Chemistry of Electronic Materials

Maharaja Institute of Technology Mysore

Department of Chemistry (BCHEE-102/202)

MODULE1: Chemistry of Electronic Materials 08Hours

Conductors and Insulators: Introduction, principle with examples, semiconductors-

production of electronic grade silicon- Czochralski process (CZ) and float zone (FZ) methods.

Polymers: Introduction, Molecular weight - Number average, weight average and numerical
problems, conducting polymers – synthesis and conducting mechanism of polyacetylene.
Preparation, properties and commercial applications of graphene oxide.

PCB: Electroless plating – Introduction, Principle of Electroless plating - copper in the

manufacture of double-sided PCB.

CONDUCTORS AND INSULATORS

Introduction
Selection of a material for a specific application is based on its properties. Property of a material
depends on the chemistry of material. Most important property of a material employed by an
Electrical and Electronics Engineer is its electrical conductivity.
Based on electrical conductivity, materials are broadly classified in to
 Conductors
 Semiconductors
 Insulators

Conductors: Conductors are the materials which allow electricity to flow through them. The
band gap in the conductors is very small (0.1 eV) and there is an overlap of valence and
conduction band due to which electrons can freely move. Metals like Copper, gold, silver are
very good conductors with conductivity in the order of 108 Siemens/meter.

Insulators: Insulators are the materials which resist or don’t allow the current to flow through
 Chemistry of Electronic Materials
them. The band gap in the insulator is very large (3- 6 eV). It is impossible to excite electrons
from valence band to conduction band crossing this high energy gap. Therefore, application of
temperature or external electric field cannot cause current flow. Plastics, rubber and glass are
very good insulators with conductivity in the order of 10-20 Siemens /meter.

Semiconductor: In case of a semiconductor, the band gap is in between a conductor and an

insulator (1eV). At absolute zero, it behaves as an insulator. But, at room temperature some of
the valence band electrons gain sufficient energy to cross band gap and move to conduction
band. Germanium, silicon and gallium-arsenide (GaAs) are very good semiconductors exhibit
electrical conductivity in the order of 102 to10-8 Siemens /meter.

Silicon:
Silicon is second most abundant element in the earth crust. It is a tetravalent element with
forbidden band gap of 1.12 eV. It is a semiconductor which can be doped with trivalent or
pentavalent atoms. Doping increases conductivity, ionizes at lower temperature, decreases its
hardness so that the material can be molded in any shape and decreases the life of minority
charge carriers. So, they are used in LEDs, diodes, bipolar transistors, field effect transistor etc.

There are two methods to obtain single-crystal silicon from polycrystalline Si crystal:
1. Czochralski method. 2. Float zone method.

1. Czochralski (CZ) method:

CZ method was developed by Jan Czochralski in 1916. Single crystal obtained by this method
will have no defects and very less impurity (i.e., 1 part of impurity/100 billion) and have unique
properties like optoelectronic, microelectronic & mechanical property.
 Chemistry of Electronic Materials
Construction:

Working:

 Polycrystalline silicon crystal is taken in quartz crucible and crucible is placed in a graphite
container.
 Graphite container is heated from the surrounding heater (furnace). Heat from graphite
container is transferred homogeneously to quartz crucible.
 Polycrystalline silicon starts melting in an inert gas atmosphere and the temperature of
melt is kept constant, roughly above the meting point of silicon (1414°C).
 Now single crystal seed is immersed into the melt and pulled slowly (1mm/minute) out of
the melt.
 During this process, the seed crystal and crucible are rotated in the opposite direction.
 When seed is pulled upward, the melt get solidified. This solid silicon obtained is
monocrystalline (single crystal) silicon.
 The crystallographic orientation, direction and the grain boundary of the newly formed
single crystal silicon (monocrystalline silicon) is same as that of seed crystal.
 The diameter of the newly formed single crystal silicon depends on pull speed and
temperature of the melt.
Float zone (FZ) method:

Construction:
 Chemistry of Electronic Materials

Working:
 A polycrystalline rod is placed in a chamber with inert gas atmosphere to prevent the
oxidation of silicon.
 A monocrystalline silicon crystal (seed crystal) is attached to one end of a polycrystalline
silicon rod.
 A RF coil is used to melt a small region of the polysilicon rod from single seed crystal end.
 As the RF coil moves, melted silicon is cooled down and forms single crystal silicon.
 The crystallographic orientation, direction and the grain boundary of the newly formed
single crystal silicon is same as that of seed crystal.
 The RF coil and the melted zone move along the entire rod.
 The impurities are less soluble in the crystal than in the melted silicon, hence molten zone
carries the impurities away with it.
 The impurities concentrate near the other end of the crystal and can be removed by cutting
that part of the rod.
POLYMERS

Introduction:
Monomers: These are simple compounds, which combine with each other to form polymers.
These are also called as building blocks of polymers. Ex: Vinyl chloride, ethene, propene etc.
Polymers: Polymers are the high molecular weight compounds obtained by repeated union of
simple molecules. Ex: Starch, Polyvinyl chloride, Polyethene, Nylon-6,6, etc.
Polymerization: The process by which the monomers are transformed into a polymer is called
polymerization.
n (H2C CH2) ( CH2 CH2 )
n
Ethene Polyethene
Degree of polymerization: The number of repeating units present in a polymer is called
degree of polymerization. It is represented by ‘n’.

n (H2C CH2) ( CH2 CH2 )

n
Molecular weight of polymers:
 Chemistry of Electronic Materials

Molecular weight of the polymer is given by, M=Dp x m

Where, Dp= Degree of polymerization
m = Molecular weight of repeating units(monomer)
Polymer properties are related to their molecular mass, size and structure. The polymer contains
chains of varying lengths and hence, molecular mass is always expressed as an average. This
is done in two ways.
1. Number – average molecular mass (̅𝑀 ̅𝑛 )
̅ ̅𝑤̅ )
2. Weight – average molecular mass (𝑀

̅ 𝒏̅ ):
1. Number – average molecular mass (𝑴
Number – average molecular mass is the mass obtained when total mass of all the
molecules of a polymer is divided by the total number of molecules.

If n1, n2, n3…are the number of molecules having molecular mass M1, M2, M3… respectively
then number – average molecular mass is given by
𝑛1𝑀1 + 𝑛2 𝑀2 + 𝑛3𝑀3+⋯……
̅ 𝑛
𝑀 =
𝑛1+ 𝑛2+ 𝑛3+ ……..
𝛴𝑛𝑖 𝑀𝑖
̅𝑀
̅ =
𝑛
𝛴𝑛𝑖

2. Weight – average molecular mass (̅𝑴

̅ w ):
Weight - average molecular mass is the mass obtained when sum of the products of total
mass of groups of molecules and their respective molecular masses is divided by total mass
of all the molecules.
If m1, m2, m3…are the mass of molecules having molecular mass M1, M2, M3…respectively
then weight – average molecular mass is given by
𝑚1 𝑀1 + 𝑚2𝑀2 + 𝑚3 𝑀3+⋯……
̅𝑀𝑤 =
𝑚1+ 𝑚2+ 𝑚3+ ……..

Where m1 = n1M1, m2 = n2M2, m3 = n3M3 …………….

Hence, weight – average molecular mass is given by
𝑛1𝑀21 +𝑛2𝑀22 + 𝑛3𝑀23 + ……….
̅𝑀
̅𝑤̅ =
𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3+ ………….
2
̅𝑤̅ = 𝛴𝑛𝑖𝑀𝑖
̅𝑀
𝛴𝑛𝑖𝑀𝑖

PROBLEMS
Problem 1: In a sample of a polymer, 100 molecules have molecular mass 10 3 g/mol, 250
molecules have molecular mass 104 g/mol and 300 molecules have molecular mass 105 g /mol,
calculate the number average and weight average molecular mass of the polymer.
Solution: Given: n1 = 100 & M1 = 103 g/mol
 Chemistry of Electronic Materials
n2 = 250 & M2 = 104g/mol
n3 = 300 & M3 = 105g/mol
(i) The number average molecular mass of the polymer is given by
𝛴𝑛𝑖 𝑀𝑖 𝑛 𝑀 𝑛 𝑀 𝑛 𝑀
̅𝑀
̅ = = 1 1+ 2 2+ 3 3
𝑛 𝑛1+ 𝑛2+ 𝑛3
𝛴𝑛𝑖
3 4 5
̅𝑛 = 100 𝑥 10 + 250 𝑥 10 + 300 𝑥 10
̅𝑀
100+250+300

̅𝑴
̅𝒏 = 50,153 g/mol
(ii) The weight average molecular mass of the polymer is given by
𝛴𝑛𝑖𝑀2 𝑛1𝑀2 +𝑛2𝑀2 + 𝑛3𝑀2
̅𝑀
̅𝑤̅ = 𝑖 1 2 3
𝛴𝑛𝑖𝑀𝑖 == 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3

̅
PDI is greater than one. Therefore, the given polymer is less homogeneous and polydisperse in
nature.

Problem 2: In a polymer sample, 20% of molecules have molecular mass 15000g/mol, 45%
molecules have molecular mass 25000g/mol and remaining molecules have molecular mass
27000 g/mol. Calculate the number average and weight average molecular mass of the polymer.
Solution: Given: n1 = 20 & M1 = 15000g/mol
n2 = 45 & M2 = 25000g/mol
n3 = 35 & M3 = 27000g/mol
(i) The number average molecular mass of the polymer is given by
𝛴𝑛𝑖 𝑀𝑖 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3
̅𝑀
̅ = =
𝑛 𝑛1+ 𝑛2+ 𝑛3
𝛴𝑛𝑖

20 𝑋 15000+45 𝑋 25000+35 𝑋 27000

̅ 𝑛
𝑀 =
20+45+35

̅𝑴
̅𝒏 = 23,700g/mol
(ii) The weight average molecular mass of the polymer is given by
𝛴𝑛𝑖𝑀2 𝑛1𝑀2 +𝑛2𝑀2 + 𝑛3𝑀2
̅𝑀
̅𝑤̅ = 𝑖 1 2 3
𝛴𝑛𝑖𝑀𝑖 == 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3

20 𝑋 (15000)2 + 45 𝑋 (25000)2+ 35 𝑋 (27000)2

̅𝑀
̅𝑤̅ =
20𝑋 15000+45 𝑋 25000+35 𝑥 27000
̅𝑴
̅𝒘̅ = 24,531.6 g/mol

Problem 3: A polymer sample contains 100, 200, 300 and 400 molecules having molecular
mass 1000, 2000, 3000 and 4000. Calculate the number average & weight average molecular
mass of the polymer.
Solution: Given: n1 = 100 & M1 = 1000g/mol
 Chemistry of Electronic Materials
n2 = 200 & M2 = 2000g/mol
n3 = 300 & M3 = 3000g/mol
n4 = 400 & M4 = 4000g/mol

(i) The number average molecular mass of the polymer is given by

𝛴𝑛𝑖𝑀𝑖 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3+𝑛4𝑀4
̅𝑀
̅ = =
𝑛 𝑛1+ 𝑛2+ 𝑛3+𝑛4
𝛴𝑛𝑖

100×1000+200×2000+300×3000+400×4000
̅ 𝑛
𝑀 =
100+200+300+400

̅𝑴
̅𝒏 = 3000 g/mol
(ii) The weight average molecular mass of the polymer is given by
𝛴𝑛𝑖𝑀2 𝑛1𝑀2 +𝑛2𝑀2 + 𝑛3𝑀2 +𝑛4𝑀2
̅𝑀
̅𝑤̅ = 𝑖 1 2 3 4
𝛴𝑛𝑖𝑀𝑖 = 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3+𝑛4𝑀4

̅𝑤̅ = 100 𝑋 (1000)2 + 200 𝑋 (2000)2+ 300 𝑋 (3000)2+ 400 𝑋 (4000)2

𝑀 =
100×1000+200×2000+300×3000+400×4000

̅𝑴
̅𝒘̅ = 3333.33 g/mol

Problem 4: A polymer sample contains 200 molecules of molecular weight of 2000, 300
molecules of molecular weight of 3000 and 500 molecules of molecular weight of 5000.
Calculate the number average & weight average molecular mass of the polymer.
Solution: Given: n1 = 200 & M1 = 2000
n2 = 300 & M2 = 3000
n3 = 500 & M3 = 5000
(i) The number average molecular mass of the polymer is given by
𝛴𝑛𝑖 𝑀𝑖 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3
̅𝑀
̅ = =
𝑛 𝑛1+ 𝑛2+ 𝑛3
𝛴𝑛𝑖
200𝑋 2000+300 𝑋 3000+500 𝑋 5000
̅𝑀𝑛 =
200+300+500

̅𝑴
̅𝒏 = 3,800 g/mol
(ii) The weight average molecular mass of the polymer is given by
𝛴𝑛𝑖𝑀2 𝑛1𝑀2 +𝑛2𝑀2 + 𝑛3𝑀2
̅𝑀
̅𝑤̅ = 1 2 3
𝑖
𝛴𝑛𝑖𝑀𝑖 == 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3

200 𝑋 (2000)2 + 300 𝑋 (3000)2+ 500 𝑋 (5000)2

̅𝑀
̅𝑤̅ =
200𝑋 2000 + 300 𝑋 3000 + 500 𝑋 5000

̅𝑴
̅𝒘̅ = 4,210.52 g/mol
 Chemistry of Electronic Materials

Problem 5: Calculate the number average and weight average molecular mass of the polymer
with the following composition. (Given: atomic weight of C = 12, H =1 & Cl = 35.5)

Solution:
Molecular mass of repeating unit is = [2×12 +3×1 + 1×35.5] = 62.5 g/mol
Molecular mass of the polymer 1: M1 = 62.5 ×200 = 12500g/mol
Molecular mass of the polymer 2: M2 = 62.5 ×400 = 25000g/mol
Molecular mass of the polymer 3: M3 = 62.5 ×500 = 31250g/mol
Given: n1 = 40 & M1 = 12500g/mol
n2 = 30 & M2 = 25000g/mol
n3 = 30 & M3 = 31250g/mol
(i) The number average molecular mass of the polymer is given by
𝛴𝑛𝑖 𝑀𝑖 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3
̅𝑀
̅ = =
𝑛 𝑛1+ 𝑛2+ 𝑛3
𝛴𝑛𝑖

40 𝑋 12500+30 𝑋 25000+30 𝑋 31250

̅ 𝑛
𝑀 =
40+30+30

̅𝑴
̅𝒏 = 21,875g/mol
(ii) The weight average molecular mass of the polymer is given by
𝛴𝑛𝑖𝑀2 𝑛1𝑀2 +𝑛2𝑀2 + 𝑛3𝑀2
̅𝑀
̅𝑤̅ = 𝑖 1 2 3
𝛴𝑛𝑖𝑀𝑖 == 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3

40 𝑋 (12500)2 + 30𝑋 (25000)2+ 30 𝑋 (31250)2

̅𝑀
̅𝑤̅ =
40𝑋 12500+30 𝑋 25000+30 𝑥 31250

̅𝑴
̅𝒘̅ = 24,821.42 g/mol
 Chemistry of Electronic Materials

Problem 6: Calculate the number average and weight average molecular mass of the polymer
with the following composition.

Solution:
Molecular mass of repeating unit is = [2×12 + 4×1] = 28 g/mol
Molecular mass of the polymer 1: M1 = 28 ×100 = 2800g/mol
Molecular mass of the polymer 2: M2 = 28 ×150 = 4200g/mol

Molecular mass of the polymer 3: M3 = 28 ×200 = 5600g/mol

Molecular mass of the polymer 3: M4 = 28 ×250 = 7000g/mol

Given: n1 = 20 & M1 = 2800g/mol

n2 = 25 & M2 = 4200g/mol
n3 = 30 & M3 = 5600g/mol
n4 = 25 & M4 = 7000g/mol

(i) The number average molecular mass of the polymer is given by

𝛴𝑛𝑖𝑀𝑖 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3+𝑛4𝑀4
̅𝑀
̅ = =
𝑛 𝑛1+ 𝑛2+ 𝑛3+𝑛4
𝛴𝑛𝑖

20 𝑋 2800 + 25 𝑋 4200 +30 𝑋 5600 +25 𝑋7000

̅𝑀𝑛 =
20+25+30+25

̅𝑴
̅𝒏 = 5,040 g/mol
(ii) The weight average molecular mass of the polymer is given by
𝛴𝑛𝑖𝑀2 𝑛1𝑀2 +𝑛2𝑀2 + 𝑛3𝑀2 + 𝑛4𝑀2
̅𝑀
̅𝑤̅ = 𝑖 1 2 3 4
𝛴𝑛𝑖𝑀𝑖 == 𝑛1𝑀1 + 𝑛2𝑀2 + 𝑛3𝑀3+𝑛4𝑀4

20 𝑋 (2800)2 + 25𝑋 (4200)2+ 30 𝑋 (5600)2 + 25𝑋 (7000)2

̅𝑀
̅𝑤̅ =
20 𝑋 2800 + 25 𝑋 4200 +30 𝑋 5600 +25 𝑋7000

̅𝑴
̅𝒘̅ = 5,483.33 g/mol

Problem 7: Calculate the molecular weight of PVC, if degree of polymerization (Dp) is 12,250
Solution: Dp = 12,250
m = Molecular weight of VC(CH2=CHCl) = 62.5 g/mol
Molecular weight of PVC, M = Dpm
M = 12,250 x 62.5
M = 7.66 x 105 g/mol
 Chemistry of Electronic Materials

Problem 8: Calculate degree of polymerization of styrene, given that number average

molecular weight (̅𝑀
̅𝑛) is 2.4x104 g/mol

Solution: ̅𝑀
̅𝑛= molecular weight of polymer = 2.4 x 104 g/mol
m = molecular weight of styrene (CH2=CHC6H5) = 104.15g/mol
M = Dpm
2.4X104 g/mol
Dp =
104.15 g/mol

Dp = 2.304 x 102

Conducting Polymer:
Definition: Polymers with highly delocalized pi-electron system, having electrical
conductance of the order of conductors are called conducting polymers.

The basic requirement for organic polymer to be inherently conducting is

a) They should have linear structure with relatively rigid chains.
b) They should have continuous conjugation (alternative single and double bonds) through
the polymer chain.
Example: Polyacetylene, polyaniline, polypyrrole, etc.

Polyacetylene
Polyacetylene films are synthesized using the Zeigler-Natta catalyst. The catalyst
tetrabutoxytitanium and triethylaluminum suspended in silicone oil through which acetylene is
passed and stirred for two hours at 120° C. Then cooled slowly to room temperature resulting
in thin sheets of polyacetylene.

Above kind of polymers in their original form are insulators. But on suitable doping, their
conductivity can be increased considerably. Doping creates charge carriers like holes or excess
electrons (similar to doped silicon) and thereby, an organic polymer becomes a conductor. The
important doping techniques are:

1. Oxidative doping(p-doping)
2. Reductive doping(n-doping)
 Chemistry of Electronic Materials

Mechanism of conduction in Polyacetylene: Oxidative doping (p-doping)

 Polyacetylene consists of carbon atoms linked by alternating single and double bonds.
 When a suitable oxidizing agent such as iodine vapour or iodine in CCl4 or perchloric
acid is added, it takes away an electron from the pi-backbone of the polyacetylene
chain.
 This creates +ve charge on one of the carbons and free electron on another carbon
making it a radical. So, a radical cation called polaron is formed.
 A bipolaron (soliton) is formed on second oxidation.
 The two radicals (electrons) migrate and combine to establish back one double bond.
 As two electrons are removed, the chain will have two +ve centers (holes). These
positivecharges are mobile. When a potential is applied, they migrate accounting for
conductivity.
 Positive charges are compensated by I3 - ions and thus the polymer is electrically neutral.

Applications: It is used
1. As electrode material for commercial rechargeable batteries. Eg: Lead-Acid battery.
2. For making sensors for pH, O2, SO2, NH3 and glucose.
3. In telecommunications systems.
4. In electronic devices such as transistors and diodes.
5. In fuel cells as the electro catalytic materials.

Department of Chemistry, Maharaja Institute of Technology Mysore 11

 Chemistry of Electronic Materials

Graphene oxide

A single sheet of carbon atoms taken out of graphite is called as graphene. It is a two-
dimensional nanosheet with thickness equal to single carbon atom. When Oxygen
containing functional groups like epoxide, carbonyl, carboxyl, and hydroxyl groups are
added to graphene layer, then the resulting material is Graphene Oxide. It contains
hydroxyl (-OH), alkoxy (C-O- C), carbonyl (C=O), carboxylic acid (-COOH) and other
oxygen-based functional groups

Preparation of Graphene Oxide:

Graphite is subjected to reaction with an anhydrous mixture of concentrated sulfuric acid,
sodium nitrate, and potassium permanganate. The oxidation reaction is completed within 2
hours at a temperature below 45oC. Hydrolysis of graphite oxide in the presence of polar solvent
dimethylformamide (DMF) and sonication results in complete exfoliation in water, yielding
individual graphene oxide sheets.

Properties:

1. It is hydrophilic due the presence of hydroxyl, alkoxy, carbonyl, carboxylic acid groups.
2. It can mix with matrix such as polymer and ceramic to improve their
mechanical andelectrical properties.
3. It is hygroscopic and forms a strong hydrogen bond with water molecules.
4. It has large surface area (890 m2/g), so it is more reactive.
5. It has low thermal conductivity (0.5-1 W/m/K) as compare to graphite (3000-5000W/m/K)
6. It has low electrical conductivity than graphene.

Department of Chemistry, Maharaja Institute of Technology Mysore 12

 Chemistry of Electronic Materials
Applications:

1. Graphene oxide can be used in coating technology, as its film can be deposited on
any substrate like steel, aluminium, etc., to produce an impermeable and transparent
conductive film, which gives better corrosion resistance and wear resistance in dry
conditions.
2. Graphene oxide papers can be used in desalination and reverse osmosis techniques
to get pure water from saline water.
3. GO can be used in the biomedical fields such as drug delivery, cancer therapy,
bioimagingand biosensor because of its biocompatibility nature.
4. Nanocomposite of GO and silver ions used for bacteria detection.
5. GO is used as a biosensor for the detection of cancer cells in early stage.

Department of Chemistry, Maharaja Institute of Technology Mysore 13