Professional Documents
Culture Documents
Unit-3 Chemical Methods
Unit-3 Chemical Methods
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 methods
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
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
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.
Ni2+ + 2e- = Ni
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 )
Cleaning Weighing
Electrolyte soln
preparation
Annealing Electrodeposition
24
Centre for Nano Technology, NIE
Electrodeposition of Cu2ZnSnS4
Deposition with standard 3-electrode setup
(working, reference, counter electrodes).
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
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
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 ?
liquid phase
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
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
44
Centre for Nano Technology, NIE
Synthesis technique:
• Sol gel
Dip coating
45
Centre for Nano Technology, NIE
Synthesis (contd):
Cleaning Weighing
Gel preparation
46
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
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
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
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
Bring the screen into intimate contact with the surface being printed.
Shear and remove the excess ink from the surface of the screen.
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.