Properties of solid material

Electrical transport in solids

Ohm’s law
V=IR [voltage (V) =Current (A). Resistance()]

Conductance (G) = 1/R (-1)(mho’s) = S(siemens)

Resistivity (r) = resistance() . area(cm2)/depth(cm)

Cell constant

Conductivity () =1/r = -1cm-1 or S/cm

Solids are grouped into 3 classes based on
their electrical conductivity

1. Conductors (metals)
 >10 S/cm eg: Cu  = 6 x 105 S/cm (298 K)

2. Semi-conductors
10    10-10 S/cm eg: Si  = 10 S/cm (298 K)

3. Insulators
  10-10 S/cm eg: diamond  = 10-11 S/cm (298 K)
 How does a metal conduct?
= work function of metal
Free electron model Energy to remove an ê to infinity

particle in a box.

 regards a metal as a box in which electrons are free to roam,

unaffected by the atomic nuclei or by each other.

 Better fits group 1 & 2 metals and Al (called simple metals)

• The theory assumes that the nuclei stay fixed on their lattice sites
surrounded by the inner or core electrons whilst the outer or valence
electrons travel freely through the solid.

For one electron in a one-dimensional solid.

Because we are ignoring the cores, there is nothing for the electron to interact with
and so it experiences zero potential within the solid. The Schrödinger
equation for the electron is

When V=0, the solutions to this equation using is

Most solids are three dimensional
hence need to extend the free electron theory to three dimensions.

For three dimensions, the metal can be taken as a rectangular box a×b×c.

The appropriate wave function is now the product of three sine or cosine functions
and the energy is given by

Each set of quantum numbers na nb , nc will give rise to an energy level.

However, in three dimensions, many combinations of na , nb , and nc exist which

will give the same energy.

The number of states with the same energy is known as the degeneracy.

Solids have many electrons ………. So ?

 where V (=abc) is the volume of the crystal.

X-ray emission spectra obtained from

(a) sodium metal and (b) aluminium metal
when conduction electrons fall into the 2p level.

A density of states curve based on the free electron model. The levels occupied
at 0 K are shaded.

The highest occupied level is called the Fermi level.

the density of states (DOS) found experimentally for metals with more electrons
per atom than the simple metals, instead of continuing to increase with energy,
the density reaches a maximum and then starts to decrease with energy.

The band structure of nickel.

Electrons in a metal in the absence of an electric

field. They move in all directions, but, overall, no
net motion occurs in any direction.
 ELECTRONIC CONDUCTIVITY

If a metal is connected to the terminals of a battery producing an electric field,

then an electron travelling in the direction of the field will be accelerated and
the energies of those levels with a net momentum in this direction will be
lowered.

Electrons moving in the opposite direction will have their energies raised and
so some of these electrons will drop down into levels of lower energy
corresponding to momentum in the opposite direction.

There will thus be more electrons moving in the direction of the field than in
other directions.

This net movement of electrons in one direction is an electric current.

 of solids
Molecules molecular orbital theory Molecular orbitals

the Linear Combination of Atomic Orbitals (LCAO).

As the number of molecular orbitals increases, the energy
difference between the lowest bonding and the highest
antibonding increases, while the space between each
individual orbital decreases.
Band theory - a physicist’s view

H2 Molecule Chain of 5 H atoms

c0 c1 c2 c3 c4
E Antibonding 4
c1 c2
3

Nonbonding 2

Bonding 0

# of Nodes
 Infinite 1D Chain of H atoms
If there are N atoms in the chain c0 c1 c2 c3 c4
there will be N energy levels and N
electronic states ("MOs"). The k=p/a
wavefunction for each electronic
state is:

Yk = S eiknacn
Where: k=p/2a
a is the lattice constant (spacing
between H atoms),
n identifies the individual atoms
within the chain,
 cn represents the atomic orbitals k=0
K(Wave vector) is a quantum #
that identifies the wavefunction and a
tells us the phase of the orbitals.
 Infinite 1D Chain of H atoms
c0 c1 c2 c3 c4
k = p/a
Yp/a = c0+(exp{ip})c1 +(exp{i2p})c2 k=p/a
+(exp{i3p})c3+(exp{i4p})c4+…
Yp/a = c0 - c1 + c2 - c3 + c4 +…

k = p/2a
k=p/2a
Yp/2a = c0+(exp{ip/2})c1 +(exp{ip})c2
+(exp{i3p/2})c3+(exp{i2p})c4+…
Yp/2a = c0 + 0 - c2 + 0 + c4 +…

k = 0 k=0
Y0 = c0+c1 +c2 +c3 +c4 +…
a
k=0  orbital phase does not change when we translate by a
k=p/a  orbital phase reverses when we translate by a
As N increases the separation is minute & the set of levels can be
considered as a continuous range of energies. Which is known as an
energy band.

In small molecules, the greater the overlap the greater the energy
difference between bonding and anti-bonding orbitals.

for continuous solids, the greater the overlap, the greater the spread of
energies or bandwidth of the resulting band.
When filling the molecular orbitals contained within the band, it
is important to start filling the bands up form the lowest
bonding molecular orbital and must follow,

the Pauli exclusion principle: No more than two electrons

may occupy a single orbital and if two do occupy a single orbital,
then their spins must be spin paired.

And

Hunds rule : When more than one orbital has the same energy,
electrons occupy separate orbitals and do so with parallel spins.

A partially full band is required for electrical conductance

 SIMPLE METALS
For example, the Group 1 elements have body-
centred cubic structures with each atom surrounded
by eight others.

This high coordination number increases the

number of ways in which the atomic orbitals can
overlap.

The ns and np bands of the simple metals are very

wide, due to the large amount of overlap, and,
because the ns and np atomic orbitals are relatively
close in energy, the two bands merge.
For a crystal of N atoms, this ns/np band contains 4N energy levels and can
hold up to 8N electrons.
The simple metals have far fewer than 8N electrons available.
Thus, the band is only partly full. Empty energy levels exist near the Fermi
level, and the metals are good electronic conductors.
example Al atomic configuration 1s22s22p63s23p1

expected to form a 1s band, a 2s band, a 2p band, a 3s band, and a 3p

band, all separated by band gaps.

the lower energy bands, formed from the core orbitals 1s, 2s, and 2p, are
very narrow and can be regarded as a set of localised atomic orbitals.

These orbitals are concentrated very close to the nuclei and there is little
overlap between orbitals on neighbouring nuclei.

In small molecules, the greater the overlap the greater the energy difference
between bonding and anti-bonding orbitals.

Likewise for continuous solids, the greater the overlap, the greater
the spread of energies or bandwidth of the resulting band.

For aluminium, hence only 3s and 3p bands are considered.

SEMICONDUCTORS
Carbon (as diamond polymorph), silicon, and
germanium form structures in which the
atoms are tetrahedrally coordinated

the ns/np bands still overlap but the ns/np

band splits into two.
Each of the two bands contains 2N orbitals
and so can accommodate up to 4N
electrons.

This lower band is known as the valence band, the

electrons in this band essentially bonding the atoms in
the solid together.

In these solids, conduction can only occur if electrons are promoted to

the higher s/p band, the conduction band, because only then will
there be a partially full band.
Fermi level - For metals it is the energy level of the highest
occupied molecular orbital (HOMO)
for semiconductors and insulators it is a
mathematically calculated Ê level at absolute zero T.

Band gap – difference between the highest & lowest energy

levels in the band.
Band width - the spread of energies
like in molecules greater the overlap of orbitals
larger the band width.
Band theory - a physicist’s view
E(k) Vs k diagram
k= a index that labels irreducible representations of a translational group
E(k) = energy of the state
 What is the meaning of k?
In our development of the electronic band structure from a
linear combination of atomic orbitals the variable k was used
to determine the phase of the orbitals.
What exactly is k?
Wavevector – It tells us the how the phases of the orbitals
change when translational symmetry is applied.
Quantum Number – Identifies a particular electronic
wavefunction (that can hold 2 electrons with opposite spin).
Crystal Momentum – In free electron theory k is
proportional to the momentum of the electron in the kth
wavefunction.
Band E(k)
Structure
Linear H Chain EF

0 k p/a
•The Fermi energy separates the filled states (E < EF at T = 0 K)
from the empty states (E > EF at T = 0 K).
•A 1D chain of H atoms is predicted to be metallic because the
Fermi level cuts a band (there is no gap so it takes only an
infinitesimal energy to excite an electron into an empty state).
Effect of Orbital Overlap
If we reduce the lattice
parameter a it has the following
effects:
•The spatial overlap of the
orbitals increases
•The band becomes more
bonding at k=0
•The band becomes more
antibonding k=p/a.
•The increased antibonding is
larger than the increased
bonding.
•The bandwidth increases.
•The electron mobility increases.

Wide bands  Good orbital overlap

 High carrier mobility
Band Structure: Linear Chain of F

Antibonding 2pz *
Doubly degenerate

EF
Antibonding 2px/2py p*
Doubly degenerate

Antibonding 2s *
Bonding 2px/2py p

Bonding 2pz 

Bonding 2s 

0 k p/a
3D: The Band Structure ReO3

spaghetti diagram
 Density of Energy States

Density of state (DOS) diagrams

or

DOS(E) = number of levels between E & E+dE

The integral of DOS up to the Fermi level = total # of occupied molecular orbitals
Absolute zero
 Absolute zero describes a theoretical system that neither emits
nor absorbs energy.
 The absolute zero temperature is known to be 0 K (–273.15 °C).
It is the point at which particles have a minimum energy,
determined by quantum mechanical effects, which is called the
zero-point energy.

 It is not possible to cool any substance to 0 K (for this to happen,

matter would also be zero and therefore cease to exist).

 In September 2003, researchers at MIT achieved a record low of

450 pK (0.45 nK).

 As of February 2003, the Boomerang Nebula, with a temperature

of –272.15 degrees Celsius; 1 K, is the coldest place known
outside a laboratory. The nebula is 5000 light-years from Earth
and is in the constellation Centaurus.
TD & absolute zero
At temperatures near 0 K, nearly all molecular motion ceases
and ΔS = 0 for any adiabatic process.

Pure substances can (ideally) form perfect crystals as T0.

Planck's strong form of the third law of thermodynamics states
that the entropy of a perfect crystal vanishes at absolute zero.
In metals
No conduction

To conduct needs e-
in CB or holes
(+,h+,p+) in VB or
both

All charge carriers originate near EF

Semiconductors & insulators
The ranges of forbidden energy between the energy bands are
known as band gaps.
Strong directional bonding result in HOMO-LUMO gap in MO sense.
In Bands it is called “ Band gap” (Eg)
For metals Eg = 0 (no band gap)

To show conductance needs

thermal energy (to promote e’s)
 In the case where the band is only half full, the occupation of the
energy levels is dictated by the Fermi-Dirac Distribution.
Under this distribution, it is found that only at T=0 K does it hold true
that the band is exactly half filled.
The Fermi function gives the probability of occupying an available energy
state, this factored by the number of available energy states determine
how many electrons would reach the conduction band. This density of
states is the electron density of states

Fermi Function (Fermi-Dirac Function)

The Fermi function f(E) gives the probability of a given available electron
energy state being occupied at a given temperature.
Fermi-Dirac Function

the Fermi Energy, EF, is defined as the energy where f(E) = 1/2. That is
to say one half of the available states are occupied. T is the temperature
(in K) and k is the Boltzman constant (k = 8.62  10-5 eV/K)
As an example consider f(E) for T = 300 K and a state 0.1 eV above EF:
f(E) = 1/[1 + exp{(0.1 eV)/((300K)(8.62  10-5 eV/K)}]
f(E) = 0.02 = 2%
Consider a band gap of 1 eV.
f(0.5 eV) = 4.01  10-9

See that for even a moderate band gap (Silicon has a band gap of 1.1 eV)
the intrinsic concentration of electrons that can be thermally excited to
move about the crystal is tiny. Thus pure Silicon (if you could make it)
would be quite insulating.
Intrinsic Semiconductor
A silicon crystal at any temperature above absolute zero
temperature, there is a finite probability that an electron in the
lattice will be knocked loose from its position, leaving behind an
electron deficiency called a "hole".

Both electrons and holes contribute to current flow in an

intrinsic semiconductor.
Semiconductor Current

the electrons which have been freed from

their lattice positions into the conduction
band can move through the material.

In addition, other electrons can hop between lattice positions to fill the
vacancies left by the freed electrons. This additional mechanism is
called hole conduction because it is as if the holes are migrating across
the material in the direction opposite to the free electron movement.

The current flow in an intrinsic

semiconductor is influenced by the
density of energy states which in turn
influences the electron density in the
conduction band. This current is highly
temperature dependent.
1 eV = 1.6 x 10-19 J
= 8065 cm-1
E(eV) = 1242/l(nm)
Energetic & Spatial Overlap
Al Si P
Constant Spatial Overlap Zn Ga Ge As Se
Increasing Ionicity (Eg )
Cd In Sn Sb Te
Si d=2.35 Å AlP d=2.37 Å
Dc=0 Dc=0.62

Ge d=2.44 Å GaAs d=2.45 Å ZnSe d=2.45 Å

Dc=0 Dc=0.43 Dc=0.90

Sn d=2.81 Å InSb d=2.80 Å CdTe d=2.81 Å

Dc=0 Dc=0 .31 Dc=0.61
Decreasing Spatial Overlap (Eg )
Slowly Decreasing Ionicity Dc (Eg )

Experimental Band Gaps InAs 0.30 eV ZnS 3.8 eV

Diamond 6.0 eV CdSe 1.8 eV PbTe 0.33 eV
Si 1.12 eV AlP 2.45 eV
Ge 0.67 eV GaAs 1.42 eV ZnSe 2.8 eV
Sn 0.08 eV InSb 0.17 eV CdTe 1.4 eV
Metals, Semiconductors & Insulators
Conduction
Band

Energy
EF
Valence
Band

DOS
Semiconductor
/Insulator
In a metal the Fermi level cuts through a band to produce a partially filled
band. In a semiconductor/insulator there is an energy gap between the filled
bands and the empty bands. The distinction between a semiconductor and an
insulator is artificial, but as the gap becomes large the material usually
becomes a poor conductor of electricity. A semimetal results when the band
gap goes to zero.
Resistivities of Real Materials
Compound Resistivity (-cm) Compound Resistivity (-cm)

Ca 3.9  10-6 Si ~ 0.1

Ti 42  10-6 Ge ~ 0.05
Mn 185  10-6 ReO3 36  10-6
Zn 5.9  10-6 Fe3O4 52  10-6
Cu 1.7  10-6 TiO2 9  104
Ag 1.6  10-6 ZrO2 1  109
Pb 21  10-6 Al2O3 1  1019
Most semiconductors in their pure form are not good
conductors, they need to be doped to become conducting.

Not all so called “ionic” materials like oxides are insulators.

 Bandstructure for Ge (semiconductor)
CB minimum
VB maximum

p-bands

s-band
No mixing
at G.
EF falls in the (0.67 eV) band gap. Carrier concentration and
conductivity are small.
Ge is an indirect gap semiconductor, because the uppermost VB energy
and the lowest CB energy occur at different locations in k-space.
Direct & Indirect Gap Semiconductors
Ge Si GaAs

Figure taken from

“Fundamentals of
Semiconductor
Theory and Device
Physics”, by S. Wang

Direct Gap Semiconductor: Maximum of the valence band and minimum of the
conduction band fall at the same place in k-space.

Indirect Gap Semiconductor: Maximum of the valence band and minimum of

the conduction band fall different points in k-space. A lattice vibration (phonon) is
involved in electronic excitations, this decreases the absorption efficiency.
Properties of Semiconductors
Compound Structure Bandgap e- mobility h+ mobility
(eV) (cm2/V-s) (cm2/V-s)
Si Diamond 1.11 (I) 1,350 480

Ge Diamond 0.67 (I) 3,900 1,900

AlP Sphalerite 2.43 (I) 80 ---

GaAs Sphalerite 1.43 (D) 8,500 400

InSb Sphalerite 0.18 (D) 100,000 1,700

AlAs Sphalerite 2.16 (I) 1,000 180

GaN Wurtzite 3.4 (D) 300 ---

Let’s break  into structural and element
specific components

=nem
m = charge carrier mobility (cm2V-1s-1)
e = charge of an electron = (1.6 x 10-19 C)
n = number of charge carriers (holes or/& electrons)(cm-3)

m = et/m*
t= the relaxation time (s) {the time between collisions}
m* = the effective mass of the electron (kg)
m* depends upon the band width, which in turn depends upon orbital overlap.

Quantity Wide Band Narrow Band

dE/dk Large Small
m High Low
Velocity Fast Slow
m* Light Heavy

Wide (disperse) bands are better for conductivity.

Entities that scatter the carriers and reduce the mobility

A defect or impurity (t increases as purity increases)
Lattice vibrations, phonons (t decreases as temp. increases)
 Temperature Dependence-Metals
Recall that
 = ne2t/m*
In Metals
 The carrier concentration, n, changes very slowly with
temperature.

 t is inversely proportional to temperature (t a 1/T), due

to scattering by lattice vibrations (phonons).
 Therefore, a plot of  vs. 1/T (or r vs. T) is essentially
linear.
 Conductivity goes down as temperature increases.
Scattering by Impurities and Phonons

Phonon scattering
•Proportional to temperature
Impurity scattering
•Independent of temperature
•Proportional to impurity
concentration
Temperature Dependence-Semiconductors
Recall that
 = ne2t/m*
In Semiconductors
 The carrier concentration increases as temperature

goes up, due to excitations across the band gap, Eg.

 n is proportional to exp{-Eg/2kT}.

 t is inversely proportional to temperature

 The exponential dependence of n dominates, therefore,

a plot of ln  vs. 1/T is essentially linear.
 Conductivity increases as temperature increases.
The Doping of Semiconductors
(extrinsic semiconductors)
The addition of a small percentage of foreign atoms in the regular crystal lattice
of a semiconductor produces dramatic changes in their electrical properties.

N-Type Semiconductor
- Pentavalent impurities

Impurity atoms with 5 valence electrons produce n(negative)-type

semiconductors by contributing extra electrons.
Dopants; P, As, Sb (substitutional)
Li (interstitial)

Li → Li+ + e- (goes to the CB)

P-Type Semiconductor

Dopants; B, Al,Ga, Zn (substitutional)

Li (interstitial)
If depletion region is in working device temperature can work
without change in conductance.
Group IV semiconductors use group V atoms as donors and group III
atoms as acceptors.

Group III-V semiconductors use group VI atoms as donors and group II

atoms as acceptors.

Group III-V semiconductors can also use group IV atoms as either

donors or acceptors.

When a group IV atom replaces the group III element in the

semiconductor lattice, the group IV atom acts as a donor.

Conversely, when a group IV atom replaces the group V element, the

group IV atom acts as an acceptor.

Group IV atoms can act as both donors and acceptors; therefore, they
are known as amphoteric impurities.
 Intrinsic
Donor atoms Acceptor atoms
semiconductor

Group IV
Silicon, Germanium Phosphorous, Arsenic Boron, Aluminum
semiconductors

Aluminum phosphide, Beryllium, Zinc,

Group III-V Selenium, Tellurium,
Aluminum arsenide, Cadmium, Silicon,
semiconductors Silicon, Germanium
Gallium arsenide Germanium
 p-n Junctions
When p-type and n-type materials are placed in contact with
each other, the junction behaves very differently than either
type of material alone.

Near the junction, electrons diffuse across to combine with

holes, creating a "depletion region".
 In the middle of the

p-n Junctions junction EF falls midway

between the VB & CB as it
would in an intrinsic
semiconductor.

When a p-type and an n-type semiconductor are brought into contact

electrons flow from the n-doped semiconductor into the p-doped
semiconductor until the Fermi levels equalize (like two reservoirs of
water coming into equilibrium). This causes the conduction and valence
bands to bend as shown above.
 Depletion Region

When a p-n junction is formed, some of the free electrons in the n-region
diffuse across the junction and combine with holes to form negative ions. In so
doing they leave behind positive ions at the donor impurity sites.
 Bias effect on electrons in depletion zone
Equilibrium of junction
Coulomb force from ions prevents further migration across the p-n junction.
The electrons which had migrated across from the N to the P region in the forming of
the depletion layer have now reached equilibrium.
Other electrons from the N region cannot migrate because they are repelled by the
negative ions in the P region and attracted by the positive ions in the N region.

Reverse bias
An applied voltage with the indicated polarity further
impedes the flow of electrons across the junction.
A reverse voltage drives the electrons away from the
junction, preventing conduction.
 Forward bias
An applied voltage in the forward direction as indicated assists
electrons in overcoming the coulomb barrier of the space
charge in depletion region. Electrons will flow with very small
resistance in the forward direction.

At the junction the electrons

and holes combine so that a
continuous current can be
maintained.
Applications of p-n Junctions
The P-N Junction Diode

the p-n junction will conduct current in the forward

direction but not in the reverse direction.
It is therefore a basic tool for rectification in the
building of DC power supplies.
 The PIN Diode

The PIN diode has heavily doped p-type and n-type regions separated by
an intrinsic region.

When reverse biased, it acts like an almost constant capacitance and when
forward biased it behaves as a variable resistor.

The forward resistance of the intrinsic region decreases with

increasing current.

Since its forward resistance can be changed by varying the bias, it

can be used as a modulating device for AC signals.

It is used in microwave switching applications.

 Step-Recovery Diode

In the step-recovery diode the doping level is gradually

decreased as the junction is approached.

This reduces the switching time since the smaller amount of

stored charge near the junction can be released more rapidly
when changing from forward to reverse bias.

The forward current can also be established more rapidly than in

the ordinary junction diode.

This diode is used in fast switching applications.

Light Emitting Diode (LED)
LEDs are p-n junction devices constructed of
gallium arsenide (GaAs), gallium arsenide
phosphide (GaAsP), or gallium phosphide
(GaP).…

Silicon and germanium are not suitable

because those junctions produce heat and
no appreciable IR or visible light. (Non
radiative-indirect bandgap material)

The junction in an LED is forward biased and

when electrons cross the junction from the
n- to the p-type material, the electron-hole
recombination process produces some
photons in the IR or visible in a process
called electroluminescence.

An exposed semiconductor surface can then

emit light.
The color of the emitted light depends on the composition and condition
of the semiconducting material used, and can be infrared, visible, or near-
ultraviolet.

The wavelength of the light emitted, and therefore

its color, depends on the band gap energy of the
materials forming the p-n junction.

LEDs are usually built on an n-type substrate, with

an electrode attached to the p-type layer deposited
on its surface. P-type substrates, while less
common, occur as well.
Conventional LEDs are made from a variety of inorganic
semiconductor materials, producing the following colors:

Aluminium gallium arsenide (AlGaAs) — red and infrared

Aluminium gallium phosphide (AlGaP) — green
Aluminium gallium indium phosphide (AlGaInP) — high-brightness orange-red,
orange, yellow, and green
Gallium arsenide phosphide (GaAsP) — red, orange-red, orange, and yellow
Gallium phosphide (GaP) — red, yellow and green
Gallium nitride (GaN) — green, pure green (or emerald green), and blue also
white (if it has an AlGaN Quantum Barrier)
Indium gallium nitride (InGaN) — near ultraviolet, bluish-green and blue
Silicon carbide (SiC) as substrate — blue
Silicon (Si) as substrate — blue (under development)
Sapphire (Al2O3) as substrate — blue
Zinc selenide (ZnSe) — blue
Diamond (C) — ultraviolet
Aluminium nitride (AlN), Aluminium gallium nitride (AlGaN), Aluminium gallium
indium nitride (AlGaInN) — near to far ultraviolet (down to 210 nm])
The red extreme of the visible spectrum, 700 nm, requires an energy release
of 1.77 eV to provide the quantum energy of the photon.

At the other extreme, 400 nm in the violet, 3.1 eV is required.

a bright blue LED was successfully produced by Nichia Chemical of Japan in

1994. The material used for the diode was gallium nitride GaN.

Nichia has also produced an InGaN laser diode which lases in the blue-violet
region of the spectrum.

Wavelengths down to 210 nm were obtained in laboratories

using aluminium nitride
 White LEDs

A combination of red green and blue LEDs can produce the impression of
white light, though white LEDs today rarely use this principle.

Most "white" LEDs in production today are modified blue LEDs:

GaN-based, InGaN-active-layer LEDs emit blue light of wavelengths
between 450 nm and 470 nm. This InGaN-GaN structure is covered with
a yellowish phosphor coating usually made of cerium-doped yttrium
aluminum garnet (Ce3+:YAG) crystals which have been powdered and
bound in a type of viscous adhesive.
The LED chip emits blue light, part of which is efficiently converted to a
broad spectrum centered at about 580 nm (yellow) by the Ce3+:YAG.

Since yellow light stimulates the red and green receptors of the eye, the
resulting mix of blue and yellow light gives the appearance of white, the
resulting shade often called "lunar white". This approach was developed
by Nichia and has been used since 1996 for the manufacture of white
LEDs.
 Organic light-emitting diodes (OLEDs)

the emitting layer material of an LED is an organic compound.

the organic emitting material must have conjugated pi bonds. The emitting
material can be a small organic molecule in a crystalline phase, or a polymer.

Polymer materials can be flexible; such LEDs are known as PLEDs or FLEDs.

Compared with regular LEDs, OLEDs are lighter, and polymer LEDs can have
the added benefit of being flexible.
 Photodiode
A photodiode is a semiconductor diode that functions as a photodetector.

A photodiode is a p-n junction or p-i-n structure.

When a photon of sufficient energy strikes the diode, it excites an electron

thereby creating a mobile electron and a positively charged electron hole.

If the absorption occurs in the junction's depletion region, or one diffusion

length away from it, these carriers are swept from the junction by the built-in
field of the depletion region, producing a photocurrent.

Materials commonly used to produce photodiodes include:

Material Wavelength range (nm)

Silicon 190–1100
Germanium 400–1700
Indium gallium arsenide 800–2600
Lead sulfide <1000-3500
Solar cell
A solar cell or photovoltaic cell is a device that converts light energy
into electrical energy by the photovoltaic effect.

1883 - the first solar cell was built, by Charles Fritts, who coated
the semiconductor selenium with an extremely thin layer of gold to
form the junctions.
 The Junction Transistor

A bipolar junction transistor consists of three regions of doped

semiconductors.
A small current in the center or base region can be used to control
a larger current flowing between the end regions (emitter and
collector).
The device can be characterized as a current amplifier, having
many applications for amplification and switching.
Bipolar junction transistors are formed from two p-n junctions, in either n-p-n
or p-n-p configuration.

The middle, or base, region between the junctions is typically very narrow. The
other regions, and their associated terminals, are known as the emitter and the
collector.

A small current injected through the junction between the base and the emitter
changes the properties of the base-collector junction so that it can conduct current
even though it is reverse biased.

This creates a much larger current between the collector and emitter, controlled by
the base-emitter current.
 Field-effect transistor

The field-effect transistor (FET) is a type of transistor that relies on

an electric field to control the shape and hence the conductivity of a
'channel' in a semiconductor material.

The metal–oxide–semiconductor field-effect transistor

(MOSFET, MOS-FET, or MOS FET)
MOSFET structure and channel formation

Cross section of an NMOS without channel formed: OFF Cross section of an NMOS with channel formed: ON
state state
Photoresistor

A photoresistor or LDR is an electronic component

whose resistance decreases with increasing incident light
intensity. It can also be referred to as a light-dependent
resistor (LDR), photoconductor, or photocell.
A photoresistor is made of a high-resistance
semiconductor. If light falling on the device is of high
enough frequency, photons absorbed by the
semiconductor give bound electrons enough energy to
jump into the conduction band. The resulting free electron
(and its hole partner) conduct electricity, thereby lowering
resistance.
Direct measurement of electric conductivity

1. Two probe method

Ohm’s law
V=IR

Conductance (G) = 1/R

Apply I and measures total R & hence

good for measuring larger R .
 2. Four probe method

Apply I and measures total V

Conductivity () =1/r = L/(w . t . V/I) = -1cm-1 or S/cm

 For irregular shaped samples – Van der Pauw technique
**The sample must be of uniform thickness

DVAB
RCD , AB =
I CD

DVAD
RBC , AD =
I BC

1 pt  RCD , AB  RBC , AD  Where t= thickness

r= =
 ln 2  2 f

f= function depending
on the ratio R AB ,CD
RBC , AD

A powder can be made in to a disc (need only one R value) but low conduction due
to electron movement restricted between particles.
 Carrier measurements –
Hall effect
Edwin Hall discovered this effect in 1879.

 Current consists of the movement of many small charge-carrying "particles"

(typically, but not always, electrons). These charges experience a force, called
the Lorentz Force, when a magnetic field is present that is not parallel to their
motion.
 When such a magnetic field is absent, the charges follow an approximately
straight, 'line of sight' path.
 However, when a perpendicular magnetic field is applied, their path is curved so
that moving charges accumulate on one face of the material.
 This leaves equal and opposite charges exposed on the other face, where there
is a dearth of mobile charges. The result is an asymmetric distribution of charge
density across the hall element that is perpendicular to both the 'line of sight'
path and the applied magnetic field.
 The separation of charge establishes an electric field that opposes the migration
of further charge, so a steady electrical potential builds up for as long as the
current is flowing.
For a simple metal where there is only one type of charge carrier (electrons)
the Hall voltage VH is given by

where I is the current across the plate length, B is the magnetic flux density,
t is the depth/thickness of the plate, e is the electron charge, and n is the
charge carrier density of the carrier electrons.

The Hall coefficient is defined as

where j is the current density of the carrier electrons, and E is the induced
electric field. In SI units, this becomes

One very important feature of the Hall effect is that it differentiates between
positive charges moving in one direction and negative charges moving in the
opposite. 
I(Amperes) H (oerstads)
Since  = nem if  and n is measured m can be calculated
Hall effect in Semiconductors

When a current carrying semiconductor is kept in a magnetic field, the carriers

of the semiconductor experience a force in a direction perpendicular to the
magnetic field and current field, this is called Hall effect in semiconductors.

The simple formula for the Hall coefficient becomes more complex in
semiconductors where the carriers are generally both electrons and holes which
may be present in different concentrations and have different mobilities. For
moderate magnetic fields the Hall coefficient is

where n is the electron concentration, p the hole concentration, me the electron

mobility , mh the hole mobility and e the electronic charge.
For large applied fields the simpler expression analogous to that for a single
carrier type holds.

with
 Sign of charge carriers
For metals – almost always- electrons are major carriers

Thompson effect
Carriers are equally distributed but when heated in one end moves to
the cold end. The effect is known as Seebeck effect in
semiconductors.

DV
= S ( Seebeck coefficient )
DT

S<0 n-type semiconductor

S>0 p-type semiconductor
 Carrier values (n)
Metals(1023/cm3) Cu  1 x 1023
Na  5 x1022

Semimetals(1017-1023/cm3) Graphite  5 x1018

Sb  7 x 1019

Semiconductors(<1017/cm3) Ge  5 x 1013
Si  3 x1010

Cu =63.55 g/mol r= 8.96 g/cm3 8.5 x 1022 atoms/cm3

~ one free electron per atom.

Carrier mobilities (m)

Compound Structure Bandgap e- mobility h+ mobility

(eV) (cm2/V-s) (cm2/V-s)
Si Diamond 1.11 (I) 1,350 480
Ge Diamond 0.67 (I) 3,900 1,900
AlP Sphalerite 2.43 (I) 80 ---
GaAs Sphalerite 1.43 (D) 8,500 400
InSb Sphalerite 0.18 (D) 100,000 1,700
AlAs Sphalerite 2.16 (I) 1,000 180
GaN Wurtzite 3.4 (D) 300 ---
Al CCP ~0 13 ---
Cu CCP ~0 35 ---
Na BCC ~0 53 ---
Transition metal effects on conductivity

Generally Ef lies in the d- orbital region --- need d orbital overlap to

form bands & get conduction.

d- bands are sharper than s and p bands ------ smaller Ē range and
are higher than the anion Ē levels (eg O2-)

TiO2 – white insulator

TiO – NaCl structure- black metallic

Partially filled
 VO – rock salt structure –metallic-partially filled d band.

NiO – rock salt structure – green insulator - filled T2g band.

2nd and 3rd row transition metals (larger atoms) more d-orbital extension hence
more overlap.
More electro positive anions (less ionic structure) less isolated hence more overlap.

NiO  NiS  NiSe  NiTe

semiconductor more metallic metallic

CuO - insulator Cu2O semiconductor More ionic less overlap.

 Magnetic properties of solids
Isolated metal centers
The interaction between an external magnetic field (H) and a material
depends upon it’s magnetic properties.
Diamagnetic  Repulsive Paramagnetic  Attractive

Magnetic Flux Lines

Diamagnetism

Diamagnetic substances are composed of atoms which have

no net magnetic moments but when exposed to a field, a
negative magnetization is produced and thus the susceptibility
is negative.

Note that when the field is zero the magnetization is zero. The
other characteristic behavior of diamagnetic materials is that the
susceptibility is temperature independent.
Paramagnetism

the material have a net magnetic moment due to unpaired electrons

in partially filled orbitals.
the individual magnetic moments do not interact magnetically, and like
diamagnetism, the magnetization is zero when the field is removed. In the
presence of a field, there is a partial alignment of the atomic magnetic
moments in the direction of the field, resulting in a net positive
magnetization and positive susceptibility.
Magnetic Ordering in solids

Paramagnetic Antiferromagnetic

Ferromagnetic Ferrimagnetic
Magnetic Susceptibility vs. Temperature

Paramagnetic substances with localized, weakly interacting electrons

obey the Curie-Weiss law.
C
cM =
T q
cm = Molar magnetic susceptibility
C = Curie constant
q = Weiss constant

A Curie-Weiss plot is a plot of 1/cm vs. temperature. Ideally it should

give a straight line if the C-W law is obeyed. From such a plot we can
then extract the Curie constant from the inverse of the slope and the
Weiss constant from the x-intercept.

1 T q 1 q
= = T
cM C C C
 Curie-Weiss Plot
0.50
90.00
3+ 5
Fe (d ) m = 5.9 m B 3+ 5
Fe (d ) m = 5.9 m B

Inverse Molar Susceptibility, (1/ c m)

0.45
80.00
0.40
Molar Susceptibility, c m

70.00
0.35 q = -50K
60.00
0.30
50.00
0.25
q = 0 40.00
q = -50K
0.20

30.00
q = 0
0.15

0.10 20.00 q = 50K

q = 50K
0.05 10.00

0.00
0.00
0 50 100 150 200 250 300 350
0 50 100 150 200 250 300 350
Temperature (K)
Temperature (K)

The Curie constant is equal to the The Weiss constant is equal to the y-
inverse of the slope. It gives us the size intercept. It’s sign tells us about the
of the moment per formula unit. short range magnetic interactions.
Q = 0  Paramagnetic
C = (NA/3k)m2
Spins independent of each other
m = (3kC/NA)1/2 = 2.84 C1/2
Q > 0  Ferromagnetic
NA = Avogadro’s Number Spins tending to align parallel
k = Boltzman’s constant Q < 0  Antiferromagnetic
Spins tending to align antiparallel
Ferromagnets & Antiferromagnets
0.10

0.09 TN Antiferromagnet
TN =100 K

Molar Susceptibility, c m
0.08

0.07

0.06

0.05

0.04

0.03

0.02

0.01

0.00
0 100 200 300 400

Temperature (K)

Ferromagnet Antiferromagnet
The susceptibility increases The susceptibility begins
dramatically at the Curie temp. As decreasing at the Neel temp. As
the T decreases further the the T decreases further the
magnetic ordering and the magnetic ordering increases and
susceptibility increase. the susceptibility decreases.

The Curie-Weiss Law characteristic of a pure paramagnet is typically only obeyed when
T  3TC in a ferromagnet. Deviations also occur in AFM systems above TN.
 Other Classes of Magnetism
Spin Glass – A random orientation of frozen spin orientations (in a
paramagnet the spin orientations are fluctuating.) Can occur when
the concentrations of magnetic ions are dilute or the magnetic
exchange interactions are frustrated.
Cluster Glass – The spin orientations lock in with magnetic order in
small clusters, but no order between the clusters (similar to a spin
glass).
Metamagnet – There is a field-induced magnetic transition from a
state of low magnetization to one of relatively high magnetization.
Typically the external field causes a transition from an
antiferromagnetic state to a different type (such as a ferromagnet).
Superparamagnet – A ferromagnet whose particle size is too small to
sustain the multidomain structure. Thus the particle behaves as one
large paramagnetic ion. Superparamagnetism is a phenomenon by
which magnetic materials may exhibit a behavior similar to
paramagnetism even when at temperatures below the Curie or the
Néel temperature.
 Super-exchange
cooperative coordination of metal ions
In order for a material to be magnetically ordered, the spins on one atom
must couple with the spins on neighboring atoms. The most common
mechanism for this coupling (particularly in insulators) is through the
semicovalent superexchange interaction. The spin information is transferred
through covalent interactions with the intervening ligand (say oxygen).

O 2p  O 2p 
Fe3+ dx2-y2 Fe3+ dx2-y2 Fe3+ dx2-y2 Cr3+ dx2-y2
½ Filled ½ Filled ½ Filled Empty

The covalent interaction through Here the oxygen based electron will
the O 2p orbital stabilizes spend some time on Cr3+ and due to
antiferromagnetic coupling. Hund’s rule polarize the t2g e-
leading to ferromagnetic coupling.
Magnetic Ordering in Rock Salt Oxides
In the rock salt structure the primary mechanism for magnetic exchange is the
linear M-O-M superexchange interaction. In all of the compounds below the eg
orbitals are ½ filled, so the exchange interaction is AFM and overall magnetic
structure is AFM as shown below.
Spin up Ni
M-O TN Moment Spin
down
Distance (K) (mB) Ni
MnO d5 2.22 Å 120 ~5
Oxygen AFM
FeO d6 2.15 Å 198 3.3 SE

d7
CoO 2.13 Å 291 3.5

NiO d8 2.09 Å 530 1.8

(M-O distance )  (Covalency )  (Superexchange )  (TN )

The moments given in this table are measured at low temperature using
neutron diffraction. Under such circumstances the moment should roughly be
equal to the number of unpaired electrons.
AFM Magnetic Ordering in Perovskites
The perovskite structure has even simpler magnetic interactions (in rock salt
there is a competing interaction across the shared octahedral edge). Some
magnetic data and the most common AFM structure for perovskite is shown
below. The coloring of the magnetic structure is analogous to the crystal
structure of NaCl. It is called the G-type magnetic structure.
Spin Spin up Fe
M-X TN Moment
down
Distance (K) (mB) Fe
LaCrO3 d3 1.97 Å 282 2.8
AFM
CaMnO3 d3 1.90 Å 110 2.6 Oxygen SE

LaFeO3 d5 1.99 Å 750 4.6

KNiF3 d8 2.00 Å 275 2.2

Note that the superexchange that involves ½ filled eg orbitals (LaFeO3) is

much stronger than the corresponding interaction of ½ filled t2g orbitals. Also
upon going from oxide (LaFeO3) to fluoride (KNiF3) the covalency decreases,
which weakens the superexchange and lowers TN.
Magnetic Ordering in LaMnO3
An interesting example that shows where the
superexchange rules do not always lead to an AFM
structure, with ferromagnetic nearest neighbor
La
interactions is the magnetic structure of LaMnO3.
Which contains HS Mn3+, a d4 ion with one
Mn electron in the eg orbitals.

This structure is
called the A-type
AFM structure. 2.18 A
1.90 A
Overlap of ½ filled and
empty eg orbitals gives FM
coupling and stabilizes FM ½ filled
layers. dz2 type
orbitals
 Fe2+ t2g4 eg2 Fe3+ t2g3 eg2
Double Exchange in Fe3O4
eg  eg 

t2g  t2g 

eg  eg 

t2g  t2g 

Oct. Sites Ferromagnetic Metallic

Double Exchange

eg  eg 
Fe3O4 is an inverse spinel, with Fe3+ on the t2g 
t2g 
tetrahedral sites and a 1:1 mixture of
Fe2+/Fe3+ on the octahedral sites. It is
ferrimagnetic, with the octahedral sites eg  eg 
and the tetrahedral sites aligned in
different directions. The ferromagnetic t2g  t2g 
alignment of the octahedral sites is Oct. Sites Antiferromagnetic
necessary for delocalized carrier Localized electrons/insulating
transport of the minority spin t2g electron.
This mechanism is called double exchange.
Neutron diffraction
a crystallographic method for the determination of the atomic
structure of a material.
This is a form of elastic scattering where the neutrons exiting the
experiment have more or less the same energy as the incident
neutrons.
The technique is similar to X-ray diffraction but the different type of
radiation gives complementary information.
Neutrons interact with matter differently than x-rays.
X-rays interact primarily with the electron cloud surrounding each
atom. The contribution to the diffracted x-ray intensity is therefore
larger for atoms with a large atomic number (Z) than it is for atoms
with a small Z.
neutrons interact directly with the nucleus of the atom, and the
contribution to the diffracted intensity is different for each isotope;
for example, regular hydrogen and deuterium contribute differently.
Non-magnetic neutron diffraction is directly sensitive to the
positions of the nuclei of the atoms.
Although neutrons are uncharged, they carry a spin, and therefore
interact with magnetic moments, including those arising from the
electron cloud around an atom.
Neutron diffraction can therefore reveal the microscopic magnetic
structure of a material.
 Superconductivity
Superconductivity is a rare phenomenon occurring in certain materials at
extremely low temperatures, characterized by

1. exactly zero electrical resistance - sample resistivity drops to 0 (ρ  0 or

σ  ∞) at a critical temperature, Tc.

2. shows the Meissner Effect - superconducting samples completely expel

externally applied magnetic field lines (behave as a perfect diamagnet!)

Fritz Walther Meissner

Meissner effect
When a superconductor is placed in a weak external magnetic field H, the field penetrates the
superconductor for only a short distance λ, called the London penetration depth, after which
it decays rapidly to zero. This is called the Meissner effect, and is a defining characteristic of
superconductivity. For most superconductors, the London penetration depth is on the order of
100 nm.
The Discovery of Superconductivity
H. Kamerlingh Onnes, after having successfully
liquified helium in 1908, investigated the low
temperature resistivity of mercury in 1911.

The mercury could be made very pure by

distillation, and this was important because the
resistivity at low temperatures tends to be
dominated by impurity effects.
He found that the resistivity suddenly dropped to
zero at 4.2K, a phase transition to a zero resistance
state.
This phenomenon was called superconductivity
and the temperature at which it occurred is called its
critical temperature.

Mercury is an example of a Type I superconductor. Its practical usefulness is limited by

the fact that its critical magnetic field is only 0.019 T, so the amount of electric current
it can carry is also limited.
 Nobel Prize in Physics, 1987
Bednorz and Müller

the highest temperature superconductor reported is a ceramic material

consisting of thallium, mercury, copper, barium, calcium, strontium and
oxygen, with Tc=138 K.
Lanthanum-Barium-Copper Oxide Superconductor

This ceramic material was the first of a new class of

high temperature superconductors. It is made by
randomly substituting some barium atoms into the
lattice of lanthanum- copper-oxide in what is termed
a solid solution.

Perovskite Structure

Yttrium-Barium-Copper Oxide
This ceramic material was the first of the high
temperature superconductors to make the phase
change at a temperature above the liquid nitrogen
temperature (77 K).
Superconductor classification
Criteria to classify superconductor are:--
By their response to a magnetic field: they can be Type I, meaning
they have a single critical field, above which all superconductivity is lost; or
they can be Type II, meaning they have two critical fields, between which
they allow partial penetration of the magnetic field.

By the theory to explain them: they can be conventional (if they are
explained by the BCS theory or its derivatives) or unconventional (if not).

By their critical temperature: they can be high temperature (generally

considered if they reach the superconducting state just cooling them
with liquid nitrogen, that is, if Tc > 77 K), or low temperature (generally if
they need other techniques to be cooled under their critical temperature).

By material: they can be chemical

elements(as mercury or lead), alloys (as niobium-titanium or germanium-
niobium or niobium nitride),ceramics (as YBCO or the magnesium diboride),
or organic superconductors (as fullerenes or carbon nanotubes, though
these examples technically might be included among the chemical elements
as they are composed entirely of carbon).
Type I superconductors:
Below Tc, increasing the strength of an applied magnetic field leads to a
critical field (Hc) where superconductivity completely breaks down and
the field lines penetrate the sample. The sample reverts back to its
normal state (usually a metal).
• In a class of superconductors known as Type II superconductors (including
all known high-temperature superconductors), an extremely small amount
of resistivity appears at temperatures not too far below the nominal
superconducting transition when an electrical current is applied in conjunction
with a strong magnetic field (which may be caused by the electrical current).

• This is due to the motion of vortices in the electronic superfluid, which

dissipates some of the energy carried by the current.
• If the current is sufficiently small, the vortices are stationary, and the resistivity
vanishes. The resistance due to this effect is tiny compared with that of non-
superconducting materials, but must be taken into account in sensitive
experiments.
• However, as the temperature decreases far enough below the nominal
superconducting transition, these vortices can become frozen into a disordered
but stationary phase known as a "vortex glass".
• Below this vortex glass transition temperature, the resistance of the material
becomes truly zero.
Type 2 superconductors:
These exhibit a partial field penetration at Hc1, followed by a total
collapse of superconductivity (full magnetic field penetration) at a higher
Hc2. A mixed state exists (normal + supercond.) in the intermediate
region.
THEORIES OF SUPERCONDUCTIVITY
LONDON THEORY(1935)

The first phenomenological theory of superconductivity was London theory. It

was put forward by the brothers Fritz and Heinz London in 1935, shortly after
the discovery that magnetic fields are expelled from superconductors. A major
triumph of the equations of this theory is their ability to explain the Meissner
effect.
THEORIES OF SUPERCONDUCTIVITY

Ginzburg-Landau theory (1950)

Ginzburg–Landau theory, named after Vitaly Lazarevich Ginzburg and Lev
Landau, is a mathematical theory used to model superconductivity. It does not
purport to explain the microscopic mechanisms giving rise to superconductivity.
Instead, it examines the macroscopic properties of a superconductor.

BCS theory(1957)
proposed by Bardeen, Cooper, and Schrieffer (BCS) in 1957, is the
first microscopic theory of superconductivity since its discovery in 1911.
The theory describes superconductivity as a
microscopic effect caused by a condensation of pairs
of electrons into a boson-like state.(Bosons are one of
the two fundamental classes of subatomic particles,)

Nobel Prize in 1972

Theories of superconductivity

An electron moving through a conductor will attract nearby positive charges in

the lattice. This deformation of the lattice causes another electron, with
opposite "spin", to move into the region of higher positive charge density. The
two electrons(Cooper pair) are then held together with a certain binding
energy. If this binding energy is higher than the energy provided by kicks from
oscillating atoms in the conductor (which is true at low temperatures), then the
electron pair will stick together and resist all kicks, thus not experiencing
resistance.
• In a normal conductor, an electrical current may be visualized as a fluid of
electrons moving across a heavy ionic lattice. The electrons are constantly
colliding with the ions in the lattice, and during each collision some of the
energy carried by the current is absorbed by the lattice and converted into heat
(which is essentially the vibrational kinetic energy of the lattice ions.) As a
result, the energy carried by the current is constantly being dissipated. This is
the phenomenon of electrical resistance.

The situation is different in a superconductor.

In a conventional superconductor, also known as a Type I superconductor, the

electronic fluid cannot be resolved into individual electrons. Instead, it consists of
bound pairs of electrons known as Cooper pairs.
This pairing is caused by an attractive force between electrons from the exchange
of phonons.
Due to quantum mechanics, the energy spectrum of this Cooper pair fluid
possesses an energy gap, meaning there is a minimum amount of energy ΔE that
must be supplied in order to excite the fluid.
Therefore, if ΔE is larger than the thermal energy of the lattice (given by kT,
where k is Boltzmann's constant and T is the temperature), the fluid will not be
scattered by the lattice.
The Cooper pair fluid is thus a superfluid, meaning it can flow without energy
dissipation.
APPLICATION OF SUPERCONDUCTORS
Superconducting magnets are some of the most powerful
electromagnets known.
They are used in:----
MRI / NMR machines,
mass spectrometers
beam-steering magnets used in particle accelerators.
digital circuits based on rapid single flux quantum Technology
and RF and microwave filters for mobile phone base stations.
Superconductors are used to build Josephson junctions
which are the building blocks of SQUIDs(superconducting
quantum interference devices)

Promising future applications include

high-performance smart grid.
electric power transmission,
transformers,
power storage devices,
electric motors
Nanotubes
 Low dimensional materials
3D – metals (Cu), Semiconductors (Si) –properties does not depend on
direction- isotropic
2D- sheet or layers (graphite,CdX2, BN.) – directional properties-anisotropic

1D – Chains,  bonded or p bonded stacking polymers

Platinum molecular systems:

PtII(L)42+ + PtII(L’)42-

PtII(NH2R)42+ + PtIICl42- Magnus’s green salt

Colorless red (R=H)
 Pt-Pt interaction –(dz2-dz2) weak bond – sq planner Pt-centers

In Pt metal Pt-Pt distance= 2.79 Å

TCP-tetracyano
platinate ion
In KCP Pt-Pt distance= 3.50 Å
KCP- K2Pt(CN)4

dz2 overlap to form filled band .

dx2-y2 used for Pt-CN bond formation.  does not act as dopant.
Bands along z-axis

But Eg >3 eV and KCP is an insulator.

P- doping

Chemical oxidation
using Br2

Br2  2Br-
K2Pt(CN)4.4H2O + 0.15 Br2 K2Pt(CN)4Br0.3.3H2O
d8  d7.7 + 0.3 e-
Pt2+  Pt2.3+ (0.3 holes/Pt)
New Pt-Pt distance = 2.89 Å removal of electrons from nonbonding orbitals
make the bonds stronger.
Doped material is a good metallic conductor along the z axis (// or z)
// =100 -1 cm-1 at high T and  =0.05 -1 cm-1 at high T

A Peierls transition or Peierls distortion is a distortion of the periodic

lattice of a one-dimensional crystal. Atomic positions oscillate so that the
perfect order of the 1-D crystal is broken.
(Hg3+)[AsF6-]
 Electrically conducting organic polymers

In 1977, Alan J. Heeger, Alan MacDiarmid and Hideki Shirakawa reported

similar high conductivity in oxidized iodine-doped polyacetylene.
2000 Nobel Prize in Chemistry "for the discovery and development of
conductive polymers

Chemical structures of some conductive polymers.

From top left clockwise: polyacetylene;
polyphenylene vinylene; polypyrrole (X = NH) and
polythiophene (X = S); and polyaniline (X = NH/N)
and polyphenylene sulfide (X = S
Solid Electrolytes
Electrolyte - A substance that conducts
electricity through the movement of ions.

Most electrolytes are solutions or molten salts, but some

electrolytes are solids and some of those are crystalline solids.
Different names are given to such materials:
 Solid Electrolyte
 Fast Ion Conductor
 Superionic Conductor

.
 Ionic vs. Electronic Conductivity
comparing the properties of ionic conductors with the conventional
electronic conductivity of metals.

Metals
 Conductivity Range = 10 S/cm <  < 105 S/cm

 Electrons carry the current

 Conductivity Increases linearly as temperature decreases.

(phonon scattering decreases as T )

Solid Electrolytes
 Conductivity Range = 10-3 S/cm <  < 10 S/cm

 Ions carry the current

 Conductivity decreases exponentially as temperature decreases.

(activated transport)
Defects
In order for an ion to move through a crystal it must hop from an
occupied site to a vacant site. Thus ionic conductivity can only occur
if defects are present. The two simplest types of point defects are
Schottky and Frenkel defects.

Schottky Defect Frenkel Defect

(i.e. NaCl) (i.e. AgCl)
Na+ + Cl-  Vna + VCl Ag+  VAg+ Ag+interstitial
 Ion Migration (Schottky Defects)
Consider the movement of Na+ ions in NaCl via vacancies originating
from Schottky defects. Note that the Na+ ion must squeeze through
the lattice, inducing significant local distortion/relaxation. This is one
factor that limits the mobility of ions. A second factor that
contributes is the relatively high probability that the ion will jump
back to it’s original position, leading to no net ionic migration.

Na Cl
Cl Na E

Cl

Na Cl

To get across the unit cell into the vacancy the Na+ ion must hop through the
center of the
Chem 754 - Solidcube where it squeezes by 4 Cl and 2 Na . The energy of this
- +

“transition state” will determine the ease of migration.

State Chemistry
Ion Migration (Frenkel Defects)
The Frenkel defects in AgCl can migrate via two mechanisms.
Ag Cl Ag Ag Cl Ag

Cl Ag Cl Ag Cl
Cl
Ag1
Ag1
Cl Ag2 Cl Cl Ag2 Cl

Ag Cl Ag Ag Cl Ag

Direct Interstitial Jump

Ag Cl Ag Ag Cl Ag

Cl Ag Cl Ag Cl
Cl
Ag2
Ag1
Cl Ag2 Cl Cl Ag1 Cl

Ag Cl Ag Ag Cl Ag

Interstitialcy Mechanism
 Applications of Ionic Conductors
There are numerous practical applications, all based on
electochemical cells, where ionic conductivity is needed and it is
advantageous/necessary to use solids for all components.
 Batteries
e-  Usef
 Fuel Cells
ul
 Gas Sensors Electrolyt
Powe
Anode e
r Cathod
e
In such cells ionic conductors are needed for either the electrodes,
the electrolyte or both.
 Electrolyte (Material needs to be an electrical insulator to

prevent short circuit)

 Electrode (Mixed ionic and electronic conductivity is needed

to avoid open circuit)

A short circuit (sometimes abbreviated to short or s/c) is an electrical circuit that allows a
current to travel along an unintended path, often where essentially no (or a very low) electrical
impedance is encountered. The electrical opposite of a short circuit is an "open circuit", which is
an infinite resistance between two nodes.
Solid Electrolyte Materials

Ag+ Ion Conductors

 AgI & RbAg4I5

Na+ Ion Conductors

 Sodium b-Alumina (i.e. NaAl11O17, Na2Al16O25)

 NASICON (Na3Zr2PSi2O12)

Li+ Ion Conductors

 LiCoO2, LiNiO2

 LiMnO2

O2- Ion Conductors

 Cubic stabilized ZrO2 (YxZr1-xO2-x/2 , CaxZr1-xO2-x)

 d-Bi2O3
 Defect Perovskites (Ba2In2O5, La1-xCaxMnO3-y, …)

F- Ion Conductors
 PbF2 & AF2 (A = Ba, Sr, Ca)
General Characteristics: Solid Electrolytes
1. A large number of the ions of one species should be mobile. This
requires a large number of empty sites, either vacancies or accessible
interstitial sites.
 Empty sites are needed for ions to move through the lattice.
2. The empty and occupied sites should have similar potential energies
with a low activation energy barrier for jumping between neighboring
sites.
 High activation energy decreases carrier mobility, very stable sites
(deep potential energy wells) lead to carrier localization.
3. The structure should have solid framework, preferable 3D,
permeated by open channels.
 The migrating ion lattice should be “molten”, so that a solid
framework of the other ions is needed in order to prevent the
entire material from melting.
4. The framework ions (usually anions) should be highly polarizable.

Chem Such
754 ions can deform to stabilize transition state geometries of
- Solid
the migrating ion through covalent interactions.
State Chemistry
I think this if going to be enough for
you for the BSc.

If you are interested, read more and continue

your path in solid state chemistry. It’s a very
wonderful and interesting field.

Good luck!