Electronic Properties of Solids

R.J. Nicholas

Electronic Properties: • Metals

• Semiconductors
• Insulators
• Paramagnets
• Diamagnets
• Ferromagnets
• Superconductors

Combination of : Crystal Structure

Atomic Structure

Free electron theory of metals

• Metals are good conductors (both electrical and thermal)

• Electronic heat capacity has an additional (temperature

dependent) contribution from the electrons.

• Why are some materials metals and others not?

Simple approximation: treat electrons as free

to move within the crystal

Metals – HT10 – RJ Nicholas 1

 Free electron theory of metals

• Alkali metals (K, Na, Rb) and Noble metals (Cu, Ag,
Au) have filled shell + 1 outer s-electron.
• Atomic s-electrons are delocalised due to overlap of
outer orbits.
• Crystal looks like positive ion cores of charge +e
embedded in a sea of conduction electrons
• Conduction electrons can interact with each other and
ion cores but these interactions are weak because:

(1) Periodic crystal potential (ion cores) is orthogonal to conduction

electrons - they are eigenstates of total Hamiltonian e.g. for Na conduct.
electrons are 3s states, but cores are n=1 and n=2 atomic orbitals.

(2) Electron-electron scattering is suppressed by Pauli exclusion

principle.

Assumptions:

(i) ions are static - adiabatic approx.

(ii) electrons are independent - do not interact.
(iii) model interactions with ion cores by using an “effective mass” m*
(iv) free electrons so we usually put m* = me

Metals – HT10 – RJ Nicholas 2

 Free Electron Model

L
Put free electrons into a very wide potential well the
same size as the crystal i.e. they are 'de-localised'

Free electron properties

Free electron Hamiltonian has
= 2 ∂ 2ψ
only kinetic energy operator: Eψ = −
2m ∂x 2

Free electrons are plane waves ψ = A e ± ikx

with:
Momentum: Energy: Group velocity:
∂ψ = 2 ∂ 2ψ =2k 2 ∂ω 1 ∂E =k
i= = ± =k ψ − = ψ = =
∂x 2m ∂x 2 2m ∂k = ∂k m

Metals – HT10 – RJ Nicholas 3

 Free Electron Model – Periodic
boundary conditions

L L
Add a second piece of crystal the same size:
The properties must be the same.

Density of states
Calculate allowed values of k. ψ ( x) = ψ ( x + L)
Use periodic (Born-von Karman) ∴ e ikx = e ik ( x + L )
boundary conditions:
∴ e ikL = 1
2π 4π
L = size of crystal ∴ k = 0, ± , ±
L L
2π
∴δk =
L

Density of allowed states in reciprocal (k-) space is:

ΔK ΔVK
in 1 − D or in 3 − D x 2 for spin states
δ k δ k3

Metals – HT10 – RJ Nicholas 4

 Density of states (2)
States have energies
ε to ε + dε 2
g (ε )d ε = g (k )dk = 4π k 2 dk ×
δ k3
dk
∴ g (ε )d ε = g (k ) dε
dε
=2 k 2 8π
1
ε = ⎛ 2m ⎞ 2
1
2m = 3 k 2
⎜ 2 ⎟ 1
dε
⎛ 2π ⎞
⎜ ⎟ ⎝= ⎠ 2ε 2
1 ⎝ L ⎠
⎛ 2mε ⎞ 2
k =⎜ 2 ⎟ 1
⎝ = ⎠ 4π 2mε ⎛ 2m ⎞ 2
1
= ⎜ ⎟ 1
dε
=2 ⎝ =2 ⎠
3
⎛ 2π ⎞
dk ⎛ 2m ⎞
1
2
1 ⎜
⎝ L ⎠
⎟ ε 2

=⎜ ⎟
dε ⎝ =2 ⎠ 2ε
1
2
⎛ 2m ⎞
3
2 1
= 4π ⎜ 2 ⎟ ε 2
dε × V
⎝h ⎠

Fermi Energy
∞

Electrons are Fermions N = ∫ g (ε ) f

0
F −D (ε ) d ε

μ
at T = 0 N = ∫ g (ε ) d ε
0

3
N 8π ⎛ 2mEF ⎞ 2
n= = ⎜ ⎟
V 3 ⎝ h2 ⎠
μ at T = 0 is known as the 2
⎛ 3N ⎞ 3
h2
Fermi Energy, EF EF = ⎜ ⎟
⎝ 8π V ⎠ 2m

Metals – HT10 – RJ Nicholas 5

 Typical value for EF e.g. Sodium (monatomic)
crystal structure: b.c.c. crystal basis: single Na atom
lattice points per conventional (cubic) unit cell: 2
conduction electrons per unit cell 2
∴ electrons per lattice point = 1

lattice constant (cube side) = a = 0.423 nm

∴ density of electrons n = N/V= 2/a3 = 2.6 x 1028 m-3
∴ EF = 3.2 eV

Fermi Temperature TF? kBTF = EF ∴ TF = 24,000 K

Finite Temperatures and Heat Capacity

Fermi-Dirac distribution function fF-D = 1/(eE-μ/kBT + 1)

electrons are excited by an energy ~ kBT

Number of electrons is ≈ kBT g(EF)

∴ ΔE ≈ kB2T2 g(EF)

∴ CV = ΔE/ ΔT ≈ 2kB2T g(EF)

Metals – HT10 – RJ Nicholas 6

 ∴ ln n = 3 ln E + const.
Previously 2
we have n = AEF3/2 dn 3 dE
∴ =
n 2 E
dn 3 n
= = g ( EF )
dE 2 EF
k BT T
∴ C v = 3nk B = 3nk B
EF TF

∴ Heat Capacity is:

(i) less than classical value by factor ~kBT/EF
(ii) proportional to g(EF)

Is this significant?
Lattice Electrons

Room
Temperature 3nat.kB π2/2 nkB (kBT/EF)

Low 12π4/5 nat.kB (T/ΘD)3 π2/2 nkB (kBT/EF)

Temperature

C/T = βT2 + γ
Debye term free electron term

Metals – HT10 – RJ Nicholas 7

 Rigorous derivation

∞ ∂f F − D
U = ∫ ε g (ε ) f F − D (ε ) d ε ?
∂T
0

∂U
∞
∂f 1 ε − μ
∴ = ∫ ε g (ε ) dε f = x
, x=
e + 1 kT
∂T 0
∂T
∂f − ex ∂x
∞
x e dx 2 x = ×
∫ ( )
2
= g ( EF ) k B T
2
+ δ ∂T ex + 1 ∂T
(e )
2
x
− EF + 1
k BT ∞
x e x dx
π2 ≈−∞
δ ∝ ∫
(e )
2 2
= g ( EF ) k B T − EF
x
+ 1
3 k BT

= 0 (why?)

Magnetic susceptibility

• Susceptibility for a spin ½ particle is:

μ B2 μ0
χ= / electron
kT
• This is much bigger than is found experimentally
- Why?

Metals – HT10 – RJ Nicholas 8

 Pauli paramagnetism

Separate density of states for spin up and spin down,

shifted in energy by ± ½gμBB (g=2)
Imbalance of electron moments Δn
Δn = ½ g(εF) × 2μBB
giving a magnetization M
M = μB Δn = μB2 g(εF) B
and a susceptibility
χ = M/H = μ0 μB2 g(εF) = 3nμ0 μB2 /2εF

k-space picture and the Fermi Surface

= 2k 2
T=0 states filled up to EF ∴ = EF
2m

Map of filled states in k-space

2mEF
= Fermi surface ∴ kF =
=2

4π k F3
N = 2×
or we can write: 3 ⎛⎜ 2π ⎞⎟ 3
⎝ L ⎠

3π 2 N
∴ k F3 =
V

Metals – HT10 – RJ Nicholas 9

 k-space picture and the Fermi Surface

= 2k 2
T=0 states filled up to EF ∴ = EF
2m

E 2mEF
∴ kF =
=2
EF

k
kF

How big is Fermi surface/sphere compared to

Brillouin Zone?

Simple cubic structure

volume of Brillouin Zone = (2π/a)3

electron density n = 1/a3

volume of Fermi sphere = 4πkF3/3 = 4π3/a3

= half of one B.Z.

Metals – HT10 – RJ Nicholas 10

 Electron Transport - Electrical Conductivity
Equation of motion: Force = rate of change of momentum
∂k
= = − e (E + B × v )
∂t
Apply electric field - electrons are accelerated to a steady
state with a drift velocity vd - momentum is lost by
scattering with an average momentum relaxation time τ
mvd
∴ momentum loss = = −eE
τ
ne 2τ
∴ current j = nevd = E
m μ is mobility with:
ne 2τ vd = μE
∴ conductivity σ = = neμ
m

What happens in k-space?

All electrons in k-space are
accelerated by electric field: = δ k = Fδ t = − eE δ t

On average all electrons E

shifted by: δ k = − eEτ
= EF

k
kF
δk

Metals – HT10 – RJ Nicholas 11

 What happens in k-space?

All electrons in k-space are

= δ k = Fδ t = − eE δ t
accelerated by electric field:

eEτ
On average all electrons shifted by: δk = −
=
Fermi sphere is shifted in k-space by δk << kF
∴ To relax electron momentum k must be changed by ~ kF
Scattering occurs at EF
∴ we need phonons with large value of k. But phonon energy is small
so only a small fraction of electrons kBT/εF can be scattered

Scattering processes

Basic Principle: Scattering occurs because of deviations

from perfect crystal arrangement

Electron scattering mechanisms:

(i) thermal vibrations i.e. phonons (vibrations of the atoms
are a deviation from perfect crystal structure)
(ii) presence of impurities - charged impurities are very
important - scattering is by Coulomb force i.e.
Rutherford scattering.

Metals – HT10 – RJ Nicholas 12

 Matthiessen’s rule: Scattering rates (1/τ) add

m
∴ρ =
ne 2
∑ 1τ = ρ T + ρ i

Mean free path (λ):

electrons are moving with Fermi velocity vF
∴ λ = v F τ ( NOT v d τ )

Low temperature mean free paths can be very long as

electrons are only scattered by impurities

Hall Effect
In a magnetic Field B the electron experiences
a force perpendicular to its velocity.
A current j causes a build up of charge at the
edges which generates an Electric field E
which balances the Lorentz force

( − e ) ( E + v d × B ) y = 0; E y = (vd ) x B z

Metals – HT10 – RJ Nicholas 13

 In a magnetic Field B the electron
Hall Effect experiences a force perpendicular to its
velocity.
A current j causes a build up of charge at
the edges which generates an Electric
Balance of forces: field E which balances the Lorentz force

( − e ) ( E + v d × B ) y = 0; E y = (vd ) x B z

The Hall coefficient RH is: RH =

Ey
j x Bz

j x = n ( − e) vd ⇒ RH = − 1
ne
Negative sign is sign of the charge on the electron

Metal Charge/Atom (units of electron charge e) Group

Hall Expt. FE Theory
Lithium -0.79 -1 I
Sodium -1.13 -1 I
Potassium -1.05 -1 I
Copper -1.36 -1 IB
Silver -1.18 -1 IB
Gold -1.47 -1 IB
Beryllium +0.1 -2 II
Magnesium -0.88 -2 II
Calcium -0.76 -2 II
Zinc +0.75 -2 IIB
Cadmium +1.2 -2 IIB
Aluminium +1.0 -3 III
Indium +1.0 -3 III

Metals – HT10 – RJ Nicholas 14

 Thermal conductivity
In metals heat is mainly carried by the electrons
Simple kinetic theory formula for thermal conductivity K:
K = 1/3CλvF [C = π2/3 kB2T g(EF) = π2/2 nkB kBT/EF]
= π2/6 λvF nkB kBT/EF [λ = vFτ ; EF = ½mvF2]
= π2/3m n kB2 τ T
Scattering processes
• Low temperatures: defects, τ independent of T
• Intermediate temp. : Low Temp phonons - Debye
model τ ∝ T-3
• High temperatures: ‘classical’ phonons τ ∝ T-1

Wiedeman-Franz ratio
Electrical and Thermal conductivities of electrons are both
proportional to the relaxation time τ
Taking the ratio of the two should make this cancel so if we
define the Lorenz number as L = K/(σT) we have the

Wiedeman-Franz Law: L = K =
π 2 2
kB
σT 3e 2
Predicted value is absolute and the same for all metals.
Works well at high and low temps, - breaks down in ‘Debye’
region where energy and charge scattering are different

Metals – HT10 – RJ Nicholas 15

 Successes and Failures of Free Electron
Model
Successes:
• Temperature dependence of Heat Capacity
• paramagnetic (Pauli) susceptibility
• Ratio of thermal and electrical conductivities (Lorentz number)
• Magnitudes of heat capacities and Hall effect in simple metals

Failures:
• Heat capacities and Hall effect of many metals are wrong
• Hall effect can be positive
• Does not explain why mean free paths can be so long
• Does not explain why some materials are metals, some insulators
and some are semiconductors

Nearly Free Electron Approximation

Use a travelling wavefunction for an electron, e ikx, with kinetic
energy =2k2/2m

Assume that this is Bragg scattered by the wavevector G=2π/a to

give a second wave e i(k-G)x with energy =2(k-G)2/2m

Crystal potential is periodic in real space. Therefore we can

Fourier Transform the potential so that:

V ( x) = ∑ G
VG exp (iGx )

For a schematic solution we calculate what happens for a

single Fourier component VG so V(x) = VG(eiGx + e-iGx)

Metals – HT10 – RJ Nicholas 16

 Nearly Free Electron Approximation
Use a travelling wavefunction for an electron, e ikx, with kinetic
energy =2k2/2m

Bragg scattering
θ
d Δk = 2|k|sinθ
2dsinθ = λ = 4π/λ sinθ = 2π/d

Δk = G = ha* + kb* +lc*

a
2θ With d =
h2 + k 2 + l 2

Formally what we are doing is to solve the Hamiltonian form of

Schrödinger equation
Hψ = Eψ
where ψ are the two travelling wave solutions. Expanding gives:

⎛ H11 − λ H12 ⎞ ⎛ eikx ⎞ ⎛ eikx ⎞

⎜⎜ ⎟⎜ ⎟ = (E − λ ) ⎜⎜ i (k −G )x ⎟⎟
⎝ H 21 H 22 − λ ⎟⎠ ⎜⎝ ei (k −G ) x ⎟⎠ ⎝e ⎠

= 2 (k − G )
2
=2 ∂2 = 2k 2
H11 = ψ1 * − ψ1 = , H 22 =
2m ∂x 2 2m 2m

H12 = ψ 1 * V ( x) ψ 2 = VG

Metals – HT10 – RJ Nicholas 17