UNIT-4

Metals
THE FREE ELECTRON MODEL

CHARACTERISATION
Physical hardness

OF METALS
High density

Good electrical and thermal conductivity

High optical reflectivity

This chapter: • Conduction electrons

• Free electron model
• Flow of current in presence of electric field
• Specific heat and Pauli exclusion principle
• Fermi level and Fermi surface
• Magnetic field and free electrons
• Thermionic emission
1

CONDUCTION ELECTRONS
What are conduction electrons?
Example: Na atom  11 electrons per atom  10 in complete shells
 1 in the outer valance shell
 Responsible for chemical reaction
Na metal: • bcc structure
• ionic radius 0.98 Å
• Nearest neighbour distance 3.7 Å
• Na+ ion cores fill only 15% of Na-crystal volume
• valance electrons no longer belong to their
respective ions but belong to the whole crystal.
Each atom contributes its own conduction electron

⇒ Delocalised electrons  Conduction electrons

 carry current under influence of applied electric field
Localised electrons  no contribution to electric current

2
Valence and density of metal → No. of conduction electrons
Atomic valence — Zv
Density — ρm
Atomic weight — M' No. of atoms
Avogadro’s No. — NA
ρ mN A
No. of conduction electrons: N = Zv
M′

Free Electron Gas

Basic assumptions:

1. A metal crystal consists of positive ions — electrons are free to

move among ions as if they constitute an electron gas.

2. The crystal is held together by electrostatic attraction between

positively charged ions and negatively charged electron gas.

3. Mutual repulsion between electrons and electron-ion interaction

ignored.

4. Potential field due to ions is uniform, so electrons can move

throughout crystal without any change in their energy.

5. Electrons collide occasionally with atoms, and at any temperature,

their velocities can be determined according to Maxwell-
Boltzmann statistics.
4
 This model could explain  electrical and thermal conductivity,
thermionic emission, thermoelectric and
galvanomagnetic effects
 failed to explain: e.g. heat capacity, magnetic susceptibility of
conduction electrons

Question:
Why condensed matter is so transparent to conduction electrons?; or

Why electrons do not interact strongly with ions?

Qualitative Answer:
(a) Electron-ion interaction
(i)  Coulomb attraction between electrons and positive ions;
 also repulsive potential due to quantum effects
→ cancel each other
⇒ The net potential pseudo potential is very weak.

(ii)  Also, when electron approaches an ion

its velocity increases → spends very
little time near it

(b) Electron-electron interaction

Pauli exclusion principle —

(i) electrons with parallel spins tend to stay away
from each other.

(ii) in case of anti-parallel spins they still stay away

from each other to minimise the energy of the
system.
two electrons very close ⇒ very high coulomb
potential

⇒ spherical region around an electron deficient of other electrons

(~ 1 Å radius) has screening effect  Fermi hole
6
As electron moves  Fermi hole moves with it ⇒ Screening effect

Difference between free electron gas and ordinary gas:

Free electron gas is charged  like plasma.

large electron concentration in metal ~ 1029 m-3
No. of molecules in ordinary gas ~ 1025 m-3

Uniform distribution of positive ions throughout → charge neutrality

⇒ Ions exert cero field on electrons

Electrical Conductivity
V
Electrical conduction in metals: Ohm’s Law I= (1)
R
let L = length of the conductor and A = area of cross-section
I V
then current density: J= and electric field: E =
A L
and
ρL (ρ is electrical resistivity, ohm-m)
R=
A
Using above in eqn. (1) V ELA E or J =σ E
J= = =
RA ρLA ρ
1
where σ= Electrical conductivity (ohm-1.m-1)
ρ

8
Motion of conduction electrons in applied electric field:
⇒ Electric current
Ions  no translational motion  no electric current

Force on an electron:  due to electric field −eE

∗
assume  resistive force  due to electron-lattice − m v τ
interaction
m*  effective electron mass (due to electron-lattice interaction)
v  velocity of electron
τ  called Collision time or Relaxation time or mean free life-time
dv v
Equation of motion of the electron: m∗ = −eE − m∗ (2)
dt τ

if
dv
=0 ⇒ Steady state,
eEτ
v=− (3)
dt m∗
Two different velocities associated with electrons:
Drift velocity: vd — due to applied electric field
Random velocity: vr — even in the absence of field
9

-
-- vd

E Random motion (zero current)

vd << vr
charge per unit volume  − Ne (N - electron concentration)
Each electron moving with drift velocity  vd
∴ Amount of charge crossing init area/unit time →
current density  J = (− Ne)vd

 eEτ  Ne τ
2
using eqn. (3): J = (− Ne) − ∗  = ∗ E
 m  m
Ne 2τ
as J =σ E Electrical conductivity : σ= (4)
m∗
10
Relaxation Time and Mean Free Path
τ is also called the relaxation time. (~10-14 sec)  time between two
successive collision
Ne 2τ
σ= increase in τ → vd increases → σ increases
m∗
Apply electric field to a sample → drift velocity, vd established
Switch off electric field → equation of motion:
dv v
m∗ = − m∗ (Q E = 0)
dt τ
1 1
or dv = − dt
v τ
t
Integrating we get: ln(v) = − + k → vd (t ) = e −t τ .e k
τ
vd (t ) = vd ,0e −t τ
→ vd(t) approaches zero exponentially with a characteristic time τ ,
 relaxation process 11

l
We can rewrite: τ = l = distance travelled between two
vr successive collisions
vr = random velocity
τ = time between two successive collisions

Ne 2τ Ne 2 l
so, electrical conductivity: σ= = ∗
m∗ m vr

Metals: σ ≅ 5 × 107 (ohm-m)-1

Semiconductors: σ ≅ 1 (ohm-m)-1
Metals: N ≅ 1029 m-3, vr ≅ 106 ms-1
Semiconductors: N ≅ 1020 m-3, vr ≅ 104 ms-1

To compare magnitudes of vd and vr : (vr ~ 106 ms-1)

using e ≈ 10−19 coul, τ = 10-14 s, m∗ ≈ 10−30 kg, E ≈ 10 V/m
in eqn. (3): v ~ 10− 2 ms -1 ⇒
d v v ≈ 10−8 d r 12
Joule heat  power dissipated by the field
= power absorbed by the electrons
Power absorbed by a particle = Fv (F is the force, v is particle velocity)

So power absorbed by the electron system per unit volume:

 eτE 
P = NFvd = N (−eE ) − ∗ 
 m 
Ne 2τ 2
= E
m∗
Origin of Collision Time
τ — Collision time or relaxation time due to some friction force
Collision model ⇒ electron-ion collision ⇒ electron momentum
decreases
Disagreement with experiment:
— calculated mean free path, l = vrτ
using vr ~ 106 ms-1 and τ ~ 10-14 s → l ~ 10-8 m ~102 Å
~20 times the inter-atomic distance!13

Question: How an electron can travel such distance without collision?

Quantum mechanical solution: Wave character of electrons!
h
Wavelength of the electron: λ= deBroglie relation
m∗vr
Theory of wave propagation in discrete structure
⇒ a wave passing through a periodic lattice, continues to
propagate indefinitely without scattering.
Atoms absorb energy from the wave and radiate back
⇒ wave continues without modification; velocity is modified

Recall — no scattering in a regular lattice , except when Bragg

condition is fulfilled.
Conclusion: in a perfect lattice, there are no collisions except under
this condition.
Therefore, l = ∞ →τ = ∞ hence σ =∞
l is finite → finiteness must be due to deviation from perfect periodicity!
Thermal vibrations or Imperfections 14
Electrical Resistivity Vs. Temperature
-3 -2
Normalised resistivity of Na: x 10 x 10

ρ (290 K ) ≈ 2.1× 10−8 Ωm 5 21

4
At T = 0  ρ has small constant

ρ (T)/ρ (290 K)

ρ (T)/ρ (290 K)
14
3
value, increases slowly with T, 2
7
1
at higher temperature  increases
linearly with T. 0 6 10 14
T (K)
18 22 0 20 40 60 80 100
T (K)

Linear behaviour  up to melting point

1 m∗
Electrical resistivity: ρ= =
σ ne 2τ

1/τ  probability of electron scattering per unit time, τ = 10 −14 s

So 1014 collisions per second due to deviation from periodicity.
15

Two types of deviations:

a) Lattice vibrations (phonons)

b) Static imperfections, such as impurities

The total probability of an electron to be scattered per unit time:

1 1 1
= + ⇒ ρ = ρi + ρ ph (T ) (Matthiessen rule)
τ τ ph τ i
(Temperature dependent)
(Residual resistivity)

m∗ m∗ (Ideal resistivity)
so ρ= +
Ne 2τ i Ne 2τ ph

Approximate calculation of τi and τph from kinetic theory.

16
Very low T:
Phonon scattering is negligible  τph → ∞, ρph → 0
therefore ρ = ρi Decreasing Boundary
Separation
l Increasing
Higher T: Defect
Concentration
Umklapp scattering by phonons  ρ ≅ ρ ph (T )
At sufficiently high T: Phonon
Scattering

ρph varies linearly with T ⇒ ρ increases

Boundary Defect

Temperature, T

Collision of electrons with impurities

ρi should increase with impurity concentration Ni

li
We write τi = li  electron mean free path for collision
vr with impurities
vr  random velocity

17

Let σi  scattering cross section of impurity atom

Ni  no. of impurity atoms per unit volume
Then according to kinetic theory of gases:
1 1
l iσ i N i = 1 ⇒ li = ⇒ τi =
σ i Ni v rσ i N i
m∗vrσ i N i
∴ ρi = ⇒ ρi ∝ N i
Ne 2
So electrical resistivity increases with impurity concentration.

Collision of electrons with phonons

1 1
l ph = ⇒ τ ph =
σ ion N ion vrσ ion N ion
σ ion  Host ion scattering N ion  Host ion concentration
cross section per unit volume

18
 m∗vrσ ion N ion
then ρ ph = ( ρ ph ∝ σ ion )
Ne 2

suppose x = distance of deviation from equilibrium,

then average cross section:
σ ion ≈ π < x >
2

Ion is like a harmonic oscillator, average of its potential energy:

1 2 hω (energy of quantum oscillator,

αx = hω kT
2 e −1 α is force constant)
hω hω
so σ ion ∝ ⇒ ρ ph ∝
ehω kT − 1 ehω kT − 1
let hω = kθ → hω / kT = θ / T 1
⇒ ρ ph ∝
(θ is Debye temperature) eθ T − 1
θ
when T >> θ , eθ T ≈ 1 + ⇒ ρ ph ∝ T
T
Electrical resistivity varies linearly with temperature, as observed. 19

−θ T
When T << θ , Electrical resistivity varies as e

Experimentally: ρ ∝ T5

Reason: — model used  neighbouring ions were

treated independently
When ionic correlation is taken into account (Debye
theory), T5 behavior is obtained.
100

10
ρ∝T
Ω m)

1
Resistivity (nΩ

0.1
ρ∝T5
0.01

0.001

0.0001

0.00001
1 10 100 1000 10000

Temperature (K)
20
Heat Capacity Of Conduction Electrons
Free electron model  electrons treated as free particles, obey classical
laws of mechanics, electromagnetism, statistical
mechanics  had to use quantum mechanics to
explain collisions
Drude-Lorentz model:
According to kinetic theory of gases:
3
Energy of free particle in equilibrium at temperature T→ kT
2
So average energy per mole → 3  3
E = N A  kT  = RT
2  2
∂(E ) 3
Therefore, electronic heat capacity: Ce = = R ≈ 3 cal/mole o K
∂T 2
now, total heat capacity of metals: C = C ph + Ce
3
so C = 3R + R = 4.5 R ≈ 9 cal/mole o K
2
At high temperature, experimental value of heat capacity in metals is
3
~ 3R and Ce < classical value of 2 R by ~10-2 21

Quantum Mechanical Solution

Energy is quantized.
Occupation of electron states  governed by Pauli exclusion principle
Ground state of the N electron system at zero
temperature
 all electronic levels filled up to Fermi energy
 all levels above are empty EF

The highest occupied level → Fermi level

Typical value in metals: EF ~ 5 eV

Distribution function, f (E)  the probability of level E being occupied

at T = 0 K:
1, for E < EF 
f (E) =  
0, for E > EF 

22
at T > 0 K:
Thermal energy → electrons near Fermi
level are excited to higher energy states
An electron may absorb energy ~ kT
= 0.025 eV (at room temp.)
At room temp. kT << EF (~5 eV)
Fermi-Dirac Distribution Function (T ≠ 0)
1
f (E ) = ( E − EF ) kT (Alonso & Finn, Fundamental University Physics, III)
e +1
Approximation to calculate heat capacity:
 Only electrons in the range kT of Fermi energy can be excited
thermally.
kT
So fraction of excited electrons :
EF
 No. of electrons excited per mole : N A
kT
EF
23

 Each electron has energy ~ kT (kT )2

⇒ Total energy per mole : E = NA
EF
 The electronic heat capacity is then:
∂E 2 N A k 2T kT
Ce = = = 2R
∂T EF EF
So Ce is less than classical value by a factor of ~ kT / EF
kT 1
For EF = 5 eV, T = 300 K → ~ (agrees with experiment)
EF 200
T
let EF = kTF ⇒ Ce = 2 R (TF Fermi temperature)
TF
for EF = 5 eV → TF = 60000 K
Therefore, such high temperature required to reach classical value!
Exact evaluation of electronic specific heat:
π2 kT Same order of magnitude
Ce = R
2 EF as the approximation.
24
The Fermi Surface
Electrons in a metal  continuous state of random motion;
free particles;
energy of an electron is entirely kinetic,
1
E = m ∗v 2
vy
Fermi surface
2
Velocity space with axes vx, vy, vz  v
Each point  a unique velocity (magnitude 0 vx
and direction) vF
Conduction electrons with random velocities
fill the space uniformly
Fermi sphere
Fermi sphere  radius vF (Fermi velocity)
1
Fermi energy: EF = m∗vF2
2
At T = 0 K: - all the points inside the sphere are completely full
- all the points outside the sphere are empty
(E > EF) 25

No appreciable effect of temperature 2 EF

on Fermi surface ⇒ vF independent of temperature vF =
m∗
When temperature raised  only a few electrons excited to outside,
little effect on FS

For EF = 5 eV: vF = (2 × 5 × 1.6 × 10−19 / 9 × 10−31 )1 2 ≈ 106 ms -1

→ 1/100 of speed of light → very fast!

Fermi energy determined by electron concentration, N.

UNIT-6
Fermi energy: EF =
h2
2m ∗
(3π 2 N )
23
→ EF ∝ N

FS may be distorted from the simple spherical shape.

→ this distortion is due to electron–lattice interaction.
26
Electrical conductivity: Effects of the Fermi Surface
How classical results modified by Fermi surface?

In the absence of an electric field:

FS centred at the origin 
Electrons moving randomly  each carry current
total current of the system is zero.
(Fermi sphere at equilibrium)
Electric field in positive x-direction:
each electron acquires a drift velocity
eτ
vd = − E
m∗
⇒ whole Fermi sphere displaced to the left.
Very small displacement ⇒ most electrons still
cancel each other
Shaded area  uncompensated electrons  produce electric current
27

Estimate the current density —

vd
fraction of electrons which remain uncompensated: ≈
vF
 vd 
⇒ Concentration of these electrons = N  
 vF 
each electron has velocity ~ -vF
v 
So the current density: J = − Ne d vF = − Nevd
 vF 

Putting value of vd:

Ne 2τ F (τF: collision time at FS)
J= E
m∗
Ne 2τ F
as J =σ E → σ= (electrical conductivity)
m∗
Ne 2τ current carried equally by all electrons,
Classical result: σ=
m∗ each moving with a very small velocity, vd

28
The fact:
 the current  carried by very few electrons only, all moving
at high velocity.
 Relaxation time  determined only by electrons at the Fermi
surface, because only these electrons can contribute to the
transport properties.

As only electrons at the Fermi surface contribute to conductivity,

Mean free path of electrons: l F = vFτ F

Ne 2 l F
σ=
m∗vF
1 1
At high temperature: lF ∝ ∴ σ∝ → ρ ∝T
T T
Since the current is transported by electrons lying close to FS,
transport phenomena are very sensitive to the properties, shape, etc.,
of this surface. 29

Thermal Conductivity In Metals

dT
Amount of thermal energy crossing a unit area per unit time ∝ ∆T =
dx
dT
Q = −K (K is the thermal conductivity)
dx
Insulators — heat carried by phonons
Metals — heat carried by electrons + phonons ⇒ K = K e + K ph
in most metals Ke >> Kph K e ≈ 10 2 K ph (we can ignore Kph)

T2 T2 > T1 T1
Electrons at T2 more energetic.
So net flow of thermal energy from hot
end towards cold end.

 Heat transport by electrons near Fermi surface.

 Net contribution of electrons below FS is zero.

30
 1
Thermal conductivity: K = Ce vFl F Ce = electronic heat capacity,
3 vF = Fermi velocity,
lF = mean free path of electrons
at Fermi energy.
π2 kT π 2 Nk 2T 1  π 2 Nk 2T 
As Ce = R = ⇒ K =  vFl F
2 EF 2 EF 3  2 EF 

1 lF
now EF = m∗vF2 and =τF
2 vF
Therefore, thermal conductivity in terms
π 2 Nk 2Tτ F
K=
of the electronic properties of the metal: 3m∗
Gustav Wiedemann and Rudolf Franz (1853):
Ratio of thermal and electrical conductivities of all metals
has nearly the same value at a given T.

Ne 2 l F Ne 2τ F
recalling σ= =
m∗vF m∗
31

1  πk 
2
K
=   T Wiedemann-Franz law
σ 3 e 

Ludwig Lorenz → this ratio scaled linearly with temperature, and

thus a Lorenz number L can be defined:

1  πk 
2
K Very nearly constant at room
≡L=  
σT 3 e  temperature and above.

Numerically, L = 5.8 × 10-9 cal-ohm/s K2  nearly equal for all metals

⇒ Electrical and thermal conductivities are related.

More refined treatment ⇒ L does depend on the metal in question

32
Motion In A Magnetic Field
Cyclotron Resonance

- B
-
Metal slab — magnetic field B applied across

Electrons move counter-clock-wise to em-signal

direction of field → cyclotron motion
eB
Frequency of motion → Cyclotron frequency ωc =
m∗
magnetic fields ~ a few kG → the cyclotron frequencies lie in the
range of a few GHz

Using free electron mass:

ν c = ωc 2π = 2.8 B GHz (microwave range)

33

Electromagnetic signal passed || B → electric field acts on electrons

Part of the energy absorbed by the electrons

Resonance condition →
when frequency of signal ω = ωc  maximum absorption

When this condition true  each electron moves

synchronously with the wave throughout the cycle
→ absorption continues all through the cycle

when condition not satisfied  electron is in phase with the wave

through only a part of the cycle → absorption only during this time
For the rest of the cycle  electron out of phase
 returns energy to wave

ωc  measured from absorption curve

 determine electronic mass in metals and semi-conductors.
34
The Hall Effect

Edwin Hall (1879)

 allows to measure the free-electron concentration
N in metals (and semiconductors) and compare to
predictions of the FEG model.

Consider a magnetic field B applied transverse Magnetic field

z
to a thin metal sample carrying a current: Electron flow
Hall voltage
When B = 0  drift velocity vx. of conduction vx
+
y

electrons in –x-direction
-
applied field  electrons deflect in –y-direction EH
x
Jx
due to Lorentz force F = e( v × B) Electron
concentration
⇒ excess electron concentration on sample
face towards –y-direction ⇒ excess Magnetic field
negative charge path with
no field single free
+y-direction  excess positive charge electron

path with
Charge accumulation ⇒ Hall field EH in field
35
−y - direction

Resulting Hall force opposes Lorentz force.

Lorentz force : F = e( v × B )
so FL = −evx B (v x ⊥ B )
In equilibrium: FH = FL

i.e. − eEH = −evx B

or EH = v x B (Hall field)

To express in more measurable quantities:

Current density: J x = N (−e)vx (N = electron concentration)

1 1
so EH = − JxB → Hall constant: RH = −
Ne Ne
Measurements of Hall voltage →

sign of predominant charge carrier.

concentration of charge carriers.

mobility of charge carriers. 36
Thermionic Emission
When a metal is heated, electrons are emitted from its surface.
This phenomenon is known as thermionic emission.
Vacuum
Consider a metal at T = 0°K:
(i) The height of potential barrier  (EF + φ), φ
where EF  Fermi energy, φ  work function.

(ii) At T = 0°K all levels up to Fermi level are filled,

and all the levels above are empty. EF

(ii) No electron can escape form the metal surface.

Increasing temperature → levels above EF start to fill

Electron energy ≥ EF + φ → electrons escape (Thermionic emission)
φ  minimum energy to remove electron from surface
φ ~ 1.5 – 5 eV  work function
37

Current density of emitted electrons:

Consider a metal surface normal to x-direction. Then for an electron
to escape:
1 2
mv ≥ ( EF + φ )
2
h2k 2
Electron energy: E=
8π 2 m∗
2π n
Wave vector: k= (L  side of cubic lattice, n  integer)
L
h2n2 1 2E
so E= as E = m∗v 2 → v=
2m∗ L2 2 m∗
h Allowed quantum state velocities form a
v= n
m∗ L cube of side h / m∗ L

Assume current density in x-direction, vy and vz  any values (-∞ to ∞),

38
So number of states with electron velocities between:
v x and v x + dvx , v y and v y + dv y , vz and vz + dvz
lie within a volume dvx dv y dvz in velocity space.
dvx dv y dvz
So No. of velocity states between v + dv =
( h m∗ L ) 3
dvx dv y dvz
No. of states per unit volume =
( h m∗ ) 3

Probability for electrons occupying a state: 1

f (E) =
(Fermi-Dirac distribution function) e ( E − EF ) / kT
+1
If E >> EF, then f ( E ) ≈ e −( E − EF ) / kT (Boltzman function)

Hence, No. of electrons (taking into account Pauli exclusion principle)

is given by: 3
 m∗ 
N (v)dv = 2 f ( E )  dvx dv y dvz
 h  39

Emitted current density: dJ x = −evx N (v)dv

∴ Total current density: J x = ∫ dJ x = − ∫ evx N (v)dv

3 ∞ ∞ ∞
 m∗  −( E − EF ) / kT
J x = −2e  ∫ ∫ ∫ vx e dvx dv y dvz
 h  vx 0 −∞ −∞

where v x 0 = 2( E F + φ ) / m ∗
1
as E = m∗ (v x2 + v y2 + vz2 )
2
∗ 2
3 − m∗vx2 ∞ −m v y
∗ 2
∞ − m vz
 m∗  F ∞
E
J x = −2e  .e kT ∫ vx e 2 kT dv
x e∫2 kT dv y e 2 kT
∫ dvz
 h  vx 0 −∞ −∞

40
Using standard form of integrals:
∞
π e −αx
2

e −αx dx =
2
−αx 2
∫ α
and ∫ xe dx =
−∞ 2α

so the 1st integral: ∞ − m∗vx2 − m∗vx2 0 −( EF +φ )

kT kT
∫ vx e 2 kT dv x = ∗e 2 kT = ∗e kT

vx 0 m m

and 2nd and 3rd integrals: ∗ 2

∞ −m v y
∗ 2
∞ −m vz
2πkT
∫e 2 kT dv = ∫e 2 kT dv =
m∗
y z
−∞ −∞

therefore 3 E −E −φ
 m∗  F kT F
2πkT
J x = −2e  e kT . ∗ e kT e kT . ∗
 h  m m

4πm∗ek 2 2  −φ 
Jx = − 3
T exp 
h  kT 
41

 −φ  Richardson-Dushman equation
or J x = AT 2 exp 
 kT 

where 4πem∗k 2
A= = 120 Amp cm-2 K -2
h3
• φ >> kT → Current density increases exponentially with temperature
• work function is characteristic of a metal

We can write:

Jx φ  1 Jx
ln = ln A-  ln
T2
T2  k T
φ
slope =
k

1/ T
42
Failure Of Free Electron Model
Free electron model → good insight into many properties of metals, e.g.
heat capacity, thermal conductivity, electrical
conductivity.
 fails to explain a number of important properties
and experimental facts, for example:
 The difference between metals, semiconductors and insulators

 Electrical conductivity is proportional to electron concentration.

Ne 2τ
FE-model → σ=
m∗
Conductivity of divalent metals (Be, Cd, Zn) and even trivalent
metals (Al, In) is less than that of monovalent metals (Cu, Ag, Au).

43

 Free electron theory predicts negative value of Hall constant.

Some metals (Be, Cd, Zn) exhibit positive Hall constant.

 Fermi surface is spherical according to FE-model.

Measurements of Fermi surface indicate that it is often non-
spherical.

⇒ need a more accurate theory, which would be able to answer

these questions – the band theory

44