THREEDIMENSIONALOPTICALDATASTORAGEINPOLYMERICSYSTEMS

By
CHRISTOPHERJ.RYAN

Submittedinpartialfulfillmentoftherequirements
ForthedegreeofDoctorofPhilosophy

DissertationAdviser:Dr.JieShan

DepartmentofPhysics
CASEWESTERNRESERVEUNIVERSITY

May,2012

CASEWESTERNRESERVEUNIVERSITY
SCHOOLOFGRADUATESTUDIES
Weherebyapprovethethesis/dissertationof

ChristopherJamesRyan

candidatefortheDoctorateofPhilosophydegree

Dr.JieShan

Dr.KennethSinger

Dr.RolfePetschek

Dr.LeiZhu

January20,2012

TableOfContents
ListofTables

ListofFigures

Acknowledgements

Abstract

1.2FeaturesofOpticalDataStorage

1.3ABriefHistoryofOpticalDataStorage

12

1.4NewTechniquesforOpticalDataStorage

15

1.53DOpticalDataStorage

19

1.6MultilayeredFilmsasStorageMedia

22

1.7CoextrudedPolymericFilms

23

1.8ChapterContent

24

Chapter1IntroductiontoOpticalDataStorage
1.1Motivation

Chapter2TwoPhotonInducedAggregateSwitchingofExcimerFormingDyes

25

2.1Introduction

25

2.2Materials

27

2.3TPAofC18RGDye

30

2.4Experiment

31

2.5ResultsandAnalysis

32

2.6ChapterConclusion

34

Chapter3HighDensityOpticalDataStorageinMultilayerPolymerFilms

36

3.1Introduction

36

3.2SampleFabrication

39

3.3FilmProperties

41

3.4OpticalPatterningandReading

42

3.5DeterminationoftheCrosstalk

47

3.6ModelingoftheLayerCrosstalk

48

3.7ComparisontoCrosstalkModel

50

3.8ChapterConclusion

52

Chapter4TheeffectofMultilayeringontheContrastof3DDataStorageMedia 53

4.1Introduction

53

4.2GeometricRestrictiontotheDataDensity

55

4.3DeterminingtheSignalContrastandBackgroundNoise

57

4.4ComparingMultilayeredFilmstoMonoliths

61

4.5Results

63

4.6ShotNoiseandDarkCurrent

66

4.7ChapterConclusion

68

Chapter5ThermalInfluenceonBiexcitonAnnihilationinZincPhthalocyanine

69

5.1Introduction

69

5.2Materials

70

5.3Experiment

72

5.4Results

73

5.5PhysicalInterpretationoftheTimeDependenceoftheCollisionRate 76
5.6ThermalDependenceoftheZnPc

80

5.7Conclusion

83

AppendixAPowerDependenceofPhotopatterninginC18RGdye

85

85

A.1Introduction

A.2ReadingfromSubdiffractionSystems

89

A.3SamplePreparation

90

A.4PhotopatterningattheTPAWavelength

90

A.5PhotopatterningwithLinearAbsorption

94

A.6AppendixConclusion

97

98

Bibliography

ListofTables

Table5.1

71

ListofFigures

Chapter2TwoPhotonInducedAggregateSwitchingofExcimerFormingDyes

25

Figure2.1

27

Figure2.2

28

Figure2.3

29

Figure2.4

29

Figure2.5

33

Figure2.6

33

Chapter3HighDensityOpticalDataStorageinMultilayerPolymerFilms

36

Figure3.1

40

Figure3.2

42

Figure3.3

42

Figure3.4

44

Figure3.5

47

Figure3.6

48

Chapter4TheeffectofMultilayeringontheContrastof3DDataStorageMedia 53
Figure4.1

55

Figure4.2

57

Figure4.3

60

Figure4.4

60

Figure4.5

62

Figure4.6

64

Figure4.7

65
5

Figure4.8

66

Figure4.9

67

Chapter5ThermalInfluenceonBiexcitonAnnihilationinZincPhthalocyanine 69
Figure5.1

71

Figure5.2

74

Figure5.3

74

Figure5.4

82

Figure5.5

83

Figure5.6

83

AppendixAPowerDependenceofPhotopatterninginC18RGdye

85

FigureA.1

91

FigureA.2

92

FigureA.3

93

FigureA.4

95

FigureA.5

96


Acknowledgements
Abroadrangeoftechniques,skills,andprinciplesarerequiredtocreateandrefinenew
ideasasrelatedtothesemultidisciplinaryprojects.Mycontributionstothefieldexist
onlyas enabledby my interactions.Throughoutthecourseofthese experimentsand
inventions,IcollaboratedwithmanyindividualsfromthevariousdepartmentsatCWRU.
Hereispresentedalistofthoseindividualswhosecontributionswerepalpable:Dr.Jie
Shan,BrentValle,AnujSiani,Dr.CoryChristenson,Dr.JackJohnson,Dr.JosephLott,Dr.
Kenneth Singer, Dr. Eric Baer, Dr. Anne Hiltner, Dr. David Schiraldi, and Dr. Christoph
Weder.

ThreeDimensionalOpticalDataStorageinPolymericSystems
Abstract
by
CHRISTOPHERJ.RYAN
Sincethelate1980sopticaldatastoragehasbeenastapleforthecirculationofdigital
information. Through the years the storage capacity of these devices has grown to
matchnewdemandsandapplications.However,fundamentalopticallimitationsexist
whichinhibitthegrowthofthecurrentparadigmofdevices.Thisworkiscomprisedof
experiments and demonstrations related to new optical data storage techniques.
Variousresultsarepresentedtoaugmentandoptimizefutureiterationsofsuchdevices.
Most notably, a 64 layer disk is fabricated and used to store data. This device is
fashioned using a polymer coextrusion technique and stores information at a high
densityon23ofits64fluorescentlayers.Tounderstandthesignificanceofsuchdevices,
a simulation is used to quantify the benefits of multilayered storage disks over
monolithicdevices.Noiseisshowntobedrasticallyreducedinmultilayeredstructures,
while the signal contrast grows under the influence of confinement effects. In the
process of making this device, an aggregrochromic dye was chosen as a candidate
material.Furtherexperimentscharacterizehowthedyechangesphasesasaresponse
to photopatterning. As presented,these projects cite specific issues with optical data
storagetechnologyandofferoptionsforcomplexityandgrowthwithinthefield.

Chapter1:IntroductiontoOpticalDataStorage

1.1Motivation
Since the late 1980s, threedimensional (3D) optical data storage has become a
significant area of interest to the scientific and engineering communities. As formats
progressedfromLaserdisctoCompactDisctoDigitalVideoDevicetoBlueRayDisc,2D
storage devices have remained a standard for cheap, stable data storage. With each
newgenerationofdevicescameinincreaseinoverallstoragedensity.[1]

However, the wave nature of light has imposed fundamental limits to the storage
density of such optical devices. There are new methodologies to circumvent these
bottlenecks. Expanding storage into the third dimension has produced devices that
pushdensityofopticalmediaoveraterabyteperdisk[2,3].

1.2FeaturesofOpticalDataStorage
The general operating principles of 2D optical storage formats rely upon modulated
reflectionpatterns.Mostcommercialdisksstoreinformationonathinaluminumfilm
thatishousedwithinatransparentplasticdisk.Informationisstoredonsuchadevice
duringthefabricationprocessasthealuminumfilmsarestampedwithapattern.The

informationislaterreadbyreflectingafocusedlaserbeamatthesurface.Thediskis
spun about its axis, which translates the pattern relative to the laser. The resultant
reflection from the disk is modulated with the information from the pattern, and the
reflection is captured by a photodiode. As a result the photodiode produces a
modulated electrical signal which conveys the information to the next step in the
process[3].

These aluminum based disks are the most prevalent kind of writeoncereadmany
(WORM)disk.Othermaterialshavebeenusedforvariationsofthisconcept.Cyanine,
phthalocyanine, and azo based dyes have been layered adjacent to the aluminum or
evenusedasareplacementforit.Inthiskindofdisk,thereisnostamping,andthedisk
ismanufacturedwithoutapattern.Instead,writingisdonebymodulatingalaserbeam
thatisfocusedonthismaterial.Absorptionofthemodulatedlightcausesheating,and
as a result there is a spatial modulation created in the phase of the disk (typically
polycrystallineoramorphous).Thereisadifferenceintherefractiveindexofthetwo
phases,sotheresultisthatthediskispatternedwithamodulatedreflectioncoefficient.
Thistypeofdiskisreadinthesamewayasitsstampedcounterparts.Thebenefitisthat
thediskiswritablepostfabrication[3,4].

For later versions of this device, the disk is also erasable. In such disks, the active
materialistypicallyasemimetalalloysuchasGeSbTe.Thebasicprinciplesarethesame,
10

but by further exploitation of the materials phase behavior, the disks are made
rewritable.Whenheatedabovethematerialscrystallizationtemperature(~150C),an
amorphous region becomes polycrystalline and more reflective. By taking any region,
polycrystallineoramorphous,aboveitsmeltingtemperature(~600C),itmeltsandcools
rapidlytoanamorphoussolid.Duringphotopatterning,thelaserpoweriscontrolledto
utilizetheseproperties.Alowpowermodeisusedtowritedataonablankregionof
the disk, and a high power setting is used to erase written regions. The resultant
photopatternislaterreadwithreflectionbasedmethods[5].

Thewavenatureoflighthas imposed afundamental limittothedatastoragedensity

(DSD)ofallopticalstorageformatsthusfar[6].Theradiusofthenarrowestpartofthe
beam is called the beam waist (0). Diffraction limits the minimum size of 0 based
uponthewavelength()ofthelightbeingfocusedandthenumericalaperture(NA)of
thelensthatisusedtofocusit.Thereexistsasimpleproportionalityrelationbetween
them(Eq1)

(1)

Thebeamwaistalsodefinestheresolutionofatypicalreadingsystem.Featureswith
separation smaller than 0 cannot be easily discriminated with linear microscopy
methods.TheminimumresolutionofthesystemthensetsanupperlimitontheDSD,
asdatapackedmoredenselythanthebeamwaistcannotberesolved.Themaximum

11

DSDofa2Dstoragesystemisthusproportionalto

.Notethatforagivendisk,the

writingandreadingprocessesdonotnecessarilyusethesameso0maybedifferent
foreachprocess.

As the standard format of optical storage has changed, the DSD has increased
significantly. Since 0 limits the DSD, each successive format has reduced the
wavelengthandincreasedtheNAoftheopticsinvolved.

1.3ABriefHistoryofCommercialOpticalDataStorage
A brief history of mainstream optical data storage starts with the Laserdisc(LD)[7, 8].
Originally produced by Pioneer, LDs and their hardware were the first commercially
availableopticaldatastoragesystems.TheLDitselfwasanaluminumsheetof30cmin
diameterwhichwasmountedinaplasticcylinder.Datawasstoredinthedeviceduring
fabrication as each aluminum disc was stamped with a pattern. For consumer video
storage, this pattern contained an analog video signal and a digital audio signal. The
patternisreadwitheithera632HeNelaseror800nmdiode.

The LD device family was replaced by the Compact Disc (CD) player. CDs occupy a
significantlysmallerformfactorthanLDs.TheCDisathinplasticcylinderwithdiameter
of12cmandheightof1.2mm.ThebulkofCDsareWORMdiskswithanaluminumfilm.
12

Laterwritableandrewritabledisksweremanufactured.CDplayersusea780nmdiode
laserandopticswithaNAof0.45.Thefeaturesonthediskarelargerthan0.5umin
eachdimensionandseparatedby1.6um.Theoverallcapacityis~700MB[9].

Thenextmajorformatof2DopticaldatastoragetobewidelyproducedwastheDigital
Versatile Disc (DVD). The DVD follows the same size and form as the CD. Similarly
writableandrewritableformatsareavailableforDVDs.ThemechanicsofaDVDplayer
arethesameasaCDplayer;however,ashorterwavelengthlaserandstrongeroptics
areused. For aDVD systema 650nmdiodelaserisused witha lensof.65NA. The
features on the disk are typically 0.32 m wide, 0.4 m long and 0.12 m tall. The
bumps are separated by about 0.74 m which leads to a device capacity of 4.7 GB.
Versions of the DVD are now made with 2 layers of storage rather than a single
aluminumlayer,asecondlayerof semitransparentreflectivematerialisused. Either
layer can be selected by changing the position of the focal point. Intuitively, the
addition of a second layer multiplies the storage by a factor of 2. DVD disks are also
sometimesmade2sided;byessentiallytaking2disksandgluingthembacktoback,the
capacityisdoubledyetagain.Howevertoreadtheothersideofsuchadisk,itmustbe
turnedoverintheplayer.

The most recent commercial format for optical data storage is the BluRay Disk (BD).
Thisdiskfollowsthesameformasthepreviousstandards.Theyareplasticcylindersof
13

the same dimensions of CDs and DVDs. BluRay technology takes its name from the
ultravioletlaserthatisusedinit.Byreducingthewavelengthofthebeamto405nm
andincreasingtheNAoftheopticsto0.85,theBDoffersasignificantimprovementin
DSDoveritspredecessors.Thebeamwaistforsuchadeviceisabout0.15um.Assuch,
thefeaturesonthediskarenosmallerthan0.15um,andtheoverallcapacityis25GB.
There are also dual layer BD that are analogous to the dual layer DVDs described
above[10].

Asmentionedabove,thetrendofdecreasingthewavelengthofthelaserandincreasing
the NA of the focusing optics has practical limitations. The best multielement lenses
availablehaveaNAofnearly1.4ifoilimmersedand0.95ifdry.Thismeansthatthere
islessthanafactor of2inimprovement in theDSDoffuturedevicesfromincreasing
theNA.Thepracticeofdecreasingthewavelengthofthelaserisalsorestricted.While
lightexistswithwavelengthsmuchshorterthan405nm,therearenogooddiodelaser
sourcesofsuchlight.Tocontinuethetrendtowardsmallereithernewhighbandgap
semiconductor materials must be developed, or other low cost methods of laser
generationmustbefound.Whileusingthecurrentparadigmofdevices,thereislittle
opportunitytoincreasetheDSD[2,6].

14

1.4NewTechniquesforOpticalDataStorage
New techniques are being developed to circumvent the limitations of the current
technology. However, these approaches stem from three basic ideas. Firstly, if each
featureonthediskcouldrepresentawiderangeofnumbers,ratherthanjust0or1,the
densitywouldincreasesignificantly.Secondly,ifthesizeofthefeaturescouldcontinue
toshrink,theDSDwouldincrease.Finally,iftheentirevolumeofthediskcouldbeused
ratherthanjustasingleplane,thentheDSDwouldriseaswell.

Regardless of the techniques used, the general task is the same for all optical storage
devices.Firstonemustcreatelocalizedchangestotheopticalpropertiesofamaterial.
These changes must be made so that they can later be detected and resolved. To
realizesuchdevices,propermechanismsforreadingandwritingofdataareimperative.
As such, this research requires significant contributions from multiple fields including
chemistry,physics,andmaterialscience.Becausethisworkissomultidisciplinary,there
are a multitude of unique approaches to such a device. However, the general task
imposesconstraintsandthuscommonalityarisesbetweendesigns.

The information on the current disks is stored as binary. Each feature on the disk
represents either a 1 or a 0. By changing the features to instead represent a wider
rangeofnumbers,theDSDcanbegreatlyenhanced.Forexample,ifeachbumpona

15

current disk could be replaced by feature on the disk had 20 different detectible
configurations, then the DSD would increase 10 fold. Data throughput would also be
significantlyincreased, aseachnumberwrittenandreadholdsmoreinformationthan
that of a binary system. Of course, such a change would require a more refined
detection system. Two methods which utilize this idea are multilevel storage and
holographicstorage[1113].

InMultilevelStoragesystemstheoverallstructureofthediskanddriveareverysimilar
tothealuminumstampedopticaldisksthathavebeenastandardforyears.However,
thebinaryfeaturesarereplacedbybumpsofmultiplediscretemagnitudes.Onewayto
achievethisistouseanarrayofdifferentheights;eachonewouldreflectthebeamtoa
uniquepointinspace.Thedetectorfromatypicalopticaldriveisreplacedbyanarray
of detectors, so the position of the reflection is accurately resolved. An alternative
would be to replace each of the bumps with features of varied discreet reflection
coefficient.Thenthedetectorcouldinterpretthemagnitudeofthereflectedbeamto
representanarrayofnumbers.Clearlythismethodincreasesthestoragedensityofa
givendiskbyamultipleofthenumberofdifferentheightsthatituses[13].

In a holographic storage system features within the disk are written to a disk by
interfering2beamsoflight.Oneofthesebeamsisencodedwithinformationthrough
spatiallightmodulation.Thematerialholdstheinformationintheformofadiffraction
16

grating.Later,areadingbeamispassedthroughthisgratingtoreproducethespatially
modulated pattern. By imaging this beam onto a CCD, the spatial pattern is resolved
andalargedigitalnumber.Thisprocesstypicallyallowsthefeaturestoholdbetween8
and 16 bits of information, rather than a single bit. The overall storage density is
thereforemultipliedbythisfactor[11,12].

Another approach to denser data storage involves decreasing the size of the data
featuresevenfurther.Asstatedearlier,improvementstoandNAareneartheirlimits.
However,byusingmaterialswithnonlinearresponsessuchasmaterialswiththreshold,
thefeaturescouldbewrittenwithsizesmallerthanthebeamwaist.Thistechnique
hasbeenwellappliedtophotoresiststogetfeaturesassmallasWhiletherearea
fewopticalstoragemechanismsthatarethresholdprocesses,noneofthemhavebeen
fullyexploitedyet[14,15].

The ODS density is also limited by the reading process. One way of resolving features
belowthediffractionlimitistousenearfieldmicroscopy.Byplacingitsdetectorvery
close to its specimen, a nearfield scanning optical microscope (NSOM) uses the
propertiesofevanescentwavestogetresolutionfarsmallerthanthediffractionlimit.
Insuchasystem,theresolvingpowerislimitedbythesizeofthedetectorratherthan
thewavelengthoflightthatisusedforillumination.NSOMhasbeendemonstratedto
detectandresolvefeatureswith0.02umlateralspacingand0.002umheight.However,
17

this kind of detection is limited in its scope. To detect features they must be on the
surfaceofthesample.

Anotherwaytothebeatthediffractionlimitisthroughstimulatedemissiondepletion
microscopy(STED).Thistechniqueisrestrictedtosystemsthatcontainfluorescentdye,
so the reflection paradigm of disks would need to change to utilize STED. STED
improvestheresolutionofamicroscopebyquenchingthefluorescenceinpartsofthe
focal volume that are not at its center. When an excitation pulse is absorbed by the
fluorescentdye,itcreatesanexcitedcarrierpopulationwithinthedye.Thispopulation
inversion typically decays exponentially with time on the nanosecond scale as the
excitationsspontaneouslyemitfluorescence.However,asecondpulsecanbeusedto
stimulateemission,andbyselectiveshapingofthispulse,thespontaneousfluorescence
isquenchedoutsideofthecentralregion.Thistechniquehasresolvedfeaturesonthe
order of 6 nm. STED microscopy is not limited in the same way as NSOM, as STED
techniquescanpenetratethesurfaceofthedisk[6,16].

Structured illumination microscopy has achieved similar resolutions. The sample is

imaged while being illuminated with a spatially periodic light source. Images are
recordedasthesourceistranslatedandrotatedthroughthesample.Aseriesofimages
areproducedthatareconvolutedwiththeknownperiodiclightsource.Byperforminga
deconvolutionanimageofthesampleisproducedwithveryfinedetail,andresolutions
18

similartoSTEDhavebeendemonstrated.Imageprocessingprovidesresolutionbetter
than10nm.Becauseitiscomputationallyheavy,suchamethodisnotusefulforoptical
datastorage[17].

1.53DOpticalDataStorage
Since the detection methods for subdiffraction data features bring problems of their
own,itremainspertinenttoconsiderotheroptions.AsseenwithDVDs,theDSDofa
disccanbedoubledbyaddingasecondplaneofdata.Infact,thedensityismultiplied
bythenumberoflayersofinformation.Thismethodofusingthedepthofthediskasa
storageparameteristhebasisof3Dopticaldatastorage.Ratherthanstoringdataona
planewithinadisk,thegoalof3Ddatastorageistousetheentirevolumeofthedisk.
Clearly, an issue arises here, as when reading deep into a disk the information that is
storedonotherplaneswillcontributetothesignal[1].

The principles of confocal microscopy are necessary to resolve data from densely
packedvolumes.Assuch,theonlystoragemechanisms with3Dutilityarethosethat
create localized changes to either fluorescenceor reflectance. A multitude of devices
exist as examples for each of these detection methods. However, fluorescence has a
greaterpotentialforalargenumberbecausetherefractiveindexmismatchinreflection
basedsystemsleadstostrongeropticalaberrationswhenreadingandwriting[1].

19


Theproblemof3Ddatastorage,however,ismorecomplexthanjustreadingthedisk.
Toproperlydemonstratetheprinciple,onemustproduceadiskwithdifferentialoptical
properties that are distributed throughout the volume of the medium. There are
generally two approaches to this problem. In many cases, data is written during the
fabrication process, and the disk cannot be changed afterward. However for more
flexibility in use, writable disks are fabricated blank and data is later written by
photopatterning[1].

The current industry standard WORM (write once read many) disks operate based on
reflection. Data is stamped onto disks as they are injection molded. The best
commercialdisksavailablecanstore30GBperlayerandhave2layers.Usingthesame
process, Pioneer has fabricated a multilayered disk of 20 layers of data with buffer
layersinbetween.Suchadevicehasthepotentialtostoreover500GB.Theabilityto
focus onto each layer is demonstrated, neither the writing data nor reading data has
beenshowninsuchadisk[3].

All designs which demonstrate the ability to create 30 or more planes of data utilize
multiphoton absorption. These disks are produced blank, and data is written post
fabrication.Amultiphotonprocessisnecessaryasitlocalizestheabsorptionoflightto

20

a single plane. Most schemes involve 2photon absorption, and a few claim higher
order effects. In most of these cases, the multiphoton absorption directly induces a
change in optical properties. However, there are many devices where the absorption
insteadinitiatesasequenceofeventsthatresultinsuchachange.

Most of the designs in the scientific literature utilize photochromic molecules. As a

general term, a molecule is photochromic if it can be transformed from species to
species by the absorption of a photon. In data storage devices, a photochromic dye
withasignificanttwophotoncrossectionisdissolvedintosomepolymermatrix.Upon
illumination,thedyechangesitsopticalproperties.Insomecases,theabsorptionand
fluorescencepropertiesofthematerialarelocallychangedenoughtomakeabasisfor
datastorage[1821].

Foreaseofproduction,mostofthedevicesinthisfieldarefabricatedashomogenous,
monolithicdisks.Highdatastoragedensities,stablestoragelifetimes,andrewritability
arealldemonstratedinavarietyofpapersusingsuchdevices.Evenwithsuchsuccess,
thereismotivationtomakeinhomogeneous,multilayereddisksinstead[2224].

21

1.6MultilayeredFilmsasStorageMedia
Thoughtherearemany issues withtheirfabrication,thereisstillmuch researchdone
involvingmultilayereddisks.Tocreatethesedevices,mostgroupsspincoatalternating
layers ofphotoactive andinactive materials. This process,whileeasy todo,produces
films with poor uniformity and also does not scale well to larger number of layers. A
less popular technique involves fabricating individual layers and later adhering them
together.Uniformityofthesedisksismuchbetterthanspincoating,butthiscomesat
thecostofamorelaborintensivefabricationprocess.Thismethodisalsomuchmore
difficult to scale into disks involving thirty or more layers. While issues exist with the
productionofmultilayereddisks,researcherscontinuetoworkwiththemastheyboast
manybenefitsoverthemonolithicdisk[2224].

The benefits of multilayer systems are multifaceted. The major arguments for
multilayered disks include reduced materials costs, increased contrast, and reduced
aberration.Becausetheactivematerialisthemostcostlyingredientinthesedesigns,
spatialconfinementoftheactiveregionreducestheamountoftheexpensiveingredient
andreducestheoverallcostofthedisk.Furthermorethespatialconfinementincreases
thecontrastofthewrittendataregionswhencecomparedtotheunwrittenareas.This
in turn augments the signal to noise ratio (SNR) and doubles the potential storage
density.Finallyspatialconfinementoftheactivelayersreducesthephaseaberrations
of a wavefront traveling through the disk. This allows for random accessibility during
22

writing,andfurthermore,thereductionofaberrationleadstosmallerfocalvolumesand
anoverallincreasedworkingdepthofthedisk[2224].

Even with the benefits of multilayering, the difficulties of established methods for
manufacturing such disks make them an unlikely candidate for real application. This
creates opportunity for other technologies and processes to attempt to solve this
problem.Hereweusethepolymercoextrusiontechniquewithdiebasedmultipliersto
createmultilayerpolymericfilmstouseas3Dstoragemedia.[25,26]

1.7CoextrudedPolymericFilms
In the polymer coextrusion process, two polymers are heated to matching viscosities.
Astheyareextrudedthroughthesamenozzle,theyarespreadintoabilayerfilm.The
ratioofthethicknessofonelayertotheotherisacontrolledbyadjustingtherateat
which each polymer flows. The overall thickness of the bilayer is also controlled by
adjustingtheflowrateofthepolymers.Diesarethenusedtocut,stackandspreadthe
film. As this is done the number of layers is multiplied while the overall thickness
remainsthesame[25,26].Furtherdescriptionofcoextrusioncanbefoundinsection
3.2aswellasafigureoftheprocessandaresultantroll.

23

Films made in such a manner are produced in rolls. These films are characterized by
theiroverallthickness,numberoflayers,andratioofbilayerthicknesses.Filmvariance
is usually less than 5% from layer to layer. The films exist with 2 to 4096 layers with
bilayerthicknessassmallas10nm.Thisprocessscaleseasilytomassproductionasitis
alreadyusedtomakefilms onthesquaremilescale.Byfocusing onthismethod,we
hope to alleviate difficulty of manufacture that has thus far outweighed the practical
benefitsofusingmultilayeredsystemsasdatastoragemedia.[25,26]

1.8Content
The bulk of this work demonstrates the design and characterization of a coextruded
multilayerpolymerfilmforuseasa3Dopticaldatastoragesystem.TheworkingWORM
diskispresentedinChapter 3. Chapter2 coversthecharacterizationof thematerials
chosenforthisdiskandaphotoinducedaggregrochromiceffect.Chapter4containsa
simulation of the contrast to noise ratio of multilayered and monolithic disks which
quantifiessomeofthebenefitsofmultilayereddisks.Chapter5containstheresultsofa
mostly unrelated paper on the charge transport properties of Zinc Phthalocyanine
(ZnPC).Theappendixcontainsinformationonphotopatterningandfarfieldmicroscopy
belowthediffractionlimitaswellasanexperimentdesignedtoyieldthiseffect.

24

Chapter2:TwoPhotonInducedAggregateSwitchingofExcimerFormingDyes

2.1Introduction
Currentcommercialopticaldatastoragetechnologiesuselinearabsorptionprocessesto
writeandreaddata.[27,28]Informationiswrittenbymakinglocalizedchangestothe
opticalpropertiesofthedisktoproduceaspatiallymodulatedreflectionpattern.The
overalldatastoragedensityofadiskisdeterminedbythespacingbetweenthewritten
features.Theminimumwidthofthefeaturesonadiskislimitedbythediffractionof
thelightusedtowriteit.Typicallynewformatsofcommercialstorageemergebyusing
shorterwavelengthsandopticswithlargernumericalaperture(NA).However,thereis
littleroomtocontinuethistrendwithoutadvancesinopticsandlasermaterials.

Newmethodsarerequiredtofurther increasethestoragedensityofdisks.Themost
prevalentapproachfordoingsoinvolveswritingdataintothedepthofthedisk.Some
models of DVD and Blu Ray disk exemplify the potential of this concept, as they are
fabricated to have up to four individually addressable storage layers. However,
complexity of producing and using multilayer systems increases with the number of
layers.Tofacilitatedenserstoragestill,othersturntononlinearoptics.

Twophotonabsorption(TPA)isthemostcommontoolforenabling3Ddatastorage.[20,
29]Sincethisprocessesscalesquadraticallywiththeincidentlightintensity,optically

25

induced changes are restricted in depth even when focusing light into a bulk
material.[30,31]Herewereportanovel,readilymanufacturedODSsystemthatrelies
on the opticallyinduced switching of the aggregation state of an excimerforming,
fluorescentTPAdyeinapolymermatrix.

Welldefinedvoxelswithdimensionsof3x3x6mwerewrittenindividuallybyexposing
thematerialtoafocused,modulatedlaserpulsetrain.Thelightpulseshaddurationof
10ns,energyof55nJ,andwerecenteredabout675nmtocorrespondtothedyesTPA
absorption maximum. Once written, the data was read by confocal laser scanning
microscopy.ThreedimensionalODSsystemsbasedonthisapproachpromiseastorage
capacityofuptoseveralTbytesonaDVDsizedisk,whichistwoordersofmagnitude
higherthanthatofcurrentcommercialODStechnologies.[32]

The majority of the systems designed for 3D ODS employ photochemical processes to
enable storage. Typical reactions include photoisomerizations,[3335] photoinduced
dimerizations,[36, 37] photodecompositions,[38] and photopolymerizations.[39, 40]
Fluorescent photochromic systems have attracted particular interest, because the
photophysicalprocessesarefast,efficient,andreversible.[19,41,42]However,ithas
been challenging to create fluorescent photochromic materials, which combine high
stability,highfluorescencequantumyield,andlargeTPAcrosssection.

26

Herewedemonstrateanapproachto3DODSmaterialsthatreliesontheswitchingof
the aggregation state of an excimerforming fluorescent dye. The dye has an
appreciable TPA crosssection, and it is blended in an inert host polymer. It is shown
elsewhere this material changes fluorescence colors as a response to heat [4346]
chemicals,[47,48]ormechanicalforces,[4953]Theopticalchangesarisefrominduced
changesoftheaggregationstateofthedyemolecules.Wesurmisedthatsuchchanges
areelicitedinsmallvolumesbyTPAinducedlocalheating.

2.2Materials
We explored a meltprocessed blend
ofpoly(ethyleneterephthalateglycol)
(PETG)and 1.1% w/w of 1,4bis(
cyano4octadecyloxystyryl)2,5
dimethoxybenzene (C18RG, Figure
2.1)

as

TPAaddressable

ODS

medium.[43,45]C18RGwasselected
on account of its significant changes
in absorption and emission spectra
upon aggregation/dissociation, its
high thermal and photochemical
stability, and, as demonstrated here,
its appreciable TPA crosssection.
27

PETGwaschosenasthematrixduetoitsglassynatureandexcellentopticalproperties.
Its glass transition temperature (Tg) of 78 C, which defines the write/erase
temperature(vide infra) is sufficiently above ambient temperature and provides
excellent stability of the storage medium as discussed below. The solubility phase
diagram and aggregation kinetics of C18RG/PETG blend sand similar materials have
beenpreviouslyinvestigated.[43,45]

Figures2.1illustratestheaggregationstateandopticalpropertiesofthe1.1%w/wC18
RG/PETG blend films as a function of thermal history. The corresponding normalized
absorption and fluorescence spectra are shown in Figure 2.3. The dissolution
temperatureatwhichthedyeisthermodynamicallysolubleisca.130Cfor1.1%w/w
ofC18RGinPETG,Figure2.1;notethatthedissolutiontemperatureisafunctionofthe
dyecontent.Thermodynamicallyunstable,butkineticallytrappedmolecularmixturesof
thedyeandthepolymercanbeproducedbyquenchingathermodynamicallymiscible,
meltedmixtureofthetwocomponents(230Cforablendcomprising1.1%w/wdye)to

28

below Tg. In this state, the blend film appears yellow (peak wavelength of the
abs
absorption spectrum max = 447 nm, Figure 2.3) and displays the green

fluorescence(peakwavelengthofthefluorescencespectrum max =508nm,Figure2.2,

fl

2.3)thatischaracteristicofamolecularlymixedblend.Subjectingthequenchedblendto
temperatures above Tg but below the dissolution temperature leads to stable and
pronouncedchangesinabsorption(orangeappearance, max =387nm,Figure2.3)and
abs

fluorescence (orange, max = 542 nm), due to aggregation of the chromophore

fl

molecules; these changes are retained if the blend is cooled back to ambient
temperature (Figures 2.2,2.3).The original state can be restored by subsequently
heating the phaseseparated blend to above the dissolution temperature(all erase
experiments reported here were carried out at 160 C) (Figures 2.1,2.2,2.3).Thus, the
above data document that the blend employed here can be used as a rewritable,
optically readable storage medium, in which local exposure to welldefined
temperatures allows one to write and erase information in two dimensions with
microscopicresolution.

29

In principle, two different modes of operation are possible. The first begins with a
quenched blend (in which the dye molecules are dissolved)into which data is written
throughannealingaboveTgbutbelowthedissolutiontemperature,anderasedthrough
heatingabovethedissolutiontemperature.Alternatively,thesecondprocessstartswith
aphaseseparatedmaterialintowhichdataiswrittenbyheatingabovethedissolution
temperatureandiserasedbyannealingaboveTg.ThecyclesillustratedinFigure2.2and
2.3 show that either starting point is a viable option and in principle, many
write/read/erasecyclesarepossible.

2.3TPAofC18
ThechoicetoutilizeC18RGforthepresentopticaldatastoragesystemswasbasedon
the expectation that this dye, like other cyanosubstituted oligo(phenylene
vinylene)s[5357] possesses an appreciable TPA crosssection, so that the above
30

describedwrite/eraseschemescouldbeachievedbyTPAinducedlocalheating.TheTPA
crosssectionofC18RGwasmeasuredusingtheopenapertureZscanmethod.[58,59].
Figure 2.4 shows the TPA crosssections of C18RGas a function of wavelength in the
rangeof625to725nm,wherethelinearabsorptionisnegligible(Figure2.3).TheTPA
crosssectionofthedyevariesbetween0and650GMwithamaximumat675nm.A
verysimilarbehaviorwasfoundforC1RG(SupportingInformation).Theseexperiments
reflect a significant nonlinear absorption, which is comparable to that of similar
moleculesreportedintheliterature.[5357]

2.4Experiment
ForTPAbasedwritingexperiments,1.1%w/wC18RG/PETGblendfilmsofathickness
of 150 m were annealed at 90C for 2 days to ensure complete aggregation of the
chromophores.DatawritingwasaccomplishedbyusingaNd:YAGlaserincombination
with an optical parametric oscillator (OPO), which produced light pulses of a center
wavelengthof675nm,durationof10ns,andenergyof3mJ.Thepulsetopulseenergy
stability was ~ 20%. These pulses were attenuated and focused onto the storage
mediumthroughanoilimmersedobjectivelenswithanumericalapertureof0.85.The
resultingGaussianbeamwasmeasuredtohaveawaistof3mandRayleighrangeof
10m.Eachdataspotwaswrittenbyexposingthesamplestoasinglelaserpulse.The
samplesweremovedin3Dbyacomputercontrolled3axistranslationstage.Ininitial
experiments,theaveragepulseenergywassystematicallyvaried.Foreachtrial,asetof
31

spotswaswrittenwhiletheaveragepulseenergywasheldconstant.Atpulseenergies
above100nJpermanentlocalizeddamagewasobserved,whilepulseenergiesbelow25
nJbroughtaboutnovisibleopticalchanges.Theenergyrangeof5065nJwasfoundto
afford the desired changes. An average pulse energy of55 nJ was used for the data
writingexperimentspresentedbelow.

Confocal laser scanning microscopy was

used to characterize the voxels written into the C18RG/PETG blend films using the
above approach. A continuous wave laser operating at a wavelength of 400 nm was
used to excite the samples and the fluorescence was recorded in two channels
corresponding to the integrated intensity in the spectral ranges of 500 525 nm and
650 800 nm, respectively. These spectral windows are sensitive to and thus were
chosentomonitortheaggregatedanddispersedstateofthechromophores.

2.5ResultsandAnalysis
Confocalmicroscopyimagesofarepresentativesampleshoweightwrittendataspotsof
10mbelowthesurfaceofthefilminFigures2.5and2.6.Thevariationsinthesedata
spots were caused by the pulsetopulse energy variation of the output of the OPO.
Figure 5a shows the raw intensity image of the sample after the application of a low
pass filter in a plane parallel to the film surface (XY plane) for fluorescence in the
spectralrangeof650800nm.Orangeexcimeremissionofaggregateddyemolecules
is observed across the entire sample, except for the written spots, which appear as
darkerareas,indicativeofdispersionofthedyeaggregatesduetotheTPAinducedlocal
32

heating. The result is further confirmed by the corresponding fluorescence intensity

imagerecordedforthespectralrangeof500525nm(Figure2.5).Theimageshowsa
complementarybehavior,i.e.thewrittenspotsappearbright,reflectinganincreaseof
the green emission in these areas. In addition, we did not observe any appreciable
photoinduceddegradationofthefilmsduringwriting.Inpreviousstudies,theratioof
theemissionintensitiesintheaboveshortandlongwavelengthwindowshasfoundto
represent a good measure of the aggregate states.[43, 45, 50, 53]Thus, we used the
ratio of the intensity of the images shown in Figure 2.5, with their respective
backgrounds subtracted, to generate a composite image, which indeed shows a
significantly improved contrast. The image contrast can be further enhanced by
applyingalowpassfilter.Thechoiceofthelowpassfilterremovestheeffectofthedye
aggregatesfromtheimage.Furtherprocessingcouldeasilyconvertthesignaltobinary.

33


AsisevidentfromFigure2.5,thespotsizeswrittenwiththesetupemployedherehave
adiameterof~3mintheXYplane.Figure2.6showstheemissionintensityprofileof
thetop4spotsfromFigure2.5casrecordedintheZXplane.Thedimensionsofthedata
spots in the ZX direction (~6 m) are a bit larger than those in the XYplane (~3 m),
whicharemostlylimitedbythesizeofthebeamfocus.Notethatbecausethewriting
process requires a threshold temperature, it is possible to achieve a data spot
substantially smaller than the writing beam size, the result of which will be reported
elsewhere.[60] The current results reveal clearly that the TPAbased writing process
allowsonetowritevoxelsthataremicroscopicallylocalizedinall3Ds.

34

Finallywecommentonthestabilityofthisnewstoragemedium.BelowthepolymersTg,
themolecularmobilityofthesystemisnegligibleandthemorphologyofthedye/host
systemsisstableforyears.Inthisregard,theTgofthechosenhostpolymerdictatesthe
stableoperatingtemperatureregimeofthesystem.Thisindicatesthatwrittenfeatures
remainintactatambientconditions,butleavesopenthepossibilityoferasingdataby
supplying sufficient thermal energy to heat the sample above Tg and reaggregate the
chromophores,ashasbeenillustratedinFigure2.2.

2.6Conclusion
In summary, we have demonstrated a new ODS system that relies on the optically
initiated, thermally induced switching of the aggregation state of an excimerforming,
fluorescent TPA dye in a polymer matrix. Such blends can easily, inexpensively and
rapidlybefabricatedinlargequantitiesusingsimplemeltprocessingtechniques.Well
definedvoxelswithdimensionsof~3x3x6mhavebeenwrittenthroughtheexposure
of the blend to single laser pulses. The voxel size is comparable to the focal point
volume of the writing laser, suggesting that thermal transport does not place a lower
limittothevoxelsize,atleastnotatthelengthscalesusedhere.Adiffractionlimited
laserbeamcanbeachievedbyoptimizingtheopticalsetup.Inthatcasethevolumefor
efficientTPAislimitedtoaspaceslightlysmallerthan0.4 mineachdimensiongiven
thewavelengthandnumericalapertureused.Suchaschemecanbeusedtopotentially
writeseveralterabytesofbinarydatainadiskofsizeofthecommonCDsandDVDs.

35

Chapter3:HighDensityOpticalDataStorageinCoextrudedMultilayerPolymerFilms

3.1Introduction
Newtransformativeconceptsforopticaldatastorageapplicationsareneededtomeet
the future requirements of applications in multimedia, archiving, security, and many
others. Commercial data storage technologies are moving to threedimensional
materials, but the known concepts suffer from limited addressability and high
fabrication costs. We demonstrate here that storage systems based on coextruded
multilayer films can overcome these problems and allow for terabyte level bitbybit
opticaldatastorage.Stratifiedfilmswith64storageand64bufferlayers,withaperiod
of 3.4 m, were fabricated by a readily scalable continuous rolltoroll process at 200
meters per hour. Information in the form of complex patterns and individual bits was
recordedinupto23superimposedlayersbyphotobleachingafluorescentdyeviaone
photon absorption. The optical resolution and crosstalk were examined. The results
demonstratethatthefabricationprocess,whichisfarsimplerthancurrentapproaches,
allowsonetofabricateBluraycompatible,highdensitymultilayerstoragemediawith
storagecapacitiesthatareordersofmagnitudehigherthanthestateoftheart.

Highcapacityopticaldatastorage(ODS)isrequiredforrobustarchiving,securitytags,
and even new media formats for threedimensional (3D) displays, and many other
applications[61].ConventionaltwodimensionalODShasadvancedtoallow25GB/layer
storage in bluray (BR) discs, which is sufficient for high definition video storage.
36

However,thestoragecapacityislimitedbydiffractionofthewritingbeam,thecostof
manylayered media, as well as the number of layers that can be fabricated and
addressed [62]. Shorter wavelengths or higher numerical aperture (NA) optics offer
some improvements, but substantial advances can only be achievedby utilizingmulti
dimensional methods including spectral and polarization multiplexing [63, 64],
holographicrecording[65],andinparticular,theefficientuseoftheaxialdimensionto
overcome the limits of surface storage [20]. The capacity of 3D storage media has
currentlyprogressedtowardterabyte(TB)levels[2].

Localizing data in a 3D storage medium is often achieved by activating the particular

material response using twophoton absorption (TPA) by high power sources, such as
nearinfraredpulsedlasers.Theuseofthisnonlinearopticalprocessgreatlyreducesthe
optical changes outside the region of interest [2, 18, 6670]. In these schemes, data
planesarewritteneitherinmonolithicmaterials[2,19,71],orinmaterialswithdiscrete
active layers. The former are easy to fabricate, while the latter allow further
confinementofthedatawithinalayer.Thisreducescrosstalkduringwriting/reading,as
well as the amount and cost of the recording material. However, the multilayer (ML)
discsreportedinpreviouseffortswerefabricatedthrougheithersequentialspincoating
[15, 21] or lamination [3, 24, 72], which are labor intensive and cannot economically
scaletolargenumbersoflayers.

While easy, lowcost multilayer fabrication is one important roadblock, other system
37

level issues are also impeding the transformation to commercial TB ODS. This
transformation will be best addressed by a evolving the system from the present
commercial state of the art. In particular, it would be desirable to develop a TB
read/write system using existing BR laser diode technology and that conforms to
existing requirements. Optical aberrations in the read/write system limit the
addressabledepthsothatthecurrentBRspecificationofatotalthicknessofthestorage
medium to 140m significantly limits the number of layers possible with a reflective
storageschemeasareflectiveschemerequireslargelayerseparationtoavoidcoherent
reflectioneffects.Thus,TBmultilayerstoragerequiresamediumandstoragescheme
thatsimultaneouslyconfinesthedatatotightaxialdimensionsandallowsreadingand
writingwithminimumcrosstalk.

Wereporthereonanapproachthatsuccessfullyaddressesalloftheseissuesandpaves
the way for future high performance, lowcost, easily scalable and manufacturable TB
ODSmedia.First,wehavedevelopedanovel,robust,andsimpleapproachfordigital
3D ODS in ML polymer films that were fabricated in a continuous, melt coextrusion,
rolltoroll process. This is truly lowcost and easily scalable both in film area and
numberoflayers.Inaddition,permanentstorageisdemonstratedin23superimposed
datalayersutilizingfluorescence(FL)quenchingofannoveloligo(pphenylenevinylene)
dye organic dye upon onephoton absorption. This was achieved with a submilliwatt
continuouswave(CW)405nmdiodelaser,enablingoperationwithcurrentcompactBR
sources. Finally, a high axial data density (3 m/layer), low crosstalk scheme was
38

realizedusingaFLreadingscheme,which,incombinationwithwritingatthediffraction
limit of the BR laser, promises TB storage capacity within commercial disc thickness
specifications.

3.2SampleFabrication
The coextrusion technique [73, 74] used to manufacture these films is illustrated in
Figure 3.1a. In this process, which has already been successfully applied to the
fabricationofphotoniccrystals[75],lasers[76],andgradientrefractiveindexlenses[77],
two thermoplastic polymers (A and B) are heated to form a melt with matching
viscosities, and then coextruded into a bilayer feedblock. The AB bilayer is sent
sequentially through a series of multiplication dies. Each die cuts, spreads, stacks the
meltanddoublesthenumberoflayers.Filmswithoverfourthousandlayersandlayer
thickness as low as 10 nm have been produced using this technique [74, 78]. The
laboratoryprocessemployedinthepresentstudyallowsfabricatingfilmsupto36cmin
widthataspeedofapproximately200m/hr,thoughmuchhigherspeedsandwidthsare
possibleincommercialproductionlinesemployedforothercommercialapplications.

39


The chromophore C18RG was synthesized as previously described [45]. PETG Eastar
6763andspectroscopicgradetoluenewereobtainedfromEastmanChemicalCompany
andBurdick&Jacksonandwereusedasreceived.AblendofC18RGandPETG(nominal
dyecontent2wt.%)waspreparedusingaHaakeRheocord9000batchmixerat230C
for 5 minutes. To coextrude the PETG solution with the PVDF, both materials were
heatedto230Cwherethepolymershavematchingviscosities.Thebilayerproducedby
thecoextruderwassentsequentiallythrough5dies.Eachdiecutperpendiculartothe
bilayers, spread, and stacked the film to multiply the number of layers by 2. The final
filmproducedwasasystemof64layerswithanoverallthicknessofapproximately200
m. Coextrusion also permits the manufacture of periodic films with more than two
distincttypesoflayers(i.e.,ABCorABCB)toaccommodatemoresophisticateddesigns
[74].

Usingthistechnique,wefabricatedastoragesystemconsistingof64dataand64buffer
40

layers,whichservetoconfinethebitswithindiscretelayers.Aphotographoftherollof
thefilmproducedinthisstudyisshowninFigure4.1b.DatastoragelayerAiscomposed
ofatransparenthostpolymer,poly(ethyleneterephthalateglycol)(PETG)thatisdoped
with 2.0 wt.% of the fluorescent chromophore 1,4bis(cyano4octadecyloxystyryl)
2,5dimethoxybenzene (C18RG) (13). Buffer layer B consisted of poly(vinylidene
fluoride) (PVDF), is optically inactive and refractive indexmatched to layer A. This
material is particularly useful to limit diffusion of the dye during processing [79]. The
averagethicknessesoflayersAandBare0.3and3.1m,respectively.Theproduction
processandwriting/readingsystemhasmuchbroaderapplicabilitythantheparticular
materialreportedhere.

3.3Filmproperties
C18RG is a cyanosubstituted oligo(pphenylene vinylene) dye with aggregochromic
properties [45]. The structure is shown in Figure 3.2. Previous studies on
thermodynamically immiscible blends of this dye and various host polymers have
demonstratedsignificantchangesoffluorescence(FL)propertiesuponexposuretolight,
heat, chemicals, or mechanical forces, which are attributed to excimer formation or
breakup[45].Theusefulnessofthisparticulardyeforopticaldatastoragehasalready
been demonstrated by twophoton switching of the excimermonomer transition in
monolithic films [70]. We prepared the dyedoped polymer layers in a molecularly
mixed blend following the procedure described in [70]. The absorption coefficient of

41

layerAis0.1m1at405nm,whereasboththePETGmatrixandthePVDFbufferlayer
aretransparentinthevisiblespectrum.

Figure3.3showstheFLspectrumofasingleactivelayerunder405nmexcitation,taken
with a spectrometer and CCD fibercoupled to the confocal microscope. An area 2.5 x
2.5 m was scanned in about 100ms at 0.01 mW/m2. The monomer and excimer
fluoresceat410and445nm,respectively.UponexposuretoCWlightofhighfluence,
bleachingoftheFLisobservedwith noshiftofthepeak,indicatingthat thedyedoes
notaggregatetoformexcimersundertheseconditions.

3.4OpticalPatterningandReading
ThedatawritingwasperformedbyFLquenchingofthestoragemediumC18RGupon
onephotonabsorptionofaCWlaserbeamat405nmfocusedontothechosenlayer.
ThisbecomespossiblebecauseoftheaxialconfinementofthedataintheMLfilms.The
reading, on the other hand, was done by FL detection as opposed to reflection, an
approachcommonlyusedforsingleandfewlayerstoragemedia.Asweshowbelow,FL
42

detection significantly increases the axial layer packing density and thus the storage
capacity. If molecularly dispersed in PETG, C18RG displays absorption and FL spectra
with maxima at 445 nm and 510 nm, respectively. An intensity on the order of 0.1
mW/m2orgreaterisrequiredtoobtainmeasurablequenchingwithsubmsexposures.
Thechangeswereobservedtobepermanentandstableoverthetimeperiodofmore
than2years.

Figure3.4depictsFLimageswrittenintothetop23storagelayersofthe64layerfilms
describedabove.ThewrittenregionscorrespondtoareasofreducedFLintensity(black).
To write the data, the output of a CW 405 nm diode laser was focused into the film
throughanOlympusMPlanApochromat,100x,1.4NAoilimmersedobjective.Patterns
were recorded using an Olympus FV1000 confocal microscope by scanning the laser
beamalongacustomizedpathatarateof75nm/ms.Writingwasperformedlayerby
layerfromthelowesttothetopmoststoragelayer.Theincidentpowerwasabout130
W and the intensity was varied between 1.5 mW/m2 (topmost) to 2.0 mW/m2
(lowest layer). The same confocal microscope and laser source subsequently collected
3DFLimagesofthesampleatareducedfluenceandincreasedscanrate(0.01mW/m2
at5m/ms).

43


TheuseoftheFLdetectionschemesallowssmallerlayerspacingscomparetoschemes
relying on phase changes and reflection, as discussed. Another limiting factor is the
responsefunctionofthereadingsystemitself.Theconfocalmicroscopeusedhere,with
a1.4NAobjective,isanextremecase.Withtheseoptics,theintensityatthedetector
planedropsbyhalfifthesampleismovedbyabout0.1maxiallyoutofthefocalplane
(for an infinitely small aperture), which is much smaller than the layer spacing [45]. If
instead the 0.85 NA objective found in BR players is used, even with an aperture
diameterafactorof10largerthanthespotsizeatthedetector,thisfigureisstillonly
0.89m.Thus,whilethefactorslimitingtheminimumlayerspacingare relaxedhere,
theopticallimitofthereadingsystemisnotyetanissue.Therearelikelyotherissues
44

thatresultsinaneedforaminimumspacing,suchasthicknessvariationandsolubility
ofthedye.

FromtheimagesshowninFigure3.4,itisevidentthatdatacanreadilyberecordedand
retrieved from each of the individual storage layers. The average reduction in the FL
intensitythroughoutthefilmforthewrittenareasisabout22%.Theimagesshowthat
thequalityoftheretrievedimagesdecreasesforthedeeperlayersduetoaberrations.
However, we demonstrated that it is readily possible to retrieve information from 23
layers, which is the largest number of recorded layers that has been reported in a
heterogeneousMLODSmedium.Wenotethattheaberrationsdependontheworking
distance of the objective, and that the quality of storage in the deep layers, and
therewith the number for layers from which information can be retrieved, can be
furtherincreaseduptotheBRspecificationbyoptimizingthelenssystem.

Stateoftheart,twoorfourlayerBRdiscshaveanaxialspacingofgreaterthan10m
in order to limit the coherent crosstalk that occurs due to multiple reflections of the
readingbeamatthereflectivelayerandspacer layerinterfaces[80]. The FLdetection
schemeemployedheregreatlyreducesthemultiplereflectionsaswellasemittingata
nondegenerate wavelength, allowing much smaller spacings to be used compared to
phase change materials. Thus, the spacing of our layers (3 m) is one of the smallest
explored[21].

45

The areal density of ODS is constrained by the beam waist at the diffraction limit. To
examine the data bit dimension of our ML films, single lines were written into a
monolithicfilmoftheactivelayerunderthesamewritingconditionsasdescribedabove.
The resulting bleaching profile is shown in Figure 3.5. A fit yields a fullwidthhalf
maximum (FWHM) of 380 nm, which is approximately the minimum bit spacing
achievable in this current system, and is consistent with the diffractionlimited beam
size. This places the areal density of our ML films close to that of BR systems, the
minimum bit spacing of which is 320 x 150 nm, owing to the threshold nature of the
phasechangewritingprocess,allowingsubdiffractionlimitwriting.

46


3.5DeterminationoftheCrosstalk
A significant factor that determines the minimum bit spacing in both the axial and
lateraldimensionisthecrosstalk.OneattractivefeatureofMLfilmsinthecontextof
3Dstorageistheconfinementofthebitsintheaxialdirection,whichreducescrosstalk
betweenneighboringbitsandlayersduringwritingandreading.Todirectlymeasurethe
crosstalk, an array of bits was written into 10 successive layers and the contrast
modulation in the middle (probe) layer was read as information was written in the
47

others. Similar writing conditions as described above were employed. The laser was
modulatedwithasquarewavegenerator toproduceonoffbit pairsseparatedby 1.0
minbothlateraldirections,andthetotalareawritten(40x40m)waslargerthanthe
beam diameter in any given layer, so as not to underestimate the total crosstalk
betweenanytwolayers.Thisalsoleadstoresultsthatarenotdependentonwhichof
the 10 layers is chosen as the probe. A subsection of the FL pattern and modulation
after select writing steps are shown in Figs. 3.6a and b. The main effect of crosstalk
appearstobeanoverallreductionintheaverageFLlevel.

3.6ModelingoftheLayerCrosstalk
Crosstalkisanissueduringbothwritingandreadingin3Dstoragesystems.Here,the
crosstalkduringwritingisexaminedforthecasesoflinearandtwophotonabsorption.
The relevant parameter, physically, is the ratio of the intensity received at a given bit
locationduringexplicitwritingofthatbitrelativetothatobtainedduringwritingofall
48

otherbitsinallotherlayers.ThesimulatedbitarrayconsistsofNzlayerswithaspacing
ofz,eachconsistingofNybyNxbits,withspacingsofyandx,respectively.Thebitarray
occupiesanvolumeofsizeLxbyLybyLz.Theoriginisplacedatthecenterofthedata
array.AssumingadiffractionlimitedGaussianbeam,thereductionintheFLasinglebit
located at the origin during explicit writing of that bit (the signal, S) should be
proportionaltosomepowerofthefluence.
N2z z

S C

w
0

(3.1)

whereCisaproportionalityconstant,istheabsorptioncoefficient, w0isthebeam
waist, and p is chosen to be either 1 or 2 to simulate either a linear or quadratic
bleachingresponse.TheFLreductionofthissamebitduringwritingofalltheotherbits
(thenoise,N)isgivenbythesum
N z z
e 2
N C
2
k N z /2 wk

N z /2

p
N y /2

N x /2

2( ix )2
wk2

j N y /2 i N x / 2

2( jy )2
wk2

(3.2)

andthe1/e2beamradius,wk,atthezoriginwhenwritinglayerkisgivenby

k z
wk w0 1

2
n w0 /

(3.3)

wherenistherefractiveindex,andisthewritingwavelength.Sissubtractedfromthis
to account for the single term in the sum which is defined as the signal. This can be
greatlysimplifiedassumingahighlyfocusedbeamandalargescanarea.Howeveritis
moreaccuratetosimplyperformthesummationnumerically(Matlab).Theparameters
werechosentocorrespondtothoseusedintheexperiment.Thebitspacingwaschosen
49

as1.0 minbothlateraldimensionswithallbitsbeingon(numericallyequivalentto
theonoffpatternof0.5 mspacingproducedbythesquarewavegenerator), z=3
m, Nx=Ny=40, Nz=10, Lx=Ly=40m, Lz=27m, and w0=0.32m. A beam waist

corresponding to the experimentally observed value of 0.32 m is used. The result

plotted in Figure 4 is the ratio S/N. Scorresponds to the modulation signal, while the
totalN results in overall constant bleaching, so this ratio can be determined from the
experimentaldatabycalculating

max min
,wheremaxistheaverageofthepeakvalues
1 max

inthemodulationandministheaverageofthetroughs.

This calculation is intended only as an orderofmagnitude comparison, as there are

manyotherphysicalprocessesthatmustbetakenintowhendesigninganoptimalML
structure (29), such as multiple reflections. One of the primary differences between
experimentandtheoryhereisthefactthatthebeamisscannedcontinuouslyandnot
discretely.Furthermore,forlargeintensitiesthebleachingwillbecomesublinear,which
isnotaccountedforinthetheory.Thelightscatteredattheinterfacesandtheinability
tocontrolallaspectsoftheconfocalwritingsystemonsmallscales(suchastheretrace
andsamplepositioning)alsocontributetotheCBR.

3.7ComparisontoCrosstalkModel
The ratio of signal modulation to the background depletion FL (carriertobackground
ratio, or CBR) is used to quantify the crosstalk. The CBR after writing each of the 10
layers (starting with the probe layer) is plotted in Figure 3.6c (triangles). The value
50

decreases from 2 to 0.15 with increasing number of layers, and is in good agreement
with numerical simulations. While this is not insignificant, this CBR ratio is more than
sufficienttoresolveindividualbitinformation,asshowninFigure3.4.Duetothehigh
NAofthewritingobjectiveandtheinertbufferlayers,thefluenceinthelayeradjacent
to one that is being written, is reduced by more than a factor of 10. Two theoretical
curvesfortheCBRarealsoplotted,oneassumingthebleachingisrelatedtothelinear
powerofthefluenceandoneassumingaquadraticdependence(e.g.inTPAscheme).
The theory, which is consistent with the experimental results, indicates nonlinear
fluenceresponsesyieldsignificantenhancementsintheCBR.

Thesimilarityofthebleachedspotsizeandcrosstalkmeasurementstothetheoretical
resultsbasedonthebeamparameterssuggestthatthebleachingprocessmaydepend
inanearlylinearfashiononthefluence;however,asthefilmreportedherehasbeen
storedundermercurycontainingfluorescentlampswithweakbluevioletlinesfortwo
years without a measurable decrease in the FL, one may speculate that a threshold
exists, below which no bleaching occurs. Onephoton absorption with a nonlinear or
thresholdfluenceresponseis thepreferredmethod forcommercialization,incontrast
to the nonlinear optical processes such as TPA which require complex pulsed laser
systems or very high power CW diode lasers, and the longer wavelength required to
write increases the spot size. Other materials such as Au nanorods [15] or organic
photopolymers[81]havealreadyshownpotentialforaonephotoninitiatednonlinear

51

orthresholdresponse.Workiscurrentlyongoingtoincorporatesuchmaterialsintothe
coextrusionprocess.

Inthefuture,wewillincorporatetheseonephoton,nonlinearfluenceresponsewriting
schemesintothemediumdescribedheresothatwecanexpecta40layer1TBcapacity,
0.8TB/cm3densitydiscinthestandardarealformat.Theresulting136 mthickfilmis
within the 140 m bluray specification compatible with the optics of compact,
commercial writing systems, which account for aberration and tilt tolerances[82]. This
presentsafeasibleapproachtofabricatingaTBlevelstoragemediuminalargescaleat
lowcostwithinthematerialspecificationsofcurrentwritingsystems.

3.8Conclusion
In summation, we have shown that coextruded ML films are feasible for use as a 3D
ODSmedium.Withthecommercialsystemspresentlyavailable,theabilitytoincrease
the density is limited not only by the optics but also by the cost needed to add and
manufacture additional layers. Coextrusion removes this serious constraint. We have
writtenfilmscontaining23activelayerswithindependentimages,thelargestnumber
of layers of any stratified storage medium. The crosstalk between layers is also
examined,andwhilenotnegligible,issmallenoughtopermitdemonstrationofthisfilm
asastoragedevice.Thelateralbitspacingislimitedbythediffractionof405nmlaser,
andtheaxialbitspacingallowsTBlevelrecordingwithinthethicknessspecificationof
currentdiscplayers.
52

Chapter4:TheEffectofMultilayeringontheContrastandNoiseof3DStorageMedia
4.1Introduction
As new 3D optical data storage technologies are developed, a variety of new disk
schematicsarecreated.Typicallythesedisksfitintooneoftwostyles.Monolithicdisks
are made from homogenous materials and as a result are easier to fabricate than
multilayereddisks.Ontheotherhandtheoperationaladvantagesofmultilayereddisks
areoftendemonstratedbythegroupswhomakethem[15,21,24].Somemultilayered
devices have been shown to offer data storage densities that are not attainable by
monolithic disks [21]. The most common claim is that higher contrast to noise ratios
(CNR)areachievedthroughmultilayering[24,83].However,theprecisenatureofthe
benefitsisnotwellunderstood.

Previous works show that the contrast to noise ratio(CNR) of a layer within a
multilayered disk changes very little when the adjacent layers are written[24]. This
resultisexpectedformultiplereasons.Inamultilayeredsystemmorelightshouldbe
deliveredtothetarget layerbecause thereis lessparasitic absorptionfromthe layers
above.Furthermore,thereshouldbelessbackgroundandnoiseproducedfromoutof
focuslayerswhenreadingamultilayereddisk.

53

It is the focus of this work to model and compare both the signal contrast and the
contrast of the background noise from out of focus regions in both multilayer and
monolithic fluorescent disks. In doing so, the benefits of reduced crosstalk and
parasitic absorption are quantified and can act as a guide for the design of future
storage media. The effect is examined for various intraplane spacings and various
degrees of confinement. Furthermore, the enhancements are examined in the cases
whenShotnoiseandphotodiodedarkcurrentarethedominantnoisesources.

Thenatureofthesignalcontrastandbackgrounddependheavilyuponthewritingand
reading mechanisms of the disk. For most 3D data storage systems, the fluorescence
properties of a material are modified by interaction with a writing beam. Typically a
sampleisnotfluorescentataparticularwavelength,andtheapplicationofthewriting
beamcreatesfluorescence.However,otherdisksexistwherefluorescenceisquenched
by the application of the writing beam. Often the change is created by a nonlinear
absorption event, however some materials exist which linear absorption leads to
nonlinear materials responses. In such systems, the mechanism for change is often
thermal or photochemical. Often these mechanisms create threshold based changes,
andproducebinaryspatialmodulations.Thisisthetypeofdevicethatisconsideredin
thissimulation.

54

Athreestepapproachistakentoevaluatethesignalcontrastandnoisecontrastofsuch
disks.Firstthesignalgeneratedbyasinglevoxeliscalculatedforafluorescentreading
process. Next, the total background noise from fluorescent regions surrounding this
voxeliscalculateddeterminethemaximumpossiblecontrastofthebackgroundnoise.
Finally, the interplane data spacing (D=a+b) and the ratio of the active layer to the
passive layer(Ra=a/D) are varied to compare the signal and noise contrasts for various
datadensitiesandsystems[figure4.1].

4.2GeometricRestrictiontotheDataDensity
In this simulation, signal contrast is compared to the noise contrast as the main
determinant of the effect of multilayering. However, geometry suggests a rough
55

estimateofthelimittothedensityofthedisksbasedsimplyuponthesizeofthewritten
spots.Thelengthscalesofinterestarethethicknessofanactivelayer(a),thethickness
ofapassive layer(b),andthezradiusofthe writtenspots(z0).Theparametersofthe
writingbeamdeterminez0.Whenwriting,theintendedlayershouldbeatthecenterof
the beam while adjacent layers should be outside of z0. Under this constraint

so

2 .Twolimitingcasesemergeforthissystem.Inthemonolithiclimit,b>0,
2 .Inthislimit,theplanesofdataarespacednocloserthanthetwicez0.In

theveryconfinedmultilayeredstructurelimit,a>0so

.Intheselimits,itisseen

thatthemultilayeredstructureallowstheplanestobespacedabouttwiceascloselyas
themonolithiclimit[figure4.2].Thisestimateisbasedsolelyontheconstraintthatthe
adjacent layers lie outside of the written spots potential diameter. By calculating
contrastofthesignalandnoise,theproblemisaddressedinamorerigorousmanner.

56


4.3DeterminingtheSignalContrastandBackgroundNoise
The contrast and noise values are calculated as sums over all fluorescent
coordinates[equ4.1].ThesearecombinedtocalculatethecontrastCNR.Thecenterof
thebitofinterestisdefinedattheoriginandthepositionoftheconfocalpinholeisfixed
accordingly. M(r, ,z) is the spatial distribution of fluorescent regions within the disk.
I(r,z)representstheintensityprofileofthereadingbeam,whichiscenteredattheorigin.
Theconfocaltransferfunction,T(z),determineshowmuchoftheemittedlightfromany
pointiscapturedbythedetector.Otherimportantquantitiesarethequantumyield(Y)

57

andabsorbance()ofthedye,andthesensitivity(r)ofthedetector.Sothenthecurrent
producedinthedetector(J)canbefoundbyevaluatinganintegral:

, ,

(4.1)

Theterminbracketsdescribesthedistributionoftheabsorbedlightandtheapplication
ofYT(z)determineshowmuchisreemittedintothedetector.Theintegralisdoneover
all space to accumulate the contribution from every point. Application of the
photodioderesponsivity,rp,convertsthecapturedphotonstoelectriccurrent.Theform
for each of these functions will be described later as the signal contrast(JS) and noise
current(JN)arecalculated.WhencalculatingtheCNR=JS/JN,thematerialsproperties
and detector sensitivity cancel out, and the result is the ratio of the integral of the
spatial properties of the system[equation 4.2]. However, the absorbance of the
materialstillaffectstheshapeandamplitudeofI(r,z).

, ,

, ,

(4.2)

Where MS and MN are the forms of M for regions producing signal and background,
respectively.Forthesimulationofthemicroscopesillumination,thereadingbeamwas
set to a wavelength() of 400nm and a numerical aperture(NA) of 0.85. I(r,z) was
assumed to be the shape of a Gaussian beam with decaying intensity in absorbing
regions[equ4.3].

58

(4.3)

Here L(z) is the effective path length through the material with absorption coefficient
atlocationz.Thisisusedtoapproximatetheattenuationofthelightasitpenetrates

thesample.z0istheRayleighrangeofthebeamandw0isthebeamwaist.Thesetwo
parameters are directly related to NA and by equation 4.4. The absorbance and
quantumyieldofthedyewaschosentomatchthedyeusedforourdatastoragebased
experimentsintheotherpapers[60,84]

(4.4)

GeometricopticsdeterminethetransferfunctionT(z).Theamountoflightfromeach
pointsourcethatmakesittothedetectorisdeterminedbycomparingthesizeofthe
imageofeachpointsourceattheconfocalpinholetothesizeoftheconfocalpinhole.
Interference effects in the point spread function were ignored, and the resulting
approximationofT(z)wasaLorentzianinz,centeredonthefocalplane[figure4.3].To
examinetheeffectofthepinholeonCNR,simulationwasdoneoncewiththepinhole
matchedtothesizeofAirydiskofthefluorescedlightandlaterwiththepinhole5times
largerthantheAiryDisk.

59


Tofind Jsand JN , M(r,z) was designedfor a material with a threshold response tothe
illumination.[15, 68] As such, the functions are populated with values of 1 in
coordinates that are written and 0 for the unwritten coordinates. The CNR will be
identicalforsystemswherewrittenregionsarerepresentedbyquenchedfluorescence.
Nearthebeamfocus,equipotentialsurfacesofI(r,z)areroughlyellipsoidal,sothespots
were assumed to be ellipsoidal with radius w0 and z0 in the r and z directions,
respectively. For this disk, only seven layers of data are simulated. The noise
contributionsfromadditionallayersdecreaseastheinversesquareofthedistancefrom
the focus because T(z) has as a Lorentzian form. Contributions beyond the first few
layersareverysmall,andthesumconvergesrapidly[figure4.3].

TosimulateJs,onlythecentervoxelispermittedtofluoresce[figure4.4A].The
backgroundnoise,JN,isdeterminedbyexaminingthevarianceofthebackground.To
60

calculatethemaximumpossiblebackground(Jmax),allsurroundingvoxelsareconsidered
tobewritten[figure4.4B].Inareal,writtendiskeachvoxelhasa50%chanceofbeing
written.TheaveragebackgroundisthenJmax/2,ashalfofthesurroundingvoxelsare
expectedtobewritten.Thevariationofthisbackgroundisthemainsourceofnoise.
Becausethebitsareeitheronoroff,theycanbedescribedbyabinomialdistribution.
I(r,z)andT(z)aresharplypeaked,sothevoxelsthatcontributethemosttothe
backgroundanditsvarianceareadjacenttothebitofinterest.Thisisseeninfigure4.3
asthecentralpeaksaremuchlargerthantheothers.Mostofthebackgroundcomes
fromthesetwobits,sothebackgroundisapproximatedbyabinomialdistributionwith
2trials.ThevarianceinthebackgroundrelatedtothemaximumbackgroundasJN=
Jmax/23/2.Insystemswithlargercontributionstothenoisecomefromotherlayers,JN
willstillbeproportionaltoJmax.However,theproportionalityconstantwillbesmaller.

61

4.4Comparingmultilayeredfilmstomonoliths
Thisprocessisrepeatedfordiskswithvaryingzaxisseparationbetweenvoxelsandalso
varyinglevelsofconfinementinthezaxisthroughmultilayering.TheratioRawasvaried
from 100% to 1% in increments of 0.1%. This provided CNR values for monolithic
systemswasaswellasmultilayeredsystemsofvariedconfinement.Ineachcase,the
multilayer effect was accomplished by applying a spatial filter in the form of a square
wavetothecorrespondingM.VaryingvaluesofRaweresimulatedbyvaryingtheduty
cycleofthesesquarewaves.[figure4.3].Datadensitywasvariedbysimplydecreasing
D.Dwasvariedfrom2z0toz0sothensimulationwouldspanthemostcommondesigns
fromexperimentsintheliterature.

62

4.5Results

Tobetterunderstandwhathappensastheparametersarechanged,onecanexamine
the signal and crosstalk noise individually [figure 4.4A]. In the figure, the simulated
contrast and background noise are normalized to the simulated contrast and
background noise(respectively) of a monolith in the geometric limiting case of D=2z0.
WhileholdingDconstant,afewtrendsareapparentinfigure4.6.ForlargevaluesofRa,
JSincreasesasRadecreases.Thisisbecausemoreofthereadingbeamisdeliveredto
thefocalregionastheotherregionscauselessparasiticabsorption.Thatis,forsmaller
Ra,thelighthasashorterpathlengththroughthedyeinlayersabovethebitofinterest.
HoweveratsmallRa,JSreachesamaxandbeginstodecreasewithdecreasingRa.This
happens when the bit of interest becomes smaller than the confocal region. JN,
however,continuouslydecreasesastheRaisdecreased.Thenoisedecreasesbecause
thereislessfluorescentmaterialoutsideofthefocalregiontocontributetothenoise.
As the pinhole size is increased, the behavior of JN remains unchanged. JS behaves
similarlyforbothlargeandsmallpinholes.However,forthelargepinholethepeakis
shiftedtolargerRa.Thisisadirectconsequenceofthewideningoftheconfocalregion.

63

In the absence of the any other noise sources, the CNR continuously increases as the
activelayersaremadethinner[figure4.7].ThereisamonotonicincreaseintheCNR
withdecreasingvaluesofRa.ItisalsonotablethattheCNRdecreasesmonotonicallyas
Disdecreased.Evenwithmultilayering,morelightfromadjacentlayersisdeliveredto
thedetectorsasthespacingisdecreased.Thebehaviorissimilarinboththelargeand
smallpinholecases.However,theenhancementisstrongerwhenthepinholeissmaller.
In the figure, the CNR values are normalized to the CNR for a monolithic device in its
closely packed geometric limit. These monolithic CNR values are 625 for the small
pinholeand127forthelargepinhole.
64


Sofromtheaboveitisseenthatmultilayeringcanproduceapalpableenhancementto
theCNR.Thisenhancementcaninsteadbespentonincreaseofdatastoragedensity.A
monolithbecomesunreadableasthedataspacingismadecloserthantheradiusofthe
data spots. However, there are multilayered samples with readable CNR values at the
samedatadensity.ForeachRathereisacorrespondingseparationthathasaCNRthat
matchesthemonolithicdevicewithnospotoverlap.Assuch,themultilayeringprocess
canincreasethedatastoragedensitywhileleavingtheCNRconstant.Thispropertyis
exemplifiedinfigure4.6.Thedensityiscappedbecausetheseparationhasalowerlimit
of approximately D/z0=1. Even with multilayering, when the plane spacing is smaller
than the written spot diameter, the information becomes imprinted on the adjacent
layers during writing. This adds noise to the layer at the focus of the beam, and it
cannotbefilteredbytheconfocalsystem.

65

4.6ShotNoiseandDarkCurrent
Thus far, the only noise term described has been the crosstalk. This result is an ideal
limitratherthananexpectation.Othersignificantsourcesofnoiseforthesedeviceswill
come from the detector. The photodiode dark current and the Shot current both
contributetotheoverallCNR.TheShotnoisewillvarydirectlyasthesquarerootofthe
generatedphotocurrent.Thephotodiodedarkcurrentnoisevaluesareconstantanddo
notscalewiththeamountoflighttakenin.AslongasJNislargewhencomparedtothe
darkcurrentandShotNoise,figure4.7shouldpredicttheeffectofaxialconfinementin
multilayered disks. However, when the JN is similar in size to the other terms,
multilayeringproducesmuchlessenhancement[figure4.9]

66

In figure 4.9 when other noise sources are dominant, the CNR enhancements seen in
figure4.7areallbuteliminated.Thisisbecausemostoftheenhancementinfigure4.7
istheresultofreducingJN.Whilereductionoftheactivelayerhaslittleeffectinthese
cases,increasingthepowerofthereadingbeamorthesensitivityofthedetectorwill
boosttheCNRofsystems.However,theCNRofamonolithscalesinthesamemanner
astheCNRofamultilayereddiskasthebeampowerisincreased,sothereremainsno
enhancement from multilayering. Although, JN scales linearly with beam power and
detectorsensitivitywhileDCisconstantandShotnoisescalesasthesquareroot.From
this,itispossibletoretaintheenhancementsofmultilayeringbyincreasingthesignal
67

and noise currents so that they are large when compared to the Shot noise and dark
current.

4.7Conclusion
OverallaclearimprovementinCNRisseenastheconfinementeffectsareincreasedin
these simulations. When the crosstalk noise is the dominant term, the multilayered
disks offer a considerable enhancement to the CNR of a disk. Increasing the reading
beam power does not offer any benefit in this case because the signal and crosstalk
noise both scale linearly with power. When the pinhole size is increased, the
enhancement is not as strong. However, increasing the pinhole size increases the
photocurrentssignificantly.WhendarkcurrentandShotnoisearethedominantterms,
there is no enhancement to the CNR from multilayering. However increasing the
generatedphotocurrentcanmakethebackgroundnoisethedominantterm.

68

Chapter5:ThermalInfluenceonBiexcitonAnnihilationinZincPhthalocyanineFilms

5.1Introduction
Metallophthallocyanine(MPC)dyesarenotedfortheirnonlinearopticalpropertiesand
electronic structure. Common features include large values of chi3, a columnar
crystalline form, liquid crystalline mesophases, and absorbance bands that span the
visiblespectrum.

While inorganic semiconductors have filled the role in the past, the mass production
capabilityoforganicmaterialsplacesthemasstrongcandidatesforactivemediainthe
next generation of optoelectronic devices. Other works present these dyes as active
media for femtosecond Kerr gates, photovoltaics, optical data storage, and optical
limiters.[8588]

For each application, carrier transport and lifetime are of paramount importance.
Various authors have measured ultrafast exciton dynamics in MPC samples.[8991]
Many report biexciton annihilation at high excitation densities. In their analyses, the
excitonexcitoncrossectionsareextractedfromdynamicsmeasurementsandarethen
usedtocalculatetheintermolecularhoppingtimes.Inallcases,thecrossectionisfound
tovaryliketime1/2,whiletheintermolecularhoppingtimesrangefrom10to400fs.

69


These calculated hopping times are derived from the interpretations of the
dimensionality of the biexciton interaction. The phenomenon of 1D diffusion of
excitonsalongMPCchainsisoftenpresentedasanexplanationoftheresult;howevera
quasistatic population of excitons interacting in 3D can produce the same time
dependence.Themainpurposeofthisworkistoproperlydiscriminatethesemodels.
Indoingso,Iintendtoexplaintheexcitonicbehaviorinbothcrystallinephaseandthe
firstmesophase.

Thefemtoseconddynamicsforthinfilmsofzincphthalocyanine(ZnPC)arepresented.
This work characterizes the temperature dependence of exciton behavior in both
crystallineandliquidcrystallinephasesoftheZnPC.Themeasuredexcitonpopulation
dynamics do not scale linearly with the initial population density, and this behavior is
accuratelydescribedbyabiexcitonrecombinationmodel.Thebiexcitonrecombination
crossection and intermolecular hopping time are presented at temperatures from 90
400K.Heretheexcitonhoppingtimeisreportedtovarysignificantlywithtemperature
in both phases. This thermal dependence is in disagreement with the model thatthe
biexciton annihilation arises from 3D interaction of static carriers. The dependence
stronglysuggeststhattheinteractionisrestrictedtoanexcitonpopulationundergoing
1D diffusion. From this, the role of temperature and structural order in the exciton
hoppingtimeisclear.

70

5.2Materials
ZnPC powder was purchased fromAldrich and purified via thin layer chromatography.
The resultant powder was placed onto a thin sheet of quartz. Then it was heated
beyonditsmeltingpointandpressedagainstanothersheetofquartz.Thethicknessof
thesamplewassetbyaonemicronspacer.Thefilmwasthencharacterizedoptically
withlinearspectrummeasurements.Thephasetransitiontemperatureofapowderof
thissamplewasthenmeasuredtobenear375Kwithdifferentialscanningcalorimetry.

TheabsorbancespectrumofthefilmwasfitusingaLorentzoscillatormodel.[9298]A
fit of seven states was chosen as there are seven distinguishable features in the
absorptionspectrum(figure 5.1). Theextracted resonant transitionenergies and their
broadeningfactorsarelistedintable5.1.

71


Linear spectrometer measurements confirm a band structure similar to MPC films
studiedinotherpapers[9298].Thelowestenergypeakisunderstoodtobethefirstpi
>pi*moleculartransition.[98]Thesymmetryoftheabsorptionandphotoluminescence
spectral lines confirms that the next highest energy peak is electronically the same.
However,thisstateincludesanopticalphononmode.[98,99]Bothofthesestatesare
commonly present in ZnPC solutions and films.[92, 96, 98, 99] Photoconductivity
measurements of ZnPC films have confirmed this state to function as a Frenkel
exciton.[97,98]

72

5.3Experiment
Ultrafast pumpprobe spectroscopy was used to study the exciton dynamics of these
ZnPC films. An amplified titanium sapphire laser provided illumination for time
dependantmeasurements.By useofathermalstage,thetemperatureofthe sample
wascontrolledandmonitored.

Carrierlifetimemeasurementsweremadewithexcitationfluencefrom110mJ/cm2at
temperatures from 80450 K. A fundamental output beam of 800 nm (1.55 eV)
wavelength was used as a probe with a frequency doubled 400nm (3.1 eV) pumping
pulse to produce dynamic absorption measurements. Pump and probe beams
intersectedata 30oangleandhad radiiof200umand50um,respectively. Data was
measuredoverarangeof180pswitha260fsresolution.

Fromthesamplesabsorption,heatcapacity,andthermalconductivity,itwasestimated
thateachpulseheatsthesampleby0.3K.Thecharacteristictimeforthermaldiffusion
acrossthelaserspotof200umwasestimatedtobe3ms.Thereforethepumpbeam
inducedheatingwasexpectedtohavenegligibleeffectsonthepsdynamics.Thebulk
temperature of the sample was expected to be within 3 K of the reading of the
thermocouple.

73

5.4Results
Toquantifytheexcitondynamics,thequantumefficiencyoftheconversionofabsorbed
photons to excitons was assumed to be near 100%. Observed photoluminescence
measurements by Bala et al suggest that this efficiency varies little as temperature is
varied.[98] From the pulse energy and sample absorbance it was clear how many
photons were absorbed, and this was taken to be equal to the number of excitons
created.Thetimedependantphotoabsorbancemeasurementswerecalibratedtothis
standard.

At 293K the initial exciton population is linear with power. However, the population
dynamics do not scale linearly with initial concentration (figure 5.2). This indicates
excitonexcitonannihilationispresent.[8991]

Similar features are observed for all temperatures from 90K400K. There is a fast
biexciton annihilation over 510 ps. A slower decay from single exciton behavior is

74

noticedover100ps. Finallyamuchslowerbackgroundtermremains nearlyconstant

overananosecond,andthislikelyfromselftrappedpi*states.[8991]

Becausethepopulationdecaydoesnotscalelinearlywithpopulation,abiexcitondecay
model(equation5.1)isusedtofitthedata.[8991]

n (t )n 2 n 1

(5.1)

Here n is the exciton concentration, is the single exciton lifetime, and (t ) is the
biexcitoncrossection.

Thetimedependenceof (t ) isbaseduponthespatialconstraintsofthesystem[91].In
each case, (t ) takes the form of (t ) 0t p where p is some real number and 0 is a
constantthatdependsuponthepropertiesofthesystem.Forhighpopulationdensities
( (t )n 1 ) the linear term in equation 5.1 is negligible. This short time
approximationisseeninequation5.2.

n 1 0 ( p 1) 1 t p 1 n01

(5.2)

Thisillustratesa waytofit thetimedependenceof 0 throughsimplegraphmethods.

Givencorrectselectionofp,aplotof1/nvs.tp+1shouldbeastraightline.Fittingn1toa
powerlawshowedthatp=1/2.Aplotofn1vst1/2forallofthemeasureddatasets
producesaseriesoflinesasseeninfigure5.3.

75

So with the result of p = 1/2, the form of (t ) is determined to be (t ) 0 t 1 / 2 .

Substitution into equation 5.1 allows the carrier population to be solved for all times
andconcentrations.Solvingtheequation5.1yieldsequation5.3.

e
n 01 0

p 1

erf t

(5.3)

This became a tool to extract the dynamics coefficients under the condition p = 1/2.
Note that in equation 5.3 the carrier concentration goes to zero when t >> . The
differential absorption, however, persists on timescales much larger than exciton
lifetimes. As such, this portion of the signal is neither from single exciton decay nor
biexciton annihilation. Therefore, this long term behavior was subtracted before
applyinganyofthefittingroutines.[91]

The time dependence of (t ) exists because the excitons which are closest to each

other at t=0 are most likely to annihilate first. At later times, the closest pairs of
excitons have already annihilated and the average time for any remaining excitons to
annihilateislonger.Theformof (t ) isdeterminedbytheexcitonexcitoninteraction
strengthandthetranslationalfreedomoftheexcitons.

76

5.5PhysicalInterpretationoftheTimeDependenceoftheCollisionRate

Intheprevioussectionsitwasshownthatthedifferentialabsorptionsignalwascaused
mainly by the presence of excitons, and that these excitons undergo a nonlinear
annihilationwitheachother.Thebiexcitonannihilationcoefficient, (t)wasshownto
havethetimedependenceof(t)=0t0.5atpumpingintensitieslower10mJ/cm2.

There are two interpretations of the excitonic kinetics that predict this result. Such a
response is characteristic of quasistatic excitons with long range interactions in 3
dimensions.Thisdependenceisalsoproducedbyapopulationofexcitonswithashort
rangeinteractionthatareallowedtodiffusein1dimension.[91]

Tobuildthesemodels,itisassumedthattheexcitonsannihilatethroughdipoledipole
interaction. The phenomenological description of the annihilation rate for a single
exciton,(t),istheintegratedinteractionbetweenthatexcitonandanyotherexcitonin
thesample[91,100].Thisisrepresentedas

(t ) d d r ( r ) g ( r , t )

(5.4)

Weredisthedimensionalityofthesystem,(r)isthedipoledipoleinteractionstrength
of the excitons, and g(r,t) is the pair correlation function between two excitations

77

spacedbyadistancerattimet.[91,100]Thedipoleterm,(r)iseasilyunderstoodasa
Forstertypeinteractionwhere
6

(r ) kop RA r

(5.5)

HereRAistheForsterRadiusofannihilationandkopistheopticalexcitationdecayrate.
Thecorrelationfunctioncanbefoundwithadiffusionequation[91,100]

g (r , t )
2 D 2 g (r , t ) 2 (r ) g (r , t ) F ( g (r , t ))
t

(5.6)

Where D is the diffusion constant for the excitons, and F describes higher order
interactions.[91,100]Togoodapproximation,
F ( g (r , t )) 2n (t )(1 g (r , t )) g (r , t )

(5.7)

Onesuchinterpretationisthestaticcase.Inthisvieweachexcitoniswelllocalizedand
does not move significantly over the course of its lifetime. Since the excitons are
considered quasistatic, the divergent term is ignored. If the higher order interactions
arealsoneglected,thenthesolutiontoequation5.6issimplyintegrated.[91,100]

g (r, t ) e2 ( r )t

(5.8)

Placementofthisfunctioninto thedefinitionof (t)providesanintegrable expression

andreducestotheform
d

(t ) 0t 6

(5.9)

78

Soclearlythisinterpretationreproducesthemeasuredbehaviorwhend=3.Inmaking
theseapproximations,itisimportanttofindtheconstraintsunderwhichtheyholdtrue.
The higherorder interaction term is negligible ifF(g(r,t)) << 2(r)g(r,t).[91, 100]Using
equations 5.1, 5.7, 5.8, and 5.9, this constraint reduces to t < (4n(t))1. Under this
constraint,itisalsotruethatt<,soitisselfconsistenttoignorethelineardecayterm
inequation5.1.Itssolutionundertheseconstraintshastheform

n(t )

1
1

n 0 (6 / d ) 0 t d / 6

(5.10)

Athighintensitieswhenn0>kd/6d/(60)theconstraintsreduceto1<6/dwhichistrue
fortheobservationofd=3.Thismeansthattheapproximationsmadeareselfconsistent
fortheobserveddimensionality.[91,100]

Tounderstanddiffusionlimitedannihilationonemustinsteadconsidertheglobalrate
lawsforinteractingpopulations.Thatis,fortimesclosetot=0,theasymptoticbehavior
iswellapproximatedbyapowerlaw[91,101]
n(t)~thforsomeh>0

(5.11)

Foraparticleundergoingarandomwalkthroughastructure,wecanexpectittovisitS
sites before reacting with its nearest neighbor.[101] The average spacing between
carriersvariesinverselywiththecarrierdensity,andso
S~n1

(5.12)

79

A well known result of random walker calculations is that the number of sites visited
increaseswiththeelapsedtimetel.[101]
S~telf

(5.13)

Herefisdeterminedbythedimensionalityofthesystem.Forsystemsofintegervalued,
fhaspiecewiseform.[102]

d for
f 2
for
1

d 2
d 2

(5.14)

(5.15)

So,fromequations5.125.14
n ~ S 1 ~ t f

For short times and high concentrations, the linear decay term in equation 5.4 is
negligible. Substitution of equation 5.18 allows the time dependence of (t) to be
shown

n n2 (t )

t f 1 ~ t 2 f (t )

(5.16)

Inordertoproducethesametimebehavioronbothsidesoftheequation,itisclearthat

(t)~tf1.Sousingthepiecewisedefinitionoffnowdefines(t)[91],

d2 1

(t ) 0t for
0
for

d 2
d2

(5.17)

The experimental time dependence of (t)~t0.5 shown in the previous section is

expectedforaonedimensionalsystem(d=1)inthisinterpretation.

80


So we see that there are two interpretations of the exciton kinetics that predict the
observedresult.Suchbehaviorischaracteristicofquasistaticexcitonswithlongrange
interactions in 3dimensions. [91] A population of excitons with a short range
interactionalsoproducesthisresultwhenconstrainedto1dimensionaldiffusion.[91]
To differentiate between these cases, it is necessary to consider the temperature
dependenceof 0 .

5.6ThermalDependanceoftheZnPc
For the next set of measurements the temperature dependence of the carrier decay
parameterswasexamined.Thesamplewasheldattemperaturesfrom90K415Kwhile
thepumpprobedynamics weremeasuredatboth ahighand alowfluence. The low
fluence measurements resulted in sufficiently low excitation density so that biexciton
annihilationwasnotobserved.Thesefitswereusedtoaccuratelydetermine ateach
temperature. The high power measurements were then fit to equation 5.3 with
constrained to extract 0 at the same temperature. The resulting values of 0 and
wereplottedinfigure5.4.

81


Here a trend is clear in the behavior of 0 . It is seen to rise with temperature in the
crystalline phase and then decreases with temperature as the disorder of the system
increases.Asseeninfigure5.4, dropsby~20%asthetemperaturegoesfrom365K
to370K.Thisshowsthatthereisasignificantlylargernumberofwaysforeachexciton
toscatterandannihilateastheliquidcrystalgoesthroughthephasetransition.

For a quasistatic system of interacting excitons, the temperature should have little
effect on the rate of interaction. The main contribution from a rising temperature
wouldbethermalexpansion.Astheaverageintermolecularspacingincreases,therate
ofreactionwoulddecrease.Thispredictiondoesnotmatchtheseresults.Theobserved
rateofreactionincreaseswithtemperatureinthecrystallinephase. Furthermorethe
intermolecularspacingofZnPCchangesverylittleasitisheatedthroughthecrystalline
phase.Thusheatingshouldhavelittleornoeffectontherateofbiexcitondecayifthe

82

systemwereinsuchaquasistaticconfiguration.Assuch,weknowtheexcitonsdonot
adheretothequasistatic3Dinterpretation.[89,91]

In this interpretation, the intermolecular hopping time, h is intrinsically linked to 0

andthemoleculardensity,N.Assuch, h wasdeterminedforeachtemperatureunder
the condition that h = 4 -1 0 N [91]. Since the density of the film varies very little
2

withtemperature,thehoppingtimewasdetermineddirectlyfrommeasurementsof 0
andplottedinfigure5.5.

It should also be noted that the intermolecular hopping time and D, the diffusion
constantareinverselyrelated.ThatisD~ h 1~ 0 2.[91,101,102]Fromthisrelation
thediffusionconstantDisdetermineduptoaproportionalityconstant(figure5.6).

Totestthisinterpretation,welooktotheArrheriusequation.Thisrelationisoftenused
tomodelthermallyactivatedprocesses.Formostsystemsthatundergodiffusion,the
83

temperature dependence of some rate constant, R, is well described as an activated

processofactivationenergyEaandcharacterizedbytheArrheniusequation,
Ea

R R0 e k B T

(5.18)

whereTistheabsolutetemperatureofthesystem,kBistheBoltzmannconstant,andR0
isthatrateatT=0K.Inthiscase,thediffusionconstant,D,willbefittotheArrhenius
equation(figure5.6).Afitforanactivatedprocessdoesnotworkwellovertheentire
range of data. However, if split into 2 segments that correspond to the phases, this
model fits 0 well. The model shows biexciton recombination to have an activation
energyof 17 2 meVinthissystem.

5.7Conclusion
So it is clear that the temperature affects both linear exciton decay and biexciton
collision rates in ZnPC. From this, the experiment determined that the exciton
recombination does not occur under the constraints of a quasistatic system with long
rangeinteractions.Instead,thesampleisinteractionisfoundtohappenatshortrange
forexcitonstravellingin1D.Itisalsofoundthatwithincreasingtemperaturetherateof
biexciton collision increases. This change has corresponding effects on the
intermolecular hopping time and diffusion constant. Furthermore, the complexity of

0 s temperature dependence shows that different phenomena dominate the

annihilationrateineachphase.

84

AppendixA:PowerDependenceofPhotopatterninginC18RGdye.

A.1Introduction
Theabilitytopatternhighdensity3Dopticalstoragedisksislimitedbytheshapeand
size of the written spots. Understanding beams effect on the sample is an important
part of optimizing any such disk. Here a series of spots are patterned into a polymer
containing a two photon absorbing dye. In separate experiments, the sample is
patterned with wavelengths corresponding to its linear and two photon absorption
peaks. By varying the power of the patterning beams, the size of these spots is also
varied. As the power of the patterning beam is decreased, the spots become smaller
andinsomecasesthepatternsareshowntobesmallerthantheshapeofthebeam.

Under simple microscopy, the potential of optical data storage is limited by the wave
natureoflight.Formostcommonkindsofmicroscope,diffractiondictatesaminimum
beamsizeforbothpatterningandresolvinginformation.Assuchthefeaturesonadisk
cannotbeutilizediftheyaresmallerthanthefocusedbeam.Thereforearestrictionis
imposedontheoverallDSDofanopticaldatastoragescheme.However,withabitof
finesse,thenextgenerationofopticalstoragecancircumventtheseissues.

85

Most of the designs for 3D data storage systems rely on two photon absorption
processes. This property benefits the storage density, as it creates spots that are
smallerthanthebeam.ForaprocessofnphotonsandawritingbeamwithaGaussian
shape,thehalfwidthofthewrittenspotisrelatedtothehalfwidthofthebeamshape
by a factor of

in the radial coordinates and 2

1 in the z direction. These

relatetopalpableincreasesinthedatastoragedensity.

Withfew exceptions,themechanisms that enable 3D datastorageusephotochemical

processes.Influorescencebasedsystems,eachtwophotonabsorptioneventcausesa
net creation of a fluorescent molecule. This is frequently produced through a ring
closingchange[66],thoughmorerecentmethodsutilizephotoacidgeneratorstocleave
the bonds of dye precursors[2]. In many reflection based systems, the index of
refraction of a polymer is changed by a photochromic ring closing[21, 24]. While the
absorptionofthewritingbeamisnonlinear,thematerialsresponsetotheabsorptionis
linear.Asaresult,allwrittenspotsretaintheGaussiancharacteristicsofthebeamthat
wasusedtowritethem.Thespotsaresimilarinsizetothebeam,andhaveasoftedge.

Theuseofamaterialwithanonlinearresponsetoilluminationisonewaytocircumvent
this limit. Some photoresist materials are frequently patterned in such a way as to
produce / 4 detail.Withfurtherapplicationofmaterialnonlinearities, / 20 features
havebeenachieved[103].Whileinapolymergelstate,thesematerialsarepatterned
86

byphotoinitiatedcrosslinking.Thecrosslinkingonlyhappensinregionswherethefree
radicalconcentrationsaretakenaboveathreshold[103,104]Whileveryinterestingfor
nanotoolingandMEMs,photoresistgelsdonotoffersuitablemechanicalpropertiesfor
opticaldatastorage.

Afewmethodsexisttobeatthediffractionlimitwithinthecontextof3ddatastorage.
OnedemonstrationofsucharestrictedthespotsizewasdonebyNakanoetal[21].The
authorsphotopatternedamaterialwithaUVlasertomakesmallwritableregions,then
later wrote to these regions with an infrared laser. Since the writable regions were
confinedtothefocalregionoftheUVbeamthatwasusedtomakethem,theresponse
to the IR beam was confined to the same regions. This produced features that were
muchsmallerthantheIRbeamthatwasusedtowritethem.Spatialconfinementwas
provided in the third dimension by the multilayering of the material itself. While this
method produced clear and useful results, the down side is that it requires
photopatterning of each layer during the fabrication process. Furthermore, while the
spotsaresmallerthantheIRbeam,theyarestillsimilarinsizetotheUVbeam.

The most common forms of nonlinear response used for optical data storage are
photothermal in nature. Current commercial writable DVD and Blu Ray disks use
thermally crystallizable material[3]. By linear absorption of the writing beam, the
materialisheatedandannealed.Fromthethermaltreatment,alocalphasechangeis
87

created. These modulations in the phase of the disks cause a modulation in the
reflection coefficient, so the disks are read by reflection. Since the change is phase
based,thechangeisthresholdedwithtemperature.Whilethediffractionlimitedspot
size of in a Blu Ray system is 580 nm(NA=0.8, =400nm) the written spots are only
150nmindiameter.

Other recent experiments have used threshold based mechanisms for 3D optical data
storage.Photoinitiatedcrosslinkingreactions[68]andphotothermalannealingofgold
nanorods [15] both produce nonlinear responses in the materials optical properties.
Furthermore,forcommercialwritableopticalmedia,theinformationisstoredthrougha
threshold based phase change[35]. However, subdiffraction patterning is not
demonstratedinthesedevices.

The benefits of threshold systems are multifacet. Others have shown that a properly
controlled threshold process can circumvent the need for 2photon based writing
processes[15]. The high contrast, spatially confined writing provides higher signal to
noiseratioswhenreading[21].Furthermore,thesizeofdataspotshasbeenshownto
varyaswritingpowerischanged[105].However,thepotentialforsmallerwrittenspot
sizes and higher DSDs has yet to be explored. In a system with these properties, the
datacanbepackedmoredensely,andsotheoverallDSDandstoragecapacityincrease.

88

Anexperimentwasdesignedtoelicitsuchadependence,shoulditexist,inamaterial
withknownthermalthresholdproperties.Intwoseparateexperimentsthesamplewas
patterned at wavelengths matching its linear absorption peak at 400 nm and its two
photonabsorptionpeakat675nm.Spotswerewrittenatvariouspowers,thesizesof
writtenspotsweremeasuredforvariouswritingpowers.

A.2ReadingfromSubdiffractionSystems
Inordertomakeuseoffeaturessmallerthanthebeam,thefeaturesmustberesolvable
duringreading.Modernimagingtechniqueshavesignificantlyincreasedtheresolution
ofboth2Dand3Dmicroscopytosuitablelevelsforthistask.Becauseofthegeometry
ofthedetection,nearfieldmethodsarenotsuitablefor3Ddatastorage.Multiplefar
field techniques have matured in the past 10 years to image features smaller than 10
nm. Stimulated Emission Depletion Microscopy (STED) offers the power to resolve
featuressmallerthan6nmbyusingstimulatedemissiontoquenchthefluorescenceof
a major portion of the focal volume around the feature of interest[106]. Structured
illumination microscopy(STIM) has achieved similar resolutions by using a light grating
toilluminateandscanthroughthesample.Imageprocessingdonetotheresultantbeat
patternprovidesresolutiontobetterthan10nm[17].BoththeI5Rand4Pimethodsuse
counter propagating beams to create interference at the focal point and thus further
reducetheresolutionto50100nm[107,108].ANonlinearSTIMapproachreliesupon
thesaturationpropertiesofcertaindiestoofferatheoreticallyinfiniteresolution[109].
89

By this method, the resolved volume is greatlyreduced, but is limited by the size and
concentration of the dye molecules, the sensitivity of the dye, and the stability of the
excitationsource[6].

A.3SamplePreparation
A film of PETg with 2 weight % of C18RG dye was fabricated as a thin film to be
photopatterned[49].Thedyewasmadeintheprocessoutlinedintheliterature[110].
ThenthedyewasaddedtothepolymerPETginitspowderformandheatedto200Cto
formasolution.Thesolutionwasmixedandpressedintothinfilmsbetweenglassslides
toproducepolymerfilms.Aftercooling,thefilmswerereheatedto90Candheldthere
for45minutestoallowthedyemoleculestomobilizeandcoalesce.

A.4PhotopatterningattheTwoPhotonAbsorptionWavelength
For the first set of photopatterning experiments, the film was exposed to focused
radiation from a pulsed laser source. Laser illumination was supplied by a Nd:YAG
operatingin10nanosecondpulsemode.Anopticalparametricoscillatorwasusedto
setthewavelengthofeachpulseto675nm,whichisthe2photonabsorptionpeakof
the dye. Each pulse was then focused by an oilimmersed lens objective with
numericalapertureof0.85.Throughuseofaknifeedgetechnique,thebeamwaistwas
directlymeasuredtobe.9umwhiletheRaleighrangeinthezaxiswas2.3 m[figure
90

A.1].Thediffractionlimitedbeamwaistforthiswavelengthandlensisabout300nm,so
theremustbesignificantaberrationintheopticalsystem.

The sample was translated through the beam focus by a computer controlled 3 axis
stage. Single pulse operation of the laser was also controlled by the computer. The
materialwaspatternedbyfirstpositioningthesample,andthensendingapulseoflight
into it. The process was repeated to make a pattern of about 15 spots within the
sample. The pulse energy was controlled with a series of neutral density filters. Six
differentpatternsweremadeinall,eachwithdifferentpulseenergy.Theenergyofthe
pulses was varied by application of a series of neutral density filters, each with a
transmissionof84%.

91


Upon the conclusion of patterning, the samples were imaged with a confocal
microscope. For these measurements, the illuminating beam was set to 405 nm to
makethedyefluoresce.Spectralfilterswereplacedtomatchthepossiblefluorescence
modesofthedye.

Theimagesofthesampleafterpulsedphotopatterningat675nmareseeninfigureA.2.
Thepatterndoesnotemitlightatanyofthedyesfluorescencemodes.However,the
patternisvisibleinatransmissionmicroscope.Fromthese,itisclearthatthepatternis
aresultofthermaldecompositionofboththedyesandthehostpolymer.

92


Toextractthefeaturesizes,eachspotwasfittoaGaussianshape.Priortofitting,alow
pass filter was applied to remove noise sources that were much smaller than the
resolution of the microscope. To account for the power fluctuations within patterns,
thereportedmeasurementsarebasedontheaveragesizeoftheallofthespotsineach
pattern [figure A.3].Onoccasion,alightpulsestrikesanimperfectioninthefilmand
produces a particularly large, and misshapen spot. Because of this, spots that are
particularlyasymmetricalareleftoutwhendeterminingstatistics.

Allofthespotspatternedinthisexperimentaresmallerthanthebeamdiameter.The
mostsignificantsourceoftheerroristhevarianceinenergyfrompulsetopulse.The
pulsetopulseinstabilitycreatesuncertaintyintheaveragepowerusedtocreateeach
ensemble.Thiseffectleadstoalargevarianceinthesizesofthewrittenspots.

93


Fromtheabsorbanceofthematerial(Figure2.3),itisseenthatthereisnoappreciable
linearabsorptionat675nm,soclearlythewritingcannotbedrivenbyasinglephoton
process when using this wavelength. Given the strong TPA crossection of the dye at
675nm (Figure 2.4) It is expected that the process is driven by TPA.

Eventhoughtheprocesscannotbecompletelyclassifiedfromthedata,itisnotablethat
there are spots observed smaller than the diffraction limit. Earlier the beam was
characterized to have a waist of 900nm. For two photon absorption this value is
reduced640nm.Manyoftheobservedspotsaresmallerthanthis(FigureA.3),and
someofthespotsareevensmallerthan300nm.Regardlessofthefitofthemodel,itis
clear that this process is making spots smaller than the effective beam waist for both
linearabsorptionandTPA.

A.5PatterningtheSamplewithLinearAbsorption
Followingtheexperimentwith the nanosecondsystem,thesinglephotonresponseof
thesystemisexaminedbywritingtothesamplewithaCWsourceat405nm.Forthis
experiment,thesamplewaspatternedwithlinesbythepreviouslymentionedconfocal
microscope, and then those lines were imaged and characterized in 3D by the same
microscope. To pattern the sample, it was first placed into the 3D stage that is
controlledbythemicroscope.Thesamplewasthenimagedatalowpowertoprovidea
94

background reference. Next, the microscope was set to sweep the laser across the
sampleinindividuallinesatpowersrangingfrom1to100mWwithascanrateof80
m/s.Giventhebeamwaistisapproximately130nmforthisopticalsystem,eachpart
ofthepatternedpartofthesampleisexposedtothelaserforabout1.6ms.Lineswere
parallelandseparatedby1mtoavoidcrosstalkeffects.Afterwritingthelineswere
images with the same beam as was used to write them, however the power was
reduced to 0.1 mW. The confocal microscope imaged the lines in slices that were
separatedby100nmindepth.OnesuchsliceisshowninfigureA.4.

In the CW experiment, the data is taken from fig A.4. By taking crossections
perpendicular to each line, the Gaussian features of the spots can be fit. Thirty
crossectionsareaveragedtodecreasetheimagenoiseforeachlinepriortofitting(Fig
A.4).

95

Tofindanypowerdependanttrend,theoveralldimensionsofthespotswereextracted
fromtheseaveragedimages.BecauseoftheGaussianbeamshape,thespotswerefit
by a Lorentzian along the beam axis and a Gaussian perpendicular to this axis. The
resultsofthesefitsarefoundinfigureA.5.Heretheplotsshowanincreaseinboththe
heightandwidthofthespotaspowerincreases.Atlowpowers,thebackgroundnoise
becomes similar in size to the signal. The fitting becomes unreliable and both spot
dimensions

appear

to

increase

drastically

as

the

power

decreases.

Here the detected spot widths are significantly larger than the beam waist. For a
Gaussianbeamof405nmlightthatisfocusedthroughalenswithnumericalapertureof
1, the beam waist is about 130 nm. In the measurements, the smallest radius of the
writtenspotsisfoundtobeabout300nm[figureA.5].

Thedatahasagenerallylineartrendwithpower.Howeveratlowerenergiesthistrend
does not match the data. This is likely because at these lower energies, the signal to
96

noiseratioissmallandthefittoaGaussianshapeisnotwellconstrained.Sincethereis
no clear threshold, it cannot be said that a thermal phase change process is present.
Thepatternedlinesarewiderthanthebeam,andtheydecreaseinsizeasthepoweris
decreased.Thissortofbehaviorischaracteristicinsystemswithasaturatedbleaching
response.

A.6Conclusion
Sub diffraction limit patterning is not something that has is frequently used in the
context of 3D optical data storage. However, the tools exist to pattern and read
informationthatissmallerthanthediffractionlimit.Hereisshowna2photonbased
system that created spots smaller than the focused beam diameter. Similar
experiments done with a single photon absorption based system do not exhibit the
same sub diffraction features, and are likely in a regime of saturated response. Both
systems show a trend in the size of the patterned features. While it is not clearly a
threshold process, the sample definitely exhibits a nonlinear response to illumination.
Whenusedaspartofastoragemediumthesystemcouldproducebothhighersignalto
noise ratio and data storage density than a system that uses a nonthreshold
mechanism[12,60].

97

Bibliography

1.

Rentzepis,P.M.,AdvancesinPicosecondSpectroscopy.Science,1982.218(4578):p.
11831189.
Walker,E.,etal.,Terabyterecordedintwophoton3Ddisk.AppliedOptics,2008.47(22):
p.41334139.
Mitsumori,A.,etal.,Multilayer500GbyteOpticalDisk.JapaneseJournalofApplied
Physics,2009.48(3):p..
Ceshkovsky,L.,Recordinginformatioinonanopticaldiscwithoutusingpre
manufacturedtracks.1996.
Miao,X.S.,etal.,Newadditionallayertorealizeinitializationfreefunctionfordigital
versatilediskrandomaccessmemorydisk.JapaneseJournalofAppliedPhysicsPart1
RegularPapersShortNotes&ReviewPapers,2000.39(2B):p.729732.
Heilemann,M.,Fluorescencemicroscopybeyondthediffractionlimit.Journalof
Biotechnology,2010.149(4):p.243251.
Gregg,D.P.,VideoSignalTransducerHavingServoControlledFlexibleFiberOpticTrack.
1970.
Gregg,D.P.,TransparentRecordingDisc.1969.
Gregg,D.P.,Discshapedmember.1990.
TDK.TDKAnnounces100GBBlueLaserDiscTechnology.[PressRelease]2005.
Curtis,K.R.,Holographicdatastorage:fromtheorytopracticalsystems.2010,Hoboken,
NJ:Wiley.xvi,420p.
Coufal,H.,D.Psaltis,andG.T.Sincerbox,Holographicdatastorage.Springerseriesin
opticalsciences,.2000,Berlin;NewYork:Springer.xxv,486p.
Earman,A.,OpticalDataStorageWithElectronTrappingMaterialsUsingMaryData
ChannelCoding.ProceedingsoftheOpticalDataStorageConference,1992.
Li,L.J.,etal.,Achievinglambda/20ResolutionbyOneColorInitiationandDeactivation
ofPolymerization.Science,2009.324(5929):p.910913.
Zijlstra,P.,J.W.M.Chon,andM.Gu,Fivedimensionalopticalrecordingmediatedby
surfaceplasmonsingoldnanorods.Nature,2009.459(7245):p.410413.
Hell,S.W.,etal.,ResolutionBeyondtheDiffractionLimit4piConfocal,Sted,andGsd.
ZoologicalStudies,1995.34:p.7070.
Gustafsson,M.G.L.,Surpassingthelateralresolutionlimitbyafactoroftwousing
structuredilluminationmicroscopy.JournalofMicroscopyOxford,2000.198:p.8287.
Corredor,C.C.,etal.,Photochromicpolymercompositesfortwophoton3Dopticaldata
storage.ChemistryofMaterials,2007.19(21):p.51655173.
Corredor,C.C.,Z.L.Huang,andK.D.Belfield,Twophoton3Dopticaldatastoragevia
fluorescencemodulationofanefficientfluorenedyebyaphotochromicdiarylethene.
AdvancedMaterials,2006.18(21):p.2910+.
Parthenopoulos,D.A.andP.M.Rentzepis,3DimensionalOpticalStorageMemory.
Science,1989.245(4920):p.843845.
Nakano,M.,etal.,Threedimensionalpatternedmediaforultrahighdensityoptical
memory.AppliedPhysicsLetters,2004.85(2):p.176178.

2.
3.
4.
5.

6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.

20.
21.

98

22.

Kawata,Y.,M.Miyamoto,andM.Nakabayashi,Newdevelopmentofrolltype
multilayeredopticalmemoryforhighdensitydatastorageart.no.662004.Optical
DataStorage2007,2007.6620:p.6200462004

23.

Kawata,Y.,Multilayeredopticalmemoryforhighdensitydatastorageinthenext
generation.2006IEEELEOSAnnualMeetingConferenceProceedings,Vols1and2,2006:
p.142143

24.

Miyamoto,M.,etal.,Fabricationofmultilayeredphotochromicmemorymediausing
pressuresensitiveadhesives.AppliedOptics,2006.45(33):p.84248427.

25.

Mueller,C.D.,etal.,NovelstructuresbymicrolayercoextrusionTalcfilledPP,PC/SAN,
andHDPE/LLDPE.PolymerEngineeringandScience,1997.37(2):p.355362.
Nazarenko,S.,etal.,Novelstructuresbylayermultiplyingcoextrusion.Antec'96:Plastics
RacingintotheFuture,VolsIIii,1996.42:p.15871592

26.
27.
28.

29.
30.
31.
32.
33.
34.
35.
36.
37.

38.
39.
40.
41.
42.

Wuttig,M.andN.Yamada,Phasechangematerialsforrewriteabledatastorage.Nature
materials,2007.6(11):p.824832.
Mustroph,H.,M.Stollenwerk,andV.Bressau,Currentdevelopmentsinopticaldata
storagewithorganicdyes.AngewandteChemieInternationalEdition,2006.45(13):p.
20162035.
Psaltis,D.,Coherentopticalinformationsystems.Science,2002.298(5597):p.1359.
Won,R.P.C.,Opticaldatastorage:Twophotonsarebetterthanone.NaturePhotonics,
2006.
Pawlicki,M.,etal.,TwoPhotonAbsorptionandtheDesignofTwoPhotonDyes.
AngewandteChemieInternationalEdition,2009.48(18):p.32443266.
Walker,E.andP.M.Rentzepis,Twophotontechnology:Anewdimension.Nature
Photonics,2008.2(7):p.406408.
GallegoGmez,F.,F.DelMonte,andK.Meerholz,Opticalgainbyasimple
photoisomerizationprocess.Naturematerials,2008.7(6):p.490497.
Carling,C.J.,J.C.Boyer,andN.R.Branda,RemotecontrolphotoswitchingusingNIRlight.
JournaloftheAmericanChemicalSociety,2009.131(31):p.1083810839.
Gindre,D.,etal.,Rewritableopticaldatastorageinazobenzenecopolymers.Opt.
Express,2006.14:p.98969901.
Iliopoulos,K.,etal.,ReversibleTwoPhotonOpticalDataStorageinCoumarinBased
Copolymers.JournaloftheAmericanChemicalSociety,2010.
Lohse,B.,etal.,Acridiziniumsubstituteddendrimersasanewpotentialrewritable
opticaldatastoragematerialforbluray.ChemistryofMaterials,2008.20(21):p.6715
6720.
Attar,H.A.A.andO.Taqatqa,Anewhighlyphotorefractivepolymercompositeforoptical
datastorageapplication.JournalofOpticsA:PureandAppliedOptics,2003.5:p.S487.
Khan,A.,etal.,Dendronizedmacromonomersforthreedimensionaldatastorage.
ChemicalCommunications,2009(4):p.425427.
Castagna,R.,etal.,SuperiorPerformancePolymericCompositeMaterialsforHigh
DensityOpticalDataStorage.AdvancedMaterials,2009.21(5):p.589592.
Kawata,S.andY.Kawata,Threedimensionalopticaldatastorageusingphotochromic
materials.ChemicalReviews,2000.100(5):p.17771788.
Irie,M.,Diarylethenesformemoriesandswitches.ChemicalReviews,2000.100(5):p.
16851716.
99

43.
44.

45.
46.

47.
48.
49.
50.
51.
52.
53.

54.

55.

56.

57.
58.
59.
60.

61.
62.

Crenshaw,B.R.,etal.,Thresholdtemperaturesensorswithtunableproperties.
MacromolecularChemistryandPhysics,2007.208(6):p.572580.
Crenshaw,B.R.andC.Weder,PhaseSeparationofExcimerFormingFluorescentDyes
andAmorphousPolymers:AVersatileMechanismforSensorApplications.Advanced
Materials,2005.17(12):p.14711476.
Kinami,M.,B.R.Crenshaw,andC.Weder,Polyesterswithbuiltinthresholdtemperature
anddeformationsensors.ChemistryofMaterials,2006.18(4):p.946955.
Kunzelman,J.,etal.,SelfAssemblyandDispersionofChromogenicMolecules:A
VersatileandGeneralApproachforSelfAssessingPolymers.Macromolecularrapid
communications,2006.27(23):p.19811987.
Tang,L.,etal.,StimuliResponsiveEpoxyCoatings.ACSAppliedMaterials&Interfaces,
2009.1(3):p.688696.
Kunzelman,J.,B.R.Crenshaw,andC.Weder,Selfassemblyofchromogenicdyesanew
mechanismforhumiditysensors.J.Mater.Chem.,2007.17(29):p.29892991.
Kunzelman,J.,etal.,Oligo(pphenylenevinylene)sasa"New"classofpiezochromic
fluorophores.AdvancedMaterials,2008.20(1):p.119+.
Kunzelman,J.,etal.,PressureSensitiveChromogenicPolyesters.Macromolecular
MaterialsandEngineering,2009.294(4):p.244249.
Crenshaw,B.R.andC.Weder,Deformationinducedcolorchangesinmeltprocessed
photoluminescentpolymerblends.ChemistryofMaterials,2003.15(25):p.47174724.
Crenshaw,B.R.andC.Weder,Selfassessingphotoluminescentpolyurethanes.
Macromolecules,2006.39(26):p.95819589.
Lott,J.andC.Weder,LuminescentMechanochromicSensorsBasedonPoly(vinylidene
fluoride)andExcimerFormingpPhenyleneVinyleneDyes.MacromolecularChemistry
andPhysics,2010.211(1):p.2834.
Chung,S.J.,etal.,Strong,lowenergytwophotonabsorptioninextendedamine
terminatedcyanosubstitutedphenylenevinyleneoligomers.JournaloftheAmerican
ChemicalSociety,2005.127(31):p.1084410845.
Pond,S.J.K.,etal.,Metalionsensingfluorophoreswithlargetwophotonabsorption
crosssections:azacrownethersubstituteddonoracceptordonordistyrylbenzenes.
JournaloftheAmericanChemicalSociety,2004.126(30):p.92919306.
Fang,H.H.,etal.,Twophotonpumpedamplifiedspontaneousemissionfromcyano
substitutedoligo(pphenylenevinylene)crystalswithaggregationinducedemission
enhancement.TheJournalofPhysicalChemistryC,2010.
Meng,F.,etal.,Linearandtribranchedcopolymersfortwophotonabsorptionandtwo
photonfluorescentmaterials.Polymer,2003.44(22):p.68516855.
SheikBahae,M.,A.A.Said,andE.W.VanStryland,Highsensitivity,singlebeamn2
measurements.Opt.Lett,1989.14(17):p.955957.
Kuzyk,M.G.andC.W.Dirk,Characterizationtechniquesandtabulationsfororganic
nonlinearopticalmaterials.1998:CRC.
Ryan,C.,etal.,Subdiffractionlimitedfeaturesinthreedimensionalphotopatterned,
twophotonexcimerformingfluorescentdyedopedfilms.BulletinoftheAmerican
PhysicalSociety,2011.56.
Blanche,P.A.,etal.,Holographicthreedimensionaltelepresenceusinglargearea
photorefractivepolymer.Nature,2010.468(7320):p.8083.
McLeod,R.R.,etal.,Threedimensionalopticaldiskdatastorageviathelocalized
alterationofaformathologram.AppliedOptics,2008.47(14):p.26962707.

100

63.
64.
65.

66.
67.
68.
69.

70.
71.
72.

73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.

Ditlbacher,H.,etal.,Spectrallycodedopticaldatastoragebymetalnanoparticles.
Opticsletters,2000.25(8):p.563565.
Li,X.,etal.,Rewritablepolarizationencodedmultilayerdatastoragein2,5dimethyl4
(pnitrophenylazo)anisoledopedpolymer.Opticsletters,2007.32(3):p.277279.
Bruder,F.K.,etal.,FromtheSurfacetoVolume:ConceptsfortheNextGenerationof
OpticalHolographicDataStorageMaterials.AngewandteChemieInternational
Edition,2011.50(20):p.45524573.
Dvornikov,A.S.,E.P.Walker,andP.M.Rentzepis,TwoPhotonThreeDimensionalOptical
StorageMemory.JournalofPhysicalChemistryA,2009.113(49):p.1363313644.
Ogawa,K.,etal.,Strongtwophotonabsorptionofselfassembledbutadiynelinked
bisporphyrin.JournaloftheAmericanChemicalSociety,2003.125(44):p.1335613357.
Cumpston,B.H.,etal.,Twophotonpolymerizationinitiatorsforthreedimensional
opticaldatastorageandmicrofabrication.Nature,1999.398(6722):p.5154.
Ganic,D.,D.Day,andM.Gu,Multilevelopticaldatastorageinaphotobleaching
polymerusingtwophotonexcitationundercontinuouswaveillumination.Opticsand
lasersinengineering,2002.38(6):p.433437.
Lott,J.,etal.,TwoPhoton3DOpticalDataStorageviaAggregateSwitchingofExcimer
FormingDyes.Advancedmaterials(DeerfieldBeach,Fla.),2011.
Shipway,A.N.,T.A.Wasserman,andO.M.Alpert.ANewMediaforTwoPhoton
VolumetricDataRecordingandPlayback.2005:OpticalSocietyofAmerica.
Miyamoto,M.,etal.,Controlofrefractiveindexofpressuresensitiveadhesivesforthe
optimizationofmultilayeredmedia.JapaneseJournalofAppliedPhysicsPart1Regular
PapersBriefCommunications&ReviewPapers,2007.46(6B):p.39783980.
Wang,H.,etal.,Confinedcrystallizationofpolyethyleneoxideinnanolayerassemblies.
Science,2009.323(5915):p.757.
Ponting,M.,A.Hiltner,andE.Baer.PolymerNanostructuresbyForcedAssembly:
Process,Structure,andProperties.2010:WileyOnlineLibrary.
Kazmierczak,T.,etal.,PolymericOneDimensionalPhotonicCrystalsbyContinuous
Coextrusion.MacromolecularRapidCommunications,2007.28(23):p.22102216.
Lott,J.,etal.CoextrudedMultilayerAllPolymerDyeLasers.2010:ACSPublications.
Beadie,G.,etal.,Opticalpropertiesofabioinspiredgradientrefractiveindexpolymer
lens.2008.
Liu,R.Y.F.,etal.,ProbingNanoscalePolymerInteractionsbyForcedAssembly.
MacromolecularRapidCommunications,2003.24(16):p.943948.
Song,H.,etal.,Continuousmeltprocessingofallpolymerdistributedfeedbacklasers.J.
Mater.Chem.,2009.19(40):p.75207524.
Ichimura,I.,etal.,Proposalforamultilayerreadonlymemoryopticaldiskstructure.
Appliedoptics,2006.45(8):p.17941803.
Wang,M.M.andS.C.Esener,Threedimensionalopticaldatastorageinafluorescent
dyedopedphotopolymer.AppliedOptics,2000.39(11):p.18261834.
vanderLee,A.andE.Altewischer,DriveconsiderationsforBluraymultilayerdiscs.
Japanesejournalofappliedphysics,2007.46:p.3761.
McLeod,R.R.,Impactofphaseaberrationscausedbymultilayeropticaldatastoragein
weaklyinhomogeneousmedia.JOSAB,2009.26(2):p.308317.
Lott,J.,etal.,TwoPhoton3DOpticalDataStorageviaAggregateSwitchingofExcimer
FormingDyes.AdvancedMaterials.

101

85.

86.
87.

88.
89.

90.
91.
92.
93.
94.

95.
96.

97.
98.
99.
100.
101.
102.
103.
104.

105.

Mizoguchi,K.,S.Fujita,andM.Nakayama,Resonanceeffectsoncoherentphonon
generationinleadphthalocyaninecrystallinefilms.AppliedPhysicsA:MaterialsScience
&Processing,2004.78(4):p.461464.
ElNahass,M.,etal.,CarriertransportmechanismsandphotovoltaicpropertiesofAu/p
ZnPc/pSisolarcell.Solidstateelectronics,2005.49(8):p.13141319.
Derkowska,B.,etal.,Influenceofthecentralmetalatomonthenonlinearoptical
propertiesofMPcssolutionsandthinfilms.OpticsCommunications,2007.274(1):p.
206212.
Guo,J.,etal.,Hybridsilicagelglasseswithfemtosecondopticalkerreffectbasedon
phthalocyanine.ChemicalPhysicsLetters,2006.431(46):p.332336.
Terasaki,A.,etal.,Femtosecondspectroscopyofvanadylphthalocyaninesinvarious
moleculararrangements.TheJournalofPhysicalChemistry,1992.96(25):p.10534
10542.
Ern,J.,etal.,FemtosecondStudyofExcitonTransportDynamicsin(Phthalocyaninato)
polysiloxane.TheJournalofPhysicalChemistryA,1999.103(14):p.24462450.
Gulbinas,V.,etal.,Excitedstatedynamicsofphthalocyaninefilms.TheJournalof
PhysicalChemistry,1996.100(6):p.22132219.
ElNahass,M.,etal.,Structuralandopticalpropertiesofthermallyevaporatedzinc
phthalocyaninethinfilms.OpticalMaterials,2004.27(3):p.491498.
ElNahass,M.,etal.,Structuralandopticalpropertiesofthermalevaporatedmagnesium
phthalocyanine(MgPc)thinfilms.AppliedSurfaceScience,2008.254(8):p.24582465.
Wojdya,M.,etal.,Stationaryandmodulatedabsorptionspectroscopyofcopper
phthalocyanine(CuPc)layersgrownontransparentsubstrate.JournalofOpticsA:Pure
andAppliedOptics,2005.7:p.463.
Mack,J.andM.J.Stillman,AssignmentoftheOpticalSpectraofMetalPhthalocyanine
Anions.InorganicChemistry,1997.36(3):p.413425.
Wojdyla,M.,etal.,Absorptionandphotoreflectancespectroscopyofzinc
phthalocyanine(ZnPc)thinfilmsgrownbythermalevaporation.MaterialsLetters,2006.
60(2930):p.34413446.
Laurs,H.andG.Heiland,Electricalandopticalpropertiesofphthalocyaninefilms.Thin
SolidFilms,1987.149(2):p.129142.
Gardens,O.G.,Trendsinopticalmaterialsresearch.2007:NovaSciencePubInc.
Tackley,D.R.,G.Dent,andW.E.Smith,Phthalocyanines:structureandvibrations.
PhysicalChemistryChemicalPhysics,2001.3(8):p.14191426.
Valkunas,L.,etal.,Nonlinearannihilationofexcitationsinphotosyntheticsystems.
BiophysicalJournal,1995.69(3):p.11171129.
Sheu,W.S.,K.Lindenberg,andR.Kopelman,Scalingpropertiesofdiffusionlimited
reactions.PhysicalReviewA,1990.42(4):p.2279.
Rammal,R.andG.Toulouse,Randomwalksonfractalstructuresandpercolation
clusters.JournaldePhysiqueLettres,1983.44(1):p.1322.
Li,L.,etal.,Achieving{lambda}/20ResolutionbyOneColorInitiationandDeactivation
ofPolymerization.Science,2009.324(5929):p.910913.
Colley,C.S.,etal.,Probingthereactivityofphotoinitiatorsforfreeradicalpolymerization:
Timeresolvedinfraredspectroscopicstudyofbenzoylradicals.JournaloftheAmerican
ChemicalSociety,2002.124(50):p.1495214958.
Gu,M.,etal.,Effectofsaturableresponsetotwophotonabsorptiononthereadout
signallevelofthreedimensionalbitopticaldatastorageinaphotochromicpolymer.
AppliedPhysicsLetters,2001.79(2):p.148150.
102

106.

107.

108.

109.

110.

Hell,S.W.andJ.Wichmann,BreakingtheDiffractionResolutionLimitbyStimulated
EmissionStimulatedEmissionDepletionFluorescenceMicroscopy.OpticsLetters,1994.
19(11):p.780782.
Gustafsson,M.G.L.,D.A.Agard,andJ.W.Sedat,(IM)M5:3Dwidefieldlightmicroscopy
withbetterthan100nmaxialresolution.JournalofMicroscopyOxford,1999.195:p.
1016.
Hell,S.andE.H.K.Stelzer,FundamentalImprovementofResolutionwitha4piConfocal
FluorescenceMicroscopeUsing2PhotonExcitation.OpticsCommunications,1992.
93(56):p.277282.
Gustafsson,M.G.L.,Nonlinearstructuredilluminationmicroscopy:Widefield
fluorescenceimagingwiththeoreticallyunlimitedresolution.Proceedingsofthe
NationalAcademyofSciencesoftheUnitedStatesofAmerica,2005.102(37):p.13081
13086.
Loewe,C.andC.Weder,SynthesisandPropertiesofPhotoluminescent1,4Bis(cyano
4methoxystyryl)benzenes.Synthesis,2002.2002(9):p.11851190.

103