CH01

Chapter 1
Boltzmann Transport
1.1 References
H. Smith and H. H. Jensen, Transport Phenomena
N. W. Ashcroft and N. D. Mermin, Solid State Physics, chapter 13.
P. L. Taylor and O. Heinonen, Condensed Matter Physics, chapter 8.
J. M. Ziman, Principles of the Theory of Solids, chapter 7.
1.2 Introduction
Transport is the phenomenon of currents flowing in response to applied fields. By current

we generally mean an electrical current j, or thermal current jq . By applied field we
generally mean an electric field E or a temperature gradient T . The currents and fields
are linearly related, and it will be our goal to calculate the coefficients (known as transport
coefficients) of these linear relations. Implicit in our discussion is the assumption that we
are always dealing with systems near equilibrium.
1
2 CHAPTER 1. BOLTZMANN TRANSPORT
1.3 Boltzmann Equation in Solids
1.3.1 Semiclassical Dynamics and Distribution Functions
The semiclassical dynamics of a wavepacket in a solid are described by the equations
dr 1 n (k)
= vn (k) = (1.1)
dt ~ k
dk e e
= E(r, t) vn (k) B(r, t) . (1.2)
dt ~ ~c
Here, n is the band index and n (k) is the dispersion relation for band n. The wavevector
is k (~k is the crystal momentum), and n (k) is periodic under k k + G, where G is
any reciprocal lattice vector. These formulae are valid only at sufficiently weak fields. They
neglect, for example, Zener tunneling processes in which an electron may change its band
index as it traverses the Brillouin zone. We also neglect the spin-orbit interaction in our
discussion.
We are of course interested in more than just a single electron, hence to that end let us
consider the distribution function fn (r, k, t), defined such that1
d3r d3k # of electrons of spin in band n with positions within
fn (r, k, t) (1.3)
(2) 3 d3r of r and wavevectors within d3k of k at time t.
Note that the distribution function is dimensionless. By performing integrals over the
distribution function, we can obtain various physical quantities. For example, the current
density at r is given by
X Z d3k
j(r, t) = e fn (r, k, t) vn (k) . (1.4)
n,
(2)3

The symbol in the above formula is to remind us that the wavevector integral is performed
only over the first Brillouin zone.
We now ask how the distribution functions fn (r, k, t) evolve in time. To simplify matters,
we will consider a single band and drop the indices n. It is clear that in the absence of
collisions, the distribution function must satisfy the continuity equation,
f
+ (uf ) = 0 . (1.5)
t
This is just the condition of number conservation for electrons. Take care to note that
and u are six -dimensional phase space vectors:
u = ( x , y , z , kx , ky , kz ) (1.6)

= , , , , , . (1.7)
x y z kx ky kz
1
We will assume three space dimensions. The discussion may be generalized to quasi-two dimensional
and quasi-one dimensional systems as well.
1.3. BOLTZMANN EQUATION IN SOLIDS 3
Now note that as a consequence of the dynamics (1.1,1.2) that u = 0, i.e. phase space
flow is incompressible, provided that (k) is a function of k alone, and not of r. Thus, in
the absence of collisions, we have
f
+ u f = 0 . (1.8)
t
The differential operator Dt t + u is sometimes called the convective derivative.

EXERCISE: Show that u = 0.
Next we must consider the effect of collisions, which are not accounted for by the semi-
classical dynamics. In a collision process, an electron with wavevector k and one with
wavevector k0 can instantaneously convert into a pair with wavevectors k + q and k0 q
(modulo a reciprocal lattice vector G), where q is the wavevector transfer. Note that the
total wavevector is preserved (mod G). This means that Dt f 6= 0. Rather, we should write

f f f f
+ r + k = Ik {f } (1.9)
t r k t coll
where the right side is known as the collision integral . The collision integral is in general
a function of r, k, and t and a functional of the distribution f . As the k-dependence is
the most important for our concerns, we will write Ik in order to make this dependence
explicit. Some examples should help clarify the situation.
First, lets consider a very simple model of the collision integral,
f (r, k, t) f 0 (r, k)
Ik {f } = . (1.10)
((k))
This model is known as the relaxation time approximation. Here, f 0 (r, k) is a static dis-
tribution function which describes a local equilibrium at r. The quantity ((k)) is the
relaxation time, which we allow to be energy-dependent. Note that the collision integral in-
deed depends on the variables (r, k, t), and has a particularly simple functional dependence
on the distribution f .
A more sophisticated model might invoke Fermis golden rule, Consider elastic scattering
from a static potential U(r) which induces transitions between different momentum states.
We can then write
2 X
0 2
Ik {f } = | k U k | (fk0 fk ) (k k0 ) (1.11)
~
k0
Z 3 0
2 dk
= | U(k k0 )|2 (fk0 fk ) (k k0 ) (1.12)
~V (2)3

where we abbreviate fk f (r, k, t). In deriving the last line weve used plane wave wave-

functions2 k (r) = exp(ik r)/ V , as well as the result
Z 3
X dk
A(k) = V A(k) (1.13)
(2)3
k
for smooth functions A(k). Note the factor of V 1 in front of the integral in eqn. 1.12.
What this tells us is that for a bounded localized potential U(r), the contribution to the
collision integral is inversely proportional to the size of the system. This makes sense
because the number of electrons scales as V but the potential is only appreciable over a
region of volume V 0 . Later on, we shall consider a finite density of scatterers, writing
PNimp
U(r) = i=1 U (r Ri ), where the impurity density nimp = Nimp /V is finite, scaling as
V . In this case U(k k0 ) apparently scales as V , which would mean Ik {f } scales as V ,
0
which is unphysical. As we shall see, the random positioning of the impurities means that
the O(V 2 ) contribution to |U(k k0 )|2 is incoherent and averages out to zero. The coherent
piece scales as V , canceling the V in the denominator of eqn. 1.12, resulting in a finite value
for the collision integral in the thermodynamic limit (i.e. neither infinite nor infinitesimal).
Later on we will discuss electron-phonon scattering, which is inelastic. An electron with
wavevector k0 can scatter into a state with wavevector k = k0 q mod G by absorption of
a phonon of wavevector q or emission of a phonon of wavevector q. Similarly, an electron
of wavevector k can scatter into the state k0 by emission of a phonon of wavevector q or
absorption of a phonon of wavevector q. The matrix element for these processes depends
on k, k0 , and the polarization index of the phonon. Overall, energy is conserved. These
considerations lead us to the following collision integral:
2 X n
Ik {f, n} = |g (k, k0 )|2 (1 fk ) fk0 (1 + nq, ) (k + ~q k0 )
~V 0
k ,
+(1 fk ) fk0 nq (k ~q k0 )
fk (1 fk0 ) (1 + nq ) (k ~q k0 )
o
fk (1 fk0 ) nq (k + ~q k0 ) q,k0 k mod G , (1.14)
which is a functional of both the electron distribution fk as well as the phonon distribution
nq . The four terms inside the curly brackets correspond, respectively, to cases (a) through
(d) in fig. 1.1.
While collisions will violate crystal momentum conservation, they do not violate conserva-
tion of particle number. Hence we should have3
Z Z 3
dk
d3r Ik {f } = 0 . (1.15)
(2)3

2
Rather than plane waves, we should use Bloch waves nk (r ) = exp(ik r ) unk (r ), where cell function
unk (r ) satisfies unk (r + R) = unk (r ), where R is any direct lattice vector. Plane waves do not contain
the cell functions, although they do exhibit Bloch periodicity nk (r + R) = exp(ik R) nk (r ).
3
R d3k
If collisions are purely local, then (2)3 Ik {f } = 0 at every point r in space.

1.3. BOLTZMANN EQUATION IN SOLIDS 5
Figure 1.1: Electron-phonon vertices.
The total particle number,

Z Z 3
dk
N= d3r f (r, k, t) (1.16)
(2)3

is a collisional invariant - a quantity which is preserved in the collision process. Other

collisional invariants include energy (when all sources are accounted for), spin (total spin),
and crystal momentum (if there is no breaking of lattice translation symmetry)4 . Consider
a function F (r, k) of position and wavevector. Its average value is
d3k
Z Z
F (t) = d3 r F (r, k) f (r, k, t) . (1.17)
(2)3

Taking the time derivative,
d3k
Z Z
dF F 3
= = d r F (r, k) (rf ) (kf ) + Ik {f }
dt t (2)3 r k

d3k
Z Z
F dr F dk
= d3 r + f + F Ik {f } . (1.18)
(2)3 r dt k dt

4
Note that the relaxation time approximation violates all such conservation laws. Within the relaxation
time approximation, there are no collisional invariants.
Hence, if F is preserved by the dynamics between collisions, then

Z Z 3
dF 3 dk
= d r F Ik {f } , (1.19)
dt (2)3

which says that F (t) changes only as a result of collisions. If F is a collisional invariant,
then F = 0. This is the case when F = 1, in which case F is the total number of particles,
or when F = (k), in which case F is the total energy.
1.3.2 Local Equilibrium
The equilibrium Fermi distribution,

1
0 (k)
f (k) = exp +1 (1.20)
kB T
is a space-independent and time-independent solution to the Boltzmann equation. Since
collisions act locally in space, they act on short time scales to establish a local equilibrium
described by a distribution function
1
0 (k) (r, t)
f (r, k, t) = exp +1 (1.21)
kB T (r, t)
This is, however, not a solution to the full Boltzmann equation due to the streaming terms
r r + k k in the convective derivative. These, though, act on longer time scales than
those responsible for the establishment of local equilibrium. To obtain a solution, we write
f (r, k, t) = f 0 (r, k, t) + f (r, k, t) (1.22)
and solve for the deviation f (r, k, t). We will assume = (r) and T = T (r) are time-
independent. We first compute the differential of f 0 ,
f 0

df 0 = kB T d
kB T
( )
f 0 d ( ) dT d
= kB T +
kB T kB T 2 kB T
( )
f 0 T
= dr + dr dk , (1.23)
r T r k
from which we read off

( )
f 0 f 0

T
= + (1.24)
r r T r
f 0 f 0
= ~v . (1.25)
k
1.4. CONDUCTIVITY OF NORMAL METALS 7
We thereby obtain
f 0

f e 1 f
+ v f E+ vB + v eE + T = Ik {f 0 + f }
t ~ c k T
(1.26)
where E = ( /e) is the gradient of the electrochemical potential; well henceforth
refer to E as the electric field. Eqn (1.26) is a nonlinear integrodifferential equation in f ,
with the nonlinearity coming from the collision integral. (In some cases, such as impurity
scattering, the collision integral may be a linear functional.) We will solve a linearized
version of this equation, assuming the system is always close to a state of local equilibrium.
Note that the inhomogeneous term in (1.26) involves the electric field and the temperature
gradient T . This means that f is proportional to these quantities, and if they are small
then f is small. The gradient of f is then of second order in smallness, since the external
fields /e and T are assumed to be slowly varying in space. To lowest order in smallness,
then, we obtain the following linearized Boltzmann equation:
f 0

f e f
vB + v eE + T = L f (1.27)
t ~c k T
where L f is the linearized collision integral; L is a linear operator acting on f (we suppress
denoting the k dependence of L). Note that we have not assumed that B is small. Indeed
later on we will derive expressions for high B transport coefficients.
1.4 Conductivity of Normal Metals
1.4.1 Relaxation Time Approximation
Consider a normal metal in the presence of an electric field E. Well assume B = 0, T = 0,

and also that E is spatially uniform as well. This in turn guarantees that f itself is spatially
uniform. The Boltzmann equation then reduces to
f f 0
ev E = Ik {f 0 + f } . (1.28)
t
Well solve this by adopting the relaxation time approximation for Ik {f }:
f f0 f
Ik {f } = = , (1.29)

where , which may be k-dependent, is the relaxation time. In the absence of any fields
or temperature and electrochemical potential gradients, the Boltzmann equation becomes
f = f / , with the solution f (t) = f (0) exp(t/ ). The distribution thereby relaxes to
the equilibrium one on the scale of .
Writing E(t) = E eit , we solve

f (k, t) f 0 f (k, t)
e v(k) E eit = (1.30)
t ((k))
and obtain
e E v(k) ((k)) f 0 it
f (k, t) = e . (1.31)
1 i ((k))
The equilibrium distribution f 0 (k) results in zero current, since f 0 (k) = f 0 (k). Thus,
the current density is given by the expression
Z 3
dk
j (r, t) = 2e f v
(2)3

d3k ((k)) v (k) v (k) f 0
Z
2 it
= 2e E e . (1.32)
(2)3 1 i ((k))

In the above calculation, the factor of two arises from summing over spin polarizations. The
conductivity tensor is defined by the linear relation j () = () E (). We have thus
derived an expression for the conductivity tensor,
Z 3
d k ((k)) v (k) v (k) f 0

2
() = 2e (1.33)
(2)3 1 i ((k))

Note that the conductivity is a property of the Fermi surface. For kB T F , we have
f 0 / (F (k)) and the above integral is over the Fermi surface alone. Explicitly,
we change variables to energy and coordinates along a constant energy surface, writing
d dS d dS
d3k = = , (1.34)
|/k| ~|v|
where dS is the differential area on the constant energy surface (k) = , and v(k) =
~1 k (k) is the velocity. For T TF , then,
e2 v (k) v (k)
Z
(F )
() = 3 dSF . (1.35)
4 ~ 1 i (F ) |v(k)|
For free electrons in a parabolic band, we write (k) = ~2 k2 /2m , so v (k) = ~k /m . To

further simplify matters, let us assume that is constant, or at least very slowly varying in
the vicinity of the Fermi surface. We find
e2 f 0
Z
2
() = d g() , (1.36)
3m 1 i
where g() is the density of states,
d3k
Z
g() = 2 ( (k)) . (1.37)
(2)3

The (three-dimensional) parabolic band density of states is found to be

(2m )3/2
g() = () , (1.38)
2 2 ~3
where (x) is the step function. In fact, integrating (1.36) by parts, we only need to know

about the dependence in g(), and not the details of its prefactor:
f 0
Z Z

d g() = d f 0 () ( g())

Z
= 23 d g() f 0 () = 32 n , (1.39)
where n = N/V is the electron number density for the conduction band. The final result
for the conductivity tensor is
ne2
() = (1.40)
m 1 i
This is called the Drude model of electrical conduction in metals. The dissipative part of
the conductivity is Re . Writing = and separating into real and imaginary parts
= 0 + i 00 , we have
ne2 1
0 () = . (1.41)
m 1 + 2 2
The peak at = 0 is known as the Drude peak.
Heres an elementary derivation of this result. Let p(t) be the momentum of an electron,
and solve the equation of motion
dp p
= e E eit (1.42)
dt
to obtain
e E it e E
p(t) = e + p(0) + et/ . (1.43)
1 i 1 i
The second term above is a transient solution to the homogeneous equation p + p/ = 0.
At long times, then, the current j = nep/m is
ne2
j(t) = E eit . (1.44)
m (1 i )
In the Boltzmann equation approach, however, we understand that n is the conduction
electron density, which does not include contributions from filled bands.
In solids the effective mass m typically varies over a small range: m (0.1 1) me . The
two factors which principally determine the conductivity are then the carrier density n and
the scattering time . The mobility , defined as the ratio ( = 0)/ne, is thus (roughly)
independent of carrier density5 . Since j = nev = E, where v is an average carrier
velocity, we have v = E, and the mobility = e /m measures the ratio of the carrier
velocity to the applied electric field.
5
Inasmuch as both and m can depend on the Fermi energy, is not completely independent of carrier
density.
Figure 1.2: Frequency-dependent conductivity of liquid sodium by T. Inagaki et al , Phys.

Rev. B 13, 5610 (1976).
1.4.2 Optical Reflectivity of Metals and Semiconductors
What happens when an electromagnetic wave is incident on a metal? Inside the metal we
have Maxwells equations,

4 1 D 4 i
H = j+ = ik B = E (1.45)
c c t c c
1 B i
E = = ik E = B (1.46)
c t c
E =B =0 = ik E = ik B = 0 , (1.47)
where weve assumed = = 1 inside the metal, ignoring polarization due to virtual
interband transitions (i.e. from core electrons). Hence,
2 4i
k2 = + 2 () (1.48)
c2 c
2 p2 i 2
= 2 + 2 () 2 , (1.49)
c c 1 i c
p
where p = 4ne2 /m is the plasma frequency for the conduction band. The dielectric
function,
4i() p2 i
() = 1 + =1+ 2 (1.50)
1 i
p
determines the complex refractive index, N () = (), leading to the electromagnetic
dispersion relation k = N () /c.
Consider a wave normally incident upon a metallic surface normal to z. In the vacuum
(z < 0), we write
E(r, t) = E1 x eiz/c eit + E2 x eiz/c eit (1.51)
c
B(r, t) = E = E1 y eiz/c eit E2 y eiz/c eit (1.52)
i
while in the metal (z > 0),
E(r, t) = E3 x eiN z/c eit (1.53)
c
B(r, t) = E = N E3 y eiN z/c eit (1.54)
i
Continuity of E n gives E1 + E2 = E3 . Continuity of H n gives E1 E2 = N E3 . Thus,
E2 1N E3 2
= , = (1.55)
E1 1+N E1 1+N
and the reflection and transmission coefficients are
2
1 N () 2

E2
R() = = (1.56)
E1 1 + N ()
2
E3 4
T () = = . (1.57)
E1 1 + N ()2
Weve now solved the electromagnetic boundary value problem.

Typical values For a metal with n = 1022 cm3 and m = me , the plasma frequency is
p = 5.71015 s1 . The scattering time varies considerably as a function of temperature. In
high purity copper at T = 4 K, 2 109 s and p 107 . At T = 300 K, 2 1014 s
and p 100. In either case, p 1. There are then three regimes to consider.
1 p :
We may approximate 1 i 1, hence

i p2 i p2
N 2 () = 1 +
(1 i )
!1/2
1 + i p2 2 2
N () = R 1 . (1.58)
2 p
Hence R 1 and the metal reflects.

1 p :
In this regime,
p2 i p2
N 2 () 1 + (1.59)
2 3
Figure 1.3: Frequency-dependent absorption of hcp cobalt by J. Weaver et al., Phys. Rev.
B 19, 3850 (1979).
which is almost purely real and negative. Hence N is almost purely imaginary and
R 1. (To lowest nontrivial order, R = 1 2/p .) Still high reflectivity.
1 p :
Here we have
p2 p
N 2 () 1 2
= R = (1.60)
2
and R 1 the metal is transparent at frequencies large compared to p .
1.4.3 Optical Conductivity of Semiconductors
In our analysis of the electrodynamics of metals, we assumed that the dielectric constant
due to all the filled bands was simply = 1. This is not quite right. We should instead
have written
2 4i()
k2 = + (1.61)
c2
( c2 )
2
p i
() = 1 + 2 , (1.62)
1 i
Figure 1.4: Frequency-dependent conductivity of hcp cobalt by J. Weaver et al., Phys.

Rev. B 19, 3850 (1979). This curve is derived from the data of fig. 1.3 using a Kramers-
Kronig transformation. A Drude peak is observed at low frequencies. At higher frequencies,
interband effects dominate.
where is the dielectric constant due to virtual transitions to fully occupied (i.e. core)
and fully unoccupied bands, at a frequency small compared to the interband frequency. The
plasma frequency is now defined as
1/2
4ne2

p = (1.63)
m
where n is the conduction electron density. Note that ( ) = , although again this
is only true for smaller than the gap to neighboring bands. It turns out that for insulators
one can write
2
pv
' 1 + 2 (1.64)
g
p
where pv = 4nv e2 /me , with nv the number density of valence electrons, and g is
the energy gap between valence and conduction bands. In semiconductors such as Si and
Ge, g 4 eV, while pv 16 eV, hence 17, which is in rough agreement with the
experimental values of 12 for Si and 16 for Ge. In metals, the band gaps generally are
considerably larger.
There are some important differences to consider in comparing semiconductors and metals:
The carrier density n typically is much smaller in semiconductors than in metals,

ranging from n 1016 cm3 in intrinsic (i.e. undoped, thermally excited at room
temperature) materials to n 1019 cm3 in doped materials.
10 20 and m /me 0.1. The product m thus differs only slightly from its
free electron value.
Since nsemi < 4

10 nmetal , one has
psemi 102 pmetal 1014 s . (1.65)
In high purity semiconductors the mobility = e /m > 5 2

10 cm /vs the low temperature
scattering time is typically 1011 s. Thus, for > 15 1
3 10 s in the optical range, we

have p 1, in which case N () and the reflectivity is

1 2

R=
. (1.66)
1 +
Taking = 10, one obtains R = 0.27, which is high enough so that polished Si wafers
appear shiny.
1.4.4 Optical Conductivity and the Fermi Surface
At high frequencies, when 1, our expression for the conductivity, eqn. (1.33), yields
ie2 f 0
Z Z

() = d dS v(k) , (1.67)
12 3 ~
where we have presumed sufficient crystalline symmetry to guarantee that = is

diagonal. In the isotropic case, and at temperatures low compared with TF , the integral
over the Fermi surface gives 4kF2 vF = 12 3 ~n/m , whence = ine2 /m , which is the
large frequency limit of our previous result. For a general Fermi surface, we can define
ine2
( 1 ) (1.68)
mopt
where the optical mass mopt is given by
f 0
Z Z
1 1
= d dS v(k) . (1.69)
mopt 12 3 ~n
Note that at high frequencies () is purely imaginary. What does this mean? If
1
E eit + e+it

E(t) = E cos(t) = 2 (1.70)
1.5. CALCULATION OF THE SCATTERING TIME 15
then
1
E () eit + () e+it

j(t) = 2
ne2
= E sin(t) , (1.71)
mopt
where we have invoked () = (). The current is therefore 90 out of phase with the
voltage, and the average over a cycle hj(t) E(t)i = 0. Recall that we found metals to be
transparent for p 1 .
At zero temperature, the optical mass is given by
Z
1 1
= 3
dSF v(k) . (1.72)
mopt 12 ~n
The density of states, g(F ), is

Z
1 1
g(F ) = 3 dSF v(k) , (1.73)
4 ~
from which one can define the thermodynamic effective mass mth , appealing to the low
temperature form of the specific heat,
2 2 m
cV = kB T g(F ) th c0V , (1.74)
3 me
where
me kB2 T
c0V (3 2 n)1/3 (1.75)
3~2
is the specific heat for a free electron gas of density n. Thus,
Z
~ 1
mth = 2 1/3
dSF v(k) (1.76)
4(3 n)
1.5 Calculation of the Scattering Time
1.5.1 Potential Scattering and Fermis Golden Rule
Let us go beyond the relaxation time approximation and calculate the scattering time
from first principles. We will concern ourselves with scattering of electrons from crystalline
impurities. We begin with Fermis Golden Rule6 ,
2 X
0 2
Ik {f } = k U k (fk0 fk ) ((k) (k0 )) , (1.77)
~ 0
k
6
Well treat the scattering of each spin species separately. We assume no spin-flip scattering takes place.
mopt /me mth /me

Metal thy expt thy expt
Li 1.45 1.57 1.64 2.23
Na 1.00 1.13 1.00 1.27
K 1.02 1.16 1.07 1.26
Rb 1.08 1.16 1.18 1.36
Cs 1.29 1.19 1.75 1.79
Cu - - 1.46 1.38
Ag - - 1.00 1.00
Au - - 1.09 1.08
Table 1.1: Optical and thermodynamic effective masses of monovalent metals. (Taken from
Smith and Jensen).
where U(r) is a sum over individual impurity ion potentials,

Nimp
X
U(r) = U (r Rj ) (1.78)
j=1
Nimp
X i(kk0 )R 2

0 2
k U k = V 2 |U (k k0 )|2 e , (1.79)
j

j=1
where V is the volume of the solid and

Z
U (q) = d3r U (r) eiqr (1.80)
is the Fourier transform of the impurity potential. Note that we are assuming a single species
of impurities; the method can be generalized to account for different impurity species.
To make progress, we assume the impurity positions are random and uncorrelated, and we
average over them. Using
NX 2
imp
iqR
e j = N
imp + Nimp (Nimp 1) q,0 , (1.81)

j=1
we obtain

2 Nimp Nimp (Nimp 1)
k0 U k =
2
|U (k k0 )|2 + |U (0)|2 kk0 . (1.82)
V V2
EXERCISE: Verify eqn. (1.81).

We will neglect the second term in eqn. 1.82 arising from the spatial average (q = 0
Fourier component) of the potential. As we will see, in the end it will cancel out. Writing
f = f 0 + f , we have
!
2nimp d3k 0 ~2 k2 ~2 k0 2
Z
0 2
Ik {f } = | U (k k )| (fk0 fk ) , (1.83)
~ (2)3 2m 2m

where nimp = Nimp /V is the number density of impurities. Note that we are assuming a
parabolic band. We next make the Ansatz
f 0

fk = ((k)) e E v(k) (1.84)
(k)
and solve for ((k)). The (time-independent) Boltzmann equation is

!
f 0 d3k 0 ~2 k2 ~2 k0 2
Z
2 0 2
e E v(k) = n eE |U (k k )|
~ imp (2)3 2m 2m

!
f 0 f 0

0 0
((k )) v(k ) ((k)) v(k) . (1.85)
(k0 ) (k)
Due to the isotropy of the problem, we must have ((k)) is a function only of the magnitude
of k. We then obtain7
Z 0
nimp 0 2 (k k ) ~
Z
~k 0 02 0
= ((k)) dk k dk |U (k k )| (k k0 ) , (1.86)
m 4 2 ~ ~2 k/m m
0
whence
m kF nimp
Z
1
= dk0 |U (kF k kF k0 )|2 (1 k k0 ) . (1.87)
(F ) 4 2 ~3
If the impurity potential U (r) itself is isotropic, then its Fourier transform U (q) is a function
of q 2 = 4kF2 sin2 21 where cos = k k0 and q = k0 k is the transfer wavevector. Recalling
the Born approximation for differential scattering cross section,
2
m

() = |U (k k0 )|2 , (1.88)
2~2
we may finally write
Z
1
= 2nimp vF d F () (1 cos ) sin (1.89)
(F )
0
where vF = ~kF /m is the Fermi velocity8 . The mean free path is defined by ` = vF .
7
We assume that the Fermi surface is contained within the first Brillouin zone.
8
The subscript on F () is to remind us that the cross section depends on kF as well as .
Notice the factor (1 cos ) in the integrand of (1.89). This tells us that forward scattering
( = 0) doesnt contribute to the scattering rate, which justifies our neglect of the second
term in eqn. (1.82). Why should be utterly insensitive to forward scattering? Because
(F ) is the transport lifetime, and forward scattering does not degrade the current. There-
fore, ( = 0) does not contribute to the transport scattering rate 1 (F ). Oftentimes
one sees reference in the literature to a single particle lifetime as well, which is given by
the same expression but without this factor:
(
1
) Z
sp

1
= 2nimp vF d F () sin (1.90)
tr1 (1 cos )
0
Note that sp = (nimp vF F,tot )1 , where F,tot is the total scattering cross section at energy
F , a formula familiar from elementary kinetic theory.
To derive the single particle lifetime, one can examine the linearized time-dependent Boltz-
mann equation with E = 0,
Z
fk
= nimp vF dk0 (kk0 ) (fk0 fk ) , (1.91)
t
where v = ~k/m is the velocity, and where the kernel is kk0 = cos1 (k k0 ). We now
expand in spherical harmonics, writing
X

(kk0 ) tot L YLM (k) YLM (k0 ) , (1.92)
L,M
where as before
Z
tot = 2 d sin () . (1.93)
0
Expanding X
fk (t) = ALM (t) YLM (k) , (1.94)
L,M
the linearized Boltzmann equation simplifies to
ALM
+ (1 L ) nimp vF tot ALM = 0 , (1.95)
t
whence one obtains a hierarchy of relaxation rates,
L1 = (1 L ) nimp vF tot , (1.96)
which depend only on the total angular momentum quantum number L. These rates de-
scribe the relaxation of nonuniform distributions, when fk (t = 0) is proportional to some
1
spherical harmonic YLM (k). Note that L=0 = 0, which reflects the fact that the total
particle number is a collisional invariant. The single particle lifetime is identified as
1 1
sp L = nimp vF tot , (1.97)
corresponding to a point distortion of the uniform distribution.
1.5.2 Screening and the Transport Lifetime
For a Coulomb impurity, with U (r) = Ze2 /r we have U (q) = 4Ze2 /q 2 . Consequently,
!2
Ze2
F () = , (1.98)
4F sin2 12
and there is a strong divergence as 0, with F () 4 . The transport lifetime

diverges logarithmically! What went wrong?
What went wrong is that we have failed to account for screening. Free charges will rearrange
themselves so as to screen an impurity potential. At long range, the effective (screened)
potential decays exponentally, rather than as 1/r. The screened potential is of the Yukawa
form, and its increase at low q is cut off on the scale of the inverse screening length 1 .
There are two types of screening to consider:
Thomas-Fermi Screening : This is the typical screening mechanism in metals. A weak

local electrostatic potential (r) will induce a change in the local electronic density
according to n(r) = e(r)g(F ), where g(F ) is the density of states at the Fermi
level. This charge imbalance is again related to (r) through the Poisson equation.
The result is a self-consistent equation for (r),
2 = 4e n
= 4e2 g(F ) 2
TF . (1.99)
1/2
The Thomas-Fermi screening length is TF = 4e2 g(F ) .
Debye-Huckel Screening : This mechanism is typical of ionic solutions, although it may
also be of relevance in solids with ultra-low Fermi energies. From classical statistical
mechanics, the local variation in electron number density induced by a potential (r)
is
ne(r)
n(r) = n ee(r)/kB T n , (1.100)
kB T
where we assume the potential is weak on the scale of kB T /e. Poissons equation now
gives us
2 = 4e n
4ne2
= 2
DH . (1.101)
kB T
A screened test charge Ze at the origin obeys

2 = 2 4Ze(r) , (1.102)
the solution of which is
Ze2 r/ 4Ze2
U (r) = e(r) = e = U (q) = . (1.103)
r q 2 + 2
The differential scattering cross section is now

!2
Ze2 1
F () = (1.104)
4F sin2 12 + (2kF )2
and the divergence at small angle is cut off. The transport lifetime for screened Coulomb
scattering is therefore given by
2 Z !2
Ze2

1 1
= 2nimp vF d sin (1 cos )
(F ) 4F sin2 12 + (2kF )2
0
2
Ze2

= 2nimp vF ln(1 + ) , (1.105)
2F 1 +
with
4 2 2 ~2 k
= kF = F2 = kF aB . (1.106)
m e
Here aB = ~2 /m e2 is the effective Bohr radius (restoring the factor). The resistivity
is therefore given by
m h nimp
= 2
= Z 2 2 aB F (kF aB ) , (1.107)
ne e n
where
1
F () = 3 ln(1 + ) . (1.108)
1 +
With h/e2 = 25, 813 and aB aB = 0.529 A, we have
nimp
= 1.37 104 cm Z 2 F (kF aB ) . (1.109)
n
Impurity per % Impurity per %

Ion (-cm) Ion (-cm)
Be 0.64 Si 3.2
Mg 0.60 Ge 3.7
B 1.4 Sn 2.8
Al 1.2 As 6.5
In 1.2 Sb 5.4
Table 1.2: Residual resistivity of copper per percent impurity.

1.6. BOLTZMANN EQUATION FOR HOLES 21
Figure 1.5: Residual resistivity per percent impurity.
1.6 Boltzmann Equation for Holes
1.6.1 Properties of Holes
Since filled bands carry no current, we have that the current density from band n is
Z 3 Z 3
dk dk
jn (r, t) = 2e fn (r, k, t) vn (k) = +2e fn (r, k, t) vn (k) , (1.110)
(2)3 (2)3

where f 1 f . Thus, we can regard the current to be carried by fictitious particles of

charge +e with a distribution f(r, k, t). These fictitious particles are called holes.
1. Under the influence of an applied electromagnetic field, the unoccupied levels of a

band evolve as if they were occupied by real electrons of charge e. That is, whether
or not a state is occupied is irrelevant to the time evolution of that state, which is
described by the semiclassical dynamics of eqs. (1.1, 1.2).
2. The current density due to a hole of wavevector k is +e vn (k)/V .
3. The crystal momentum of a hole of wavevector k is P = ~k.
4. Any band can be described in terms of electrons or in terms of holes, but not both
simultaneously. A mixed description is redundant at best, wrong at worst, and
confusing always. However, it is often convenient to treat some bands within the
electron picture and others within the hole picture.
Figure 1.6: Two states: A = ek hk 0 and B = ek hk 0 . Which state carries

more current? What is the crystal momentum of each state?
It is instructive to consider the exercise of fig. 1.6. The two states to be analyzed are

A = c,k v,k 0 = ek hk 0 (1.111)

B = c,k v,k 0 = ek hk 0 , (1.112)

where ek c,k is the creation operator for electrons in the conduction band, and hk v,k
is the creation operator for
holes (and hence the destruction operator for electrons) in the

valence band. The state 0 has all states below the top of the valence

band filled, and
all states above the bottom of the conduction band empty. The state 0 is the same state,
but represented now as a vacuum for conduction electrons and valence holes. The current
density in each state is given by j = e(vh ve )/V , where V is the volume (i.e. length) of the
system. The dispersions resemble c,v 21 Eg ~2 k 2 /2m , where Eg is the energy gap.

State A :
The electron velocity is ve = ~k/m ; the hole velocity is vh = ~k/m . Hence,
the total current density is j 2e~k/m V and the total crystal momentum is
P = pe + ph = ~k ~k = 0.

State B :
The electron velocity is ve = ~k/m ; the hole velocity is vh = ~(k)/m . The
1.6. BOLTZMANN EQUATION FOR HOLES 23
total current density is j 0, and the total crystal momentum is P = pe + ph =

~k ~(k) = 2~k.
Consider next the dynamics of electrons near the bottom of the conduction band and holes
near the top of the valence band. (Well assume a direct gap, i.e. the conduction band
minimum is located directly above the valence band maximum, which we take to be at the
Brillouin zone center k = 0, otherwise known as the point.) Expanding the dispersions
about their extrema,
v (k) = v0 12 ~2 mv 1 k k (1.113)
1 2 c 1
c (k) = c0 + 2 ~ m k k . (1.114)
The velocity is
1
v (k) = = ~ m1
k , (1.115)
~ k
where the + sign is used in conjunction with mc and the sign with mv . We compute the
acceleration a = r via the chain rule,
v dk
a =
k dt
1 1
= e m E + (v B) (1.116)
c

1
F = m a = e E + (v B) . (1.117)
c
Thus, the hole wavepacket accelerates as if it has charge +e but a positive effective mass.
Finally, what form does the Boltzmann equation take for holes? Starting with the Boltz-
mann equation for electrons,
f f f
+ r + k = Ik {f } , (1.118)
t r k
we recast this in terms of the hole distribution f = 1 f , and obtain
f f f
+ r + k = Ik {1 f} (1.119)
t r k
This then is the Boltzmann equation for the hole distribution f. Recall that we can expand
the collision integral functional as
Ik {f 0 + f } = L f + . . . (1.120)
where L is a linear operator, and the higher order terms are formally of order (f )2 . Note
that the zeroth order term Ik {f 0 } vanishes due to the fact that f 0 represents a local
equilibrium. Thus, writing f = f0 + f
Ik {1 f} = Ik {1 f0 f} = L f + . . . (1.121)
and the linearized collisionless Boltzmann equation for holes is
f f
0
e f
vB v eE + T = L f (1.122)
t ~c k T
which is of precisely the same form as the electron case in eqn. (1.27). Note that the local
equilibrium distribution for holes is given by
1
(r, t) (k)
f0 (r, k, t) = exp +1 (1.123)
kB T (r, t)
1.7 Magnetoresistance and Hall Effect
1.7.1 Boltzmann Theory for (, B )
In the presence of an external magnetic field B, the linearized Boltzmann equation takes
the form9
f f 0 e f
ev E vB = L f . (1.124)
t ~c k
We will obtain an explicit solution within the relaxation time approximation L f = f /
and the effective mass approximation,
(k) = 12 ~2 m1
k k = v = ~ m1
k , (1.125)
where the top sign applies for electrons and the bottom sign for holes. With E(t) = E eit ,
we try a solution of the form
f (k, t) = k A() eit f (k) eit (1.126)
where A() is a vector function of to be determined. Each component A is a function of

k through its dependence on = (k). We now have
e f 0
( 1 i) k A v B (k A ) = e v E , (1.127)
~c k
where is the Levi-Civita tensor. Note that

A
v B (k A ) = v B A + k
k k
A

= v B A + ~ k v

= v B A , (1.128)
9
For holes, we replace f 0 f0 and f f.
1.7. MAGNETORESISTANCE AND HALL EFFECT 25
owing to the asymmetry of the Levi-Civita tensor: v v = 0. Now invoke ~ k =

m v , and match the coefficients of v in each term of the Boltzmann equation. This
yields,
h e i f 0
( 1 i) m B A = ~ e E . (1.129)
c
Defining
e
( 1 i) m B , (1.130)
c
we obtain the solution
0
f
f = e v m 1
E . (1.131)

From this, we can compute the current density and the conductivity tensor. The electrical
current density is
Z 3
dk
j = 2e v f
(2)3

d3k f 0
Z
= +2e E2
v v m 1
() , (1.132)
(2)3

where we allow for an energy-dependent relaxation time (). Note that () is energy-
dependent due to its dependence on . The conductivity is then
(Z )
3k 0

d f
(, B) = 2~2 e2 m1
k k 1
() (1.133)
(2)3

Z
f 0

2 2 1
= e d g() () , (1.134)
3

where the chemical potential is measured with respect to the band edge. Thus,
(, B) = ne2 h1
i , (1.135)
where averages denoted by angular brackets are defined by

R 0

d g() f
1
()

h1
i . (1.136)
R 0

d g() f

The quantity n is the carrier density,

Z (
f 0 () (electrons)
n = d g() (1.137)
1 f 0 ()

(holes)

EXERCISE: Verify eqn. (1.134).

For the sake of simplicity, let us assume an energy-independent scattering time, or that the
temperature is sufficiently low that only (F ) matters, and we denote this scattering time
simply by . Putting this all together, then, we obtain
= ne2 1
(1.138)
1 1 h 1 e
i
= 2 = 2 ( i)m B . (1.139)
ne ne c
We will assume that B is directed along one of the principal axes of the effective mass
tensor m , which we define to be x, y, and z, in which case
1
( i) mx

eB/c 0
1
(, B) = 2 eB/c ( 1 i) my 0 (1.140)
ne
0 0 ( 1 i) mz
where mx,y,z are the eigenvalues of m and B lies along the eigenvector z.
Note that
mx
xx (, B) = (1 i ) (1.141)
ne2
is independent of B. Hence, the magnetoresistance,
xx (B) = xx (B) xx (0) (1.142)
vanishes: xx (B) = 0. While this is true for a single parabolic band, deviations from
parabolicity and contributions from other bands can lead to a nonzero magnetoresistance.
The conductivity tensor is the matrix inverse of . Using the familiar equality
1
a b 1 d b
= , (1.143)
c d ad bc c a
we obtain

mx my
c /

(1i )/mx
0
(1i )2 +(c )2 (1i )2 +(c )2

(, B) = ne2 c / mx my (1i )/my (1.144)

(1i )2 +(c )2 0
(1i )2 +(c )2

1
0 0 (1i )mz
where
eB
c , (1.145)
m c
with m
p
mx my , is the cyclotron frequency. Thus,
ne2 1 i
xx (, B) =
(1.146)
mx 1 + (c 2 ) 2 2i
2
ne2 1
zz (, B) =
. (1.147)
mz 1 i
Note that xx,yy are field-dependent, unlike the corresponding components of the resistivity
tensor.
1.7.2 Cyclotron Resonance in Semiconductors
A typical value for the effective mass in semiconductors is m 0.1 me . From

e
= 1.75 107 Hz/G , (1.148)
me c
we find that eB/m c = 1.75 1011 Hz in a field of B = 1 kG. In metals, the disorder is
such that even at low temperatures c typically is small. In semiconductors, however, the
smallness of m and the relatively high purity (sometimes spectacularly so) mean that c
can get as large as 103 at modest fields. This allows for a measurement of the effective mass
tensor using the technique of cyclotron resonance.
The absorption of electromagnetic radiation is proportional to the dissipative (i.e. real) part
of the diagonal elements of (), which is given by
0 ne2 1 + (2 + 1)s2
xx (, B) = , (1.149)
mx 1 + 2(2 + 1)s2 + (2 1)2 s4
where = B/B , with B = m c /e, and s = . For fixed , the conductivity xx 0 (B)
is then peaked at B = B . When 1 and c 1, B approaches B , where

0 (, B ) = ne2 /2m . By measuring B one can extract the quantity m = eB /c.
xx x
Varying the direction of the magnetic field, the entire effective mass tensor may be deter-
mined.
For finite , we can differentiate the above expression to obtain the location of the cyclotron
resonance peak. One finds B = (1 + )1/2 B , with
p
(2s2 + 1) + (2s2 + 1)2 1
= 2
(1.150)
s
1 1
= 4
+ 6 + O(s8 ) .
4s 8s
As depicted in fig. 1.7, the resonance peakshifts to the left of B for finite values of .
The peak collapses to B = 0 when 1/ 3 = 0.577.
Figure 1.7: Theoretical cyclotron resonance peaks as a function of B/B for different values
of .
1.7.3 Magnetoresistance: Two-Band Model
For a semiconductor with both electrons and holes present a situation not uncommon to
metals either (e.g. Aluminum) each band contributes to the conductivity. The individual
band conductivities are additive because the electron and hole conduction processes occur
in parallel , exactly as we would deduce from eqn. (1.4). Thus,
(n)
X
() = () , (1.151)
n
(n)
where is the conductivity tensor for band n, which may be computed in either the
electron or hole picture (whichever is more convenient). We assume here that the two
distributions fc and fv evolve according to independent linearized Boltzmann equations,
i.e. there is no interband scattering to account for.
(n)
The resistivity tensor of each band, exhibits no magnetoresistance, as we have found.
However, if two bands are present, the total resistivity tensor is obtained from 1 =
1 1
c + v , and
1 1
= 1

c + v (1.152)
will in general exhibit the phenomenon of magnetoresistance.

Explicitly, then, let us consider a model with isotropic and nondegenerate conduction band
minimum and valence band maximum. Taking B = B z, we have

0 1 0 c c 0
(1 ic )mc B
c = I+ 1 0 0 = c c 0 (1.153)

nc e2 c nc ec 0 0 0 0 0 c

v v 0

0 1 0
(1 iv )mv B
v = I 1 0 0 = v v 0 , (1.154)

nv e2 v nv ec 0 0 0 0 0 v
where
(1 ic )mc B
c = c = (1.155)
nc e2 c nc ec
(1 iv )mv B
v = v = , (1.156)
nv e2 v nv ec
we obtain for the upper left 2 2 block of :
" 2 2 #1
v c v c
= + + +
v2 + v2 c2 + c2 v2 + v2 c2 + c2
v c
c

2
+
v
2 + 2
c +c2 2
v +v2 + 2
c +c2
v v
, (1.157)

2+v
2 c
2 + 2
v
2 + 2
+ c
2 + 2
v v c c v v c c
from which we compute the magnetoresistance

2
c v
xx (B) xx (0) c v B2
nc ec nv ec
= 2 (1.158)
xx (0) (c + v )2 + (c v )2 1 + 1 B2
nc ec nv ec
where
nc e2 c 1
c = c1 = (1.159)
mc 1 ic
nv e2 v 1
v = v1 = . (1.160)
mv 1 iv
Note that the magnetoresistance is positive within the two band model, and that it saturates
in the high field limit:
2
c v
xx (B ) xx (0) c v
nc ec nv ec
= 2 . (1.161)
xx (0) (c v )2 1 + 1
nc ec nv ec
The longitudinal resistivity is found to be

zz = (c + v )1 (1.162)
and is independent of B.
In an intrinsic semiconductor, nc = nv exp(Eg /2kB T ), and xx (B)/xx (0) is finite
even as T 0. In the extrinsic (i.e. doped) case, one of the densities (say, nc in a p-type
material) vanishes much more rapidly than the other, and the magnetoresistance vanishes
with the ratio nc /nv .
1.7.4 Hall Effect in High Fields
In the high field limit, one may neglect the collision integral entirely, and write (at = 0)
f 0 e f
e v E vB =0. (1.163)
~c dk
Well consider the case of electrons, and take E = E y and B = B z, in which case the
solution is
~cE f 0
f = kx . (1.164)
B
Note that kx is not a smooth single-valued function over the Brillouin-zone due to Bloch
periodicity. This treatment, then, will make sense only if the derivative f 0 / confines k
to a closed orbit within the first Brillouin zone. In this case, we have
Z 3
E dk f 0
jx = 2ec kx (1.165)
B (2)3 kx

E d3k f 0
Z
= 2ec kx . (1.166)
B (2)3 kx

Now we may integrate by parts, if we assume that f 0 vanishes on the boundary of the
Brillouin zone. We obtain
Z 3
2ecE dk nec
jx = f0 = E . (1.167)
B (2)3 B

We conclude that
nec
xy = yx = , (1.168)
B
independent of the details of the band structure. Open orbits trajectories along Fermi
surfaces which cross Brillouin zone boundaries and return in another zone post a subtler
problem, and generally lead to a finite, non-saturating magnetoresistance.
For holes, we have f0 = 1 f 0 and
d3k f0
Z
2ecE nec
jx = 3
kx =+ E (1.169)
B (2) kx B

Figure 1.8: Nobel Prize winning magnetotransport data in a clean two-dimensional electron
gas at a GaAs-AlGaAs inversion layer, from D. C. Tsui, H. L. Stormer, and A. C. Gossard,
Phys. Rev. Lett. 48, 1559 (1982). xy and xx are shown versus magnetic field for a set of
four temperatures. The Landau level filling factor is = nhc/eB. At T = 4.2 K, the Hall
resistivity obeys xy = B/nec (n = 1.3 1011 cm2 ). At lower temperatures, quantized
plateaus appear in xy (B) in units of h/e2 .
and xy = +nec/B, where n is the hole density.
We define the Hall coefficient RH = xy /B and the Hall number
1
zH , (1.170)
nion ecRH
where nion is the ion density. For high fields, the off-diagonal elements of both and
are negligible, and xy = xy . Hence RH = 1/nec, and zH = n/nion . The high
field Hall coefficient is used to determine both the carrier density as well as the sign of the
charge carriers; zH is a measure of valency.
In Al, the high field Hall coefficient saturates at zH = 1. Why is zH negative? As it turns
out, aluminum has both electron and hole bands. Its valence is 3; two electrons go into a
filled band, leaving one valence electron to split between the electron and hole bands. Thus
Figure 1.9: Energy bands in aluminum.
n = 3nion The Hall conductivity is
xy = (nh ne ) ec/B . (1.171)
The difference nh ne is determined by the following argument. The electron density in

the hole band is n0e = 2nion nh , i.e. the total density of levels in the band (two states per
unit cell) minus the number of empty levels in which there are holes. Thus,
nh ne = 2nion (ne + n0e ) = nion , (1.172)
where weve invoked ne + n0e = nion , since precisely one electron from each ion is shared
between the two partially filled bands. Thus, xy = nion ec/B = nec/3B and zH = 1. At
lower fields, zH = +3 is observed, which is what one would expect from the free electron
model. Interband scattering, which is suppressed at high fields, leads to this result.
1.8 Thermal Transport
1.8.1 Boltzmann Theory
Consider a small region of solid with a fixed volume V . The first law of thermodynamics
applied to this region gives T S = E N . Dividing by V gives
dq T ds = d dn , (1.173)
where s is the entropy density, is energy density, and n the number density. This can be
directly recast as the following relation among current densities:
jq = T js = j jn , (1.174)
1.8. THERMAL TRANSPORT 33
Figure 1.10: Fermi surfaces for electron (pink) and hole (gold) bands in Aluminum.
where jn = j/(e) is the number current density, j is the energy current density,
d3k
Z
j = 2 v f , (1.175)
(2)3

and js is the entropy current density. Accordingly, the thermal (heat) current density jq is
defined as

jq T js = j + j (1.176)
e
Z 3
dk
=2 ( ) v f . (1.177)
(2)3

In the presence of a time-independent temperature gradient and electric field, linearized

Boltzmann equation in the relaxation time approximation has the solution
f 0

f = () v eE + T . (1.178)
T
We now consider both the electrical current j as well as the thermal current density jq .
One readily obtains
d3k
Z
j= 2 e v f L11 E L12 T (1.179)
(2)3

Z 3
dk
jq = 2 ( ) v f L21 E L22 T (1.180)
(2)3

where the transport coefficients L11 etc. are matrices:
e2 f 0 v v
Z Z
L
11 = 3 d () dS (1.181)
4 ~ |v|
0 v v
Z Z
e f
L
21 = T L12 = 3 d () ( ) dS (1.182)
4 ~ |v|
0 v v
Z Z
1 f
L
22 = 3 d () ( )2 dS . (1.183)
4 ~ T |v|
If we define the hierarchy of integral expressions
f 0 v v
Z Z
1
Jn 3 n
d () ( ) dS (1.184)
4 ~ |v|
then we may write
1
L 2
11 = e J0 L
21 = T L12 = e J1 L
22 = J . (1.185)
T 2
The linear relations in eqn. (1.180) may be recast in the following form:
E = j + QT (1.186)
jq = u j T , (1.187)
where the matrices , Q, u, and are given by
= L1
11 Q = L1
11 L12 (1.188)
u = L21 L1
11 = L22 L21 L1
11 L12 , (1.189)
or, in terms of the Jn ,
1 1 1
= J Q= J 1 J1 (1.190)
e2 0 eT 0
1 1
u = J1 J01 = J2 J1 J01 J1 , (1.191)
e T
The names and physical interpretation of these four transport coefficients is as follows:
is the resistivity: E = j under the condition of zero thermal gradient (i.e. T = 0).
Q is the thermopower: E = Q T under the condition of zero electrical current (i.e.

j = 0). Q is also called the Seebeck coefficient.
u is the Peltier coefficient: jq = uj when T = 0.
is the thermal conductivity: jq = T when j = 0 .

Figure 1.11: A thermocouple is a junction formed of two dissimilar metals. With no electri-
cal current passing, an electric field is generated in the presence of a temperature gradient,
resulting in a voltage V = VA VB .
One practical way to measure the thermopower is to form a junction between two dissimilar
metals, A and B. The junction is held at temperature T1 and the other ends of the metals
are held at temperature T0 . One then measures a voltage difference between the free ends
of the metals this is known as the Seebeck effect. Integrating the electric field from the
free end of A to the free end of B gives
ZB
VA VB = E dl = (QB QA )(T1 T0 ) . (1.192)
A
What one measures here is really the difference in thermopowers of the two metals. For an
absolute measurement of QA , replace B by a superconductor (Q = 0 for a superconductor).
A device which converts a temperature gradient into an emf is known as a thermocouple.
The Peltier effect has practical applications in refrigeration technology. Suppose an electrical
current I is passed through a junction between two dissimilar metals, A and B. Due to
the difference in Peltier coefficients, there will be a net heat current into the junction of
W = (uA uB ) I. Note that this is proportional to I, rather than the familiar I 2 result
from Joule heating. The sign of W depends on the direction of the current. If a second
junction is added, to make an ABA configuration, then heat absorbed at the first junction
will be liberated at the second. 10
10
To create a refrigerator, stick the cold junction inside a thermally insulated box and the hot junction
outside the box.
Figure 1.12: A sketch of a Peltier effect refrigerator. An electrical current I is passed through
a junction between two dissimilar metals. If the dotted line represents the boundary of a
thermally well-insulated body, then the body cools when uB > uA , in order to maintain a
heat current balance at the junction.
1.8.2 The Heat Equation
We begin with the continuity equations for charge density and energy density :

+j =0 (1.193)
t

+ j = j E , (1.194)
t
where E is the electric field11 . Now we invoke local thermodynamic equilibrium and write
n T
= +
t n t T t
T
= + cV , (1.195)
e t t
where n is the electron number density (n = /e) and cV is the specific heat. We may
now write
T
cV = +
t t e t

= j E j j
e
= j E jq . (1.196)
11
Note that it is E j and not E j which is the source term in the energy continuity equation.
Invoking jq = uj T , we see that if there is no electrical current (j = 0), we obtain

the heat equation
T 2T
cV = . (1.197)
t x x
This results in a time scale T for temperature diffusion T = CL2 cV /, where L is a typical
length scale and C is a numerical constant. For a cube of size L subjected to a sudden
external temperature change, L is the side length and C = 1/3 2 (solve by separation of
variables).
1.8.3 Calculation of Transport Coefficients
We will henceforth assume that sufficient crystalline symmetry exists (e.g. cubic symme-
try) to render all the transport coefficients multiples of the identity matrix. Under such
conditions, we may write Jn = Jn with
f 0
Z Z
1 n
Jn = d () ( ) dS |v| . (1.198)
12 3 ~
The low-temperature behavior is extracted using the Sommerfeld expansion,
Z
f 0

I d H() = D csc(D) H() (1.199)

=

2
= H() + (k T )2 H 00 () + . . . (1.200)
6 B

where D kB T is a dimensionless differential operator.12
To quickly derive the Sommerfeld expansion, note that
f 0

1 1
= , (1.201)
kB T e()/kB T + 1 e()/kB T + 1

hence, changing variables to x ( )/kB T ,
Z Z
H( + x kB T ) exD
I = dx = dx H()

(ex + 1)(ex + 1) (ex + 1)(ex + 1)

=

" #
X exD
= 2i Res H() , (1.202)

(ex + 1)(ex + 1)

=
n=0 x=(2n+1)i
12
Remember that physically the fixed quantities are temperature and total carrier number density (or
charge density, in the case of electron and hole bands), and not temperature and chemical potential. An
equation of state relating n, , and T is then inverted to obtain (n, T ), so that all results ultimately may
be expressed in terms of n and T .
where we treat D as if it were c-number even though it is a differential operator. We have

also closed the integration contour along a half-circle of infinite radius, enclosing poles in
the upper half plane at x = (2n + 1)i for all nonnegative integers n. To compute the
residue, set x = (2n + 1)i + , and examine
e(2n+1)iD eD 1 + D + 12 2 D2 + . . . (2n+1)iD

= e
(1 e )(1 e ) 1 4
2 + 12 + ...
( )
1 D 1
21 D2 + O() e(2n+1)iD .

= 2 + 12 (1.203)

We conclude that the residue is D e(2n+1)iD . Therefore,

X
I = 2iD e(2n+1)iD H()

=
n=0

= D csc(D) H() , (1.204)

=
which is what we set out to show.

Let us now perform some explicit calculations in the case of a parabolic band with an
energy-independent scattering time . In this case, one readily finds
0 3/2 3/2

n
Jn = 2 D csc D ( ) , (1.205)
e =
where 0 = ne2 /m . Thus,
2 (kB T )2

0
J0 = 2 1 + + ... (1.206)
e 8 2
0 2 (kB T )2
J1 = + ... (1.207)
e2 2
0 2
J2 = (k T )2 + . . . , (1.208)
e2 3 B
from which we obtain the low-T results = 01 ,
2 kB2 T 2 n 2
Q= = k T , (1.209)
2 e F 3 m B
and of course u = T Q. The predicted universal ratio

2
= (k /e)2 = 2.45 108 V2 K2 , (1.210)
T 3 B
is known as the Wiedemann-Franz law. Note also that our result for the thermopower
is unambiguously negative. In actuality, several nearly free electron metals have positive
low-temperature thermopowers (Cs and Li, for example). What went wrong? We have
neglected electron-phonon scattering!
Figure 1.13: QT product for p-type and n-type Ge, from T. H. Geballe and J. W. Hull,
Phys. Rev. 94, 1134 (1954). Samples 7, 9, E, and F are distinguished by different doping
properties, or by their resistivities at T = 300 K: 21.5 -cm (7), 34.5 -cm (9), 18.5 -cm
(E), and 46.0 -cm (F).
1.8.4 Onsager Relations
Transport phenomena are described in general by a set of linear relations,
Ji = Lik Fk , (1.211)
where the {Fk } are generalized forces and the {Ji } are generalized currents. Moreover,
to each force Fi corresponds a unique conjugate current Ji , such that the rate of internal
entropy production is
X S
S = Fi Ji = Fi = . (1.212)
Ji
i
The Onsager relations (also known as Onsager reciprocity) states that
Lik (B) = i k Lki (B) , (1.213)
where i describes the parity of Ji under time reversal:
T Ji = i Ji . (1.214)
We shall not prove the Onsager relations.

The Onsager relations have some remarkable consequences. For example, they require, for
B = 0, that the thermal conductivity tensor ij of any crystal must be symmetric, indepen-
dent of the crystal structure. In general,this result does not follow from considerations of
crystalline symmetry. It also requires that for every off-diagonal transport phenomenon,
e.g. the Seebeck effect, there exists a distinct corresponding phenomenon, e.g. the Peltier
effect.
For the transport coefficients studied, Onsager reciprocity means that in the presence of an
external magnetic field,
(B) = (B) (1.215)
(B) = (B) (1.216)
u (B) = T Q (B) . (1.217)
Lets consider an isotropic system in a weak magnetic field, and expand the transport
coefficients to first order in B:
(B) = + B (1.218)

(B) = + $ B (1.219)

Q (B) = Q + B (1.220)

u (B) = u + B . (1.221)
Onsager reciprocity requires u = T Q and = T . We can now write
E = j + j B + QT + T B (1.222)
jq = u j + j B T $ T B . (1.223)
There are several new phenomena lurking!
Hall Effect ( T
x =
T
y = jy = 0)
An electrical current j = jx x and a field B = Bz z yield an electric field E. The Hall
coefficient is RH = Ey /jx Bz = .
Ettingshausen Effect ( T
x = jy = jq,y = 0)
T
An electrical current j = jx x and a field B = Bz z yield a temperature gradient y .
The Ettingshausen coefficient is P = T

y jx Bz = /.
T
Nernst Effect (jx = jy = y = 0)
A temperature gradient T = T x and a field B = Bz z yield an electric field E.
x
T
The Nernst coefficient is = Ey x Bz = .
Righi-Leduc Effect (jx = jy = Ey = 0)

A temperature gradient T = T x x and a field B = Bz z yield an orthogonal tem-
T T T

perature gradient y . The Righi-Leduc coefficient is L = y x Bz = /Q.
1.9. ELECTRON-PHONON SCATTERING 41
1.9 Electron-Phonon Scattering
1.9.1 Introductory Remarks
We begin our discussion by recalling some elementary facts about phonons in solids:
In a crystal with r atoms per unit cell, there are 3(r 1) optical modes and 3 acoustic
modes, the latter guaranteed by the breaking of the three generators of space transla-
tions. We write the phonon dispersion as = (q), where {1, . . . , 3r} labels the
phonon branch, and q . If j labels an acoustic mode, j (q) = cj (q) q as q 0.
Phonons are bosonic particles with zero chemical potential. The equilibrium phonon
distribution is
1
n0q = . (1.224)
exp(~ (q)/kB T ) 1
The maximum phonon frequency is roughly given by the Debye frequency D . The
Debye temperature D = ~D 100 K 1000 K in most solids.
At high temperatures, equipartition gives h(Ri )2 i kB T , hence the effective scattering

cross-section tot increases as T , and > 1 2
1/nion vF tot T . From = m /ne , then,
we deduce that the high temperature resistivity should be linear in temperature due to
phonon scattering: (T ) T . Of course, when the mean free path ` = vF becomes as
small as the Fermi wavelength F , the entire notion of coherent quasiparticle transport
becomes problematic, and rather than continuing to grow we expect that the resistivity
should saturate: (T ) h/kF e2 , known as the Ioffe-Regel limit. For kF = 108 cm1 ,
this takes the value 260 cm.
1.9.2 Electron-Phonon Interaction
Let Ri = Ri0 + Ri denote the position of the ith ion, and let U (r) = Ze2 exp(r/TF )/r
be the electron-ion interaction. Expanding in terms of the ionic displacements Ri ,
X X
Helion = U (r Ri0 ) Ri U (r Ri0 ) , (1.225)
i i
where i runs from 1 to Nion 13 . The deviation Ri may be expanded in terms of the vibra-
tional normal modes of the lattice, i.e. the phonons, as
!1/2
1 X ~ 0
Ri = e (q) eiqRi (aq + aq ) . (1.226)
Nion q 2 (q)
13
We assume a Bravais lattice, for simplicity.
Figure 1.14: Transverse and longitudinal phonon polarizations. Transverse phonons do

not result in charge accumulation. Longitudinal phonons create local charge buildup and
therefore couple to electronic excitations via the Coulomb interaction.
The phonon polarization vectors satisfy e (q) = e (q) as well as the generalized orthonor-
mality relations
X
e (q) e0 (q) = M 1 0 (1.227)

e (q) e (q) = M 1 ,
X
(1.228)

where M is the ionic mass. The number of unit cells in the crystal is Nion = V /, where
is the Wigner-Seitz cell volume. Again, we approximate Bloch states by plane waves
k (r) = exp(ik r)/ V , in which case
2 0
i 0 0 4Ze (k k )
k0 U (r Ri0 ) k = ei(kk )Ri

2 . (1.229)
V (k k0 )2 + TF
The sum over lattice sites gives
Nion
0 0
X
ei(kk +q)Ri = Nion k0 ,k+q mod G , (1.230)
i=1
so that
1 X
Helph = g (k, k0 ) (aq + aq ) k

k0 k0 ,k+q+G (1.231)
V kk0
q G
with
!1/2
~ 4Ze2
g (k, k + q + G) = i (q + G) e (q) . (1.232)
2 (q) (q + G)2 + 2
TF
In an isotropic solid14 (jellium), the phonon polarization at wavevector q either is parallel

to q (longitudinal waves), or perpendicular to q (transverse waves). We see that only
longitudinal waves couple to the electrons. This is because transverse waves do not result
in any local accumulation of charge density, and it is to the charge density that electrons
couple, via the Coulomb interaction.

Restricting our attention to the longitudinal phonon, we have eL (q) = q/ M and hence,
for small q = k0 k,
1/2
4Ze2 1/2 1/2

~
gL (k, k + q) = i cL q , (1.233)
2M q 2 + 2
TF
where cL is the longitudinal phonon velocity. Thus, for small q we that the electron-
longitudinal phonon coupling gL (k, k + q) gq satisfies
~cL q
|gq |2 = elph , (1.234)
g(F )
where g(F ) is the electronic density of states, and where the dimensionless electron-phonon
coupling constant is
!2
Z2 2Z m F
elph = = , (1.235)
2M c2L g(F ) 3 M kB s
with s ~cL kF /kB . Table 1.3 lists s , the Debye temperature D , and the electron-phonon
coupling elph for various metals.
EXERCISE: Derive eqn. (1.235).
Metal s D elph Metal s D elph

Na 220 150 0.47 Au 310 170 0.08
K 150 100 0.25 Be 1940 1000 0.59
Cu 490 315 0.16 Al 910 394 0.90
Ag 340 215 0.12 In 300 129 1.05
Table 1.3: Electron-phonon interaction parameters for some metals. Temperatures are in
Kelvins.
14
The jellium model ignores G 6= 0 Umklapp processes.
1.9.3 Boltzmann Equation for Electron-Phonon Scattering
Earlier we had quoted the result for the electron-phonon collision integral,
2 X n
Ik {f, n} = |g (k, k0 )|2 (1 fk ) fk0 (1 + nq, ) (k + ~q k0 )
~V 0
k ,
+(1 fk ) fk0 nq (k ~q k0 )
fk (1 fk0 ) (1 + nq ) (k ~q k0 )
o
fk (1 fk0 ) nq (k + ~q k0 ) q,k0 k mod G .
(1.236)
The four terms inside the curly brackets correspond, respectively, to cases (a) through (d)
in fig. 1.1. The (1 + n) factors in the phonon emission terms arise from both spontaneous
as well as stimulated emission processes. There is no spontaneous absorption.
EXERCISE: Verify that in equilibrium Ik {f 0 , n0 } = 0.
In principle we should also write down a Boltzmann equation for the phonon distribution
nq and solve the two coupled sets of equations. The electronic contribution to the phonon
collision integral is written as Jq {f, n}, with

nq 4 2 X
Jq {f, n} = g (1 + nq ) fk+q (1 fk )
t coll ~V q
k

nq fk (1 fk+q ) (k+q k ~q ) . (1.237)
Here, we will assume that the phonons are always in equilibrium, and take nq = n0q .
Phonon equilibrium can be achieved via anharmonic effects (i.e. phonon-phonon scattering),
or by scattering of phonons from impurities or crystalline defects. At low temperatures,

2
1 A
impurity scattering
= B T 2 3 anharmonic phonon scattering (1.238)
()
C/L boundary scattering (L = crystal size)

where A, B, and C are constants.

We now linearize Ik {f }, and obtain

2 X 2 h i
L f = gq (1 fk0 + n0q )fk+q (fk+q
0
+ n0q )fk (k+q k ~q )
~V
q
h i
0 0 0 0
(1 fk+q + nq )fk (fk + nq )fk+q (k+q k + ~q ) . (1.239)
This integral operator must be inverted in order to solve for fk in

f 0

L f = e v E . (1.240)

Unfortunately, the inversion is analytically intractable there is no simple solution of the

form fk = ek vk E (f 0 /) as there was in the case of isotropic impurity scattering.
However, we can still identify the coefficient of fk in L f as the scattering rate k1 . As
before, k in fact is a function of the energy (k):
|g 0 |2 n 0 0
Z Z
1 1
= 2 2 d dS0 k k
0
f ( ) + n0k0 k (0 ~k0 k )

() 4 ~ |vk0 |
o
+ 1 + f 0 (0 ) + n0kk0 (0 + ~kk0 )

(1.241)
p
In an isotropic system, ((k)) is independent of k. This means we can take k = 2m /~2 z
in performing the above integral.
It is convenient to define the dimensionless function
|g 0 |2
Z
1
2 F () 3 2 dS0 k k ( k0 k ) . (1.242)
8 ~ |vk0 |
For parabolic bands, one obtains
elph ~ m 2
Z
1
2 F () = dk0 cL kF |k0 z|

3 2
kF
8 ~ m kF / 2 ~2 ~kF
~ 2

= elph (2kB s ~) . (1.243)
kB s
The scattering rate is given in terms of 2 F () as
Z
1 n o
= 2 d 2 F () f 0 ( + ~) f 0 ( ~) + 2n0 () + 1 . (1.244)
()
0
At T = 0 we have f 0 () = (F ) and n0 () = 0, whence

Z
1 n o
= 2 d 2 F () (F ~) (F + ~) + 1
()
0

elph 2 |F |3
12 ~ (kB s )2 if | F | < 2kB s

= (1.245)

2elph 2

3 ~ (kB s ) it | F | > 2kB s .
Note that (F ) = , unlike the case of impurity scattering. This is because at T = 0 there
are no phonons! For T 6= 0, the divergence is cut off, and one obtains
2elph kB T 3

1 2s
= G (1.246)
() ~ 2s T

7
Zy
x 2 4 (3) if y =

G(y) = dx = (1.247)
2 sinh x 1
0
4y if y 1 ,
and so
7(3) kB T 3

2~
elph
2s
if T s
1
= (1.248)
()
2 k T

if T s
~ B elph
This calculation predicts that T 3 at low temperatures. This is correct if is the

thermal lifetime. However, a more sophisticated calculation shows that the transport lifetime
behaves as tr T 5 at low T . The origin of the discrepancy is our neglect of the (1 cos )
factor present in the average of the momentum relaxation time. At low T , there is only
small angle scattering from the phonons, and h2 i hq 2 /kF2 i T 2 . The Wiedemann-Franz
law, = , is valid for kB T >
~cL kF , as well as at low T in isotropic systems, where
impurity scattering is the dominant mechanism. It fails at intermediate temperatures.

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Chapter 1

H. Smith and H. H. Jensen, Transport Phenomena

N. W. Ashcroft and N. D. Mermin, Solid State Physics, chapter 13.

P. L. Taylor and O. Heinonen, Condensed Matter Physics, chapter 8.

J. M. Ziman, Principles of the Theory of Solids, chapter 7.

Transport is the phenomenon of currents flowing in response to applied fields. By current

1.3 Boltzmann Equation in Solids

1.3.1 Semiclassical Dynamics and Distribution Functions

The semiclassical dynamics of a wavepacket in a solid are described by the equations

The differential operator Dt t + u is sometimes called the convective derivative.

Figure 1.1: Electron-phonon vertices.

The total particle number,

is a collisional invariant - a quantity which is preserved in the collision process. Other

Taking the time derivative,

Hence, if F is preserved by the dynamics between collisions, then

1.3.2 Local Equilibrium

The equilibrium Fermi distribution,

f (r, k, t) = f 0 (r, k, t) + f (r, k, t) (1.22)

from which we read off

1.4 Conductivity of Normal Metals

1.4.1 Relaxation Time Approximation

Consider a normal metal in the presence of an electric field E. Well assume B = 0, T = 0,

Well solve this by adopting the relaxation time approximation for Ik {f }:

Writing E(t) = E eit , we solve

For free electrons in a parabolic band, we write (k) = ~2 k2 /2m , so v (k) = ~k /m . To

The (three-dimensional) parabolic band density of states is found to be

Figure 1.2: Frequency-dependent conductivity of liquid sodium by T. Inagaki et al , Phys.

1.4.2 Optical Reflectivity of Metals and Semiconductors

Weve now solved the electromagnetic boundary value problem.

We may approximate 1 i 1, hence

Hence R 1 and the metal reflects.

1.4.3 Optical Conductivity of Semiconductors

Figure 1.4: Frequency-dependent conductivity of hcp cobalt by J. Weaver et al., Phys.

The carrier density n typically is much smaller in semiconductors than in metals,

Since nsemi < 4

psemi 102 pmetal 1014 s . (1.65)

In high purity semiconductors the mobility = e /m > 5 2

1.4.4 Optical Conductivity and the Fermi Surface

where we have presumed sufficient crystalline symmetry to guarantee that = is

where the optical mass mopt is given by

The density of states, g(F ), is

1.5 Calculation of the Scattering Time

1.5.1 Potential Scattering and Fermis Golden Rule

mopt /me mth /me

where U(r) is a sum over individual impurity ion potentials,

where V is the volume of the solid and

EXERCISE: Verify eqn. (1.81).

and solve for ((k)). The (time-independent) Boltzmann equation is

we may finally write

1.5.2 Screening and the Transport Lifetime

and there is a strong divergence as 0, with F () 4 . The transport lifetime

Thomas-Fermi Screening : This is the typical screening mechanism in metals. A weak

A screened test charge Ze at the origin obeys

The differential scattering cross section is now

With h/e2 = 25, 813 and aB aB = 0.529 A, we have

Impurity per % Impurity per %

Table 1.2: Residual resistivity of copper per percent impurity.

Figure 1.5: Residual resistivity per percent impurity.

1.6 Boltzmann Equation for Holes

where is the Levi-Civita tensor. Note that

owing to the asymmetry of the Levi-Civita tensor: v v = 0. Now invoke ~ k =

is then peaked at B = B . When 1 and c 1, B approaches B , where

e(2n+1)iD eD 1 + D + 12 2 D2 + . . . (2n+1)iD