Nanostructures and Nanomaterials

Guozhong Cao University of Washington, Materials Science and Engineering, Seattle, WA, gzcao@u.washington.edu

Introduction  Contents of the Lectures

        Introduction and surface properties Nanoparticle synthesis Nanowire and nanotube synthesis I Nanowire and nanotube synthesis II Thin films Special nanomaterials Nanolithographic techniques Properties and Applications

 Nanostructures and Nanomaterials

Nanotechnology
Nanotechnology is design, fabrication and application of nanostructures and nanomaterials, and the fundamental understanding of the relationships between physical properties and material dimensions (nanoscience)  Nanostructures of desired size and shape with uniform distribution, as well as chemical composition and crystallinity
 Methods to make them  Means to control them: size, shape, composition, and crystallinity  Mass production at low cost  Ability to integrate with other processes  Ability to integrate to macroscopic systems
Au nanoparticles on TiO2 substrate, Valden, et al., Science 281, 1647 (1998) 3

Why is nanotechnology so important?

 New physical phenomena or properties
 Surface plasmon resonance (surface electronic polarization)
 Theory is 100 years old & practice is several thousand years old

    

Superparamagnetism (surface energy overcomes coercivity) Quantum lasers (size confinement leads to an increased band gap) Enhanced mechanical properties (reduced imperfections) Surprising catalytic properties (relativistic effect) Structural control and manipulation

 Miniaturization
 Semiconductor and electronic industry have been doing this in many decades  There remains a large room for further size reduction before reaching physical limits  Smaller size does offer many new possibilities

 Kinetic and transport properties

 Large surface area for heterogeneous processes: catalysis, photoelectrochemical processes,  Short distance for transport processes
4

What can nanotechnology do?

Phospher screen

Carbon nanotube emitter Murakami, et al., Appl. Phys. Lett. 76, 1776 (2000)

Aluminum film (Anode) Control grid

Carbon nanotube (Cathode)

Biological applications of nanoparticles Parak, et al., Nanotechnology 14, R15 (2003)

What can nanotechnology do (II)?

Nanoparticle plasmon waveguide Maier, et al., Adv. Mater. 13, 1501 (2001)

2D photonic crystal waveguide Zijlstra, et al., J. Vac. Sci. Techn. B17, 2734 (1999) 6

What can nanotechnology do (III)?

Molecular man Zeppenfeld and Eigler, New Scientist 129, 20 (23 Feb, 1991).

Miniature bull Kawata, et al., Nature 412, 697 (2001) 7

Nanostructures and nanomaterials

  1 nm = 10-9 m = 10-6 mm = 10-3 Qm = 10 ~ 5 silicon or 10 hydrogen atoms

105
Macro particle Pollens

Sand

Human hair

104 Size (nm) 1000

Micro particle Bacteria Red blood cells

Yeast cells Pet dander

Macro molecule

Paint pigment

Clay Cooking smoke

100
Virus Colloidal silica

10

Micro molecule

Pyrogen Sugars Quantum dot

Micelles

1
Gas ion salts

0.1 Substance

Nanostructures or nanomaterials
 Nanoparticles (0 D)
 Quantum dots with quantum confinement or nanocrystals with single crystal structure  Dispersed in a matrix (liquid: colloidal dispersion or solid)  Assembled to nanoparticle crystals (e.g., photonic crystals)

 Nanorods, nanowires, nanofibers, and nanotubes (1 D)

    Spontaneous anisotropic growth Vapor-liquidVapor-liquid-solid (VLS) growth with catalyst Electrospinning Template growth

 Thin films (2 D)

 Chemical and physical vapor deposition  Solution deposition: electrochemical and electrophoretic deposition, selfselfassembly, and Langmuir-Blodgett films Langmuir-

 Bulk nanomaterials (3 D)


 Mesoporous materials (surfactant micelles and sol-gel processing) solAlso xerogels, aerogels, zeolites

 Organic-inorganic hybrids Organic Nanograined bulk materials and nanocomposites 9

Nanostructure fabrication and processing

 TopTop-down and bottom-up approaches bottom
  Thermodynamically driven Less imperfection

Bottom up: self-assembly, spontaneous growth self-

Top down: lithography

  MultiMulti-step approach Surface defects

Fabrication techniques
   Spontaneous approaches (self-limiting processes) (selfTemplateTemplate-assisted approaches Kinetically or spatially confined approaches

10

Challenges in Nanotechnology
 Building of novel tools to study at the nanometer level
 How to pick up a single carbon nanotube?

 Integration of nanostructures into macroscopic systems

 A single nanoparticle has no use in practice

 Fundamental limitations

 Doping in nanomaterials and nanostructures (1 ppm)  New physical properties (desired or desired, unknown)  Change of orders of domination

 Against the intrinsic tendency to reduce imperfection  Against statistic distribution (one dopant in one nanoparticle)

 Huge surface energy (fundamentally not stable)

 Fabrication of nanostructures and nanomaterials  Preservation of nanostructures

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Surface energy
 Driving force to convert small to big  Opposing force to make and stay small
 Solid surface has a lot of broken bonds which are highly energetic Ks = (xG/ x A)T,P,ni = 1/2 NbVaIb (x
Nb: number of broken chemical bonds per atom Va : number of atoms per unit surface area Ib : chemical bond strength

12 Shih, et al., Surface Sci., 60, 445 (1976)

Surface to volume ratio

100

Surf ace atom 60 s [%]

40

80 (1.2nm, 76%)

(5nm, 45%) (7nm, 35%)

20 (63 m, ~0%) 0 0.1 1 10 100 104 105

d cluster [nm]

13

Vapor Pressure and Solubility

 The Kelvin Equation
ln (P/Po) = 2 Ks ; r k T P: vapor pressure of a curved surface Po: vapor pressure of a flat surface r: radius of a curved surface
 

Positive for a convex surface Negative for a concave surface

k: Boltzmann constant T: temperature

 

Convex surface has a higher vapor pressure or solubility Concave surface has a lower vapor pressure or solubility

14

Vapor pressure and solubility of curved surface

La Mer & Gruen, Trans. Faraday Soc. 48, 410 (1952).]

The Chemistry of Silica by R.K. Iler, 1979. 15

Ways to reduce surface energy

Inward shift Lateral shift

G.Z. Cao, Nanostructures and Nanomaterials, Imperial College Press, London, UK, 2004

16

Sintering and Ostwald ripening

G.Z. Cao, Nanostructures and Nanomaterials, Imperial College Press, London, UK, 2004

17

Electrostatic stabilization

Double layer structure

Various potentials 18

Electrostatic stabilization

max

Electrical double layer thickness -1 (10-6 cm) 10

Electrical double layer

30 kT
max

3.33 1 d 0.1

r
charged particle

S0

r
charged particle

20 kT

Liquid A) No overlap = no repulsion Ite rac 10 kT toi n ene rgy 0

max

0.5

1.0

1.5 d 2d S0

Separation distance S0 (10-6 cm)

r
-10 kT S0 charged particle

S0

r
charged particle

-20 kT

B) Overlap = repulsion

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Steric stabilization
G Low coverage High coverage

Polymer in a poor solvent

L H A G Low coverage High coverage L B 2L H

Polymer in a good solvent

L H A L B 2L H

20