Lecture 4

Band theory of solid

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Energy quanta

Thermal radiation: packet of

energy Photon momentum p=
De Broglie wavelength

E=hν

Concept of photon

Photoelectric effect

Wave particle duality

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Uncertainty principle

No precise prediction of atomic events

Average values of position, momentum, energy of particles

Magnitude of uncertainty: Heisenberg uncertainty principle

1. ∆x∆px ≥ ℏ/2

2. ∆E ∆t ≥ ℏ/2

Probability Density Function

=1

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 Schrödinger wave equation

1. Each particle in a physical system is described by a wave function:

Ψ(x,y,z,t)
2. Classical quantities linked with quantum operaters

3. Probability of finding particle with wave function Ψ within volume dxdydz:

=1

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Classical eqn. of particle energy

P2/2m + V = E

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Electron in Free Space

motion of an electron in free space Total

energy= E

no force acting on the particle E > V(x)

time-independent wave equation

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The Infinite Potential Well

For bound particle

If E is finite ψ(x) =0 at I and III

boundary condition is that the wave function must be

continuous

At x=0 A1 = 0 at x=a A2sin(ka) =0 ka=nπ

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n = quantum =1
number

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Crystalline solids: large number of
interacting particles
Basic simplifying
assumptions/approximations

1.Nuclei in crystalline solid at rest

2.One electron approximation

Bloch function/Bloch scheme:

An electron belongs to a crystal rather than

to one particular atom

Behavior of an electron in periodic potential

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a lattice crystal 1
Free electron theory
Free electron theory: an electron moves in constant potential V 0 =
0

K= wave vector=

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Bloch theorem:

Free electron theory: an electron moves in

constant potential V0

Solution has the form of

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Schrodinger equation for an electron moving in an
one dimensional periodic potential

Potential energy of an electron: V(x) = V(x+a): a=

lattice periodicity

Solution take the form:

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Solution: Plane waves modulated by
function uk(x) (periodic function) with
same lattice periodicity

Bloch function:

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The Kronig-Penney model:

Simpler periodic function assumption

Potential energy of an electron has the

form of a periodic array of square well

Period of the potential: a+b

Region: 0<x<a: potential energy=0

Region: -b<x<0 : potential energy= V0

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Kronig –Penney suggested delta
function to represent potential
barrier:

V0 approaches infinity
b - approaches 0
Product V0b remains finite

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The k-Space Diagram

consider V0 =0. In this case P=0, which

corresponds to a free particle

potential is equal to zero, the total energy

E is equal to the kinetic energy

relate the energy and momentum

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 Energy E of particle as function of
wave number k

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 1.Energy spectrum of
electrons consist of
a number of allowed
energy bands
separated by
forbidden regions
2.Width of the
allowed energy band
increases with
energy

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 Bonding forces in solid

Ionic

Metallic

Covalent

Mixed

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 Ionic bonding
Exhibited by compounds formed by electron
exchange

NaCl (Na:11, Cl: 17)

Electron exchange in outermost orbit

Net attractive force= net repulsive force

Almost perfect insulator

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 Metallic bonding
 Outermost shell filled by maximum 3 e

 Loosely bound to core

 Ions in sea of electrons

 Jellium approximation

 Coulombic attractive force

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 Covalent bonding

Both electrons in bond belong to that bond

and indistinguishable

At absolute zero no free electron

Excitation imparts energy

Distinguished by insulator

Conductivity can be engineered

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 Mixed bonding
 Compound semiconductor

 Combination of both ionic-covalent

 GaAs

 Dissimilar valency

 Dominant ionic characteristics in II-VI

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 Energy bands

Individual atoms: discrete energy

Solids are ensemble of atoms
Certain energy: forbidden gap
Difference: band/range of available energies

Wave-particle duality
Schrödinger’s wave equation
De Broglie relation
Λ=h/p
Set of allowed energy values: eigen energy

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 Close quantum mechanical interaction of
isolated atoms

 Overlapping wave function

 Non-localized electron around particular atom

 Shared influence: alteration of overall wave

function

 Electron-electron interaction: change in

Schrödinger equation

 Perturbation: shifting: splitting

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Large number atoms → split energy forms 1
 Single electron model

Limited number of allowed quantum states

Accommodate all electrons →many energy levels

Quasi-continuous energy distribution

ro

Equilibrium interatomic
distance Band of allowed energies

Discrete energy level within

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 Multiple electron

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 Band formation in Carbon

1s22s22p2

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Effect of external stimuli on band
gap

Metals , semiconductors, insulators

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 Kronig-Penney model

 One dimensional single crystal lattice

 Modified periodic potential

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 One dimensional single crystal
material

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 Concept of E-K diagram

Wave function for periodic potential at

one dimension x
Lattice periodicity a
Wave function at x→ Ψ(x) and at (x+a) →
Ψ(x+a)
Periodic boundary condition: Ψ(x+a)=
λΨ(x)
λ= travelling wave constant in x-
direction
λ=eikx

K=wave vector/propagation
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 Bloch function

Generalized expression of electron wave function in three dimensions

Ψk(r)=eik.ruk(r)

R=three dimensional positional

vector
uk(r)=modulating function
K=three dimensional wave vector=
akx+bky+ckz

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 Crystal momentum

Crystal momentum p: wave vector k

p=ħk: ħ=h/2π

λ=h/p
p=h/λ=2πħ/λ=ħk

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Bloch function in one dimension

Ψkx(x)=eikx.xuk (x)
x

Conclusion:
 All energies are not accessible to
electrons
 Electrons reside in band of energies
separated by forbidden gaps

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 A J Dekker
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Extension to three dimension

Allowed values of energy E : function of wave vector k

Dispersion relation E-k domain

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