Synthesis of Nanomaterials

Course code: ME0438

chandu
Scientist-B
Classification of Nanomaterials
 How to get at nano scale?
There are two general approaches to the synthesis of nanomaterials and the
fabrication of nanostructures

Bottom up approach Top-Down approach

These approaches include the These approaches uses
miniaturization of materials components large (macroscopic) initial
(up to atomic level) with further selfassembly structures, which can be
process leading to the formation of externally-controlled in the
nanostructures. processing of nanostructures.

During self-assembly the physical forces examples : etching through

operating at nanoscale are used to combine the mask, ball milling, and
basic units into larger stable structures. application of severe plastic
deformation.
Ex: quantum dot formation during epitaxial
growth and formation of nanoparticles from
colloidal dispersion.
 Top-down vs. bottom-up
Top-down methods

begin with a pattern generated on a larger scale,

then reduced to nanoscale.

Slow and not suitable for large scale production.

Bottom-up methods

start with atoms or molecules and build up to

Nanostructures
Fabrication is much less expensive
 Classification of Nanomaterials

No nanostructures 2D nanostructures 1D nanostructures 0D nanostructures

or or or or
No confinement 1D confinement 2D confinement 3D confinement

Ex: Bulk materials Ex: Coatings, Ex: Wires, Ex: Quantum Dots,
Multilayer's Carbon Nano tubes Nanoparticles

Synthesis Methods: Gas or vapor Phase Synthesis Methods: Spray Pyrolysis, CVD
Earth abundant & Sputtering Techniques
Materials, rare earth
materials
Liquid Phase Synthesis: Electrodepostion, Sol-Gel, Screen
Printing and Solution based techniques

Mechanical Synthesis: Ball Milling

 Liquid Phase Synthesis
Electrodepostion
Sol-Gel
Screen Printing
Solution based techniques
History Jaroslav Heyrovský was the inventor of the polarographic
method, and the father of electroanalytical chemistry, for which
he was the recipient of the Nobel Prize. His contribution to
electroanalytical chemistry can not be overestimated. All modern
voltammetric methods used now in electroanalytical chemistry
originate from polarography.

On February 10, 1922, the "polarograph" was born as Heyrovský recorded the current-voltage
curve for a solution of 1 M NaOH. Heyrovský correctly interpreted the current increase between
-1.9 and -2.0 V as being due to deposition of Na + ions, forming an amalgam.
VOLTAMMETRY- Electrodeposition
1.) Voltammetry: electrochemical method in which information about an analyte is
obtained by measuring current (i) as a function of applied potential
- only a small amount of sample (analyte) is used

Instrumentation – Three electrodes in solution

containing analyte

Working electrode: microelectrode whose

potential is varied with time

Reference electrode: potential remains constant

(Ag/AgCl electrode or calomel)

Counter electrode: Hg or Pt that completes

circuit, conducts e- from signal source through
solution to the working electrode

Supporting electrolyte: excess of nonreactive

electrolyte (alkali metal) to conduct current
Apply Linear Potential with Time Observe Current Changes with Applied Potential

2.) Differences from Other Electrochemical Methods

a) Potentiometry: measure potential of sample or system at or near zero
current.

voltammetry – measure current as a change in potential

b) Coulometry: use up all of analyte in process of measurement at fixed current

or potential

voltammetry – use only small amount of analyte while vary potential

An example of Current vs. Potential Curve
for electroplating of metal
Faraday's laws of electrolysis

Michael Faraday, perhaps the greatest experimental scientist in history, enunciated

his laws of electrolysis in 1833.

1. The amount of chemical change produced by an electrical current is proportional

to the quantity of electricity that passes.

2. The amounts of different substances liberated by a given quantity of electricity

are inversely proportional to their chemical equivalent weights.

 Faraday’s Laws of Electrolysis

Amount of material = amount of electrical energy

q [ C]
n [mol] 
[C mol 1 ]
zF
n = amount of material
q = electrical charge
z = number of electrons
F = Faraday constant
Faraday’s Laws of Electrolysis:
Expanded Relationship

q n = amount of material
n w = mass of material
zF
M = molar mass of
material
w It I = current

M zF t = time
z = number of electrons
F = Faraday constant
 Current, Current density, Surface area

I
j
A
j = current density [mA cm-2]
I = current [A]
A = surface area of the electrode
[cm 2
]
jelectroplate
= electroplating current density (metal electroplate)
jcorrosion = corrosion current density (metal
corrosion/dissolution)
 Faraday’s Laws of Electrolysis:
Average thickness

M .I .t w = weight (mass) of
w metal
z .F M = molar mass of metal
I = current
M .I .t t = time
x z = number of electrons
 .A.z .F F = Faraday constant
x = thickness of plating
 Faraday’s Laws of Electrolysis:
Average deposit thickness
M .I .t
x
 .A.z .F
The thickness of plate depends on:
- the current (I)
- the time for which it passes (t)
- the exposed area of the work-piece (A)
- a constant (M/AzF)
which depends on the metal and the bath
 Faraday’s Laws of Electrolysis:
Question - Nickel Plating
Nickel is plated from a Watts bath at
a current density of 3 A dm-2.

The current efficiency is 96%.

The molar mass of nickel is 58.71 g mol-1.
The density of nickel is 8.90 g cm-3.
The Faraday constant is 96 485 C mol-1.

What will be the averaged plating thickness

in 1 hour?
 Faraday’s Laws of Electrolysis:
Answer - Nickel Plating
Assume that the reaction is:

Ni2+ + 2e- = Ni

So, two electrons are involved for every Ni atom,

and z = 2

The current density used in plating nickel is

96% of the total current, i.e., 0.96 x 3 A dm-2.
 Faraday’s Laws of Electrolysis:
Answer - Nickel Plating
The average deposit thickness is given by:

M .I .t
x
 .A.z .F
1
(58.71 g mol )(0.96 x 3 A)(3600 s )
x 3 2 1
(8.90 g cm )(100 cm )(2)(96485 C mol )

x  3.54 x 10 cm  35.4 x 10 cm  35m

3 4
 Electrodeposition
Electrodeposition is a long-established way
to deposit metal layers on a conducting
substrate.

 Ions in solution are deposited onto the

negatively charged cathode, carrying charge at
a rate that is measured as a current in the
external circuit.

 The process is relatively cheap and fast and

allows complex shapes.

 The layer thickness simply depends on the

current density and the time for which the
current flows.

 The deposit can be detached if the substrate

is chosen to be soluble by dissolving it away.
 Synthesis of CZTS Thin films:
Substrate: Indium Tin Oxide (ITO) coated glass.
Materials: Copper Sulphate CuSO4(0.02M)

Zinc Sulphate ZnSO4(0.01M)

Tin sulphate SnSO4(0.02M)

Sodium Thiosulphate Na2S2O3(0.02M)

Tri Sodium Citrate C6H5Na3O7(0.02M)

Preparation: All above materials mixed in aqueous solution.
Electrodes : AgCl ( Reference Electrode)
Platinum (Pt) ( Counter Electrode)
ITO glass substrate ( Working Electrode)
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Potential: -1.5 to 0V Centre for Nano Technology, NIE
Synthesis (contd):

Cleaning Weighing

Electrolyte soln
preparation

Annealing Electrodeposition

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 Electrodeposition of Cu2ZnSnS4
Deposition with standard 3-electrode setup
(working, reference, counter electrodes).

Working Electrode: ITO glass Plate

Counter Electrode: Platinum

Reference Electrode: AgCl

 0.001

CZT CV curve 2+
2+ Cu - Cu
0.000 Sn - Sn

-0.001

2+
-0.002 Zn - Zn
Current/ A

2+
Sn - Sn
-0.003

-0.004

-0.005

-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0

Potential/ V

Fig 1: CV curve of CZTS solar absorber.

Electrodeposited CZTS Thin films:

Fig 5: CZTS thin film by Electrodeposition

method.

Fig 6: Polymer substrate. 28

Centre for Nano Technology, NIE
Fig : a. before annealing b. After annealing by Electro deposition
 Counts (A.U)

20
(Cu S)
CZTS (2x 0 0)

30
ITO (2 2 2)
(Cux)(S SnxS)
CZTS (200)
ITO (4 1 1)
ITO (4 2 0)
CuxS

40
CuZnx
CuxS SnyS

CZTS (220)

50
ITO (4 4 0)

2Theta (degree)
CZTS (312)
60

CuxSny
70
o
CZTS annealed at 500 C

CZTS(332)
80

Fig : X-rd patterns of CZTS thin film by electrodepositon

 Summary
• Electrodeposition is a versatile coating technique.

• There is a high degree of control over deposit thickness.

• Many metals can be electroplated from aqueous baths.

• So can some alloys, conductive polymers and composites.

• Rates of electroplating can be expressed via Faraday’s Laws

of electrolysis.
The sol-gel process is very long known since the late 1800s. The
versatility of the technique has been rediscovered in the early 1970s when
glasses where produced without high temperature melting processes.

Precursors ?

Difference between sol gel and electrodepostion

Sol = a stable suspension of colloidal solid particles or polymers in a liquid

Gel = porous, three-dimensional, continuous solid network surrounding a continuous

liquid phase

Colloidal (particulate) gels = agglomeration of dense colloidal particles

Polymeric gels = agglomeration of polymeric particles made from subcolloidal units

Agglomeration = covalent bonds, van der Walls, hydrogen bonds, polymeric chain

entanglement
Sol-gel is a chemical solution process used to make ceramic and glass
materials in the form of thin films, fibers , or powders .
A sol is a colloidal (the dispersed phase is so small that gravitational forces
do not exist; only Van der Waals forces and surface charges are present) or
molecular suspension of solid particles of ions in a solvent.
A gel is a semi-rigid mass that forms when the solvent from the sol begins to
evaporate and the particles or ions left behind begin to join together in a
continuous network
Random Network of SiO2
 Sol-Gel Methods

Hydrolysis
Condensation
Gelation
Ageing
Drying
Densification

What we can get from Sol Gel Methods:

Powders: microcrystalline, nanocrystalline, amorphous

Monoliths, Coatings, Films, Fibers
Aerogels
Glasses, Ceramics, Hybrid materials
Sol-Gel process overview
 Factors affecting Reactivity
• pH
• Water content
• Concentration
• Temperature
• Drying conditions 
 Structure of CZTS cell:

Fig 3: structure of CZTS cell

 ITO (back contact) – good conductivity, stability against

corrosion.
 CZTS – absorber-p-type.
 CdS – buffer layer- n-type. p-n-junction.

 ZnO:Al – n-type.
 Al-Front contact. 43
Centre for Nano Technology, NIE
 Synthesis of CZTS Thin films:
Substrate: Soda Lime Glass
Materials: Copper (II) acetate monohydrate (1.0M)
Zinc (II) acetate dihydrate (1.0M)
Tin (II) Chloride dihydrate (1.0M)
Preparation: All above materials mixed in 2-methoxyethanol.
Stabilizer: Ethanolamine ≈5ml

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 Synthesis technique:
• Sol gel
 Dip coating

Fig 7: Dip Coating.

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Centre for Nano Technology, NIE
Synthesis (contd):

Cleaning Weighing

Gel preparation

Annealing Dip coating

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Centre for Nano Technology, NIE
Figure : a and b (from left): a) CZTS film by Sol Gel method b) Peeled thin film
 Advantages of Sol-Gel Technique

Can produce thin bond-coating to provide excellent adhesion between the

metallic substrate and the top coat.

Can produce thick coating to provide corrosion protection performance.

Can easily shape materials into complex geometries in a gel state.

Can produce high purity products because the organo-metallic precursor

of the desired ceramic oxides can be mixed, dissolved in a specified
solvent and hydrolyzed into a sol, and subsequently a gel, the composition
can be highly controllable.

Can have low temperature sintering capability, usually 200-600°C.

Can provide a simple, economic and effective method to produce high

quality coatings.
Pyrolysis is a thermo chemical decomposition of organic material at
elevated temperatures , it involves the simultaneous change of chemical
composition and physical phase, and is irreversible.
 fundamentals – some language
atomization – is the production of droplets and their dispersion into the gas.
[Okuyama et al, Chem. Eng. Sci., 2003]

aerosol – defined as a suspension of solid or liquid particles in a gas.

[Okuyama et al, Chem. Eng. Sci., 2003]

“Spray pyrolysis is the aerosol process that atomizes a solution

and heats the droplets to produce solid particles.” [Che et al, J. Aero. Sci., 1998]

Messing et al, J. Am. Ceram. Soc., 1993

 fundamentals – the process
there are a number of different atomizers

Messing et al, J. Am. Ceram. Soc., 1993

atomization variables:
droplet size – relates to the size of the end particle
size dispersion – homogeneity of end products
atomization rate – scalability of process is affected (i.e. industrial processes)
droplet velocity – affects residence time within the furnaces
 fundamentals – droplet evolution

Messing et al, J. Am. Ceram. Soc., 1993

evaporation – evaporation of solvent from the surface, diffusion of solvent vapour
away from droplet, change in droplet temperature, diffusion of solute toward the
center of the droplet, change in droplet size

precipitation/drying – involves volume precipitation or surface precipitation of the

solute, followed by the evaporation of the solvent through the nanoporous crust

thermal decomposition or pyrolysis – forms a nanoporous structure

sintering – involves the adhesion/solidification of the crystallites

 fundamentals – precipitation control
Messing et al, J. Am. Ceram. Soc., 1993

Che et al, J. Aer. Sci., 1998

precipitation behaviour can be controlled by the solubilities of the starting materials

or by introducing a precipitation reaction into the droplet
 fundamentals – creating nano particles
requires dilute solutions and small initial droplet sizes

conventional spray pyrolysis can produce particles that

have multiple nanosized crystallites, but these crystallites
are virtually inseparable due to the formation of a three-
dimensional network.

[Xia et al, Adv. Mater., 2001]

 fundamentals – salt-assisted spray pyrolysis

method depends on the distribution of salt

on the nanocrystallite surfaces to prevent
them from agglomerating

[Xia et al, Adv. Mater., 2001]

 benefits/limitations
– does not require high quality targets or substrates
– does not require a UHV system [Patil, Mater. Chem. Phys., 1999]

– continuously produces the material

One of the unique characteristics of spray pyrolysis is that the

chemical reaction occurs within the created micron to sub-micron
sized liquid droplets – a microcapsule reactor. [Che et al, J. Aero. Sci., 1998]

technique is quite empirical, with a number of variables that can affect the final product
– solute concentration
– atomization technique
– temperature, temperature gradient
– residence time in furnace
– carrier gases
Screen Printing
There are several different methods of printing and by far the most versatile is
Screen Printing Suitable substrates (surfaces) for the process include plastics,
paper, card, wood, textiles, ceramics, metals, leather, glass and many others.

The process is not restricted to flat surfaces only Circular items such as plastic
bottles and glassware can be screen printed on purpose made machines.

The first essential is to generate a one to one positive of the exact image it is
required to print. This should be in the form of a solid black image on clear or
opaque light transmitting material such as tracing paper or plastic films purpose
made for the process.
The essential items for making a screen print

A screen, comprising a frame upon which is stretched a mesh.

A photo stencil of the required design attached to the mesh.
A squeegee, comprising a holder into which is fitted a flexible, resilient blade.
An ink or paste (These terms are used interchangeably).
A secure base on which to position the component to be printed.
An operator to combine these five items.

The Print Cycle

The mesh of the screen is brought into line contact with the article by the squeegee as it
is moved across the screen. Ink is pushed into the open area forming the pattern and the
surplus is removed by the edge of the squeegee. The mesh should peel away from the
surface immediately behind the squeegee, leaving all the ink that was in the mesh
deposited on the printing surface. The screen can then be lifted clear without fear of the
print being spoiled.
The basic screen print process
THE SCREEN.

Screen Frame Material

The material used can be any that will form a rigid support for the mesh - usually metal or wood.
Today, since there is little difference in raw material cost, metal is usually employed as it does not
suffer the disadvantages of warping when immersed in water during the processing of the
photostencil. Plastic could be used but must be of a type which will not be affected by the various
types of solvent used for inks and screen cleaning. For applications demanding precision, metal is
always used.

Screen / image size

 the Screen Mesh

The mesh serves as a net to hold the photostencil and to meter the amount of
printing medium deposited. It should be flexible so that the squeegee can make
it conform to surface variations of the component being printed. It should be
resilient so that it will return to its original shape after the passage of the
squeegee, with an action which allows the complete removal of the ink from the
open mesh and the minimum distortion of the printed area.

Three types of material are in general use today: Nylon, Polyester and Stainless
Steel.
While each job must be evaluated in its own right, the following table provides general guidance for
selecting a mesh type. (1 is first choice)

Stainless
  Nylon Polyester
Steel
Flexibility 3* 1 2
Resilience 3* 1 2
% open area 2 2 1
Stability of
3 2 1
print size
Squeegee wear 1 2 3
Accidental
1 2 3
damage
Cost 1 1 3
Easy peel from
3 2 1
large areas
Screen Tension
 PHOTOSTENCILS.
Emulsion Thickness

 Effects of emulsion thickness on print definition

Effect of emulsion on print thickness over a large area
THE SQUEEGEE.

The functions of the squeegee are to:

Bring the screen into intimate contact with the surface being printed.

Force the ink into the open areas of the screen.

Shear and remove the excess ink from the surface of the screen.

Control the rate of release of screen.

Affect of squeegee angle

Effect of squeegee wear

Screen gap
Squeegee Material

The degree of wear must be minimal and the material should be available in
a range of hardness to suit the great variety of different types of application.
Polyurethane is currently the most universally used material for squeegees.