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Introduction to Nanomaterials

One Dimensional Nanostructures

Approaches for Synthesis of

1D Nanostructures
Spontaneous Growth:
1. Evaporation (or dissolution) condensation
2. Vapor (or solution) – liquid-solid growth
3. Stress-induced recrystallization

Template Based Synthesis:

1. Electroplating or electrophoretic deposition
2. Colloidal dispersion, melt or solution filling
3. Conversion with chemical reaction

Electrospinning
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Spontaneous Growth
• A growth driven by reduction of Gibbs free
energy - by recrystallization or a decrease
in supersaturation

• Growth along a certain orientation faster

than other direction – anisotropic growth

• For nanowire, growth occurs only along

one direction, but no growth along other
directions
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Evaporation (Dissolution) –
Condensation Growth

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Step 2 as Rate Limiting Process

• The growth rate is determined by condensation rate, J

(atoms/cm2sec).
P0
J
2mkT
α - the accommodation coefficient,
σ= (P – Po)/Po ~ supersaturation of the growth species in the vapor
Po - equilibrium vapor pressure at temperature T,
m - atomic weight of the growth species,
k - Boltzmann constant
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Step 2 vs. Step 4 as Rate

Limiting Process
• With increasing concentration change from adsorption
limited to growth limited process

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Adsorption or Escape of
Growth Species
Impinging of growth species on surface = f(residence time
and diffusion distance)
- vibrational frequency of adatom
1 E  (typically 1012 /sec
Residence time  s  exp des 
  kT  Edes – desorption energy to escape
back

a0- size of growth species

1   Es 
Surface Diffusion Ds  2 a0 exp kT  Es – activation energy for surface
Coefficient
  diffusion

Adsorption or Escape of
Growth Species

 E  Es 
Mean Diffusion X  2 Ds s  a0 exp des 
Distance  kT 

Distance between two growth sites - d

In cases where X > d,  ~ 1

When X < d,  ~ 0

 = f (Edes, Es and density of growth sites)

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Step Growth or KSV (Kossel,

Stranski, Volmer) Theory
4. Kink site (4 CB)
5. ledge-kink site (3 CB)

7. adatom (1 CB, unstable)

8. ledge site (2 CB)

BCF (Burton-Cabrera-Frank)Theory
of Growth
Presence of screw dislocation ensures continuous
growth and enhances the growth rate

Can Synthesize nanowires and nanorods 10

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Differential Growth at Different facets

PBC (Periodic Bond Chain)Theory
(100), F-face, unstable

(110), S-face

(111), K-face

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Dependence of Grown Structure on

Supersaturation

 A low supersaturation is required for anisotropic

growth.

 A medium supersaturation supports bulk crystal

growth

 A high supersaturation results in secondary or

homogeneous nucleation leading to formation of
polycrystalline or powder

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Growth of Single Crystal Nanobelts

of Semiconducting or Metal Oxides
• Evaporating the metal oxides at high
temperatures under vacuum

• Condensing on an alumina substrate, placed

inside the same alumina tube furnace, at
relatively low temperature.

• Nanowires such as ZnO, SnO2, In2O3, CdO can

be made by this method.

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ZnO Nanobelts by Evaporation-Condensation

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CuO Nanowires by Evaporation-Condensation

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Dissolution and Condensation Growth

• The growth species first dissolve into a solvent
or a solution

• Generally the growth species is formed by some

chemical reaction of precursor (reduction) in
solution

• The growth species then diffuses through

solution

• Deposits as nanorods or nanowires

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Dissolution and Condensation Growth:

Se Nanowires
 Aqueous Solution of selenious acid and hydrazine –
results in ~ 300nm amorphous selenium particles in
solution

 Cooled to room temperature – nanocrystalline trigonal

selenium structures are precipitates

 Solution aged at room temperature in dark – amorphous

selenium dissolves, whereas crystallites grew

 Se crystals – found to grow predominantly along [001]

direction – nanowires synthesized

 Structure is free of defects – e.g. kinks, dislocation –

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characteristics of this method

Growth at Different Substrates

• Nanowires can grow on alien crystal nanoparticles –
seed for heteroepitaxial growth – Ag nanowires on Pt
surface

Precursor - AgNO3
Reduction agent: ethylene glycol
Surfactant: polyvinyl pyrrolidone
(PVP)

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Disadvantages of Evaporation –
Condensation Deposition
 Nanowire grown by EC most likely have faceted
morphology

 Generally short in length with relatively small

aspect ratios, particular when grown in liquid
medium.

 However, anisotropic growth induced by axial

imperfections, such as screw dislocation,
microtwins and stacking faults, or by impurity
poisoning, can result in the growth of nanowires
with large aspect ratios. 19

Vapor (or solution)-Liquid-solid (VLS)

Growth
The surface of liquid has a large accommodation coefficient, and is
therefore a preferred site for deposition.

VLS (Vapour Liquid Solid) method

Modification of VLS
CVD (Chemical Vapour Deposition)
LCG (Laser Ablation catalytic Growth)

FLS (Fluid Liquid Solid) mechanism

SLS (Solid Liquid Solid) mechanism
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Vapour Liquid Solid Method

Basics about phase diagrams

Alloys have phase diagrams

Lever rule:

gs  gtot
a  s
l

T g  gl
liquid
liquid and solid
liquidus al + a s = 1

solidus

mixed
crystal

gl gtot gs
A B
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Vapour Liquid Solid Method

Eutectic:
- coexistence of 3 phases
lowest temperature where system is still totally liquid
minimum of liquidus curve -
solid in solid + liquid phase consists of only one material

liquidus

T
liquid

Eutectic A + liquid B+ liquid

Mixed crystal

A
solidus B 22

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Vapour Liquid Solid Method

• Mix of semiconductor and metal at eutectic
• Melting point of Semiconductor with metal lower - growth of
one pure material
T
 metal as catalyst l

A+l B+ l

Mixed crystal

Growth procedure: A B

reactant reactant vapour reactant vapour reactant vapour

vapour

metal metal +Sc metal +Sc metal +Sc Sc

Liquid Nanowire Nanowire

catalytic supersaturating nucleation growth
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nanocluster

Vapour Liquid Solid method

Synthesis of multicomponent semiconductor, like
binary III-V materials (GaAs, GaP, InAs, InP)
ternary III-V materials (GaAs/P, InAs/P)
binary II-VI materials ( ZnS, ZnSe, CdS, CdSe)
binary Si Ge alloys

Pseudobinary phase diagram

T
liquid
E.g. Au - GaAs pseudobinary
Au + GaAs+ liquid
phase diagram liquid
Au + GaAs

Au GaAs 24

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Vapour Liquid Solid Method

In general, the nanowires grown by VLS
- cylindrical morphology
- without facets on the side surface
- uniform diameter

Growth rate is much faster

(60 times for Si nanowire using a liquid Pt-Si alloy than directly
on the silicon substrate at 900C)
- liquid acts as a sink for the growth species
- act as a catalyst for the heterogeneous nucleation

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VLS – Criterion for Choice of

Catalyst

• The nanowire component elements should be

soluble in the catalyst in liquid phase

• Both should not form solid compounds more stable

than the desired nanowire phase; i.e., the ideal metal
catalyst should be physically active but chemically
stable.

• Noble metals (e.g. Au) in general should act as good

catalyst

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VLS: Other Considerations for Catalyst

 The equilibrium vapour pressure of the

catalyst must be small

 Catalyst must be chemically inert

 Interfacial energy – small wetting angle gives

large diameter for nanostructures

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VLS – Diameter of Nanostructures

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VLS – Diameter of Nanostructures

Critical Diameter- liquid catalyst clusters are stable in equilibrium

= surface free energy

 = molar Volume
4
dc  R = gas constant
 C  T = absolute temperature
RTln  C = concentration of semiconductor component in
 C  liquid alloy
C  equilibrium concentration

Problem:
in fluid at according temperature  critical diameter
d = 0.2 mm
Goal:
finding methods to get smaller metal clusters to start 29
NW growth

Chemical Vapour Deposition

Fine catalyst particles can be formed by
- Thin film deposition – which cracks to small island upon
heating
- Colloidal suspension of metallic nanocrystals – dried on
substrate
- Evaporated growth species or precursor gas introduced
to reaction chamber
- Supersaturation in Catalyst particle
- Precipitation as nanowire or naontube

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GaN nanowires grown in CVD reactor

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Laser Ablation Catalytic Growth

Nanometer sized cluster with laser ablation
SC SC
h SC M

M, SC
SC
M SC SC SC
Laser Vapour Supersaturation Transport from
ablation condenses in until start of wire growth zone
cluster growth

5 μm
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Laser Ablation Catalytic Growth

with Si:
- uniform Diameter down to 3 nm.
- Amorphous coating, consisting of SiO2
- Nanocluster at the end of the wire,
consisting of metal and Si (e.g. FeSi2)
- [111] growth direction

Nanowire diameter depends on nanocluster catalyst

diameter:
Nanocluster nm 4.9 +/- 1.0 9.7 +/- 1.5 19.8 +/-2.0 30.3 +/- 3.0
Nanowire nm 6.4 +/- 1.2 12.3 +/- 2.5 20.0 +/- 2.3 31.1 +/- 2.7
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Fluid/Solution Liquid Solid Mechanism

Growth of Si nanowires
- alkanethiol coated Au nanocrystals (d = 6.7 +/- 2.6 nm) in Si prcursor
solution
- diphenysilane (C12H12Si) decomposes to Si atoms

Si Precursor Si Si
Solution
Si
Si Si
Au Au Au Si

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Solid Liquid Solid Mechanism

Amorphous Si nanowires with SLS Si nanowires
Si - Ni alloy
Ni

Si substrate Si Si Si Si Si Si Si Si

Heat Heat Heat

Ni coated Si Heat  diffusion of Supersaturating Growth of Si
substrate of Ni nanowires
Si into Ni

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Stress Induced Recrystallization

 Application of pressure on solids at elevated
temperature
 Growth of Whiskers or nanowires of diameter
50 nm or less
 Growth rate increases with pressure
 Whiskers are based on dislocations – and
growth is confined at surface between metallic
film and nanowires...no growth in other
directions
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Template Based Synthesis

Features:

• This is widely used method and applicable to various

material systems

• Used in fabrication of nanorods, nanowires, and

nanotubes of polymers, metals, semiconductors, and
oxides.

• Some porous membrane with nano-size channels

(pores) are used as templates for growing nanowires

• Pore size ranging from 10 nm to 100 mm can be

achieved.
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Template Based Synthesis

Electrochemical Deposition
– Negative template
– Positive template

• This method can be understood as a special

electrolysis resulting in the deposition of solid material
on an electrode

• Only applicable to electrically conductive materials:

metals, alloys, semiconductors, and electrical
conductive polymers.

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Electrochemical Deposition
Negative Template

• Prefabricated cylindrical nanopores in a solid material -

as templates

• Method is a general and versatile method to fill nanopores.

• Electrodeposition - Requires a metal film on one side of the

freestanding membrane to serve as a working electrode on
which electrodeposition takes place

• Free-standing nanowires – by dissolving the template

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Electrochemical Deposition

• The diameter of the nanowires is determined by the

geometrical constraint of the pores

• Fabrication of suitable templates is clearly a critical

first step
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Electrochemical Deposition:
Free Standing Nanowires

•To have freely standing nanowires we have to remove the

template hosts after forming the nanowires in the templates by
dissolving away the template materials in a suitable solvent.
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Electrochemical Deposition

A porous Template Nanowire array

Picture: “Fabrication of Polypyrrole Nanowire and Nanotube Arrays,” Fa-Liang Cheng*, Ming-Liang Zhang and Hong Wang,
http://www.mdpi.net/sensors/papers/s5040245.pdf 41

Electrochemical Deposition

75 nm

Nanowires grown in
a 80nm template
membrane after
dissolution of the
210nm
membrane.

100nm
Picture: “Fabrication of Polypyrrole Nanowire and Nanotube Arrays,” Fa-Liang
Cheng*, Ming-Liang Zhang and Hong Wang,
http://www.mdpi.net/sensors/papers/s5040245.pdf 42

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Electrochemical Deposition
Advantages

• The ability to create highly conductive nanowires.

Because electrodeposition relies on electron transfer, which
is the fastest along the highest conductive path.

• electrodeposited nanowires tend to be dense, continuous,

and highly crystalline in contrast to other deposition
methods.

• Ability to control the aspect ratio of the metal nanowires by

monitoring the total amount of passed charge.

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Electrochemical Deposition: Stages

Stage I: corresponds to the electrodeposition of

metal into the pores until they are filled up to
the top surface of the membrane (stage I)

Stage II: the pores are filled up with deposited

metal, metal grow out of the pores and forms
hemispherical caps on the membrane surface

Stage III: When the hemispherical caps

coalescence into a continuous film

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Electrochemical Deposition

stage I
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Picture: Template Synthesis of Nanowires in Porous Polycarbonate Membranes: Electrochemistryand Morphology, http://www.phys.ens.fr/~bachtold/publication/wire-JPCB.pdf

Electrochemical Deposition

stage II

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Picture: Template Synthesis of Nanowires in Porous Polycarbonate Membranes: Electrochemistryand Morphology, http://www.phys.ens.fr/~bachtold/publication/wire-JPCB.pdf

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Electrochemical Deposition

stage III

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Picture: Template Synthesis of Nanowires in Porous Polycarbonate Membranes: Electrochemistryand Morphology, http://www.phys.ens.fr/~bachtold/publication/wire-JPCB.pdf

Electrochemical Deposition

Positive Template Method

• Use wire-like nanostructures, such as DNA and carbon
nanotubes as templates.

• Nanowires are formed on the outer surface of the templates

• Diameter of the nanowires is not restricted by the template sizes

and can be controlled by adjusting the amount of materials
deposited on the templates

• Removing the templates after deposition, wire-like and tube-like

structures can be formed

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Electrochemical Deposition
DNA is an excellent choice as a template to fabricate nanowires because
its diameter is ~2 nm and its length and sequence can be precisely
controlled
DNA based template: General Procedure
• Fix a DNA strand between two electrical contacts

• Exposed to a solution containing some ions

• Ions bind to DNA - form some nanoparticles decorating along the DNA
chain

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Electrophoretic Deposition
Differs from electrochemical deposition in several
aspects
The deposit need not be electrically conductive
Particularly for oxide nanowires: SiO2, TiO2, Bi2O3,
etc.

Different sizes of TiO2 nanorods grown in a membrane by sol

electrophoretic deposition.
Diameters: (A) 180 nm, (B) 90 nm, (C) 45 nm

Picture: “A study on the growth of TiO2 nanorods using sol electrophoresis,” S. J. LIMMER, T. P. CHOU, G. Z. CAO, University of Washington,
http://faculty.washington.edu/gzcao/publications/papers/31.pdf 50

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Electrophoretic Deposition
Method:
• Over the surface of nanoparticles develops an electrical
charge via some chemical techniques. Forms like a
colloidal suspension.

• Upon application of an external electric filed to a system

of charged nanosize particle system, the particles are set
in motion in response to the electric filed

• This type of motion is referred to as electrophoresis.

• The rest of this technique, in general, is the same as

electrochemical deposition.
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Electrophoretic Deposition

Stabilization of colloids is generally achieved by electrostatic

double layer mechanism.
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Different Methods of Filling

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Colloidal Dispersion Filling

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Incomplete Filling of the

Template

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Template Filling Assisted with

Centrifugation Force

Centrifugation Force which must be greater than the repulsion force between 56
particles

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Converting Through Chemical

Reactions

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Electrospinning

• A polymer is dissolved in a volatile solvent and placed in a

syringe.

• The solution is charged with a high voltage.

• The high voltage creates an electric field that causes

the polymer to be spun out in thin threads (nanofibers) to a
collector plate.

• A fibrous mat is formed.

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Fibers by Electrospinning

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