Solid State Physics

Chapter 8: Transport Properties

Boltzmann Equation
Martin Dressel
1. Physikalisches Institut der Universität Stuttgart
Outline
1. Is there a simple description of the electrons moving?
2. Why are electrons scattered?
3. How do metals conduct heat?
4. What happens to the electrical transport in the presence of a magnetic
field?
 Transport Properties
Boltzmann equation

Transport phenomena like the electrical current balance two opposing mechanisms:
the active influence from outside driving the system
the inhibitory effect by scattering of the charge carriers at phonons or impurities.
The Boltzmann equation describes this interaction.

In equilibrium the distribution is given by

1
f 0 ( E (k ) =
 E (k ) − E F ) 
exp   +1
 k BT 
The electrons will approach this final state from some initial state f (r − vdt , k + eEdt / η, t − dt )
by scattering:
 ∂f 
f (r, k , t ) = f (r − vdt , k + eEdt / η, t − dt ) +   dt
∂
  scatter
t
The first terms of a Taylor expansion yield:
∂f e 1   ∂f 
+ v ⋅ ∇r f −  E + v × H  ⋅ ∇k f =  
∂t η c   ∂t  scatter
diffusion field scattering
term term term
 Transport Properties
Boltzmann equation

The Boltzmann equation reads

∂f e 1   ∂f 
+ v ⋅ ∇r f −  E + v × H  ⋅ ∇k f =  
∂t η c   ∂t  scatter
The first term describes the time dependence of the distribution function f(t).
In relaxation time approximation after some perturbation
we assume an adiabatic approach of the equilibrium value.
∂f f − f0 τ is the relaxation time
=− which in general may be k-dependent.
∂t τ

In the following we want to consider equilibrium conditions with df/dt = 0,

i.e. the stationary case.

The second term describes the spatial dependence of the distribution function f.
In the following we want to focus at cases where f is constant in the entire sample df/dr = 0
 Transport Properties
Boltzmann equation

The Boltzmann equation reads

∂f e 1   ∂f 
+ v ⋅ ∇r f −  E + v × H  ⋅ ∇k f =  
∂t η c   ∂t  scatter
The scattering term describes the transitions due to scattering:
 ∂f 
dk '{[1 − f (k )]Wkk' f (k ' ) − [1 − f (k ' ) ]Wk'k f (k )}
V
  = 3∫
∂
  scatter ( 2π )
t
empty occupied empty occupied
states states states states
with k with k’ with k’ with k

with the transition probabilities W kk’ and W k’k

Again, for simplicity we choose the relaxation time approximation:
 ∂f  f (k ) − f 0 (k )
  =−
 ∂t  scatter τ (k )
 Transport Properties
Boltzmann equation

The Boltzmann equation

∂f e 1   ∂f 
+ v ⋅ ∇r f −  E + v × H  ⋅ ∇k f =  
∂t η c   ∂t  scatter
then has the solution:
e  1 
f (k ) = f 0 (k ) + τ (k ) E + v × H  ⋅ ∇ k f (k )
η  c 
We also want consider only electric fields:
e
f (k ) = f 0 (k ) + τ (k )E ⋅ ∇ k f (k )
η
In a linearized version, the perturbation does not change the distribution function:
e
f (k ) = f 0 (k ) + τ (k ) E ⋅ ∇ k f 0 (k )
η
 e 
≈ f 0  k + τ (k ) E 
 η 
It looks as if the entire Fermi sphere is shifted by (eτ/h)E.
 Transport Properties
Boltzmann equation

From
e
f (k ) = f 0 (k ) + τ (k ) E ⋅ ∇ k f 0 (k )
η
e ∂f 0 (k ) ∂E (k )
= f (k ) + τ (k )E
0
η ∂E (k ) ∂k
we see that we get some contribution
only at the Fermi surface.

Ziman, Solid State Theory

 Transport Properties
Boltzmann equation

The electrical conductivity relates the current density to the electric field (Ohm’s law):
J = σE
The current density for both spin directions is given by
J = ∫ e v(k ) f (k ) dk
With
e e ∂f 0 (k )
f (k ) = f (k ) + τ (k ) E ⋅ ∇ k f (k ) = f (k ) + τ (k )E
0 0 0
η η ∂k
∫ evf (k ) dk = 0
0
due to inversion symmetry

∂ f 0
(k ) ∂ f 0
(k ) ∂ E (k ) ∂ f 0
(k )
and = = ηv
∂k ∂E (k ) ∂k ∂E (k )
we obtain
1  ∂f 0 
J= 3 ∫∫
e τv( v ⋅ E ) −
2  dk

( 2π )  ∂E 

If we consider only one direction, the conductivity becomes

1 2
∂f 0 

σ= ∫∫ e τ v x  −
2
dk
(2π ) 3  ∂ E 
 Transport Properties
Boltzmann equation

Depending on the temperature,

the only the states in the range 4kB T
around the Fermi energy contribute to the transport.
∂f 0 (k )
≈ δ {E − EF }
∂E (k )
The integration over all k-values can be expressed as
the integration over the surface of constant energy SE
and the k-value perpendicular to it k⊥.
dE dE
dk = dS E dk ⊥ = dS E = dS E
∇k E ηv(k )
The conductivity becomes
e2 v x 2 (k ) e2 v x 2 (k )
σ= ∫ dS E dE v(k ) τ (k )δ {E − E F } = ∫ τ (k ) dS E
(2π ) 3 η (2π ) 3 η E = E v(k )
F

In the case of a Fermi sphere of quasi free electrons, we can evaluate an average value:
vx2 (k )τ (k ) 1
= v( EF )τ ( E F )
v(k ) 3
EF
Only the velocity and relaxation time of the electrons at the Fermi energy are relevant.
Ziman, Solid State Theory
 Transport Properties
Boltzmann equation

Only the electrons close to the Fermi energy contribute to the electronic conductivity.
In the case of a metal with kB T << EF we can assume parabolic dispersion and constant mass:
v( E F ) = ηkF / m (
∫ dS = 2 4πk
E
2
F )
EF
and
N 2 43 πk F3
n= = k F3 = 3π 2 n
V (2π )3
The conductivity becomes
e2 n
σ= τ (EF )
m
as already derived by the Drude model.

Here the mass is determined by the curvature of the energy bands.

The electron concentration n is given by the integration in k-space.
For metals the temperature dependence of the resistivity is given by
the temperature dependence of the scattering rate:
1 1 1
= + + ...
τ τ phon τ imp
In semiconductors n changes with temperature and
thus the scattering rate τ(k) has to averaged properly.
 Transport Properties
electronic conductivity

The electrons at the surface of the Fermi sphere (k ≈ kF)

can be scattered into empty states at the backside.
This is called Umklapp scattering
Relaxation is possible
by Umklapp processes
 Transport Properties
electronic conductivity

The electrical resistivity ρ(T) of metals can be considered as

the sum of various contributions:
ρ (T ) = ρ imp + ρ phon (T ) + ρ ee (T ) + ρ mag (T )

where Na
ρimp residual resistivity due to impurities
independent of T
ρphon scattering of conduction electrons
on lattice phonons
∝ T5
ρmag scattering on magnetic moments
diff. T dependences: afm, fm,
ρee electron-electron scattering
∝ T2

Kittel, Solid State Physics

 Transport Properties
electronic conductivity

For simple metals the main contributions are

ρ (T ) = ρ imp + ρ phon (T )
Matthiessen’s rule states that at low temperatures
the resistivity is governed by an impurity contribution
which is independent of temperature.
For T >> Θ ρphon(T) ∝ T
For T << Θ ρphon(T) ∝ T5
Thus at low temperatures
increasing
ρ (T ) = ρ 0 + ρ P T 5 disorder
rapid cooling

thermal
treatment

Pospisil et al. 1956

van den Berg et al. 1964
 Transport Properties
thermal conductivity

In the Boltzmann equation

∂f e  ∂f 
+ v ⋅ ∇r f − E ⋅ ∇k f =  
∂t η  ∂t  scatter
the diffusion term can be written as
∂f (k )
vk ∇T
∂T
and thus
∂f 0
f (k ) = f (k ) − τ (k )
0
v ⋅ ∇ rT
∂T
The heat current density thus becomes
∂f  ∂T 
0
J Q = ∫ dk ( E − EF )v 2x (k )τ (k ) − 
∂T  ∂x 

In the case of thermal conductivity experiments,

there is no net current of electrons and
thus no net electrical current.
Hot electrons move in one direction
cold electrons in the opposite direction.

Ziman, Solid State Theory

 Transport Properties
thermal conductivity

The thermal conductivity was given by v velocity

λ = 13 Cvλ C heat capacity
l mean free path
For a free electron gas
π 2 nkB2T π 2 nkB2Tτ
λel = vF λ =
3 mv 2F 3m

In pure metals the electronic contribution to

the heat current dominates the phonon part.
In impure metals or alloys both contributions Cu
are comparable.

Kittel, Solid State Physics

 Transport Properties
thermal conductivity

The ratio of thermal conductivity and

electrical conductivity is expressed by the
Wiedemann-Franz law
2 λ th Cu
λel π 2 k B2Tnτ / 3m π 2  kB 
= =   T
σ ne τ / m
2 3  e 
L
Lorenz number

The Lorenz number is given by

L = 2.45×10-8 WΩ/K2
λ el/σT

σ
 Transport Properties
thermoelectric effect

Starting again from the Boltzmann equation

∂f e  ∂f 
+ v ⋅ ∇r f − E ⋅ ∇k f =  
∂t η  ∂t  scatter
we want to consider the electrical transport in the presence of a temperature gradient.
e
f (k ) = f 0 (k ) + τ (k )E ⋅ ∇ k f 0 (k ) − τ (r) v (r)∇ r f 0 (r )
η
The distribution function can change due to an electric field and due to a temperature gradient.
With
 ∂f 
∇ r f 0 (r) =  ∇ r ⋅ T
 ∂T 
we get the current density in x-direction
2 ∂f  ∂ T  12  ∂ T 
0
e 1
J = σE + ∫ dk τ v x  −  = σ E' + L xx  −  E' = E + ∇ r E F (r)
(2π ) 3 ∂ T  ∂x   ∂x  e
In the case of a spherical Fermi surface the transport coefficient becomes:
1 ∂f 0
Lxx = e∫ dE τ ( E ) v ( E ) D( E )
12 2 D(E) Zustandsdichte
3 ∂T cV(T) specific heat
1
= eτ ( E F ) v 2 ( E F )cV (T )
3
 Transport Properties
thermoelectric effect

This means that a temperature gradient can cause an electric current (Seebeck effect);
and vice versa: an electric current can cause a temperature gradient (Peltier effect).

For the electrical and

heat current density
we obtain
J = L11E'+ L12 (− ∇ rT )
J Q = L21E '+ L22 (− ∇ rT )
T1 ≠ T2 ≠ T0

Ibach/Lüth: Festkörperphysik
 Transport Properties
thermoelectric effect

In the one-dimensional case of two soldered metals with T1 ≠ T2 ≠ T0 and J = 0

and the energy E’ = E.
The electric field is
L12 ∂T ∂T
E = 11 =K
L ∂x ∂x
and the measured voltage
1 2 0
U = ∫ E B d x + ∫ E Ad x + ∫ E Bd x
0 1 2
1 ∂T 2 ∂T T2
= ∫ KB dx + ∫ K A dx = ∫ ( K A − K B )dT
2 ∂x 1 ∂ x T1

The voltage depends on the difference in temperature T2 – T1 of the two solder joints and
the difference in thermopower K A and KB between the two metals.

In the opposite case the temperature is constant dT/dx = 0 and thus

J = L11E J Q = L21E
J Q = L21 / L11J = Π J
with Π the Peltier coefficient.
Ibach/Lüth: Festkörperphysik
 Transport Properties
thermoelectric effect

Example of thermoelectric effects for pairs of metals commonly used as thermocouples.

Weißmantel, Hamann, Festkörperphysik

 Transport Properties
magneto transport

The resistivity of a solid may change in the presence of a strong external magnetic field.
Starting from Boltzmann equation
∂f e 1   ∂f 
+ v ⋅ ∇r f −  E + v × B  ⋅ ∇k f =  
∂t η c   ∂t  scatter
we now explicitly use the magnetic field dependence for a B-field along the z-axis:
e  1 
f (k ) = f 0 (k ) + τ (k ) E + v × B  ⋅ ∇ k f (k )
η  c 
 ∂f 0 
= f + eτ  −
0
∂E
 1
[( ) ( ) ]
 1 + ω 2τ 2 E x − E yωcτ vx + E y − E xω cτ v y
  c
with the cyclotron frequency
eB
ωc =
m
Two phenomena can be distinguished:
• Hall effect: the moving carriers experience a Lorentz force perpendicular to the vx.
This leads to a Hall voltage Ey which compensates this force: thus jy = 0 and vy = 0.
• magneto resistance: the magnetic field leads to a larger resistance
 Transport Properties
Hall effect

In an external magnetic field moving charge carriers experience a Lorentz force.

Fy = e(v × B ) y = evB
The magnetic field B is along the z-direction.
The velocity v of the electrons is along the x-direction.
The current density j is given by
I
jx = = −env x
L y Lz
The electrons build up charge at the side of the
sample, leading to an electric field E y = UH/L y
which acts opposite to the Lorentz force
leading to some equilibrium.
ρ ρ
ρ ρ  j x × Bz  ρ
EH ≡ E y =   = RH ⋅ j x ⋅ B z ⋅ ey
 n⋅e 
The parameter
1
RH = −
n⋅e
is called the Hall constant.

Weißmantel, Hamann, Festkörperphysik

 Transport Properties
Hall effect

The Hall effect is the standard method to determine

the carrier concentration of semiconductors.
The Hall voltage is inversely proportional
to the carrier density;
i.e. small concentrations give a large effect and
can be measured very accurately.
Electron and hole conduction give different signs
in the Hall constant, which allows to distinguish them.
The situation is more complicated if different carriers
contribute to the electrical current.

Ibach/Lüth: Festkörperphysik
 Transport Properties
Hall effect

The Hall effect can also be explained

using the displacement of the Fermi sphere.
The external electric field Ex shifts the sphere.

The magnetic field leads to a rotation

by the Hall angle

The induced electric field shifts the Fermi sphere along ky

until the center is on the kx axis.

Weißmantel, Hamann, Festkörperphysik

 Transport Properties
magneto resistance

The effect of magneto resistance changes the electrical conductivity

if a magnetic field is applied.
We can distinguish the longitudinal magneto resistance and the transverse magneto resistance,
depending on the orientation of the magnetic field with respect to the current direction.

Jx Jx
Bx Bz

In general for small magnetic fields the relative change is described by a square dependence
σ 0 −σ B
∝ B2
σ0
with some saturation for higher fields.
 Transport Properties
magneto transport effects

There is a number of other effects,

which describe the change of physical properties due to magnetic fields
• Ettinghausen effect
There is a temperature gradient perpendicular to a magnetic field and current:
∂T
= γ E J x By
∂z
• Nernst effect
A magnetic field B y acts on a heat current wx, leading to an electric field Ez:
E z = γ N wx B y

• Righi-Ledue effect
If a magnetic field By is applied while a heat current wx flows,
a temperature gradient occurs in z-direction:
∂T
= γ RL wx B y
∂z
• Nernst-Ettinghausen effect
The thermo power can change in the presence of a magnetic field.