Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

MODULE-1

Chemistry of Electronic Materials

Syllabus
[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.
Electroless plating – Introduction, Principle of Electroless plating - copper in the

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manufacture of double-sided PCB.]

Conductors, Semiconductors and Insulators:

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Conductivity of materials can be explained on the basis of band theory.

According to this theory, there are three types of bands namely i)
Conduction band ii) Valence band and iii) Forbidden gap
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The band formed by a series of energy levels containing the valence electrons
is called the Valence Band (VB).
 It is highest occupied energy band.
 It may be completely filled or partially filled with electrons.
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The next higher permitted energy band is called the Conduction Band (CB).
 It is lowest unoccupied energy band.
 It may be empty or partially filled with electrons.
 The electrons can move freely in the conduction band and hence
the electrons in conduction band are called conduction electrons.
 The energy gap between the VB and CB is called the Forbidden
Energy Gap or Forbidden Band.
 It is formed by a series of non-permitted energy levels above the top
of valence band and below the bottom of the conduction band.
 It is the amount of energy to be supplied to the electron in VB to get excited
into the CB.
 When an electron gains sufficient energy, it ejects from the
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

valence band creating hole, which is supposed to behave as a

positive charge.

Conductivity of a material depends on the available charge carriers (ionic)

and their mobility, valency of ions and the temperature. It is based on
Ohm`s law, which states that “the current (I) flowing through a conductor is
directly proportional to the applied potential (E) and inversely proportional to
the resistance (R)”.
i.e. I = E/R or E = I R
The reciprocal of resistance is called conductance.
i.e. C = 1/R
Conductors: A conductor or electrical conductor is a substance or

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material that allows electricity to flow through it. In conductors, electrical
charge carriers (electrons or ions), move easily from atom to atom when
voltage is applied and also, conduction band and valence band are
overlapped. Therefore there is easy flow of electrons and thus they are

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good conductors of heat and electricity. Typically, metals, metal alloys,
electrolytes and even some nonmetals, like graphite and liquids, including
water, are good electrical conductors. Pure elemental silver is one of the
best electrical conductors. Other examples include copper, steel, gold,
silver, platinum, aluminium, brass, etc. Copper has the second-highest
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electrical conductivity of all metals (5.9×107 Siemens/m).

Insulators: Materials that don't allow electrical current or heat to pass

through them are known as insulators. In insulators, due to a large
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forbidden gap between conduction and valence band, there is no easy flow
of charge carriers. Therefore, they are bad conductors of heat and
electricity. Most insulators are solids in nature. Ex:- wood, glass, quartz,
plastic, etc. The electrical conductivity of polymer is in the range of 10-10 to
10-8 S/m.
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Semiconductor: Any of a class of solids (such as germanium or silicon)

whose electrical conductivity is between that of a conductor and an
insulator. In semiconductors, because of small gap (forbidden gap) in
between conduction band and valence band, there conductivity lies
between that of conductors and insulators. However, their conductivity
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can be increased by increasing temperature or by adding dopants. The

conductivity of Silicon is 16.7 S/m.

Preparation of Single Crystal Silicon: Silicon obtained by above process

is polycrystalline. But for the fabrication of semiconductor device,
silicon should be a single crystal. Czochralski and Float Zone methods
are used to obtain single crystals.
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Czochralski (CZ) process

OR

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Czochralski method is used obtain single crystals of semiconductors
(silicon, germanium), metals (palladium, platinum, gold), salts and
synthetic gemstones. This method was invented by Jan Czochralski in
1915.
Process:
e.
 High-purity, semiconductor-grade silicon is melted in a quartz
crucible at 1425 °C using RF coil.
 Dopant such as boron or phosphorus can be added to the molten
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silicon in precise amounts to obtain p-type or n-type silicon.
 A monocrystalline seed crystal fixed to the puller rod is rotated
slowly at the rate of 50 rpm and dipped into the melt.
 Then the rod is slowly pulled upwards at the rate of 1.5 to 5 cm per
hour and rotated simultaneously.
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 By precisely controlling the temperature, rate of pulling and speed of

rotation, it is possible to extract a large, single-crystal of silicon
from the melt.
 This process is normally performed in an inert atmosphere, such as
argon. (OR)
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The float zone (FZ) method

 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

The float zone method is based on the zone-melting principle and was invented by
Theuerer in 1962. In this process high purity silicon crystal with extremely low
concentrations of impurities, such as carbon and oxygen, can be obtained. It is carried
out in an inert atmosphere.
Process
 The process starts with a high-purity polycrystalline rod fixed to the
clamp and a monocrystalline seed crystal fixed to the seed holder.
 They are held face to face in a vertical position and rotated as
shown in the figure. Melt the feed rod using radio frequency heating
coil and the seed crystal is brought up from below to make contact
with the drop of melt formed at the tip of the poly silicon feed rod.
 The molten silicon solidifies into a single crystal and the material is

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purified simultaneously.
The crystals are can be doped by adding the doping gas like phosphine (PH3) or
diborane (B2H6) to obtain n- and p-type, respectively. Unlike CZ method, in FZ method
crystal is not in contact with any substances except dopant gas. Therefore crystal

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obtained in FZ process can easily achieve much higher purity and higher resistivity.
Polymers:

Definition: “Polymers are macro sized molecules of high molecular mass formed
by the combination of a large number of simple molecules by covalent bonds”.
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Ex: Polyethylene, polyacetylene, polystyrene, polyvinyl chloride, natural and
synthetic rubbers etc.
Polymerization: “The process by which the monomers are converted into polymers
is called Polymerization”.
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MOLECULAR WEIGHT OF POLYMERS:

Due to the varying chain lengths, a polymer is considered to have average

molecular mass. 2 types of average molecular masses have been recognized
namely, number average and weight average molecular masses.
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Number average molecular mass: It is obtained by dividing the total weight of the
monomers with the number of monomer molecules present in polymer i.e.,

Where n1, n2, n3 are the number of molecules having masses M1, M2, M3
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respectively. The above equation can be written as

Where Mi is the masses of monomers and ni is the number of monomers.

Weight average molecular mass: It gives the representation to different molecular

species in proportion to their weight in the given polymer molecule.
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Where w and M represent the weight and molecular masses of each species present
in polymers. Since w= nM,

Poly Disparity index [PDI]:

Mw
PDI 
Mn
If PDI =1 polymer is mono disperse & Homogeneous.
PDI >1 polymer is poly disperse & less Homogeneous.

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CONDUCTING POLYMERS
Definition: “An organic polymer with highly delocalized pi-electron system having
electrical conductance is called conducting polymer”.
Ex: Polyacetylene, polypyrrole, polythiophene, polyphenylene, polyaniline, etc.

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Synthesis of Polyacetylene:
From Acetylene: In this method polyacetylene is synthesized by using monomer
gaseous acetylene in the presence of Ziegler-Natta catalyst such as Titanium
isopropaxide (Ti(OPr))4) and triethyl aluminium (Al(C2H5)3).
e.
Ti(OPr)4/Al(C2H5)3
CH HC
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Acetylene Polyacetylene

This polymerization involves metal insertion into the triple bond of the monomer.
Commercial Applications of Polyacetylene:
1. Used in the manufacture of chemical sensors, corrosion inhibitors.
2. Used in compact electronic devices such as polymer-based transistors, LEDs etc.
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Mechanism of conduction in polyacetylene: Conducting polymers are generally

produced by doping an oxidizing or a reducing agent into an organic polymer with
conjugated back bone consisting of pi-electron system.
An organic polymer can be converted into a conducting polymer if it has
1. Linear structure
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2. Extensive conjugation in polymeric back bone (Pi-back bone)

The conducting polymers are synthesized by doping, in which charged species are
introduced in organic polymers having pi-back bone. The important doping
reactions are;

1. Oxidative doping (p-doping)

2. Reductive doping (n-doping)
3. Protonic acid doping (p-doping)
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

1. Oxidative doping (p-doping): In this process, pi-back bone of a polymer is

partially oxidized using a suitable oxidizing agent. This creates positively charged
sites on polymer back bone, which are current carriers for conduction.
The oxidizing agents used in p-doping are iodine vapor, iodine in CCl4, HBF4,
perchloric acid and benzoquinone.

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 The removal of an electron from the polymer pi-back bone using a suitable
oxidizing agent leads to the formation of delocalized radical ion called polaron.
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 A second oxidation of a chain containing polaron followed by radical

recombination yields two charge carriers on each chain.
 The positive charges sites on the polymer chains are compensated by anions
I3- formed by the oxidizing agent during doping.
 The delocalized positive charges on the polymer chain are mobile, not the
dopant anions.
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 Thus, these delocalized positive charges are current carriers for conduction.
 These charges must move from chain to chain as well as along the chain for
bulk conduction On doping polyacetylene using iodine in CCl4, for partial
oxidation, the conductivity increases from 10-5 S.cm-1 to 103-105 S.cm-1.
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Applications:
 Fabrication of organic thin transistors.
 Non-volatile memory devices based on organic transistors.
 Fabrication of organic photovoltaic cells.
 Fabrication of organic light-emitting devices (OLED).
 Conducting polymer actuators and Micropumps.
 Focused upon polymer membranes that incorporated electronically
conducting polymers and piezoelectric polymers.
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Graphene Oxide:

Graphene oxide (GO) is two-dimensional material formed by the oxidation of graphene.

It is a single-atomic-layered material, when stacked together forms graphite oxide. It
contains hydroxyl (-OH), alkoxy (C-O-C), carbonyl (C=O), carboxylic acid (-COOH) and
other oxygen-based functional groups. These groups are attached to both the sides of
a single graphite sheet and overcome the inter-sheet van der Waals force and enlarges
the interlayer spacing and disturbs the sp2 bond of graphene so reduces the

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conductivity of graphene oxide. It has been successfully used in several applications in
electronics, conductive films, electrode materials and nano composites.

Synthesis:

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Take 2g graphene and 2g of NaNO3 (catalyst) in 50 ml of H2SO4 bath in 1000 ml
volumetric flask kept in an ice bath (0-5 oC) with continuous stirring for 2 hours. Then
add 6g KMnO4 (oxidizing agent) very slowly at temperature kept below 15 oC. After
some time, remove the ice bath and allow the mixture for stirring at 35 oC for 48
hours. Then dilute it with slow addition of 200 ml of water. Finally, treat the solution
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with 10 ml H2O2 to terminate the reaction and filter. After filtration, dry it in vacuum
at room temperature to get powdered graphene oxide.
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Properties:

 It is hydrophilic due the presence of hydroxyl, alkoxy, carbonyl, carboxylic acid groups.
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 It can mix with matrix such as polymer and ceramic to improve their
mechanical and electrical properties.
 It is hygroscopic and forms a strong hydrogen bond with water molecules.
 It has large surface area , so it is more reactive.
 It has low thermal conductivity (0.5-1 Wm-1K-1) as compare to graphite (3000-5000
Wm-
1K-1).
 It has low electrical conductivity than graphene.
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Applications:

 Graphene oxide can be used in coating technology,

 Graphene oxide papers can be used in desalination and reverse osmosis
techniques to get pure water from saline water.
 GO can be used in the biomedical fields such as drug delivery, cancer therapy,
bio- imaging and biosensor because of its biocompatibility nature.
 Nanocomposite of GO and silver (Ag) ions used for bacteria detection.

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 GO can be as a bio-imaging tool for cancer cells.
 Reduced GO that can be produced from GO is used as a transparent electrode
in polymer solar cells and LED.
 Reduced GO can be used as energy storage material in supercapacitors and in

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a lithium- ion batteries.
 Graphene Oxide-gold nanocomposites are good absorbents used for the
removal of industrial dyes from aqueous atmosphere and aromatic pollutants.

Electroless plating
e.
Definition: “The process of depositing a metal over substrate by controlled chemical
reduction of metal ion by a reducing agent without using electric current is called
electroless plating”
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Metal ions + reducing agent Metal + oxidized product

Electroless plating of copper: Electroless plating of copper involves the following features.

Pretreatment and activation of the surface: The surface to be plated is first degreased by
using organic solvents followed by acid treatment. PCBs are activated by first dipping in
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SnCl2 solution containing HCl followed by dipping in palladium chloride solution.

Composition of the bath:
Coating solution : CuSO4.5H2O (15g/L)
Reducing Agent : Formaldehyde (8g/L)
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Buffer : NaOH (15g/L) + Rochelle salt (14g/L)

Complexing agent : EDTA solution (20g/L)
PH 11
Temperature : 25 °c
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Chemical Reactions:

𝐀𝐧𝐨𝐝𝐢𝐜 𝐑𝐞𝐚𝐜𝐭𝐢𝐨𝐧: 𝟐𝐇𝐂𝐇𝐎 + 𝟒𝐎𝑯 → 𝟐𝑯𝑪𝑶𝑶 + 𝟐𝑯𝟐 𝑶 + 𝑯𝟐 + 𝟐𝒆

𝐂𝐚𝐭𝐡𝐨𝐝𝐢𝐜 𝐑𝐞𝐚𝐜𝐭𝐢𝐨𝐧: 𝑪𝒖𝟐 + 𝟐𝒆 → 𝑪𝒖

𝐍𝐞𝐭 𝐑𝐞𝐚𝐜𝐭𝐢𝐨𝐧: 𝟐𝐇𝐂𝐇𝐎 + 𝑪𝒖𝟐 + 𝟒𝐎𝑯 → 𝑪𝒖 + 𝟐𝑯𝑪𝑶𝑶 + 𝟐𝑯𝟐 𝑶 + 𝑯𝟐

Applications:

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 Widely used for metalizing printed circuit boards.
 For plating on non-conductors.

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 As an undercoat for electroplating.
 For decorative plating on plastics.
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Process: Activated plastic board on which circuit to be drawn is dipped in the

electroless plating bath solution. Two sides of the plastic board is get coated with
copper. Selected areas are protected and the copper in remaining area is etched away.
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Thus circuits are produced on either sides of the board. The connection between
circuits of two sides is made by drilling hole followed by plating through-holes. The
steps involved are shown above.

Distinguish between electroplating and electroless plating:

Property Electroplating Electroless plating

1. Driving force Power supply Autocatalytic redox reaction
2. Anodic reaction M Mn+ + ne- or -----

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Metal salt Mn+ + Xy-+ Metal salt Mn+ + Xy-+ ne-
ne-
3. Cathodic Mn+ + ne- M Mn++ Reducing agent M
reaction +
Oxidized product

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4.Anode Separate anode is required Separate anode is not required
5.Cathode Article to be plated (Pre- Article to be plated ( Pre-treated
treated to to
remove impurities) make the surface catalytically
active)
6. Nature of
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Not satisfactory for complex Satisfactory for all types of
deposit surfaces and intricate parts surfaces
7. Applicability Only for conductors For conductors, semiconductors
and insulators.
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