UNIT 1

ELECTRONIC MATERIALS: Inorganic semiconductors – Elemental – Si and Ge - band

theory, doping, compound semiconductors – band gap engineering – applications. Organic
semiconductors – conjugated polymers – mechanism of charge transport, doping, states of
aggregation, material properties – thermal, mechanical, electrical, chemical, electrochemical.
Applications – OLED, OPV – working principle. Liquid crystalline materials – display
application.
ELECTRICAL CONDUCTIVITY IN MATERIALS

Electrical conductivity in materials may be due to movement of electrons (electronic

conductors) or movement of ions (ionic conductors).

Examples:
For electronic conductors:
Metals like Ag, Au, Cu etc.,(electrical conductivity ranging 103 to 107 S/m),
semiconductors like Si, Ge, GaAs (10-3 to 107 S/m) and
Insulators like diamond, teflon (10-12 to 10-25S/m).
For ionic conductors:
Ionic crystals (Crystal defects: Frenkel, Schottky, metal excess, metal deficient) (10-16 to 10-2
S/m) and Solid electrolytes(lithium ion batteries) and liquid electrolytes ( lead acid batteries)
(10-1 to 103 S/m)

The high electrical conductivities in metals can be explained by the electron sea theory,
where metals are in a sea of delocalised free valence electrons. It explained all the
properties of metals.

It could not explain the electrical conductivity exhibited in semiconductors or in insulators.

Explanation for the electronic conductivity of semiconductors is explained by band theory of
solids. Band theory is extension of Molecular orbital theory (MOT) of covalent bonds to
solids. According to MOT, bonding between two atoms results from the linear combinations
of atomic orbitals (AO’s).

MOLECULAR ORBITAL THEORY (MOT)

Salient features of MOT:

• When two atoms approach each other, the atomic orbitals (AO’s) of one atom overlap
(linear combination of AO’s)with those of the other, generating Molecular orbitals
(MO’s).

• Only AO’s having similar energies and similar symmetries overlap with each other.

• The overlapping atoms lose their identity and their electrons are delocalised.

• When two AO’s overlap two new MO’s is formed. This is illustrated below for the overlap
between the s-orbitals of two atoms.
ORBITAL OVERLAP – BONDING AND ANTIBONDING ORBITALS:

Axial overlap – overlap along nuclear axis

1s-orbital of one atom and1s-orbital of another atom overlap to from two new molecular
orbitals, namely σ 1s and σ*1s. The two MOs are formed by constructive or destructive
overlapping of AOs.

Electron waves in-phase Electron waves out-of-phase

( Additive overlap) (subtractive overlap)
 Additive overlap – Bonding Subtractive overlap – Antibonding
Molecular orbitals Molecular orbitals
When electron waves in the two When electron waves in the two
approaching atoms are in-phase, approaching atoms are out-of-phase,
additive overlap or constructive subtractive overlap or destructive
overlap occurs. overlap occurs
Additive overlap leads to formation of Subtractive overlap leads to formation
a molecular orbital (or energy of a molecular orbital (or energy state)
state)that has lower energy than the that has higherenergy than the
overlapping atomic orbitals and is overlapping atomic orbitals and is called
called the BONDING MOLECULAR the ANTIBONDING MOLECULAR
ORBITAL (BMO). ORBITAL (ABMO), .
Since, the electrons in the BMOare Since the electrons in the ABMO are
most probably found between the most probably found away from the
nuclei of the two atomstheyare more region between the nuclei of the two
attracted to the nuclei and are atomsthey are less attractedto the
stabilised. nuclei and are destabilised. Hence
Hence, BMOs have lower energy ABMOs have higher energy than the
than the corresponding AOs. corresponding AOs.

The molecular orbital diagram for s-s overlap is as shown below:

EXTENSION OF MOLECULAR ORBITAL THEORY(MOT) TO SOLIDS – BAND THEORY:

Solids consist of large aggregation of atoms forming closely packed structures.

According to MOT, when two AOs overlap, two MOs are formed. One BMO and another
ABMO.

 In the case of a solid crystal, one mole of the solid will contain N ( Avogadro number
≈1023) atoms. When N atomic orbitals overlap N/2 BMOs and N/2 ABMOs ( in total N
MOs) are formed.
 The MOs are extended over the entire solid.
 As the number of overlapping atoms increase - the energy level spacing between
adjacent MOs decreases.
 In case of large aggregation of atoms, the spacing between adjacent MOs decrease to
such an extent that the levels appear to be almost continuous and are called energy
bands.
The formation of such energy bands in solids is illustrated below.

The electronic structure of solids can thus be described by a series of energy bands
consisting of allowed energy states or MOs.

 Electrons are distributed in the MOs following Afbau principle, Hund’s rule and Pauli’s
exclusion principle. Each MO can accommodate two electrons.
 The energy band containing MOs occupied by valence electrons is called the Valence
Band (VB). Every solid has energy bands that contain vacant MOs which can
accomodate electrons. These bands are called conduction bands (CB).
 The energy bands may or may not be separated by forbidden energy gaps, depending
on the type of material.
 ENERGY BAND FORMATION IN DIAMOND - INSULATOR

Diamond, one of the allotropes of carbon is an insulator (conductivity 10-13 S/m)

 The crystal structure of diamond

contains an extensive network of
C-atoms.
 Each carbon atom is linked to
four other C-atoms through
covalent bonds having equal bond
lengths.
 The bond angle is found to be
109⁰28’ i.e., each C-atom is
tetrahedrally surrounded by four
other C-atoms in the crystal lattice.

The tetrahedral orientation can be explained by invoking the concept of hybridisation.

The hybrid orbitals are formed by mixing of atomic orbitals within an atom and hence they are
atomic orbitals. These sp3 hybrid orbitals are then used to form covalent bonds with other carbon
atoms.
The energy band consisting of 2N completely filled BMOs is called the valence band and the energy
band consisting of 2N vacant ABMOs is called the conduction band.

The energy separation between the VB and CB ( BMOs and ABMOs) is high i.e., there is a
forbidden energy gap (Eg) which is around 5 eV ( 1 eV = 1.602 X 10-19 J).

Since C-atoms are small, overlapping of orbitals of one C-atom with neighbouring C-atoms is highly
effective. This high degree of overlapping between orbitals leads to a large energy gap between VB
and CB.

Excitation of electrons from VB to CB requires high energy and therefore there are no electrons
available in the conduction band at room temperature. This is the reason why diamond is an
insulator.

ENERGY BAND FORMATION IN SEMICONDUCTORS

INTRINSIC ELEMENTAL SEMICONDUCTORS - SILICON AND GERMANIUM:

Si and Ge belong to C- group but solid Si and

Ge are semiconductors.

Si – conductivity - 1.56 X 10-3 S/m ;

Ge – conductivity - 2.17 S/m; Ge has better

conductivity than Si

SILICON: Solid silicon also crystallizes into a

diamond like lattice with each silicon atom
tetrahedrally surrounded by four silicon atoms.
Each Si atom uses its four sp3 hybrid orbitals
to overlap with the sp3 hybrid orbitals of other
SI atoms.
The energy band consisting of 2N completely filled BMOs is called the valence band and the energy
band consisting of 2N vacant ABMOs is called the conduction band.

The energy separation between the VB and CB is intermediate and Eg is around 1.1 eV

This gap is lesser than that in diamond. This is because Si atoms are larger than C-atoms and the
orbitals of Si do not overlap effectively. Lesser the degree of overlapping smaller is the energy gap
between bonding and antibonding states.

Since the energy gap is small, at room temperature, there is significant population of electrons in the
conduction band (due to thermal excitation). These electrons in the conduction band are responsible
for the intrinsic semiconducting nature of Si (conductivity is 1.56 X 10-3 S/m).

GERMANIUM :
Ge – electronic configuration [Ar] 3d10 4s2 4p2
Ge also is a diamond like crystal and the bonding is similar to that in Si and diamond. But Ge is
larger than silicon. Hence the extent of overlapping between the orbitals of Ge is less compared to
that in Si and the forbidden energy gap is smaller than in silicon (0.7 eV).
SMALLER THE BAND GAP GREATER IS THE CONDUCTIVITRY. Hence Ge has better
conductivity than Si ( 2.17 S/m).
GENERAL CHARACTERISTICS OF SEMICONDUCTORS:

 Forbidden energy gap is between 1 to 3 eV.

 The Fermi level of a semiconductor is the level at which the statistical probability of finding
electrons is 50% and it lies in the mid of the forbidden gap.
 At zero kelvin (0K), there are no electrons in the conduction band. Therefore at 0K a
semiconducting material behaves as an insulator.
At higher temperatures, few electrons gain enough energy to overcome the energy gap and enter
the conduction band, where they are free to move and conduct electricity.
 Charge carriers:
 In semiconductors, as electrons leave the VB and enter the CB, they leave holes in the VB.
Holes are electron deficient sites and holes also act as charge carriers.
 In an intrinsic semiconductor, one which has no impurity and defects, the concentration of
holes and electrons are equal.
n = p where n is the number of electrons and p is the number of holes.
 At a given temperature the square of the intrinsic carrier concentration is equal to the product
of hole and electron concentration.
ni2 = n X p ; ni is the intrinsic carrier concentration.
 The electrical conductivity for an intrinsic semiconductor,
σ = ni X e X (µe + µh) where
ni is the intrinsic carrier concentration;
e is the electronic charge;
µe and µhare the mobilities of electrons and holes, respectively.
Mobility of holes is lower than mobility of electrons.

 Factors influencing electrical conductivity:

 Temperature: As temperature increases, more number of electrons are excited to the
conduction band and conductivity increases.
 Band gap : Smaller the band gap, greater is the conductivity
 Impurities:Conductivity in semiconductors is very sensitive to minute levels of defects such
as substitutional [Link] impurities can be added to semiconductors to
improve their [Link] deliberate addition of impurities is called as doping.
EXTRINSIC SEMICONDUCTORS OR DOPED SEMICONDUCTORS :

Substitutional impurities added deliberately to Silicon. When a pentavalent element is doped in

silicon in n-type silicon is obtained and when a trivalent impurity is added a p-type Si is
obtained. Doping is done by diffusion from gas phase or by ion implantation. Doping concentration
for Si semiconductors may range anywhere from 1013 to 1018 atoms/cm3. (Silicon atomic density is 5
x1022atoms/cm3). But generally doping is done in the range of parts per billion parts of silicon.

n-type semiconductors:

Si wafer is doped with pentavalent impurity atoms like P,As or Sb. Suppose a few atoms in Si are
replaced by P atoms. P is about the same size and electronegativity as Si. Thus the lattice structure
maintains the diamond structure and the band structure is also unaltered.

4 SP3 hybrid orbitals forms covalent bonds with neighbouring four Si atoms. The extra electron acts
as charge carrier. In the energy band diagram, the energy of the additional electron that does not
participate in bonding is near the conduction band. Thus, the additional electrons can easily get
excited to the conduction band. Thus results in improved conductivity in Si.

The conductivity of doped Si will be proportional to the number of P atoms

substituted for Si atom. Since doping introduces extra electrons, majority charge
carriers are the electrons and hence give a n-type silicon.

p-type semiconductors

They are obtained by doping Si or Ge with trivalent impurities like B, Ga, In and Al.
When B is substituted for Si atom, it forms three covalent bonds with three Si atoms using its
three sp3 hybrid orbitals. The fourth sp3 hybrid orbital of B is non-bonding. The fourth Si atom
nearby the B atom has a missing electron or hole. With little energy, an electron from a near
by Si-Si bond can jump to the electron deficient centre. This leaves the nearby Si atom with
a hole. This hole is free to move through the solid if a voltage is applied. The holes travel
through the solid by breaking an existing covalent bond in the adjacent Si atom and
formation of a new bond.

In the case of energy bands of Si doped with trivalent impurities, the non-bonding MOs of the
impurities are close to the valence bond. Thus, electrons from the VB can be easily excited
to the non-bonding MOs and thus conductivity is improved. Excitation of electrons leave
behind holes in the VB. These holes can move in an applied field and hence they are the
majority charge carriers. Thus, they are p-type semiconductors.

Energy band: n-type semiconductor p-type semiconductor

COMPOUND SEMICONDUCTORS OR MIXED VALENCE SEMICONDUCTORS:

Binary compounds:

Compound semiconductors are combination of III and V group elements or group II and VI
elements or IV group with another IV group element in 1:1 ratio.

(A) III-V compound semiconductor :

Example - Gallium phosphide ,GaP

It is a mixed valence solid with crystal structure similar to Zinc blende. The crystal structure
consists of a cubic lattice of Ga and P atoms in 1:1 ratio wherein each Ga-atom tetrahedrally
surrounded by four P –atoms and each P-atom tetrahedrally surrounded by four Ga –atoms.

The crystal structure and semiconducting nature of GaP can be explained as follows.

Each atom is bonded to four other atoms, with all four bonds with equal bond length and
bond angle. This can be explained by considering the atomic orbital hybridisation and their
overlap as shown below.

The sp3 hybridised orbitals are oriented in a tetrahedral manner.

Energy band diagram:

In one mole of solid GaP i.e., N atoms, there will be N/2 Ga-atoms and N/2 P-atoms. All the
Ga and P atoms provide 4 N sp3 hybrid orbitals for covalent bonding and the average
number of valence electrons per atom that are involved in bonding are four. The 4 N sp3
hybrid orbitals overlap to form 4 N MOs i.e., a band of closely spaced 2N Bonding MOs and
another band of closely spaced 2N antibonding MOs. There is an energy gap of 2.3 to 2.5
eV. All 4 N valence electrons occupy the 2N bonding energy states and this band and the
antibonding states are vacant. The energy band consisting of completely filled bonding
energy states is the valence band and that consisting of vacant energy states is called the
conduction band.

At ambient temperatures, some electrons in the VB are overcome the energy gap and are
excited to the conduction band, and are responsible for the semiconducting nature of GaP.
(A) II-VI compound semiconductor :

Example - Zinc selenide, ZnSe

It is also a mixed valence solid with crystal structure similar to Zinc blende i.e., each Zn-atom
is tetrahedrally surrounded by four Se –atoms and each Se-atom istetrahedrally surrounded
by four Zn –atoms.

The crystal structure and semiconducting nature of ZnSe can be explained as follows.

The tetrahedral orientation of atoms in the crystal lattice is explained by hybridisation and
overlap of atomic orbitals as shown below.

The sp3 hybridisation explains the tertrahedral orientation of the atoms in the crystal
structure.

Energy band diagram:

In one mole of solid ZnSe i.e., N atoms, there will be N/2 Zn-atoms and N/2 Se-atoms. All
the Zn and Se atoms provide 4 N sp3 hybrid orbitals for covalent bonding and on an average
four valence electrons per atom are involved in bonding.

Overlapping of the orbitals leads to the formation of energy bands, one of lower energy,
consisting of closely spaced 2N bonding MOs and is completely filled with the 4N valence
electrons, denoted as valence band and the other of higher energy consisting of closely
spaced 2N antibonding MOs, denoted as conduction band. There is an energy gap of 2.7 eV
between the valence band and conduction band. The excitation of electrons from valence
band to conduction band leads to its semiconducting nature.

BAND GAP ENGINEERING IN COMPOUND SEMICONDUCTORS - EFFECT OF

PERIODIC PROPERTIES

Band-gap engineering is a powerful technique for the design of new semiconductor materials
and devices. One of the ways of band gap engineering is alloying different elements of
mixed valency and controlling the composition of the alloys. The band gap in mixed valence
semiconductors depends on extent of overlapping between orbitals of the combing atoms.
Greater the extent of overlapping, larger will be the band gap. The extent of overlapping
between orbitals depends on two factors:

(a) Atomic size:

The extent of overlapping of orbitals increases as the size of the component elements
decreases. The atomic size increases down the group in the periodic table and hence the
band gap of a compound semiconductor decreases, as an element with larger size is
combined to form the semiconductor.

For example,

The band gap in GaAs is smaller than that in GaP. As is larger than P. Therefore the extent
of overlapping of orbitals of Ga and As is less than that found in GaP.

The band gap of GaP is smaller than that in AlP. Al is smaller than Ga. Therefore the atomic
orbitals of Al and P overlap more effectively than Ga and P. Therefore the band gap is larger
in AlP.
(a) Electronegativity difference:

When there is significant electronegativity difference between two combining atoms, the
atoms approach close to each other due a partial ionic character of the bond and the atomic
orbitals overlap more effectively, leading to a large band gap. Greater the electronegativity
difference between the component elements in a compound semiconductor, the larger is the
band gap. Electronegativity increases along a period in the periodic table.

For example,

The band gap in GaAs is 1.35eV and that in ZnSe is 2.58eV though the average size of Ga
and As is the same as that of Zn and Se. Therefore the differences in the band gap energy
can be explained only by the differences in the electronegativities. The electronegativity
difference between Zn and Se is more than twice as in GaAs i.e., electronegativity
difference is 0.9 in ZnSe and 0.37 in GaAs.

APPLICATIONS :

Several applications like laser diodes for optic fibre communication, LEDs, photodetectors
require materials with tuned band gap. For such applications mixed valence - binary, ternary
and quarternary alloys with controlled composition are useful.

Examples:

1. For making a blue diode ( band gap 3eV or wavelength 415nm), Binary alloys, Group III
element can be combined with nitrogen (highly electronegative and small size). Example:
GaN – band gap 3.34eV.

2. Ternary and quaternary alloys also can be synthesized with the desired band gap for
optical applications, by controlling the mole fractions of each element in the alloy.

For example

Alloys Color of light emitted

Ga P0.4 As0.6 red

Ga p0.65 As0.35 Orange

Ga P0.35 As0.15 Yellow

GaP Green

3. Gallium Indium Arsenide Phosphide (GaInAsP) is used in optic fibre communication.

4. Copper Indium Gallium Selinide semiconductor (CIGS) used in solar cells.

5. Mercury Cadmium Telluride (HgCdTe) is used in infrared photodetectors.

ORGANIC SEMICONNDUCTORS - CONJUGATED POLYMERS

Inherently, organic polymers with all carbon backbones are insulators and their resistivity is
decreased by adding metals or with carbon black etc.,

Intrinsically conducting polymers have a backbone chain containing conjugated π- bonds

(alternative double and single bonds). The conductivities in such polymers is due to the
delocalization of π-electrons along the chains.

ELECTRICAL PROPERTIES OF CONJUGATED POLYMERS:

Majority of conjugated polymers are semiconducting and have energy gaps in the range of
1.5 to [Link] conductivity can be tuned by chemical manipulation of the polymer
backbone, by doping or by blending with other polymers. These conducting polymers are
used because of their light weight, easily processable and flexible.

Examples of conjugated polymers are given below.

Polymer Structure Typical methods Typical Band
of doping conductivity in gap in
S cm-1 eV
Electrochemical / 500-1.5 x 105 1.4 for
Polyacetylene Chemical (AsF5 , trans
n I2, Li, K) 2.0 for
cis
Chemical (AsF5, 1
Polyphenylene Li, K) 3.0
n

Poly(phenylene Electrochemical 600 --

sulphide) S
n
Polypyrrole Electrochemical 100 2.5

N n
H
Electrochemical / 50 2.0
Polythiophene Chemical
n (sodium
S
naphthanilide)

Polyaniline Electrochemical / 5 --
N Chemical (HCl)
n
(I) EXPLANATION FOR SEMICONDUCTING BEHAVIOUR:
Electronic Structures and energy bands:

Let us consider polyacetylene , In the polymer

chain each carbon is sp2 hybridized and it is planar.

H unhybrid p-orbitals
H
C
C C
C 2
SP hybrid orbitals
C
H
H

Excited electronic configuration of C :

one p-orbital left unhybridised

4 SP2 hybrid orbitals

Each carbon uses two of its sp2 hybrid orbital to overlap with the hybrid orbitals of
two neighbouring C-atom and the third hybrid orbital to overlap with s-orbital of H-atom.
Each C-atom has an unhybridised p-orbital which overlaps with the p-orbital of
neighbouring C-atom laterally, to form a π-bond; these π-electrons are delocalized.

Formation of energy bands:

For applying the molecular orbital theory to systems having conjugated π-bonds, the
Huckel’s approximation is used. According to this theory only π- molecular orbitals are
considered in the energy level diagram and σ – molecular orbitals are ignored.

When the number of C-atoms or conjugation increases, the energy levels (π-MO’s) can be
given as:
  There is a forbidden energy gap between the highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO).
 Most conjugated polymers have energy gap in the range of 1 to 3.5 eV. Hence the
polymers are semiconducting. The energy gap reduces as the length of
conjugation increases.
 As temperature increases conductivity of organic semiconductor increases.

(II) DOPING OF π-CONJUGATED SYSTEM:

Undoped conjugated polymers show poor conductivity (in the range of 0.1 – 1 S/cm).
Their conductivities can be improved by introducing charge carriers in the polymers
by doping.

 Doping is a charge transfer reaction between the polymer and dopant resulting in
partial oxidation or reduction of the polymers. Dopants are either electron acceptors
(oxidising agents) or electron donors (reducing agents).
 Oxidation of the polymer chain (removal of electron called oxidative doping results
in the formation of electron deficient centres in the polymer chain and hence is called
p-type doping. The charge carriers formed are called positive polarons or
bipolarons.
 Reductive doping (addition of electrons) results in formation of electron rich centres
in the polymer and hence is called n-type doping. The charge carriers formed are
called negative polarons or bipolarons.
 In the doping of inorganic semiconductors, the dopant concentration required is in
ppm or ppb. But in doping of conjugated polymers 1 to 6 % of dopant is required to
increase the conductivities.
 For example : Polyacetylene

(A) Oxidative doping (p-type doping): p-type doping is the removal of electrons from the
valence band (HOMO) of the conjugated polymer by an oxidizing agent. The common p-type
dopants are Br2, I2, AsF5, FeCl3 etc.,

I2 vapours
removal of e-s

COUNTER ION

RADICAL CATION OR POSITIVE

POLARON
removal of e-s
The combination of charged site
(positive) coupled with a free radical is
called as positive polaron.
.
The polaron can further lose an
electron to form a bication or a
bipolaron.

POSITIVE BIPOLARON

The counter ion of the dopant is attached to the charge carriers and travel along with the
carriers during conduction. In the above case, the counter ion is I3- . The counter ion
neutralises the extra charge created by oxidation or reduction and hence the doped
polymer is essentially electrically neutral.

The energy band diagrams shown above clearly indicate that due to formation of positive
charge carriers in the polymer chain, energy states are introduced between the valence and
conduction bands. This leads to decrease in band gap energy and hence conductivity
of the polymer is increased.
(B) Reductive Doping (N-Type Doping): The addition of electrons by a reducing agent to
the vacant conduction band states (LUMO) of the conjugated polymers. Examples for n-type
dopants are sodium naphthalinide, Na/K alloy, molten potassium, LiI etc.

addition of e-s sodium naphthalinide

COUNTER ION

RADICAL ANION OR NEGATIVE

POLARON

The combination of charged site

(negative) coupled with a free radical
is called as negative polaron.

Addition of electron The polaron can further gain an

electron to form a bianion or a
bipolaron.

NEGTIVE BIPOLARON

bianion or a bipolaron.

Due to reductive doping negatively charged conjugated polymer chains with counter cations
are formed. Conjugated polymers are already electron rich due to the π conjugated system.
n-type doping requires strong reducing agents like alkali metals.
Energy states of the charge carrier sites on the polymer are introduced between the valence
band and conduction band. And there is a decrease in band gap and hence increase in
conductivity.

Effects of Doping:
 In both oxidative and reductive doping, polarons and bipolarons are formed, which
act as charge carriers and enhance the electrical conductivity. In both cases less
energy is required for excitation of electrons from HOMO to LUMO due to
intermediate energy states of the charge carrier sites, thus increasing the
conductivity.
 Doping leads to stiffening of the polymer chains due to increase in intermolecular
forces of attraction.
 . Due to the intercalation of counter ions between polymer chains during doping,
there is slight swelling in the polymer.
 In some cases the solubility of the polymer is improved by the use of a dopant with a
suitable counter-ion.
(III) CHARGE TRANSPORT IN CONJUGATED POLYMERS:
(A) Intrachain, interchain and intergrain charge transport
Inorganic semiconductors are perfectly crystalline and hence facile charge transport occurs
in them.
But polymers generally have a semicrystalline morphology with crystalline (polymer
molecules are arranged in order) and amorphous (polymer molecules are randomly coiled)
regions. (THE DEGREE OF CRYSTALLINITY DEPENDS ON THE SYNTHESIS AND
FABRICATION METHODS)

For a conjugated polymer to exhibit electrical

conductivity charge transport should occur
a) within a polymer chain – Intra chain charge
Amorphous region
transport
b) between polymer chains – Interchain charge
Tie molecules
transport
c) between crystal grains – Intergrain charge
Crystalline region
transport

i) Intrachain charge transport : The intrachain charge transport occurs by migration of the
π - electrons along the backbone chain and is facilitated by charge carriers (polarons and
bipolarons)

Migration of holes along the chain Migration of electrons along the

chain

ii) Interchain charge transport : The polarons and bipolarons can be transferred from one
polymer chain to another through redox reactions between neighbouring chains. This
process is favourable if the neighbouring polymer chains are properly aligned.

This electron transfer requires proper alignment of polymer chains and hence the interchain
charge transport is favoured by greater crystallinity.
iii) Intergrain charge transport: The charge transport occurs by migration of electrons from
one crystal grain to another through tie molecules ( which connects the crystalline and
amorphous region)

(B) CHARGE CARRIER MOBILITY:

Conjugated polymers have much lower carrier nobilities (10-5 to 10-6 cm2 V-1 s-1) compared to
inorganic semiconductors (in GaAs its about 103 to 104 cm2 V-1 s-1).
Reasons for lower charge carrier mobility:
1. Disorder in polymer chains: The most important requirement for facile π-electron
delocalisation is planarity in the polymer chains. Structural defects in the polymer chain can
cause a disruption in π-conjugation or distortion from planarity in the chains and hence
decrease the mobilities of the charge carriers. The common defects are:

(i) SP3 defects : All C- atoms are sp2 Polyacetylene

hybridised. Some C-atoms along the chain ii) branching of the chains : It distorts
3
may be sp hybridised thus breaking the the planarity of the π-conjugated chains.

conjugation. On either side of the defect

the π-conjugated chains lie on different
planes.

iv) Cis-segments within trans segments

: Distorts planarity in the polymer chain.

iii) Crosslinks: It breaks the π-

conjugation and distorts the planarity.

2. Lesser crystallinity in polymers: Highly crystalline conjugated polymers have lower

solubilities and this makes their processing difficult. In order to improve their solubility,
conjugated polymers are synthesised using substituted monomers. For example: To
synthesis polythiophene, alkyl substituted monomers can be used.

This side groups prevent the close packing of polymer chains and thus increase its solubility
of the polymers. But this decreases the interchain charge transport.
[Link] weight :

Smaller crystal grains are formed but

polymer molecules are oriented in different
directions in neighbouring grains, though
interchain transport is favoured, there are no
tie molecules, intergrain charge transfer is
If the molecular weight of polymer is less, hindered. Thus it lowers the charge carrier
molecules are arranged in shorter chains. mobilities.

If the molecular weight of polymer is high,

larger crystal grains are formed with
connecting tie molecules, Intergrain charge
transport is favoured.

Since the carrier mobilities are less due to the reasons mentioned above, higher
levels of doping is carried out to achieve higher conductivities

ACHIEVING GOOD CONDUCTIVITY IN CONJUGATED POLYMERS:

From the above explanation it is clear that the conductivity of conjugated polymers can be
improved by synthesising the polymers with the correct morphology and by doping.
Conductivity
 increases slightly with increasing molecular weight of the polymer as shown in Fig.2
 increases considerably with increasing crystallinity in the polymers.
Highly ordered crystalline polymers can be produced by forming fibrous polymers by
spinning techniques and ordered thin films can be produced by electrochemical synthesis
and by self- assembly methods.
Further improvement in crystallinity is achieved by stretching or drawing the fibres or
films to different extents. Stretching aids in orientation of the polymer chains, thus increasing
the crystallinity. The conductivity increases with increasing crystallinity and hence the
stretching increases conductivity shown in Fig 1.
Fig.1 Fig.2
OTHER PROPERTIES OF CONJUGATED POLYMERS:

SOLUBILITY:
One of the important criterion for easy processability of conducting polymers is their solubility.
Many of the conducting polymers are soluble in specialised solvents which are difficult to handle
and hazardous. Also the doped polymers are less soluble than the undoped ones.
In order to improve their solubility, one of the methods adopted is introducing side
groups in the backbone chain. This reduces the close packing of the polymer chains and hence
improves their solubility.

For example

THERMAL PROPERTIES:
When a conducting polymer is heated, phase transitions and decomposition occur in the
polymer. Conducting polymers exhibit thermoplastic behaviour i.e., they soften on heating and
harden on cooling.
The thermal transitions observed in the polymers when heated are :
1. Glass transition 2. Melting 3. Degradation

(i) Glass transition:

At low temperatures molecular motion in the amorphous regions is restricted to molecular
vibration, but chains cannot rotate or move in space. This form is the glassy state of the
amorphous region. It can be thought of as being a super cooled liquid where the molecular
motions have been frozen. This state is hard, rigid and brittle like a crystalline solid, but retains
the molecular disorder of a liquid.
When the material is heated the polymer will reach a temperature at which segments
(20-50atoms long) of the entangled chains can move. At this temperature, called the glass
transition temperature, the amorphous region of the polymer becomes rubbery. In this state the
polymer will be soft and flexible. Thus the temperature at which polymer undergoes
transition from glassy solid state to rubbery state is known as “glass transition
temperature”(Tg).
Above the glass transition temperature,
segmental mobility sets in the polymer
chains and there is considerable expansion
in the polymer as shown in the specific
volume Vs temperature graph i.e., the
polymer loses its dimensional stability
above its Tg.

In electronic applications the polymers may be exposed to higher temperatures due to

electrical heating and if they undergo glass transition they may expand and get detached from
the substrate. Hence it is desirable to use polymers with high glass transition
temperatures.
Most of the conducting polymers satisfy this requirement as they have high Tg (~ 70-
80℃ ) because the π- conjugated backbone gives rigidity to the chains (thus restricting
segmental mobility). Moreover, doping causes stiffening of the chains and further increases the
Tg.

(ii) Melting:
On heating further, the polymer is converted into molten state at a particular temperature called
the melting point (Tm) this is transition is the characteristic of the crystalline region of the
polymer. Polymers do not have a sharp melting point and melt in a given temperature range.
Conducting polymers have fairly high melting points. Their melting points depend on the side
groups attached to the backbone. If longer alkyl groups are attached, the melting point
decreases.
For example:
In poly (3-alkyl thiophenes), with butyl, hexyl and octyl substituents have [Link] of 275, 190 and
150°C respectively.

(iii) Decomposition – Thermal stability:

Conjugated polymers have reasonable thermal stability upto ~140℃ without any conductivity
loss. Thermal stability of polymers are determined by thermal analysis called thermogravimetric
analysis (TGA) in which the mass of the polymer is monitored with increase in temperature. If
there is any mass loss, it indicates that there could have been a decomposition in the polymer
and the temperature at which mass loss occurs is called the decomposition temperature.
The decomposition temperature depends on the dopant ions present in the
polymer sample because the dopant ions undergo decomposition. The Fig 1 shows the
TGA of (A) polyacetylene, (B) polyacetylene prepared using AsF5, and (C) polyacetylene
prepared using AsFs/AsF3. The curves B and C clearly show that the doped polymers undergo
decomposition (weight loss) at lower temperatures ~200-250℃ and the undoped polyacetylene
(Curve A) undergoes decomposition (weight loss) at ~400℃

Fig. 1 Fig.2
Similarly Fig.2 shows the TGA curves of undoped (curve A) and doped
poly(phenylenesulphide). The doped polymers stability is drastically decreased.
When the polymers are subjected to thermal/environmental stability test by monitoring
the conductivity as a function of prolonged exposure to high temperatures or extreme
environments, some polymers show that upto a temperature of 70℃ an initial, thermally induced
conductivity increase is found but it is followed by steady decrease, even after heat is turned off,
until the temperature reaches room temperature; the effect is more pronounced for a thinner
polymer film.

The above figure shows the conductivity decay with time in 15µm and 90μm poly(3-
octylthiophene) films when exposed to temperatures above 70℃.
Thus the side groups attached to the polymer backbone and the dopant used have a
profound effect on the thermal properties of conjugated polymers.

MECHANICAL PROPERTIES OF POLYMERS USED IN ELECTRONICS:

(A) Significance of mechanical properties in flexible electronics:
Flexible electronics are the latest development in the electronics field. Flexible electronics may
involve electronic devices mounted on plastic substrates like polyimide, polyether ether ketone
(PEEK) or a transparent polyester film which is made conductive.

The active electronic components may be organic electronic materials attached to plastic
substrates. Their applications include flexible displays (curved Tv’s, flexible mobile phones),
wearable electronics for sensor applications, organic photovoltaics ( Which can be attached to
window screens or even attached to textile fabrics that can be used to power mobile phones).
These materials are light weight, in addition to being flexible.

Causes of failure in flexible electronic devices:

Failure may occur in a flexible electronic device due to bending and stretching forces during
their service life.
A flexible electronic material contains a plastic substrate coated on either side by a film of the
active materials. While bending different layers in the material experience different kinds of
stress as shown below and may fail due to cracking and delamination.
Hence the mechanical properties of the individual polymeric materials are tested.

Other causes of premature damage in flexible electronic materials:

Premature damage in a flexible electronic device may be caused due to other types of stresses
developing in the materials.
 Intrinsic stress -: Flexible electronics are usually fabricated by vapour deposition of
films on substrate or by solution processing (film is formed by evaporation of solvent).
During such fabrication stresses may develop in the film due to shrinkage. This is called
intrinsic stress and may cause damage.

 Thermal stresses - develop during cooling of the materials from the process
temperature during fabrication or temperature variations during service because of the
mismatch in the thermal expansion coefficients of substrate and the active film.

 Hygroscopic stresses - develop on exposure to ambient humidity because of mismatch

in hygroscopic expansion between material constituents. All the above kinds of stresses
may be tensile or compressive.

In order to achieve high-dimensional stability and avoid premature damage in multilayer

architectures, advanced analyses of coefficients of thermal expansion and hygroscopic
expansion of all the material constituents are done, in addition to mechanical testing.

The mechanical properties that are usually measured are tensile strength, flexural strength, tear
strength, fatigue, impact resistance and hardness. These mechanical properties are analysed
using their stress-strain analysis.

(B) Stress-strain analysis of polymers:

This experiment is done by subjecting the polymer to a stress and the force developed and the
extent of deformation in the material is measured continuously.
There are three basic types of stress measurement namely
(i) Tensile stress – material is subjected to stretching force.
(ii) Compressive stress – material is subjected to ‘squashing’ forces.
(iii) Shear stress – material is subjected to ‘push – pull’ forces.

The response of the polymer to the mechanical force applied is given as a stress-strain data by
the instrument, where
Stress ( σ ) is defined as the force per unit area.

Stress ( σ ) = Force / Area

Strain (ϵ) is the amount of deformation per unit length of the material due to the applied load.

ϵ = l –l0 / l0 Where l is the instantaneous length and l0 is the original length of the polymer
sample.

From the stress-strain graphs obtained drawn from the data, several useful quantities like
modulus or stiffness, yield stress and strength and elongation at break can be determined.
Young’s modulus: It is evident from the stress-strain graphs, that the initial portion is fairly
straight indicating a linear relationship between the stress and the strain. The material behaves
like a spring initially i.e., when the load is removed, the material recovers its original length.
The slope of the stress-strain graph in the initial linear region gives the young’s modulus
or tensile modulus or modulus of elasticity. In other words, young’s modulus is the ratio of
stress to strain. For many polymers, the initial elastic region is not linear and hence it is not
possible to determine the modulus from the slope. In such cases, a tangent modulus may be
used.
The modulus indicates the stiffness of the polymer (ability to resist deformation).

Yield point : The linear part of the stress-strain curve further gives way to a bend and beyond
this point the polymer is no longer elastic. Large extensions are produced by relatively small
increases in the stress and most of the stretch is irrecoverable. This bending or yielding region
is called as yield point and is defined in terms of the yield stress and yield strain.

Toughness : This is the energy or work required to break the polymer sample. The area under
the stress-strain graph is a measure of the toughness of the material.

Tensile strength: The stress at which the fracture of the material occurs is called as the tensile
strength i.e., the maximum stress than can be sustained by a material in tension.

The different types of stress-strain graphs

that can be obtained while testing polymers,
and the inference drawn regarding the
mechanical properties for each type of
graph is shown in the figure.
The properties like tensile modulus and tensile strength increase with increase in
crystallinity in a conducting polymer. This is shown by the following figures , which
indicate that these parameters increase on stretching the polymer (draw ratio).

Also conductivity of the polymers increases as the modulus increases as shown in the
figure given below.

Selection of polymers for flexible electronics based on bending tests:

The stress-strain analysis of multilayer

(b) critical strain, εcrit. -the
electronic devices under bending is
extent of deformation occurring
important.
before fracture.
The selection of material for designing a
flexible electronic device is based on two
critical parameters that are obtained
from bending tests,
(a) critical radius of curvature, Rcrit, - the
radius of curvature at which device failure
occurs because of mechanical damage or
functional failure.

The selection critera are given below:

For designing flexible electronics – Thin films that can be safely bent down to a radius of
curvature of 10mm with εcrit < 2% (less stretchable) are suitable.
For designing compliant electronics - Films which can be bent to a radius of curvature of
few mm and can be stretched more ( εcrit = 2 to 10%), are suitable for use in compliant
electronics, as in actuators. They can be attached to thicker substrates.
For designing stretchable electronics - Films for which εcrit > 10%, can be bent to a small
radius below a few millimeters. Such films are suitable for stretchable electronics like
electronic skin.
The calculation of the critical radius requires knowledge of critical strain, thickness and
young’s modulus of both film and substrate.
ELECTROCHEMICAL PROPERTIES OF CONDUCTING POLYMERS:

 One of the most important characteristics of conducting polymers is their ability to undergo
reversible electrochemical redox processes.
 When conducting polymers are soaked in electrolytes, connected to electrodes and made
positively biased (using a potentiostat), electrochemical oxidation occurs, resulting in the
formation of positive polarons and bipolarons in the polymer.
 The formation of positive charge carriers is accompanied by the entry of counter anions into the
polymer. This process can be reversed by changing the polarity of the polymer (negative). In the
reverse process, reduction occurs and the positive charge carriers that were created in the
previous step are nullified. This is accompanied by the expelling out of the counterions.
 The entry and exit of counter-ions during the electrochemical reversible redox process, makes
the polymer to expand and contract, respectively.
 Similarly if the polymer is made negatively biased, negative charge carriers are formed in the
polymer by reduction and it is accompanied by the entry of counter cations into the polymer.
This process also can be reversed by changing the polarity imposed on the polymer.
 Such electrochemical redox reactions are stable and reversible in a given potential range.
 At higher potentials the conducting polymer undergoes rapid structural degradation and loss of
electroactivity.
 This electrochemical redox capability is made use of in several applications like
pseudocapacitors, battery electrode materials, electrochromic displays,
electrochemomechanical actuators.

1. Electrochemical Capacitors: In pseudocapacitors the charge storage is by redox reactions ( Faradaic

mechanism). Pseudocapacitors provide higher specific capacitance and energy density.
2. Actuators : During the electrochemical doping (redox processes), insertion and deinsertion of
ions/solvent into and out of the conducting polymer matrix, leads to swelling and deswelling of
conducting polymers.

Polymer chains become positively charged when electrons are extracted by oxidation. Small anions are
inserted into the polymer matrix in order to maintain overall charge neutrality. Ionic crosslinks are
formed between polymer chains and anions, resulting in an increase in the total volume. The dopant
anions can be expelled during electrochemical reduction by the application of negative voltages.
Such electrochemically induced expansion and contraction is termed as
Electrochemomechanical actuation which implies an applied potential which leads to a chemical redox
reaction, which in tum leads to a mechanical deformation.
if a bilayer of a CP and another substrate which is flexible but does not swell or contract is created,
electrochemical or chemical redox of the CP will lead to bending of this bilayer.

This mechanism can be utilised to create artificial muscles. The angle of bending depends on the applied
voltage and the muscle can be held at any position by simply switching off the potential.

3. Electrochromism : During electrochemical redox processes, color changes are produced in the
polymer, a pheneomenon called electrochromism. This makes the CP’s attractive for electrochromic
displays, smart windows and rear view mirrors. The electrochemical doping results in reduced energy
gap for the π to π* transition.

For example, polyaniline exhibits color changes from transparent yellow to green, blue, and
violet. The electrochromic properties of CPs depend on chemical structures, redox capability,
temperature, and the pH of the electrolyte solution.
CHEMICAL PROPERTIES - DEGRADATION

Conducting polymers tend to undergo degradation when exposed to UV light and oxidative
environments. The photo and oxidative attack most often leads to the generation of free radicals.
Impurities present in the polymer may form free radicals or free radical sites may be formed in the
polymer itself. Free radical further attack polymer molecules leading to fragmentation of the
polymer chains into low molecular weight chains.
PROTECTIVE ADDITIVES:
In order to protect polymers from the above types of degradations protective additives are added.
PHOTOSTABILISERS OR UV STABILISERS:
These additives absorb harmful UV light and dissipate the energy as heat, thus protecting the
polymer from UV attack.
Examples TiO2, and other organic additives like benzophenone derivatives
METAL ION DEACTIVATORS:
 ORGANIC LIGHT EMITTING DIODES:

An OLED is a device which emits light under application of an external voltage, a phenomenon called
electroluminescent. These are made with organic electroluminescent material (emit light when
stimulated by applying an electric field) . These materials are small organic molecules or organic
polymers.
Advantages of OLEDS over inorganic Advantages of OLED based flat panel displays over
semiconductor based LEDs: Liquid crystal displays (LCDs):

 Light weight  Ease of fabrication of large area flat panel

 flexiblility displays
 color tenability by varying substituents  Fast switching speed
 Ease of processability  Light weight and flexibility
 Low operating voltage
 No backlight is required
 Wider viewing angle

COMPONENTS OF AN OLED:

1. Substrate emitting diodes, PLED).

The substrate is used to support the OLED.
The substrate most commonly used may be a In addition to the organic electroluminescent
plastic, foil or even glass. The material should material layer (EML), OLEDs normally include
be transparent. at least two additional organic semiconductor
2. Anode layers, interposed between the EML and the
The anode component usually used is indium electrodes, called the Electron Transport
tin oxide ITO. This material is transparent to Layer(ETL) and Hole TransportLayer(HTL).
visible light and is sufficiently conducting and
has a high work function which promotes
injection of holes into the HOMO level of the
organic layer.
3. Cathode
Usually metals like barium, calcium and
aluminium are used as a cathode because
they have low work functions which help in
injecting electrons into the LUMO level of the
different layers.
4. Emissive layer:
The light emitting material may be small
organic molecules or polymers(Polymer light
Examples for Light emitting polymers:

Poly-p-phenylene PPV Polyfluorene

Working Mechanism:
 When an electric bias is applied across the electrodes electrons are injected from cathode to
the LUMO (Lowest Occupied Molecular Orbital) of the organic material and holes are injected
from anode into the HOMO (Highest Occupied Molecular Orbital) states of the organic
material.

 The electrons and holes then drift under the effect of the applied electric across the organic
layer towards each other.
 They then recombine producing singlet and triplet excited states called excitons. Excitons are
essentially electrostatically bound electron–hole (e–h) pairs that comprise an electron in a
LUMO state and a hole in a HOMO state of the same molecule.
 Singlets and triplets—are generated at a ratio of 1:3 i.e., more number of triplet excitons.


 The electrons in excited state relax from the higher energy state(LUMO) and fills the holes in the
lower energy state(HOMO), emitting the energy radiatively as a photon. Usually the singlet excitons,
decay radiatively, and are primarily responsible for Electroluminescence.
 The energy or wavelength of the emitted photon corresponds to the HOMO–LUMO energy
difference, which is the band-gap Eg of theorganic electroluminescent material.

Roles of ETL and HTL:

 These layers help facilitate charge carrier (holes or electrons) injection from the electrodes.
 The interfaces at HTL/EL and EL/ETL act as electron and hole barriers, respectively and
reduce the leakage of carriers to the counter electrodes. Thus, the electrons and holes are
confined to the emissive layer, thereby increasing e–h recombination probability. Hence the
device electroluminescent efficiency is increased.
CHALLENGES IN OLED TECHNOLOGY:
 Lifetime is only 40,000 hours (when it loses 50% of its initial luminance). This is the the
biggest technical problem for OLEDs. In particular, blue OLEDs have a lifetime of around
14,000 hours when used for flat-paneldisplays.
 High brightness levels in OLED displays require the high voltages which also reduces expected
lifetime.
 High sensitivity to to O2 and moisture. Over time, moisture and O2 can react with the organic
layers and cause oxidative degradation and defects in an OLED display. The materials are also
prone to photodegradation.
 Since multilevel architectures are used, the thermal expansion coefficients willbe different for
different layers which may also influence the lifetime of the devices.•
PHOTOVOLTAICS:

The large production costs for the silicon solar cells is one of the major disadvantages. Even when
the production costs could be reduced, large-scale production of the current silicon solar cells is
limited by the scarcity of some elements required, e.g. solar-grade silicon. Hence many other types
of solar cells come into the field of solar cells and are classified as first, second and third generations
of solar cells.

Third generation solar cells:

This generation includes a many types of solar cells like polymer solar cells, perovskite and dye-
sensitised solar cells.
Polymer solar cells based on conjugated polymers have the immense advantage of providing
environmentally safe, flexible, lightweight, inexpensive electronics. The cost reduction mainly results
from the ease of processing from solution and hence large scale production.

WORKING PRINCIPLE OF POLYMER PHOTOVOLTAIC CELL:

CELL COMPONENTS
A polymer photovoltaic cell consists of a photoactive layer consisting of a Donor-Acceptor (D+A)
bilayer sandwiched between two dissimilar (metallic) electrodes which collect the photogenerated
charges. One of the electrodes is transparent, namely glass coated with Indium tinoxide (ITO) and
the other electrode is made of silver or gold. ITO electrode is used to collect the positive charges and
silver (Ag) to collect the negative charges.

Examples for donor and acceptor materials:

WORKING PRINCIPLE:

 Illumination of donor through a transparent electrode (ITO) results in the photoexcited state
of the donor, in which an electron is promoted from the highest occupied molecular orbital
(HOMO) to the lowest unoccupied molecular orbital (LUMO) of the donor.
This state consisting of an excited electron-hole pair is called as an exciton.

 The exciton then diffuses to the D-A interface.

 Subsequently, the excited electron is transferred to the LUMO of the acceptor (in blue),
resulting in an extra electron on the acceptor (A•-) and leaving a hole at the donor (D•+).

 After the charge transfer reaction, the photogenerated charges are then transported and
collected at opposite electrodes. The electron flows in the external circuit from the n-type
layer to the p-type layer.
 The excitons have very short lifetimes and low mobility and hence the exciton diffusion
length of the organic material is in general limited to 5-10nm. The excitons are lost due to
recombination before they reach the D-A interface. Only absorption of light within a very
thin layer around the interface contributes to the photovoltaic effect. This limits the
performance of double-layer devices.

BULK HETEROJUNCTION SOLAR CELLS:

To improve the efficiency the p-type and n-

type materials are intimately mixed wherein
the interface where charge transfer can occur
is increased enormously. The intimate
bicontinuous network of donor and acceptor
materials in the nanometer range decreases
exciton loss and thus leads to separation of
photogenerated charges. The mixing also
ensure percolation pathways for both electron
and hole transport to the collecting electrode
Liquid crystal phase in thermotropic liquid crystal material

The molecules in a liquid crystal tend to orient

in a particular direction. The direction of
preferred orientation in the liquid crystal is
called the director (n).

Different phases of thermotropic liquid crystals :

Structural requirements for Liquid Crystal behaviour :
Molecules exhibiting LC behaviour are of two types
1. Molecules having a rigid central part with flexible ends in their structure.
2. Polymers having backbone chain in which rigid segments are attached by short flexible spacers.
Molecules exhibiting LC behaviour are aromatic systems of the following general structural
arrangements
POLYMERIC LIQUID CRYSTALS

In polymers the mesogens (aromatic or cycloaliphatic units joined by rigid links) form a part of the
polymer main chain or it is attached to the side chain.