One Dimensional Assemblies of Nanoparticles

Pratheesh V. Nair

Photosciences & Photonics Group Chemical Sciences and Technology Division NIIST (CSIR) Trivandrum

 Introduction to nanoscale assemblies

One dimensional assemblies; preparation methods

Properties and applications Future perspectives Conclusion

What is nano ?
The prefix nano- comes from the Greek word for dwarf.
In science, nano means a measure of 10-9 units.

Nanomaterials Definition:- Particles of any matter having one of its dimensions in the range 1-100 nm

Capability to manipulate, control, assemble, produce and manufacture things at atomic precision

Nanoscience and nanotechnology pertain to the synthesis, characterization,

exploration, integration and utilization of materials, which are characterized by at least one dimension in the nanometer (1 nm = 10-9 m) range

Importance Exhibit characteristic physical and chemical properties different from that of bulk Properties can be tailored by varying their size and shape

For any application their integration into higher order assemblies is essential

Nanoscale Building Blocks

Metal Nanostructures (Au, Ag, Cu, Pt, Pd )

Semiconductor Nanostructures (CdS, CdSe, CdTe InP, GaN)

Carbon Nanostructures (CNTs, Fullerenes, Graphene )

Au Nanorods

Quantum Dots

Carbon nanotubes

20 nm

Ag Nanoprisms

Quantum Rods

Fullerene clusters

20 nm

Where are we now ?

Current research on nanoparticles can be classified into two main trends

Manipulation and exploration of single NPs in devices thus reaching the limit of miniaturization possible for electronic circuits. Application of NPs/polymer composites as macroscale thin films producing a new generation of currently using devices.
Bio-imaging
Quantum dot Solar cells Paper batteries

J. Am. Chem. Soc. 2006, 128, 2115.

J. Am. Chem. Soc. 2006,128, 1385 PNAS, 2007, 104, 13574. Nano LEDs

Angew. Chem. Int. Ed. 2006, 45, 5796

Why nanoscale assemblies ?

they provide direct bridges between nanometer scale objects and macroscale world can play critical roles in the improvement of efficiencies of various devices based on nanoparticles and their composites can help in the understanding of various biological processes and quantum mechanical concepts

How can we integrate nanomaterials into higher order structures having

well defined size, shape and function ?
Top down Lithography Stamping (microcontact printing) Bottom up Self-assembly Template assisted

Nanoparticle assemblies can be classified into three categories ;

a) One dimensional (1 D) b) Two dimensional ( 2 D) c) Three dimensional (3 D)

Techniques for 2D and 3D NP assemblies; a) Solvent Evaporation b) Langmuir Blodgett Transfer c) Layer by layer assembly

Solvent Evaporation

The relatively weak attractions between nanocrystals, which are efficiently screened in
solution, become manifest as the solvent evaporates, initiating assembly of intricate, slowly evolving structures.

TEM images of nanoparticle aggregates after solvent evaporation

Dissipative dewetting followed by self-assembly of NPs

J. Colloid Interface Sci. 2006, 301, 703.

Langmuir Blodgett Transfer

Generally, a LangmuirBlodgett film contains one or more monolayers of an organic

material, deposited from the surface of a liquid onto a solid by immersing (or emersing) the solid substrate into (or from) the liquid.

Well ordered ultra thin films Direct detection of defects/cracks on surface

layer stability and contamination..!

Layer by layer assembly Layer-by-layer (LBL) assembly is a simple and versatile method for material design with nanometer scale control over internal architecture
Scheme of the LBL film-deposition Steps 1 and 3 represent the adsorption of polyanion and polycation, steps 2 and 4 are washing steps.

Device fabrication Functional Coatings

Biomedical Applications

1-D assemblies of NPs: Preparation methods

Preparation methods

Linear template method

Self assembly method

Polyelectrolytes

Magnetic dipole moment

Electric dipole moment Oriented attachment Hydrogen Bonding

biomolecules

Inorganic NWs and tubes

Other templates

Linear template method

Directional organization ; critical step for the fabrication of 1 D assemblies
Soft templates Organic Polyelectrolytes and biomolecules

Hard templates Inorganic nanotubes and nanowires

Polyelectrolytes are polymers whose repeating units bear an electrolyte group ; Dissociates in aqueous solutions, making the polymers charged. Polystyrene sulfonate (PSS)

How they act ?

Act as a scaffold for the adsorption of metal ions with opposite charges Ion adsorbed polyelectrolyte templates can transform to 1 D NP assemblies

Mineralization of Single Flexible Polyelectrolyte Molecules

Minko et al, J. Am. Chem.Soc. 2002, 124, 10192.

Poly(2-vinylpyridine) (P2VP) was deposited on the surface of Si-wafer or mica in

different conformations from an elongated wormlike coil to compact globule.

Poly(2-vinylpyridine) (P2VP)

AFM images of various conformations of P2VP molecules on a solid substrate

conformational transitions from stretched wormlike coil to necklace-like globule, and to compact globule the fraction of charged monomers decreases with an increase of pH and ionic strength.

Mineralization of PE
Electrostatic adsorption of PdCl42onto cationic P2VP chains

Reduction

with

dimethylamine

borane to get Pd NP assemblies

AFM images of Pd NP decorated PE chains ( single Pd nanoparticles are visible )

Cross-section profiles of Pd-nanowires

Biomolecules as templates
A perfect choice for 1 D assembly of nanoparticles !!!!!
The versatility of experimental methods for the manipulation of their structure Excellent experimental foundation for such studies developed in the life-science field

Biological templates, such as DNA, protein cages, viroid capsules, bacterial rhapidosomes, the deposition, multicellular assembly, superstructures, and patterning biolipid of Cylinders, linear fibrous and biomacromolecules like fibrin, dextran and collagen have been utilized to direct inorganic nanoparticles microstructures.

DNA: A Programmable Nanoscale Assembly Material

Attractive Nanomaterial Properties of DNA:
Strong electrostatic and coordination interactions with metal nanoparticles Synthetic versatility: vary length, sequence, backbone, branched Easily modified for conjugation to molecules, nanoparticles
DNA-linked nanoparticles

100 nm

Chem. Mater. 2005, 17, 1628. DNA-wrapped CNTs

Inorg. Chem. 2000, 39, 2258.

Science, 2003, 302 , 1545.

Linear Assemblies of Nanoparticles Electrostatically Organized on DNA Scaffolds

Warner et al, Nat. Mater. 2003, 2, 272-277.

Electrostatic assembly of cationic NPs onto the anionic backbone of DNA Wide range of structures including closely spaced linear arrays, ribbons or bundles and branched assemblies.

linear arrays

branched assemblies

ribbons or bundles

Linear arrays

Ribbons or bundles

Branched assemblies

Monitoring the assembly process in solution by UV-Vis spectroscopy

Precipitation of the hybrid system as a function of time

Au Nanocrystal Growth on Nanotubes Controlled by Conformations and Charges of Sequenced Peptide Templates
Matsui et al, J. Am. Chem.Soc. 2003, 125, 5873. Self-assembly of bis(N-R-amido-glycylglycine)-1,7-heptane dicarboxylate molecules into nanowires. Immobilization of a histidine-rich peptide on the nanowires at the binding sites.

Addition of Au salt into nanowire solution and reduction using hydrazine hydrate

bis(N-R-amido-glycylglycine)-1,7heptane dicarboxylate

A-H-H-A-H-H-A-A-D

Scheme of the Au nanowire fabrication

The Influence of pH upon Au Nanocrystal Growth

78 %

43 % pH - 8
Higher packing density at higher pH

pH - 12

packing density increases with incubation time

Inorganic NWs and Nanotubes

Known as hard templates most common templates are carbon nanotubes
Greater hardness and toughness ; preservation of structure and shape intact

Preparation methods can be classified into three

1, Direct chemical deposition 2, Sol-gel decoration 3, Specific adsorption
Chem. Eur. J., 2003, 9, 1898. Nano Lett. 2004, 4, 225. Science 2004, 304, 1787. Adv. Mater., 2004, 16, 929.

Nature. 1993, 361, 333. Adv. Mater., 2000, 19, 1430. Chem. Mater., 2001, 13, 2864. Nano Lett. 2003, 3, 723.

J. Phys. Chem. C. 2003, 107, 2453.

Nano Lett. 2002, 2, 1253.

Aligning Au Nanorods by Using Carbon Nanotubes as Templates

Liz-Marzan et al, Angew. Chem. Int. Ed. 2005, 44, 4375.

uniform electrostatic assembly of Au nanorods on MWNTs

rods form strings with end-to-end contacts uniaxial plasmon coupling

TEM images of Au assembled on MWNTs (average diameter 30 nm)

Surface plasmon coupling in Au nanorods

Carbon Nanotubes as Templates for One Dimensional Nanoparticle Assemblies

Liz-Marzan et al, J. Mater. Chem. 2006, 16, 22.

Simple and reproducible procedure for the assembly of nanoparticles on carbon nanotubes in aqueous solution

SEM image of one monolayer of Au@SiO2 nanoparticles assembled onto a carbon nanotube;

TEM micrographs of thick (a) and thin (1) Polymer wrapping using poly(sodium 4-styrenesulfonate) (PSS). (bc) MWNTs (50 and 15 nm diameter), coated with 1 (ab) and 2 (2) Self-assembly of poly-(diallyldimethylammonium chloride) of (PDDA). (c) monolayers Au@SiO2 NPs.

(3) Nanoparticle deposition.

Templated Gold Nanowire Self-Assembly on Carbon Substrates

Template ; a corrugated thin film of amorphous carbon with topographical features of nanometer dimensions.

PTFE lines on a glass substrate

Vapour deposition of carbon film

Carbon replica

Au NP solution

Evaporation Self-assembly of Au NPs in rows

AFM image of PTFE lines on glass substrate

TEM image of self-assembled lines of Au NPs on carbon replica

Au nanowire obtained after heat treatment

Brust. M and co workers, Adv. Mater. 2001, 13,1800.

Template- Free, Self - Assembly method

Demerits of template assisted synthesis 1. Templates may affect the properties of nanoparticle assemblies.

2. Removal of templates is not easy.

3. Morphological or structural alterations to the NP chains. Magnetic Dipole Moments The magnetic NPs can self-assemble into one-dimensional chains on substrates and in colloid dispersions through magnetic dipolar

interaction without the help of an applied magnetic field.

Chain formation and anisotropy of magnetic NPs have been well-known in nature
Magnetotactic bacterium a biological compass

TEM image of a magnetotactic bacterium, Desulfovibrio magneticus strain RS-1, showing a chain of bullet-shaped magnetosomes aligned along the Earth's magnetic field.

Tokyo University of Agriculture and Technology

Magneto Spirillum (MS-1)

Magnetosomes in eukaryotic algae

NP chains in frontal tissues of Chinook salmon

Self-Assembly of iron oxide nanoparticles through magnetic dipole interactions

Zhang et al, J. Phys. Chem. C. 2008, 112, 15151.

Magnetic dipole interactions in weakly ferromagnetic nanoparticles

TEM images of aligned nanoparticles

Under an applied magnetic field, the nanostructures can be oriented aligning with the external magnetic field.

Electric Dipole Moments

prevalent in semiconductor nanoparticles due to either the presence of an anisotropic crystal lattice or surface defects.
Strong electrostatic or steric repulsion from stabilizers overcompensates electric-dipole attractions between NPs.

DLVO Theory

VT = VA + VR
VA = -A/(12 D2) - attractive forces VR = 2 a 2 exp(-D) - repulsive forces
Attractive forces van der Waals interactions and dipoledipole interactions Repulsive forces electrostatic interactions

How to overcome the repulsion..?

Partial removal of the stabilizer !!!

Organization of CdTe NPs into nanowires upon partial removal of the of organic stabilizer

Kotov and co workers, Science , 2002, 297, 237.

CdTe quantum dot to nanowire transformation in phosphate buffer solution

Rogach and co workers, J. Phys. Chem. C. 2007, 111, 18927.

Hydrazine induced one dimensional organization of CdTe QDs

CdTe QDS

CdTe nanowire

Hydrazine is a Bronsted base and can gently react to remove the capping ligands from the nanocrystal surface. Hydrazine is a reducing agent, preventing oxidation of QD surface and repairing any

oxidized tellurium surface sites.

Hydrazine Ligand removal

Pratheesh V. Nair and K. George Thomas J. Phys. Chem. Lett. 2010

Oriented Aggregation
Oriented aggregation is a special case of aggregation that provides an important route by which nanocrystals grow and unique, often symmetry-defying, crystal morphologies are produced. Oriented attachment may occur by
collisions of aligned nanocrystals in suspension or rotation of misaligned NPs in contact toward low-energy interface configurations

Oriented attachment
misaligned NPs aligned NPs

1D growth Nanowires

Formation of Ag nanowires from Ag NPs through oriented attachment Liz-Marzan et al, J. Mater. Chem. 2004, 14, 607.

Evidence of an aggregative mechanism during the formation of silver nanowires in DMF

Formation of Ag nanowires by solvent reduction in DMF, in the presence of poly(vinylpyrrolidone) (PVP) at high temperature

HRTEM images showing the various steps during the formation of Ag nanowires from individual Ag nanoparticles

Self-Assembly of ZnO: From Nanodots to Nanorods

Weller et al, Angew. Chem. Int. Ed. 2002, 41, 1188.

Formation of high-quality single crystalline ZnO nanorods from spherical ZnO nanoparticles through oriented attachment.

individual nanoparticles

aligned nanoparticles

nanorods

lattice planes go straight through the contact areas particles are epitaxially fused together

bottlenecks between the adjacent particles are still visible

Hydrogen Bonding
A hydrogen bond is the attractive force between the hydrogen
attached to an electronegative atom of one molecule and an electronegative atom of a different molecule.
Hydrogen-Bonding-Assisted Self-Assembly of polymers

J. Am. Chem. Soc. 2009, 131, 13594

Langmuir, 2008, 24, 7727.

Uniaxial Plasmon Coupling through Longitudinal Self-Assembly of Gold Nanorods

George Thomas and co workers, J. Phys. Chem. B. 2004, 108, 13066.

Absorption spectra of gold nanorods recorded immediately after the addition of MPA

Properties and applications

1D NP assemblies exhibit many collective properties, which are evidently different from single NPs.

Drastic effects on the optical response from surface plasmon absorption is found when metallic NPs form rods, chains or sheets

Time-dependent optical studies to elucidate the mechanism of chain self-assembly

Decrease in intensity of surface plasmon band at 520 nm and formation of a shoulder at higher wavelength

Adv. Mater. 2005, 17, 2553.

One-Dimensional Energy Transfer in CdTe Nanoparticle Chains

Nanochains of CdTe QDs formed from individual particles through dipole dipole interaction

Red shift of 36 nm

Presence of Frster resonance energy transfer (FRET) between QDs in the chain.

J. Phys. Chem. B. 2004, 108, 6927.

Gas sensors

Hydrogen Sensors and Switches from Electrodeposited Palladium nanowire Arrays

Absorption of H2 led to the expansion of the crystalline lattice of Pd. Gap between Pd NPs in an array decreased, leading to higher electron transfer. On venting the H2, a reversible affect was observed.

Science, 2001, 293, 2227

Sensors for biomolecules

Selective Detection of Cysteine and Glutathione Using Gold Nanorods

George Thomas and co workers, J. Am. Chem. Soc. 2005, 127, 6516.

1-D Assembly of Peptide-Functionalized Au NPs: An Approach Toward Mercury Ion Sensing

Detection limit 4 ppm

Mandal, T. K. and co workers, J. Phys. Chem. C. 2007, 111, 1248.

Future Perspectives
Development of preparation methods for large-scale production as well as
precise positioning of 1D NP arrays. Better understanding of the formation mechanism of template-free NP chains. Control of interparticle distances in NP chains, so that distance-dependent

photonic and electronic transfer along the NP chains could be realized.

Production of NP chains consisting of multiple components, for example, 1D hybrid chains of metal and semiconductor NPs.

Conclusions
Controlled organisation of nanoparticles is an essential step for the fabrication of nanomaterial based devices.

One dimensional organisation of NPs can be achieved either by template

assisted synthesis or by self assembly method. The collective properties of 1D NP assemblies are evidently different from single NPs. 1 D NP assemblies can be used as sensors for gases, bimolecules and toxic metal ions. There are plenty of unknown phenomena awaiting exploration and there are also many problems requiring resolution.

Thank You