1

MTLE-6120: Advanced Electronic Properties of Materials

Classical Drude theory of conduction

Contents:
I Drude model derivation of free-electron conductivity
I Scattering time estimates and Matthiessen’s rule
I Mobility and Hall coefficients
I Frequency-dependent conductivity of free-electron metals
Reading:
I Kasap: 2.1 - 2.3, 2.5
 2
Ohm’s law

I Local Ohm’s law: current density driven by electric field

~
~j = σ E

I Current in a sample of cross section A is I = jA

I Voltage drop across a sample of length L is V = EL
I Ohm’s law defines resistance
V EL L
R≡ = = σ −1
I jA A
I Units: Resistance in Ω,
resistivity ρ = σ −1 in Ωm,
conductivity σ in (Ωm)−1
 3
Typical values at 293 K

dρ
Substance ρ [Ωm] σ [(Ωm)−1 ] ρdT [K−1 ]
Silver 1.59 × 10−8 6.30 × 107 0.0038
Copper 1.68 × 10−8 5.96 × 107 0.0039
Tungsten 5.6 × 10−8 1.79 × 107 0.0045
Lead 2.2 × 10−7 4.55 × 106 0.0039
Titanium 4.2 × 10−7 2.38 × 106 0.0038
Stainless steel 6.9 × 10−7 1.45 × 106 0.0009
Mercury 9.8 × 10−7 1.02 × 106 0.0009
Carbon (amorph) 5 − 8 × 10−4 1 − 2 × 103 -0.0005
Germanium 4.6 × 10−1 2.17 -0.048
Silicon 6.4 × 102 1.56 × 10−3 -0.075
Diamond 1.0 × 1012 1.0 × 10−12
Quartz 7.5 × 1017 1.3 × 10−18
Teflon 1023 − 1025 10−25 − 10−23

Note 1/T = 0.0034 K−1 at 293 K ⇒ approximately ρ ∝ T for the best

conducting metals.
 4
Temperature dependence
4
i
%N
+2
Resistivity [10-8 m]
3
i
%N
+1
2
ed
ork
dw
Col
per
e cop
1 Pur

0
0 100 200 300
Temperature [K]

I Linear at higher temperatures

I Residual resistivity (constant at low T) due to defects and impurities
 5
Drude model setup
I Fixed nuclei (positive ion cores) + gas of moving electrons
I Electrons move freely with random velocities
I Electrons periodically scatter which randomizes velocity again
I Average time between collisions: mean free time τ
I Average distance travelled between collisions: mean free path λ
I In zero field, drift velocity (averaged over all electrons)

~vd ≡ h~v i = 0
+ + + + +
but electrons are not stationary: e-
e- e-
e-
hv 2 i = u2 + + + + +
e- e-
I Current density carried by electrons: e-
e-
+ + + + +
~j = n(−e)~vd = 0 e-
e-
e-
e-
where n is number density of electrons + + + + +
 6
Apply electric field
I Electron starts at past time t = −t0 with random velocity ~v0
I Force on electron is F~ = (−e)E~
I Solve equation of motion till present time t = 0:
d~v ~
m = (−e)E
dt
~ 0
eEt
~v = ~v0 −
m

I Need to average over all electrons

I Probability that electron started at −t0 and did not scatter till t = 0 is
P (t0 ) ∝ e−t0 /τ = e−t0 /τ /τ (normalized)

I Probability distribution of initial velocities satisfies

Z
d~v0 P (~v0 ) = 1 (normalized)
Z
d~v0 P (~v0 )~v0 = 0 (random)
 7
Drift velocity in electric field
I Drift velocity is the average velocity of all electrons

~vd ≡ h~v i
!
Z Z ∞ ~ 0
eEt
≡ d~v0 P (~v0 ) dt0 P (t0 ) ~v0 −
0 m
Z Z ∞ Z Z ∞ ~ 0
eEt
= d~v0 P (~v0 )~v0 dt0 P (t0 ) − d~v0 P (~v0 ) dt0 P (t0 )
0 0 m
∞ ~ 0
e−t0 /τ eEt
Z
=0·1−1· dt0
0 τ m
~ Z ∞
−eE
= · t0 dt0 e−t0 /τ
mτ 0
~ Z ∞ 
−eE 2 n −ax n!
= ·τ x dxe = n+1
mτ 0 a
~
−eEτ
=
m
 8
Drude conductivity

I Current density carried by electrons:

!
~ ne2 τ ~
~j = n(−e)~vd = n(−e) − eEτ = E
m m

I Which is exactly the local version of Ohm’s law with conductivity

ne2 τ
σ=
m
I For a given metal, n is determined by number density of atoms and
number of ‘free’ electrons per atom
I e and m are fundamental constants
I Predictions of the model come down to τ (discussed next)
I Later: quantum mechanics changes τ , but above classical derivation
remains essentially correct!
 9
Classical model for scattering
I Electrons scatter against ions (nuclei + fixed core electrons)
I Scattering cross-section σion : projected area within which electron would
be scattered
I WLOG assume electron travelling along z
I Probability of scattering between z and dz is

−dP (z) = P (z) σion dz nion

| {z }
dVeff

+ + + + +
where nion is number density of ions
and dVeff is the volume from which
ions can scatter electrons + + + + +
I This yields P (z) ∝ e−σion nion z
I ⇒ Mean free path
+ + + + +
1
λ=
nion σion e-
+ + + + +
 10
Classical estimate of scattering time

I From Drude model, τ = σm/(ne2 )

I Experimentally, σ ∝ T −1 ⇒ τ ∝ T −1
I From classical model, τ = λ/u, where u is average electron speed
I λ = 1/(nion σion ) should be T -independent
1 2 3
p
Kinetic theory: 2 mu = 2 kB T ⇒ u = 3kB T /m
I

I Therefore classical scattering time

λ 1
τ= = p ∝ T −1/2
u nion σion 3kB T /m

gets the temperature dependence wrong

 11
Comparisons for copper
I Experimentally:
σ = 6 × 107 (Ωm)−1 (at 293 K)
4
n = nion = = 8.5 × 1028 m−3
(3.61 Å)3
σm 6 × 107 (Ωm)−1 · 9 × 10−31 kg
τ= 2 = = 2.5 × 10−14 s
ne 8.5 × 1028 m−3 (1.6 × 10−19 C)2

I Classical model:
σion ∼ π(1 Å)2 ∼ 3 × 10−20 m2
1 1
λ= ∼ ∼ 4 × 10−10 m
nion σion 8.5 × 1028 m−3 · 3 × 10−20 m2
r s
3kB T 3 · 1.38 × 10−23 J/K · 293 K
u= = = 1.2 × 105 m/s
m 9 × 10−31 kg
λ
τ= ∼ 3 × 10−15 s
u
I Need σion to be 10x smaller to match experiment
 12
What changes in quantum mechanics?

1. Electron velocity in metals is (almost) independent of temperature

I Pauli exclusion principle forces electrons to adopt different velocities
I ‘Relevant’ electrons have Fermi velocity vF (=1.6 × 106 m/s for copper)
2. Electrons don’t scatter against ions of the perfect crystal
I Electrons are waves which ‘know’ where all the ions of the crystal are
I They only scatter when ions deviate from ideal positions!
I Crude model σion = πx2 for RMS displacement x
I Thermal displacements 12 kx2 = 21 kB T
√
I Spring constant k ∼ Y a ∼ (120 GPa)(3.6Å/ 2) ∼ 30 N/m
I

πkB T
σion = ∼ 4 × 10−22 m2 (at room T )
k
I

1 k
τ = = ∼ 1.7 × 10−14 s (at room T )
nion σion vF nion πkB T vF
I Correct 1/T dependence and magnitude at room T (expt: 2.5 × 10−14 s)!
 13
Matthiessen’s rule
I Perfect metal: τT ∝ T −1 due to scattering against thermal vibrations (so
far)
I Impurity and defect scattering contribute τI ∝ T 0
I Scattering rates (not times) are additive, so net τ given by

τ −1 = τT−1 + τI−1 + · · ·

I Resistivity ρ ∝ τ −1 ∼ ρ0 + AT with residual resistivity ρ0 due to τI

4
i
%N
+2
Resistivity [10-8 m]

3
i
%N
+1
2
ked
wor
Cold
er
opp
Pu re c
1

0
0 100 200 300
Temperature [K]
Is the experimental data strictly ρ0 + AT ?
 14
Mobility

I Drude conductivity in general

nq 2 τ
σ= = n|q|µ
m
where n is the number density of charge carriers q with mobility

|q|τ
µ=
m
effectively measuring the conductivity per unit (mobile) charge
I In metals, q = −e since charge carried by electrons (so far)
I In semiconductors, additionally q = +e for holes and

σ = e(ne µe + nh µh )

I Semiconductors have typically higher µ, substantially lower n and σ

 15
Hall effect

I Apply magnetic field perpendicular to current: voltage appears in third

direction
I Hall coefficient defined by

Ey VH /W VH d
RH = = =
jx Bz I/(W d)Bz IBz
I Simple explanation in Drude model
I Average driving force on carriers now

F~ = q(E
~ + ~vd × B)
~
= q(Ex x̂ − (vd )x Bz ŷ)

I Steady-state current only in x̂

I ⇒ Ey = (vd )x Bz develops to cancel Fy
 16
Hall coefficient in metals

I Note Ey = (vd )x Bz , while jx = nq(vd )x

I Eliminate (vd )x to get

Ey 1
RH ≡ =
jx Bz nq
I In particular, q = −e for electronic conduction ⇒ RH = −1/(ne)
I Compare to experimental values:
Metal Experiment RH [m3 /C] Drude RH [m3 /C]
Cu −5.5 × 10−11 −7.3 × 10−11
Ag −9.0 × 10−11 −10.7 × 10−11
Na −2.5 × 10−10 −2.4 × 10−10
Cd +6.0 × 10−11 −5.8 × 10−11
Fe +2.5 × 10−11 −2.5 × 10−11
I Good agreement for ‘free-electron’ metals
I Wrong sign for some (transition metals)!
 17
Hall coefficient in semiconductors

I Remember: conductivities due to electrons and holes add

σ = e(ne µe + nh µh )
I Different drift velocities for electrons and holes
I For each of electrons and holes
I ~ , drift velocity ~vd = F
Given driving force F ~ τ /m
I Mobility µ ≡ |q|τ /m, so ~vd = F ~ µ/|q|
I Driving force Fy = q(Ey − (vd )x Bz )
I Corresponding drift velocity (vd )y = Fy µ/|q|
I And corresponding current
jy = nq(vd )y = nqFy µ/|q| = nq 2 (Ey − (vd )x Bz )µ/|q|
I Substitute (vd )x = (qEx )µ/|q| to get
jy = nµ(|q|Ey − qEx µBz )
I Net jy must be zero (that’s how we got Hall coefficient before):

0 = ne µe (eEy + eEx µe Bz ) + nh µh (eEy − eEx µh Bz )

 18
Hall coefficient in semiconductors (continued)
I Net zero jy yields:

0 = ne µe (eEy + eEx µe Bz ) + nh µh (eEy − eEx µh Bz )

= (ne µe + nh µh )Ey + (ne µ2e − nh µ2h )Ex Bz
Ey Ey
⇒ RH = =
jx Bz σEx Bz
ne µ2e − nh µ2h
=−
(ne µe + nh µh )σ
−ne µ2e + nh µ2h
=
e(ne µe + nh µh )2
I Reduces to metal result if nh = 0
I Note holes conrtibute positive coefficient, while electrons negative (not
additive like conductivity)
I Transition metals can have positive Hall coefficients for the same reason!
(Explained later with band structures.)
 19
Frequency-dependent conductivity
I ~ constant in time
So far, we applied fields E
I ~
Now consider oscillatory field E(t) ~ −iωt (such as from an EM wave)
= Ee
I Same Drude model: free electron between collisions etc.
I Only change in equation of motion:

d~v qE~
= e−iωt
dt m
Z t ~
qE
~v (t) = ~v0 + dt e−iωt Note: must account for t explicitly
t−t0 m
qE~  e−iωt t
= ~v0 +
m −iω t−t0
~ e−iω(t−t0 ) − e−iωt
qE
= ~v0 + ·
m iω
 20
Frequency-dependent conductivity: drift velocity
I Drift velocity (at t = 0) is the average velocity of all electrons
!
Z Z ∞ ~ e−iω(t−t0 ) − e−iωt
qE
~vd (t) ≡ d~v0 P (~v0 ) dt0 P (t0 ) ~v0 + ·
0 m iω
Z ∞ ~ e−iω(t−t0 ) − e−iωt
qE
= dt0 P (t0 )
0 m iω
Z ∞ −t0 /τ ~ iωt0
e qE e − 1 −iωt
= dt0 e
0 τ m iω
qE~ Z ∞  
= dt0 e−t0 (1/τ −iω) − e−t0 /τ e−iωt
imωτ 0
~   Z ∞ 
qE 1 n!
= − τ e−iωt xn dxe−ax = n+1
imωτ 1/τ − iω 0 a
qE~ 1 − (1 − iωτ ) −iωt
= · e
imωτ 1/τ − iω
~
q Eτ 1
= · e−iωt
m 1 − iωτ
 21
Frequency-dependent conductivity: Drude result

I As before, ~j(t) = nq~vd (t), which yields conductivity

nq 2 τ σ(0)
σ(ω) = =
m(1 − iωτ ) 1 − iωτ
I Same as before, except for factor (1 − iωτ )
(which → 1 for ω → 0 as expected)
I What does the phase of the complex conductivity mean?
I Current density has a phase lag relative to electric field
I When field changes, collisions are needed to change the current, which
take average time τ
I From constitutive relations discussion, complex dielectric function

iσ(ω) nq 2 /m
(ω) = 0 + = 0 −
ω ω(ω + i/τ )
 22
Plasma frequency
I Displace all electrons by x
I Volume xA containing only electrons with charge −xAne
I Counter charge +xAne on other side due to nuclei
I Electric field by Gauss’s law:

~ = xne x̂
E
0
I Equation of motion of electrons:

d2 x ne2
m 2
= (−e)Ex = −x
dt 0

I Harmonic oscillator with frequency ωp given by

ne2
ωp2 =
m0
 23
Drude dielectric function of metals
I Simple form in terms of plasma frequency
!
nq 2 /m ωp2
(ω) = 0 − = 0 1−
ω(ω + i/τ ) ω(ω + i/τ )

I For ω  1/τ ,
!
iωp2 τ
(ω) ≈ 0 1+
ω

imaginary dielectric, real conductivity (Ohmic regime)

I For 1/τ  ω < ωp ,
!
ωp2
(ω) ≈ 0 1 − 2
ω

negative dielectric constant (plasmonic regime)

I For ω > ωp , positive dielectric constant (dielectric regime)
 24
Copper dielectric function

40
20
0
-20
ε/ε0

-40
-60 Re ε Expt
Im ε Expt
-80 Re ε Model
Im ε Model
-100
0 0.5 1 1.5 2 2.5 3
-hω [eV]

I For copper, ωp = 10.8 eV and τ = 25 fs

I Note 1 eV corresponds to ω = 1.52 × 1015 s−1 and ν = 2.42 × 1014 Hz