SELF-ASSEMBLY

NANOMATERIALS

Contents
1.

Introduction

2.
3. 4. 5. 6. 7. 8. 9.

Self-assembly
Self-assembled monolayer (SAM) Self-assembly by chemisorption Electrostatic self-assembly Microcontact printing of SAM

Microdisplacement printing of SAM

Conclusions References

Introduction
Nanomaterials and its fabrication

Dimension

Zero-Dimensional

One-Dimensional
Two-Dimensional

Nucleation

Homogeneous Heterogeneous

Introduction contd..
Nanostructure fabrication techniques

Top-down approach
Bottom-up approach

Film growth methods

Vapour-phase
Liquid-phase

Filament growth modes

Island growth
Layer growth Island-Layer growth

Self-assembly

Definition: Self-Assembly (SA) is the spontaneous

organization of molecules or objects into well

defined aggregates via non covalent interactions (or forces)

Forces:

Chemisorption Electrostatic force Hydrophobicity and hydrophilicity Capillary force

Features of SA nanostructures

Self-assembled structures are capable of self-correcting and self-healing

Complex structures with fewer defects Self-assembled structures are robust Fabrication in inaccessible spaces Repetitive or reconfigurable structures

Simple, parallel, low-cost processing

Self-assembled monolayer (SAM)

SA surfactant molecule
1.

Headgroup Surface group Alkyl or derivatized alkyl group

2.

3.

Self-assembled surfactant molecule

SAM contd..

Arrangement of SA molecules

Self-assembly by chemisorption
Self-assembly methods

Organosilicon

or

alkylsilane

Organosilicon group

derivatives on Si

Alkanethiols on gold, silver Dialkyl sulfides on gold Alcohols and amines on

Alkanethiols group

platinum

Carboxylic acids on aluminium oxide and silver silane

Silane (Silicon hydride)

Self-assembled monolayers of alkylsilane

SAM on Si substrate Surfactant:

R - Si - X3
Alkylsilane

Alkyltrichlorosilane (C3H5Cl3Si)

103M concentration

Organic solvent:

Mixture of 80/20 Isopar-G/CCl4

SAM on Si substrate

Reaction time: 23 mins Washed using methanol

SAM of alkylsilane contd..

Self-assembled multilayer structure

SA of alkanethiol monolayer on gold

Alkanethiol solution (20M 0.1mM)

Gold substrate 0.50.5cm

Immersion time 24h Ethanol to wash The adsorption process

Alkanethiol

Sulfur adsorption (10s)

Orientation ordering (10h)

S-H bond with the gold surface

SAM on gold contd..

STM topograph of an octanethiol monolayer on Au

Alkanethiol monolayer on gold

Coreshell structures
Definition Types:

Novel metaloxide (Gold-Silica)

Novel metalpolymer (Silver-polystyrene)

Oxidepolymer (Silica-polypyrrole)

Gold-silica core-shell structure

Using alkylsilane (APS) SAM (3-aminopropyl trimethoxysilane)

Gold is vitreophobic

(NH2-(CH2)3-Si-(OCH3)3 )

Colloidal

solution

of

gold

(APS)

(15nm) 500ml; pH- 2 to 3

Silica sol (Na2SiO3), pH- 10 to11

Vigorous stirring for 24 hours

Silane (Silicon hydride)

Fig. 1: (a) Formation of monosized gold particles (b) Introducing SAM on gold (c) Deposition of silica shell.
Fig. 2: TEM Images of silica-coated gold particles. shell thicknesses are (a, top left) 10 nm, (b, top right) 23 nm, (c, bottom left) 58nm, and (4 bottom right) 83nm.

Electrostatic self-assembly

Principle:

Two

oppositely

charged

particles, suspended in a fluid, will attract

Gold discs
Alkanethiol 1 mM Silicon substrate PDMS stamp (Poly-dimethylsiloxane) Inks

Photoresist HS(CH2)11NH3+Cl- + HS(CH2)15COOH

Step 1: Fabrication of patterned surfaces

Step 2: Fabrication of charged gold microstructures

Step 3: Assembly of particles

Fig.: SEMs of patterns of disks (or stars) after electrostatic self-assembly in ethanol:

Microcontact printing of SAM

Photolithographic techniques Elastomeric stamp Polydimethylsiloxane (PDMS) Ink Alkanethiol (0.11.0 mM) Gold films 50 to 2000 A thick Silicon - Substrate Titanium Adhesion provider b/w Au and Si

Fig.: Schematic of the procedure for microcontact printing of alkanethiol SAMs on Au coated Si

Microdisplacement printing of SAM

Pre-assembled monolayer1- adamantanethiolate (AD)

PDMS stamp Gold substrate

Schematic depicting microdisplacement printing

Applications

Manufacturing of ICs, transistors, chips and other electronic circuit components.

Semiconducting oxide nanorods, and nanoribbons. Current research in nanoscale semiconducting

nanowires for devices applications span from fieldeffect transistors, bio/chemical sensors, ultra-violet

lasers, light emitting diodes, and photo-detectors.

Nanoscale

self-assembly

of

thin-film

molecular

materials for electro-optic switching.

Applications contd..

Improved self-assembly of enhance solar cells

nanomaterials may

Self-assembly in magnetic nanowire arrays and

microarrays production.

Applications contd..
Fabrication of Arrayed LEDs by Self-Assembly

Applications contd..
Arrayed polymer micro lenses used in imaging

Applications contd..

Organic thin film transistors (OTFT) for flexible electronic devices

Rollable OTFT based display

Applications contd..
Lipid molecules and cell membranes

Applications contd..

Tobacco mosaic virus

Conclusions

Self-assembled structures are capable of self-correcting

and self-healing resulting in fewer defect.

Two

strategies

have

received

significant

research and

attention

Self-Assembled

Monolayers

(SAMs)

Electrostatic Self-Assembly (or layer- by-layer assembly) due to the easiness in processing.

Self-assembly has big role to play in future in synthesis of many perfect and cost-effective nanostructures

References

A book titled Nanostructures and nanomaterials by Guozhong Cao, 2004 edition. Technical papers and presentations:

Microfabrication through electrostatic self-assembly by Joe Tien, Andreas Terfort, and George M. Whitesides, 1997.

Microcontact

printing

of

self-assembled

monolayers:

applications

in

microfabrication by James L Wilbur, Amit Kumar, Hans A Biebuyck, Enoch Kim

and George M Whitesidesy, 1996.

Microdisplacement printing by A. A. Dameron, J. R. Hampton, R. K. Smith, T. J. Mullen, S. D. Gillmor, and P. S. Weiss, 2005.

Self-assembled monolayers on gold substrate made from functionalized thiols and dithiols by Michaela Georgeta Badin, 2007.

Molecular self-assembly by Sigma-Aldrich, Volume 1 and 2, 2006.

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