NANOMETALS

1. Fundamental concepts
2. Synthesis and Examples
 Nucleation and Growth

FUNDAMENTALS OF HOMOGENEOUS
AND HETEROGENEOUS NUCLEATION
AND GROWTH

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Synthesis: Zero Dimensional Nanostructures

1. Thermodynamic approach
(i) generation of supersaturation
(ii) nucleation
(iii) subsequent growth

2. Kinetic approach
(i) limitation of precursor
(ii) process confinement/limiting space

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Reduction of Gibbs free energy of a supersaturated solution

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Change of volume free energy, surface free energy and total
free energy as function of radii

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Effect of temperature on the critical size and free energy

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Processes of nucleation and subsequent growth

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Relationship between nucleation and growth rates and
concentration of growth species

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Subsequent growth of nuclei

(1) Generation of growth species

(2) Diffusion of the growth species from bulk to the growth surface
(3) Adsorption of the growth species onto the growth surface
(4) Surface growth through irreversible incorporation of growth
species onto the solid surface

Processes:
(1) Growth controlled by diffusion
(2) Growth controlled by surface process (mononuclear and
poly-nuclear growth)

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Radius difference as a function of particle size

• Monolayer growth for small nuclei

• Poly-nuclear growth as nuclei
become bigger
• Diffusion-controlled growth for
relatively large particles
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Radius difference as a function of growth time

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Effect of controlling synthesis parameters

1. Identical particle size

2. Identical shape/morphology
3. Identical chemical composition and crystal structure
4. Monodisperse

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SYNTHESIS METHODS AND
PRINCIPLES

0-D
Metallic Nanoparticles

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 Metal Nanoparticles
General method of synthesis: Reduction of metal complexes in dilute solutions
Result: Metal colloidal dispersions
Challenge: Control the reduction reactions!

Monosized metallic nanoparticles:

Low centration of solute + Polymeric
monolayer adhered onto the
growth surface
Both hinder the diffusion of growth
species from the surrounding solution to
the growth surfaces, so that the diffusion
process is likely to be the rate limiting step
of subsequent growth of initial nuclei,
resulting in the formation of uniformly
sized nanoparticles

Pot ingredients:
 Precursors
 Reduction reagents
 Polymeric stabilizers

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Synthesis of Metallic nanoparticles
Precursors, Reducing reagents, and Polymer stabilizers
PRECURSOR
REDUCING
AGENT

Contains the
metals in ion
STABILIZER
form

Supplies METAL NANOPARTICLE

electrons to
metal ions

Surrounds the nanoparticles to protect from:

uncontrolled growth, oxidation, agglomeration

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 Example: Colloidal Gold
Most common method to synthesize gold
nanoparticles:

Sodium citrate reduction of chlorauric acid at

Colloidal gold has been studied extensively for
100°C (developed more than 50 years ago)
a long time. most commonly used method.

1857: Faraday published a comprehensive Chlorauric acid in water to make 20 ml very dilute
study on the preparation and properties of solution of 2.5 X 10-4 M.
Then 1 ml 0.5% Sodium citrate is added into the
colloidal gold.
boiling solution.
The mixture is kept at 100°C until color changes,
while maintaining the overall volume of the
solution by adding water.
Prepared colloidal sol has excellent stability and
uniform particle size of 20 nm diameter.
https://yuchinhuan
g.files.wordpress.co
m

video

http://education.mrsec.wisc.edu/277.htm

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Synthesis of Nanoparticles
using the Turkevich Method

HAuCl4 tetrachloroauric acid

Na3C3H5O7 trisodium citrate

SADC
Sodium
acetate
dicarboxylate

https://chem553project.wikispaces.com/Synthesis+of+aqueous+Gold+Nanoparticles

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 Colloidal Gold

Large number of initial nuclei

formed in the nucleation stage
would result in a larger number of
nanoparticles with smaller size and
narrower size distribution

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 Stronger reduction reagents:
Transition metallic colloidal
nanoparticles: Stronger reduction reagent would generate an abrupt surge of
the concentration of growth species, resulting in a very high
Size depends on strength of reducing agent supersaturation.

Stronger reducing reagents – smaller nanoparticles. Large number of initial nuclei would form.

Formation of a larger number of nuclei would result in a

smaller size of the grown nanoparticles.

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Rhodium (Hirai, et al.)
Refluxing a solution
Rhodium chloride + PVA in
1:1 (v:v) methanol:water at
79°C.
Refluxing in argon or air for
0.2 to 16 hours.
Methanol = reduction
reagent
Reaction:
RhCl3 + 2 CH3OH + Rh + 2
HCHO + 3 HCl
PVA = polymer stabilizer,
diffusion barrier.
Platinum (Henglein et al.)
Pt nanoparticles:
• Radiolysis
• Hydrogen reduction
• Citrate reduction
Gamma-rays of 60-Co
generate hydrated
electrons, H atoms and 1-
hydroxylmethyl radicals
Radicals subsequently
reduce Pt2+ in K2PtCl4 to Pt
Pt particles form (mean
diameter=1.8 nm)
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Metallic nanoparticles by an
electrochemical deposition
Silver Electrochemical cell containing
Sonochemical reduction of only a metal anode and a metal
aqueous silver nitrate or glassy carbon cathode.
solution at a temperature Electrolyte - tetraalkylammonium
of 10°C, argon and halogenides, serve as stabilizers
hydrogen atmosphere for metal nanoparticles.
20nm particles
Electric field, oxidative
Ultrasound resulted in dissolution of metal ions, which
decomposition of water would migrate toward the
into hydrogen and hydroxyl cathode.
radicals.
Reduction of metal ions by
Hydrogen radicals reduce ammonium ions leads to the
Ag+ to Ag atoms nucleation and growth of metallic
nanoparticles in the solution.
Ag atoms nucleate and
grow to silver Nanoparticles of Pd, Ni and Co
nanoclusters. diameters from 1.4-4.8 nm.
Current density effect: increase J
- reduced particle size
20
 https://www.lem.kit.edu/english/158.php

http://www.chem.wisc.edu/courses/801/Spring00/Chapter1/PdSiO2.html

http://www.spring8.or.jp/en/news_publications/press_release/2013/130410_2/

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https://www.researchgate.net/figure/262066862_fig7_Fig-8-Possible-mechanisms-of-antibacterial-activity-of-
silver-nanoparticles

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•
Polymer stabilizer
Form a monolayer on the surface of nanoparticles
• Prevent agglomeration of nanoparticles

Particle surface - polymer stabilizer interaction:

Depends on:
– Surface chemistry of solid
– Polymer
– Solvent
– Temperature

Strong adsorption of polymer stabilizers occupy growth sites

- Reduce the growth rate of nanoparticles.

Full coverage polymer stabilizer

- Hinder diffusion of growth species from the surrounding solution to the surface of growing particle.

Polymer stabilizers may also interact with solute, catalyst, or solvent,

- Effective quantity of reactants is not as initially calculated

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SYNTHESIS METHODS AND
PRINCIPLES

0-D
Semiconductor Nanoparticles

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Semiconductor nanoparticles

1. Reaction and growth in the formation of nanoparticles are

difficult to manipulate and sol-gel process is the commonly
used fabrication technique

2. Nonoxide semiconducting nanoparticles are usually

synthesized by pyrolysis of organometallic precursors with
anhydrate solvents and capping agents at elevated
temperature
Sigma-Aldrich

http://www.nanosysinc.com/what-we-do/quantum-dots/

mit.edu
 http://pubs.rsc.org/en/content/articlelanding/
Quantum dot synthesis 2014/tc/c3tc32564d/unauth#!divAbstract
Stabilizing Nanoparticles

1. Electrostatic
2. Steric
VAN DER WAAL’S

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 VAN DER WAALS

Hamaker Constant, A

A material constant that measures the rela-

tive strength of the attractive van der Waals
forces between two surfaces.

Particles interacting through an intervening

fluid medium will experience a reduced
attractive potential due to the presence of the
third component.

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Stabilization

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 Stabilization in solution

• When nanoparticles are taken out of the

solvent (polar) or electrolyte:
- Surface becomes charged

• Mechanisms:
1. Adsorption of ions preferentially
2. Surface charged species dissociates
3. Ions are substituted with isomorphs
4. Electrons are depleted on the surface
5. Charged species are adsorbed on surface

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DOUBLE LAYER

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Steric Stabilization

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SYNTHESIS METHODS AND
PRINCIPLES

1-D
Nanowires, nanotubes, etc

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Growth of 1D Nanostructures

1. Top-down approach – gradual reduction in the size of bulk

materials to nanometer scale using etching techniques
with the help of various lithography techniques

2. Bottom-up approach – self-assembly of basic blocks into

1D nanostructures and the process can be controlled by
the growth dynamics (solution-based and vapor-based)
Solution-based Methods: low growth temperature

1. Solvothermal – mixture of precursor and reagent for

regulating/templating crystal growth like amine and
subsequent reactions at elevated temperature and
pressure; low yield and purity
2. Solution-liquid-solid method – introduction of liquid-solid
interface in creating growth anisotropy; low-melting metal
(ex. Bi, In, Sn) is used as catalyst and organometallic
precursors are decomposed to generate desired
nanostructures
3. Template-directing – can be nanoscaled channels in
porous materials, steps or edges on the surface of
substrate, biological molecules or existing nanostructures
http://www.tms.org/pubs/journals/jom/1004/picraux-1004.html
Vapor-based fabrication

1. Thermal evaporation
2. Chemical reaction
3. Laser ablation
4. Arc discharge
5. Sputtering
6. Carbothermal reduction
7. Oxide-assisted/Direct oxidation
8. Vapor-solid-liquid interphase (anisotropic growth); use of
metallic catalysts, which form eutectic liquids with the
source materials. During growth, the precursor vapor
dissolves into the liquid drops and solid nuclei precipitate
after saturation for the subsequent growth of 1D
nanostructures
Capping reagents

• Extensively used to break the growth symmetry for

obtaining 1D nanostructures
• Introduction of reagents can change the free energy of the
crystallographic surfaces and thus their growth rates
• Typical example is the synthesis of silver nanowires with
poly(vinyl pyrrolidone) (PVP) was used as a polymeric
capping reagent
• When the silver nanoparticles, reduced from silver
nitride,grew through the Ostwald ripening process, the
presence of PVP confined and directed the growth of
particles into nanowires with uniform diameters
http://nanotechweb.org/cws/article/tech/65884

http://pubs.acs.org/doi/abs/10.1021/acsnano.
6b03806
Mechanical Properties:

• Single crystalline 1D nanostructures are supposed to be

stronger than their bulk counterparts due to the reduction
in the number of defects per unit length
• Exhibit strength, stiffness and toughness approaching the
theoretical limits of perfect crystals
Thermal Properties:

1. Melting point of nanostructures can be much lower than

their bulk counterparts

Electronic Transport:

1. Readily considered as electron transport channels or

interconnects
2. Explored as building blocks in electronic devices
SYNTHESIS METHODS AND
PRINCIPLES

2-D
Semiconductor Nanoparticles

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Growth of 2D Nanostructures

1. Evaporation Technique

• Thin film deposition and most widely-used technique

involving the synthesis of single-phase metals and ceramic
oxides by the inert-gas evaporation technique

• Evaporated atoms or molecules lose energy via collisions

with the gas atoms or molecules and undergo a
homogeneous condensation to form atom clusters in the
vicinity of a cold-powder collection surface
Growth of 2D Nanostructures

2. Sputtering Technique

• Generally involves the ejection of atoms or clusters of

designated materials by subjecting them to an accelerated
and highly focused beam of inert gas such as helium or
argon

• Different kind of sputtering systems include ion-assisted

deposition, ion beam, reactive, high-target utilization, high
power impulse magnetron and gas flow sputtering
Growth of 2D Nanostructures

3. Lithographic Processes

• more versatile and easy to implement process for

producing self-assembled nanomaterials
• rapid and effective method for surface patterning, which is
compatible with large variety of materials
• unconventional approaches include soft nano-imprint
lithography, nanosphere lithography, colloidal lithography,
nano-imprint lithography and solution-phase synthesis
• conventional approaches include e-beam lithography and
focused ion beam lithography (FIB)
Growth of 2D Nanostructures

5. Spray pyrolysis

• solution process in which nanoparticles are direct

deposited by spraying a solution on a heated substrate
surface, where the constituent react to form a chemical
compound
• chemical reactants are selected such that the products
other than the desired compound are volatile at the
temperature of deposition.
• represents a very simple and relatively cost-effective
processing method (particularly in regard to equipment
costs) as compared to many other film deposition
techniques
Growth of 2D Nanostructures

12. Hydrothermal and solvothermal technique

• hydrothermal system can be defined as the use of water as

reaction medium in a sealed reaction container when the
temperature is raised above 100oC
• very similar to the hydrothermal route (where the synthesis
is conducted in a stainless steel autoclave), the only
difference being that the precursor solution is usually not
aqueous but this is not always
Schematic experimental system for the
Schematic drawing of solvothermal setup
hydrothermal fabrication of NSMs
2D Structures
SEM images of the CuS architectures
prepared in different solvents: (A and
B) ethanol, (C–F) ethylene glycol, and
(G and H) dimethylformamide
SEM images of the hexagonal starlikeb-MnO2crystals synthesized from (A) 1.2 M and (B)
2.0 M Mn(NO3)2 solution. (C–F) SEM images at different magnifications of the dendritelike
hierarchicalb-MnO2nanostructures synthesized from Mn(NO3)2-nitric acid solution
(A) SEM and (B) TEM images of ZnO nanodisks