifetimes of the electrons in these blends were very sensitive to the laser intensity and varied as function of the WPCBM from several tens to several hundreds of microseconds. These values imply that even without phase separation the electron diffusion length amounts to ca. 60 nm for blends with a WPCBM of 0.5. At a WPCBM of 0.75, which is applied in photovoltaic devices this value increases to ca. 90 nm. More interesting is that a much larger fraction of the electrons arrive at the TiO2 interface, which is attributed to a retardation of the geminate charge carrier recombination.
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Figure 1. TRMC transients observed on pulsed excitation (3ns FWHM) of a 143 nm thick blend lm with a WPCBM of 0.5 at wavelengths as indicated. The vertical-axis denotes the fraction of electrons injected into TiO2 as compared to number of incident photons. Fits, represented by the full lines were obtained using a diffusion coefcient of 3.510-10 m2/s and a lifetime of the electrons of 10 s. (1) (2) Choulis S.A. et al. Applied Physics Letters 2003, 83, 1. Mihailetchi V.D. et al. Advanced Functional Materials 2005 15, 795.
W40 POLARIZED EMISSION MICROSPECTROSCOPY OF THIOPHENE/PHENYLENE CO-OLIGOMER CRYSTALS Takeshi YAMAO, Kazunori YAMAMOTO, Yuki TANIGUCHI, Takayuki OHIRA, and Shu HOTTA Dept. of Polymer Science and Engineering, Kyoto Inst. Tech., Kyoto 606-8585, Japan
Thiophene/phenylene co-oligomers[1] (TPCOs; see Fig. 1 as typical examples) are a novel class of organic semiconductors. These materials are characterized by the following aspects in light of the molecular and crystal design: (i) Non-straight but well-dened molecular shape and symmetry (e.g. bent, zigzag, pseudo-straight, etc.) are systematically accessible (Fig. 1). (ii) In relation to this feature the non-straight molecules produce peculiar crystallographic structures where the molecular long axes stand upright against the bottom crystal face.[2] Those structures are responsible for exciting electronic and photonic characteristics of the thiophene/phenylene co-oligomers. The laser oscillation[3] is a typical example. Related spectrally-narrowed emissions (SNEs) such as amplied spontaneous emission, stimulated resonant Raman scattering, etc.[4] have been observed as well. In the present studies we have measured polarized emission spectra of the TPCO crystals on a ~10-m size. Figure 2 depicts a schematic measuring conguration. This setup enables us to closely inspect different crystal faces of a single crystal carefully mounted on a substrate. Peculiar aspects arise from the microspectroscopy. Examples include a SNE under a relatively weak excitation. Polarized features of emissions from crystal edges and cleavage surfaces are quite different from those of other parts of the crystal. The details will be presented and discussed. [1] For example, S. Hotta, H. Kimura, S. A. Lee, and T. Tamaki, J. Heterocyclic Chem. 37, 281 (2000). [2] (a) S. Hotta, M. Goto, R. Azumi, M. Inoue, M. Ichikawa, and Y. Taniguchi, Chem. Mater. 16, 237 (2004). (b) S. Hotta and M. Goto, Adv. Mater. 14, 498 (2002). [3] (a) M. Ichikawa, R. Hibino, M. Inoue, T. Haritani, S. Hotta, K. Araki, T. Koyama, and Y. Taniguchi, Adv. Mater. 17, 2073 (2005). (b) K. Shimizu, Y. Mori, and S. Hotta, J. Appl. Phys. in press. [4] H. Yanagi, A. Yoshiki, S. Hotta, and S. Kobayashi, Appl. Phys. Lett. 83, 1941 (2003).
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Fig . 1 Var ious thi ophen e/phen ylen e co -olig omers.
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Fig. 2 Sch ematic measur eme nt setu p. T he left-hand side is an enlarge d profile of a hexago n sin gle crystal to be m easured. This exam ple indic ates a case where the c -axi s is ve rtical to bo th the uppe r and b ot tom hex agon plane s of th e crysta l.
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W41 MULTILAYER ORGANIC SOLAR CELLS BASED ON POLYCRYSTALLINE SEMICONDUCTORS Bernard Kippelen Georgia Institute of Technology, USA The strong excitonic nature of excited states in organics generally limits the photovoltaic conversion efciency of multilayer organic solar cells because exciton diffusion lengths are generally short and smaller than the optical penetration depth needed to absorb all incident radiation. Recently, we showed that pentacene combined with fullerenes in multilayer geometries can result in an efcient carrier generation with external quantum efciencies as high as 68%. This result can be attributed lo large excitonic diffusion lengths of 50 - 70 nm. In this talk, we will describe the modeling and characterization of such solar cells. We will focus on the modeling of the external quantum efciency that includes solving excitonic diffusion equations combining optical interference effects that are needed to describe the spatial distribution of the light in the multilayer structure. We will also discuss equivalent circuit models and how they can predict ll factors. Finally, we will review the overall performance of these devices that exhibit power conversion efciencies of 1.8% under AM 1.5 illumination.
W42 TAMING CARBON NANOTUBES FOR ELECTRONICS Eleanor E.B. Campbell Dept. of Physics, Gteborg University, SE-41296 Gteborg, Sweden
Carbon nanotubes have considerable potential as device elements in future electronics due to their high current carrying capability, high mechanical stability and high thermal conductivity. Very impressive demonstrations of individual carbon nanotube devices have been made in recent years underlining the large potential of these materials for incorporation with silicon electronics. A brief overview will be given of some of the advances in this eld but emphasis will be placed on how nanotubes can be grown and manipulated in ways that may allow the development of practical fabrication processes. Some discussion of the possibility of bulk separating metallic and semiconducting nanotubes as well as the advantages of using nanotubes within present-day microelectronics and examples of more novel electronic and nanoelectromechanical devices will be given.
W43 WHITE LIGHT FROM OLEDS A NEW LIGHTING SOURCE Karsten Walzer, Institut fr Angewandte Photophysik, Technische Universitt Dresden During the last few years, organic light emitting diodes (OLEDs) have attracted much interest of the scientic and technical community, since OLED displays offer a new route to brilliant, highly efcient displays. The knowledge gained from this work may now be used to develop a new source for general lighting, based on white light emission from OLEDs. I will briey discuss different ways to create white light from organic materials, and then discuss some of our work on the development of highly energy efcient white OLEDs. One of the essences is the use of doped charge transport layers, allowing for low ohmic losses in the devices, resulting in low operation voltage and high power efciency. Another is the use of triplet emitters, harvesting (theoretically) 100% of the excitons created in the device. By combining this knowledge with highly efcient emitter dyes we currently reach power efciencies of up to 17 lm/W at a brightness of 1000 cd/m. To reach this, the device needs an operating voltage of only 3.7 V and reaches a very good colour rendering index of 85. Currently, further device structures are under investigation to reach even higher efciency. The work is funded by the European commission within the project OLLA. Contact: walzer@iapp.de, tel. 0049-351-463-33504, fax: 0049-351-463-37065
W45 TUNABILITY OF THE OPTICAL PROPERTIES OF NANOSTRUCTURED COMPOSITE POLYMERIC MATERIALS A. Camposeo, P. Del Carro, E. Mele, L. Persano, R. Cingolani and D. Pisignano National Nanotechnology Laboratory of CNR, Distretto Tecnologico ISUFI, Universit di Lecce, via per Arnesano, I-73100 Lecce, Italy Polymer composite materials have become increasingly attractive for a large number of applications, including photonics1, biotechnology2 and optoelectronics3. Blends of different materials can be effectively used to tailor the spectral properties of the resulting composite, enabling for example the realization of white light-emitting OLEDs, efcient solar cells and low threshold laser devices. In these composite materials, the energy transfer by dipole-dipole coupling (Frster transfer) occurs, provided that the emission spectrum of the donor component overlaps with the absorption spectrum of the acceptor, and the dipoles are sufciently close to each other. In this work, we have studied different polymeric composite materials based on conjugated polymers. White light emission was obtained by tuning the relative donor-acceptor concentration and a ne tuning of the resulting colour was observed in planar one-dimensional photonic crystal (PhC) realized by room temperature imprinting 4. We realized one dimensional gratings (600 nm period) as shown in Fig. 1a, where an atomic force microscopy image of the imprinted composite polymer is shown. The photoluminescence (Fig. 1b) analysis of the imprinted polymer composites shows that both the colour and the polarization of the emission have an angular dependence, due to the Bragg scattering inside the PhC, a result which is relevant for the realization of polarized colour displays. Furthermore, we found that also the optical gain properties of polymeric composite can be tailored by tuning the donor/acceptor relative content (Fig. 1c), and amplied spontaneous emission can be observed from the donor or acceptor component depending on the doping concentration 5,6. Our
ABSTRACTS
results show that polymeric composite materials have unique optical properties, relevant for the realization of tuneable, highly polarized lasers and multicolour optoelectronics.
Figure 1: AFM image (a) and photoluminescence spectra (40 emission detection angle) (b) of a room temperature imprinted polymer composite. Amplied spontaneous emission spectra of binary composites, made by a green and blue light emitting polymer (relative content 1:10000, 1:10). [1] P. K. H. Ho, D. S. Thomas, R. H. Friend and N. Tessler, Science 285, 233 (1999). [2] S. Wang, N. Mamedova, N. A. Kotov, W. Chen, and J. Studer, Nano Letters 2, 817 (2002). [3] M. T. Bernius, M. Inbasekaran, J. OBrien, and W. Wu, Adv. Mater. 12, 1737 (2000). [4] E. Mele, F. Di Benedetto, L. Persano, R. Cingolani and D. Pisignano, Nano Letters 5, 1915 (2005). [5] A. Camposeo, E. Mele, L. Persano, D. Pisignano, and R. Cingolani, Phys. Rev. B In press (2006). [6] A. Camposeo, E. Mele, L. Persano, D. Pisignao and R. Cingolani, Opt. Lett. In press (2006).
W46 A THEORETICAL STUDY ON THE EXCITON BINDING ENERGY IN COUPLED POLY(P-PHENYLENE VINYLENE) MOLECULES K. Gao, X. J. Liu, D. S. Liu, and S. J. Xie* School of Physics and Microelectronics, State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, China The exciton binding energy, EB, is a key parameter for the understanding of the opto-electronic properties in organic semiconductors. It is dened as the energy required to separate a bound electron-hole pair, the exciton, into a free electron and a free hole [1]. It has been predicted in earlier studies [2-5] that inter-molecule interactions have a visible effect on the exciton binding energy in a solid-state sample. Using rigid polyacetylene chains as a model system, Moore and Yaron demonstrated that interchain interactions may substantially lower the exciton binding energy, while having a relatively minor effect on the exciton state itself. Ruini et al. performed ab initio calculations of optical properties for poly(p-phenylene vinylene) (PPV) in both isolated chain and crystalline packing. They found that the details of crystalline arrangement crucially affect the optical properties, leading to a richer exciton structure and opening nonradiative decay channels. This has implications for the optical activity and optoelectronic applications of polymer lms. In this abstract, we report our investigation about the effect of inter-molecule couplings and the conjugation lengths on exciton binding energy in PPV. A two-chain system is modelled and the dependence of the exciton binding energy on the coupling strength is calculated. As shown in Fig. 1, it is found that the exciton binding energy quickly reduces to be a constant (0.22eV) for the two equivalent PPV molecules. A result in the case of a typical conjugation length (L=42a with a the lattice constant [6]) is presented here. But for two nonequivalent molecular chains, it is found that the exciton binding energy decreases smoothly and nally closes to the same constant (0.22eV). An exciton state will spread between molecules by the inter-molecule couplings, which results in the variation of the binding energy.
0.7 0.6 0.5 0.4 0.3 0.2 0.0 0.1 0.2 0.3 t / e V 0.4 0.5
42a-42a 42a-36a 42a-48a
Fig. 1. Effect of interchain interactions on exciton binding energy EB in two coupled poly(p-phenylene vinylene) molecules. Squares represent the two PPV molecules with the same conjugation lengths; Circles and triangles represent the two PPV molecules with the conjugation length discrepancy of 6a. References: [1] M. Knupfer, Appl. Phys. A 77, 623 (2003). [2] E. Moore, B. Gherman, and D. Yaron, J. Chem. Phys. 106, 4216 (1997). [3] E. E. Moore, and D. Yaron, J. Chem. Phys. 109, 6147 (1998). [4] A. Ruini, M. J. Caldas, G. Bussi, and E. Molinari, Phys. Rev. Lett. 88, 206403 (2002). [5] J. W. van der Horst, P. A. Robbert, and M. A. J. Michels, Phys. Rev. Lett. 83, 4413 (1999). [6] E. M. Conwell, H. A. Mizes, Phys. Rev. B 51, 6953 (1995).
W47 -CONJUGATED ORGANIC IONIC CRYSTALS FOR TERAHERTZ-WAVE GENERATION
ABSTRACTS
Shuji Okada,1 Tetsuo Taniuchi,2 and Hachiro Nakanishi2 1Department of Polymer Science and Engineering, Faculty of Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510, Japan 2Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 211 Katahira, Aoba-ku, Sendai 9808577, Japan An organic ionic crystalline compound DAST has attracted attention for its large second-order nonlinear optical properties,1 and its single crystal growth has been extensively investigated for device applications. By difference frequency generation (DFG) using DAST single crystals, tunable and coherent THz-waves from 2 THz to 30 THz can be obtained. Although DAST is a promising THz-wave generation material, there are some regions where generated THz-wave intensities are attenuated due to absorption of the crystal. For example, there is a valley of the THz-wave intensity at 8.5 THz in the region between 2 THz and 14 THz. On the other hand, we found that DASC, which is a DAST derivative with p-chlorobenzenesulfonate instead of p-toluenesulfonate, has the isomorphous crystal structure with DAST.2 DASC also generates intense THz waves like DAST and the valley of the THz-wave intensity was observed at 7.6 THz. In this study, we prepared DAST-DASC mixed crystals to decrease strong absorption and their THz-wave generation were investigated. For preparation of quality DAST-DASC mixed crystals, an equal amount of saturated methanol solutions at 45oC of DAST and DASC was mixed in a Teon bottle with tight capping and solution slow-cooling process was utilized. Grown DAST-DASC mixed single crystals have a plate-like shape with dimension of 3 to 6 mm in side and about 1 mm in thickness. Figure 1 shows THz-wave intensities of DAST, DASC and DAST-DASC crystals obtained by DFG. Although there are the valleys of the THz-wave intensity at 7.6 and 8.5 THz for the DAST-DASC mixed crystal, their depth becomes small compared with the original crystals. Thus, DAST-DASC mixed crystals are a better candidate for tunable THz-wave generation. 1. Japan Patent Application 61-192404; Japan Patent 1716929; H. Nakanishi, H. Matsuda, S. Okada, and M. Kato, Mater. Res. Soc. Int. Mtg. Adv. Mater., 1, 97 (1989); S. R. Marder, J. W. Perry, and W. P. Schaefer, Science, 245, 626 (1989). 2. Z. Glavcheva, H. Umezawa, Y. Mineno, T. Odani, S. Okada, S. Ikeda, T. Taniuchi, and H. Nakanishi, Jpn. J. Appl. Phys., 44, 5231 (2005); T. Taniuchi, S. Ikeda, Y. Mineno, S. Okada, and H. Nakanishi, Jpn. J. Appl. Phys., 44, (2005).
W48 POLYMER MATRIX BASED PHOSPHORESCENT EMITTERS Hartmut Krueger, Manuel Thesen, Silvia Janietz, Bert Fischer, Armin Wedel Fraunhofer Institute Applied Polymer Research, Geiselbergstr. 69, D-14476 Potsdam, Germany, tel.: +49-331-5681920, email: krueger@iap.fhg.de Polyvinylcarbazole (PVK) is the most widely used matrix for polymeric phosphorescent emitters. PVK fulls mainly two purposes in this system. It acts as hole transporting material and it is responsible for the solvent processing of the phosphorescent material. Efciencies of about 45 cd/A were realized with PVK1,2. But there are still two main disadvantages connected with PVK-based phosphorescent emitters. One is the relatively high onset voltage, the other the short lifetime of the devices. Therefore it is still a challenge to look for more stable polymeric phosphorescent systems. Here we will present a new polymer matrix, which leads to an improvement of these two properties. On the basis of the new polymer matrix all components of the phosphorescent system including triplett emitter, hole and electron transporting material were optimized at rst. In a second step these components were covalently linked to the chosen polymer matrix to prevent aggregation and migration of the components by thermal uctuation processes during lifetime of the device. The synthesis strategy of the new polymeric phosphorescent emitters and rst results of their characterization will be presented. 1 X. H. Yang, D. Neher, Appl. Phys. Lett. 2004, 84, 2476 2 M. Sudhakar, P. Djurovich, T.E. Hogen-Escg, M. Thompson; J.Am. Chem. Soc. 2003, 125, 7796-7797
W49 ELECTROCHEMICAL AND SPECTROSCOPIC PROPERTIES OF PHOTOLUMINESCENT OLIGOMERS AND POLYMERS WITH MIXED ELECTRONIC AND REDOX CONDUCTIVITY 1,2Mieczyslaw Lapkowski, Jerzy Zak1, Jerzy Suwinski1, Jadwiga Soloducho3, 1 Department of Chemistry, Silesian University of Technology, ul.. Strzody 9, 44-100 Gliwice, Poland; 2 Institute of Coal Chemistry, PAS, ul. Sowinskiego 5, 44-121 Gliwice, Poland; 3Department of Chemistry, Institute of Organic Chemistry, Biochemistry and Biotechnology, Wroclaw, University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland A correlation between the molecular structure and both electrical and optical properties is fundamental, when any applications of conjugated systems are considered. Short oligomers are excellent model systems that can be used to study basic properties of corresponding polymers, since they have exactly dened structure. Oligomers of thiophene, oligoparaphenylvinylene (PPV) and molecules with redox phenothiazine unit are probably the most often studied recently. In contrast to oligothiophenes, the PPV oligomers are not a subject of further polymerization. Therefore, our interest was focused on molecules that combine features of those three molecules. First part of the presentation will be focused on oligomers and polymers obtained from thiophene and (PPV) molecules. A new series of ZZ, EZ i EE stereoisomers of 1,4-dimetoksy-2,5 bis [2-(tien-2-yl)ethenyl]benzene was synthesized and separated. These thienylene-PPV derivatives are interesting due to their ability of electrochemical polymerization and photoluminescent properties of both monomers and obtained polymers. We have found that under illumination or during electrochemical oxidation ZZ and EZ forms are subject to isomerization towards the most stable EE form. UV-Vis spectra have been found specic for each individual isomer. Besides, these isomers appear to be evidently distinguishable during cyclic
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voltammetry (CV) experiments, since potentials of the rst oxidation peak are evidently different for each of them. These potentials increase from the lowest value for EE isomer, through the EZ to the highest value for oxidation for ZZ form. A series of successive CV curves have been recorded for the sample containing solution of ZZ isomer in acetonitrile that was exposed to mercury lamp radiation. These voltammograms indicate that the peak height corresponding to the oxidation of ZZ isomer gradually decreases, whereas a new peak, found earlier for EZ isomer, starts to appear and grow with increasing exposure time. The last peak is nally transformed to a less positive one, which is nearly identical to the peak recorded for a pure EE isomer. In the second part we will present an effect of the alkyl substituent length on electrochemical and spectroelectrochemical properties of new N-alkyl3,7-bis(thienylene)phenothiazine oligomers. This type of oligomer may undergo of multistep electrochemical oxidation. Typically, only the rst step of the oxidation is electrochemically reversible, besides it is not accompanied by polymerization of the initial compound. Radical cation is then formed at phenothazine molecule, which is subject to consecutive oligomerization and/or polymerization upon further oxidation to dication. For the obtained polymer two well separated redox systems have been found. The rst of them that occurs at lower potential is assumed to be a result of oxidation (and reduction) of the phenothiazine to radical cation, whereas the second redox process is a result of charge delocalization along the polymer chain. The observed electrochemical behavior of these polymers is assigned to mixed conductivity mechanism. Their electrochemical properties are affected by the length of the alkyl substitutent. The proposed mechanism is supported by spectroelectrochemical data.
W50 POLYMER LIGHT-EMITTING ELECTROCHEMICAL CELLS WITH MULTIPLE OR RELAXED HOMOJUNCTION Prof. J. Gao, Y. Zhang, Y. Hu, and C. Tracy Department of Physics, Queens University, Kingston, Ontario, K7L 3N6, Canada Electroluminescence (EL) from luminescent conjugated polymers is commonly achieved in polymer light-emitting diodes (PLEDs).1 Polymer EL can also be realized in polymer light-emitting electrochemical cells (LECs), which possess many desirable device characteristics suitable for potential display applications.2 The operating mechanism of an LEC involves in situ electrochemical doping and the formation of a light-emitting pn junction, which has been conrmed by our recent demonstration and direct imaging of extremely large planar LECs with an interelectrode spacing up to 11 mm.3-5
Figure 1. An operating planar LEC with an interelectrode spacing of 11 mm, imaged under UV illumination Both p- and n-doped polymers show High-resolution uorescence imaging of planar LEC structures reveals two fundamental problems of a conventional LEC, as shown in Figure 1. First, the luminescent polymer suffers signicant photoluminescence (PL) quenching due to heavy doping throughout the polymer lm. Second, the EL emission zone in an LEC is limited to less than 10% of the entire interelectrode spacing. Both factors severely limit the ultimate EL efciency of an LEC. Here we show that a frozen p-n junction6 in an LEC can relax into a p-i-n junction when heated briey to above the glass transition temperature of the polymer electrolyte used. This results in a less doped quasi intrinsic emission zone with much reduced PL quenching. A 26fold increase in EL efciency has been demonstrated by this simple doping relaxation technique and veried by spatially resolved imaging of the doping prole. In addition, a 20-fold increase in effective emitting area has been achieved by introducing oating metallic strips or particles between the electrodes, which leads to the formation of multiple light-emitting p-n junctions.7 These two approaches promise revolutionary LECs with the highest EL efciency of all polymer light-emitting devices. References 1 R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks, C. Taliani, D. D. C. Bradley, D. A. Dos Santos, J. L. Bredas, M. Logdlund, and W. R. Salaneck, Nature 397, 121-128 (1999). 2 Q. B. Pei, G. Yu, C. Zhang, Y. Yang, and A. J. Heeger, Science 269, 1086-1088 (1995). 3 J. Gao and J. Dane, Appl. Phys. Lett. 83, 3027-3029 (2003). 4 J. Gao and J. Dane, Appl. Phys. Lett. 84, 2778-2780 (2004). 5 J. Gao and J. Dane, J. Appl. Phys. 98, 063513 (2005). 6 J. Gao, G. Yu, and A. J. Heeger, Appl. Phys. Lett. 71, 1293-1295 (1997). 7 C. Tracy and J. Gao, Appl. Phys. Lett. 87, 143502 (2005).
W51 PROTEIN FUNCTIONALISATION OF CARBON NANOTUBES Alan B. Daltona, Eric Brunnera, Gregg R. Dieckmannb , Vasiliki Zorbasb, Alfonso Ortiz-Acevedob, Hui Xieb, Ray H. Baughmanb, Rockford K. Draperc , Inga H. Musselmanb, Paul Pantanob. a Physics Department, University of Surrey, Guildford, UK;. b Chemistry Department, The University of Texas at Dallas, Richardson, Texas, USA c Molecular and Cell Biology Department, The University of Texas at Dallas, Richardson, Texas, USA e-mail : a.dalton@surrey.ac.uk; fax :+44(1)483686781 As-produced carbon nanotubes (CNTs) form insoluble hydrophobic aggregates and are not biocompatible. We have demonstrated that designed amphiphilic peptides effectively disperse CNTs in an aqueous environment through noncovalent hydrophobic interactions with the CNT surfaces, generating individual peptide-wrapped CNTs (PWNTs). A signicant advantage of coating CNTs with peptides is that the amino acid sequence can be controlled, allowing us to promote the interaction of PWNTs with each other, with surfaces designed to interact with the peptides, or with
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complementary protein epitopes such as protein receptors on cell surfaces. We have exploited the structural diversity of peptides to generate a library of amphiphilic peptides with varied CNT afnities and assembly properties. We have also developed two different protein motifsamphiphilic helical peptides, and closeable cyclic peptides preventing peptide dissociation from the CNT surface and providing a stable platform for targeting CNTs to specic cell types. The results from this work will ultimately aid in the development of biocompatible CNT-based technologies, such as articial muscles or sensors that can be placed inside the human body. References Zorbas, V., A. Ortiz-Acevedo, et al. J. A. Chem. Soc. 2005 126, 7222. Dalton A.B., A. Ortiz-Acevedo, et al. Adv. Funct. Mat. 2004 14, 1147.
W52 DISPERSION OF SINGLE-WALLED CARBON NANOTUBES Silvia Giordani1, Jennifer Treanor1, Grainne Cunniffe1, Anna Drury1, Valeria Nicolosi1, Shane D Bergin1, Sergei Lebedkin2, Jonathan N Coleman1 & Werner J Blau1 1 School of Physics, Trinity College Dublin, Ireland 2 Institute of Nanotechnology, Research Centre Karlsruhe, Germany, giordans@tcd.ie
The ability to miniaturise devices has completely changed our society, and modern technology is constantly pushing towards smaller and lighter devices with enhanced and more diverse functionalities. Single-walled carbon nanotubes (SWNTs) display unique structures and remarkable physical properties and are promising candidates for the realization of smart nanomaterials. They have nanoscale dimensions, and can be modied through covalent bonding of functional organic molecules, opening the way to structural materials of high technological importance. One of the major bottlenecks to applications is their aggregation into bundles. In this talk I will show our simple methodology to disperse and de-bundle SWNT using polymers, oligomers, small organic molecules and solvents as dispersants. (a) Giordani, S.; Bergin, S.; Drury, A.; Mhuircheartaigh, E.N.; Coleman, J. N.; and Blau, W. J., SPIE 2005, 5842, 42-49
W53 ELECTROCHEMICAL DEVICES PREPARED FROM CONDUCTING POLYMER FILM AND FIBRE UTILIZING ROOM TEMPERATURE IONIC LIQUID ELECTROLYTE Benjamin R. Mattes Santa Fe Science & Technology Inc., 3216 Richards Lane, Santa Fe, New Mexico, 87507, USA Improved synthetic conditions have been developed for the synthesis of polyaniline that employ highly acidic reaction media. New methods for the continuous production of polyaniline textile and hollow bre have been developed at commercial scale. The volume conductivity of the bre is 1,000 S/cm, the Youngs modulus of elasticity is 5 GPa, the ultimate strength is 200 MPa, and the strain at break is 15%. Analysis of the resistivity and thermopower data taken from 298 to 2 K show that these bre materials reside on the metallic side of the insulator-metal boundary. The bre is easily formed into yarns, braided structures, and woven and knitted fabrics. The polymer is also readily processed into optically transparent thin lm. Thin lms, bre, and hollow bre prepared from conducting polymers, such as polyaniline, POT, PEDOT, may be used to construct longlived electrochemical devices. These devices include electrochemical actuators, electrochromic windows, and super-capacitors. We have prepared electrochemical devices that exhibit enhanced life cycles without failure and fast cycle switching speeds under ambient conditions without a loss in electrochemical efciency. These performance advantages are obtained by employing room temperature ionic liquids composed of 1-butyl-3-methyl imidazolium cations together with small mobile anions such as phosphorus hexauoride or tetrauoroborate.
W54 HIGH OPTICAL QUALITY CARBON NANOTUBE-POLYMER COMPOSITES FOR PHOTONICS APPLICATIONS V. Scardaci1, F. Wang1, A. G. Rozhin1, F. Hennrich2, I. H. White1, W. I. Milne1, A. C. Ferrari1 1Department of engineering, University of Cambridge, Cambridge CB3 OFA, UK 2Institut fur Nanotechnologie, Forschungszentrum Karlsruhe, Germany Carbon nanotubes (CNTs) are promising for photonic devices, since they are good saturable absorbers, i.e. they show photobleaching with ultrafast recovery time1. The CNT saturable absorbers must be designed carefully to keep a balance between high modulation depth and undesired non-saturable losses, such as scattering on bundles and non-saturable absorption from surfactant, polymer matrix and carbon impurities2. CNTs have to be homogeneously dispersed within a host polymer material on a sub-micrometer scale, smaller than the 1.55m wavelength used in optical communications. Here we report the fabrication and characterization of CNT-PVA and CNT-polycarbonate composite lms. CNTs are dispersed in water or organic solvents by surfactant-assisted ultrasonication. Residual bundles are removed by either micro-ltration or ultracentrifugation of the solution, which is then mixed with a polymer solution and dried. The resulting free-standing lms are studied by absorption spectrophotometry and micro-Raman spectrometry. Optical microscopy shows no resolvable bundles in the lms, but a strong CNTs Raman signal is uniformly detected, showing a homogeneous CNTs distribution. The lms are then used as mode-lockers in an Erbium-doped bre laser, allowing the generation of laser pulses as short as 600fs3 . Multi-wavelength Raman spectroscopy and spectro-photometry shows no damage on lms after a continuous long-time laser operation. 1. Y. C. Chen et al, Appl Phys Lett 81, 975 (2002)
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2. A. G. Rozhin et al Chem Phys Lett 405, 288 (2005) 3. A. G. Rozhin et al. submitted (2005) W55 ELECTROACTIVE POLYMER-CARBON NANOTUBE COMPOSITES: Smart Materials for Optoelectronic Applications W.K. Maser1, R. Sainz1, A.M. Benito1, M.T. Martnez1, W.R. Small2, M. in het Panhuis2 1 Instituto de Carboquimica (CSIC), C/Miguel Luesma Castn 4, E-50018, Zaragoza, Spain 2 Department of Chemistry, University of Hull, Hull HU6 7RX, United Kingdom Only a bit more than 10 years after the discovery of intrinsically conducting polymers1 the development of the rst organic light emitting devices (OLEDs)2 has become a tremendous boost for the further development of various types of electronic and opto-electronic devices made out of electroactive polymers3. Novel nanoscale concepts will play an essential role to further progress in this eld. In this sense, carbon nanotubes (CNTs)4 are considered as a natural partner for intrinsically conducting polymers. Their dimensions and electronic structure combine well with the chain structure and the delocalized electron system of these electroactive polymers. Their mutual interactions thus let expect highly favorable synergetic effects between both constituents. Bearing these considerations in mind, we carried out intensive research on novel composite materials based on intrinsically conducting polymers and carbon nanotubes5-7. Hereby we were focusing on two key issues: Enhanced functionality and processibility of the obtained materials. Both points are directly linked to favorable interactions between carbon nanotubes and the polymer chains and thus intimately related to the synthesis approach and self-assembling processes. In the following we will describe our research approach and resume our main ndings related to polyaniline-carbon nanotube composites. We will focus especially on their improved conducting, optical, (luminescence and chirality) properties and their stability and processing behaviour, of great importance for the development of smart optoelectronic devices. References: 1 Shirakawa, H, Louis, E.J., MacDiarmid, A.G., Chiang, C.K., Heeger, A.J., J. Chem. Soc. Chem. Commun., 578-580 (1977) 2 Burroughes J.H,. Jones C.A., Friend R.H., Nature 335, 137-141 (1988). 3 Skotheim T.A., Elsenbaumer, R.L., Reynolds, J.F. (Eds.), Handbook of Conducting polymers 2nd ed., Marcel Dekker, New York, 1998 4 Baughman, R.H., Zakhidov, A.A., De Heer, W.A., Science 279, 787-782 (2002) 5 Sainz, R., et al., Adv. Mater. 17, 278-281 (2005) 6 R. Sainz, et al., Nanotechnology 16, S150-154 (2005) 7 M. in het Panhuis, et al., J. Phys. Chem. B 109 (2005), 22725.
W56 EXPERIMENTAL AND THEORETICAL STUDIES OF NANO-SCALE PERIODIC POROUS CARBON Katsumi YOSHINO1), Senku TANAKA1), Masayoshi OJIMA2), Shinji HIWATASHI2), Hiroyuki TAKEDA2), Nobuya MORI2) and Masanori OZAKI2) 1) Research Project Promotion Institute, Shimane University, 1060 Nishikawatsu-cho, Matsue, Shimane 690-8504 Japan 2) Department of Electronic Engineering, Graduate School of Engineering, Osaka University, Yamada-Oka 2-1, Suita, Osaka 565-0871 Japan
Upon inltration of phenol resin in the interconnected voids of the synthetic opal prepared by sedimentation of the suspension of mono-dispersed silica spheres of various diameters (1000, 550, 300, 120, 74, 43, 23 and 11nm) and then removing silica with HF, the inverse opals composed of phenol resin were obtained. These phenol inverse opals can be transformed into the carbon inverse opals with various void sizes depending on the initial silica spheres by the heat treatment higher than 600oC. By the treatment above 2700oC, graphitization process was observed in these porous carbons. In the carbon inverse opals made from synthetic opal sintered at different temperatures, not only the size of voids but also the diameter of the interconnecting channel between the voids can be well controlled as shown in Fig.1. Electrical and optical properties were dependent on the size of voids, diameter of the interconnecting channel and on heat treatment temperature. These carbon inverse opals exhibit unique optical properties as photonic crystals depending on the periodicity of the inverse opal determined by the initial silica sphere size and heat treatment temperature. Electrical and electrochemical characteristics are also discussed as functions of the pore size and the channel diameter. It should also be mentioned that these nanoporous structure of carbon exhibit excellent characteristics as electron emitter. The main emitter sites of porous carbon are interpreted to be the edges formed in the boundary of the neighbouring pores. Electronic band structures of nanoscale periodic porous carbons have been calculated based on the tightband approximation of -electrons and was found to depend on the inter-pore distance and the pore size. Moreover, some porous carbons with relatively large periodic nanopores possess at bands, which may cause singular properties in magnetism. We demonstrated that graphite/porous graphite quantum structures can be an alternative system for band Fig. 1. SEM im age s o f carbo n inverse opals o pyrolyzed at 800 C. The diam eters of u sed S iO 2 gap engineering. The electronic states of graphite/porous graphite quantum wires was also calculated sphe res are (a) 1 m , (b ) 550 nm, ( c) 300 nm, ( d) within an effective-mass approximation.
120 nm, ( e) 74 nm , (f) 43 nm .
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W57 CHARGE TRANSPORT IN DOPED SINGLE-WALLED CARBON NANOTUBES V. Krsti1, G.L.J.A. Rikken1, S. Roth2, M. Glerup3 1Laboratoire National des Champs Magntiques Pulss, CNRS/INSA/UPS, 143, Ave. de Rangueil, 31400 Toulouse, F 2Max-Planck-Institut fr Festkrperforschung, Heisenbergstr. 1, 70569 Stuttgart, D 3Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo, N
The concept of doping by atom substitution and its consequences will be introduced. Charge transport measurements on individual metallic singlewalled carbon nanotubes doped with different atom species (e.g., nitrogen, boron) at varying temperature and in the presence of a magnetic eld will be presented. The temperature-dependent measurements reveal that for doped carbon nanotubes the conductance at zero bias can not be described by a power-law dependence as known for Luttinger liquids. In the presence of a magnetic eld, the conductance of the doped nanotubes is compared with trends predicted by theory in the low-eld limit. The experimental data suggest that secondary effects are present which are not accounted by theory. corresponding author: V. Krsti, krstic@lncmp.org
W58 SATURABLE AND REVERSE SATURABLE ABSORPTION OF ASYMMETRIC PUSH-PULL PORPHYRINS Eleni G. A. Notarasa, Marijana Fazekasa, Mathias O. Sengea and Werner J. Blaub a School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity College Dublin, Dublin 2, Ireland b School of Physics, Molecular Electronics and Nanotechnology, Trinity College Dublin, Dublin 2, Ireland There is considerable interest in understanding the optical nonlinearities of dyes for widespread applications. Dye molecules are used mostly to generate tunable laser sources and in optical shutters, optical signal-processing devices,1 two photon microscopy, up conversion lasers2, optical limiting,3-6 optical data storage7 and three-dimensional microfabrication.8 Nonlinear absorption is dened as a nonlinear change (increase or decrease) in absorption with increasing intensity. This can either be two types: Saturable absorption (SA) and reverse saturable absorption (RSA). Most molecules show nonlinear absorption, depending on the pump intensity and on the absorption cross section at the excitation wavelength. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. If however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Porphyrins are highly conjugated planar molecules with an extensive delocalized -electron system. They have been of interest for nonlinear optical applications because they exhibit high third-order hyperpolarizabilities leading to high values of third-order susceptibility (3).5, 9 meso-Substituted porphyrins bearing specic functional groups are valuable components in biomimetic systems and crucial building blocks for applications in materials chemistry.10 Porphyrins of the A2B2-type (2, 4, and 5) substituted with appropriate donor and acceptor groups are an especially attractive class of compounds. Until now, no rational method to synthesize porphyrins of this type has been described in the literature. A new synthetic route to 5,10-A2B2 pushpull porphyrins is described below.
The rst step is the synthesis of 5,10-disubstituted porphyrins bearing electron donating groups (pentyl, hexyl, phenyl, tolyl, 3-methoxyphenyl, 2,6diuorophenyl) by condensation of tripyrrane with different alkyl or aryl aldehydes.10 For the introduction of electron withdrawing groups in the second step, two different routes are possible: organolithium reactions11or bromination of the free meso positions, followed by the introduction of an electron withdrawing group (-COOMe, -CN, -NO2) using Heck or Suzuki reactions.12 We report for the rst time in porphyrins of this type, using an open aperture Z-scan technique at 532 nm with nanosecond pulses, a transition from RSA to SA at an increase of intensity. 1. Sutherland, R. L., Handbook of Nonlinear Optics. Second Edition, Revised and Expanded ed.; Marcel Dekker, Inc.: New York, 2003. 2. He, G. S.; Zhao, C. F.; Bhawalkar, J. D.; Prasad, P. N., Two-photon pumped cavity lasing in novel dye doped bulk matrix rods. Applied Physics Letters 1995, 67, (25), 3703-5. 3. He, G. S.; Xu, G. C.; Prasad, P. N.; Reinhardt, B. A.; Bhatt, J. C.; Dillard, A. G., Two-photon absorption and optical-limiting properties of novel organic compounds. Optics Letters 1995, 20, (5), 435-7. 4. Martin, R. B.; Li, H.; Gu, L.; Kumar, S.; Sanders, C. M.; Sun, Y.-P., Superior optical limiting performance of simple metalloporphyrin derivatives. Optical Materials (Amsterdam, Netherlands) 2005, 27, (8), 1340-1345. 5. Chen, Y.; El-Khaty, M. E.; Doyle, J. J.; Notaras Eleni, G. A.; Blau Werner, J.; OFlaherty, S., Handbook of Organic Electronics and Photonics. (In press). In 2006. 6. Hollins, R. C., Goals, architectures, and materials for broadband eye protection. MCLC S&T, Section B: Nonlinear Optics 2001, 27, (1-4), 1-12. 7. Parthenopoulos, D. A.; Rentzepis, P. M., Three-dimensional optical storage memory. Science (Washington, DC, United States) 1989, 245, (4920), 843-5. 8. Cumpston, B. H.; Ananthavel, S. P.; Barlow, S.; Dyer, D. L.; Ehrlich, J. E.; Erskine, L. L.; Heikal, A. A.; Kuebler, S. M.; Lee, I. Y. S.; McCord-Maughon, D.; Qin, J.; Rockel, H.; Rumi, M.; Wu, X.-L.; Marder, S. R.; Perry, J. W., Two-photon polymerization initiators for three-
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dimensional optical data storage and microfabrication. Nature (London) 1999, 398, (6722), 51-54. 9. Claessens, C. G.; Blau, W. J.; Cook, M.; Hanack, M.; Nolte, R. J. M.; Torres, T.; Wohrle, D., Phthalocyanines and phthalocyanine analogues: the quest for applicable optical properties. Monatshefte fuer Chemie 2001, 132, (1), 3-11. 10. Hatscher, S.; Senge, M. O., Synthetic access to 5,10-disubstituted porphyrins. Tetrahedron Letters 2002, 44, (1), 157-160. 11. Senge, M. O., Nucleophilic Substitution as a Tool for the Synthesis of Unsymmetrical Porphyrins. Accounts of Chemical Research 2005, 38, (9), 733-743. 12. Shi, B.; Boyle, R. W., Synthesis of unsymmetrically substituted meso-phenylporphyrins by Suzuki cross coupling reactions. Journal of the Chemical Society, Perkin Transactions 1 2002, (11), 1397-1400.
TH1 ET COMPOUNDS; PLAYGROUND OF SPIN AND CHARGE WITH FRUSTRATION K. Kanoda1,2 1Department of Applied Physics, University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-8656, Japan 2CREST, Japan Science and Technology Corporation (JST), Kawaguchi, Saitama, 332-0012, Japan Mutually interacting electrons show various phases with interesting organization in the spin and charge degrees of freedom. In the various emergent phases, the structure of the lattice on which electrons are sitting plays a distinctive role. In particular, the triangular lattice is an annoying stage for electrons because it forces frustration to spin orientation and charge location. The ground states of correlated electrons on the triangular lattice are nontrivial. The layered organics, -(ET)2X and (ET)2X, have anisotropic triangular lattices of ET2 and ET, respectively. The -(ET)2X with half-lled band is a model system for Mott physics on triangular lattice, while (ET)2X with quarter-lled band is for charge-order physics on triangular lattice. I review observations of interesting competition between various exotic phases in these salts; spin order/liquid, Fermi liquid and superconductivity in -(ET)2X ; charge order/glass/liquid and valence bond order/glass in (ET)2X. This work is a collaboration with Y. Shimizu, F. Kagawa, Y. Kurosaki, H. Kasahara, M. Kodama, K. Ohno, K. Miyagawa, M. Maesato and G. Saito.
TH2 SUPERCONDUCTORS, METALS AND SEMICONDUCTORS OF BEDT-TTF WITH MAGNETIC [FE(C5O5)3]3- AND [M(C2O4)3]3COMPLEXES (M = FE AND CR) Carlos J. Gmez-Garca,a Eugenio Coronado,a Simona Curreli,a Carlos Gimnez-Saiz,a Paola Deplanob and Maria Laura Mercurib aInstituto de Ciencia Molecular, Universidad de Valencia, Dr. Moliner 50, E-46100, Burjasot, Spain. Fax: +34.963544859 E-mail: carlos.gomez@ uv.es bDipartimento di Chimica Inorganica ed Analitica, S.S. 554 Bivio per Sestu I09042 Monserrato (Cagliari) Italy In this communication we report the last results obtained in the search of multifunctional molecular materials combining magnetic and electrical properties. These results include: (1) The synthesis, X-ray structures at high and low temperatures, magnetic properties (AC and DC susceptibilities and ESR studies), electrical properties (resistivity and magnetoresistance) and surface studies (AFM/STM) of the radical salts (BEDT TTF)4[H3OM(C2O4)3].PhX (M/X = Fe/Br, Fe/Cl, Fe/F, Cr/Br and Cr/Cl). In this series of salts the Fe/Br, Fe/F and Cr/Br present superconducting transitions at 4.0 K, 1.2 K and 1.8 K, respectively, whereas the Fe/Cl and Cr/Cl salts are metallic down ca. 100-120 K and do not present any superconducting transition above 0.4 K. (2) The synthesis, X-ray structure and magnetic and electrical properties of an phase generated in a BEDT-TTF salt thanks to the use of the recently prepared chiral anion [Fe(C5O5)3]3-: (BEDT-TTF)5[Fe(C5O5)3].5H2O, where C5O52- is the dianion of the croconic acid = 4,5dihydroxycyclopent-4-ene-1,2,3-trione. In this salt, although the structure is not chiral (since there is a racemic mixture of the and enantiomers of the [Fe(C5O5)3]3- anion), the disposition of the chiral anions in the bc plane induces an alternation in the orientation of the BEDT-TTF stacks in such a way that the BEDT-TTF columns above and below each [Fe(C5O5)3]3- anion present different relative orientations, giving rise to the wellknown phase (gure 1).
S. Curreli, P. Deplano, C. Faulmann, M. L. Mercuri, L. Pilia, A. Serpe, E. Coronado, C. J. Gmez-Garca Inorg. Chim. Acta, 2006, 359, 1177
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Figure 1
TH2 THE COUPLING BETWEEN MAGNETIC TRANSITION AND CONDUCTING PROPERTIES IN A SPIN-CROSSOVER MOLECULAR CONDUCTOR Kazuyuki Takahashi,a HengBo Cui,a Yashinori Okano,a Hayao Kobayashi,a Yasuaki Einaga,b and Osamu Satoc aInstitute for Molecular Science and CREST, JST, Myodaiji-cho, Okazaki 444-8585, Japan, e-mail: ktaka@ims.ac.jp bKeio University, Yokohama 223-8522, Japan cInstitute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 816-8508, Japan The recent discovery of antiferromagnetic molecular superconductors, which clearly exhibited the interplay between magnetism and electrical conductivity, has aroused much attention to the development of novel multi-functional molecular materials. Along this line, realization of externally controllable molecular conductors is considered to be one of the attracting targets in this eld. We have focused on a spin-crossover (SCO) phenomenon in order to control electrical conducting properties by external perturbations, because the SCO complex is wellknown as a molecular switch which can be induced by temperature, pressure, and light. Since the spin conversion between the low-spin and the high-spin states accompanies a signicant structural change in coordination bond lengths and geometries and molecular conductors are usually sensitive to structural modications, embedding of the SCO ions into molecular conductors is expected to afford the synergic coupling between SCO phenomena and electrical conducting properties. In this conference we will report preparation and characterization of novel Fe(III) SCO complexes of an Fe(qsal)2 cation with Ni(dmit)2 and its related anions [qsalH = N-(8-quinolyl)salicylaldimine, dmit = 4,5-dithiolato-1,3-dithiole-2-thione]. The starting compound, [Fe(qsal)2][Ni(dmit)2]2CH3CN, that showed a cooperative spin transition and the light-induced excited spin state trapping (LIESST) effect was reported previously. The conducting complex was prepared by electrochemical oxidation of the starting complex in acetonitrile. The crystal analyses revealed that the composition of the conducting complex was 1:3, and Fe(qsal)2 cations and Ni(dmit)2 anions formed magnetic and conducting layers, respectively. This complex was a semiconductor with relatively high room temperature conductivity (rt = 2 S cm-1). Interestingly, the anormaly of resistivity was observed in the same temperature range of the hysteresis loop of magnetization between 90 and 120 K, suggesting that the coupling between SCO and electrical conducting properties through a structural change was realized. Mssbauer and absorption spectra, and the LIESST effect on the 1 : 3 complex will also be discussed.
1 K. Takahashi et al., Chem. Lett., 2005, 34, 1240.
TH4 HIGH PRESSURE OPTICAL SPECTROSCOPY OF THE NEUTRAL-IONIC PHASE TRANSITION IN TTF-CA M. Masino1, A. Girlando1, A. Brillante2 1Dip. Chimica G.I.A.F and INSTM UdR-Parma, Parma University, I-43100 Parma, Italy 2Dip. Chimica Fisica e Inorganica and INSTM UdR-Bologna, Bologna University, I-40136 Bologna, Italy
Mixed stack charge transfer (CT) molecular crystals are quasi one dimensional systems where highly conjugated electron-donor (D) and electronacceptor (A) molecules alternate along a stack direction in a -D-A-D-A- structural motif. The great richness of organic molecular solids lies in the possibility to tune ground state properties by changing external thermodynamic parameters such as temperature or pressure. Of particular interest in mixed stack CT crystals is the possibility to tune the degree of charge transfer (ionicity) between donors and acceptors: we can therefore distinguish between two different states of matter: i) a neutral phase, van der Waals molecular crystals with degree of CT less than 0.5e-, and ii) a ionic phase, a ionic crystals with degree of CT above 0.5e-. The corresponding neutral-ionic phase transition (NIT) represents another intriguing example of the complex interplay between electronic and lattice degrees of freedom. In fact on the ionic side of the transition the stacks are unconditionally unstable towards dimerization due to Peierls instability, which may results in ferroelectric or antiferroelectric ordering of the molecular lattice. For example the prototype CT system exhibiting NIT, Tetrathiafulvalene-Chloranil (TTF-CA), undergoes a temperature induced phase transition at ambient pressure from a neutral uniform stack phase to a ionic dimerized phase, where the stacks organize in a three dimensional ferroelectric ground state. In this communication, we extend the study of the phase diagram of the TTF-CA in the high pressure regime, by performing for the rst time a combined polarized infrared and Raman study on the same crystal within the diamond anvil cell. We show that TTF-CA undergoes the NIT phase transition on increasing the pressure. On the other hand, some anomalous spectral features in the pressure evolution of the IR and Raman spectra can be easily identied, a clear evidence that the microscopic mechanism driving the pressure and the temperature induced NIT of TTF-CA are different. In particular, high pressure spectra clearly indicate the emergence of an intermediate phase between the neutral phase and the ionic ferroelectric phase, where dimerized species with two different ionicities coexist. The aim of the nal discussion is to bring insight into the nature of this emergent phase in connection factors that may trigger NIT, such as uctuation and hysteresis phenomena, electron-phonon interactions, and low-lying excited states.
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TH5 MAGNETIC TORQUE IN SUPERCONDUCTING STATE OF -(BETS)2FEXGA1-XCLO4 S. Uji, T. Terashima, T. Yamaguchi, T. Konoike, M. Nishimura, H. Cui1, H. Kobayashi1, A. Kobayashi2, H. Tanaka3, and M. Tokumoto3 National Institute for Materials Science, Tsukuba, Ibaraki 305-0003, Japan 1Institute for Molecular Science and CREST JST, Okazaki, Aichi 444-8585, Japan 2Research Centre for Spectrochemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033, Japan 3National Institute of Advanced Industrial Science and Technology, and CREST JST, Tsukuba, Ibaraki 305-8568, Japan The discovery of the magnetic eld induced superconductivity (S) in the organic conductor, -(BETS)2FexGa1-xCl4, where BETS is bis(ethyle nedithio)tetraselenafulvalene, has renewed the interest in the anisotropic superconductors. The overall features of the eld induced S phases in (BETS)2FexGa1-xCl4 are well understood by Fischer theory based on Jaccarino-Peter (J-P) effect, where a strong negative exchange interaction J between the Fe 3d moments and electron spins is essential. The spins experience a strong internal eld -Hint (>0) created by the 3d moments, which compensates the external eld H i.e. suppresses the Zeeman effect. For H<Hint, a novel vortex phase, an antivortex phase is theoretically predicted, where the vortices carry paramagnetic currents instead of diamagnetic currents. However, any clear evidence of the antivortex phase has not been obtained. In order to clarify the presence of the antivortices, we have measured the magnetic torque for -(BETS)2FexGa1-xCl4(x=045). The phase diagram determined by the resistance measurements is shown in Fig. 1. The dotted and solid lines show, respectively, the calculated result based on the Fisher theory with appropriate parameters and the phase boundaries of the vortex phases: S1 and S3: normal vortex phase (H>Hint) and S2: antivortex phase (H<Hint). The torque is measured as a function of the eld direction (from negative to positive) in the b*c plane (Fig. 2). A characteristic change near 0o (H//c) is evident, which is superimposed on a sin(2+) curve arising from the localized 3d moments. The irreversible sharp dip and peak structure near 0o is ascribed to a lock-in transition of the ux lines penetrating the FeCl4 layers. This behavior is the most enhanced at 13 T, which is close to the vortex phase boundary. The detailed analyses suggest that the vortices disappear at 13 T, i.e. the antivortices are formed below Hint(=13 T).
Fig 1. M agnetic phas e diagr am of (BE TS)2 Fe x Ga 1-x Cl 4 (x=045) for H//c .
Fig 2. M agnetic torque un der field H in th e b*c plane.
TH6 STRUCTURAL STUDIES OF 2D ORGANIC CONDUCTORS HAVING CHARGE ORDERED AND SUPERCONDUCTING PHASES Ryusuke Kondo1, Momoka Higa1, Seiichi Kagoshima1, and Hiroyuki Nishikawa2 1Department of Basic Science, University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan 2Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan In order to investigate relationships between a superconducting phase and a charge ordered one, we performed crystal structure analyses of (BEDT-TTF)2CsCd(SCN)4 under uniaxial strain and -(DODHT)2PF6 under hydrostatic pressure. -(BEDT-TTF)2CsCd(SCN)4[1] has the same molecular arrangement as the well-known superconducting salt -(BEDT-TTF)2NH4Hg(SCN)4. At ambient pressure the salt showed metallic behaviour down to low temperature, and the upturn in the resistivity was observed below 6 K. Under a-axial strain the metallic behaviour was enhanced and the upturn disappeared with increasing strain while clear insulating behaviour was observed under the stacking c-axial strain. The crystal structure analyses are performed under a-axial strain of 5 kbar, and c-axial strain of 5 kbar and 10 kbar. -(DODHT)2PF6[2] has a charge ordered phase below 255 K at ambient pressure. The application of hydrostatic pressure suppressed the charge ordered phase and induced a superconducting phase above 13.2 kbar. The crystal structure under hydrostatic pressure of 7.5 kbar and 19 kbar are obtained. Based on the obtained crystal structures, we estimated transfer integrals, t and nearest-neighbour Coulomb repulsions, V [3]. We found that under the suppression of charge ordered phase, V/t perpendicular to the charge stripe, which was one of important key parameters for a strip charge ordered system, increased in -(BEDT-TTF)2CsCd(SCN)4, as was the same as -(BEDT-TTF)2CsZn(SCN)4[4], and decreased in -(DODHT)2PF6. The difference in the dependence of V/t is ascribed to whether or not they have frustration in their charge ordering. Reference [1] R. Kondo, M. Higa, and S. Kagoshima: Sol. Stat. Commun. 137 (2006) 637640.
ABSTRACTS
[2] H. Nishikawa et al.: Phys. Rev. B 72 (2005) 052510. [3] T. Mori: J. Phys. Soc. Jpn. 72 (2003) 1469-75. [4] R. Kondo et al.: to be published in J. Phys. Soc. Jpn.
TH7 NEW COMPLEXES BASED ON EXTENDED TTF LIGANDS: A BASIS FOR NEW SINGLE-COMPONENT MOLECULAR METALS M. J. Figueiraa, J.P.M. Nunesa, I. C. Santosa, L.C.J. Pereiraa, D. Beloa,b, R.T. Henriquesc, M. Almeidaa, J. Vidal-Gancedob, C. Rovirab and J. Vecianab aDep. Qumica, ITN/CFMCUL, P-2686-953 Sacavm, PORTUGAL, E-mail: malmeida@itn.pt bInstituto de Telecomunicaes, Plo de Lisboa, IST, P-1049-001 Lisboa, PORTUGAL cInstitut de Cincia de Materials Barcelona(CSIC) Campus UAB, E-08193 Bellaterra SPAIN
Most of molecular metals use charge transfer between donor and acceptor species to generate charge carriers, therefore containing more than two chemical species. However recently high electrical conductivity was found in a neutral based complex [Au(-tpdt)2] obtained as a policrystalline sample1, and A. Kobayashi et al. reported during the last few years metallic properties on single crystals of a series of neutral bisdithiolene complexes based on ligands with an extended TTF structure2 prepared using a strategy rst devised in the middle 1990s by Underhill3 et al. This work lead to a series of new materials based on a neutral molecular component, some with high and truly metallic conductivity, with rt ~ 400 Scm1, the so called single-component molecular metals (SCMM) which have attracted a lot of attention as new type of molecular metals. Aiming at the preparation of new SCMM and the study of structure properties correlation in these single component materials, the Au and Ni complexes based on the new extended ligands -tdt = tiophenetetrathiafulvalenedithiolate, dtdt = dihydrothiophentetrathiafulvalene-dithiolate and tdt = tiophenetetrathiafulvalenedithiolate were prepared.
S S S
S M S
S S
M(-tdt)2
S
S M
M(dtdt)2
S S
S M
S S
M(tdt)2
These complexes initially obtained under anaerobic conditions as monoanic species for Au and dianionic for Ni are easily oxidised to the stable neutral species, so far obtained only as a polycrystalline sample. In this communication we report the characterization of these ligands and corresponding complexes by Cyclic Voltammetry, X-ray diffraction, EPR, magnetic susceptibility and electrical conductivity measurements. [1] D. Belo, H. Alves, E. B. Lopes, M. T. Duarte, V. Gama, R. T. Henriques, M. Almeida, A. Prez-Bentez, C. Rovira, J. Veciana; Chem. Eur. J., 2001, 7, 511. [2] Tanaka, H.; Okano, Y; Kobayashi, H.; Suzuki, W.; Kobayashi, A.; Science 2001, 291, 285-287. [3] Narvor, N.L.; Robertson, N.; Weyland, T.; Killburn, J. D.; Underhill, A. E.; Webster, M.; Sventrup, N.; Becker, J.; J. Chem. Soc., Chem. Commun. 1996, 1363-1364. TH8 MAGNETIC FILED INDUCED CONFINEMENT IN LAYERED CONDUCTORS Sonia Haddad, S. Char-Kaddour, M. Hritier LPMC, Dpartement de Physique Facult des Sciences de Tunis, 1060 Tunis, Tunisia
ABSTRACTS
Layered organic conductors are characterized by an extremely high electronic anisotropy which makes them excellent candidates for the study of magnetic eld induced dimensional crossover. We suggest a theoretical approach to describe the connement of the electronic motion in the transverse direction perpendicular to the most conducting layers. We show the existence of a metal-insulator crossover as the magnetic eld increases. The results are compared to the experimental data showing an impressing connement effect in the case of the quasi-one dimensional organic superconductor (TMTSF)2ClO4 [1,2]. Within the proposed model, we can reconcile different experimental results which has been thought to be controversial [1-3]. We, in particular, explain the existence of the connement in the transverse direction whereas the two othor ones remain metallic even at high magnetic eld.
References:
[1] G. M. Danner, N. P. Ong and P. M. Chaikin, Phys. Rev. Lett. 78, 983 (1997) [2] N. Joo et al., to be submitted to EPJB. [3] K. Behnia et al., Phys. Rev. Lett. 74, 5272 (1995)
TH9 POLYAZULENE AND ITS DERIVATIVE: ELECTROSYNTHESIS AND SPECTROELECTROCHEMICAL CHARACTERIZATION 5 m
Fig. 1 Spiral morphology of clockwise B. Meana-Esteban1, C. Lete2, C. Kvarnstrm1, A. Ivaska1 1Process Chemistry Centre, c/o Laboratory of Analytical Chemistry, bo Akademi University, FIN- screwed fibril bundles in helical polyacetylene 20500, bo-Turku, Finland 2Institute of Physical Chemistry I. G. Murgulescu of Romanian Academy, Bucharest, Romania In the present work we have studied the electrochemical and spectroscopic properties of a new conjugated azulene-vinyl thiophene polymer using polyazulene as a model compound. Electropolymerization of azulene (A) and 2-[(E)-2-azulen-1-ylvinyl] thiophene (B) in TBAPF6-ACN and characterization of the formed lms were studied by Cyclic Voltammetry (CV), in situ UV-vis absorption spectroscopy, Raman spectroscopy and by Fourier Transform Infrared-Attenuated Total Reectance, FTIR-ATR spectroscopy. The redox response of polyazulene is characteristic of a polymeric system, whereas the symmetric and well-dened redox peaks in 2-[(E)-2-azulen1-ylvinyl] thiophene lms indicates a macromolecular or oligomeric structure. The structures of the electrosynthesized lms in their pristine form were studied by Raman spectroscopy using different lasers excitation lines exc= 514 nm and exc = 780 nm. Vibrations originating from either quinoid or benzenoid units will be resonance enhanced differently depending on the applied excitation lines. In situ UV-vis and FTIR-ATR measurements were made during charging-discharging of the electrosynthesized lms in monomer free solution. Experimental data conrms that an electrically conducting conjugated structure with different redox properties and conjugation length was formed after the electrosynthesis of the two monomers.
(A)
(B)
TH10 NANOSCALE COMPOSITES OF CONDUCTING POLYMERS: CHARACTERISATION AND POSSIBLE APPLICATIONS I. Cszi, C. Janky, Z. Fekete, G. Bencsik, . Patzk, E. Pintr, C. Visy University of Szeged P.O.box 105 Szeged, Hungary Due to the perspectives of combining together the different properties of the individual components, conducting polymer/inorganic compound composites are in the focus of researches, as they open opportunity for the combination of electrical and optical, magnetic or photocatalytic properties, leading to electrodes of special capabilities. Here we report on different nanocomposites: 1. Poly(3-octylthiophene)/-Fe2O3 (POT/ Fe2O3) 2. Polypyrrole/silver (PPy/Ag) and poly(3-octylthiophene)/silver (POT/Ag) 3. Poly(3-octylthiophene)/iron oxalate (POT/Fe-ox) 4. Polypyrrole/piperazine-1,4-bis(ethane sulfonate)/vitamin B12 (PPy/PIPES/B12) The nanocomposites are characterised on the basis of ICP-AAS, UV-Vis, FT-IR spectroscopy, MALDI-TOF MS, XRD, XPS, TEM, SEM, electric conductance and electrochemical measurements. In the case of POT/ Fe2O3 the maghemite nanoparticles were prepared by successive reduction-oxidation in reverse micelles, and the monomer was chemically polymerised in the presence of the particles. The concurrent polymerisation and immobilisation method was applied also in the case of the electrochemical formation of PPy/PIPES/B12. The other composites were obtained in post-polymerisation processes.
ABSTRACTS
While Fe2O3 , Ag and Fe-ox containing polymer composites are promising as new electrodes possessing magnetic, tunable conductivity and/or photocatalytic behaviour, the redox activity of cobalamin, immobilized in PPy/PIPES/B12 composite electrode, may give the opportunity to achieve mediated reduction processes in bio-electrochemical systems. The electrochemical behaviour of the composite proved that the redox transformation of the cobalt centre of built-in B12 takes place at potentials less negative than the complete reduction of the lm occurs, i.e. before the polymer electrode loses its conductivity.
Acknowledgement: Financial support from the Hungarian National Research Fund (OTKA) no. T42539 as well as from the Hungarian National Ofce of Research and Technology (NKTH) and the Agency for Research Fund Management and Research Exploitation (KPI) no. RET-07/2005 is gratefully acknowledged.
TH11 HELICAL CONJUGATED POLYMERS - CHIRAL POLYMERIZATION AND SUPER HIERARCHICAL STRUCTURE Kazuo Akagi Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan Tel: +81-75-383-2595, Fax: +81-75-383-2599, E-mail: akagi@star.polym.kyoto-u.ac.jp We present current progress in helical conjugated polymers by focusing on helical polyacetylene. (i) Helical polyacetylene was synthesized through recently developed chiral polymerization method, in which chiral nematic liquid crystal (N*-LC), consisting of host nematic LC and a small amount of chiral dopant, was used as a solvent for asymmetric reaction eld. The helical polyacetylene was found to have a super hierarchical structure characterized by a screw direction-controllable spiral morphology1, as shown in Fig. 1. Subsequently, macroscopically aligned helical polyacetylene was synthesized through the chiral polymerization method using the N*-LC with mono domain structure, which had been constructed by applying gravity ow or magnetic force as an external perturbation to the N*-LC. Screwed and aligned bril bundles, parallel to the external force, were thus produced. The formation mechanism of helical structure in N*-LC was also examined2. (ii) Next, we synthesized novel chiral binaphthyl derivatives by substituting phenylcyclohexyl moieties into 2, 2 positions or 2, 2, 6 and 6 ones of binaphthyl rings, and adopted them as chiral dopants to prepare N*-LCs available for synthesis of highly twisted helical polyacetylene. The N*-LC containing the tetra-substituted binaphthyl derivative showed a helical pitch of 270 nm, which was narrower one-tenth than those (2~5 m) of the N*-LC containing the di-substituted one. The former gave rise to highly screwed bril morphology without bundles of brils. This is in quite contrast to the bril morphology reported so far, where the screwed brils are gathered to form a helical bundle of brils (see, Fig. 1). The helical pitch (270 nm) of N*-LC including the tetra-substituted binaphthyl derivative is much smaller than the diameter of the bundle of bril (ca. 1 m), which should depress the formation of the bundle. The morphology free from the bundle of bril might allow us to easily evaluate intrinsic electromagnetic properties of the single screwed bril3.
References 1. K. Akagi, G. Piao, S. Kaneko, K. Sakamaki, H. Shirakawa, M. Kyotani, Science, 282, (1998) 1683 - 1686. 2. K. Akagi, S. Guo, T. Mori, M. Goh, G. Piao, M. Kyotani, J. Am. Chem. Soc., 127, (2005) 14647 - 14654. 3. N. Aleshin, H. J. Lee, Y. W. Park, K. Akagi, Phys. Rev. Lett., 93, (2004) 196601(1-4).
TH 12 HYBRID SYSTEMS OF CONJUGATED POLYMERS AND PLATINUM GROUP METALS Magdalena Hasik1, Edyta Stochmal1, Anna Adamczyk1, Andrzej Bernasik2 1Faculty of Materials Science and Ceramics, AGH-University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakw, Poland 2 Faculty of Physics and Applied Computer Science, AGH-University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakw, Poland Polymer-transition metal systems are the subject of current scientic interest. This is due to their potential applications which include sensors, optical storage devices, new type of catalysts, etc. In catalysis, the use of conjugated polymers as matrices for incorporation of metallic species is particularly attractive since specic electronic properties of these polymers can facilitate catalytic processes involving electron transfer. The work is devoted to the chemical preparation of conjugated polymer-platinum group metal systems. Three polymers of polyaniline family, i.e. unsubstituted polyaniline (PANI), poly(o-toluidine) (POT) and poly(o-methoxyaniline) (POMA) have been applied as matrices for incorporation of palladium, platinum and rhodium ions from aqueous PdCl2, PtCl4, K2PtCl4 and RhCl3 solutions. The systems obtained have been investigated by various experimental methods (elemental analysis, FTIR, UV/VIS, XPS spectroscopies, X-ray diffraction and scanning electron microscopy combined with microanalysis). This has made it possible to nd out that two types of processes can proceed in the systems studied: doping of the polymers with incorporation of platinum group metals counteranions and redox reactions resulting in partial oxidation of polymer chains taking place with simultaneous reduction of metal ions. The process prevailing in the system depends on the kind of platinum group metal species dominating in the reaction medium: in the dominant presence of chlorocomplexes ([PdCl4]2-, [PtCl4]2-, [RhCl6]3-) polymer doping is the main process, whereas the major presence of aquachlorocomplexes ([PdCl2(H2O)2]) favours the redox reaction. It has been also established that bulky octahedral complexes ([PtCl6]2-, [RhCl6]3-) are incorporated in small amounts only into unsubstituted PANI. This can be explained by steric effects. For the incorporation of square planar complexes ([PdCl4]2-, [PtCl4]2-) the presence of strongly electrodonating substituent (-OCH3 group in POMA) is advantageous. Catalytic properties as well as possiblity of preparation of polymer-platinum group metals nanocomposites using the systems obtained will be also discussed.
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TH13 COMPARISON OF POLARON PAIRS AND BIPOLARONS AS DOUBLY CHARGED STATES OF CONJUGATED POLYMERS Gernot Paasch1, Susanne Scheinert2, Andreas Petr1, Lothar Dunsch 1 IFW Dresden, PF 270116, D-01171 Dresden, Germany 2 TU Ilmenau,Solid State Electronics, PF 100565, D-98648, Germany In conjugated polymers polarons (P) are singly charged states with an extension of several (m) monomer units denoted as chain segments. Earlier bipolarons (BP) have been considered as the doubly charged states1 (approximately the same extension) in accordance with ESR spectroelectrochemical experiments. However, two alternatives to BPs have been discussed which are Fig.1. Equ ilibrium con cent rations of either Ps also ESR (electron spin resonance) silent. One is the -dimer model2 and the other one the more recent and BPs or Ps and PPs as fun ctions of the two polarons on a single chain model3. Giving a consistent explanation of optical data, the latter seems electroch emical po tential, zero at m idga p to be preferable compared to the BPs. Concerning equilibrium and kinetics the -dimer (on two adjacent posi tion, oxi dation pote ntial (polarons) 1eV , m=10. Th e equ ilibrium cons tant is 100. chains) and two polarons on a single chain are basically equivalent and denoted as polaron pair (PP). The interesting case is when the equilibrium with Ps lies on the side of either BPs or PPs. The basic difference between the BPs and the PPs is, that in their formation from two polarons in the case of the BPs 10.00 BP 1.00 there occurs in addition one neutral chain segment, whereas two Ps and one PP occupy both two chain P segments. This leads to a signicant difference in the equilibrium concentrations. For the system with Ps PP 0.10 P and BPs, the BP concentration saturates for high potential and the P concentration shows a maximum at c x ) a 0.01 ( the potential for the two-electron reaction. This dependency is in accordance with the maximum in the m spin concentration observed in ESR spectro-electrochemical experiments. In contrast, in the system with c 10 Ps and PPs, both the PP and the P concentrations saturate at high potentials. The absence of a maximum 10 in the P concentration for higher potentials contradicts the results of ESR spectroelectrochemical 10 experiments. Therefore, the PP model is reasonable only, if an additional subsequent second oxidation 10 step is possible at a standard potential near to that one of the rst oxidation step. On the other hand, for 0.6 0.7 0.8 0.9 1.0 1.1 1.2 E (V) lower potentials the concentrations in both models are virtually the same. The kinetics differs by the order of the dissociation process, which is of pseudo rst order for BPs and of rst order for PPs. As in the equilibrium, the time behaviour is for both systems almost the same for sufciently low concentrations (i.e. low potential), but it is rather different for higher potentials. Our summary is: Although the PP model is in accordance with optical spectra, a subsequent oxidation step must exist, leading to BPs and hence to the observed maximum in the spin concentration.
2+ + 2+ +
-3
-4
-5
-6
[1] J. Tang, R.D. Allendoerfer, R.A. Osteryoung, J. Phys. Chem. 96 (1992) 3531. [2] L.L. Miller, K.R. Mann, Acc. Chem. Res. 29 (1996) 417. [3] J.A.E.H. van Haare, E.E. Havinga, J.L.J. van Dongen, R.A.J.J. Janssen, J. Cornil, J.-L Brdas, Chem. Eur. J. 4 (1998) 1509.
TH14 EVIDENCE OF EFFECTIVE CONJUGATED SEGMENT DISTRIBUTION IN PPV AND PPV-SWCNT COMPOSITE FILMS:ROLE OF PRECURSOR AND CONVERSION TEMPERATURE E. Mulazzi*, R. Perego*, H. Aarab#, F. Massuyeau#, S. Lefrant#, E. Faulques#, J. Wry# *Dipartimento di Fisica, Universit di Milano, Italia #Laboratoire de Physique des Matriaux et Nanostructures, U.M.R CNRS-Universit de Nantes, France We present experimental and calculated optical absorption, photoluminescence (PL) and Raman scattering spectra of PPV thin lms and of PPVcarbon nanotube (SWCNT) composite lms. In particular we study the changes of PL spectra of PPV lms as function of precursor dilution with ethanol (1/4-1/20) and of PPV-SWCNT compounds at different SWCNT concentrations (x=0%-64% in weight) as function of precursor conversion temperature. Dramatic changes are observed in all these spectra with respect to the ones reported for standard PPV lms1. By the analysis of the PL spectra it is found that the modications induced in the band shapes due to low conversion temperature are similar to those due to the increase of the SWCNT concentration x and to the increase of the precursor solution dilution. In fact in all these conditions the PL spectra peaks which are due to the short segment transitions (~2.43eV or 2.55eV) become more intense than those due to the longer segment (~2.23eV) contributions. This trend is also observed in optical absorption and Raman scattering spectra recorded in the same conditions. A theoretical model based on the distributions of PPV conjugated segments of different effective lengths (identied by n=2-10) and on their electronic and vibrational properties is able to reproduce all these spectra in very good agreement with the experimental data1-3. By using this model we account for the contributions of transitions from disordered regions (short segments n=2-6), as well as those from well packed4 regions (long segments n=7-10). Consequently, we can simulate the inhomogeneity of the samples, in a consistent way with the X-ray diffraction data on PPV standard and partially converted lms5 and with SEM images of PPV-SWCNT composite lms at increasing x values6. In addition from the modications of the band relative intensities in the PL spectra, taken at 300K and 87K, we can show, that the temperature dependent charge migration process between segments is the most important mechanism for the energy transfer from short to long conjugated segments. In fact in standard PPV samples at 300K, the peak which is determined by the emission transitions occurring on long segments, constitutes the most intense feature of the spectra. On the contrary, at 87K, due to the hindered charge migration, all the peaks which are due to the radiative recombinations on the short segments become more intense with respect to all the other features in the spectra. REFERENCES 1. Mulazzi E., Ripamonti A., Wry J., Dulieu B. and Lefrant S., Phys. Rev. B60, 16519, (1999) 2. Mulazzi E., Botta C., Facchinetti D., Bolognesi A., Synth. Metals 142, 85, (2004) 3. Wry J., Aarab H., Lefrant S., Faulques E., Mulazzi E. and Perego R., Phys. Rev. B67, 115202, (2003) 4. Wang P.,Cuppoletti C.M. and Rothberg L.J., Synth. Metals 137, 1461, (2003). 5. Wry J., Dulieu B.,Baitoul M.,Buisson J.P. and Deniard P., Polymer, 40, 519,(1999). 6. Aarab H.,Baitoul M., Wry J., Almairac R., Lefrant S., Faulques E.,Duvail J.L.and Hamedoun M., Synth. Metals, 15, 63, (2005).
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TH15 EFFECTS OF GOLD NANO-PARTICLES ON OPTICAL AND TRANSPORT PROPERTIES OF CONJUGATED POLYMERS
Daniel Moses1, In-Wook Hwang1, Cesare Soci1, John Coyne2, Nabil M. Lawandy2, Alan J. Heeger1 1Institute for Polymers and Organic Solids, University of California, Santa Barbara Santa Barbara CA 93106, USA 2Solaris Nanosciences Corporation, 321 South Main Street, Providence, Rhode Island 02903
Two of the important properties of plasmon resonances are the signicant enhancement of the optical elds near the metal particle and the orientational dependence of their absorption of light. Thus, nanoscale metallic structures act as high-gain antennas for light sensitive molecules. The enhanced optical absorption can be utilized effectively by implementing a thinner semiconducting active layer in polymer-based photovoltaic devices and thus improving the photocarrier collection efciency. Our studies explored the fundamental effects of plasmon resonances on the optical and transport properties of systems comprising a bi-layer structure of gold nanoparticles and conjugated polymer polythiophene. These included studies of charge and energy transfer phenomena in this system using steady-state absorption and photoconductivity, ultrafast photoinduced absorption, transient photoconductivity, as well as photoluminescence. We will present our experimental ndings and discuss their ramication for polymerbased photovoltaic device applications.
TH16 PHOTOPHYSICAL PROPERTIES OF DYES INSERTED IN NANOSTRUCTURED ORGANIC HOSTS C. Bottaa, J. Moreaua, G. Macchib, F. Meinardib, , R. Tubinob, G. Di Silvestroc, L. Spadacinic, J. Mysliwiecd, A.Murad, G. Bongiovannid a ISMAC-CNR, via Bassini 15, I-20133 Milano, Italy b Dip. di Scienza dei Materiali, Universit di Milano Bicocca, via R.Cozzi 53, I-20125 Milano, Italy c Dipartimento di Chimica Organica e Industriale, Universit di Milano, via Venezian 21, 20133 Milano (Italy) d Dipartimento di Fisica, Universit di Cagliari, I-09042 Monserrato (Ca), (Italy) and Istituto Nazionale di Fisica della Materia (INFM).
Stable materials absorbing at short wavelengths and efciently emitting photons at lower energies provide low cost solutions for tuning the colour of light emitting diodes across the entire visible spectrum and for sensitising photovoltaic cells or silicon detectors. The inclusion of conjugated dyes in the parallel nanochannels of perhydrotriphenylene (PHTP)1 and the formation of adducts with -cyclodextrine and deoxhycolic acid represents a novel method to obtain all organic host-guest materials able to funnel the excitation to a desired site and to perform the specic function of efcient photon down conversion. In this communication, we describe the preparation and characterization of a new nanostructured fully organic material, where one, two or three thiophene and phenylene based dyes are co-included.2 The main advantages of these co-inclusion compounds are i) increased chemical stability of the active molecules, ii) emission with negligible self-absorption effects, iii) efcient light conversion.. By using cw and time resolved photoluminescence techniques we monitor the energy transfer processes occurring among the active dyes and show that the co-inclusion of several types of dyes can be suitably exploited to realize transport of energy and efcient light converters. [1] G. Bongiovanni, C. Botta, G. Di Silvestro, M.A. Loi, A. Mura, and R. Tubino. Chem. Phys. Lett 345, 386 (2001). [2] C. Botta, G. Patrinoiu, P. Picouet, S. Yunus, J.E. Communal, F. Cordella, F. Quochi, A. Mura, G. Bongiovanni, M. Pasini, S. Destri, and G. Di Silvestro. Adv. Mater. 16 (19), 1716-1721 (2004).
TH17 EXCITON MOBILITY, STATIC DISORDER, AND LATTICE PHONON-EXCITON COUPLING IN OLIGOTHIOPHENE CRYSTALS
L. Raimondo,1 M. Campione,1 M. Laicini,1 L. Silvestri,2 P. Spearman,1,3 S. Tavazzi,1 and A. Borghesi1 1 CNISM and Dipartimento di Scienza dei Materiali, Universit di Milano Bicocca, Via Cozzi 53, I-20125 Milano, Italy 2 Scuola Normale Superiore Piazza dei Cavalieri 7, I-56100 Pisa (Italy) 3 School of Chemical and Pharmaceutical Sciences, Kingston University Kingston upon Thames, KT1 2EE, United Kingdom
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Materials based on -conjugated oligomers such as the oligothiophenes have been widely studied over these last decades for their suitable physical properties for the application in the eld of the so-called organic opto-electronics in either thin lm, crystal, or polymer form. Investigations on Frenkel excitons were concerned with intermolecular coupling, excited electronic states, energy relaxation by coupling to vibrations, charge-transfer states, transport properties. In particular, a deep understanding of the dynamics of excitons in the presence of disorder is fundamental in the study of coherent phenomena. In these solids, UV-VIS absorption and emission optical spectra display typical vibrational structures which appear to arise principally from the exciton coupling with intramolecular and intermolecular vibrations to excitons. The former interactions usually lead to vibronic
excitons and gives rise to a progression of absorption lines approximately separated by intramolecular-vibrations energies. The interactions with lattice phonons, on the other hand, inuence the exciton translational motion throughout the crystal, and thus, play an important role in absorption line narrowing for the singlet excitons. In this work, we discuss the competition between intermolecular transfer interactions, exciton-phonon lattice coupling and structural disorder, which determines the exciton mobility within the crystal, by reporting polarized absorption spectra of several quaterthiophene crystals with different degrees of structural order as a function of temperature down to 7 K. The degree of static disorder of each crystal is evaluated from the ultimate shape, width, relative intensity, and position of the absorption peaks at the lowest temperature. The absorption lineshape of the exciton transitions is explained in the framework of the weak exciton-lattice phonons coupling and its evolution and motional narrowing as a function of temperature are discussed on the basis of exciton scattering on lattice phonons. In particular, the asymmetry of the absorption line related to the lowest exciton transition and the energy dependence of its low energy tail is discussed as a function of the degree of disorder of the samples. The results are relevant for the comprehension of the role of disorder on the exciton mobility also in the case of materials based on conjugated polymers.
TH18 MOLECULAR WEIGHT EFFECTS ON PHASE SEPARATION AND PERFORMANCE OF LIGHT-EMITTING DIODES FABRICATED WITH POLYFLUORENE-BASED CONJUGATED POLYMER BLENDS Keng-Hoong Yim, Richard Friend, Walter Doherty, William Salaneck, Ji-Seon Kim,*, Cavendish Laboratory, University of Cambridge, J J Thomson Avenue, Cambridge CB3 0HE, UK Department of Physics (IFM), University of Linkping, S-581 83 Linkping, Sweden Phase separation in polyuorene-based electroluminescent polymer blends consisting of poly(9,9-di-n-octyluorene-alt-benzothiadiazole) (F8BT) and poly(9,9-di-n-octyluorene-alt-(1,4-phenylene-((4-sec-butylphenyl)imino)-1,4-phenylene) (TFB) of different molecular weights were studied. Detailed analyses were performed on spin-cast blend thin lms (~80nm) using atomic force microscopy and X-ray photoelectron spectroscopy (XPS). Different length-scale of F8BT and TFB polymer chains results in remarkably different morphology in the blend lms, which have signicant impact on the performance of light-emitting diodes (LEDs) fabricated with these blend lms. At the lm-air interface, micron-scale lateral phase separation is observed in blend lms that consist of high molecular weight F8BT and TFB (Mn > 60 kg/mol) , whose domain sizes and surface roughness increase with molecular weight of each polymer. However, in blend lms that consist of low molecular weight F8BT or TFB (Mn < 10 kg/mol), the lm surface is relatively smooth with no observable micron-scale lateral phase separation. For these blend lms, XPS analysis reveals general enrichment of the short polymer chains at the lm-air interface, indicating that the vertical phase segregation at the lm-air interface is driven mainly by molecular weight (i.e. chain length) contrast between two polymers due to higher chain mobility in a low molecular weight material. On the other hand, at the lm-substrate interface, there is enrichment of the lower surface energy materials (TFB) in all the blend lms studied, the extent of which increases with the molecular weight of both F8BT and TFB, suggesting that surface energy contrast (as oppose to molecular weight contrast) is the predominant driving force in determining the vertical phase segregation at the lm-substrate interface. The power efciency voltage characteristics of LEDs fabricated with these blend lms are closely related to the lm morphology. For blend lms with micron-scale lateral phase separation, the efciency peaks quickly after turn-on (~ 10 Lm/W at 2V) but decreases rapidly at high voltages (~ 1 Lm/W at 5V). We attribute such device characteristics to a spatial connement of charge-carriers and thus recombination at the domain boundaries between the lower-lying and higher-lying phases (~40-50 nm height difference). At higher voltages, there is signicant leakage current due to thin lower-lying phase, which leads to a dramatic drop in efciency. On the other hand, some of the blend lms with no micron-scale lateral phase separation show relatively slow decay in power efciencies at high voltages (eg. from ~ 7 Lm/W at 3V to ~ 4 Lm/W at 5V), which we attribute to improved balance between electron and hole currents during device operation, and better thickness uniformity across the thin lm. On the basis of these studies, we conclude that for LEDs fabricated with F8BT:TFB blend thin lms, micron-scale lateral phase separation in the blend lms is critical in achieving high initial efciency just after turn-on, whereas having balanced electron and hole currents during device operation together with lm thickness uniformity are important in maintaining high efciency at high operating voltages. These observations will provide a new way of controlling polymer-polymer interfaces and thus the performance of polymer-based devices. J.-S. Kim; P. K. H. Ho; C. E. Murphy; R. H. Friend Macromolecules 37, 2861 (2004).
TH19 CONTROLLED CRYSTALLIZATION OF ORGANIC SEMICONDUCTORS BY RETICULATE DOPING AND ZONE-CASTING TECHNIQUES Jacek Ulanski Department of Molecular Physics, Technical University of Lodz, ul. Zeromskiego 116, 90-924 Lodz, Poland Jacek.Ulanski@p.lodz.pl The reticulate-doping technique technique consists in crystallisation of organic metals (like TTT-TCNQ or TTF-TCNQ) in situ, in polymer solution during the cast lm solidication1. Spatially correlated and diffusion limited crystallisation leads to formation of very ne, but continuous, 3D isotropic network of the organic metals penetrating the polymer matrix. These nanocomposites show several unique properties, e.g. extremely low percolation threshold (below 0.003 volume fraction) and relatively high conductivity, exceeding 1 S/cm at low concentration of the conducting phase. Further modications of this technique have made possible producing polymer composites with other topologies: quasi-2D bilayers by the socalled two-step reticulate doping2, or quasi-1D highly oriented composites by the zone-casting technique3, which show extremely high anisotropy of conductivity4. The two-step reticulate doping can be used to produce bilayer composites made of p-type semiconducting polymer and n-type organic low molecular weight semiconductor. Such composites can be used as active layers with developed p/n junctions in photovoltaic devices. The zone-casting technique was in last years successfully applied to produce oriented layers of liquid crystalline discotics5, 6. First FET produced by
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the zone-casting technique was made of hexa(n-dodecyl)hexa-peri-benzo-coronene7. This paper presents the high performance OFET devices based on large areas of the zone-cast aligned lms of several different organic semiconductors. The charge-carrier mobility and the On/Off ratio determined from the output and transfer characteristics are approaching the values of 0.1 cm2/Vs and 106 respectively8. The OFET devices produced with the zone-cast technique demonstrate good reproducibility and stability. Acknowledgements The recent results presented in this work were obtained by Mr. Pawel Miskiewicz, Dr. Jaroslaw Jung, Ms. Sylwia Kotarba, Dr. Ewa Dobruchowska, Mr. Michal Wiatrowski and Dr. Ireneusz Glowacki from DMP, TUL. This work was partially nancially supported through the EC NAIMO integrated project, No NMP4-CT-2004-500355. [1] J.K. Jeszka, J. Ulanski and M. Kryszewski, Nature, 289, 390 (1981). [2] J.K. Jeszka, A. Tracz, Polym. Adv. Technol., 3, 139 (1992)[3] L. Burda, A. Tracz, T. Pakula, J. Ulanski and M. Kryszewski, J. Phys. D: Appl. Phys., 16, 1737 (1983); A. Tracz, T. Pakula, J. Ulanski, M. Kryszewski, Polish Patent P-231177. [4] J. Ulanski, A.Tracz, E.El. Shafee, G. Debrue and R. Deltour, Synth. Met., 35, 221 (1990). [5] P. Miskiewicz, A. Rybak, J. Jung, I. Glowacki, J. Ulanski, Y. Geerts, M. Watson and K. Mllen, Synth. Met., 137, 905 (2003). [6] A. Tracz, J. K. Jeszka, M. D. Watson, W. Pisula, K. Mullen, T. Pakula, J. Am. Chem. Soc., 125, 1682 (2003). [7] P. Miskiewicz et al, unpublished results, presented at DISCEL Discussion Meeting, MPI-P, Mainz, March 10-11, 2003 [8] P. Miskiewicz, J. Jung, S. Kotarba, I. Glowacki, E. Gomar-Nadal, D. B. Amabilino, M. Mas-Torrent, C. Rovira, J. Veciana, B. Krause, D. Carbone, and J. Ulanski, J. Am. Chem. Soc., (2006) submitted.
TH20 CONTROLLING MOLECULAR LEVEL ALIGNMENT AND INTERFACE DIPOLES IN SELF-ASSEMBLED MONOLAYERS ON NOBLE METALS: A THEORETICAL STUDY Georg Heimel,1 Lorenz Romaner,2,1Peter Pacher,2,1 Mathis Gruber,2,1 Simon Jones,1 Stephen Barlow,1 Jean-Luc Brdas,1 and Egbert Zojer,2,1 1 School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400 2 Institute of Solid State Physics, Graz University of Technology, Petersgasse 16, A-8010 Graz, Austria
There is currently signicant interest in highly-ordered, self-assembled monolayers (SAMs) on (noble) metal surfaces, inspired both by the emergence of the eld of molecular electronics alongside the high potential for SAMs to improve the properties of more conventional device structures. SAMs are also used to control surface reactivity and for chemical sensing applications. In order to tune the interface properties and to endow the self-assembled systems with functionality suitable for use in either macroscopic or nanoscale devices, the use of -conjugated systems is highly promising and the focus of intense, multidisciplinary research. The goal of the present study is to provide an in-depth description of the electronic structure of the interface between metallic substrates and covalently bound conjugated molecules. In this way, we expect to devise strategies to tune the interaction and thus the properties of the investigated systems and eventually to gain a full understanding of the processes governing the electronics of metal/organic interfaces. Here, we describe a rst step in that direction: We study conjugated SAMs consisting of molecules with widely varied molecular ionization potentials and conjugated backbones with different polarizabilities; mixed monolayers consisting of an alternating pattern of donor and acceptor substituted molecules; and monolayers with varying degrees of coverage. We consider noble metals with varying workfunctions such as Au, Ag, and Pt different molecule docking groups and docking sites and investigate the effects of mechanical stress on the organic system. Using DFT band-structure-type methods, the details of the interface morphology, charge transfer between the metal and the molecules, interface dipoles, molecular layer depolarization, and workfunction modications as well as the alignment between metallic and molecular levels are described. Our thorough analysis provides results that are sometimes a priori unexpected.
TH21 NEW POLYMERS FOR ORGANIC ELECTRONICS EFFECT OF MOLECULAR AND SUPRAMOLECULAR PARAMETERS ON THE PERFORMANCE OF FIELD EFFECT TRANSISTORS AND PHOTOVOLTAIC CELLS Jean-Marie Verilhac1, Renaud Demadrille2, Muriel Firon3, Rmi De Bettignies3, Jean-Pierre Travers2, Gilles Le Blevennec1, Malgorzata Zagorska4 and Adam Pron2. 1 Laboratoire des Composants Hybrides DRT-LITEN-DTNM, CEA-Grenoble. 2Laboratoire dElectronique Molculaire Organique et Hybride, UMR5819-SPrAM, DRFMC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble, France 3Laboratoire Cellules Solaires, DRT-LITEN-GENEC, CEA-Saclay, 91191 Gif sur Yvette Cedex, France. 4Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland We have synthesized a series of regioregular alkylthiophene homopolymers, their alternate copolymers with uorenone and terpolymers containing alkylthiophene, uorenone and vinylene units (see Figure), with the goal to use them in the fabrication of organic electronic devices such as eld effect transistors (FETs) and photovoltaic cells. By studying sharp fractions of the obtained homopolymers we have demonstrated strong effects of the molecular weight on structural (GIXD) and morphological (AFM) properties of thin lms of these polymers as well as on charge carriers mobility, measured in the FET conguration. These studies have been completed by detailed voltammetric and spectroelectrochemical (UV-vis-NIR, Raman) investigations aimed on the determination the inuence of Mn on redox properties of the new polymers which are crucial for the selection of the most promising candidate for the fabrication of an environmentally stable FET with acceptable electrical parameters. The same molecular and supramolecular engineering concepts have been applied to the development of new polymers for photovoltaic cells. In particular, we have shown that by changing the regiochemical structure of alkylthiophene-uorenone copolymers it is possible to controllably modify their structural (STM, WAXD) and redox (cyclic voltammetry, UV-vis-NIR, Raman spectrolectrochemistry) properties as well as to tune their
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absorption spectrum towards its better matching the solar spectrum. This set of complementary investigations has led us to the selection of the most promising co- and terpolymers for the fabrication of photovoltaic cells. In very preliminary studies on such polymer based photovoltaic cells (in bulk heterojunction conguration with PCBM) efciencies of ca. 1.50% have been obtained under simulated solar light conditions (AM1.5/1000W.m-2), without any optimization of the cell fabrication.
S S O ct O ct O ct S S Oct S S n S O ct n Oct O
Figure: Examples of homopolymers, copolymers and terpolymers synthesized and studied as components of organic electronic devices.
TH22 SPIN-ORBITAL COUPLING EFFECTS ON MAGNETORESISTANCE IN ORGANIC SEMICONDUCTING MATERIALS Yue Wu, Jane Howe, Bin Hu Department of Materials Science and Engineering 608 Dougherty Engineering Building University of Tennessee Knoxville, TN 37996, USA
This presentation reports the studies on magnetoresistance and magnetic eld-dependent electroluminescence by uniformly mixing strong-spinorbital-coupling fac-tris (2-phenylpyridinato) iridium [Ir(ppy)3] molecules and weak-spin-orbital-coupling poly(N-vinyl carbazole) (PVK). The magnetic eld-dependent injection current indicates that the PVK of weak spin-orbital coupling exhibits a signicant magnetoresistance while the electrical resistance of Ir(ppy)3 of strong spin-orbital coupling shows an independence of magnetic eld up to 3000 Gauss. We nd that the magnetoresistance from the Ir(ppy)3+PVK composite displays a gradual change with the concentration of Ir(ppy)3. The magnetic eld-dependent electroluminescence indicates that the dispersion of Ir(ppy)3 molecules introduces an intermolecular spin-orbital coupling in the Ir(ppy)3+PVK composite. The intermolecular spin-orbital coupling modies the magnetic eld-dependent intersystem crossing and electron-hole pair dissociation, consequently leading to concentration-tunable magnetic eld effects in organic materials.
TH23 HIGH TEMPERATURE MAGNETORESISTANCE IN THIN FILM ORGANIC SEMICONDUCTORS Jeremy D. Bergeson, Dept. of Physics, The Ohio State University Derek M. Lincoln, Dept. of Chemistry, The Ohio State University Vladimir N. Prigodin, Dept. of Physics, The Ohio State University Arthur J. Epstein, Dept. of Physics and Dept. of Chemistry, The Ohio State University
We report magnetoresistance (MR) effects in organic semiconductor thin lms showing anomalous behavior near low eld. These effects are very pronounced at room temperature (up to 8% at 100 Oe and 15% at 1000 Oe) and are diminished, but still present, at 5K. Although such effects have been reported elsewhere1, a clear mechanism has thus far not been identied. The oligomer 6T demonstrates MR behaviour that, depending on bias and temperature, may be positive or negative. When the small molecule organic semiconductor Alq3 is doped with Ir(ppy)3, the usually negative MR ~ 8% MR is reduced by an order of magnitude. When doped with PtOEP, the MR vanishes. These results are in accord2 with phosphorescent energy transfer in Alq3 and suggest that spin-orbit coupling plays a signicant role in the mechanism responsible for the anomalous MR. We propose a model where the interconversion of singlets and triplets account for this effect. 1. E. Frankevich, et al., Phys. Rev. B 53 (1996) 4498; T.L. Francis, et al., New J. Phys. 6 (2004) 185; B. Hu, et al., Appl. Phys. Lett. 88 (2006) 022114. 2. M.A. Baldo, et al., Nature 395 (1998) 151; and M.A. Baldo, et al., Appl. Phys. Lett. 75 (1999) 4; I. Tanaka, et al., Phys. Rev. B 71 (2005) 20507.
Fig. 1 GMR effect in C60 -Co11 at 4.2 K
*Supported by AFOSR Grant No. F49620-03-1-0175 and DOE Grant Nos. DE-FG02-86ER45271 and DE-FG02-01ER45931
TH24 ADVANCES IN THE STRUCTURING AND PATTERNING OF SINGLE-MOLECULE MAGNETS ON SURFACES
Single-molecule magnets (SMM), derived from Mn12 molecules, have a large high-spin ground state (S = 10) with appreciable magnetic anisotropy resulting in a barrier for the spin reversal. As a consequence, an interesting magnetic bistability, due to individual molecules rather than to long-range ordering, is observed. Such molecules may therefore become materials with a potential impact in ultra-high density magnetic storage and quantum
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J. Gmez-Segura1, Ruiz-Molina1, M. Cavallini2, M. Massi2, M. Mas-Torrent1, C. Rovira1, F. Biscarini2, and J. Veciana.1 1 Institut de Ciencia de Materials de Barcelona (C.S.I.C.), Campus Universitari de Bellaterra, 08193 Cerdanyola, Spain. 2 CNR - ISMN, Via P. Gobetti 101, I-40129 Bologna, Italy.
computation, provided they can be organized into addressable domains. Here we present new methods, based on unconventional parallel lithography, for patterning Mn12 SMMs on a large area and with nanometer resolution on surfaces with different nature. The rst method uses a stamp-controlled deposition of molecules from a solution and exploits the competing interactions between the molecules and a substrate permitting the nanopatterning of Mn12 molecules on the surface.1 In the second method, a Mn12 derivative has been used to fabricate patterns of magnetic bits on a polycarbonate polymeric surface by a modied micro-transfer molding with a subsequent solvent exposure. This system can be used effectively as a permanent information medium with magnetic readout.2 Finally a method that permit the structuring of Mn12 molecules in the form of nano-objects will be presented.
Figure. Left: Isolated Mn12 SMMs appearing at a polymeric surface. Right: Patterned surface with aggregates of Mn12 SMMs.
1 M. Cavallini, J. Gmez, D. Ruiz-Molina, F. Biscarini, J. Veciana. Nano Lett. 2003, 3, 1527. 2 M. Cavallini, J. Gmez, D. Ruiz-Molina, F. Biscarini, C. Albonetti, C. Rovira, J. Veciana, F. Biscarini, Angew. Chem. Int. Ed., 2005, 44, 888.
TH25 PHOTO-INDUCED SWITCHIING BETWEEN SINGLE-CHAIN QUANTUM MAGNET AND PARAMAGNET, AND CONDUCTING SINGLE-MOLECULE QUANTUM MAGNETS AND SINGLE-CHAIN QUANTUM MAGNETS Masahiro Yamashita Graduate School of Science, Tohoku University & CREST(JST), Sendai 980-8578, Japan (yamasita@agnus.chem.tohoku.ac.jp) In the elds of the molecule-based magnets, the quantum molecular magnets have been attracting much attention. While the bulk magnets or classic magnets are based on the 3D ferro- or ferromagnetic interaction, the quantum molecular magnets are based on the double-well potential barrier dened with DS2, where D and S are uni-axial anisotropy and spin quantum number, respectively. Therefore, while the memory capacity of the bulk magnets such as oppy disc is 109 bits, the quantum magnets may have the memory capacity of 1023 bits if one quantum molecule magnet works as one memory. The realization of the quantum molecular magnets may make a huge progress in memory devices as well as quantum computers. Recently many single-molecule quantum magnets such as Mn12 have been reported and attracting much attention from the viewpoints of both basic sciences and applied sciences, while only a few nano-wire quantum molecular magnets or single-chain quantum magnets have been reported. So far 11 single-chain magnets have been reported. Among them, we have synthesized seven types of single-chain magnets so far. More recently, we have synthesized the novel single-chain quantum magnet formed by a twisted arrangement of easy-plane magnetic anisotropy (D>0) for the rst time. The compound consists of an alternating high-spin Fe(II) and low-spin Fe(III) mixed-valence chain complex, catena-[FeII(ClO4)2{FeII I(bpca)2}]ClO4, which shows the frequency dependence of AC susceptibility and semi-circle of Cole-Cole plot, and obey the Arrhenius law. The parameters of J and D are estimated to be -10.0 and 14.9 K, respectively. The D>0 is also evidenced by HF-EPR measurement. The compound shows the photo-induced switching between a single-chain quantum magnet and a paramagnetic state, reversibly. Moreover, we have tried to synthesised the bi-functional nano-materials with single- molecule magnets (or single-chain magnets) and conductivities, because the conducting electrons will make the spin ops difcult in the single-molecule magnets or single-chain magnets, due to the longer coherence of the quantum magnets. According to such a strategy, we have synthesizes the conducting single-molecule magnets and conducting single-chain magnets.
TH26 GIANT MAGNETORESISTANCE EFFECT IN C60-CO NANO-COMPOSITES S. Miwa, Y.V. Hamada, S. Nishioka, K. Ohta, M. Mizuguchi, T. Shinjo, Y. Suzuki and M. Shiraishi Graduate School of Engineering Science, Osaka University 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan Recently properties of electrons, both charge and spin, have been utilized to establish molecular spintronics. Because of a comparably weak spin orbit interaction, organic molecules are thought to have longer spin lifetime than conventional materials for spintronics, such as metals and inorganic semiconductors. And molecules are expected to realize novel spin based devices such as spin transistors. The rst experimental result of molecular spintronics was reported by Tsukagoshi et al.1 in 1999. They observed spin injection into molecules and the giant magnetoresistance (GMR) effect using a multi-walled carbon-nanotube as an organic spacer. But comparably large contact resistance and uncontrolled nature of the interfaces between ferromagnetic electrodes and molecules impede further studies of this research eld, and hence only a restricted number of studies have been reported2. In the present work, we bypass this problem and inject spins into fullerene (C60) by synthesizing novel C60-Co nano-composites. We think fullerene is one of the most suitable molecules for spintronics because of its comparatively high mobility, highly symmetric molecular structure which induces high quality crystallization, and composition of a light element, only carbon. In preparation of samples, we fabricated gold electrodes, of which gap was 10 m (length) 3.5 mm (width), onto glass substrates by photolithography and then C60-Co nano-composites were deposited in high vacuum.
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Here Co nano-particles are embedded in C60 molecules and therefore C60s are expected to play a role of a matrix in the samples. The ratio of C60 and Co was estimated to be C60-Co11 (11 Co atoms per one C60 molecule). Finally we covered the nano-composite by capping layers for preventing the Co clusters from oxidization. Magnetoresistance (MR) measurements were carried out using cryostat with superconducting solenoids and we observed the MR effect to be about 8% at 4.2 K (g. 1). The appearance of this MR effect is probably ascribed to a GMR effect as observed in Cu-Co granular systems3, 4 and we also conduct the various characterization of the sample, SQUID,I TEM, X-ray diffraction and Raman spectroscopy. We believe that these results provide a reliable proof of spin dependent transport in C60s, and this work can be of help to develop the nascent eld of molecular spintronics. This study was supported by New Energy and Industrial Technology Development Organization (NEDO). [1] K. Tsukagoshi et al., Nature 401, 572 (1999). [2] Z.H. Xiong et al., Nature 427, 821 (2004). [3] A.E. Berkowitz et al., Phys. Rev. Lett. 68, 3745 (1992). [4] J.Q. Xiao et al., Phys. Rev. Lett. 68, 3749 (1992). Author for correspondence :M. Shiraishi (shiraishi@mp.es.osaka-u.ac.jp) Phone & Fax :+81-6-6850-6426
TH27 TOWARDS CONTROLLED MAGNETISM IN ELECTRON-DOPED METAL-PHTHALOCYANINE MATERIALS Monica F. Craciun (1), Sven Rogge (1), Marc-Jan L. den Boer (1), Serena Margadonna (2), Kosmas Prassides (3), Yoshihiro Iwasa (4), and Alberto F. Morpurgo (1) (1) Kavli Institute of Nanoscience, Lorentzweg 1, 2628 CJ Delft, The Netherlands (2) School of Chemistry, West Mains Road, Edinburgh EH9 3JJ, UK (3) Department of Chemistry, University of Durham, South Road, Durham DH13LE, UK (4) Institute for Materials Research, Katahira 211, Aoba-ku, Sendai 980-8577, Japan The development of molecular materials that provide the ability to induce and control magnetic phenomena is a key aspect of the emerging eld of organic spintronics. One strategy towards the development of such materials relies on the use of molecules possessing a spin in their ground state. The spins can be made to interact via delocalized charge carriers (e.g., RKKY or double exchange interaction). The possibility to control the density of charge carriers should then enable the experimental control of magnetic phenomena. Here, we report on our investigations of the electronic and structural properties of a large class of molecular materials the Metal-Phthalocyanines (MPcs)- that give control over the spin of the constituent molecules and are therefore particularly suited for these investigations. Our investigations1, 2 are based on a comparative study of the electronic properties of thin lms of CuPc, NiPc, ZnPc, FePc, CoPc and MnPc, with a molecular spin S ranging from S=3/2 to S=0. Control of the charge density is achieved through intercalation with alkali atoms1. From temperature-dependent conductivity measurements we nd that for all the initially insulating molecules, a metallic state is obtained upon doping. This demonstrates the possibility to introduce delocalized charge carriers in the materials, which are capable of mediating the interaction between the molecular spin. Upon further doping, the lms are turned back in the insulating state, similar to what has been so far observed only in C60. Measurements based on scanning tunnelling spectroscopy, Raman spectroscopy, and X-Ray structural analysis suggest that the observed behavior is due to lling of electronic bands originating from the molecular orbitals of the constituent molecules1. Interestingly, we observe experimentally robust differences in the doping dependence of the conductance of different MPcs, which correlate to the known structure of the molecular orbitals of the individual molecules2. Specically, in CuPc, NiPc and ZnPc, where the added electrons occupy orbitals localized on the ligands, exhibit identical behavior, whereas in CoPc, FePc and MnPc, where the orbitals centered on the metal atoms are also occupied by electrons upon charge transfer, the behavior observed experimentally is different. In combination with the large exchange energy characteristic of many different MPcs, the observed sensitivity of the transport properties to the molecular orbitals of the constituent molecules make these molecular materials an ideal candidate for the control of magnetism at the molecular scale3. References [1] Craciun MF, Rogge S, den Boer MJL, et al., ADVANCED MATERIALS 18 (3), 320-324, 2006. [2] Craciun MF, Rogge S, Morpurgo AF, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 127 (35), 12210-12211, 2005. [3] Taguchi Y, Miyake T, Margadonna S, et al., JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 128 (10), 3313 3323, 2006.
TH28 LARGE MAGNETORESISTANCE IN OLEDS M. Wohlgenannt1, . Mermer1, G. Veeraraghavan2, T. L. Francis2, Y. Sheng1, D. T. Nguyen1 (1) Department of Physics and Astronomy and Optical Science and Technology Center, The University of Iowa, Iowa City, IA 52242, USA (2) Department of Electrical and Computer Engineering, The University of Iowa, Iowa City, IA 52242, USA. We recently discovered a large and intriguing magnetoresistance (MR) effect in semiconducting polymer and small molecular OLEDs, which we dubbed organic magnetoresistance (OMAR). Its magnitude equals up to 10% at room temperature for magnetic elds, B = 10mT. OMAR is therefore, amongst the largest MR effects in any bulk material, organic or inorganic. To the best of our knowledge, the mechanism causing OMAR is currently not known. The existence of OMAR poses a signicant scientic puzzle, since it is the only known example of large MR at room temperature in non-magnetic devices. Our devices, just like OLEDs, can be manufactured cheaply on exible substrates, and can be transparent. Our devices therefore hold promise for applications such as pen-input touch OLED display screens where the position of a magnetic stylus is detected (patent pending). Our devices do not require ferromagnetic electrode materials resulting in exibility in material choice not achievable for other MR devices.
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0 -2 -4
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Figure 1. Magnetoresistance, R/R curves, measured at 300K in (a) a PFO (100 nm) and (b) an Alq3 (100 nm) device with PEDOT (100 nm) anode and Ca (50 nm including capping layer) cathode at different voltages. The insets show the device resistance as a function of voltage and the respective molecular structures. Figure 1 a) and b) shows measured OMAR traces at room-temperature for different voltages in polyuorene (PFO) and Alq3 devices, respectively. We nd that the measured MR traces are independent of the angle between the lm plane and applied magnetic eld, and only weakly temperature dependent. We show that OMAR is a bulk magnetotransport effect . By varying the injection efciency for the minority carriers, we show that OMAR is only weakly dependent on the ratio between excitons formed and carriers injected, excluding the so-called pair mechanism as a possible explanation. The functional dependence of OMAR on B and the magnitude of the B scale point on electron-spin dynamics induced by the hyperne interaction as the underlying cause. We present a careful analysis of this spin-dynamics and derive the functional dependence on B from the standard hyperne Hamiltonian. Our treatment shows that hyperne interaction may severely limit the spin-transport length in organic semiconductors.
TH29 REACTION OF IRON WITH C60 AT HIGH TEMPERATURE HIGH PRESSURE CONDITIONS: FORMATION OF FE3C AND IMPLICATIONS FOR MAGNETIC CARBON. A.V.Talyzin1, A.Dzwilweski1, L. Dubrovinsky2, A. Setzer3, and P. Esquinazi3 1Department of Physics, Umea University, S-90187 Umea, Sweden 2Bayerisches Geoinstitut, Universitat Bayreuth, D-95440 Bayreuth, Germany 3Division of Superconductivity and Magnetism, University of Leipzig, D-04103 Leipzig, Germany
Polymeric C60 samples synthesized in this study at high-pressure high-temperature conditions close to the point of fullerene molecule collapse showed absence of bulk ferromagnetic properties. Samples of mixed C60 and iron powders (3-10% of Fe) were subjected to high temperature high pressure treatment at the conditions very similar to those of the reported previously magnetic carbon. It is found that iron induce collapse of C60 molecules with formation of iron carbide Fe3C while the rest of the sample transformed into a standard for these conditions C60 polymeric phases. It is also established that iron oxides can be reduced by carbon from C60 at the conditions of polymer synthesis. Magnetic properties (Curie temperature and magnetic moment) of these composite C60 polymeric/Fe3C samples are very similar to ferromagnetism of the polymerec Rh-C60 samples reported previously. It is suggested that the main ferromagnetic signal reported previously for high pressure high temperature polymers of C60 was due to Fe3C and not related to the magnetism of carbon as originally interpreted.
TH30 ADVANCED MATERIALS AND APPLICATIONS FOR MEDICAL DEVICES Jim McLaughlin; NIBEC and Nanotechnology Research Institute; University of Ulster In this paper I will review some of the important research that has been required to enhance the biocompatibility of medical devices from stents to point-of-care sensors. I will highlight where nanotechnology is playing a role and demonstrate particular work undertaken at the University of Ulster. With the development of critical areas of interdisciplinary research, scientists will lead to an enhanced understanding and control of the key processing stages involved in the design and manufacture of medical devices, smart catheters, bio-coatings, bio-chips, bio-arrays and DNA sensors. It is anticipated that this fundamental work will lead to tangible technology transfer in the areas of long life implantable devices blood analysis, cardiac enzyme detectors, liver and renal function, infectious diseases, gene disorders, etc. These will obviously have major benets to healthcare delivery. The development of miniaturised, integrated sensor/electrode-based devices are revolutionising both the delivery of health care. In this paper, I identify some of the most exciting research themes in these areas, as well as novel underpinning fabrication technologies and transduction principles, which should make future advances possible. I will review our work in the area of ultra-thin lm Diamond Like Carbon and its key interactions with cells and in particular proteins. Nanotechnology offer much promise for new sensor devices particularly in the biomedical sector. Miniaturisation, integration, nano-fabrication, quantum effects and the joining of disciplines such as biology, physics and engineering in particular offer many new opportunities for new scientic discoveries.
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F ig 1 Highly orientated Nanotubesforests suitable for biosensingelectrode
Among the anticipated applications of carbon nanotubes, CNTs is their use as components in miniature biological devices such as probes and sensors. A nanotube might provide the nest needle for in vivo probing, for example monitoring chemical dynamics at the single cell level. These devices exhibit advantages over existing technology not only in size but also in performance. The better performance of the CNT electrodes in detecting biomolecules in solutions in comparison to the conventional used carbon electrodes lies in the high conductance/surface area of CNTs, which is suitable for the promotion of fast electron transfer, as well as in their inherent high surface area and tubular structure. Several issues are important regarding CNT biosystems. One of them is development of chemical methods to immobilise biological molecules onto CNTs in a reliable manner. Central to tackling this issue is surface-functionalisation of CNT and elucidating the interfaces and interactions between CNT and biosystems. Currently our overall understanding of the interactions between protein molecules and CNT surfaces is immature, in that we generally lack mechanistic and predictive structure reactivity relations. Our work seeks to provide insights into the nature of the biomolecular junction and utilise that knowledge in the design of smart nanotubes that are bio-engineered and tailoreddesigned so as to accomplish detection of micro-organisms and biomolecules with high sensitivity and selectivity. Some recent 2005 Publications T.I.T. Okpalugo, P. Papakonstantinou, H. Murphy, J. McLaughlin, N.M.D. Brown, Oxidative functionalization of carbon nanotubes in atmospheric pressure lamentary dielectric barrier discharge (APDBD) Carbon, 43, pp 2951-2959, 2005. G.A Abbas, P. Papakonstantinou, J.A. McLaughlin, et al Hydrogen softening and optical transparency in Si-incorporated hydrogenated amorphous carbon lms. Journal of Applied Physics 98, n 10 103505-1-6, 2005. G.A Abbas, P. Papakonstantinou, J.A. McLaughlin, Investigation of local ordering and electronic structure in Si-and hydrogen doped tetrahedral amorphous carbon thin lms. Applied Physics Letters 87, n 25 p251918, 2005. G.A. Abbas, S.S. Roy, P. Papakonstantinou, J.A. McLaughlin, Structural investigation and gas barrier performance of diamond-like carbon based lms on polymer substrates. Carbon, 43, 2, pp303-309, 2005. T.I.T. Okpalugo, P. Papakonstantinou, H. Murphy, J. McLaughlin, N.M.D. Brown, High resolution XPS characterization of chemical functionalised MWCNTs and SWCNTs. Carbon, 43, 1, pp153-16 1, 2005. P. Papakonstantinou, R. Kern, L. Robinson, H. Murphy, J. Irvine, E. McAdams, J. McLaughlin, T McNally, Fundamental Electrochemical Properties of Carbon Nanotube Electrodes. Fullerenes, Nanotubes and Carbon Nanostructures, Vol. 13 Supp 1, pp91-108, 2005. T.I.T. Okpalugo, P. Papakonstantinou, H. Murphy, J. McLaughlin, N.M.D. Brown, T McNally, Surface-to-Depth Analysis of Functionalized Multiwall Carbon Nanotubes (FMWCNTS). Fundamental Electrochemical Properties of Carbon Nanotube Electrodes. Fullerenes, Nanotubes and Carbon Nanostructures, Vol. 13 Supp 1, pp275-285, 2005. R. McCann, S.S. Roy, P. Papakonstantinou, J.A. McLaughlin, Ray SC, Spectroscopic analysis of a-C and a-CNx lms prepared by ultrafast high repetition rate pulsed laser deposition. Journal of Applied Physics 97, n7, p73522-1-11, April 2005.
TH31 AMYLOID-LIKE PROTEIN FIBRILS FOR ALIGNMENT AND ASSEMBLY OF CONJUGATED POLYELECTROLYTES INTO NANOWIRE GEOMETRIES. Anna Herland1, Per Bjrk1, K. Peter R Nilsson1, Ralph Hania2, Ivan Scheblykin2, Per Hammarstrm1, Olle Ingans1 1Biomolecular and Organic Electronics, IFM, Linkping University, SE-581 83 Linkping, Sweden 2 Department of Chemical Physics, University of Lund, SE-22100, Sweden The development of self-assembled nanoscopic materials for controlled bottom-up fabrication of electronic devices is of current interest. In this regard, the self-assembly and the three-dimensional well-ordered structures of biomolecules could be used as excellent construction tools for the assembly of electronic devices. Among the geometries needed, wires are ubiquitous, either carrying current to devices, or formed into integrated devices. Amyloid-like protein brils have earlier been used to create templates for metal nanowires, where metals were associated post-self-assembly of the brils. We have taken two different routes to combine conjugated polymers with amyloid-like brils into electroactive luminescent nanowires with ~10 nm width and lengths up to 10 m. First, based on the afnity between the amyloid bril structure and conjugated polyelectrolytes (CPE)1,2 we have complexed amyloidlike protein brils with a CPE, poly(thiophene acetic acid) PTAA. Individual CPE decorated brils can be aligned through molecular combing on hydrophobic surfaces or through molecular combing on patterned PDMS stamps and transferred to hydrophilic surfaces. The aligned brils have been studied with single molecule spectroscopy (SMS) techniques to evaluate the uorescence from single objects. Through measurements of the anisotropy of the emitted light from the brillar complexes we can conclude that the PTAA is highly oriented on the brils. The molecular axis of the CPE chain is preferentially aligned along the brillar axis. The second approach is to let the protein amyloid bril co-assembly with conjugated oligoelectrolytes (COE) with a thiophene backbone3. The
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luminescent oligomers were integrated into the bril, which was evident from intensity and spectral distribution of the uorescence and from the morphology of supramolecular structures in the form of bundled nanowires. The electro-optical properties of the wires are demonstrated with reversible electrochemical doping induced uorescence quenching, thus demonstrating both electrical transport and electroactivity. We suggest that this self-assembly method can be used for several types of electroactive organic materials. The possibility to synthesize and design amyloid forming peptides and proteins can be used in the formation of wires or devices. The peptides can further be designed with address functions for anchoring of the wire to electrodes or other wires. Furthermore, changes in optical properties of the CPE or COE can be used to probe amyloid bril formation. The conformation changes of the protein result in alterations in the geometry and the electronic structure of the conjugated chains, which have been monitored with absorption and emission spectroscopy. As stated above COEs can be present during amyloid bril formation or added to pre-formed brils, which results in a different spectral distribution. A development towards more complex samples in biodetection with CPE is that we have shown selective staining of amyloid deposits with CPE in tissue samples4. 1) Nilsson KPR, Herland A, Hammarstrm P, et al., BIOCHEMISTRY 44 (10): 3718-3724 2005 2) Herland A, Nilsson KPR, Olsson JDM, et al. JACS 127 (7): 2317-2323 2005 3) Herland A, Bjrk P, Nilsson KPR, et al. ADV MAT 17 (12): 1466-1471 2005 4) Nilsson KPR, Hammarstrm P, Ahlgren F, Herland A et al. in manuscript
TH32 PICOSECOND INFRA-RED TRANSIENT ABSORPTION STUDIES OF DNA IN DIFFERENT CONFORMATIONS John M. Kelly, Gerard Doorley, David A. McGovern and Susan Quinn, School of Chemistry, Trinity College Dublin, Dublin 2, Ireland Kate Ronayne Ultrafast Laboratory, Rutherford Appleton Laboratory, Chilton, UK There continues to be enormous interest in the physico-chemical properties of DNA such as its (photo)conductivity and excited state behaviour 1 investigations of interest to materials scientists given the demonstrated potential of DNA to self-assemble into structures of remarkable complexity.3 The exceedingly short lifetime of the free DNA bases or nucleotides1 (e.g. in 5-GMP or 5-CMP) have been shown to be followed by a 2-5 ps process, attributed to vibrational relaxation within the ground state.2 However as will be discussed in this presentation, linking of the nucleotides to form dinucleotides, oligonucleotides (ODNs) and eventually polynucleotides results in longer-lived species, which can be ascribed to excimerlike states. We present data on the vibrational spectra and decay kinetics of a series of dinucleotides, single-stranded ODNs, duplex, triplex and quadruplex polynucleotides, including ones with the tandem (TTAGGG) sequence, characteristic of human telomeric DNA.
Figure 1 Transient IR signals from (a) GMP aggregates and (b) telomere DNA sequence 1. Ultrafast Excited State Dynamics in Nucleic Acids, C. E. Crespo-Hernndez, B. Cohen, P.M. Hare and B. Kohler, Chem Rev., 2004, 104, 1977 2. Monitoring the Effect of Ultrafast Deactivation of the Electronic Excited States DNA bases, Polynucleotides and DNA Following 266 nm Laser Excitation using Picosecond Time-resolved Infrared Spectroscopy; M. K. Kuimova, J. Dyer, M. W. George, D. C. Grills, J. M. Kelly, P. Matousek, A. W. Parker, X. Z. Sun,a M. Towrie and A. M. Whelan, Chemical Commun.,2005, 1182. 3. Y.V. Pinto, J.D. Le, N.C. Seeman, K. Musier-Forsyth, T.A. Taton, and R.A. Kiehl, Sequence-encoded self-assembly of multiple-nanocomponent arrays by 2D DNA scaffolding Nano Letters., 2005, 5, 2399.
TH33 PHOTO-INITIATED SYNERGISTIC PROCESSES IN BACTERIORHODOPSIN-CONDUCTING POLYMER SYSTEMS N. Arun, A. G. Manoj, K. S. Narayan* Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientic Research, Bangalore 560064, India. *E-mail: narayan@jncasr.ac.in
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Bacteriorhodopsin (bR), a protein existing in the halobacterial purple membrane serves as a light driven pump which sets up an electrochemical gradient and transports protons across the cell membrane. We explore the synergistic processes occurring at the conducting polymer/bR interface due to the photoexcitation. The surface potential of the polymers can be controlled by an external voltage bias. The net effective dipole moment of the bR molecule can be used for orientating it on conducting polymer blend lms such as poly (3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) and polyaniline (Pani-emeraldine salt). The spectral and temporal characteristics of the photoelectric signals from oriented bR lms on
the conducting polymer substrates show several interesting features. The possibility of changing the oxidation state of the polymer electrochemically, is coupled to the optically-activated proton gradient in the bR side in these unique hybrid systems. It was recently demonstrated that the internal conversion of the intermediate deprotonated M state of bR and the proton transfer/transport can be controlled by the electrochemical reactions at the adjacent PEDOT:PSS layer leading to interesting solid-state device prospects in the process.1,2 We generalize the principles involved by studying this effect on a variety of conducting polymers with different doping levels. Upon photoexciting bR, the conductance variation of the adjacent polymer lm was monitored. Measurements were also carried out in an electrolytic medium, with the electrolyte in contact with bR. We correlate the observed electronic changes in the polymer lm with the proton-pump action across the interface upon photoexciting the bR. Reference: 1. A. G. Manoj and K. S. Narayan, Appl. Phys. Lett. 83, 3614, 2003. 2. A. G. Manoj and K. S. Narayan, Biosens. Bioelectron. 10, 967, 2004.
TH34 HIERARCHICAL STRUCTURE AND EL PROPERTIES OF PHOTOPOLYMERIZED DNA/POLYANILINE COMPLEX Norihisa Kobayashi*, Yuuki Nishiyama and Daisuke Nishioka Department of Information and Image Sciences, Graduate School of Science and Technology, Chiba University, Chiba 263-8522, Japan A DNA/polyaniline (PAn) complex has been successfully prepared by the photopolymeization of dimeric aniline via photocatalytic reaction with Ru(bpy)32+ complex in the presence of DNA template, a reaction which occurs, even in the solution at pH 3.0 6.0, due to the specic local lowerpH environment provided by DNA. The DNA/PAn complex contained Ru(bpy)32+ in its structure even after purication. The complex was revealed to work as a material for novel organic red light-emitting diode1,2). Figure 1 shows the change in the absorption spectrum of an HCl aqueous solution containing 610-5 M Ru(bpy)32+, 1.010-3 M PPD and 1.0103 M DNA at pH 4.0 upon visible light illumination. The polaron absorption emerged at 600 800 nm in case at pH 4.0 in the absence of DNA. Its absorption maximum (max), however, is signicantly sifted to the longer wavelength by ca. 4 200 nm in the presence of DNA. The shift is explained by the expanded coil formation of PAn photo-polymerized even at pH 4.0 in the presence of DNA. Differential CD spectra of the solution containing DNA and PPD and that containing only DNA at pH 4.0 showed a negative 3 1 h interval CD band at 280 nm assignable to -* transition of PPD. These results indicate that PPD in the DNA solution at pH 4.0 is aligned along main chain of DNA through intercalation and/or 2 electrostatic interaction, leading to the formation of expanded-coil PAn structure in PAn/DNA complex.
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The EL device was fabricated by employing the complex. The current-voltage curve of the device indicated that the current abruptly increased above the bias voltage of 7 V, and large current of 1600 mA was obtained at 11 V. This relatively higher current than that of the device commonly fabricated by vacuum evaporation is due to the employment of conducting PAn in the complex. On reecting of the I-V characteristics, the device was emitted over the bias voltage of 7V, and the luminance of the device increased with the bias voltage. The maximum luminance of 1500 cd/m2 was observed at 11 V. References [1] N. Kobayashi et al., J. Mater. Chem., 2001, 11, 267. [2] N. Kobayashi et al., J. Mater. Chem., 2001, 11, 1766.
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Fig.1 Change of abs or ption sp ectra induce d b y vis. illu m inati on (420 -600 n m) of aque ous H Cl s olu tion -5 -3 2+ containing 6 10 M Ru(bp y) 3 , 1.0 10 M PPD, -3 and 1.0 10 M DNA.
TH35 A NOVEL CATIONIC CONJUGATED POLYMER FOR DNA DETECTION

O
Br N + O
Jadranka Travas-Sejdic, Hui Peng, Christian Soeller

+ B rN
Polymer Electronics Research Centre,The University of Auckland, Private Bag 92019, Auckland, New Zealand Cationic water-soluble cojugated polymers (CCPs), which combine potential properties and structural possibilities of conventional conjugated polymers and polyelectrolytes, have proven to be useful for DNA sequence detection through electrostatic interaction1. On the other hand, anionic poly(pphenylenevinylene) derivatives have been reported as good substrates for chemo- or bio-sensors2,3. However, the anionic charge limits application to the detection of anionic biomolecules, such as DNA. Here we report the synthesis of a novel cationic water-soluble PPV derivative, poly({2,5-bis[2-(N,Ndiethylamino)-1-oxa propyl]-p-phenylenevinylene}-alt-p-phenylenevinylene) dibromide (PPVNEt2Br2) (structure shown in Fig. 1) and its application to DNA detection. The synthesized polymer is photoluminescent in aqueous solution with an emission peak wavelength of 492 nm when excited at 412 nm. An oligonucleotide (ODN) probe was labelled with a chromophore dye, Cy3, chosen in order to facilitate Frster resonance energy transfer (FRET)4 between the dye and the polymer. Fig. 1 shows the FRET emission spetra of Cy3-ODN after hybridization with different concentrations of comlementary ODNs. It is apparent that FRET ratios decreased with an increase in the concentration of complementary ODN reecting increasing sample hybridization. In summary, we synthesized a novel cationic water-soluble cojugated polymer, PPVNEt2Br2 and
PPVN Et 2 B r 2
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Fig. 1 .Em issio n sp ectra of a PPV NE t2 / ODN -Cy3 (1.2 M) duplex af ter hybridiz ation with dif feren t co ncent rations of comp lem entar y ODN targ et. (a) 0 nM; (b) 7.41 n M; (c) 22.2 nM ; (d) 32.1 nM ; (e) 279.1 nM . Th e sp ectra w ere norm alised to poly m er em issio n.
applied it to homogeneous DNA hybridization detection. The results illustrate that it is possible to detect hybridization in solution by using a singly labeled ODN strand. Further optimization of the structure and property of CCPs may lead to simple and practical platforms for DNA detection. References: 1. B. S. Gaylord, A. J. Heeger and G. C. Bazan, Proc. Natl. Acad. Sci. U.S.A., 2002, 99, 10954. 2. C. Fan, K. W. Plaxco and A. J. Heeger, J. Am. Chem. Soc., 2002, 124, 5642. 3. B. S. Gaylord, S. Wang, A. J. Heeger and G. C. Bazan, J. Am. Chem. Soc., 2001, 123, 6417. 4. J. R. Lakowicz, Principles of Fluorescence Spectroscopy; Kluwer Academic/Plenum Publishers: New York, 1999.
TH36 ORGANIC CONDUCTORS AND MEDICAL BIONICS: CURRENT STATUS AND FUTURE OPPORTUNITIES Gordon Wallace ARC Centre of Excellence for Electromaterials Science Intelligent Polymer Research Institute, University of Wollongong Northelds Avenue, Wollongong, NSW 2522, Australia e-mail : gordon_wallace@uow.edu.au; fax :+61 2 42213114
The interaction of biomolecules with carbon nanotubes is of interest to those involved in the development of new bioseparation technologies, biosensing and bionics (the interfacing of electronics and living biological systems). In the latter area the use of organic conductors has gained momentum over the past decade. Not only have such materials been shown to be compatible with biological systems supporting the growth of endothelial, oesteoblast and even nerve cells, but they also provide an excellent conduit through which electrical stimulation can be applied. Such stimulation has proven to be benecial in a number of areas. Carbon nanotubes are highly effective organic conductors. They have excellent mechanical properties and have been shown to undergo specic interactions with biomolecules such as DNA, hylaronic acid and chitosan. In this presentation our most recent work on the non-covalent attachment of biomolecules to carbon nanotubes will be presented. The ability to assemble these components into useful structures such as bres and mats, and the properties of the resultant structures will be discussed. Of particular interest is their mechanical, electronic and electrochemical properties. Preliminary cell culturing data will also be presented.
TH37 TUNABLE PLASMONIC PHOTONIC CRYSTALS USING HEAVILY-DOPED ORGANIC CONDUCTING POLYMERS T. Matsui1, Z. V. Vardeny1, A. Agrawal2, A. Nahata2, and R. Menon3 1Physics Department, University of Utah, Salt Lake City, UT 84112, USA 2Department of Electrical and Computer Engineering, University of Utah, Salt Lake City, UT 84112, USA 3Physics Department, Indian Institute of Science, Bangalore 560 012, INDIA Since the discovery of the surface plasmon polariton (SPP) assisted phenomenon of anomalous transmission through a two-dimensional subwavelength aperture array perforated on optically think metallic lms,1 numerous studies have been carried out to explore both fundamental issues and potential device applications. So far, this so-called plasmonic crystals have been fabricated on various kinds of Drude-type conductors such as metals and doped-semiconductors. Here we report, for the rst time, the observation of anomalous transmission of terahertz (THz) radiation using more exotic class of conductors, namely heavily-doped organic conducting polymers.2 Among the class of conducting polymers, polypyrrole [PPy] heavily-doped with PF6 [PPy(PF6)] is one of the highly conducting polymer.3 It has been postulated that heavily doped PPy(PF6) has two plasma frequencies, where the lower frequency seems to be caused by a Drude free electron dielectric response with a plasma frequency in the THz spectral range.4,5 Therefore, we fabricated 2D aperture arrays on the PPy(PF6) lms with lattice periodicities in the mm wavelength range, so that the a = 1.0 mm expected SPP assisted transmission band occurs in the THz spectral range. The optical transmission spectrum a = 1.5 mm of the lms was measured using a conventional THz time-domain spectroscopy technique. The attached gure shows the transmission spectra through plasmonic crystals fabricated on thick free-standing PPy(PF6) lms. Several transmission peaks are observed in the spectra of the plasmonic crystals. Transmittance perforated at the lowest energy band is much larger than the fractional aperture area, implying that anomalous transmission was obtained. Our results indicate that in spite of the intrinsic disorder, doped PPy(PF6) contains unperforated large density of free carriers that allow direct excitation of SPP, in a manner similar to conventional metals. Frequency (THz) From the viewpoint of device applications, we believe that our ndings are quite exciting because of the possibility of in-situ spectral tunability. Using an electrochemical process, the polymer doping level can be Fig. 1: Trans mis sion spe ctra for free-stan ding hea vily dop ed PPy(P F6) film s with 1 mm readily controlled in a reversible manner using an externally applied voltage. Therefore, it would be possible (solid trace) an d 1.5 mm ( dashe d trace) to control the electrical conductivity of the doped conducting polymer lms, and consequently tune the SPP period icity, an d an un perforated film ( do tted trace). transmission bands.
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References 1. T. W. Ebbesen et al., Nature 391, 667 (1998). 2. T. Matsui, et al., Appl. Phys. Lett. 88, 071101 (2006). 3. R. Menon et al., in Handbook of Conducting Polymers, edited by T. A. Skotheim et al. (Dekker, New York, 1998). 4. K. Lee et al., Phys. Rev. B 52, 4779 (1995). 5. R. S. Kohlman et al., Phys. Rev. Lett. 74, 773 (1995).
TH38 THIOPHENE-BASED DENDRITIC MATERIALS Amaresh Mishra, Peter Buerle* Department Organic Chemistry II, University of Ulm, Albert-Einstein-Allee 11, D-89081 Ulm, Germany Email: amaresh.mishra@uni-ulm.de Oligo- and polythiophenes are widely used bench mark materials and have attracted a great deal of attention in recent years not only from the synthetic view point but also for their extensive application in solar cells, photovoltaics etc.1,2 The search for new functional materials with good performance as well as improvement in device fabrication has been a subject of importance. In advancement to dendrimer chemistry, a number of dendritic thiophene-ethynylene-based molecules with modied physical and chemical properties were designed and synthesized in a convergent way up to 3rd generation as 3D-analogues of linear oligomers and polymers. The synthesis, optical and electronic properties of these dendritic materials will be discussed, in dependence of the generational site and their relevance to organic electronics.
R S S R S S S S R S S R S S S R S S R S S S R R S S S S S S S R S S S S S S S S S S R S S S R S R S S R S S R S R
42 T T 12 A : R = TMS 42 T 12 A : R=H
1. 2.
McCullough, R. D. Adv. Mater., 1998, 10, 93. Cremer, J.; Mena-Osteritz, E.; Pschierer, N. G.; Mullen, K.; Buerle, P. Org. Biomol. Chem. 2005, 3, 985.
TH39 ENERGY MODULATED HETEROSTRUCTURES FOR CHARGE TRANSFER AND CONFINEMENT BASED ON CONJUGATED POLYMERS H. Favarim, D. Spadacio, V. Zucolotto, O. N. Oliveira Jr., F. E.G. Guimares Instituto de Fsica de So Carlos, Universidade de So Paulo, C.P. 369, 13560-970, So Carlos-SP, Brazil. It is demonstrated that multilayer structures with modulated band gaps can be used for efcient directional energy migration and carrier connement inside of a light emitting polymer sample. The lms were produced with the layer-by-layer technique (LBL) with a poly(p-phenylene vinylene) (PPV) precursor and a long chain dodecylbenzenesulfonate ion (DBS). DBS is incorporated selectively into the precursor chain, and with a rapid, low temperature conversion process (100oC) superstructures with variable HOMO-LUMO gap can be formed along the deposition direction by changing the DBS concentration. Structures with different stair-type energy modulations were produced, which are thermally stable and reproducible, as demonstrated by UV-VIVS absorption measurements. Energy differences of up to 0.5 eV between the lowest and highest conjugated layers inside the stair structure could be achieved. Photoluminescence and excitation spectroscopy measurements show that this energy separation is sufcient to produce an efcient charge transfer via Frster processes from the highest energy to the lowest band gap stair. Structures with 2 bilayers of PPV-DBS per stair display higher emission intensities compared to an equivalent highly conjugated PPV layer, demonstrating that emission can be improved in organic semiconductors by directional transfer and carrier connement in a very thin layer. An acceptor layer based on an azochromophore, separated by an optically inert spacer from the stair structure, was also used to probe the strength and the range of transfer process inside the energy modulated structures. These multilayer lms having a specic modulated energy gap, controlled at the nanometer level, can be used to enhance various organic optoelectronic and photovoltaic devices. It is envisaged that the wide energy modulation obtained for PPV can be used for producing a ne tuning of metal/polymer workfunctions in OLED devices as well as for transferring excitation way from the metal/polymer interfaces in order to avoid the well know plasmon luminescence quenching near the metallic interfaces [1].
Acknowledgment: FAPESP and CNPq. [1] C A. M. Borges, C. A Rodrigues, R. M. Faria; F. E. G. Guimares, Strong luminescence intensity modulation near a metal-organic interface, In: Synthetic Metals, 154 (2005) p. 133-136.
TH40 CORRELATED CHARGE TRANSPORT THROUGH MOTT-INSULATOR-METAL INTERFACES K. Yonemitsu1,2 and N. Maeshima1,3 1 Institute for Molecular Science, Okazaki 444-8585, Japan 2 Graduate University for Advanced Studies, Okazaki 444-8585, Japan
ABSTRACTS
3 Department of Chemistry, Tohoku University, Aoba-ku, Sendai 980-8578, Japan The characteristics of a eld-effect transistor (FET) fabricated on a crystal of an organic charge-transfer complex depend on the electronic state of the crystal. Ambipolar characteristics are observed for the Mott-insulator state by T. Hasegawa et al.,1 while unipolar ones for the band-insulator state. The mechanism is theoretically studied in one-dimensional electron systems. We show that combined effects of umklapp processes in a Mott insulator and Schottky barriers at the insulator-electrode interfaces lead to the ambipolar FET characteristics. This mechanism also leads to the nonrectifying characteristics for a simpler geometry (without a gate electrode) of a Mott insulator attached to two metallic electrodes with very different work functions. The Hubbard model for a Mott insulator is attached to the tight-binding model for metallic electrodes.2 Schottky barriers at the interfaces are reproduced by solving the Poisson equation for the electrostatic potential and adding its solution to these models. The time evolution of the current density is calculated by solving the time-dependent Schrdinger equation with different techniques: the Hartree-Fock approximation for large systems and the Lanczos exact-diagonalization method for small systems. The numerical results for Mott insulators show the ambipolar FET characteristics irrespective of the work-function difference. For the gate-bias polarity causing the higher Schottky barriers, the effect of electron correlation is weakened by deviating from half lling. This balancing always occurs in Mott insulators, reecting the collective charge transport due to electron correlation. The same mechanism is shown to lead to non-rectifying (rectifying) characteristics for a Mott (band) insulator attached to two metallic electrodes with very different work functions, as shown in the left (right) gure below. A remnant of rectier is observed just after the application of the electric eld to the Mott insulator. These results agree with recent experimental observation by T. Hasegawa et al.
Fig. 1: I-V characteristics for Mott (left panel) and band (right panel) insulators. The work-function differences R and L are such that the Fermi level of the right electrode, if isolated, is set at the lower Hubbard (left panel) and valence (right panel) band and that of the left electrode at about 3/4 times the charge gap higher than the upper Hubbard (left panel) and conduction (right panel) band.
1 T. Hasegawa, K. Mattenberger, J. Takeya, and B. Batlogg, Phys. Rev. B 69, 245115 (2004). 2 K. Yonemitsu, J. Phys. Soc. Jpn. 74, 2544 (2005). TH 41 TETRACENE LIGHT EMITTING TRANSISTORS ON UNUSUAL SUBSTRATES C. Santato1, F. Cicoira1,2, R. Zamboni1, M. Muccini1
1Consiglio Nazionale delle Ricerche (CNR), Istituto per lo Studio dei Materiali Nanostrutturati, Via Gobetti 101, 40129 Bologna, Italy. 2Present address: Universit du Qubec-INRS-EMT, 1650, boulevard L. Boulet, Varennes (QC) J3X 1S2, Canada.
Light Emitting Field Effect Transistors (LETs) constitute a class of optoelectronic devices integrating the switching function of a transistor with the light emission. They are attractive since the gate bias allows to minimize the unbalanced number of holes and electrons in the active layer, a crucial topic to obtain high exciton density, and to control the location of the exciton recombination region in the transistor channel. We produced LETs based on vacuum-sublimated tetracene lms deposited onto SiO2/n-Si and exible plastic (e.g. Mylar foils) substrates1. To investigate the underlying physics of the device, we employed a bottom contact device structure based on concentric Au source/drain electrodes deposited onto SiO2 dielectric via a molecular adhesion layer2. The shape of the electrodes allowed to circumventing parasitic currents due to the unpatterned organic semiconducting lm, thus permittingcontributing to an unambiguous interpretation of the optoelectronic characteristics of the device (i.e. transistor current vs light emission). The use of the molecular adhesion layer instead of standard metallic layers (e.g. Cr), enabling the minimization of electrodes thickness, weakens reduces the inuence of the pre-patterned substrate on the growth of the organic active lm, thus leading to better interconnected tetracene grains at the semiconductor/electrode interface. Moreover, it results in a smoother gate dielectric surface leading to increased tetracene grain size. Tetracene LETs employing a molecular adhesion layer exhibit signicantly higher hole FET mobility and electroluminescence intensity compared to results obtained on standard substrates. We investigated how deposition parameters such as the deposition ux, inuencing the early stages of the growth of the lms, inuence charge transport properties3. We observed that an increase in the deposition ux determines an increase in the substrate surface coverage leading to an increase in FET mobility. References [1] C. Santato et al., Tetracene light-emitting transistors on exible plastic substrates, Applied Physics Letters 2005, 86, 141106. [2] C. Santato et al., Organic Light-Emitting Transistors that use concentric source/drain electrodes on a molecular adhesion layer, accepted for publication in Applied Physics Letters. [3] F. Cicoira, C. Santato et al., Correlation between morphology and eld-effect transistor mobility in tetracene thin lms, Advanced Functional Materials 2005, 15, 375.
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TH42 ENERGY TRANSFER PROCESSES IN HYBRID ORGANIC-INORGANIC NANOCOMPOSITES Carsten Dosche,a Eyal Aharon,b Gitti L. Frey,b Anna Khlera University of Potsdam, Institute of Physics, Am Neuen Palais 10, 14469 Potsdam, Germany Technion, Department of Materials Engineering, Technion, Haifa 32000, Israel
a b
In the last years, organic light emitting devices (OLEDs) based on semiconducting polymers have emerged as one of the most potent technologies for the development of new display applications. However, the efciency of the emitting process in semiconducting polymers is dramatically affected by migration of excited states in the polymer matrix. For the optimisation of OLEDs it is therefore essential to retrieve the mechanisms of excited state migration and energy transfer processes. In general, excited state diffusion in polymers has to be devided in intrachain processes, where the excited state migration is located on a single polymer chain, and interchain processes. For interchain processes, the direction of migration and type of interaction can hardly be controled for bulk samples and lms. Hybrid organic-inorganic polymer composites provide an extremely attractive possibility for the design of model systems in which the energy transfer can be restricted to 1D energy transfer in channel type systems or 2D energy transfer in sandwich type systems. We have studied excited state diffusion on two different kinds of inorganic matrices. The one is represented by mesoporous silca composites, which are channel type materials. The other group of hybrid systems are SnS2 sandwich type composites. The photophysics of the composites were characterised using ultrafast time resolved uorescence spectroscopy and uorescence lifetime imaging microscopy (FLIM). The energy transfer was monitored in polyuorene composites by the poly-uorene emission lifetime Fig. 1: Emission from polyfluorene inside a and the effect of insertion of energy trapping sites, e.g. blends with acceptor molecules or selectively SnS2 composite crystal observed with generated uorenone defect sites. In SnS2 composites, we observe polyuorene emission lifetimes the FLIM setup.Upper right: >2 ns; of 400 ps, that are unusually long compared to polyuorene lms.1 In addition, there is a long lived left: < 2 ns. emission of 5 ns due to uorenone defects. These two components are spacially separated (Fig.1). We discuss the relationship between lifetime and ordered energy transfer in 1D and 2D systems. 1Wegner et. al., J. Chem. Phys. 124 (2006) 024907.
TH43 EFFECTS OF DIFFERENT LENGTH-SCALE ORGANIC-ORGANIC HETEROJUNCTIONS ON PHOTOPHYSICAL PROCESS. Annamaria Petrozza1, Igor Avilov2, Richard H. Friend1, Ji-Seon Kim1. 1Department of Physics, Cavendish Laboratory, University of Cambridge, J.J. Thomson Avenue, Cambridge CB3 0HE, UK. 2 Laboratory for Chemistry of Novel Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, Belgium Recent works have highlighted the importance of organic-organic semiconductor heterojunctions, in particular interchain heterojunctions formed in blend systems1,2. However, there has been very little work to address the photophysical processes which depend on the nature of the organic interfaces (i.e. interchain vs intrachain) and the length-scale of these interfaces (i.e. from micron-scale in blends to molecular-scale in random copolymers). Here, we report the detailed studies of photophysical processes including triplet absorption and decay dynamics on a range of wellcontrolled organic-organic interfaces, which are formed both as a function of the polymer chain-length (molecular weight, MW) and of the different nature of molecular units present within the polymer chain (intrachain heterojunctions). We have studied spin-coated lms of poly (9,9-dioctyluorene-co-benzothiadiazole) (F8BT) of different molecular weights (Mn = 9K 255K) both in the pristine and annealed states and F8BT random copolymer (RC) synthesised by random copolymerisation with Poly(9,9-dioctyluorene-co-N(4-butylphenyl)diphenylamine) (TFB), which result in the presence of both strong electron acceptor and donor units within the polymer chain. Using a photoinduced absorption (PIA) spectroscopy we observe that (1) the triplet absorption increases in the pristine lms as the MW of F8BT decreases; (2) upon annealing above the glass transition temperature of F8BT triplet dynamics differ depending on the MW: high MW samples show a strong enhancement of the triplet absorption, whereas the lowest MW sample shows a decrease in the intensity of the PIA signal; (3) RC present a much stronger triplet absorption and the main T1 Tn transition band is blue-shifted compared both to pure F8BT and F8BT:TFB blends. Based on detailed intensity and frequency dependence PIA spectra analysis, we conclude that the triplet generation efciency based on the intersystem crossing (ISC) from singlet to triplet states is signicantly reduced in high molecular weight pristine lms, and the triplet lifetimes are enhanced upon annealing. We consider that these changes are strongly correlated with a solid state packing of F8BT molecules which varies as a function of molecular weight and upon annealing3, i.e. different packing structures will induce different relative population of the emissive states which are differently coupled to the non-emissive triplet states. Previous studies have demonstrated that the ISC process in blends systems is efciently mediated by interfaces induced excited states, such as very short lived inter-chain charge transfer (CT) states and long lived exciplex states2. We consider that in the RC the ISC process is even more efcient than in blend systems due to its long lived intra-chain CT state and a molecular-scale phase separation. Our results clearly demonstrate the importance of the nature of the organic-organic interfaces and the length-scale of these interfaces on photophysical processes. A potential control of these well-dened structures provides a powerful tool for the smart design of organic semiconductors for diversied applications. [1] A. Morteani et al, Adv. Mater. 15, 1708 (2003) [2] T. A. Ford et al., Phys. Rev. B 71, 125212 (2005) [3] C. Donley et al., J. Am. Chem. Soc. 127, 12890 (2005) Presenting author contact details: ap377@cam.ac.uk
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TH44 NANOSHUTTLES AND FORCE-ACTIVATED NANOADHESIVES Viola Vogel Department of Materials, ETH Zrich, Switzerland (viola.vogel@mat.ethz.ch). One key objective in bionanotechnology is to convert discoveries in the molecular sciences of how biological nanosystems work into new technologies even envisioning applications that can go far beyond their natural uses. Examples to be discussed will include the use of motor proteins for lab-on-the-chip applications and the utilization of bacterial adhesion proteins as force-enhanced nanoadhesives. The molecular motor protein project is motivated by the fact that a large number of specialized biological motors are used by cells to actively transport molecules and organelles along cytoskeletal laments to dened locations. This ATP-driven process enables cells to dynamically recongure their intracellular building blocks to meet specic cellular tasks. Borrowing from nature, we are developing insights into how to engineer nanoscale transport systems based on biological motors that allow to shuttle cargo between user-specied locations. Methods have been furthermore developed to control the speed of the nanoshuttles with light, and we evaluated how various synthetic polymers affect the lifetime of these biomolecules embedded in integrated hybrid devices. We could also show that kinesin-driven transport can be utilized to drive the selfassembly of mesoscopic structures that would not form in the absence of active transport. Asking how to utilize catch bonds that strengthen under loads was stimulated by our recent discovery that bacterial adhesion to surfaces can be enhanced under ow conditions. This is in contrast to common expectations since the adhesive strength of most receptor-ligand interactions is exponentially reduced if pulled apart by force. However, some receptor-ligand complexes exist that strengthen if strained which is the hallmark for catch bonds. Mechanisms of how these bonds work will be discussed as well as rst technical applications. Selected Readings: 1. H. Hess, G. D. Bachand, V. Vogel, Powering nanodevices with biomolecular motors, Chemistry, 10 (2004) 2110-2116 2. H. Hess, J. Clemmens, C. Brunner, R. Doot, S. Luna, K.-H. Ernst and V. Vogel, Molecular self-assembly of nanowires and nanospools using active transport, Nanoletters 5 (2005) 629-633 3. C. Brunner, K.-H. Ernst, H. Hess, V. Vogel, Lifetime of biomolecules in polymer-based hybrid nanodevices, Nanotechnology 15 (2004) S 540-548 4. W. E. Thomas, E. Trintchina, M. Forero, V. Vogel, E. Sokurenko, Bacterial adhesion to target cells enhanced by shear-force, Cell, 109 (2002) 913. 5. M. Forero, W. Thomas, C. Bland, L. Nilsson, E. Sokurenko, V. Vogel, A catch-bond based smart nano-adhesive sensitive to shear stress, Nanoletters, 4 (2004) 1593. 6. Thomas, W. E., Forero, M., Yakovenko, O., Nilsson, L., Vicini, P., Sokurenko, E., Vogel, V. (2005). Catch Bond Model Derived from Allostery Explains Force-Activated Bacterial Adhesion. Biophys J. 90 (2006) 753-64
TH45 NEW MOLECULAR AND SUPRAMOLECULAR MOTIFS FOR THE CONSTRUCTION OF ORGANIC SEMICONDUCTORS Klaus Mllen Max-Planck-Institute for Polymer Research, Mainz, 55128, Germany, muellen@mpip-mainz.mpg.de
Quite naturally, the ICSM community is interested in the performance of electronic devices. The race for record values should not obscure, however, the importance of gaining fundamental understanding of the underlying principles. Herein, a plea is made that chemical research into the synthesis and processing of electronic materials is an essential part of these endeavours. Some representative examples of synthesis-driven work are i) conjugation in 1, 2 and 3 dimensions including nanographenes and dendrimers, ii) conjugated macrocycles as building blocks of organic coaxial cables, iii) biosynthetic hybrids, and iv) columnar arrays as highly ordered supramolecular systems and channels for charge transport. These cases will be presented without too many synthetic details, but will emphasize the build-up of complex structural hierarchies for achieving increasingly complex electronic functions. The relationship of this approach to the miniaturization of devices, e.g., single-molecule eld effect transistors, is also described.
ABSTRACTS
H.-J. Rder, A. Rouhanipour, A. M. Talarico, V. Palermo, P. Samori, K. Mllen, Nature Materials 2006, 5, in press; F. Jckel, M. D. Watson, K. Mllen, J. P. Rabe, Phys. Rev. B 2006, 73, 454231 454236; J. Wu, J. Li, U. Kolb, K. Mllen, Chem. Comm. 2006, 48 50; J. Warman, J. Piris, W. Pisula, M. Kastler, D. Wasserfallen, K. Mllen, J. Am. Chem. Soc. 2005, 127, 14257 14262; E. V. Andreitchenko, C. G. Clark, R. E. Bauer, G. Lieser, K. Mllen, Angew. Chem., Int. Ed. 2005, 44, 2 9; L. Zhi, T. Gorelik, J. Wu, U. Kolb, K. Mllen, J. Am. Chem. Soc. 2005, 127, 12792 12793; F. Bonino, S. Burtti, P. Reale, B. Scrosati, L. Gherghel, J. Wu, K. Mllen, Adv. Mater. 2005, 17, 743 746; J. Li, A. C. Grimsdale, J. Wu, K. Mllen, J. Mater. Chem. 2005, 16, 96 100; S. Bernhardt, M. Baumgarten, W. Wagner, K. Mllen, J. Am. Chem. Soc. 2005, 127, 12392 12399; F. C. De Schryver, T. Vosch, M. Cotlet, M. van der Auweraer, K. Mllen, J. Hofkens, Acc. Chem. Res. 2005, 38, 514 522; W. Pisula, A. Menon, M. Stepputat, I. Lieberwirth, U. Kolb, A. Tracz, H. Sirringhaus, T. Pakula, K. Mllen, Adv. Mater. 2005, 17, 684 689; A. C. Grimsdale, K. Mllen, Angew. Chem., Int. Ed. 2005, 44, 5592 5629; F. Schindler, J. Jacob, A. C. Grimsdale, J. M. Lupton, U. Scherf, K. Mllen, J. Feldmann, Angew. Chem., Int. Ed. 2005, 44, 1520 1525.
TH46 EXPLORATION OF CHARGE TRANSFER SALTS BASED ON CYTOSINE-TCNQ DERIVATIVES Gunzi Saito Kyoto University, Japan One of the nucleobases, cytosine, afforded three kinds of CT salts with a variety of TCNQ derivatives (R-TCNQ): 1) Ionic insulators of (CHC+)(RTCNQ-OMe), 2) Fully ionic CT salts of (CHC+)(R-TCNQ) with conductivity less than 102 Scm1, and 3) Highly conductive and partially ionic CT salts of (CHC+)(R-TCNQ0.5)2, where (CHC+) is the hemiprotonated cytosine pair. The proton transfer interactions and complementary hydrogen bonds are the key factors to control the crystal and electronic structures of R-TCNQ for electronic conductors.
TH47 THE SLOW, HOT DEATH OF INTERLAYER COHERENCE IN -PHASE BEDT-TTF SUPERCONDUCTORS John Singleton,a Paul A. Goddardb, Arzhang Ardavanb, Alimamy Bangurac, Ross D. McDonalda, John Schlueterd aNational High Magnetic Field Laboratory, Los Alamos National Laboratory, TA-35, MS-E536 NM87545 USA. b Clarendon Laboratory, University of Oxford, Parks Road, Oxford, OX1 3PU, UK. cH.H. Wills Physics Laboratory, Bristol University, Tyndall Avenue, Bristol, BS9 1TL, UK. dMaterials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA. The -phase BEDT-TTF superconductors possess a very interesting (chemical-) pressure-temperature phase diagram which includes a Mott insulator, unusual superconductivity and the coexistence of superconductivity and antiferromagnetism. Lurking at temperatures just above the superconducting state is a poorly-understood phase variously referred to as a bad metal, dirty metal or paramagnetic metal. This phase appears to have some Fermi-liquid-like properties at low temperatures, but its conductivity tensor exhibits some unusual traits, especially as the temperature rises. One key question concerns the interlayer coherence of the electron orbitals, and whether it is destroyed by thermal uctuations as the temperature rises. It has been assumed that the criterion for this to occur is kBT > tz, where tz is an average interlayer transfer integral. This is sometimes known as Andersons criterion. Using magnetic elds of up to 45 T, we have studied angle-dependent magnetoresistance oscillations (AMROs) and related effects in -(BEDTTTF)2Cu(NCS)2 at temperatures of up to 50 K; the interlayer transfer integral in this material is known to be equivalent to 0.5 K in temperature units [1,2]. The phenomena measured include the so-called coherence peak or SQUIT, reckoned to be a denitive signature of interlayer coherence. The latter feature survives to suprisingly large temperatures (approximately 25 K). Indeed, we nd that all of the magnetotransport features can be described in terms of orbits on a three dimensional Fermi surface (strongly suggesting interlayer coherence), even at temperatures 80 times higher than suggested by Andersons criterion. The AMROs due to orbits on the quasi-one-dimensional and quasi-two-dimensional Fermi-surface sections are suppressed by rising temperature with a dependence that appears to be characteristic of small-angle phonon scattering. By contrast, the SQUIT decreases in amplitude rather more slowly with increasing temperature, and the background magnetoresistance at 45 T is relatively temperature independent. These features can be understood with reference to the characteristics of the quasiparticle k-space paths that give rise to the magnetoresistance. [1] Goddard, PA et al., Phys. Rev. B 69, 174509 (2004). [2] Singleton, J., et al., preprint.
TH48 NATURE OF PHOTO-INDUCED METALLIC PHASE IN (EDO-TTF)2PF6 Studied by Ultrafast IR Spectroscopy Ken Onda,1,2 Sho Ogihara,1 Tadahiko Ishikawa,1 Matthieu Chollet,1 Xiangfeng Shao,2,3 Hideki Yamochi,2,3 Gunzi Saito,4 and Shin-ya Koshihara1,2 1 Department of Materials Science, Tokyo Institute of Technology, Meguro, Tokyo, 152-8551 Japan 2 Non-equilibrium Dynamics Project, ERATO/JST, Tsukuba, Ibaraki, 305-0801 Japan 3 Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan 4 Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan A conducting charge-transfer complex (EDO-TTF)2PF6 shows metal-insulator (M-I) phase transition at near room temperature (Tc = 280 K) [1]. In addition this material shows ultrafast photo-induced insulator-to-metal (I-to-M) phase transition at temperatures less than Tc [2]. To investigate the mechanism of the ultrafast photo-induced I-to-M phase transition, we have been measuring reectivity change using infrared-to-visible tunable femtosecond lasers. We measured temporal proles of reectivity changes at 0.25 eV - 2.2 eV photon energies under the excitation of one of the charge transfer (CT) bands with 1.58 eV pulse, and found large and ultrafast reectivity change by 10% to 100% within pulse duration (~120 fs). Figure 1 shows the spectra of reectivity change at 3 ps at 180K along with that of thermally induced reectivity change from insulator phase (180 K) to metallic phase (290 K). Compared with these spectra, the reectivity change in the probe energies at around the higher CT band for insulator phase (1.0 eV - 2.2 eV) was very similar to that of thermally induced phase transition; however, the changes in the mid-gap state region for metallic state (less than 1.0 eV) differed considerably. This indicates that the nature of metallic phase induced by photon is different from thermally induced one. We also found that the decay proles of the reectivity change were accompanied with 0.5-ps or 1.0-ps period oscillation and these periods depended on character of CT bands. The
ABSTRACTS
dependence of excitation photon energy on decay prole also depended on character of CT bands, indicating that the ultrafast dynamics of photoinduced phase transition is strongly related to electronic transitions of the complex including CT bands. [1] A. Ota, H. Yamochi, G. Saito, J. Mater. Chem. 12, 2600 (2002). [2] M. Chollet, L. Guerin, N. Uchida et al. Science, 307, 86 (2005).
TH49 AB INITIO ELECTRONIC-STRUCTURE CALCULATIONS FOR SINGLE-COMPONENT MOLECULAR CONDUCTORS Shoji Ishibashi,1 Tomoyuki Tamura,1 Masanori Kohyama,2 Hisashi Tanaka,3 Madoka Tokumoto,3,7 Akiko Kobayashi,4 Hayao Kobayashi5,7 and Kiyoyuki Terakura6 1Research Institute for Computational Sciences (RICS), National Institute of Advanced Industrial Science and Technology (AIST) 2Research Institute for Ubiquitous Energy Devices (UBIQEN), AIST 3Nanotechnology Research Institute (NRI), AIST 4Research Centre for Spectrochemistry, Graduate School of Science, The University of Tokyo 5Institute for Molecular Science 6InstituteCreative Research Initiative Sousei, Hokkaido University 7JST-CREST Subsequent to the discovery of the rst single-component molecular metal Ni(tmdt)2 (tmdt = trimethylenetetrathiafulvalenedithiolate),1 various related compounds have been synthesized and they are forming a new class of materials. Au(tmdt)2 is an example2. The crystal structure of Au(tmdt)2 is very similar to that of Ni(tmdt)2, while their electronic properties are different from each other reecting the difference in the valence electron numbers. Au(tmdt)2 undergoes a magnetic phase transition,2 which is not observed for Ni(tmdt)2.1 As for Ni(tmdt)2, electronic structure calculations by Rovira et al.3 predicted two types of Fermi surfaces and recent magnetic-quantum-oscillation measurements4 conrmed the presence of the Fermi surfaces. In contrast, in the paramagnetic state of Au(tmdt)2, there is one type of Fermi surface showing a strong nesting character.5 Magnetic calculations for Au(tmdt)2 gave an antiferromagnetic ground state though the calculated magnetic moment seems to be underestimated.5 Another compound Au(tmstfdt)2 has a very similar crystal structure to that of Au(tmdt)2. The difference is that outermost four sulfur atoms are replaced by selenium atoms. In spite of the similarity in their crystal structures, the nesting characters of their Fermi surfaces are different from each other. The above three compounds are composed of planer molecules. We have also investigated compounds composed of twisted molecules Cu(dmdt)26 and Zn(tmdt)2.7 From non-magnetic calculations, it has been revealed both are semi-metals though the latter has only very tiny Fermi pockets. We made magnetic calculations for Cu(dmdt)2 and obtained a magnetic-moment value of 0.8 B/molecule, which is close to the experimental value. In addition to the calculations for solid states, the electronic structure for each molecule has been investigated as a function of dihedral angle between two ligands (tmdt or dmdt) to clarify the origin of the difference in the molecular shape. Ni(tmdt)2 and Au(tmdt)2 show total-energy minima at 0 degrees while Cu(dmdt)2 and Zn(tmdt)2 show their minima in the range 80-90 degrees.6,7 These results are consistent with the experimental ones. Anti-bonding orbitals between metal dxy and ligand S atoms are empty for Ni(tmdt)2 and Au(tmdt)2 and it is thought that planer arrangements are stabilized for these material. In contrast, for Cu(dmdt)2 and Zn(tmdt)2, such a stabilization mechanism seems not to work because of the lling of the 3d orbital. [1] H. Tanaka, Y. Okano, H. Kobayashi, W. Suzuki and A. Kobayashi, Science 291, 285 (2001). [2] W. Suzuki, E. Fujiwara, A. Kobayashi, Y. Fujishiro, E. Nishibori, M. Takata, M. Sakata, H. Fujiwara and H. Kobayashi, J. AM. Chem. Soc. 125, 1486 (2003). [3] C. Rovira, J.J. Novoa, J.-L. Mozos, P. Ordejn and E. Canadell, Phys. Rev. B 65, 081104(R) (2002). [4] H. Tanaka, M. Tokumoto, S. Ishibashi, D. Graf, E.S. Choi, J.S. Brooks, S. Yasuzuka, Y. Okano, H. Kobayashi and A. Kobayashi, J. Am. Chem. Soc. 126, 10518 (2004). [5] S. Ishibashi, H. Tanaka, M. Kohyama, M. Tokumoto, A. Kobayashi, H. Kobayashi and K. Terakura, J. Phys. Soc. Jpn. 74, 843 (2005). [6] H. Tanaka, H. Kobayashi and A. Kobayashi, J. Am. Chem. Soc. 124, 10002 (2002). [7] K. Yamamoto, E. Fujiwara, A. Kobayashi, Y. Fujishiro, E. Nishibori, M. Sakata, M. Takata, H. Tanaka, Y. Okano and H. Kobayashi, Chem. Lett. 34, 1090 (2005).
TH50 CHARGE CARRIER DYNAMICS IN THE VICINITY OF THE MOTT TRANSITION IN -(BEDT-TTF)2X Michael Dumm1, Daniel Faltermeier1, Natalia Drichko1, Martin Dressel1, Ccile Mzire2, Patrick Batail2 11. Physikalisches Institut, Universitt Stuttgart, 70550 Stuttgart, Germany 2Laboratoire CIMI, FRE 2447 CNRS-Universit dAngers, 49045 Angers, France Physics close to the Mott transition is one of the central issues in strongly correlated electron systems. Interactions between charge and spin degrees of freedom result in rich phase diagrams including insulating, antiferromagnetic, exotic metallic and superconducting phases. The quasi 2D organic charge-transfer salts -(BEDT-TTF)2X are model compounds for these phenomena. On cooling down the materials, -(BEDT-TTF)2Cu[N(CN)2]Cl goes through a sequence of semiconducting, Mott insulating and antiferromagnetically ordered states while -(BEDT-TTF)2Cu[N(CN)2]Br goes through a sequence of semiconducting, bad metal, strongly correlated Fermi liquid and superconducting states. Here, we present a comprehensive study of the charge dynamics at the border between Mott insulating and Fermi liquid states which gives insights into the inuence of electronic correlations on the properties itinerant and localized charge carriers. The Mott transition from the insulating to the metallic part of the phase diagram is achieved by changing the spacing between the molecules, i.e., by changing the width of the conduction band. We controlled the bandwidth by a systematic variation of the Br content in the anions X = Cu[N(CN)2]BrxCl1x .
ABSTRACTS
Single crystals of -(BEDT-TTF)2Cu[N(CN)2]BrxCl1x were measured by polarized infrared spectroscopy as a function of temperature (5 K < T < 300 K), frequency (50 cm1 < < 10000 cm1) and Br-substitution (x = 0%, 42%, 73%, 85%, and 90%). At low temperatures, in the insulating Cl-rich samples an energy gap is observed which extends to approximately 1000 cm1 for T 0 K. With increasing Br concentration, spectral weight shifts into the gap region and eventually lls it up completely. As these compounds (x = 73%, 85% and 90%) become metallic at low temperatures, a Drude-like component develops due to the coherent quasiparticles in the far-infrared spectral region. The scattering rate of these itinerant charge carriers increases quadratic in frequency indicating strong electronic correlations which is in agreement with the T2 dependence of the dc resistivity and the predictions of Fermi liquid theory. A detailed analysis of the frequency and temperature dependence of the optical conductivity at mid-infrared frequencies helped us to clearly distinguish between contributions of itinerant and localized charge carriers. The mid-infrared absorptions can be separated into a transition between the two Hubbard bands around 2000 cm-1 and an absorption due to the charge transfer between the two molecules of a (BEDT-TTF)2 dimer. The intensity of the former correlates with the intensity of the Drude-like component we observed at low temperatures in the far infrared, while the latter is coupled to the totally symmetric vibronic modes. Interestingly, if we subtract the intra-dimer excitation from the spectra, we obtain a very similar optical conductivity along both in-plane directions, except for the absolute values which are 20% higher along a axis.
TH51 UNCONVENTIONAL INTERLAYER MAGNETOTRANSPORT IN THE WEAKLY INCOHERENT REGIME M. V. Kartsovnik,a W. Biberacher,a S. V. Simonov,b D. Andres,a N. D. Kushch,c H. Mller,d and I. Sheikine a Walther-Meissner-Institut, Bayerische Akademie derWissenschaften, D-85748 Garching, Germany b Institute of Solid State Physics, Russian Academy of Sciences, 142432 Chernogolovka, Russia c Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernoglovka, Russia d European Synchrotron Radiation Facility, F-38043Grenoble, France e Grenoble High Magnetic Field Laboratory, CNRS, BP 166, 38042 Grenoble Cedex 9, France The breakdown of the interlayer coherency of the charge transport is an important issue in understanding electronic properties and ground states in many quasi-two-dimensional materials, such as, for example, molecular conductors and layered metal-oxide superconductors. It was recently found that samples of the layered organic conductor -(BEDT-TTF)2KHg(SCN)4, depending on the crystal quality, exhibit either a coherent or weakly incoherent interlayer transport.1 A comparison between different samples, thus, gives an opportunity to directly draw out features characteristic of the interlayer incoherency. Here, we present comparative studies of the coherent and weakly incoherent interlayer magnetotransport in -(BEDTTTF)2KHg(SCN)4 as a function of the strength and orientation of magnetic eld at different temperatures and pressures. The cleanest samples display the behaviour typical of a highly anisotropic yet three-dimensional Fermi liquid.2 In particular, the angle-dependent magnetoresistance shows a sharp peak structure centered at the eld orientation parallel to the conducting layers, which is a ngerprint of a slightly warped three-dimensional Fermi surface.3 A drastically different behaviour is observed in the weakly incoherent regime obtained on lower quality samples. The angular dependence of the interlayer magnetoresistance undergoes a crossover from a conventional form (low magnetic elds) to an anomalous one (high elds, above ~1 T). The latter turns out to be largely independent of both the strength and orientation of the in-plane eld component, in striking contrast to the existing Fermi liquid theories. Based on the comparison between the low-pressure and high-pressure electronic states of -(BEDT-TTF)2KHg(SCN)4 as well as on some previously reported data on other highly anisotropic compounds,4-7 we argue that the main features of the incoherent interlayer magnetotransport are basically insensitive to the topology of the in-plane Fermi surface. We discuss the role of different scattering mechanisms in destroying the interlayer coherency and possible reasons for the anomalous magnetoresistance in the incoherent regime. [1] M. V. Kartsovnik, D. Andres, S. V. Simonov, W. Biberacher, I. Sheikin, N. D. Kushch, and H. Mller, cond-mat/0512455, submitted to Phys. Rev. Lett. [2] M. V. Kartsovnik, Chem. Rev. 104 (2004) 5737. [3] P. Moses and R. H. McKenzie, Phys. Rev. B 60 (1999) 7998. [4] E. I. Chashechkina and P. Chaikin, Phys. Rev. Lett. 80 (1998) 2181. [5] H. Kang, Y. J. Jo, and W. Kang, Phys. Rev. B 69 (2004). [6] M. Kuraguchi, E. Ohmichi, T. Osada, and Y. Shiraki, Synth. Met. 133-134 (2003) 113. [7] J. Wosnitza, J. Hagel, J. S. Qualls, et al., Phys. Rev. B 65 (2002) 180506(R).
TH52 DISPERSIONS AND ORDERED ASSEMBLIES OF CARBON NANOTUBES Philippe Poulin Centre de Recherche Paul Pascal CNRS, Bordeaux, France We study the phase behavior of nanotube suspensions stabilized by surfactants or amphiphilic polymers. Varying the composition of the dispersion media allows the interaction potential between the nanotubes to be nely tuned. As a consequence, it is possible to quantitatively analyze important phenomena such as percolation or liquid crystalline phase transitions. In particular, we describe how the percolation threshold of rod-like particles is quantitatively decreased in the presence of attractive interactions (1). We show that rod-like particles respond much more strongly than spheres to attractive interactions; strengthening thereby the technological interest of carbon nanotubes to achieve low percolation thresholds for electrostatic dissipation or electromagnetic shielding. By contrast, carbon nanotubes which experience repulsive interactions can spontaneously order and form liquid crystalline solutions (2). Aligning and packing nanotubes is a major challenge to obtain macroscopic materials with improved properties. We will briey discuss at the end of the presentation, our latest results concerning the fabrication of bers of aligned nanotubes (3). In particular, we will present new treatments of these bers which lead to unusual mechanical properties and shape memory effects with giant stress recovery (4).
ABSTRACTS
(1) (2) (3) (4)
B. Vigolo, C. Coulon, M. Maugey, C. Zakri, P. Poulin, Science 2005. S. Badaire, C. Zakri, M. Maugey, A. Derr, J. Barisci, G. Wallace, P. Poulin, Adv. Mat. 2005. P. Miaudet, M. Maugey, A. Derr, V. Pichot, P. Launois, P. Poulin, C. Zakri, Nanoletters 2005. P. Miaudet, A. Derr, M. Maugey, C. Zakri, P. Poulin, in preparation.
TH53 CONTROL OF CARRIER DENSITY BY THE SOLUTION METHOD IN CARBON NANOTUBE TRANSISTORS T. Takenobu1, T. Kanbara1,2, N. Akima1, M. Shiraishi3, T. Tsukagoshi2,4, H. Kataura5, Y. Aoyagi2, and Y. Iwasa1 1IMR, Tohoku Univ., Sendai, Japan, and CREST-JST, Kawaguchi, Japan 2RIKEN, Wako, Japan 3Graduate School of Engineering Science, Osaka Univ., Toyonaka, Japan 4PRESTO-JST, Kawaguchi, Japan 5Nanotech. Res. Ins., AIST, Ibaraki, Japan Single-walled carbon nanotube (SWNT) is the most promising material for molecular based transistors because of ultimate miniaturization and tremendous high mobility. For further evolution of SWNT electronics, Fermi energy engineering of carrier type and density in air are important for constructing complementary electronics. In general, the nanotube transistor is very sensitive to the presence of air. Thus, a stable carrier control method is highly desirable. Recently, several doping techniques have been demonstrated, however, a controllable doping technique that can be used in an ambient environment and would not degrade the SWNT has yet to be developed. Herein, we present simple stable methods for precise control of hole density in SWNT transistors by solution-processed chemical doping. Toward this goal, we have investigated the use of organic molecules, which adsorb on carbon nanotubes from solution. The charge transfer between SWNTs and organic molecules is controlled by the ionization energy or the electron afnity of guest organic molecules and the concentration of molecules [1]. We conrmed controllable carrier doping in SWNT lms using optical absorption measurements [1], then applied this technique in an SWNT-bundle Field Effect Transistors (FETs) [2]. The nanotube transistors controlled in this manner displayed continuous and precise shifts of threshold voltages even in air (see gure). This is the rst p-type controllable doping in SWNT-FETs. The key for further evolution of SWNT electronics is the tuning of switching voltages since this is directly related to the power consumption of the devices. The current study provides a simple way to control channel charge density continuously at a very low density level, which should be useful for fabricating SWNT FETs with improved functionality.
F 4TCNQ doping
) A n -300 (
-200 -100 0 -20 -400 V D= -50 mV
ID
-10
V (V)
G
10
20
Figure. Transfer characteristics of the SWNT FET upon dispensing of a drop of F4TCNQ/solution. References [1] T. Takenobu et al., Nat. Mat. 2003, 2, 687., M. Shiraishi et al., Phys. Rev. B 2005, 71, 125419. [2] T. Takenobu et al., Adv. Mater. 2005, 17, 2430
TH54 THE ROLE OF THE ENCAGED SPECIES ON FULLERENE STABILITY: DYSPROSIUM-BASED ENDOHEDRAL FULLERENES Lothar Dunsch and Shangfeng Yang Group of Electrochemistry and Conducting Polymers, Leibniz-Institute for Solid State and Materials Research Dresden, D-01171 Dresden, Germany Among endohedral fullerenes the dysprosium-based structures received a strong interest as the new and highly selective route to trimetallic nitride endohedral fullerenes (clusterfullerenes) [1] opened the gate to new fullerenes not isolated so far. In this way tridysprosium nitride clusterfullerenes the Dy3N@C2n (38 n 49) family have been isolated, which represents the largest clusterfullerene family explored up to now, extending even the Tm3N@C2n (38 n 44) family presented earlier by our group [2,3]. 10 Dy3N@C2n clusterfullerenes (39 n 44) have been isolated with extended different cage sizes and cage symmetries [4]. In particular a third isomer of Dy3N@C80 was isolated for the rst time [5] as well as two isomers for Dy3N@C78 and Dy3N@C84. The formation of the clusterfullerenes is in the case of dysprosium accompanied by multimetallofullerenes with very large cage sizes. We have produced for the rst time a stable Dy2@C100 dimetallofullerene, the largest fullerene cage isolated to date, Dy3@C98 trimetallofullerene and two Dy2@C94 isomers at high yields [6]. Thus we have extended the fullerene cage size from C94 up to C100. All structures were characterized by high performance liquid chromatography (HPLC), mass spectrometry and UV-Vis-NIR spectroscopy. The UV-Vis-NIR spectroscopic study indicates that the Dy3N@C2n clusterfullerenes with small cages (n=39-41) are large band-gap (1.38 1.51 eV) materials while the band-gaps for those with larger cages (n=42-44) and the four multimetallofullerenes Dy2@C100, Dy3@C98 and two Dy2@C94 isomers are signicantly smaller (0.78 - 0.91 eV). Since the stability of the fullerenes is strongly correlated with the optical band-gap, the differences for these endohedral fullerenes are used to discuss their stability with respect to the charge distribution in the endohedral fullerene dependent on the type of the encaged structure.
ABSTRACTS
REFERENCES [1] L. Dunsch, M. Krause, J. Noack, P. Georgi. J. Phys. Chem. Sol. 2004, 65, 309. [2] M. Krause, J. Wong, L. Dunsch, Chem. Eur. J., 2005, 11, 706. [3] M. Krause, X. Liu, J. Wong, T. Pichler, M. Knupfer, L. Dunsch, J. Phys. Chem. A, 2005, 109, 7088. [4] S. Yang, L. Dunsch, J. Phys. Chem. B 2005, 109, 12320. [5] S. Yang, L. Dunsch, Chem. Eur. J. 2006, 12, 413. [6] S. Yang, L. Dunsch, Angew. Chem. 2006, in press.
TH55 DESIGN, SYNTHESIS, AND ELECTROCHEMICAL CHARACTERISTICS OF HIGHLY NEAR-INFRARED ABSORBING EMERALD GREEN [60]FULLERENE ACCEPTORS Long Y. Chiang,a Taizoon Canteenwala,a and Hsing-Ling Wangb a Department of Chemistry, University of Massachusetts Lowell, Lowell, MA 0185, USA (Emial: Long_Chiang@uml.edu) b Bioscience Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA We unexpectly found a new approach toward the synthesis of Emerald Green [60]Fullerene (EFn) compounds in gram-quantity by using hexaanionic C60 intermediate (C606), as a reagent in one-pot reaction, for attaching 6 addends on one C60 cage. Ultra-high negative charge density with repulsion among 6 same charges in a close vicinity on the spherical surface of only 10 in diameter makes the chemistry versatile for new derivatives preparation. The nding led to synthesis of dodecaalkylated emerald green fullerenes C60[C(CH3)(CO2Et)2]6 (EF-6MC2) as a new class of C60 hexaadducts exhibiting near-infrared absorption at 760 ( = 6,632 L/mol-cm) and 850 ( = 12,755 L/mol-cm) nm and named according to their intrinsic green color. X-ray diffraction data analysis of the heptad EF-6MC4t in a single crystal form allowed us to mark all sp3 cage carbon positions each bound with one di(t-butyl)--methylmalonate subunit. Structurally, formation of a double-triphenylene interconnected all-trans 18trannulene electronic conguration on the fullerene cage was proposed to be responsible for its near(a) Front view (b) Back view IR absorption. Electrochemical characteristics of highly symmetrical EF-6MC2 molecules in solution substantiated high multielectron accepting capability with a low rst reduction potential in a similar value as that of pristine C60, indicating no reduction of electron accepting capability of the fullerene cage even after functionalization with 6 addends. Coupling of these near-IR optical properties with electron R accepting characteristics of the C60 cage may allow the utility of EF-6MCn as n-type photosensitizers R in conjunction with the devices addressing near-IR sensing and light energy harvesting, such as R R broadband photovoltaic cells, 700940 nm.
R : C(CH 3)(CO 2 -t-Bu) 2
TH56 ULTRASHORT PULSE MODE-LOCKED LASER BASED ON NANOTUBE SATURABLE ABSORBERS A.G. Rozhin1, V. Scardaci1, F. Wang1, F. Hennrich2, I. H. White1, W. I. Milne1, A. C. Ferrari1 1Department of Engineering, University of Cambridge, Cambridge, UK. 2Institut fur Nanotechnologie, Forschungszentrum Karlsruhe, Germany Saturable absorption makes carbon nanotubes (CNT) ideal building blocks for ultrafast optoelectronic devices, such as all-optical switches and passive laser mode-lockers1,2. Existing mode-locking technology based on semiconductor saturable absorption mirrors (SESAMs)3 requires molecular beam epitaxy of multiple quantum wells, followed by post-growth ion implantation. On the other hand CNT can be processed into devices by simple wet chemistry. Their band gap can be tuned by changing the average diameter distribution. This allows to cover a broad spectral range between 900 nm and 2500 nm. Here, we report the stable operation of an ultrafast fast (~600 fs) mode-locked laser utilising CNT-polymer lms as mode-lockers. These lms are fabricated combining polyvinyl alcohol or polycarbonate with CNT solutions. We demonstrate wide spectral tunability of the output laser pulse (from 1560 to 1530 nm), by adding a dispersion control element in the cavity4. The laser has a large (~10 dBm) dynamic range of operation in modelocking regime. The output pulses are stable for operation of more than 600 hours. The CNT mode-lockers are stable against laser and environment damage. Our simple wet chemistry fabrication process makes CNT based mode-lockers very cheap and easy to integrate in photonics systems. 1. Y.C. Chen et al., Appl. Phys. Lett. 81, 975 (2002) 2. A.G. Rozhin et al. Chem. Phys. Lett. 405, 288 (2005) 3. U. Keller, Nature 424, 831 (2003). 4. A. G. Rozhin et al. submitted (2005).
ABSTRACTS
TH57 STERICALLY HINDERED DIPHENYLAMINOFLUORENE-C60 DYADS AND TRIADS: SYNTHESIS, MULTIPHOTON ABSORPTION AND ENERGY-TRANSFER STUDIES Prashant A. Padmawar,a Joy E. Rogers,b Guang S. He,c Long Y. Chiang,* a Taizoon Canteenwala,a Loon-Seng Tan,* b Qingdong Zheng,c Jonathan E. Slagle,b Daniel G. McLean,b Paul A. Fleitz,b and Paras N. Prasadc a Department of Chemistry, University of Massachusetts Lowell, Lowell, MA 0185, USA (Emial: Long_Chiang@uml.edu) bMaterials & Manufacturing Directorate, Air Force Research Laboratory, AFRL/ML, Wright-Patterson Air Force Base, Dayton, OH 45433, USA (Email: Loon-seng.tan@wpafb.af.mil) c Institute for Lasers, Photonics and Biophotonics, and Department of Chemistry, State University of New York, Buffalo, NY 14260, USA O
H 61 N A series of fullerenyl(C60)-diphenylaminouorene(DPAF) dyads and triads, C60(>DPAFN Cn)x (x = 1 or 2), was synthesized and fully characterized. A salient feature of these [ C 6 0 ( > D P A F -C 2 ) ] chromophores is the C9-substitutions at the uorene moiety with two alkyl or alkylether 2 chains (Cn), especially the sterically hindered 3,5,5-trimethylhexyl groups that greatly [ C 6 0 ( > D P A F -C 9 ) 2 ] H3CO improve the solubility and impede the direct, intermolecular-stacking contact of the O C H3 O H 3C O fullerene cages and the DPAF components. Another important feature is the strained O CH 3 O cyclopropylcarbonyl connecter between the C60 cage and DPAF unit. We speculate that N the mechanism of photo-induced keto-enol tautomerization of the cyclopropylcarbonyl N moiety may be operating in extending the -conjugation length between the DPAF and C60, [ C 6 0 (> D P A F -C 2 M ) ] 2 resulting in enhancing the electronic interactions, molecular polarization, and ultimately [ C 60 (> D P A F -C 2 M ) 2 ] the multiphoton absorption cross-sections. It is noteworthy that C60(>DPAF-Cn) and C60(>DPAF-Cn)2 are the rst examples of C60-containing compounds showing high three-photon absorptivity (3PA); specically, C60(>DPAFC9)2 exhibits large 2PA and 3PA cross-sections at the values of 622 1048 cm4sec photon-1-molecule-1 and 6.30 1025 cm6/GW2, respectively. The transient absorption data from femtosecond pump-probe experiments at 800 nm and nanosecond laser ash photolysis at 355 nm conrmed unambiguously the occurrence of two-photon excitation processes of C60(>DPAF-C9) in air-saturated benzene and a subsequent efcient energy transfer from the two-photon pumped DPAF-C9 moiety to the C60 cage. O
TH58 COHERENT PHONONS IN CARBON-BASED NANOSTRUCTURES: PROBING MOLECULAR DYNAMICS IN THE TIME DOMAIN Guglielmo Lanzani1; Moreno Meneghetti2; Enzo Menna2; Giulio Cerullo 1; Cristian Manzoni1;Alessio Gambetta1; Christoph Gadermaier1 S. Tretiak3, A. Piryatinski3, A. Saxena3, R.L. Martin3, A.R. Bishop3 1Dip. di Fisica, Politecnico di Milano, INFM-CNR, P.za. L. da Vinci 32, 20133, Milano (I) 2 Dep. of Chemical Sciences, University of Padova, Via Marzolo1 35131, Padova(I) 3 Theoretical Division and Center for Nonlinear Studies, Center for Integrated Nanotechnology, Los Alamos National Laboratory, Los Alamos, NM 87545 Photophysics in Single Walled Carbon Nanotubes, SWCNT-PEG, prepared by HiPco embedded PMMA is investigated with cw and pulse photoexcitation. Using ultra-short pulses in the visible and near infrared, with time duration of 7 fs and 20 fs respectively, pump-probe spectroscopy is carried out in SWCNT-PEG lms in air at room temperature. Photo-bleaching recovery and photoinduced absorption build-up, upon excitation into the second absorption band, are time resolved providing a time constant of 40 plus/minus 5 fs. This is associated to exciton relaxation within semiconducting NT. The role of exciton-exciton non-radiative annihilation is investigated by carrying out density dependent and three pulse experiments. The process of second Exciton regeneration from rst exciton annihilation is demonstrated. When using the shortest pulses (sub-10 fs) coherent phonons are clearly detected in the transmission difference traces. A radial breathing mode (RBM) at 250 wavenumber is observed, with dephasing of 1.2 ps. Anharmonic coupling between the RBM mode and the G-mode is detected for the rst time in the time domain. Molecular dynamics simulation give full account for the process. Finally, the quasi-steady state photoexcited population is investigated by cw excitation at 2.3 and 1.3 eV. We observed photorefractivity in SWCNTPEG samples, in close analogy with conjugated polymers. The observation is rationalized by assuming that charges, which are photogenerated in the lms, can separate giving rise to local electric elds which in turn induce Stark shift of the excitonic resonance.
TH59 ABERRATION-CORRECTED SCANNING TRANSMISSION ELECTRON MICROSCOPY FOR THE ATOMIC AND ELECTRONIC STRUCTURE CHARACTERISATION OF NANOMATERIALS
ABSTRACTS
P.D. Nellist, E.C. Cosgriff, V.Nicolosi and J.N. Coleman Trinity College Dublin, School of Physics, Dublin 2, IRELAND In a scanning transmission electron microscope (STEM), the imaging electron optics are placed before the specimen to focus an electron beam to form a small electron probe that is scanned across a thin specimen. Various transmitted signals can be detected and displayed as a function of probe position to form an image. In particular, high angle elastic scattering can be detected by an annular dark-eld (ADF) detector to form an
image that depends strongly on the atomic number of the species illuminated (Z-contrast). Lower angle scattered electrons can be passed through a spectrometer to form an electron energy-loss spectrum (EELS). Analysis of near-edge ne structure in EELS allows measurements of electronic structure on extremely small length scales. Recently, electron-optical correctors for the inherent spherical aberration of electron lenses has enabled dramatic improvements in STEM spatial resolution, with corrected instruments now routinely achieving sub-angstrom resolution [1]. In addition to improving the resolution, a benet of aberration correction that will perhaps turn out to be an even more epoch-dening advance in electron microscopy is the increased beam current that becomes available. It is likely that elemental mapping by electron energy-loss spectroscopy at 1-2 angstrom resolution will become possible in a minute or so for a 256 by 256 pixel elemental map. We will discuss how these developments can impact the structural analysis of nanomaterials. As an example of this, nanowire bundles of composition Mo6S9-xIx have diameters down to around 1 nm and are a class of material that are a promising alternative to carbon nanotubes [2]. Figure 1 shows how STEM can be used to provide atomic resolution images with the ADF detector providing much higher contrast for these inorganic nanowires than would be seen in conventional high-resolutino TEM.
8 nm
FIG. 1. (A) An annular dark-eld (ADF) STEM image of a Mo6S4.5I4.5 nanowire bundle showing a kink and the rotation of the bundle through a high symmetry direction. (B) An ADF STEM image of a Mo6S3I6 nanowire bundle along a high symmetry direction showing the atomic structure resolved. [1] P.D. Nellist et al. Science 305 (2004) 1741. [2] D. Vrbanic et al. Nanotechnology 15 (2004) 635.
TH60 PHOTOINDUCED ELECTRON TRANSFER IN DONOR-ACCEPTOR FULLERENE BASED COMPOUNDS IN SOLID STATE R.N. Lyubovskayaa*, D.V. Konareva, P.A. Troshina, R. Koeppeb, and N. S. Sariciftcib aInstitute of Problems of Chemical Physics RAS, hernogolovka, MD, 142432, Russia, E-mail: lyurn@icp.ac.ru bLinz Institute for Organic Solar Cells (LIOS), Johannes-Kepler-Universitt Linz, Austria 1. A series of molecular crystals of fullerenes with various organic donors with neutral ground state has been obtained. Electron transfer in these compounds induced by photoexcitation has been studied by light induced electron spin resonance (LESR)- and reaction yield detected magnetic resonance (RYDMR)- spectroscopy and the possibility of charge separation has been established [1-2]. 2. Photoconductivity and the effect of magnetic eld (B0<1 T) on photoconductivity have been studied for the rst time in single crystals of layered donor-acceptor complexes of fullerene 60 with tetrabenzyl-p-phenylenediamine (TBPDA(C60)2), tetrabenzo(1,2-bis[4H-thiopyran4-ylidine]ethene) (Bz4BTPE60) [3], and metal dithiocarbamates, (M= Cu, Co [M(dedtc)2]260) [4]. Spin mechanism of free charge carrier generation in magnetic eld was established. It is shown that mainly direct charge transfer from donor molecules to acceptor C60 ones and photoexcitation of chromophore donor component contribute to the generation of free charge carriers in fullerene complexes. 3. An efcient method for the synthesis of a range of novel pyrrollidinofullerenes bearing pyridyl groups (PyPyF) have been developed [5]. These compounds became available in bulk and, therefore, very promising for material science applications. PyPyF are capable of axial coordination with the central metal atom in various metal porphyrins (ZnPor) and phthalocyanines (ZnPc); such complexation provides a facile route to non-covalently linked donor-acceptor dyads. The complex formation between a set of different PyPyF and macrocyclic donors was studied in solution and in solid state by means of UV-VIS and NMR spectroscopy, uorescence measurements, X-ray single crystal diffraction and LESR spectroscopy. The efcient charge separation was observed in solid donor-acceptor dyads by LESR measurements that revealed separate signals from PyPyF radical anions and ZnPor+ or ZnPc+ radical cations in the spectra. The activation energies for electron transfer in the studied dyads were estimated to be in the range16-50 meV. 4. Some PyPyFs have been utilized as acceptor materials in organic solar cells comprising zinc phthalocyanine ZnPc as a donor component [6]. High solubility of PyPyFs in organic solvents allowed their wet-processing and deposition on the sublimed ZnPc layer by spin-coating. The PyPyF-ZnPc photovoltaic devices exhibited advanced performance over reference PCBM-ZnPc solar cells. This effect was attributed to the coordination complex formation at the interphase between ZnPc and PyPyFs layers that improve charge separation under solar cell operation conditions. 1. D.V. Konarev, R.N. Lyubovskaya, G. Zerza, S.N. Sariciftci, Mol. Cryst Liq. Cryst, 2005, 427, 315-333. 2. D.V. Lopatin, V.V. Rodaev, A.V. Umrikhin, D.V. Konarev, A.L. Litvinov, R.N. Lyubovskaya, J. Mat. Chem., 2005, 15, 657-660. 3. D. V. Konarev, D. V. Lopatin, V. V. Rodaev, A. V. Umrikhin, S. S. Khasanov, G. Saito, K. Nakasuji, A. L. Litvinov, R. N. Lyubovskaya, J. Phys. Chem. Sold. 2005, 66, 711-715 4. D.V. Konarev, A.Y. Kovalevsky, D.V. Lopatin, V.V. Rodaev, A.V. Umrikhin, E.I. Yudanova, P. Coppens, R.N. Lyubovskaya, G. Saito, Dalton Trans., 2005, 1821-1825 5. P. A. Troshin, A. S. Peregudov, D. Muhlbauer, R. N. Lyubovskaya, Eur. J. Org. Chem. 2005, 3064-3074. 6. R. Koeppe, N.S. Sariciftci, P.A. Troshin, R. N. Lyubovskaya, Appl. Phys. Lett. 2005, 87 (24), 244102
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TH61 SIZE-DEPENDENCE OF ELECTRONIC COUPLING REVEALED BY SELF-ASSEMBLING OLIGOTHIOPHENES Sebastian Westenhoff1*, Agnese Abrusci1, Jenny Clark1, Oliver Henze2, W. James Feast2, AlbertP. H. J. Schenning3,Carlos Silva4 1Cavendish Laboratory, University of Cambridge, Madingley Road, Cambridge CB3 0HE, United Kingdom 2Durham University, South Road, Durham DH1 3LE, United Kingdom 3Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands 4Dpartement de physique, Universit de Montral, C.P. 6128, succ. Centre-ville, Montral, Qubec H3C 3J7, Canada *Electronic mail: sw372@cam.ac.uk We investigate the photophysics of a recently developed series of ,-disubstituted oligothiophenes that self-assemble into chiral, soluable aggregates in semipolar solvents.1 The molecules are shown to be molecularly dissolved at high temperatures and to form chiral, vesicular aggregates at low temperatures governed by a fully reversible one-step phase transition. This makes them ideal model systems to study the effects of aggregation on the photophysics of conjugated compounds. The gure illustrates the phase transitions. The absoprtion and photo-luminescence spectra undergo dramatic changes due to the aggregation upon lowering the temperature. We show that the spectra and lifetimes are consistent with the formation of H-aggregates. Importantly, the magnitude of the splitting of the excited state decreases with increasing length of the oligomers.2 We compare the nding to computations of the electronic couplings beyond the point-dipole approximation that show excellent agreement with the experiments. The results are important for the understanding of the electronic coupling in extended conjugated systems. In particular, we will discuss the consequences for the spectroscopy of lms of regioregular P3HT, which is shown to form aggregates with weak interchain coupling despite their close interchain contact. (1) Schenning, A. P. H. J.; Kilbinger, A. F. M.; Biscarini, F.; Cavallini, M.; Cooper, H. J.; Derrick, P. J.; Feast, W. J.; Lazzaroni, R.; Leclere, P.; McDonell, L. A.; Meijer, E. W.; Meskers, S. C. J. Journal of the American Chemical Society 2002, 124, 1269. (2) Westenhoff, S.; Abrusci, A.; Feast, J. W.; Henze, O.; Kilbinger, A. F. M.; Schenning, A. P. H. J.; Silva, C. Advanced Materials, in press.
TH62 ELECTRONIC PROPERTIES OF HELICALLY-WRAPPED NANOTUBES Andrew Wall & Mauro Ferreira Physics Department, Trinity College Dublin College Green, Dublin 2 Nanotubes are an example of low-dimensional nanostructures that have been under intense scientic scrutiny for the last decade. Not only do they have physical properties that are remarkable, but they may be used to form composite materials which can have properties suitable for engineering applications. Much recent interest has focused on composites formed with one-dimensional structures, such as with polymers and with strands of DNA. Such materials are found to coat the surface of the nanotube walls, and to form materials with intriuging properties. In this light, we have carried out theoretical investigations into the interaction between metallic nanotubes and such one-dimensional structures, utilising a number of different models and techniques. Irrespective of the model, it is found that a helical ordering is energetically favoured for such systems. The effect such an ordering on the transport properties of the system, within the linear response regime, will be presented.
TH63 SOLUTION-PROCESSED THIN FILM TRANSISTORS USING RANDOM-NETWORK CARBON NANOTUBES M. Shiraishi1, S. Nakamura1, T. Fukao1, M. Ohishi1, T. Takenobu2, Y. Iwasa2, H. Kataura3 1 Graduate School of Engineering Science, Osaka Univ., Toyonaka 560-8531, Japan 2 IMR, Tohoku Univ., Sendai 980-8577, Japan, and CREST-JST, Kawaguchi 350-1111, Japan 3 Nanotech. Res. Ins., AIST, Ibaraki, Japan After the rst success in operating solution-processed thin lm eld effect transistors (FETs) using random-network single-walled carbon nanotubes (RN-SWNT) [1], drastic improvements in device performance has been carried out, for instance, compatibility of comparably larger mobility (3.6 cm2/Vs) and large on/off ratio (104) [2], realization of transparent and exible RN-SWNT-FETs [3], polarity control (carrier doping) using molecular encapsulation [4] and so on. Especially, it should be emphasized that this type of the FETs exhibited about 100 times larger mobility than solution-processed organic and polymer FETs and also exhibited comparable performance than pentacene FETs fabricated by an evaporation method. Hence this FET can be a pivotal device in the eld of molecular electronics. Here we present a recent progress and the latest analyses of the characteristics of the RN-SWNT-FETs. The SWNTs were synthesized by a laser ablation method and puried by a conventional method [5]. After the purication, they were ultrasonicated for 10 h to dissolve SWNT bundles and centrifuged for 30 min at 10000 rpm. Then, decantation to select well-debundled SWNTs was carried out and they were dispersed onto a Si substrate with a back gate FET structures. In pristine RN-SWNT-FETs, a clear ambipolar behaviour was observed in vacuum, although a p-type character was observed in air because of oxygen adsorption. From temperature evolution of a source-drain current, the combination of a tunnelling and a thermionic component in the current was seen, which indicates the RN-SWNT-FETs behave as Schottky-FETs as in the case of an individual SWNT-FETs although intertube carrier hopping is probably occurred in a channel. In other words, interface Schottky barrier (SB) plays a dominant role even in this type of FETs. Whilst the SB for hole was estimated to be about 170 meV, the SB can be modulated by carrier doping. For instance, in a tetracyano-p-quinodimethane (TCNQ) encapsulated p-type SWNT-FET, the SB for hole was decrease to be 70 meV. This change is ascribable to the carrier doping and the band modulation in the SWNTs. A similar change was observed in the case of n-type doped RN-SWNT-FETs by polyethyleneimine adsorption and the SB for electron was estimated to be 100 meV.
ABSTRACTS
This work is partially supported by NEDO. References [1] M. Shiraishi et al., CPL 394, 110 (2004). [2] T. Fukao, M. Shiraishi et al., JJAP accepted. [3] T. Takenobu et al., APL accepted. [4] T. Takenobu, M. Shiraishi et al., Nature Mat. 2, 687 (2003), M. Shiraishi et al., PRB 71, 125419 (2005), M. Shiraishi et al., APL 87, 93107 (2005), S. Nakamura, M. Shiraishi et al., APL submitted. [5] M. Shiraishi et al., CPL 358, 213 (2002).
80 40 0 -40 -80 300 K 194 K 143 K 113 K 94 K 80 K 10k 100k
TH64 DISENTANGLING ELECTRON AND HOLE CURRENTS IN BIPOLAR DEVICES H.H.P. Gommans, M. Kemerink, and R.A.J. Janssen Dept. of Applied Physics, Eindhoven University of Technology, The Netherlands The simultaneous presence of electrons and holes in photo-voltaic and light-emitting devices is obviously inherent to their operation. However, disentangling the electron and hole contributions to the total current in an operational device is a far from trivial task as both contributions strongly interact with each other via recombination and space charges.
-120 10
100
1k f [Hz]
Figure . Measured ca pacitance, C ( f), in a PP V :PCB M solar cell stru cture at 1.25 V for diffe rent temper ature s. Points are exper imen tal data, lines are mod el calculation s, using -6 the fo llowing (m ain) par ameters. 143 K: n = 1. 3 10 2 -7 2 -14 3 = 3 10 cm /s. 113 cm /Vs, p = 1 10 cm /Vs and -7 2 -8 2 = K: n = 1 10 cm /Vs, p = 2 10 cm /Vs and -15 3 -8 2 -9 3 10 cm /s. 94 K: = 3 10 cm /Vs, n p = 5 10 2 -15 3 cm /Vs and = 1 10 cm /s.
We have performed temperature and eld dependent admittance spectroscopy measurements on PPV:PCBM solar cells and PPV LEDs. Good agreement is found between the experimental data and the outcome of model calculations (see gure), in which the time-dependent drift-diffusion and continuity equations are numerically solved. Despite interference of trap-related contributions to the capacitance, reasonable estimates for the electron and hole mobilities as well as for the bimolecular recombination rate are obtained. This method allows one to investigate electron and hole transport simultaneously, i.e. without the need to build separate hole- and electron-only devices, by making use of the following scaling rules: (a) The well-known transit time effect, which shows up as a simultaneous decrease in conductance G and increase in capacitance C, remains present and can directly be related to the majority carrier mobility. The corresponding characteristic frequency scales with majV/L2 with V the applied bias, L the device thickness and maj the majority carrier mobility. (b) The onset frequency of the negative capacitance that is observed at low frequencies (see gure) can be related to the minority carrier mobility and is found to scale as with 0.6. (c) The depth of the negative capacitance is found to depend on the bimolecular recombination rate . On a more fundamental level, the present modelling is, to the best of our knowledge, the rst numerical treatment of bipolar AC transport under space-charge limited conditions. As such, our results are a formal justication of the common interpretation of negative capacitances at low frequencies in terms of a minority carrier current.
TH65 FROM CONDUCTIVE POLYMER COMPOSITES WITH CONTROLLED MORPHOLOGY TO SMART MATERIALS G. Boiteux1, Ye.P. Mamunya2, E.V. Lebedev2, C. Boullanger1, A. Adamczewski1, P. Cassagnau1, G. Seytre1 1 IMP UMR CNRS 5627, Laboratoire.des Matriaux Polymres et Biomatriaux, UCB-Lyon 1, 69 622 Villeurbanne Cedex, France,e-mail: Gisele.Boiteux@univ-lyon1.fr 2 Institute of Macromolecular Chemistry, National Academy of Sciences, Kiev, Ukraine 48, Kharkivske Chausse, 02160 Kyiv, Ukraine, e-mail: yemamun@i.kiev.ua The more common PTC materials are based on thermoplastic homopolymers or thermoplastic blends and thermoset matrices lled with carbon black. More recently attention has been paid to metallic ller [1-4] in view to support higher intensity and voltage working constraints. In this work, polypropylene PP or blends of polypropylene with polypropylene/co-polyamide 6, 6.6, 6.10) PP/CoPA are mixed with conductive iron particles to elaborate conductive polymer composites so called CPC which can present a PTC effect to be used in particular for a specic current limited function. A PTC element looks like a conductive sheet which, under heating, presents a change of its resistivity at so-called commutation temperature Tc within a narrow range of temperature. Conductive polymer composites based on polypropylene-polyamide copolymers blends lled with conductive iron possess the heterogeneous polymer matrix that leads to inhomogeneous spatial distribution of ller, namely the ller is localized in one phase or in one of two polymer phases. To explain more about, lled polymer phase (Pol-1+ Fe) is conductive while second polymer phase (Pol-2) is insulating. According to the relationship (Pol-1+ Fe)/Pol-2 three types of the composite structure can exist: 1) the matrix is insulating Pol-2 phase with inclusions of conductive (Pol-1+ Fe) phase, 2) pure Pol-2 and lled (Pol-1+ Fe) phases create the co-continuous structure, 3) the matrix is conductive (Pol-1+ Fe) phase with inclusions of nonconductive Pol-2 phase. The structure of type 2) exists in the region of phase inversion Pol-1/Pol-2. Due to this fact the percolation curve has two-step character with a presence of a plateau in the region of the phase inversion. These structure features lead to various conductive characteristics of composites: the percolation threshold fc of lled polymer blend is much lower than for individual lled polymers, for example fc = 5 % for the blend PP/CoPA lled with dispersed Fe versus fc = 13 to 25% for PP-Fe depending of the mixing tool and fc = 25 % for CoPA-Fe. Looking at the results of the analysis of the PTC effect, it can be observed that the electrical behaviour of the samples is depending quite a lot of the morphology of the systems under investigation. Double PTC will be shown in such smart materials. References : [1] S. K. Bhattacharya, Metal-Filled Polymers (Properties and Applications), Marcel Dekker ed, New-York, Basel 1986. [2] M. Narkis, J. Yacubowicz, A. Vaxman, A. Marmur, Polym. Eng. Sci., 26, 139-143 (1986).
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[3] Y.P. Mamunya, Y.V. Muzychenko, P. Pissis, E.V. Lebedev, M.I. Shut, Polymer Engineering and Science, 42 (1) (2002) 90-100 [4] G. Boiteux, C. Boullanger, P. Cassagnau, R. Fulchiron, G. Seytre, Macromolecular Symposia, in press Aknowledgements : The authors are very grateful for the nancial support and fruitful scientic collaboration of the Areva company and for NATO grant of Professor Y. Mamunya.
TH66 ENHANCEMENT OF THE SPONTANEOUS EMISSION RATE OF A FLUORESCENT MOLECULAR DYE IMBEDDED IN A MICROPILLAR MICROCAVITY A. M. Adawi1, A. Cadby1, L. G. Connolly1,W. C. Hung2, R. Dean1, A. Tahraoui2, A. M.Fox1, A. G. Cullis2, D. Sanvitto1, M. S. Skolnick1, & D. G. Lidzey1 1 Department of Physics and Astronomy, The University of Shefeld, Hicks Building, Hounseld Road, Shefeld S3 7RH, United Kingdom 2 Department of Electronic and Electrical Engineering, The University of Shefeld, Mappin Street, Shefeld S1 3JD, United Kingdom By placing a luminescent material within an optical microcavity, a range of fascinating fundamental phenomena can be explored, which in many cases have direct relevance in advanced opto-electronic devices. One structure of particular interest is the micro-pillar micro-cavity. Here an emitting layer is placed between two high reectivity mirrors separated by a distance of the order of the emitted wavelength of the emitted light. The mirrors are then etched vertically to create a pillar having a lateral dimension of several microns. The three dimensional optical connement imposed by the pillar can signicantly enhance the optical density of states at certain frequencies and therby increase spontaneous-emission rates. This process is termed the Purcell effect [1, 2]. Previous studies on micro-pillars have however been restricted to structures containing inorganic semiconductors such as In(Ga)As quantum dots or CdTe quantum wells as the active emitter. Due to the low binding energy of Mott-Wannier excitons, phenomena such as spontaneous emission rate enhancement is thus generally restricted to cryogenic temperatures. In contrast, organic materials support Frenkel excitons, which have large binding energies (~0.5 eV) and high oscillator strengths. This often permits enhanced light-matter interactions to be observed at room temperature. Organic materials are also characterised by relatively low refractive index (n ~ 1.6) compared to inorganic materials (e.g. n ~3.5 for GaAs). This suggests that organic materials are a very favourable system for achieving enhanced Purcell effects in a micropillar, as spontaneous emission enhancement is proportional to n-3 [2]. In this work [3] we demonstrate for the rst time the construction and evaluation of micro-pillars containing a layer of a uorescent organic-dye. Such structures are created from a planar organic microcavity using focused ion beam (FIB) lithography. Importantly, we show that such lithography can be employed to pattern an micropillar without creating unwanted damage to the organic active region. Two techniques were used to characterise the photoluminescence (PL) from the structures at room temperature; far-eld optical spectroscopy and time-resolved scanning near-eld optical microscopy. The results from the far-eld PL spectroscopy showed that the emission from the micropillar is composed of a series of sharp lines, providing evidence of three-dimensional optical connement. The linewidths of such optical modes are signicantly narrower than that of the planar cavity. The narrowest optical mode recorded had a linewidth of 0.33 nm - corresponding to a cavity Q-factor of 2100. Time-resolved scanning neareld mapping of the pillars showed that due to the relatively high Q-factor of the cavity and small mode volume, the radiative rate of the organic dye was enhanced by a factor up to 2 times. Such structures are anticipated to be of interest in the creation of new-types of low-threshold lasers and room-temperature single-photon light-sources for quantum-cryptography. [1] E.M. Purcell, Phys. Rev. 69 6 81-681 (1946) [2] Grard et al, Phys. Rev. Lett. 81 1110-1113 (1998) [3] Adawi et al, Advanced Materials (2006 in press)
TH 67 A HIGH WORK-FUNCTION CONDUCTING POLYMER FOR ENHANCED OLED PERFORMANCE C-H. Hsua, H. Skulasonb, S. Kimb, I. D. Parkerb, C. Tengstedtc, M. Fahlmanc, W. R. Salaneckd a: DuPont Displays, E. I. DuPont de Nemours & Co, Wilmington, DE. 19880, USA b: DuPont Displays, 6780 Cortona Drive, Santa Barbara, CA 93117, USA c: Department of Science and Technology, Linkping University, Norrkping, Sweden. d: Department of Surface Physics and Chemistry, Linkping University, Linkping, Sweden. The development of polymer based organic light-emitting diodes (p-OLEDs) is currently an area of intense interest for variety of display and lighting applications. At the moment, however, device performance needs improvement before achieving the levels required for commercial devices. In this presentation we report a signicant improvement in operating lifetimes (up to 20x) and operating efciency (2-3x), which closes the required performance gap. A simple replacement of the traditionally used Hole-Injection Layer (HIL), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid), (commonly known as PEDOT-PSSA, or Baytron-P from H. C. Starck Company) with PEDOT-poly(peruoroethylenesulfonic acid) (hereafter called DuPont Buffer, or DB) is the only processing change. The water-based DB dispersions can be formulated to be much less acidic than PEDOTPSSA, and coated in a variety of ways including spin-coating and ink-jet printing, which yield high quality lms. The lms still have hole injection characteristics even from pH neutral. Dried lms are transparent, electrically conducting (in the range of 10-6 to 10-1 S/cm), and have very low moisture uptake. The most important property of this new material is that dried lms possess very high work-function, up to 6.0eV, considerably higher than any alternative material. As a result, spontaneous hole-injection into light-emitting polymers with large ionization potentials (such as blue emitters) readily takes place across the interface between the materials. We demonstrate that the work-function is high enough to pin the resulting polaron-type level of the blue emitting poly(9,9-dioctyluorene) (PFO) polymer to the Fermi-level of the DB, thereby eliminating any charge-injection barriers and giving ohmic contacts. Furthermore, we show that the improved hole-injection into a commercial green light emitting material, LUMATION Green 1303 (Sumitomo Chemical Company), signicantly improves the device performance. These characteristics make this new material unique as a highly efcient hole-injection and hole-transporting layer for organic electronics.
ABSTRACTS
TH68 INFLUENCE OF DOPING ON SPIN DEPENDENT EXCITON FORMATION IN ALQ3 BASED OLEDS Fernando A. Castro1,2, George B. Silva1, Frank Nesch2, L. Zuppiroli3 and Carlos F. O. Graeff1 1 Departamento de Fsica e Matemtica, FFCLRP USP, Av. Bandeirantes 3900, 14040-901, Ribeiro Preto SP, Brazil 2 Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for Functional Polymers, berlandstr. 129, CH-8600 Dbendorf, Switzerland 3 Laboratoire doptolectronique ds matriaux molculaire, IMX-STI-EPFL, CH-1015 Lausanne, Switzerland Organic electronics has been the subject of intensive research during the last decade. For several applications, such as color displays or electrically pumped lasers, not only color tunability is important but also color purity or color saturation is an important factor. Doping a host matrix with highly uorescent dyes has proven to be an efcient strategy to achieve narrow emission spectra. Although doping may bring advantages, such as increased device lifetime and efciency, the mechanism of light generation is still not fully understood. In particular, the process of exciton formation on the doping molecule is subject of debate. In this work we have used electrically detected magnetic resonance (EDMR) to investigate the effect of doping and trapped charges on spin dependent exciton formation in aluminum (III) 8-hydroxyquinoline (Alq3) based OLEDs. As dopants we have used both 4-(dicyanomethylene)-2-methyl-6-{2-[(4-diphenylamino)-phenyl]ethyl}-4H-pyran (DCM-TPA) and 5,6,11,12-tetraphenylnaphthacene (Rubrene). We observed signicant differences (in g-factor, Hpp and amplitude) between EDMR signals from doped and undoped devices. The signal from DCM-TPA doped OLED was found to be strongly dependent on temperature, with signal intensity increasing by 2 orders of magnitude below 200 K. It was attributed to spin-dependent exciton formation, as found in undoped OLEDs1, which our results indicate that takes place between a trapped electron in the dopant and a hole from Alq3, in the current/bias range investigated. For Rubrene doped devices and undoped Alq3 OLEDs, the signal is only weakly dependent on temperature, and it is always much less intense for the doped sample. The observed differences between doped and undoped devices are discussed in terms of a change in exciton precursor reaction rates and/or decrease in spin coherence time. [1] C.F.O. Graeff, G.B. Silva, F. Nesch and L. Zuppiroli, European Physical Journal E 18, 21-28 (2005).
TH70 EXCITON-PHONON COUPLING IN TETRAFLUOROACRIDINE SINGLE CRYSTALS: FREE AND SELF-TRAPPED EXCITONS S. Tavazzi1, L. Raimondo1, P. Spearman1,2, M. Moret1, A. Papagni1, A. Sassella1, S. Trabattoni1 1 CNISM and Dipartimento di Scienza dei Materiali, Universit di Milano Bicocca, Via Cozzi 53, I-20125 Milano, Italy 2 School of Chemical and Pharmaceutical Sciences, Kingston University Kingston upon Thames, KT1 2EE, United Kingdom
In recent years there has been an increasing interest in the investigation of the electronic and optical properties of organic semiconductor materials due to their suitability for nano-technology applications. In particular, uorinated molecules are receiving a large interest for their applications as uorescent dopant molecules for organic light emitting devices, as uorescent probes in biological systems, as electron conductors in photovoltaic systems. Indeed, one or more hydrogen atoms can be substituted with uorine atoms, thus modifying the structural and optical properties in the solid state. Moreover, it is also possible by chemical substitution to convert an organic p semiconductor into a n semiconductor. Our interest was focused on a class of uorinated molecules, namely tetrauoroacridines, easily accessible from standard organic synthesis, in particular 1,2,3,4tetrauoro 7 (N,N)dimethylaminoacridine and 1,2,3,4 tetrauoro 7 metossiacridine, taken as prototypical members of this class of molecular solids. The optical properties of molecular solids are typically described in the framework of the theory of molecular excitons under a uctuating potential eld due to lattice vibrations. Indeed, excitons can be created in molecular solids by absorption of light. In principle, this elementary process can take place only with a photon with denite energy equal to that of the exciton with the same wave vector due to energy-momentum conservation. However, a real exciton, which is under a uctuating potential eld due to lattice vibrations, has a nite lifetime of being scattered to states with different wave vectors and the resulting energy width of the exciton is reected in shape and width of the optical bands. However, if the amplitude of the local potential uctuation is larger than the intermolecular transfer energy, one should consider a localized exciton subject to occasional transfer to neighboring site, rather than a free exciton subject to occasional scattering since the time for the exciton to be transferred to a neighboring site is longer than the minimum time required by the uncertainty principle for that the exciton experiences the local uctuation. In this situation, the spectral bands show Gaussian lineshape, the uctuation of local potential obeying a Gaussian distribution. On the basis of these considerations, the UV-VIS absorption and photoluminescence spectra of tetrauoroacridine single crystals are reported as taken at different temperatures down to 9 K and discussed. While the absorption spectra give information about the behavior of an exciton immediately after its creation, the emission tells us about the behavior immediately before its annihilation. Since these crystals present a face-toface arrangement of the molecules, exciton-phonon coupling has been found to cause self-trapping of the exciton. This is evident in the lineshape of the emission spectra and in the square-root dependence on temperature of the width at half maximum of the emission band, thus conrming the attribution to a localized state. Only at the highest temperatures, shoulders are detected on the high energy tail of the main band. These shoulders are attributed to the emission from the free exciton state observed if the temperature is high enough for the system to overcome the potential barrier separating the free and self-trapped states.
TH71 HYBRID METAL/ORGANIC SYSTEMS FOR PHOTONICS: POLYDIACETYLENES MONO-LAYERS ON Au NANOPARTICLES AND SELF-ASSEMBLED FILMS ON FUNCTIONALIZED SURFACES Marina Alloisio a, Carla Cuniberti a, Giovanna Dellepiane a, Anna Giusti a, Massimo Ottonelli a, Emilia Giorgetti b a INSTM Dipartimento di Chimica e Chimica Industriale, Universit di Genova, Via Dodecaneso 31 16146 Genova, Italia b INSTM Istituto dei Sistemi Complessi, CNR, Via Madonna del Piano 10 50019 Sesto Fiorentino (Fi), Italia The critical role in the performance of molecule-based optical and electronic devices played by the contacts between a metal surface and a thin lm
ABSTRACTS
of molecules is generally recognized as the most relevant obstacle to the development of molecular-electronics and has stimulated the growth of many different experimental approaches for preparing ordered arrays of molecules on metal as well as for their careful experimental scrutiny. Among organic materials with properties suitable for applications in this eld, the conjugated polymers play a signicant role. In particular, thin lms of polydiacetylenes show quite large values of the non-resonant third order hyperpolarizability which is strongly enhanced when they are deposited on nanostructured silver1. Self-assembled monolayers (SAMs) prepared on gold substrates from disulde compounds containing the photopolymerizable diacetylene groups have shown relevant durability and robustness as well as unique optical and electronic properties connected with the highly conjugated polydiacetylene backbone obtained after their photochemical treatments and its chromatic variations2,3. On these bases, we have recently synthesized a novel diacetylene disulde carrying carbazol substituents (CDS9) and, for comparison, also a symmetrical dialkyl-substituted diacetylene disulde (DS9). The polydiacetylene monolayers, obtained by UV-polymerization of CDS9 chemisorbed on Au (111) terraces grown on different substrates3 and on Ag-coated glass slides4, were characterized by optical, spectroscopic and micrographic techniques. In this communication some our recent results from Raman and microscopy studies of the photopolymerized CDS9 and DS9 chemisorbed on 20 nm rough Au lms sputtered onto glass slides surfaces functionalized with (3-mercaptopropyl)trimethoxysilane will be discussed. In Figure 1 are reported: (a) the polymerization scheme of self-assembled CDS9 and (b) the Raman spectrum of polyCDS9 monolayer. The presence in this spectrum of the conjugated C=C and C=C bond stretching signals at around 2100 and 1500 cm-1, respectively, indicates that the polymerization has occured with formation of the red-phase polymer and that both resonance and SERS effects contribute to the Raman spectrum. The larger C=C relative to C=C stretching intensity of the polymer and the remarkable contributions of the aromatic C=C of the carbazole group to the band at around 1500 cm-1 indicate, on the basis of SERS selection rules, that the double bonds of the polymeric backbone are nearly perpendicular to the plane of the metal, while the triple bonds are nearly parallel to it. These data agree with the assembly scheme described in (a) and have been corroborated by the results of the photopolymerization of DS9.
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Films of CDS9 and DS9 chemisorbed on colloidal gold nanoclusters have also been prepared and investigated. For this purpose, size-dened gold nanoparticles (AuNP) capped with both the diacetylene monomers have been synthetized in organic solvent and then deposited onto glass or quartz slides surfaces thiol-functionalized as above, following the scheme of Figure 2.
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Solutions and lms of the diacetylene-derivatized AuNPs have been studied by different morphological (TEM, optical microscope) and spectroscopic (UV-Vis, uorescence, Raman) techniques. The results obtained are fully consistent with the presence of interacting gold nanoparticles coated by CDS9 and DS9 chains. In particular, Raman spectra collected on samples exposed to UV irradiation clearly show the blue-phase polydiacetylene formation, so indicating that in these monolayer assemblies a high backbone conjugation is not hindered. References 1. Giorgetti, E.; Margheri, G.; Sottini, S.; Toci, C.; Muniz-Miranda, M.; Moroni, L.; Dellepiane, G. Phys. Chem. Chem. Phys. 2002, 4, 2762 2. Mowery, M.D.; Cook Smith, A.; Evans, C.E. Langmuir 2000, 16, 5998 3. Cavalleri, O.; Prato, M.; Chincarini, A.; Rolandi, R.; Canepa, M.; Gliozzi, A.; Alloisio, M.; Lavagnino, L.; Cuniberti C.; DellErba, C.; Dellepiane, G. Appl. Surf. Sci. 2005, 246, 403 4. Giorgetti, E.; Muniz.Miranda, M.; Margheri, G.; Giusti, A.; Sottini, S.; Alloisio, M.; Cuniberti C.; Dellepiane, G. Langmuir 2006, 22, 1129
TH72 COLOUR-TUNING OF LIGHT-EMITTING DEVICES BASED ON POLYFLUORINE DERIVATIVES THROUGH THE MASKLESS DYE-DIFFUSION TECHNIQUE Kazuya Tada and Mitsuyoshi Onoda Division of Electrical Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan E-mail: tada@eng.u-hyogo.ac.jp Organic light-emitting devices have been used in consumer products for many years. The spin-coating technology is known to yield thin polymer lms uniform enough to be used in light-emitting displays. However, if we target the patterned multi-colour display, this advantage turns into a kind of drawback, unless some patterning methods compatible with the spin-coating technology are available. To tackle this problem, we have proposed the maskless dye-diffusion technique, which is based on thermally activated diffusion of dye molecules from a reservoir lm to a receiver lm. Recently, we have studied the colour-tuning of poly(9,9-dioctyluorene) (PDOF) devices through the maskless dye-diffusion technique and have found that the Nile red, which was worked as a red-emitter in poly(N-vinylcarbazole) (PVK), is not suitable for PDOF1. Here we report that the maskless dye-diffusion of a red-emitting phosphorescent dye BtpIr into PDOF results in excellent red emission. Figure 1 shows the schematic procedure of the maskless dye-diffusion technique. A PDOF lm, which is indicated as receiver lm in the gure, was spin-coated on the lm from toluene solution on the PEDOT: PSS lm deposited on patterned ITO on a glass substrate. The dye reservoir lm was spin-coated on another glass plate from chloroform solution containing equivalent weights of PVK and one of the dyes indicated in Fig. 1.
ABSTRACTS
Then, the two polymer lms are brought into contact and selected ITO lms on the receiver lm are heated by means of the Joule heating to initiate the diffusion of dye molecules in the reservoir lm into the receiver lm. The vacuum deposition of MgAg electrode as cathode was carried out to complete the polymer light-emitting device. Figure 2 shows the emission spectra from devices using pristine PDOF and PDOF upon maskless dye-diffusion. The emission colour of PDOF which is initially blue modied to green peaked at around 500 nm after the diffusion of Coumarin 6. When Coumarin 6 is replaced with Nile red, the emission spectrum of the device becomes one consists of the original emission from PDOF and additional broad emission peaked at around 560 nm. The peak wavelength of the additional emission is much shorter than the case of PVK-based device, suggesting the exciplex formation between PDOF and Nile Red. However, by using BtpIr instead of Nile red, red emission was successfully obtained. [1] K. Tada and M. Onoda: Jpn. J. Appl. Phys. 44 (2005) 4167.
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Figure 2 Emission spe ctra of the polyme r light -em itting dev ices with pri stine, Couma rin 6-diffused, N ile red -diffu sed, and BtpIr -diffused PDOF.
TH73 RESONANCE ENERGY TRANSFER FROM ORGANIC CHROMOPHORES TO PCBM: A MECHANISM FOR IMPROVED EXCITON HARVESTING IN ORGANIC PHOTOVOLTAIC CELLS? Melissa A. Summers,1 Shawn R. Scully,1 Yuxiang Liu,2 Michael D. McGehee1 1. Materials Science & Engineering, 2. Department of Chemistry Stanford University, Stanford, CA 94305 USA The mechanism of charge separation in polymer/fullerene bulk heterojunction (BHJ) photovoltaic cells is usually described as electron transfer from the absorbing polymer to the fullerene, usually PCBM [(6,6)-phenyl C61 butyric acid methyl ester]. We consider the possibility of energy transfer from the polymer to PCBM followed by hole transfer from the PCBM to the polymer as an alternative mechanism for charge separation in these devices. We show evidence of efcient long-range resonance energy transfer from a red-emitting organic dye molecule (Nile Red) to PCBM: when low concentrations both molecules are blended in a polystyrene matrix, the quenching of Nile Red uorescence yields a Frster energy transfer radius R0 of about 3 nm (see illustration below).1 For a polymer/fullerene pair with this R0 value, our Frster energy transfer modelling predicts excellent exciton harvesting in a bilayer lm, resulting in a ~12 nm effective exciton diffusion length (LD), about double the usual LD measured for organic polymers. This would suggest that long-range energy transfer from conjugated polymers to PCBM improves the performance of these devices, and that we could utilize this mechanism in designing new cells. However, we show calculations indicating that the R0s of polymers such as MDMO-PPV and P3HT with PCBM are signicantly lower than the 3 nm calculated for Nile Red and PCBM, leading to little improvement in long-range exciton harvesting. Thus, while long-range resonance energy transfer from MDMO-PPV or P3HT to PCBM is not expected to signicantly improve exciton harvesting in blend or bilayer devices, an energy transfer mechanism is implicated in exciton splitting at the BHJ interface in the most efcient devices, where the phase separated polymer domain size does not exceed 5-10 nm.
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Liu, Y. X., Summers, M. A., Scully, S.R., McGehee, M. D., Journal of Applied Physics accepted.
TH74 FLEXIBLE, LONG LIVED, LARGE AREA ORGANIC SOLAR CELLS
a b
Linz Institute for Organic Solar Cells (LIOS), Johannes Kepler University Linz, Altenbergerstrasse 69, 4040 Linz, AUSTRIA NOVA-PLASMA Inc., 41 Durham, Dollard des Ormeaux, QC H9G 1Z9, CANADA
ABSTRACTS
Christoph Lungenschmieda, Gilles Dennlera, Gregory Czeremuszkinb, Mohamed Latrcheb, Helmut Neugebauera and Niyazi Serdar Sariciftcia
In this contribution we present large area plastic solar cells encapsulated in a new exible and transparent poly(ethylene naphthalate) (PEN)-based ultra-high barrier substrate. The barrier material is entirely fabricated by plasma enhanced chemical vapor deposition (PECVD). These foils show high transparency in the visible (>85 %), good resistance to common organic solvents and survive accelerated Calcium tests (50C, 85% relative humidity) for more than 1,000 hours. Poly(2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene-vinylene) (MDMO-PPV):1-(3-methoxycarbonyl)propyl-1-phenyl[6,6]C61 (PCBM) solar cells elaborated on and encapsulated with these foils have reached shelf life-times (power conversion efciency under AM1.5 conditions remaining above 50% of the initial value) exceeding 3,000 hours [1]. This time is comparable to that previously reported for the same material encapsulated between two glass plates [2]. We therefore attribute the origin of the degradation to the intrinsic instability of MDMO-PPV and not limited by inadequacy of our encapsulation solution. Other conjugated polymers like polythiophenes are known for a stability in atmosphere superior to that of PPV derivatives. Thus, we have observed that fabricating organic solar cells based on blends consisting of poly(3-hexylthiophene) and PCBM does not only allow higher power conversion efciencies, but also longer shelf-lifetimes using the same exible ultra-high barrier encapsulation solution. We have measured shelf life-times of 6,000 hours, or more than eight months. We furthermore present large area solar cells (12 cm) built on this ultra-high barrier foil. Increasing the surface area of solar cells the problem of increased series resistance in the indium-tin-oxide (ITO) transparent electrode becomes evident and can even dominate the current-voltage characteristics of the device under illumination. To fabricate efcient large area solar cells it is therefore necessary to connect several solar cells in series. We present a model calculation correlating the surface area of the solar cell with the conductivity of the ITO and the irradiated light intensity. While for high quality ITO on glass, power conversion efciencies of up to approximately 1.4% under AM1.5 conditions could be realized over an active area of 12 cm, the low conductivity ITO deposited on the ultra-high barrier limits the efciency to 0.5% for the same device geometry under the same conditions.
[1] G. Dennler, C. Lungenschmied, H. Neugebauer, N. S. Sariciftci, M. Latrche, G. Czeremuszkin and M. R. Wertheimer: A new encapsulation solution for exible organic solar cells. Thin Solid Films (in press) [2] H. Neugebauer, C. J. Brabec, J. C. Hummelen, and N. S. Sariciftci: Stability and photodegradation mechanisms of conjugated polymer/fullerene plastic solar cells. Sol. Energy Mater. Sol. Cells 61, 35 (2000)
TH76 SOLAR CELLS AND OLEDS WITH TRANSPARENT CARBON NANOTUBE ELECTRODES Anvar A. Zakhidov, Hasan Shodiev, Ross Ulbricht, Chris Williams, Mei Zhang, Sergey B. Lee, John Ferraris, Ray H. Baughman NanoTech Institute, The University of Texas at Dallas, Richardson, TX 75083, USA. We have recently developed a method to make mechanically strong and optically transparent multiwall carbon nanotube (T-CNT) sheets [1], which are chemically stable, mechanically strong and have a combination of other interesting properties. In the talk we will describe how this CNT sheets can be used as interfacial electrode for charge collection in two types of solar cells (SC): organic photovoltaic cells (OPV) and dye sensitized cells (DSC). This T-CNT lms have been used as charge injectors, instead of conventional ITO coatings in two types of organic LEDs: both in polymeric PLEDS and low molecular OLEDs. It is demonstrated, that T-CNT lms can be laminated on any exible substrates, starting from free standing aerogel T-CNT sheets, obtained by dry drawing self-assembly from a CNT-forest [1], and densied to thicknesses of 50-100 nm. Such a lm, with initial sheet resistance of 500 ohm/sq, should be rst coated by optimal layers of PEDOT-PSS for its planarization and further used as charge collecting/injecting porous three-dimensional network. The typical efciency of OPV solar cells based on PHT/PCBM bulk heterojunctions with T-CNT is ~ 2.4 % at low light intensity of 10 mW/cm2, due to low serial resistance. To increase the conductivity and electrochemical activity of such a novel transparent anode the T-CNT sheets are coated with highly conductive single wall tubes (SWCNT) from various ink-solutions and also by vacuum deposited metals and compared with pure multiwall T-CNT sheets. We show that the transparent sheets of SWCNT/MWCNT perform as a exible anode for polymeric bulk heterojunction solar cells (SC) combined with DSCs. Nanocomposite T-CNT sheets are good for electrochemical DSC SCs and can be used in tandems of polymeric and dye sensitized solar cells as transparent charge recombination or interconnect layers. The newest data on CNT sheets as hole injectors in OLEDs with polymers (MEH-PPV) and low molecular light emitting layers, combined with quantum dots (QD) will be also presented and discussed.
[1] M. Zhang, S. Fang, A. Zakhidov, S. B. Lee, A. Aliev, R.H. Baughman, Science, 309,(2005) 1215
TH77 EFFECT OF SOLUBLE FULLERENE ADDITION IN POLYMER:POLYMER SOLAR CELLS Y. Kim1,*, S. Cook2, S. M. Tuladhar1, J. Nelson1, J. R. Durrant2, and D. D. C. Bradley1,* 1Blackett Laboratory, Department of Physics, Imperial College London, Prince Consort Road, London SW7 2BW, UK (y.kim@ic.ac.uk, d.bradley@ ic.ac.uk) 2Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, UK Organic solar cells, based on polymers and/or small molecules, have recently exhibited improved power conversion efciency.1-3 The most versatile polymer for polymer based solar cells is regioregular poly(3-hexylthiophene) (P3HT) owing to its particular self-organising characteristics that help high charge carrier mobilities.4-5 The highest polymer solar cell performances have been achieved with devices made from blends of P3HT and a soluble fullerene. In contrast to the polymer:fullerene solar cells, the power conversion efciency of polymer:polymer solar cells lags far behind that required for commercialization, even though some improvement has been reported.6-8 The relatively low performance of polymer:polymer devices
ABSTRACTS
has been attributed to the low electron mobility of the electron-accepting polymers used and to the stable excitations generated at donor-acceptor interfaces.8,9 In our previous work, we showed that the addition of an electron-transporting polymer improved the nanomorphology of P3HT: soluble fullerene blend lms and enhanced the efciency of the corresponding devices.10 In this work, we have looked at adding a soluble fullerene component to polymer:polymer solar cells in order to investigate the effect on charge separation yields. The results of time-of-ight charge carrier mobility and transient absorption spectroscopy measurements, carried out in order to better understand the device performance, will be reported. [1] C. J. Brabec, Solar Energy Mater. Solar Cells, 83, 273 (2004). [2] S. R. Forrest, MRS Bulletin, 30, 28 (2005). [3] Y. Kim, S. Cook, S. M. Tuladhar, J. Nelson, J. R. Durrant, D. D. C. Bradley, M. Giles, I. McCulloch, C. S. Ha, and M. Ree, Nature Mater., 5, 197 (2006) and references therein. [4] H. Sirringhaus, N. Tessler, and R. H. Friend, Science, 280, 1741 (1998). [5] S. A. Choulis, Y. Kim, J. Nelson, D. D. C. Bradley, M. Giles, M. Shkunov, I. McCulloch, Appl. Phys. Lett., 85, 3890 (2004). [6] S. C. Veenstra, W. J. H. Verhees, J. M. Kroon, M. M. Koetse, J. Sweelssen, J. J. A. M. Bastiaansen, H. F. M. Schoo, X. Yang, A. Alexeev, J. Loos, U. S. Schubert, and M. M. Wienk, Chem. Mater., 16, 2503 (2004). [7] A. J. Breeze, Z. Schlesinger, S. A. Carter, H. Tillmann, H.-H. Hrhold, Solar Energy Mater. Solar Cells, 83, 263 (2004). [8] Y. Kim, S. Cook, S. A. Choulis, J. Nelson, J. R. Durrant, D. D. C. Bradley, Chem. Mater., 16, 4812 (2004). [9] A. C. Morteani, P. Sreearunothai, L. M. Herz, R. H. Friend, C. Silva, Phys. Rev. Lett., 92, 247402 (2004). [10] Y. Kim, S. Cook, S. A. Choulis, J. Nelson, J. R. Durrant, D. D. C. Bradley, Synth. Met., 152, 105 (2004).
TH78 MOLECULAR HETEROSTRUCTURE ORGANIC SOLAR CELLS F.Meghdadi, D.Meissner, N.S. Sariciftci Linz Institute for Organic Solar Cells (LIOS) Physical Chemistry, Johannes Kepler University, Linz, A-4040, Austria We discuss two types of organic solar cells, rst the layer by layer devices which are formed by deposition of p-type and n-type small molecules like zinc phthalocyanine (ZnPc) and fulleren (C60) sandwiched between two electrodes. Thermally annealing of the substrates and the thickness optimization of C60 layers result in better performance and higher power conversion efciency of devices. The second part represents p-i-n type organic solar cells. Thermal annealing of p-i-n type heterojunctions, results in increased photocurrent and power conversion efciency. Using this concept with a co-deposited interlayer of ZnPc and C60 as a photoactive region, devices show short circuit photocurrents over 14 mA/cm at 100 mW/cm2. Comparative results of current-voltage characteristics with variation and optimizing of different electrode materials and different parameters on device performance will be discussed.
TH79 LIGHT-HARVESTING HOST-GUEST ANTENNA MATERIALS FOR PHOTONIC DEVICES Andr Devaux, Stefan Huber, Arantzazu Zabala Ruiz, Huanrong Li, Olivia Bossart, Le-Quyenh Dieu, Gion Calzaferri Department of Chemistry and Biochemistry, Freiestrasse 3, University of Bern, CH-3012 Bern, Switzerland In device engineering, a high degree of supramolecular organisation is required to achieve certain desired macroscopic properties. Dye-loaded zeolite L host-guest materials have been successfully used in the realisation of efcient light-harvesting antenna systems.[1] A new hierarchy of structural order is introduced by arranging the zeolite L crystals into densely packed, oriented monolayers on a substrate.[2] We developed methods to synthesise such monolayers, to ll them with dyes and to terminate them with a luminescent stopcock. By the subsequent insertion of different types of dye molecules in a zeolite L monolayer, the rst unidirectional antenna system was realised. Such antenna P(Bu) Pt materials open possibilities for the design of a novel thin layer, silicon based solar cell, as illustrated in Figure 1. The P(Bu) small composite crystals, arranged with their c-axes perpendicular to the surface of a semiconductor, allow the transport of excitation energy towards the zeolite-semiconductor interface by energy migration. The stopcock molecules, which c are located at only one channel end, enable radiationless energy transfer from the antenna to the semiconductor layer. n e c This layer can be very thin (< 200 nm) as the electron-hole pair forms near the surface. Direct transfer of electrons s e from antenna to semiconductor is prevented by introducing an insulating layer. UV-VIS absorption as well as NIR r Polymer o luminescence spectroscopy was carried out on such dye-loaded zeolite L monolayers. Monomer h
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Fig . 2 Temper atur e de pendenc e of th e phosphorescence for pol ymer an d mono m er

i t e f i l /
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Figure 1. Schematic representation of a novel concept for the preparation of thin layer, silicon based solar cells.[2] References [1] G. Calzaferri, S. Huber, H. Maas, C. Minkowski, Angew. Chem. Int. Ed., 42 (2003), 3732-3758. [2] G. Calzaferri, S. Huber, A. Devaux, A. Zabala Ruiz, H. Li, O. Bossart, L.-Q. Dieu, Proceedings of SPIE, Photonics Europe 2006, (2006), manuscript 6192-39, in press.
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Fig . 3 Arrheniu s plot o f the decay rate vs. 1/T emper atur e for th e pol ymer
TH80 THE INFLUENCE OF NANOMORPHOLOGY OF TREATED AND UNTREATED BULK-HETEROJUNCTION SOLAR CELLS TO THE CHARGE CARRIER TRANSPORT AND RECOMBINATION A. Pivrikas1,2, G. Juka3, M. Scharber5, G. Sliauys3, K. Geneviius3, G. Dennler4, K. Arlauskas3, N.S. Sariciftci4, and R. sterbacka1,* 1Dept. of Physics and Center for Functional Materials, bo Akademi University, Turku, Finland. 2Graduate School of Materials Research, Turku Universities, Finland. 3Vilnius University, Department of Solid State Electronics, Vilnius, Lithuania. 4Johannes Kepler University, Linz Institute for Organic Solar Cells, Linz, Austria. 5Konarka Austria, Altenberger Str. 69, Linz, Austria. * Corresponding author: phone: 358 2215 4923, e-mail: rosterba@abo.
Thermal treatment and right choice of solvent has a huge impact on the power conversion efciency of bulk-heterojunction solar-cells through changes in nano-morphology of the lm. In order to choose suitable materials to fabricate efcient bulk-heterojunction solar cells it is very important to understand the effect of the nano-morphology on the charge carrier transport and recombination. In this work we clarify the difference in charge transport and recombination between treated and untreated bulk-heterojunction solar cells. The samples were fabricated from a 1:2 mixture of regioregular poly(3-hexylthiophene) (RRPHT) and 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]methanofullerene (PCBM) in chloroform. The reason for choosing a low-boiling point solvent as chloroform is to get a large difference between the treated and untreated devices. The samples were made by doctor-blading on top of a poly ethylene dioxythiophene doped with polysulfonate styrene (PEDOT:PSS) coated indium-tin oxide (ITO) covered glass substrate after which the treated samples were kept at 140C for 5 minutes. We have used a multitude of experimental techniques such as Time-of-Flight (TOF), Double Injection (DoI) and Charge Extraction by Linearly Increasing Voltage (CELIV) techniques to measure charge carrier transport and recombination. We found that the charge carrier bimolecular recombination is present in both types of solar cells at very high carrier densities. However, in the heat-treated solar cells the bimolecular recombination was found to be strongly reduced compared to Langevin-type recombination accompanied with electric eld-independent quantum efciency for charge generation. In the untreated samples the recombination of charge carriers is close to Langevin-type with electric eld-dependent quantum efciency as a result. The charge carrier mobilities for both electrons and holes as a function of applied external electric eld are measured and the results are presented for both types of solar cells.
TH81 INTRA- AND INTERCHAIN TRIPLET DIFFUSION IN A PT-CONTAINING POLYMER AND MONOMER Anna Khler1, Carsten Dosche1, Lekshmi Sudha Devi2, Richard H. Friend2 1Institute of Physics, University of Potsdam, Potsdam, Germany, 2Cavendish Laboratory, University of Cambridge, Cambridge, UK Triplet states play a major role in organic light-emitting diodes (LEDs) that are based on host-guest composites with phosphorescent dopants. Due to their relatively long lifetime, triplet excitons can diffuse over considerable distances. Consequently, quantitative knowledge about their diffusion along a polymer chain or between chains is paramount for the design of phosphorescent LEDs. We have determined triplet diffusion rates for intra- and interchain diffusion using time, temperature and intensity dependent phosphorescence spectroscopy in lms and in solutions. For this study we used a well-investigated phosphorescent model system containing platinum in the polymer chain (Fig. 1). By comparing the polymer with its corresponding monomer we also asses the effect of chain length on triplet diffusion (Fig. 2). Here we present a quantitative study of the diffusion rates. For polymer lms, we nd a high intrachain diffusion rate in the order of 104 s-1 that is only slightly activated by temperature. In contrast, the interchain diffusion rate is strongly temperature dependent with an activation energy around 30 meV so that it becomes the prominent mechanism at room temperature (Fig. 3). For the monomer, diffusion rates are low and not temperature activated. As a consequence, triplet-triplet annihilation occurs at lower excitation densities in the polymer than in the monomer. We attribute the different diffusion rates to the variation in the coupling of chromophores along a chain and between chains.
TH82 APPARENT VIBRONICS IN -CONJUGATED SYSTEMS; COALESCED RAMAN MODES E. Ehrenfreund1, and Z.V. Vardeny2 1Physics Department, Technion-Israel Institute of Technology, Haifa 32000, ISRAEL 2Physics Department, University of Utah, Salt Lake City, UT 84112, USA The photoluminescence (PL), absorption, and electro-absorption (EA) spectra of many -conjugated systems (PCS), including polymers and oligomers in the form of lms, solutions or crystals, contain side-band replicas with apparent frequencies that do not t to any specic mode of their many-mode Raman active vibrations. As an example we show in Fig. 1a, the PL spectra of distyrylbenzene (DSB) at low and high temperatures; the frequencies of the vibronic replica do not match any of the DSB Raman modes shown in Fig. 1c. In order to account for the apparent modes, we employ a time dependent analysis, in which each spectrum is expressed as the Fourier transform of the time dependent auto-correlation function of the transition dipole moment. We quantify the relative Huang-Rhys factor for each of the vibrational modes using the pre-resonance Raman scattering spectrum. We then utilize the experimentally determined relative Huang-Rhys factors within the time dependent model, with disorder or temperature induced damping, in order to calculate the relevant spectrum. We show that in many PCS [e.g., distyrylbenzene, Fig.1 (c)] the multi-vibrational mode manifold effectively coalesces into a single apparent mode as damping increases [Fig. 1 (b), bottom curve]. Using the apparent-mode model based on the measured Raman scattering spectrum, we are able to explain quantitatively the frequency and relative intensities
ABSTRACTS
of the single-frequency vibronic-side-band spectrum observed in distyrylbenzene [Fig. 1 (a), bottom curve] and in many other PCS. Furthermore, we show the special importance of the low frequency Raman modes in determining the vibronic replicas in PCS where the damping is low (i.e., ordered morphology and/or low temperatures). In particular, the low frequency mode modulating an apparent high frequency progression observed in solutions and crystals of short oligomers, such as distyrylbenzene, is fully accounted for in detail, [compare Fig.1 (b) and (a), top curves].
(c
E -E 0 (eV)
Fig. 1. (a) [(b)] Experimental [model] PL spectra of DSB. (c) Pre-resonant Raman spectrum. Similarly, we can account for the apparent vibronic modes in the EA spectra, which measure the changes in absorption due to an externally applied eld. For centro-symmetric systems, we nd that the vibronically structured EA spectrum can be described by the rst derivative of the absorption. Second derivative EA spectra in disordered lms are indicative of broken symmetry and the presence of permanent dipoles. TH83 UNRAVELLING STRUCTURE-PROPERTY RELATIONS IN POLYFLUORENE-BASED ORGANIC SEMICONDUCTORS USING SINGLE MOLECULE SPECTROSCOPY K. Becker, J. M. Lupton Photonics and Optoelectronics Group, Ludwig-Maximilians-Universitt Mnchen, Munich, Germany U. Scherf Macromolecular Chemistry Group, Bergische Universitt Wuppertal, Wuppertal, Germany Conjugated polymers offer a broad spectrum of device applications as well as raising many fundamental issues relating to the nature of excited state species in complex macromolecules. A driving force in their optical spectroscopy has been the desire to unravel the relationships between chemical structure and conformation on the one hand and their optical and photophysical properties on the other hand. By invoking low temperature single molecule uorescence spectroscopy, disorder broadening can be overcome and the optically active subunit on the polymer chain -the chromophore- is identied1. In this contribution we demonstrate the strong inuence of chain conformation of single polyuorene chains on their emission properties2. Energy transfer processes are resolved on the molecular level and conclusively demonstrate how traces of chemical defects, such as keto groups, dramatically impact the luminescence properties3. Conformational information on the chromophores can be obtained from polarized absorption and emission spectroscopy4, but is also available from uorescence signatures such as the spectral linewidth and temporal dynamics5. Chain folding is a prominent conformational effect, which can give rise to self-aggregation of the polymer and resultant spectral broadening5. Polyuorene exhibits a particularly interesting conformational transition of the chain between a planar and a twisted structure2. This transition bares a number of spectral signatures such as a change in vibrational coupling strength. Most importantly, we nd that the photophysical stability is strongly affected by the chain conformation2. Planarisation of the polymer backbone effectively inhibits photoquenching (blinking) of the single polymer molecule. This study suggests that a mechanical force, exerted by the embedding polymer matrix in this case, is capable of changing both the electronic as well as the photochemical properties of a polymer molecule. Our results therefore provide important input into material design by demonstrating that structure-property relations in conjugated polymers derive from the chain morphology rather than from the chemical details of the conjugated backbone. An important exception to this rule is given by oxidative defects on the polymer backbone, which yield well-dened spectroscopic signatures in the single molecule emission, red shifted by over 100 nm from the backbone transition3. We demonstrate with the aid of single molecule spectroscopy of well-dened uorene:uorenone copolymers that the green emission band frequently observed in polyphenylenes is of monomolecular origin. This effect implies exceptionally efcient intramolecular energy transfer. We investigated this further using a dye-endcapped model polymer, which displays efcient intramolecular energy transfer towards the dye acceptor even in the absence of appreciable spectral overlap between donor and acceptor, required by Frster theory6. Accordingly, efcient funnelling of the excitation also occurs under all circumstances to the uorenone defect. As a consequence of this fact we can spectrally identify a single oxidation step on a polymer molecule of high molecular weight. [1] F. Schindler et al., Angew. Chem. Int. Ed. 44, 1520 (2005). [2] K. Becker et al., J. Am. Chem. Soc. 127, 7306 (2005). [3] K. Becker et al., Adv. Funct. Mater. 16, 364 (2006). [4] F. Schindler et al., Nature Mat. 5, 141 (2006). [5] F. Schindler et al., Proc. Natl. Acad. Sci. USA 101, 14695 (2004). [6] K. Becker et al., J. Am. Chem. Soc., 128, 680 (2006).
TH84 MULTILAYER LIGHT-EMITTING DIODES BASED ON CROSSLINKED POLYFLUORENES
Jorge Morgadoa,b, Ana Charasa, Helena Alvesa, Lus Alccera,b aInstituto de Telecomunicaes, Instituto Superior Tcnico, Av. Rovisco Pais 1, P-1049-001 Lisboa, Portugal b Dep. de Eng. Qumica e Biolgica, Instituto Superior Tcnico, Av. Rovisco Pais 1, P-1049-001 Lisboa, Portugal
Light-emitting diodes, both based on low molecular weight materials (OLEDs) and on polymers (PLEDs), consisting on multilayer structures
ABSTRACTS
have shown signicant efciency improvements, mainly due to a connement of the recombination zone, away from the electrodes, and balanced charge injection into the emissive layer. While this approach is easily implemented in OLEDs, fabricated by sublimation techniques, its use in PLEDs, where the polymers are deposited from solution, usually by spin coating, depends on the combination of polymers with different solubilities (orthogonal approach). This strongly limits the materials that can be combined. In this communication we present the characterization of various multilayer PLEDs, where a previous layer is rst converted into an insoluble network, prior to the deposition, by spin coating, of the following layer. In order to fabricate these structures we use three different crosslinkable polyuorenes. These copolymers carry oxetane side groups which, upon acid catalised polymerisation, form a polymeric network with optical properties similar to those of the soluble precursor polymer.
TH85 EFFICIENT FRSTER COUPLING BETWEEN INORGANIC AND ORGANIC EXCITONS
G. Heliotis1, G. Itskos1, P. G. Lagoudakis2,3, C. Belton1, M. D. Dawson4, I. M. Watson4, J. Feldmann3, R. Murray1 and D. D. C. Bradley1 1Blackett Laboratory, Imperial College London, UK 2School of Physics & Astronomy, University of Southampton, UK 3Photonics and Optoelectronics Group, Department of Physics and CeNS, Ludwig-Maximilians-Universitt, Munich, Germany 4Institute of Photonics, University of Strathclyde, UK Hybrid organic/inorganic semiconductor structures offer the prospect of devices that possess a combination of the attractive electrical properties of inorganic materials and the high luminescence yields typical of organic materials. Specically, efcient dipole-dipole energy transfer from an inorganic semiconductor to an organic semiconductor may lead to novel devices in which highly efcient emission can be achieved across the entire visible spectrum. Here, we report hybrid structures containing InGaN/GaN single quantum wells (QWs) that are spaced from a blue-light-emitting poly(9,9dioctyluorene-co-9,9-di(4-methoxy)phenyluorene) (F8DP) lm by GaN cap layers of variable thickness. In such structures, when the two materials are in close proximity and their electronic states are properly matched [1, 2], non-radiative (Frster dipole-dipole) energy transfer is expected to occur on timescales that are short relative to the other competing QW decay mechanisms. Temperature-dependent spectrally-resolved measurements indicate that Frster transfer from the nitride QWs (energy donor) to the F8DP lm (energy acceptor) can result in a signicant enhancement in the organic emission, with as much as a twenty-fold increase over that resulting from simple radiative energy transfer [3]. Control measurements (without the QWs) verify that the intensity enhancement is due to energy transfer from the UV-light emitting QW rather than any other effect related to the polymer/GaN cap layer interface. New time-resolved experiments provide further insight into the non-radiative nature of the transfer as for instance evident from a signicant reduction in the QW decay time. This allows a more detailed characterization of the nature and efciency of the transfer process. [1] D. Basko, G.C. La Rocca, F. Bassani and V.M. Agranovich, Eur. Phys. J. B 8, 353, (1999) [2] . Kos, M. Achermann, V.I. Klimov and D.L. Smith, Phys. Rev. B, 71, 205309, (2005) [3] G. Heliotis, G. Itskos, R. Murray, M.D. Dawson, I.M. Watson and D.D.C. Bradley, Adv. Materials 18, 334, (2006)
TH86 ENHANCED GAIN INDUCED BY SURFACE-PLASMON-RESONANCE IN DYES-GOLD NANO-PARTICLES IN POLYMER RANDOM LASERS O.Popov, A. Silberstein, V. Lirtsman and D.Davidov Racah Institute of Physics, the Hebrew University of Jerusalem, Israel Random lasing is due to the interaction of light with disordered amplifying media. It is associated with multiple light scattering events and the formation of closed loop paths for light. This feedback mechanism may serve as an effective resonant cavity and no mirrors alignment are required. There are already several examples of random lasing in various systems including conjugated polymer, organic dyes-doped gel lms and semiconductor nano-particles (NP). We report here on the effect of gold NP on the lasing characteristics using three different laser congurations, namely, (a). random laser based on polymer lms containing Rohdamin6G dye and NP, (b) random laser based on polymer lm on Au coated prism and (c) ring laser based on the same polymer. Gold NP exhibit surface plasmon resonance (SPR) which can be tuned easily, by changing the particle size, to completely overlap with the narrow band emission spectrum of the laser dyes. This allows a critical check of the role of SP on random lasing in the Au-based polymer system. We have used a frequency doubled, pulsed Nd:YAG laser at a wavelength of 532nm with a pulse length of 10 ns with 5 Hz repetition rate and performed comprehensive studies as a function of the dyes and NP concentrations and pumping intensity. Generally, we nd that the presence of the Au NP signicantly lowers the lasing threshold and increases the peak intesity for the Au-based random lasers. The effect is opposite in the case of ring laser. The results could be explained by efcient scattering of the Au NP and therefore a better feedback mechanism. In fact, the results allow a separation between the role of (a) scattering and (b) surface plasmon contributions in the different laser congurations.
TH87 -ELECTRON DELOCALIZATION AND REVERSIBLE OPTICAL SWITCHING IN NEW PHOTOCHROMIC OLIGOMERS AND POLYMERS. FROM MOLECULES TO DEVICES.
ABSTRACTS
C. Bertarelli, A. Bianco, G. Zerbi Politecnico di Milano - Dip. di Chimica, Materiali ed Ingegneria Chimica G. Natta Piazza L. da Vinci 32 - 20133 Milano A few years ago a new class of photochromic organic materials containing thiophene units (see g. 1) was discovered either as monomers or as
polymers1,2, the photochromic properties are modulated by the photoactivated closing/opening of the intramolecular structure which allows delocalization/localization of pi electrons. Obviously in going from delocalized to localized states the energy gap changes and several optical properties are consequently modied.
Figure 1 chemical structure of the basic unit of diarylethene The interest in these materials is strong both by science and technology. The reversible and repeatable photoactivated switching of the colour produces cyclic changes of refractive index and of the related optical properties. Also molecular hyperpolarizabilities have been estimated and do change from the open to the closed form3. Optical imaging and information technology have been the rst applications considered. The interest by technology is due to the possibility of preparing either blends of the materials with other polymers and also to prepare thin lms of the pure materials. In addition to the studies of the chemistry (synthesis of new material with aimed properties) and physics (origin the phenomenon and its handling) these materials have been already used in specic technological applications so far mainly in the eld of astrophysics. The photo-switchable transparent to opaque property has allowed to produce, by suitable optical writing, re-usable Focal Plane Masks, which have been mounted and tested on a telescope at the Observatory of Asiago4. At present the interest is to replace traditional gratings in the telescopes with rewritable volume phase holographic gratings made with these materials. The amplitude mode or Effective Conjugation Mode or mode nds the nicest verication with these materials which show an extremely strong line near 1600 cm-1 when - delocalization is on, while it disappears completely when delocalization is off. Moreover a few strong bands in infrared occur for the closed and disappear in the open structure. This forms the basis for on/off signals in infrared useful for optical recording and imaging; suitable laser sources and detectors in the infrared offer the possibility to develop memory devices for information technology. References 1. M. Irie, Chem. Rev., 100, 1685 (2000) 2. F. Stellacci, C. Bertarelli, F. Toscano, M.C. Gallazzi, G. Zotti, G. Zerbi, Adv. Mater., 11, 292 (1999) 3. A. Bianco et. al., Astron. Nachr., 326 (5), 370 (2005
F1 SINGLE-COMPONENT MOLECULAR METALS AND NOVEL MONOANIONIC METAL COMPLEXES WITH EXTENDED-TTF TYPE LIGANDS Akiko Kobayashi Nihon University, College of Humanities and Sciences, Sakurajosui 3-25-40, Setagaya-Ku, Tokyo156-8550, Japan Recently, a considerable interest has been attracted to the conducting systems consisting of single-component molecules. We have previously reported the electromagnetic properties of [Au(tmdt)2]. But the quality of the sample was not satisfactory. We have recently succeeded to prepare the single crystals with the small size of ca. 30 m and the powder sample of high-quality. The room-temperature conductivity and susceptibility of newly obtained high-quality crystalline powder sample was 50 S cm-1 and 4.2 x 10-4 emu mol-1, respectively. The showed almost constant value in the high temperature region and below 110 K, it showed characteristic temperature and magnetic-eld (H) dependences, indicating an antiferromagnetic transition at 110 K. The H-dependence of M was measured at 40K, which suggested the spin-op transition around 23 kOe. The magnetic moment produced at TN was roughly estimated as 0.3 B. The large low-temperature magnetic susceptibility of 2.6 x 10-4 emu mol-1 at low magnetic eld is consistent with the theoretical calculation suggesting the existence of the Fermi-surface pockets below TN To our knowledge, [Au(tmdt)2] is the rst highly conducting molecular system where the same electrons bear electrical conductivity and magnetic order. (nBu4N)[Ni(dmstfdt)2] is a unique molecular conductor exhibiting weakly metallic state with small room-temperature conductivity. In spite of very small calculated intermolecular transfer integral t, the delocalization of frontier electrons over the left and right extended-TTF ligands will reduce the effective on-site Coulomb repulsion U to make the system conducting at least at high temperature. The temperature dependence of the susceptibility was also very unique, which indicated the gradual increase of the magnetic moments associated with the slow increase of the resistivity with lowering temperature. Around 150 K, the insulating transition due to the electron localization takes place. Below the insulating transition temperature (T<150 K), [Ni(dmstfdt)2] molecule has one S=1/2 spin and the spin system transforms to a weak ferromagnet around 7 K. Similar weakly metallic monoanion complexes (nBu4N)[Ni(dmstfdt-B)2] and highly conducting (Et4N)[Ni(dmstfdt)2] will be presented.
F2 ANNIHILATION OF MAGNETISM DUE TO FAINT MOLECULAR DISPLACEMENTS IN (TP-EDOT)3(SB2F11)(BENZENE) Hideki Yamochia, Jun Hagiwarab, Masaya Soedab, and Gunzi Saitob a Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8502 JAPAN, and ERATO/JST b Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 JAPAN Ethylenedioxy-1,3-dithiole (EDOT) moiety has provided interesting donor molecules. For example, EDO-TTF afforded quasi-one-dimensional 2:1 PF6 complex which exhibited the peculiar metal-insulator transition associated with the distinct deformation of the donor molecule. Furthermore, this complex showed the ultra-fast and highly efcient photo-induced insulator-to-metal transition; within the response time of ca. 1.5 ps, one photon converted around 500 donor molecules. It is noteworthy that the electron-phonon coupling is claimed to play an important role to show the peculiar
ABSTRACTS
features. To squeeze out the functionalities of EDOT moiety, the combination with the thiopylan-4-ylidene (TP) was examined by the authors. As a result, the new donor molecule, TP-EDOT constructed a novel three-dimensional spin arrangement which showed a two-dimensional magnetic behavior in (TP-EDOT)2PF6. Here, we report the details of the title complex, which is the second single crystalline complex based on this donor molecule. The composition of the title complex was determined by x-ray crystal structure analysis (P21/m, a = 19.599(3), b = 10.951(3), c = 10.534(2) , = 101.11(2), V = 2222(1) 3, Z = 2, R = 0.068). As was reported roughly in ref. 3, TPEDOT formed columnar stacks of head-to-tail-to-head type trimers consisted of the donor molecules of D1, D2 and D3 in Fig. 1. Although the optical absorption spectra showed a low-energy charge-transfer (CT) band at around 5000 cm-1, this complex was a semiconductor (rt = 5 103 cm, Ea = 0.18 eV). The calculated intermolecular overlap integrals (IOIs) indicated that the uniformly arranged trimers are almost isolated to each other. Based on the composition, a donor trimer accommodates one localized spin. Since neither superlattice nor breaking of screw axis symmetry were detected within the experimental errors of our x-ray diffraction examinations, the title complex should exhibit paramagnetism as a Mott insulator or as a charge-ordered system. The magnetic susceptibility measurements, however, showed a non-magnetic behavior. To understand the discrepancy between the expected and observed magnetic behavior, IOIs based on the articial crystal structures were calculated, in which each donor molecule was translated along a crystallographic axis by 0.1 from the observed position. The displacement is within the range of thermal motion of the atoms under ambient condition. As a result, the faint displacements of the donor molecules modulated IOIs signicantly; the magnitude of s3 was increased by more than 70 % in a case; the magnitude of s3 was comparable to that of t1 in another case. Multiple types of the dimerization patterns of trimers are expected to form the singlet pairs of the localized spins by the faint displacements of TP-EDOT. At present, the most plausible reason for the non-magnetic behavior of the title complex without superlattice and symmetry breaking is the formation of plural kinds of small sized domains in which TP-EDOT trimers are dimerized due to the faint molecular displacements. The sensitivity of the electronic structure of the title complex to the molecular displacements suggests that TP-EDOT is a potential donor to construct CT complexes having strong electron-phonon couplings.
O O O O
S S E D O -T T F S
S S
S S T P -E D O T
Fig. 1 Donor packing p attern in (TP-EDOT)3 (Sb 2 F11 )(benzene). The bott om panel shows the schematic representation viewed along the a -axis along with the notation of int ermolecular overlap integrals (s1 = -13.52, s2 = -16.32, s3 = -2.19, t1 = 0.89, t2 = -3 -0.21, t3 = 0.19 10 ).
F3 CONDUCTION MECHANISM OF NETWORK STRUCTURES BETWEEN MOLECULAR-ASSEMBLY NANOWIRES AND NANOPARTICLES Tomoyuki Akutagawa,1, 2 Yoko Tatewaki,2 Hiroyuki Hasegawa,3 Shinro Mashiko, 3 Jan Becher4 Takayoshi Nakamura,1,2 1Research Institute for Electronic Science, Hokkaido University, 2Graduate School of Environmental Earth Science, Hokkaido University, 3Kansai Advanced Research Center, NICT, 4Department of Chemistry, University of Southern Denmark. Molecular conductors were fabricated to electrically active nanostructures through self-assembly approach of amphiphilic bis-TTF macrocycles (1). We already reported a variety of molecular-assembly nanostructures such as nanodots (0D), nanowires (1D), and nanowire-networks (2D).[1, 2] Here we fabricated integrated molecular-assembly networks between the 1D nanowires and Au-nanoparticles. The (1)(F4-TCNQ)2 nanowires were assembled by the Langmuir-Blodgett (LB) technique with Au-nanoparticles with diameters of 2.6 and 13 nm, which formed novel hybrid network structures (Fig. 1). The number and aggregation states of Au-nanoparticles on the substrate surface were adjustable by controlling the concentration of Au-nanoparticles in LB trough. The surface morphology of nanowires / Au-nanoparticles hybrid network structures was characterized by AFM and optical spectra. The LB multilayers were fabricated to evaluate the electrical conducting mechanism of nanoscale hybrid structures. Fig. 2 shows the temperature-dependent electrical conductivity of LB lms with high Aunanoparticles concentration on the lm. Three kinds of conducting regions were clearly identied. The temperaturedependent conductivities were reproduced by the following equation, In high temperature region, the semiconducting behaviour of molecular nanowires (Ea = 0.14 eV) was attributed to that of nanowires. On the other hand, hopping and/or tunnelling processes between the Au-nanoparticles were observed at lower temperature. Almost temperatureindependent electrical conductivity in low-temperature region (Ea = 0.01 and ~0 eV) suggested a quantum conduction between Au-nanoparticles. [1] T. Akutagawa et al. PNAS. USA, 99, 5028-5033 (2002). [2] T. Akutagawa et al. Angew. Chem. Int. Ed. Engl. 44, 7283-7287 (2005).
O C 10 H21S C 10 H21S S S S S S S O O O S S S S S S SCH 3 SCH 3
Fig. 1. Molecular structures of donor 1 and hybrid nanostruct ure between (1 )(F4 TCNQ)2 nanow ires and A unanopart icles.
ABSTRACTS
Fig. 2. Temperature-depende nt electrical conductivity of hyb rid nanostruct ures between nanow ires and Au-nanopart icles with d iameter of 2.6 and 13 nm.
F4
NON-LINEAR CURRENT-VOLTAGE CHARACTERISTICS OF -(BEDT-TTF)2MZN(SCN)4 (M=CS, RB) Yamaguchi Takahide*, T. Konoike, K. Enomoto, M. Nishimura, T. Terashima, S. Uji H.M. Yamamoto1 National Institute for Materials Science (NIMS), 3-13 Sakura, Tsukuba, 305-0031 Japan. 1 RIKEN, 2-1 Hirosawa, Wako, 351-0198, Japan. * YAMAGUCHI.Takahide@nims.go.jp We measured current-voltage characteristics of charge-ordered organic crystals -(BEDT-TTF)2MZn(SCN)4 (M=Cs, Rb) in a low current range down to 10-1210-13 A. The I-V curves show a crossover from ohmic behavior at low bias voltage to a power law at high bias voltage (the left panel of the gure). The value of the power-law exponent increases with decreasing temperature, and exceeds 10 for M=Rb. The non-linear I-V characteristics are attributed to electric eld-induced unbinding of electron-hole pairs that are thermally excited in the background of the twodimensional charge order; the measured I-V curves are tted by a simple model (the right panel of the gure). From analysis of a crossover electric eld from the ohmic to the power-law characteristics, we obtain strong evidence that the electron-electron Coulomb interaction is signicantly long-ranged, i.e., the screening length is greater than 10 molecule sites. Our ndings suggest that such long-range interactions are essential for a full understanding of charge ordered phases in BEDT-TTF compounds1. We also measured the I-V curves in magnetic elds up to 17.5 T. The I-V curves on the log-log plot are shifted towards the lower current with increasing magnetic eld; the current for a constant voltage decreases by more than one order of magnitude for M=Cs at T=0.3 K. The magnetoconductance curves depend little on the magnetic-eld orientation, and are described by a simple universal function of BB/kBT, where B is the Bohr magneton. The magnetoconductance effect may be explained by a blockade of electrical conduction due to the Pauli exclusion principle. [1] Y. Takahide et al., to appear in Phys. Rev. Lett.
Left: I-V curves of a rapidly cooled -(BEDT-TTF)2RbZn(SCN)4 at different temperatures. The I-V curves were measured with a two point conguration using a current preamplier. The electrode spacing is 30 m. Right: Calculated current-voltage characteristics.
F5 TRENDS IN THE SUPERFLUID STIFFNESS OF MOLECULAR SUPERCONDUCTORS Stephen J. Blundell1 and Francis L. Pratt2 1Oxford University Department of Physics, Clarendon Laboratory, Parks Road, Oxford OX1 3PU, United Kingdom 2ISIS Facility, Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX, United Kingdom
Molecular superconductors have recently been shown1 to exhibit a remarkable scaling relation between the superuid stiffness s=c2/2, the conductivity (Tc) at Tc and the transition temperature Tc. This scaling relation, derived from muon-spin rotation (SR) measurements on a variety of one-dimensional, two-dimensional and three-dimensional molecular superconductors1,2, is in marked contrast to that exhibited by elemental and cuprate superconductors3,4 which follow a dependence which can be expressed as h0s/0(Tc)h/=kBTc, where is a scattering rate and is a numerical constant which takes the value 1 in the so-called Planckian limit and 2.24 in the weak-coupling BCS dirty limit. For the cuprates, this relation has several possible origins including Josephson coupling, dirty-limit superconductivity and marginal Fermi-liquid behaviour.5 For the molecular superconductors, we nd that the inverse scattering rate instead follows a dependence which is closer to h/=(kBTc)3/2/E1/2, where E is a characteristic energy 0.2 meV which seems to be common for all the superconductors which we have investigated. Further, the molecular superconductors show that the superuid stiffness decreases with increasing conductivity at Tc, in contrast to the case of the cuprates for which an increase is observed. We discuss the implications of these results for understanding the origin of superconductivity in these molecular systems. 1F.L. Pratt and S.J. Blundell, Phys.Rev.Lett. 94, 097006 (2005) 2F.L. Pratt, S.J. Blundell, T. Lancaster, M.L. Brooks, S.L. Lee, N. Toyota and T. Sasaki, Synth. Met. 152, 417 (2005); F. L. Pratt, S. J. Blundell, I. M. Marshall, T. Lancaster, C. A. Steer, S. L. Lee, A. Drew, U. Divakar, H. Matsui and N. Toyota, Polyhedron 22, 2307 (2003) 3C.C. Homes et al., Nature (London) 430, 539 (2004) 4C.C. Homes, S.V. Dordevic, T. Valla and M. Strongin, Phys. Rev. B 72, 134517 (2005) 5J.L. Tallon, J.R. Cooper, S.H. Naqib and J.W. Loram, cond-mat/0410568
F6 DIRECT MICRO-PATTERNING OF TTF-BASED ORGANIC CONDUCTORS ON FLEXIBLE SUBSTRATES Marta Mas-Torrent,a Elena E. Laukhina,a, Vladimir Laukhin,a,c Caitriona M. Creely,b Dmitri V. Petrov,b,c Concepci Roviraa and Jaume Vecianaa, aInstitut de Cincia de Materials de Barcelona (ICMAB-CSIC), Campus de la UAB, 08193 Bellaterra, Spain. bInstitut de Cincies Fotniques (ICFO) C. Jordi Girona, 29, 08034 Barcelona, Spain. cInstituci Catalana de Recerca i Estudis Avanats (ICREA), Barcelona, Spain.
ABSTRACTS
Micro and nanocrystals of conducting tetrathiafulvalene (TTF) salts embedded in a polymeric matrix offer great potential for applications in electronic devices. Novel composite materials called bi-layer (BL) lms, which consist of a polymeric matrix with a top-layer formed by a nano and microcrystalline network of a TTF based conductor, have been reported.1 These materials are very promising since they combine the unique physical properties of molecular conductors and the processability and exibility of polymeric lms. The BL lm shown in Fig. 1 is formed by -(BETTTF)2Br3H2O [BET-TTF: bis(ethylenethio)tetrathiafulvalene] crystals and exhibited a metallic behaviour and a high room temperature conductivity of 120 Scm-1.1b The design of electronic components or devices calls for patterning techniques that permits one to place the organic conductors on the substrate at will. We have developed a novel technique, namely thermochemical printing of organic conductors (TCPOC), for patterning the BL lms.2 The patterning is realized employing a local heat source and by taking advantage of the chemistry of the organic conductors, as at high temperature the anion forming the conducting TTF-based crystals can be partially or totally removed. Consequently, by local heating the lm surface the conducting areas, formed by the TTF salts, can be converted into insulating areas, formed mainly by the neutral TTF derivatives. We further demonstrate here the potential of this novel technique for the design of electronic components and devices (Fig. 2)
Fig.1 View through a metal-like BL lm with a surface layer of -(BET-TTF)2Br3H2O nanocrystals and SEM image of the surface layer.
Fig. 2. Electronic circuits in which the BL lms of nanocrystals -(BET-TTF)2.5I3 without patterning (left) and after patterning (right) are used as micro-resistors. The light zones in the right gure correspond to the laser writing path and are insulating. We acknowledge nancial support from EC by the IP no. NMP4-CT-2004-500355 NAIMO. [1] a) E. E. Laukhina, V. A. Merzhanov, S. I. Pesotskii, A. G. Khomenko, E. B. Yagubskii, J. Ulanski, M. Kryszewski and J. K. Jeszka, Synth. Met., 70, 797 (1995). b) M. MasTorrent, E. Laukhina, C. Rovira, J. Veciana, V. Tkacheva, L. Zorina and S. Khasanov, Adv. Funct. Mater., 11, 299 (2001). [2] M. Mas-Torrent, E. E. Laukhina, V. Laukhin, C. M. Creely, D. V. Petrov, C. Rovira, J. Veciana, J. Mater. Chem. 16, 543 (2006).
F7 ELECTRICAL PROPERTIES OF CONDUCTIVE LANGMUIR-BLODGETT FILMS OF DIALKYLDIMETHYLAMMONIUMAU(DMIT)2 SALT
Yasuhiro F. Miura*1, Masaaki Kitao1, Haruki Matsui1, Shin-ichi Morita1, Michio Sugi1, Masato Hedo2 and Yoshiya Uwatoko2 1Department of Functional Chemistry, Toin University of Yokohama, 1614 Kurogane-cho, Aoba, Yokohama 225-8502, Japan 2Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashinoha, Kashiwa 277-8581, Japan Phone: +81-45-972-5881, FAX: +81-45-972-5972, *E-mail:yfmiura@cc.toin.ac.jp S C H CH
14 29
N+ C 14 H 29 CH
S Au S
S S
S S S
S
3
We have already reported that the Langmuir-Blodgett (LB) lms based on ditetradecyldimethylam monium-Au(dmit)2 [2C14-Au(dmit)2] salt exhibits a high room temperature conductivity of 40100 S/cm with a metallic temperature dependence in the range of 230-300 K after electrochemical oxidation [1]. Furthermore, we have also reported that the ac magnetic susceptibility and resistance measurements suggest the existence of a superconducting phase below 4 K [2-4]. At the air/water interface, charge-transfer (CT) complexes and radical salts tend to form domains, which are several microns in lateral sizes, in spite of the introduction of alkyl chains in the molecular systems. In our previous papers, the resistance data were obtained by electrode gaps of 0.5 mm. However, in order to evaluate the intrinsic electrical properties of the LB lms, the resistance should be measured using an electrode gap equal to the domain size or even smaller one. In this paper, we report on the resistance of the 2C14-Au(dmit)2 LB lms measured using an inter-digitated electrode gap of 5 m together with the morphological studies by atomic force microscopy (AFM). Figure 1 shows the temperature dependence of the resistance measured along the lm plane by an ac four-probe method (13.7 Hz, 1-3 A rms). In case the electrode gap is 0.5 mm (Sample A), the LB lm shows a weak metallic behaviour from room temperature down to 216 K, but it turns to be of activation-type below the temperature. The location of the broad resistance minima differs from sample to sample but they are mostly in the range of 200-250 K in case the electrode gap is
ABSTRACTS
Fig. 1. R esistan ce m easu red by th e e lectrode gap s of 0.5 mm ( S am ple A ) an d 5 m ( S am ple B1 an d Sam ple B2).
0.5 mm. In case the electrode gap is 5 m, the metallic behaviour extends down to lower temperatures (Sample B1: 106-290 K, Sample B2: 58-290 K). The AFM has revealed that the LB lm consists of crystallites, which are 1-5 m in lateral sizes and 4-20 nm in thickness. We hypothesize that the broad minimum of the resistance vs. temperature plot emerges in a crossover region, where the metallic nature inside the crystallites is competing with the random potentials set up by disorders such as grain boundaries and/or defects, and then, the metallic nature extends down to lower temperatures by narrowing the electrode gap. We would like to further touch upon the effect of hydrostatic pressure on the resistance behaviour [5] together with the structural characterization by infrared (IR) spectroscopy [6, 7]. Reference [1] Y. F. Miura et al., Jpn J. Appl. Phys., 37 (1998) L1483. [2] Y. F. Miura et al., Solid State Commun., 113 (2000) 603. [3] Y. F. Miura et al., Synth. Met., 120 (2001) 727. [4] Y. F. Miura et al., Synth. Met., 133-134 (2003) 663. [5] Y. F. Miura et al., Intl J. Nanoscience, 1 (2002) 627. [6] S. Morita et al., J. Phys. Chem. B, 108 (2004) 19354. [7] S. Morita et al., Chem. Phys. Lett. 402 (2005) 251.
F8 SPATIALLY CONTINUOUS PHASE OF HIGHLY CONDUCTIVE POLYPYRROLE ON POLYETHYLENE POROUS FILMS G.K.Elyashevich, M.A.Smirnov, O.A.Andreeva, I.S.Kuryndin Institute of Macromolecular Compounds, Russian Academy of Sciences, Saint-Petersburg, Russia Conductive composite systems were prepared by in situ oxidative polymerization of polypyrrole (PPy) layers on oriented polyethylene (PE) porous supports in water-methanol solutions of monomer. FeCl3 was used as initiator and also as dopant. The porous structure and strongly developed surface of PE support provide a very high adhesion between components of composites. Spatially continuous phase of PPy is formed in the composites due to the formation of PPy layer on the surface of support and also on the walls of pores and through channels. Electrical properties of the samples are characterized by three conductivity values: two components of surface conductivity (parallel and perpendicular to the PE support texture, || and , respectively) and by the volume conductivity v. By varying and optimizing the conditions of polymerization and by increasing the degree of orientation of support, the values 200 S/cm for surface conductivity and 10-3 S/cm for volume conductivity for these composites were achieved. These values are the highest reported for polymer composite systems1 and also the highest achieved in our samples prepared by the formation of PPy phase in vapour of monomer2. These conductivities are close to the ones for pure doped polypyrrole. Investigation of IR spectra revealed a correlation between electrical and optical properties. It was established that IR absorption increases with conductivity. The samples become completely non-transparent over the whole IR wavelength range when their surface conductivity reaches 1 S/cm and the volume conductivity exceeds 10-6 S/cm. The high specic surface of porous supports and properties of conductive polypyrrole permits to consider the composites as perspective chemosensor materials. That is due to their capability to change conductivity under a contact with low molecular weight substances (vapors of organic solvents and gases). The inuence of substrate and electrically active component on sorption properties of the composites has been investigated. References 1. Malinauskas A, 2001, V42, P3957, Polymer. 2. Elyashevich GK, Kuryndin IS, Rosova EYu, 2002,V13, P725, Polym Adv Technol 3. Nicolas-Debarnot D, Poncin-Epaillard F. 2003, V475, P1, Anal Chim Acta. The work is supported by Russian Foundation of Basic Research (grant 04-03-32229) and by the Programme for Basic Research, Russian Academy of Sciences, Division of Chemistry and Material Sciences, Synthesis and Investigations of New Polymer Systems Containing Polyconjugated Polymers and Possessing Semiconducting and Conducting Properties.
F9 ESR, RAMAN AND CONDUCTIVITY AND STUDIES ON FRACTIONATED POLY(2-METHOXY-ANILINE-5-SULFONIC ACID) P.C. Innis, F. Masdarolomoor, S. Ashraf and G.G. Wallace ARC centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northelds Avenue, Wollongong, NSW 2522, Australia Poly(2-methoxyaniline-5-sulfonic acid) (PMAS) is a water soluble self-doped conducting polymer that has been synthesised via electrochemical or chemical oxidation routes, with both methods giving a mixture of two distinct fractions having molecular weights of approximately 2 KDa and 8 -15 KDa.1 The low molecular weight (LMWT) PMAS fraction is redox inactive and non-conducting, while the high molecular weight (HMWT) PMAS is electroactive and conducting. The as-synthesised PMAS mixture, dialysed to remove unreacted monomer but not fractionated, has a signicantly lower electrical conductivity, typically 4 to 5 times less than the puried HMWT PMAS fraction. This signicant difference in electrical conductivity was probed by preparing mixtures of the conducting HMWT and non conducting LMWT PMAS forms containing 0, 25, 50, 75 and 100% w/w HMWT. ESR, Raman and electrical conductivity studies were performed on these mixtures simulating the as synthesised PMAS. The HMWT fraction was observed to have a conductivity of 260 mS/cm while the 50:50 mixture had a conductivity of 2.6m S/cm, considerably lower than would be expected for the addition of an insulating ller. Clearly, the LMWT fraction interacts strongly with the electronic structure of the HMWT PMAS in addition to functioning as insulating ller. ESR on lms cast from these mixtures when compared to pure HMWT, at equivalent dilution levels, exhibited a lower level of electron spin in the presence of LMWT PMAS (Figure 1). This result, coupled with the Raman evidence of the formation of an isolated bipolaron at ca.1340cm-1 (Figure 2) suggests that the presence of the LMWT PMAS converts the HMWT PMAS from a high spin polaron state into a low spin bipolaron state. The chemical similarity of the LMWT and HMWT fractions would suggest that the non-electroactive
ABSTRACTS
LMWT interacts strongly with the charge carriers in the HMWT PMAS, presumably via intercalating between adjacent HMWT chains via stacking, inhibiting intrachain charge transfer and resulting in the observed loss of electrical conductivity.
9 .0 E + 1 0 8 .0 E + 1 0
500
100% LMWT
400
7 .0 E + 1 0 6 .0 E + 1 0 5 .0 E + 1 0
300
200
4 .0 E + 1 0 3 .0 E + 1 0 2 .0 E + 1 0 1 .0 E + 1 0 0 .0 E + 0 0 0% 20% 40% [H M W T ] 60% 80% 100%
0% LMWT
HMWT Dilution with LMWT HMWT PMAS
0 100
1 2 00
13 0 0
14 0 0 W a v e num be r (c m -1 )
1 50 0
1 60 0
Figure 1 . Spi n con cent ration effects for mixtures of HM W T and LM WT PMAS
Figure 2 . Raman of m ixtu res of HM WT and LMWT PMA S
1.
F. Masdarolomor, P.C. Innis, S. Ashraf and G.G. Wallace, Synth. Met. 153(2005)181-184.
F10 CONDUCTING POLYMER PHOTOPOLYMERIZATION: THE ROLE OF NITRATE ONS R. A. de Barros and W.M. de Azevedo Departamento de Qumica Fundamental, CCEN-UFPE, Cidade Universitria 50740-540, Recife, PE, Brazil Electrically conducting polymers have been investigated intensively in the last decades due to their intriguing physical properties and potencial application in advanced technologies. Usually, polymerization can be achieved by chemical or electrochemical process, which provide polymeric material with different morphologies, and consequently slightly different physical and chemical properties. A less studied route to synthesize conducting polymer is the photopolymerization process1,2. Recently we developed a synthesis route for photopolymerization of aniline monomer3 assisted by silver ons, in this paper polyaniline and silver particles are simultaneously obtained. In this work we extended this result, and propose a mechanism to explain the photo polymerization process, using photons and nitrate ons (NO3-) only. The mechanism involves the NO3- photolyis4, 5, where the hydroxyl radicals (OH radicals) generated, acts as a oxidant in the polymerization of the conducting polymer monomer. (Figure 1).
Figure1: Proposed photopolymerization mechanism. The characterization of polyaniline and polypirrole obted by new methods was performed by UV-VIS, infrared, Raman and SEM mersuments. References 1. N. Kobayashi, K. Teshima, R. Hirohashi, J. Mater.Chem. 8 (1998) 502. 2. S. Uemura, K. Teshima, S. Tokuda, N. Kobayashi, R. Hirohashi, Synth. Met. 101 (1999) 701. 3. R.A. de Barros, W.M. de Azevedo, F.M. de Aguiar, Mater.Charact. 50 (2003) 131. 4. R.G. Zepp, J. Holgn, H. Bader, Environ. Sci. Technol. 21 (1987) 443. 5. J. Mack, J.R. Bolton, J. Photochem. Photobiol. A: Chem. 128 (1999) 1.
F11 PROBING ELECTRONIC STATES EXISTING OUTSIDE OF -CONJUGATED POLYMER SURFACE X.T. Hao, T. Hosokai, N. Mitsuo, S. Kera, K. Sakamoto, K.K. Okudaira and N. Ueno Faculty of Engineering, Chiba University, Chiba 263-8522, Japan. Email: dr.xthao@gmail.com Studying surface-induced electronic structures in conjugated poly(3-hexylthiophene) (P3HT) is of fundamental importance for their application to organic devices1. To achieve efcient heterojunction that is prerequisite for high performance devices, HOMO wave function overlapping between underlying layer and the overlayer materials is desired. Thus, it is essential to investigate the electronic density existing outside of the conjugated polymer surface. The ordinary spectroscopic technique using photons or electrons to investigate the surface electronic properties like ultra-violet photoelectron spectroscopy (UPS), in which the spectral intensity comes from the top ~1nm layer inside the surface, however, is not suitable for probing the electronic states outside the surface. On the contrary, Penning ionization electron spectroscopy (PIES) using metastable atoms2 as probes Fig. 1 Schem ati c dia gra m show ing wo rk ing mec ha nism of Penn ing (shown in Fig.1), can observe the electronic density existing outside of the surface selectively since Ion izati on El ec tron Spec trosco py (PIES ) on po lyme r sur face . metastable atoms do not penetrate into the bulk of the solid. In this work, PIES was adopted to detect the electronic states existing outside the surface of regio-regular conjugated conducting P3HT thin lms on SiO2/Si substrates. UPS measurements were also performed for comparison. The PIES and UPS spectra are shown in Fig. 2. In UPS spectra,
ABSTRACTS
X10 HOMO UPS
C 6H 13
S S
HOMO with pure character can be observed clearly, whereas it does not appear in the PIES spectra. The difference is because the HOMO state is shielded by the alkyl-chain rather than spreading outside the surface. Thus, an ultra thin insulating layer may exist at the outermost surface of the P3HT thin lm due to the non-conducting alkyl chains. The effective charge transfer to the overlayer deposited on such a surface cannot be expected. In such a case, the charge transfer between overlayer molecules and P3HT would be possibly realized via tunnelling effect. Or, alternatively, it also could be realized by some kind of surface engineering to remove the side chains at outermost surface. References: 1. A. J. Cascio, J. E. Lyon, M. M. Beerbom, R. Schlaf, Y. Zhu, and S.A. Jenekhe, Appl. Phys. Lett. 88(2006) 062104. 2. Y. Harada, S. Masuda, H. Ozaki, Chem. Rev. 97 (1997) 1987.
X10
n
C 6H 13
PIES
12
10
Binding energy (eV)
Fig.2 Comp ari son of H e* PI E S and H e I U PS spec tra on the sur face of P3H T thin film
F12 STRONG EFFECT OF THE DIAMETER ON THE ELECTRICAL PROPERTIES OF SINGLE PEDOT NANOWIRES J.L. Duvail 1; Y. Long 1, 2; S. Cuenot 1 ; Z. Chen 3; C. Gu 3; O. Chauvet 1 1. 2. 3. Institut des Matriaux, Universit de Nantes, 2 rue de la Houssinire, 44322 Nantes, France. School of Materials Science and Engineering, Shandong University, Jinan, China. Institute of Physics, Chinese Academy of Sciences, Beijing, China.
Nanowires and nanotubes made of conjugated polymers are much investigated for both fundamental and applied reasons. The resulting nanomaterials are promising as support for bio- and chemical sensors, eld emission displays, nanodevices... It is thus crucial to understand and to control the mechanisms responsible for their improved properties in comparison to the bulk materials. Electrical properties of poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires have been investigated both on individual nanowires and on arrays of nanowires. It is shown that the conductivity and the electrical behaviour down to low temperature strongly depends on the nanowire diameter. Spectroscopic studies on these nanowires made possible to point out the mechanisms responsible for the electrical properties [1]. The improvement of the molecular and the supermolecular structure for the smaller nanowire diameters has been addressed from a Raman spectroscopic study. Changes in the doping level due to the conning effects was determined by a X.P.S. study. Moreover, a decrease in the spin/charge ratio when the nanowire diameter goes from 100 nm to 50 nm has been evidenced by Electron Spin Resonance study. Such a decrease is attributed to an increase in the bipolaron population ratio. Then, it corroborates the improved chain ordering for the smaller nanowire diameters. This study gives a better understanding of the effects of both the conned synthesis and the nanometric scale on the mechanisms responsible for the conduction in conjugated polymer nanowires. This is of importance for future devices based on such building blocks.
Figure 1. SEM image of a PEDOT nanowire connected by 4 platinum leads fabricated by FIB References [1] Duvail, J. L.; Rtho, P. ; Fernandez, V. ; Louarn, G.; Molinie, P.; Chauvet, O. ; J. Phys. Chem. B 2004, 108, 18552
F13 CALCIUM SILICATE FACILITATED POLYMERISATION OF MAS T. Borrmann*, J. H. Johnston, A. J. McFarlane, B. G. Anderson, D. Witkowski, T. H. Lim School of Chemical and Physical Sciences Victoria University of Wellington, P O Box 600, 6005 Wellington, New Zealand Iodine is a known dopant for conducting polymers and a weak oxidising agent. It tends to over-oxidise doped polymers, but iodine does not have the oxidative strength to facilitate polymerisation for quite a range of monomers, for example aniline. The polymerization of 3-amino-4-methoxy-phenyl sulfonic acid, MAS, one of the water-soluble forms of aniline, in basic environments is studied. A proprietary nano-structured calcium silicate with a unique open framework structure of nano-size platelets and a consequent high pore volume and surface area is found to activate iodine absorbed onto the platelets thereby enhancing its oxidative strength to facilitate the formation of Poly (2-methoxy-aniline-5-sulfonic acid), PMAS. Presented are yields and UV-visible spectra (Figure 1) measured after completion and during the polymerization reaction. The resulting PMAS coats the nano-size platelets of the calcium silicate structure but the open framework and high pore
ABSTRACTS
volume and surface area are retained. It is likely the iodine forms a charge transfer complex with the calcium ions in the silicate and as such is able to effect polymerisation.
Fig. 1. Development of an UV-visible spectrum during the polymerization of MAS with iodine in the presence of nano-structured calcium silicate.
F14 INDUCTION OF TITANIUM DEPOSITION THROUGH NUCLEATION WITH PYRROLE IN AN IONIC LIQUID. Jie Ding1, Jian Wu1, Douglas MacFarlane2, William E. Price*1, Gordon Wallace1 ARC Centre of Excellence for Electromaterials Science 1Intelligent Polymer Research Institute, University of Wollongong, Wollongong, NSW 2522, Australia 2School of Chemistry, Monash University, Clayton VIC 3800, Australia * : wprice@uow.edu.au; Tel: +61 2 42 213 509; Fax: +61 2 42 214 287; Room Temperature ionic liquid (IL) electrolytes, with good solvent properties and wide electrochemical windows show promise for electrowinning or reduction of different metals 1. Reports of direct electrodeposition of titanium from a range of ILs at room temperature have not been convincing or successful. 2, 3. Other work has reported that trace amounts of titanium metal can be electrodeposited 4 on Au(111) and 5 HOPG (highly oriented pyrolytic graphite) from ionic liquids. Titanium electro-deposition from organic solvents has also been achieved using a foreign metal (such as silver) as a nucleating agent 3. Previous work demonstrated the ability of conducting polymers to electrochemically separate metals through polymer coated membranes. 6-9. This work was extended to show that metals such as gold could be deposited from ions in solution through reduction by conducting polymers 10, , 11 in an electroless fashion. In the case of gold Au3+ is reduced to Au through the oxidation of the polymer. It is thus possible to use a conducting polymer coated substrate to nucleate metals such as gold to form good deposits, using a variety of substrates.12, 13. In this study, we used a similar approach by using pyrrole in the ionic liquid ethyl-methyl-imidazolium bis(triuoromethanesulphonyl)amide (EMI TFSA) to rst deposit polymer to provide a stable nucleation site for titanium to deposit on. The results were very surprising. Titanium deposition experiments were carried out using rstly a preformed polypyrrole TFSA coated glassy carbon electrode and secondly using mixtures of pyrrole and 0.59 M titanium(IV) in the same solution. Using preformed polypyrrole and cyclic voltammetry with a potential range of -1.8V to 0.9 V vs Ag/Ag+ in a three electrode cell using Pt gauze as the auxiliary electrode, it was found that the extent of metallic deposition was very limited. This might have been expected because of the decreased conductivity of PPy at negative potentials. Even if a good nucleating surface was available the electrochemical efciency would likely to be very poor particularly at the low potentials needed for reduction of the titanium (-1.8 V). This was true also for experiments carrying out reduction at -18.V for extended periods of time (16h). Subsequent experiments involved the addition of pyrrole monomer (0.06M) to the ionic liquid media containing TiCl4 using initially CV and also constant reduction potential conditions. This allowed us to consider the role of pyrrole itself and the possibility of creating conducting polymer nucleation sites in situ. The results showed obvious polypyrrole deposition by optical microscopy and shown by the growth in the CV. In addition, a distinct metallic lustre was also observed on substrates subjected to 16h constant potential reduction and optical micrographs indicated the presence of numerous metallic particles. Scanning electron microscopy (SEM), simultaneous Energy Dispersive X-ray Analysis (EDX) and X-ray photoelectron spectroscopy (XPS) revealed smooth lms rich in titanium, indicated that pyrrole was able to induce nucleation during the reduction process. Further work is being conducted to investigate in more detail the mechanism by which this occurs. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. Endres, F., Electrochemical and Solid-State Letters, 2002, 5, C38-C40. Chen, G.Z. and Fray, D.J., Nature, 2000, 407, 361-364. Abbott, A.P., Bettley, A., and Schiffrin, D.J., J. Electroanal. Chem, 1993, 347, 153-164. Mukhopadhyay, I., et al., Electrochimica Acta, 2005, 50, 1275-1281. Mukhopadhyay, I. and Freyland, W., Langmuir, 2003, 19, 1951-1953. Price, W.E., Too, C.O., Wallace, G.G., and Zhou, D.X., Synthetic Metals, 1999, 102, 1338-1341. Huijun, Z., Price, W.E., and Wallace, G.G., Polymer, 1993, 34, 16-20. Huijun, Z., Price, W.E., and Wallace, G.G., J. Electroanal. Chem., 1992, 334, 111-120. Price, W.E., Ralph, S.F., and Wallace, G.G., Australian Journal of Chemistry, 2001, 54, 615-619. Kang, E.T., Ting, Y.P., Neoh, K.G., and Tan, K.L., Synthetic Metals, 1995, 69, 477-8. Ding, J., Price, W.E., Ralph, S.F., and Wallace, G.G., Polymer International, 2004, 53, 681-687. Tsekouras, G., Ralph, S.F., Price, W.E., and Wallace, G.G., Fibers and Polymers, 2004, 5, 1-5. Ding, J., et al., Synthetic Metals, 2003, 135-136, 35-36.
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F15 FABRICATION OF CONDUCTING POLYMER NANOWIRE DEVICES N.T. Kemp, J.W. Cochrane, R.N. Newbury School of Physics, The University of New South Wales, Sydney, NSW 2052, Australia.
One-dimensional nanostructures such as carbon nanotubes, metal and oxide nanowires, conducting polymer nanotubes, nanobres and nanowires have received much attention due to their unique physical and electrical properties and their prospects for application in devices such as ultrasensitive biochemical and chemical sensors1, transistors2, logic gates3 and in the miniaturization of electronic circuits4, 5. Although conducting polymer nanowires and nanotubes have been around for some time now, integration into devices in a cost-effective manner for large-scale production still remains a challenge. In this report we demonstrate a template-free method for growing ordered conducting polymer nanowires within prefabricated devices such that electrical contacts are made in situ during the growth procedure, thereby avoiding the difculties associated with positioning the nanowires and making electrical contacts post-synthesis. The devices we have made show excellent and robust electrical connections and the controllable geometry of the nanowire growth allows both multiple (highly aligned arrays consisting of thousands of nanowires) and single nanowire devices to be realized. To demonstrate the effectiveness of the technique we have developed nanowire chemical sensors that show high sensitivity to ammonia gas. We also report on the electrical transport properties of the nanowires from measurements of the low temperature DC conductivity and current-voltage characteristics. References
1. F. Patolsky and C. M. Lieber, Materials Today, 8(4) 20 (2005). 2. J. T. Sander, R. M. Tans, A. R. M. Verschueren, et al., Nature, 393 49 (1998). 3. Y. Huang, X. Duan, C. M. Lieber, et al., Science, 294 1313 (2001). 4. G. Y. Tseng and J. C. Ellenbogen, Science, 294(9) 1293 (2001). 5. A. Bachtold, P. Hadley, T. Nakanishi, et al., Science, 294 1317 (2001).
F16 ELECTRONIC TRANSPORT PROPERTIES OF CARBON NANOTUBES AND NETWORKS Alan B. Kaiser1, Viera Skkalov2 and Swee K. Goh1 1 MacDiarmid Institute for Advanced Materials and Nanotechnology, SCPS, Victoria University of Wellington, P O Box 600, Wellington, New Zealand 2 Max-Planck-Institut fr Festkrperforschung, 70569 Stuttgart, Germany For small bundles of two or three parallel metallic SWNTs (as measured by Skkalov, Woo and Roth), the conductance data are consistent with tunneling through an interfacial barrier into a Luttinger liquid, but this interpretation is not unique. For thick SWNT networks, we show that backscattering by zone-boundary phonons in SWNTs of energies around 160 meV can explain the changeover to metallic sign for the conductivity above 230 K, in analogy with the suppression of conductance at high bias voltages by optical and zone-boundary phonons as proposed by Yao et al.1 When these thick SWNT networks are exposed to different molecules, systematic correlated changes are observed in their physical properties.2 Ionic acceptor doping causes an increase of electrical conductivity that correlates with an increase of the absorbance in the far infrared region and an increase in the frequency of Raman spectral lines. Conversely, treatment with other molecules leads to a decrease in both conductivity and far infrared absorption. We infer that the primary cause of these systematic changes in properties is the change in free carrier density arising from the different treatments (whether acceptor and donor doping of the SWNTs or the formation of covalent bonds). We propose that the temperature dependence of the conductance of individual MWNTs can be accounted for by an extension of the two-shell scenario of Bourlon et al.3 1 Z. Yao, C.L. Kane and C. Dekker, Phys. Rev. Lett. 84, 2941 (2000). 2 V. Skkalov, A.B. Kaiser, U. Detlaff-Weglikowska, K. Hrnarikov and S. Roth, J. Phys. Chem. B, 109, 7174 (2005). 3 B. Bourlon, C. Miko. L. Forr, D.C. Glattli and A. Bachtold, Phys. Rev. Lett. 93, 176806 (2004).
F17 ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY OF MULTIPLE ATOMS ENCAPSULATED FULLERENES Shojun Hino1,2)*, Masayuki Kato2), Konosuke Furukawa2), Daisuke Yoshimura3,4), Hiroe Moribe5), Haruya Okimoto5), Takao Akachi5), Takeshi Inoue5), Yasuhiro Ito5), Toshiki Sugai5), Hisanori Shinohara5) 1) Faculty of Engineering, Chiba University, Chiba-263-8522 Japan 2) Graduate School of Science and Technology, Chiba University, Chiba-263-8522 Japan 3) UVSOR, Institute for Molecular Science, Okazaki 444-8585 4) Research Center of Material Science, Nagoya University, Nagoya 464-8602 Japan 5) Graduate School of Science, Nagoya University, 464-8602 Japan Band gap of fullerenes varies from almost 0 eV of metallofullerenes to 2 eV of C60. Because of this wide range, fullerenes are one of the most
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prospective candidates to fabricate nano-scale molecular electronic devices. Their electronic structure is crucial information to construct such devices. Ultraviolet photoelectron spectroscopy is a powerful tool to elucidate the electronic structure of fullerenes. Thanks to accumulation of ultraviolet photoelectron spectral data of mono-metal atom encapsulated fullerenes, it has been revealed that the electronic structure of such metallofullerenes is principally dominated by the cage structure and electron donation from the incorporated metal atom to the fullerene cage modies the electronic structure of upper valence band region1-7). This seems to relate to the small interaction between the entrapped atom and the cage. The inner space of the fullerene cage is wide enough to accommodate single atom. Fullerene cages also entrap multiple atoms7) and metal cluster encapsulated fullerenes have been isolated8,9). The inner space of fullerenes is rather too narrow to accommodate two or more atoms in it, so that the interaction between the entrapped species and the cage might be much stronger than that in mono-atom encapsulated metallofullerenes. Ultraviolet photoelectron spectra of the same cage structure Y2@C82 and Y2C2@C82 have been measured and their electronic structure is fairly analogous10). This observation indicates that the electronic structure of multiple atom incorporated fullerenes is also governed mainly by the cage structure. In the conference we will present our resent results on the ultraviolet photoelectron spectral measurement of Lu2C2@C82, Lu2@C82 and Ti2@C82 and examine whether the electronic structure of multiple atoms encapsulated fullerenes is governed by the cage structure and investigate other possible origins that may inuence their electronic structure.
References 1) S. Hino et al., Phys. Rev. Lett. 71, 4261 (1993). 2) S. Hino et al., Chem. Phys. Lett. 281, 115 (1997). 3) S. Hino et al., Chem. Phys. Lett. 300, 145 (1999). 4) S. Hino et al., Chem. Phys. Lett. 337, 65 (2001). 5) K. Iwasaki et al., Chem. Phys. Lett. 398, 389 (2004). 6) S. Hino et al., Chem. Phys. Lett. 402, 217 (2005). 7) S. Stevenson et al., Nature (London) 401, 55 (1999). 8) T. Inoue et al., J. Phys. Chem. B 108, 7573 (2004). 9) B. Cao et al., J. Am. Chem. Soc. 126, 9164 (2004). 10) S. Hino et al., Phys. Rev. B 72, 195424 (2005).
F18 IN VITRO CYTOXICITY TESTING OF SINGLE WALLED CARBON NANOTUBES ON HUMAN A549 LUNG CELLS A CELLULAR AND SPECTROSCOPIC STUDY. Alan Casey, Eva Herzog, Maria Davoren, Hugh Byrne, Gordon Chambers Department of Physics Dublin Institute of Technology Kevin Street, Dublin 8, Ireland The in vitro cytotoxicity testing of a nanomaterial generally requires its dispersion within a cell culture medium, followed by its subsequent addition to a cell line of interest for a dened incubation period, after which its effect on cell viability (in relation to time matched controls) can be assessed by a variety of different endpoints. This practice essentially assumes the interaction between the materials under test is minimal within the medium in which it is dispersed. Parallel spectroscopic and cytoxicity studies were thus conducted on HiPco single walled carbon nanotubes dispersed within a commercial cell culture medium (F-12K Kaighins modication) prepared both with and without foetal bovine serum. The ndings of both the spectroscopic and cytotoxicity test will be presented and possible relations between the two discussed. Upon addition of raw SWNTs to the medium a noticeable colour change was observed. UV/Vis absorption spectroscopy revealed a dramatic reduction in the absorption attributable to the phenol red, a pH indicator within the medium, without an associated change in pH. Reductions were also observed in absorbance features attributed to various components of the medium indicating an interaction with the SWNT. Concentration dependent studies of the uorescent emission of the various components of the media were modelled to show a differing degree of interaction between the SWNTs and the various components of the medium. Raman spectroscopy gave no indication of differences between the raw SWNT and those deposited from the medium suspension indicating that no debundling of the SWNT occurred. Notable differences were observed between the behaviour with and without serum, these differences and the implications for toxicity and in vitro studies will be discussed. Finally this paper will describe the in vitro toxicity evaluation of HiPco SWNTs in A549 cells, a human epithelial-like lung carcinoma cell line. Cytotoxicity following 24 hour exposure to increasing concentrations of these SWNTs was assessed using multiple endpoint measurements. Results from all the in vitro endpoints will be presented and each endpoint will be evaluated in terms of sensitivity and their relative utility and importance.
F19 COULOMB BLOCKADE AND NON-OHMIC TRANSPORT IN DISORDERED NANOFIBERS M. M. Fogler (UCSD), S. V. Malinin (WSU), T. Nattermann (Universitat zu Koln) A theoretical model of a nanober is considered where it is viewed as a long one-dimensional wire with a nite density of strong random impurities. This model is shown to behave as a chain of weakly coupled quantum dots. Its conductivity is found to have a surprisingly rich dependence on bias voltage V and temperature T due to the interplay of Coulomb blockade, Luttinger-liquid, and disorder effects. Different regimes appear because of competition between sequential and co-tunnelling transport mechanisms. At low T and V the conductivity is limited by breaks: randomly occurring clusters of impurities with a particular spatial distribution pattern that inhibits the transport no matter how the activation and tunnelling are combined. As either T or V increases, the breaks become shorter and less resistive. The conductivity can exhibit an exponential, a stretched exponential, and a power-law dependence on T and V depending on the position at the T-V diagram. Unlike the transport through a single impurity barrier, in a long 1D
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wire the effect of T and eV is not symmetric. Our results imply that the exponents of the power-laws in V and T reported in a number of recent transport measurements of polymer nanobers and related one-dimensional systems may be determined not only by the intrinsic interaction parameters but also by statistics of unavoidable impurities and defects. References [1] cond-mat/0602008 and in preparation. [2] M. M. Fogler and R. S. Kelley, Phys. Rev. Lett. 95,166604 (2005).
F20 LIGHT ACTUATION OF POLYMER-NANOTUBE COMPOSITES Samit Ahir, Ali Tajbakhsh and Eugene Terentjev Cavendish Laboratory, University of Cambridge, UK
Rubbery composites containing multi-walled carbon nanotubes exhibit reversible photo-mechanical actuation under irradiation with near infrared light1. We demonstrate that this IR-actuation is reproducible across differing polymer systems, and that the nanotube response to photon absorption is predominantly responsible for the observed effect2. We show that the speed of the nanocomposite actuation mechanism is faster than classical Debye relaxation3. The magnitude, and most spectacularly - the sign of the response, are directly related to the degree of uniaxial alignment of the nanotubes in the matrix. We study this stress-induced alignment in some detail, both theoretically and experimentally (using synchrotron WAXs). The actuation stroke depends on the polymer being tested, however, the general response features are qualitatively identical for all nanotube-polymer systems tested. We discuss a number of theoretical models for the reversible actuation behaviour. The underlying concepts should be applicable to various other (non-carbon) nanotube systems. [Parts of this work have appeared in Nature Materials, Physical Review B and Physical Review Letters.] 1. S. V. Ahir and E. M. Terentjev, Nat. Mater. 4, 491 (2005). 2. S. V. Ahir et. al., Phys. Rev. B 73, 084520 (2006). 3. S. V Ahir and E. M. Terentjev, Phys. Rev. Lett. 96, 133902 (2006).
F21 RAMAN ANALYSIS OF HIGHLY CONJUGATED POLYPYRROLE ON MULTIWALLED CARBON NANOTUBE NANOTEMPLATES Bin Chen, Jun Li, Lance Delzeit, Qibing Pei MS 245-3, NASA Ames Research Center, Moffett Field, CA 94035, USA Polypyrrole (PPy) has high electronic conductivity and air stability , , it has great potential for actuator and battery applications , . The device performance is crucially depending on mechanical strength and polymer conductivity. Traditionally, the conductivity is enhanced through ion doping. However, this process normally decreases the mechanical strength of PPy thin lms. On the other hand, an increase in mechanical strength by forming a co-polymer is usually achieved at the expense of electronic conductivity. Alligned multiwalled carbon nanotubes (MWNTs) are an ideal nanotemplate, providing both high mechanical strength and high electric conductivity for PPy/MWNT composites. Such core-shell architecture is particularly important for photovoltaic applications since the photoemission efciency is improved due to the increased hole-electron pair (excition) separation . The well-dened graphitic structure at the outer surface of MWNTs may improve the ECP packing through -stacking, although this has not been fully investigated. We report studies of the polypyrrole (PPy) lms electropolymerized around vertically aligned bamboo-like multiwall carbon nanotube (MWNT) arrays. Raman spectroscopy shows large percentage of the dipolarons, resulting from high PPy conjugation in this highly conductive PPy-MWNT composite. The conductivity is also demonstrated by electrochemical studies. The SEM and TEM observations of the high mechanical strength, dense packing and strong adhesion of this composite are also results of the -stacking of the PPy backbone and the aromatic MWNT sidewalls. Overall, the high efciency of the electropolymerization of PPy on MWNT array as well as the extraordinary properties in mechanical strength, electrical conductivity, and chemical stability can be attributed to the combination of three factors of the unique MWNT nanotemplates. These include: (1) initiation: The broken graphitic shell at the sidewall of the bamboo-like MWNT electrode form various oxygen containing function groups, playing as active sites to initiate the electropolymerization of PPy. (2) propagation: The direct attachment of MWNTs to the metal electrode improves the electron transfer rate at the MWNT surface so that PPy can be uniformly deposited in the 3-D structure. (3) stacking: The -stacking of the conjugate PPy backbone on the nanotemplate of the graphitic MWNT sidewall results in highly ordered PPy packing, which improves adhesion, mechanical strength, and electrical conductivity. Similarly, we have applied resonant Raman excitation under 633 nm to investigate the PMMA carbon nanotube composite. We demonstrated that metallic carbon nanotube can be increased through dispersion in melt blended PMMA composite. The Raman studies provide composite structure and electric properties simultaneously, which is an important tool to monitor growth and processing conditions .
F24
P.A. Bobbert1, W.F. Pasveer2, J. Cottaar1, R. Balasubramanian1, M. Bouhassoune1, R. Coehoorn2 1Group Polymer Physics, Department of Applied Physics, Technische Universiteit Eindhoven, P.O. Box 513, NL-5600 MB Eindhoven, The Netherlands 2Philips Research Laboratories, Professor Holstlaan 4, NL-5656 AA Eindhoven, The Netherlands
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CONDUCTION IN DISORDERED SEMICONDUCTING POLYMERS: NEW THEORETICAL PERSPECTIVES
Electrical conduction in disordered semiconducting polymers takes place by hopping of charge carriers in an energetically disordered landscape of hopping sites. In polymer eld-effect transistors, where the number of carriers per site can become of the order of a few percent, it has been established that the density of charge carriers has a strong inuence on the charge carrier mobilities [1]. On the other hand, mobilities in polymer diodes, where the number of carriers per site is very low, have always been assumed to have an important dependence on the electric eld. The concept of correlated disorder was introduced in order to explain a eld-dependence for a wide region of electric eld strengths [2]. Recently, however, we have demonstrated that the current-voltage characteristics of diodes of PPV-based polymers can be very well described assuming an uncorrelated Gaussian energy disorder and taking into account a numerically [3] or analytically [4] determined dependence of the mobility on the carrier density (see Fig. 1). The reason for the unexpected dependence on the carrier density at such low densities is the fact that at the relevant temperatures the carriers are energetically located in the low-energy tail of the Gaussian density of states, such that state-lling effects are still important. Only at very high voltages the dependence of the mobility on the electric eld becomes relevant (see Fig. 1). In line with recent experimental observations [5,6] we come to the conclusion that the previously assumed dependence of the mobility on electric eld in diodes is, for a large part, actually a density-dependence. Our numerical studies of conduction in disordered semiconducting polymers have revealed a very interesting behavior of the electro-chemical potential and the current distribution in the polymer. The electro-chemical potential has a structure of terraces on which the potential only gradually varies, interrupted by cliffs at which the potential suddenly drops. The current is very inhomogeneously distributed, with high current regions coinciding with the terraces (see Fig. 2). This behavior, which is related to the percolative nature of the conduction, has important consequences for the functioning of polymer devices. We are presently exploring these consequences.
Fig . 1 E xper imental and ca lcula ted cur r ent-voltage charac ter istics of a hole-only diode of NRS -P PV (thi ckness L). T he effects of the dependences on density (p) and e lectr ic field (E ) i s demonstra ted.
Fig. 2 E lectro-chemical potentia l (equipotentia l lin es) and cur rent s trength (yellow r egions: more than 10x the a verage) in a s lice of a simula tion box with Gau ssian energy disord er, repr esenting a polymer l a yer of about 100 nm under typica l condi tions, with a horizo ntal electr ic field.
[1] M.C.J.M. Vissenberg and M. Matters, Phys. Rev. B 57, 12964 (1998). [2] Y.N. Gartstein and E.M. Conwell, Chem. Phys. Lett. 245, 351 (1995). [3] W.F. Pasveer, J. Cottaar, C. Tanase, R. Coehoorn, P.A. Bobbert, P.W.M. Blom, D.M. de Leeuw, and M.A.J. Michels, Phys. Rev. Lett. 94, 206601 (2005). [4] R. Coehoorn, W.F. Pasveer, P.A. Bobbert, and M.A.J. Michels, Phys. Rev. B 72, 155206 (2005). [5] C. Tanase, E.J. Meijer, P.W.M. Blom, and D.M. de Leeuw, Phys. Rev. Lett. 91, 216601 (2003). [6] P.W.M. Blom, C. Tanase, D.M. de Leeuw, and R. Coehoorn, Appl. Phys. Lett. 86, 092105 (2005).
F25 THE FABRICATION OF INTERDIGITATED ELECTRODES WITH LOW COST NANOIMPRINT LITHOGRAPHY AND ELECTROPLATING FOR PHOTOVOLTAIC APPLICATIONS Ravin Ginige, Nikolaos Kehagias, Vincent Reboud, Colm ODwyer and Clivia Sotomayor Torres, Tyndall National Institute, Lee Maltings, Cork, Ireland
The performance1 of low cost organic photovoltaics has been improving in recent years but is still well behind the more costly inorganic solar cell technology2. For improved performance and cost competitiveness, issues of exciton diffusion, charge separation, series resistance and stability need addressing using low cost technology. To address the rst two issues, we demonstrate that the low cost technologies of nanoimprinting3 and electroplating4 can be adapted to generate interdigitated electrodes with nanometer spacing of the order of the electron and hole diffusions lengths in organic polymers. The technique we have adapted uses three steps: a nanoimprint interdigitated electrode template of large separation typically of the order of several hundred nanometers created using electron beam writing, optical lithography to dene the large area anode and cathode contacts, and electroplating of the interdigitated electrode imprints to tailor the required electrode spacing to tens of nanometers. In this paper we present and discuss this low cost photovoltaic nanofabrication technique for photovoltaic cells.
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Fig. 1 Nanoimprint Stamp (Template)
Fig. 2 Imprint in PMMA
References: 1. www.laserfocusworld.com, February 2006, news breaks: Polymer solar cells achieve 5.2% efciency, David Carroll, Wake Forest University, USA 2. Characterisation of Ge-on-Si virtual substrates and single junction GaAs solar cells, Ravin Ginige et.al., submitted to Semiconductor Science and Technology, March 2006 3. Nanoimprint lithography for the fabrication organic photovoltaic cells, N. Kehagias, A. Goldschmidt, C. Clavijo-Cedeno, A. P. Kam, J. Seekamp, M. Zelsmann, U Scherf, T. Farrell and C. M. Sotomayor Torres, 2nd Volkswagen Stiftung Symposium on Complex Materials, June 2-3, 2005, Stuttgart, Germany 4. Organic eld-effect transistors with electroplated platinum contacts L. A. Majewski, R. Schroeder, M. Grell, Applied Physics Letters. 2004, 85, 3620
F26 HIGH-PERFORMANCE AMBIPOLAR TRANSISTORS AND SCHOTTKY DIODES BASED ON RUBRENE SINGLE CRYSTALS T. Takenobu1, T. Takahashi1, J. Takeya2,3, and Y. Iwasa1 1IMR, Tohoku Univ., Sendai, Japan, and CREST-JST, Kawaguchi, Japan 2Materials Science Research Laboratory, CRIEPI, Tokyo 201-8511, Japan 3RIKEN, Wako, Japan Since its realization in 1986, organic eld-effect transistors are attracting increasing attention for their possible used in exible low-cost electronic circuits. The current benchmark material for organic single crystal FETs is rubrene (a tetraphenyl derivative of tetracene, C42H28), for which the reported eld-effect mobility of single crystals reaches 20 cm2/Vs.[1] The Hall effect in the eld-induced accumulation layer on the surface of rubrene single-crystal samples have been investigated.[2] Although the transport properties of rubrene transistors have been claried, a very little is known so far about carrier injection and accumulation mechanism. Very recently, ambipolar organic eld-effect transistors (OFETs) have been realized using a polymethylmethacrylate (PMMA) gate dielectric.[3] Thus, the remaining problem is the control of carrier injection. Herein, we have rstly studied a series of metal contacts on rubrene single crystal transistors and nd systematic dependence of the transport barrier on the metal workfunction. We used PMMA as the buffer gate dielectric. On these substrates, thin rubrene crystals with a thickness of approximately 1 m were laminated using a technique described in Takeya et al.[2] Finally, source and drain contacts were fabricated by thermally evaporated gold, magnesium, calcium and painted silver paste, which have various work functions. We observed ambipolar behavior for all devices and nd systematic dependence of the transport barrier on the metal workfunction (see gure). These data provide insight into surface states that strongly inuence the contact resistance and direct evidence of the weak Fermi level pinning. In the process of the study of metal-rubrene heterojunctions, we have realized a highperformance ambipolar transistor (hole mobility = 0.4 cm2/Vs, electron mobility = 0.2 cm2/Vs) and an efcient single-crystal rubrene schottky diode by single device, employing both a Schottky contact and an Ohmic contact.
r u 10 -5 C10 -6 n 10 -8 i 10 -9 -10 a 10 r10 -11 -12 D 10

10
-7
VDS = 50V In N2 glove box
r u 10 -5 C10 -6 n 10 -8 i 10 -9 -10 a 10 r10 -11 -12 D 10

10
-7
VDS = 150V In N2 glove box
50 100 150 200
50 100 150 200
Gate Voltage (V)
Gate Voltage (V)
Figure. Transfer characteristics of a rubrene OFET using Au (left) and Ca (right), respectively. References [1] E. Menard, V. Podzorov, S.-H. Hur, A. Gaur, M. E. Gershenson, and J. A. Rogers, Adv. Mater. 16, 2097 (2004). [2] J. Takeya, K. Tsukagoshi, Y. Aoyagi, T. Takenobu, and Y. Iwasa, Jpn. J. Appl. Phys. 44, L1395 (2005); V. Podzorov, E. Menard, J. A. Rogers, and M. E. Gershenson, Phys. Rev. Lett. 95, 226601 (2005). [3] T. Takahashi, T. Takenobu, J. Takeya, and Y. Iwasa, Appl. Phys. Lett. 88, 033505 (2006).
F27 TEMPERATURE DEPENDENCE OF ELECTRICAL CHARACTERISTICS OF THIN-FILM FIELD-EFFECT TRANSISTORS P. Stallinga, H. L. Gomes, Universidade do Algarve, Faculdade de Ciencias e Tecnologia, Campus de Gambelas, 8005-139 Faro, Portugal
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The temperature dependence of thin-lm eld effect transistors (TFTs) is described. As a starting model, the theory of two-dimensional TFTs is used 1. This model predicts a current and mobility that is independent of temperature, contrary to what is normally observed in (organic) TFTs. To explain temperature dependence, the model is extended with the inclusion of abundant traps. It is shown that a discrete trap will cause a temperature dependence of current and as-measured mobility. To further extend the theory and explain gate-bias-dependent mobilities, non-discrete distributions of trap states and conduction states are tried. It is shown that when the traps have an exponential density of states (DOS), the mobility is both temperature and bias dependent, resulting in the observation of the Meyer-Neldel Rule 2. When also the conduction states are non-discrete, the
temperature dependence disappears, although the mobility is still strongly bias-dependent. The table below summarizes this. The results are compared to models of Poole and Frenkel 3 and Shur and Hack 4. The results are also compared to results obtained by us in TFTs of sexithiophene (T6)5. Table: summary of results. Figures: Density of states used for the calculations (left). In the case of discrete conduction states (a) and exponentially distributed trap states (solid line), the resulting Arrhenius plots of as-measured mobility FET, are bias dependent, as shown on the right, resulting in so-called Meyer- Neldel Rule.
[1] P. Stallinga, H. L. Gomes, this conference. [2] W. Meyer and H. Neldel, Z. Tech. 18, 588 (1937) (german). [3] S. M. Sze, Physics of semiconductor devices, 2nd edition, Wiley Interscience, (1981). [4] M. Shur and M. Hack, J. Appl. Phys. 55, 3831 (1984). [5] P. Stallinga, H.L. Gomes, F. Biscarini, M. Murgia, D.M. de Leeuw, J. Appl. Phys. 96, 5277 (2004). F28 MAGNETIC STATES AND PEIERLS INSTABILITY IN POLYACENE M. C. dos Santos Instituto de Fsica, Universidade de So Paulo CP66318, 05315-970, So Paulo, SP, Brazil Polyacene, the prototype of one-dimensional graphite of formula (C8H4)x, is an organic conjugated polymer formed from fused benzene rings. Although acene chains longer than heptacene have not been synthesized to date, polyacene (PAc) received attention in the last decades due to theoretical predictions of a vanishing band gap and superconductivity. Renewed attention has been drawn to the acene series of molecules after the use of tetracene and pentacene as active materials in organic thin lm transistors. Theoretical studies on conformation and electronic structure of PAc have given controversial results regarding the existence of Peierls instability and other phenomena related to the low dimensionality1. More recently, oligomers up to decacene have been theoretically studied in the framework of density functional theory (DFT). It was proposed that oligocenes higher then heptacene should present a triplet ground state and a vanishing band gap2. These calculations have also led to the conclusion that oligoacenes should present uniform bond lengths and absence of Peierls distortion. Further work within the same level of theory predicted a singlet ground state with diradical character3. The present work deals with oligoacenes having from 20 to 23 fused rings and the innite system PAc. The conformations and the electronic structures were theoretically investigated through density functional theory adopting the hybrid B3LYP/6-31G(d) functional. The long oligoacenes present a cis conformation (see gure) and soliton-like distortions along the chain. The defective regions having uniform bond lengths produce localized states in the top of the oligomer valence band. The spontaneous creation of bond alternation defects leads to high spin magnetic ground states. The non-magnetic state of polyacene presents a Peierls distorted trans conformation which is lower in energy by few meV per unit cell from the symmetric (non-alternating) state. The lowest energy structure is predicted to present a cis pattern of bonds with alternation defects and a triplet state per unit cell.
1 C. Raghu, Y. A. Pati, and S. Ramasesha, Phys. Rev. B 65, 155204 (2002). 2 M. Bendikov, F. Wudl, and D.F. Perepichka, Chem. Rev. 104, 4891 (2004). 3 M. Bendikov et al., J. Am. Chem. Soc. 126, 7416 (2004).
F29 BLOCH OSCILLATIONS IN A ONE-DIMENSIONAL CONDUCTING POLYMER Y. Li, 1 X. J. Liu, 1 J. Y. Fu, 1 D. S. Liu, 1,2,S. J. Xie, 1,2 L. M. Mei 1,2 1School of Physics and Microelectronics, Shandong University, Jinan, 250100, China 2State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, China One of the most important problems in conducting polymers is to understand the underlying mechanisms of charge transport under an external electric eld. Many interests of theoretical researchers have been attracted into the study of dynamics of polarons in a weak electric eld. [1-2] It has been shown that there exist upper critical electric eld over which a preexisted polaron dissociates and the electron propagates in the form of a free charge. [3] However, the dynamic behaviour of the free charge has scarcely been studied up to now. We simulate the dynamics of charge transport of a dissociated polaron under a strong external eld in a one-dimensional conducting polymer. The simulations are performed within the framework of Su-Schrieffer-Heeger model coupled by a Newtonian equation of motion with a nonadiabatic evolution method.[4] It is shown that, eliminating the effects of lattice uctuations, the electron derived from the dissociation of a polaron propagates freely along the polymer chain in the form of a wave packet and performs temporal and spatial Bloch oscillations (BOs), see Fig 1. Unlike the characteristics of the normal BOs in a rigid lattice, [5] the mean displacement of the oscillating electron is not zero but causing an effective forward movement in the direction of electric eld. It is found that the electron-lattice coupling plays an important role in the effective forward movement of the electron in the process of BOs. Although the BOs are induced at an electric eld under which a preexisted polaron cannot survive anymore, there still exist transient polaron states due to the electronlattice couplings when the electronic wave packet reaches the bottom of conduction band.
ABSTRACTS
Fig. 1. Time evolution of the free electronic wave packet at an electric eld of V/cm. The red curves correspond to the time when the electronic wave packet velocity is zero. References: [1] . Johansson and S. Stafstrm, Phys. Rev. Lett. 86 (2001) 3602. [2] C. Q. Wu, Y. Qiu, Z. An, and K. Nasu, Phys. Rev. B 68 (2003)125416. [3] S. V. Rakhmanova and E. M. Conwell, Appl. Phys. Lett. 75 (1999) 1518. [4] Z. An, C. Q. Wu, and X. Sun. Phys. Rev. Lett. 93 (2004) 216407. [5] V. G. Lyssenko, G. Valuis, F. Lser, T. Hasche, K. Leo, M. M. Dignam, and K. Khler, Phys. Rev. Lett. 79 (1997) 301. Corresponding author. Tel.: +86-531-8837-7035-8369; fax: +86-531-8837-7031. E-mail: liuds@sdu.edu.cn
F30 LIGHT-EMITTING DENDRIMERS: TUNEABLE OPTOELECTRONIC MATERIALS I.D.W. Samuel1 , and P.L. Burn2 1 Organic Semiconductor Centre, School of Physics and Astronomy, University of St Andrews, UK 2 Chemistry Research Laboratory, University of Oxford, UK Innovation in materials has played a crucial role in development of organic light-emitting diodes, and most research has concentrated either on small organic molecules or conjugated polymers. We have pursued an alternative approach to materials for LEDs based on conjugated dendrimers. These molecules consist of a core, conjugated dendrons (branches) and surface groups, and by suitable choice of these components, extremely efcient solution-processed LEDs can be made [1]. In addition, dendrimers have proved convenient model systems in which to study important issues for all OLED materials such as the role of intermolecular interactions. Recent advances in understanding and improving dendrimer materials and devices will be reported. A combination of photophysical and charge transport measurements has been used to study the role of the host in OLEDs. These measurements show that (for hole transport at least) the host is not directly involved in charge transport, and instead acts as a spacer. The development of host-free red, green and blue materials will be discussed. It will be shown how dendrimers allow intermolecular interactions, colour, charge transport and exciton diffusion to be tuned. [1] S.-C. Lo et al. Adv. Mater. 13, 975 (2002)
F31 SUB-WAVELENGTH STRUCTURES FOR POLYMER LASERS Colin R. Belton, Paul N. Stavrinou, Ruidong Xia, George Heliotis, Donal D. C. Bradley Experimental Solid State Physics Group, Department of Physics, Imperial College London, Prince Consort Road, London SW7 2BW, United Kingdom In this presentation, we will show how close attention to the shape and form of sub-wavelength structures that provide optical feedback in semiconducting polymer lasers can have a dramatic impact on reducing the operating threshold of these devices. Worldwide effort over the last few years has illustrated the considerable appeal of using these materials as novel laser gain media, with lasing being observed in a variety of resonator structures. The distributed feedback (DFB) geometry has proved particularly promising, where high quality polymer lms can be readily formed on pre-patterned substrates.
The presentation will describe some recent results on optically pumped DFB lasers. Laser structures, using several polymer gain materials, have been
ABSTRACTS
In order to study the inuence of sub-wavelength structures on the lasing performance we apply rigorous electromagnetic modelling to characterise the optical elds therein. This provides valuable insights into how to improve laser performance and also allows a detailed critical assessment of the signicant limitations (for the types of polymer structures under study) of the traditionally used perturbative methods. In one respect rigorous methods can be used to supplement and parameterise perturbative methods. In a wider context, establishing such parameters via rigorous techniques is particularly useful in the general study of polymer-photonic microstructures involving sub-wavelength features.
tuned to illustrate emission across the entire visible spectrum. Variation of the grating ll factor has been shown to play an important role in reducing laser threshold. The inuence that structures embossed on the surface of the polymer lm have on laser action will also be considered. Comparison between laser action in 1-D and 2-D resonator structures also serves to highlight the importance of the optical environment, an effect that will play an important role in progress towards the realisation of low-threshold electrically pumped structures.
F32 CONTRADICTORY ROLES OF EXCITED STATE ABSORPTION IN LASER MATERIALS Hacene Manaa Physics Department, University of Bahrain, POBox 32038, Isa Town, Bahrain
Since the invention of the rst laser in the early sixties, the research of new laser media has never stopped. The main objective was to provide laser light at different wavelengths in order to respond to the increasing demand of laser applications. Along these last forty years, the laser effect has been demonstrated in hundreds of gas, liquid or solid media. Nevertheless, only few of them have reached the commercial level. Many intrinsic problems such as non radiative transitions, excited state absorption, or non linear effects often rise and negatively affect the performance of the laser material. The excited state absorption (ESA), in particular when its spectrum overlaps with the ground state absorption or the emission spectra, becomes like a poison for the laser effect, and can prevent it to happen. In the other hand, it has been shown that, the ESA phenomenon plays a positive role in a certain number of kinds of lasers, especially those based on rare earth ions doped single crystals. The up-conversion and avalanche laser types for example are based on ESA transitions. The UV or visible laser light is emitted after one or many optical transitions from the excited states. Moreover, ESA process plays a key role in the nonlinear properties of the laser materials that are generated inside the laser cavity by the high light intensities. The imaginary part of the induced non linear refractive index is directly related to the ESA cross section. In this paper, the two contradictory aspects of the ESA phenomenon will be treated in details. The different experimental techniques, such as pump/ probe and Z-scan are reviewed and discussed. ESA cross sections of the order of 10-22 cm2 can be measured with these kinds of experimental techniques. The case of Cr3+ and Co2+, as transition metal ions doped several laser crystals will be considered, as well as, Nd3+ and Tm3+ as rare earth ions doped laser crystals. For the liquids, the example of some PPV conjugated polymers will also be presented.
F33 CHARGE TRANSFER RATES, QUENCHING AND NON-ADIABATICITY Donal MacKernan Molecular Electronics and Nanotechnology School of Physics Trinity College Dublin
The Born-Oppenheimer assumption is common to many theoretical models of charge transfer rates, yet it can be violated for various charge quantum processes, for example when quenching takes place, and change drastically charge transfer rates. We present here a general theoretical framework where non-adiabatic effects can be computed, and apply it to simple representative models of charge transfer.
F34 WAVEGUIDING, MICROCAVITY EFFECTS AND OPTICALLY PUMPED LASING IN SINGLE POLYMER NANOWIRES Deirdre OCarroll and Gareth Redmond Nanotechnology Group, Tyndall National Institute, Prospect Row, Cork, Ireland Semiconductor nanowires are an emerging class of nanostructures that represent attractive building blocks for nanoscale electronic and photonic devices. However, while inorganic materials have been explored in depth, the challenge of fabricating organic nanodevices has yet to be addressed in such detail. To this end we have developed methods to create new conjugated polymer semiconductor nanowires, which demonstrate optical functions such as waveguiding, microcavity effects and optically pumped lasing. We use template assembly to form high-yields of pristine nanowires with controlled dimensions from an important blue light-emitting, liquid crystalline conjugated polymer material, poly(9,9dioctyluorenyl-2,7-diyl), PFO. By selective removal of the template the polymer nanowires are freed and dispersed, yielding on the order of 109 single nano-optical elements with diameters in the range of 250 350 nm and lengths of between 3 and 30 m. When the nanowires are optically excited with ultra-violet light they exhibit blue uorescence. The corresponding uorescence spectrum spans from 434 nm as far as 600 nm with a series of dominant vibronic peaks positioned at 434, 457 and 492 nm indicative of emission from the crystalline phase of PFO. Under epi-uorescence microscopy inspection, a signicant fraction of the nanowires (ca. 50%) are observed to behave as active waveguides, whereby the uorescence is guided along the nanowire axis and emitted from the nanowire ends, rather than radiating directly from the body of the nanowire. We have investigated the active polymer nanowire waveguides using a high-resolution optical microscope whereby a nanowire can be locally excited, using a highly focused laser, at one end and the waveguided emission can be collected at the other end. We have observed the waveguided spectra collected from the nanowire end to show waveguiding of the uorescence between 457 nm and 600 nm. When compared to the directly excited spectra from the nanowires the waveguided spectra are attenuated more signicantly at longer wavelengths and there is almost complete suppression of the rst vibronic at 434 nm due to self-absorption. Single nanowire loss measurements of 9 waveguiding nanowires reveal
ABSTRACTS
loss coefcients that vary between 800 cm-1 and 1850 cm-1 and it is concluded that the primary loss mechanisms in our active nanowire waveguides are material absorption and substrate coupling. In addition to the longitudinal propagation of light along our polymer nanowire active waveguides, we have also detected resonant peaks superimposed on the broader PFO second vibronic peak of the nanowire tip emission spectrum for approximately 25% of the active waveguides studied. These resonances are explained by an inherent microcavity structure of these nanowires. Regular internal packing of the polymer strands inside the nanowires results in a strong tendency for the nanowires to break during dispersion yielding cleaved end facets. As a result of this selfcleaving process and due to their homogenous cylindrical shape, the nanowires can form intrinsic microcavity structures, which have the ability to reect an amount of their waveguided light at the end facets back in to the nanowire. These nanowire optical resonances have mode spacings of between 1.5 to 5.9 nm. By sampling the emission spectra of 17 nanowire microcavities with lengths ranging from 10.1 to 3.3 m we have determined that the mode spacing is inversely proportional to the length of the nanowire and hence concluded that longitudinal Fabry-Prot modes are propagating within the nanowires. We have performed optically pumped lasing experiments on nanowires which display longitudinal Fabry-Prot modes. In these experiments single nanowires are excited with a nanosecond laser source and emission spectra are collected from one end of the nanowire as a function of increasing pump energy. The spectra collected from the ends of the optically pumped nanowires are observed to progress from the relatively broad, waveguided emission spectrum to one showing pronounced Fabry-Prot modes on the rst vibronic peak just below threshold which then develop into spectrally narrowed peak(s) above a particular threshold pump power (typically, 2 3 mJ/cm2). It was observed that the dominant, spectrally narrowed emission peak(s) develops directly from the selective amplication of one or more of the Fabry-Prot modes. The peak wavelength of the spectrally narrowed emission for different nanowire microcavities varies between 453 nm and 460 nm and for a single nanowire the peak blue shifts with increasing pump power. We observed that the peak width narrows from 19.6 nm to 1.4 nm (the instrument resolution) at threshold and is effectively clamped at 1.4 nm as the pump power is increased further above threshold. We attribute this spectral narrowing to lasing within our polymer nanowires as a result of their intrinsic Fabry-Prot microcavity structure.
F35 VISIBLE AND NEAR-INFRARED OPTICAL GAIN AND LASER EMISSION IN PHOTOPUMPED MICRO- AND NANOSTRUCTURED POLYMER LASER CAVITIES Takeyuki Kobayashi, Martin Djiango, Michael Flmmich,a) Estelle Bouron,b) Nino Walenta,c) Grace Jordan,d) Manuel Rther, and Werner J. Blau, Materials Ireland Polymer Research Centre, School of Physics, Trinity College Dublin, Dublin 2, Ireland Yasuhiro Suzuki and Toshikuni Kaino Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan The large gain inherent in organic gain media offers the possibility of constructing very compact devices having strong potential for integration with passive waveguide components in optical communication networks. Some polymeric waveguide materials have low loss windows in the visible and the near-infrared. Therefore, organic and polymer waveguide lasers and ampliers operating in these spectral regions may nd applications in the growing technologies associated with polymer-based guided wave-optics. We have explored stimulated emission and optical gain due to the electronic transitions in -conjugated systems and rare earth ions in solid-state polymers. Laser emission has been demonstrated from a variety of polymer cavity structures that possess relatively high cavity quality factors. These structures include microcylindrical cavities, waveguide lasers using scattering polymer gain media, and nanoparticles-dispersed luminescent polymer waveguides. Our result provides an impetus for the development of very compact polymeric amplication devices. a)Present address: Physikalisch-Astronomische Fakultt, Friedrich-Schiller-Universitt Jena, Germany. b)Present address: Nouvelle Formation dIngnieurs en Optronique, Universit Paris XI, France. c)Present address: Institut fr Physik, Universitt Potsdam, Germany. d)Present address: Bell Laboratories, Lucent Technologies, Ireland.
F36 FLUORESCENCE UP-CONVERSION AND LASING IN SEMICONDUCTING POLYMERS G. Tsiminis, G.A. Turnbull & I.D.W. Samuel Organic Semiconductor Centre & Ultrafast Photonics Collaboration, School of Physics and Astronomy, SUPA, University of St Andrews, St Andrews, U.K.
2 2
Fig. 2: Nor m alised PL and 1/T vs . pump in tens ity
ABSTRACTS
Conjugated polymers have attracted great interest over the past few years for a number of Two-photon PL vs pump wavelength Two-photon abs orption vs pump wavelength 1.0 optoelectronic applications. Notably, they combine efcient photo- and electroluminescence with very 0.6 0.5 0.8 simple processing, leading to applications in displays, photovoltaics, exible electronics and lasers. 0.4 0.6 0.3 0.4 They are also known to exhibit strong non-linear optical properties, which opens up the way for their 0.2 0.2 0.1 use in new applications, such as up-conversion lasing1 and two-photon excited uorescence imaging. 0.0 0.0 600 650 700 750 800 600 650 700 750 800 For such applications it is important to have materials that will exhibit strong two-photon absorption, Wavelength (nm) Wavelength (nm) Fig. 1: Absorption and PL of PFO as a function of the pump combined with efcient photoluminescence (PL). In this work, we investigate the non-linear optical wave length properties of dioctyl-polyuorene (PFO), as a rst step towards developing efcient frequency upconversion lasers. Two-photon absorption (TPA) and photoluminescence excitation (PLE) spectra were measured for solutions of PFO in toluene, using 4-nanosecond long pulses from an optical parametric oscillator, in the region of 570 nm to 1000 nm. The TPPL vs square pump intens ity 1/T vs pump intensity 2.5 1.0 excitation beam was focused to a stripe and then directed onto a quartz cuvette containing the 570 nm 620 nm 0.8 670 nm sample. 2.0 0.6 570 nm TPA and PLE spectra were observed in the region of 570 nm to 800 nm (Fig.1), with maxima 0.4 620 nm 1.5 670 nm occurring at 640 nm for absorption and 630 nm for PLE. These maxima appear to be blue-shifted 0.2 0.0 from the corresponding one-photon transition by 76 nm and 81 nm respectively, probably due to 1.0 0.0 0.1 0.2 0.3 0.0 0.1 0.2 0.3 0.4 0.5 0.6 Intensity ((GW/cm ) ) Intensity (GW/cm ) the different excited state symmetries for the one- and two-photon processes. A comparison
of these two spectra provides a measure of the PL quantum efciency, which reaches a maximum for 630 nm excitation. To conrm that the PL originated from a two-photon absorption, we measured both transmittance and PLE as a function of the pump intensity. Results for three different excitation wavelengths are shown in Figure 2. The photoluminescence shows a square dependence on the pump intensity, providing conrmation for the presence of a two-photon process. The TPA coefcients were calculated to be in the region of 1-4cm/GW. For TPA, the inverse of the transmittance (1/T) should depend linearly on the pump intensity2. The absorption data for wavelengths longer than 600 nm are in good agreement with theory. At shorter wavelengths though, the experimental data deviates from the simple theory. Our results indicate that there must be some other process at shorter excitation wavelengths that competes with TPA, which also reduces the PL efciency. A possible candidate for this effect could be the presence of excited-state linear absorption for higher photon energies3. We will present an analysis of these competing processes and progress towards TPA pumped lasing in PFO, both in solution and the solid state.
References 1. C. Bauer et al., Advanced Materials 14 (9): 673-676 May 3 2002 2. R. Scroeder et al., J. Phys.: Condens. Matter 13 (2001) L313-L318 3. C. Zhou et al., Optics Communications 241 (2004) 215-219
F37 ORGANIC-BASED MAGNETS AND SPINTRONICS* Arthur J. Epstein The Ohio State University Columbus, Ohio, U.S.A. Organic-based magnets have been studied for the past twenty years. The initial organic-based magnet, decamethylferrocenium tetracyanoethanide, with magnetic ordering temperature TC of 4.8 K, showed the opportunity to achieve and control the magnetic state in organicbased materials. Since then increasing numbers of families of organic-based magnets have been reported with magnetic phenomena common in conventional magnets (ferromagnetism, ferrimagnetism, glassy and cluster glass behaviors, etc.). I focus here on new magnetic phenomena of interest for both fundamental and applied science. Among these new phenomena are multiphotonic responses of organic-based magnets to light. Earlier studies showed that light of the appropriate wavelength may modulate the magnetism in Prussian Blue and also Mn[tetracyanoethylene]x (Mn[TCNE]x, x~2). Films of V[TCNE]x, x~2, prepared by chemical vapor deposition (CVD) are magnetic semiconductors with room temperature conductivity of up to 10-3 S/cm and TC of up to ~ 400 K. This rst known organic-based magnetic semiconductor is proposed to have fully spin polarized valence and conduction bands as a result of Coulomb repulsion split * level, thereby forming a half-semiconductor. Optically exciting this semiconductor in the * - * transition band results in a reduction of the magnetization below 0.3 T, a shift in the ferromagnetic resonance (FMR), and a signicant photoconductivity. The reversible photoinduced change in the conformation of the TCNE- is proposed to be the origin of the reversible changes in the magnetism and charge transport. The potential for organic-based materials in spintronic devices is explored. The spin dependent transport properties were measured in magnetic FM/O/FM multilayers where FM and FM are inorganic or organic magnetic contacts with coercive elds Hc and Hc respectively, and O is an electrically active organic spacer layer. Organic layers have a low spin orbit coupling which should reduce the effects of interfacial scattering as well as allow for a much thicker spacer layer due to weak intralayer spin-ip scattering. Data collected for organic spacer layers of sexithiophene (~500 - ~1200 nm) with conventional and V[TCNE]x, magnetic contacts and of aligned carbon nanotubes (7 microns) show MR as large as 25% at low temperatures. We also report magnetoresistance (MR) effects in organic semiconductor thin lms showing anomalous behavior near low eld. These effects are very pronounced at room temperature (up to 8% at 100 Oe and 15% at 1000 Oe) and are diminished, but still present, at 5K. Similar effects have been reported elsewhere, though a clear mechanism has thus far not been identied. The oligomer 6T demonstrates MR behavior that, depending on bias and temperature, may be positive or negative. When the organic semiconductor Alq3 is doped with Ir(ppy)3, the usually negative MR is reduced by an order of magnitude. If doped with PtOEP, the MR vanishes. These results suggest that spin-orbit coupling plays a signicant role in the mechanism responsible for the anomalous MR. We propose a detailed model where the interconversion of singlets and triplets accounts for this effect. *Supported by AFOSR Grant No. F49620-03-1-0175 and DOE Grant Nos. DE-FG02-86ER45271 and DE-FG02-01ER45931
ABSTRACTS
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Noam Rappaport Keiji Nagai

KEYNOTE TUE 1 , CHAIR: J M KELLY

ORGANIC CONDUCTORS & SUPERCONDUCTORS 3, CHAIR:B KORIN-HAMZIC

Serguei Brazovskii Takashi Yamamoto

FULLERENES, CARBON NANOTUBES & RELATED NANOSTRUCTURES 2, CHAIR: D FUTABA

15:45 16:00 16:15

Fotios Papadimitrakopoulos B. Raquet Katsumi Yoshino Sumit Mazumdar

TU57 TU86 TU58

SELF ASSEMBLY, CHAIR: J M KELLY

ELECTROCHEMICAL APPLICATIONS, ACTUATORS & SENSORS 2, CHAIR: G WALLACE

15:15 15:30 15:45