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# Classical and Quantum Free

## Electron Models of Electrical

Conductivity
(Garcia Chapter 23)
Classification of Solids
Electrical Properties
Some solids conduct current at all temperatures
and, generally, the resistivity of such solids
increases with temperature. These are METALS
Other solids stop conducting at low temperatures
and their resistivity falls with increasing
temperature. These INSULATORS and
SEMICONDUCTORS
Classical Model for Electrical
Conduction
Ohms Law for Electrical
Resistance
-
q

A
v
d
At
Let v
d
be the average velocity (drift velocity) of an electron when an external
electric field, E, is applied to a conductor as a result of a voltage difference V
applied across the conductor. The particles have a charge q (for electrons q = -e).
The number of charges per unit volume is N. The charge Aq that moves across
an area A in a time At is:
d
d
d
qNv
A
i
J
qNAv
t
q
i
t Av qN q
= =
=
A
A
=
A = A ) (
Ohms Law
L A R G
ANq Lm A L A L R iR V
A
L
i V L AV i
L V E AE JA i
m
Nq
E E
m
Nq
E
m
q
qN qNv J
E
m
q
v v
m
qE
a v
at v v v
m
qE
a ma qE F
v qNv
A
i
J
d
d d
d d
/ / 1 e, conductanc and
/ , / / , resistance with , or , or /
/ and ,
ty conductivi the is where ,
, time, free mean a during electron an for velocity in change The
,
, ,
: calculate Now .
2
2 2
0
o
t o
o
o
o
t
o o
t t
t
t t
t
= =
= = = = = =
= = =
= = = = =
= = = = A
= = A
= = =
= =
Temperature dependence of R according to this classical model is in t
Resistance, Resistivity,
Conductance, Conductivity
Resistance is R = V/I
Conductance is G = I/V = 1/R
Resistance is higher for longer wires and for wires with
smaller cross section
R ~ L/A R = (L/A)
G ~ A/L G = (A/L)
is called resistivity. The units are [m]
Conductivity is inverse of resistivity = 1/
Conductivity and Resistivity are material properties, and do
not depend on the size or shape of the material
G A
L
A
L
R
1 1
= = =
o

Examples of Resistivity ()
Ag (Silver): 1.5910
-8
m
Cu (Copper): 1.6810
-8
m
Graphite (C): (3 to 60)10
-5
m
Diamond (C): ~10
14
m
Glass: ~10
10
- 10
14
m
Pure Germanium: ~ 0.5

m
Pure Silicon: ~ 2300

m
Classical Model for Electrical
Conduction
T ~ gives s Experiment
T ~ predicts model classical this Hence,
T of t independen if , ~ ~
, ,
300 re, temperatu room
s
m
10
3
2
3
2
1
1/2
2
6 2
2
o
o
t
t t t o

T v
v
v Ne
K T at
m
T k
v v
T k v m
RMS
e
B
RMS
B e
= = =
= ~ = =
=
The average thermal velocity for ideal gas depend
on temperature, T
Microscopic Model of Current
For current carried by electrons, |q| = e

Estimate drift speed
d d
eNv
A
i
J eNAv i = = =
m/s 10
) 10 )( 10 )( 10 6 . 1 (
6 . 1
) m (10 mm 1 and A 6 . 1
C 10 6 1 ; m 10 cm 10 ~
4
6 - 29 19
2 6 - 2
19 3 29 3 23

= =
= =
= =
= =
eNA
i
v
A i
. e N
eN
J
v eNv J
d
d d
Drift Speed and Current
) m/s 10 ( ) m/s 10 (~
5 4
RMS d
v v <<

## While charges move chaotically and very fast,

their average motion is slow
However, the onset of current moves along a wire with
the speed of light, since the electric field moves with
the speed of light and electrons are already inside
the wire
Quantum Free Electron
Theory of Metals
(Garcia Chapter 23)
3D Cubic Infinite Potential Well

1-D Well

3-D Cubic Well (with sides length L)
2
2
2 2
2 / 1
2
sin
2
) (
n
mL
E
n
L
x
L
x
n
n
t
t

=
|
.
|

\
|
|
.
|

\
|
=
( )
2
0
2
3
2
2
2
1
2
2 2
3 2 1
2 / 3
2
sin sin sin
2
) (
3 2 1
3 2 1
n E n n n
mL
E
n
L
z
n
L
y
n
L
x
L
x
n n n
n n n
= + + =
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
=
t
t t t

## 3D Infinite Potential Well :

Degeneracy
Consider three different
wavefunctions (quantum
states) for a particle in
the 3-D Well:
i, j, and k are integers

Although the states are
different, the energy of
these states are the same,
i.e. these are degenerate
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
=
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
=
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
=
i
L
z
j
L
y
k
L
x
L
x
k
L
z
i
L
y
j
L
x
L
x
k
L
z
j
L
y
i
L
x
L
x
kji
jik
ijk
t t t

t t t

t t t

## sin sin sin

2
) (
sin sin sin
2
) (
sin sin sin
2
) (
2 / 3
2 / 3
2 / 3
( )
( )
( )
2
2 2
0
2 2 2
0
2 2 2
0
2 2 2
0
2

mL
E
i j k E
k i j E
k j i E E
t

+ +
= + +
= + + =
Electrons in 3D Infinite Potential Well
Each electron is described by the wavefunction of a
particle in the infinite well, i.e. the electron state is
defined by three quantum number n
1
, n
2
, n
3
;
however, in addition, we have to include the spin
quantum number, m
s

The electron states are thus determined by four quantum
numbers: n
1
, n
2
, n
3
, m
s

The energy, of course, still depends only on n
1
, n
2
, n
3
!
It is convenient to use the following notations:
for m
s
= , we shall call it the spin up (|)
for m
s
= -, we shall call it the spin down (+)

Example: ) , , , ( ) 2 1 , , , (
3 2 1 3 2 1
| = = n n n m n n n
s
Electrons in 3D Infinite Potential Well:
Paulis Principle
What is the ground state configuration of
many electrons in the 3D infinite potential
well?
Electrons cannot be in the lowest energy
state, since this would violate the Pauli
Exclusion Principle.
consider case of solid with 34 electrons
34 Electrons in 3D Infinite Well
(n
1,
n
1,
n
1
)
The lowest energy for this system is 3E
0
, which corresponds
to n
1
= n
2
= n
3
= 1
Thus only 2 (two) electrons can have this energy: one with spin
| and one with spin +
Next energy level (6E
0
), for which one of ns is 2
Thus total of 6 (six) electrons can have this energy
Next energy level (9E
0
) can also accommodate 6 electrons
What are the combinations of ns for this energy level?
Next energy level (11E
0
) also accommodates 6 electrons
What are the ns?
Next energy level (12E
0
) is two-fold degenerate
34 Electrons in 3D Infinite Well
So far we have placed 22 electrons, so we
need to add another 12 electrons
What is the next energy level?
The next energy level is 14E
0

What are n
1
, n
2
, and n
3
?
What is the degeneracy?
This energy can be had by 12 electrons
We have placed all 34 electrons!!
1, 2, 3
34 Electrons in 3D Infinite Well
Can demonstrate with
diagram
Energy is plotted in terms
of E
0

Each arrow represents an
electron with up or
down spin
Numbers in parenthesis
show the set of ns for a
given energy level
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
(3,2,2)
(3,2,1)
(3,1,1)
(2,2,2)
(2,2,1)
(2,1,1)
(1,1,1)
E
n
e
r
g
y

(
i
n

u
n
i
t
s

o
f

E
0
)
( )
2
2 2
0
2
3
2
2
2
1 0
2
,
3 2 1
mL
E with n n n E E
n n n
t
= + + =
34 Electrons in 3D Infinite Well
In this configuration,
What is the probability at
T =0 that a level with
energy 14E
0
or less will be
occupied?
It is 1!
What is the probability
that the level with energy
above 14E
0
will be
occupied?
It is 0!
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
(3,2,2)
(3,2,1)
(3,1,1)
(2,2,2)
(2,2,1)
(2,1,1)
(1,1,1)
E
n
e
r
g
y

(
i
n

u
n
i
t
s

o
f

E
0
)
Fermi Energy
Generally:
The highest filled energy is
called the Fermi Energy
It is often denoted as E
F

In our case: E
F
= 14E
0
An electron with E

= 14E
0
is
said to be at the Fermi level

0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
(3,2,2)
(3,2,1)
(3,1,1)
(2,2,2)
(2,2,1)
(2,1,1)
(1,1,1)
E
n
e
r
g
y

(
i
n

u
n
i
t
s

o
f

E
0
)
Density of States of Metal
Consider a free electron gas in a
macroscopic sample
Density of states of free electrons confined
within a metal by reflecting walls can be
calculated in the same way as the density
of states of EM modes in a cavity with
reflecting walls
Recall
Einsteins Photon Interpretation of
a n k a n k a n k t z k y k x k t z y x y / , / , / , cos sin sin sin ~ ) , , , (
3 3 2 2 1 1 2 2 1
t t t e = = =
t kx A t kx A t kx A t x y e e e cos sin 2 ) sin( ) sin( ) , ( = + + =
Two sine waves traveling in opposite directions create a standing wave
For EM radiation reflecting off a perfect metal, the reflected amplitude
equals the incident amplitude and the phases differ by t rad
E = 0 at the wall
For allowed modes between two walls separated by a. Therefore have
sin(kx)=0 at x = 0, a
ka = nt, or k = nt/a, n = 1,2,3
In terms of the wavelength, 2t/ = nt/a, or /2 = a/n = a, a/2, a/3
This is for 1D, in 2D a standing wave is proportional to
In 3D a standing wave is proportional to
a n k a n k t y k x k t y x y / , / , cos sin sin ~ ) , , (
2 2 1 1 2 1
t t e = =
EM Modes:
Density of EM Modes, 1
) , , ( ) , , (
3 2 1 3 2 1 3 2 1
n n n
a
k k k z k y k x k k
t
= = + + =

## May represent allowed wave vectors k by points on a unit lattice in a 3D

abstract number space
Since k = 2t/ and f = c, f = c/ = (1/2t)(c/(/2t)) = (1/2t)ck
f is proportional to the |k| = k = n t/a , which is The
,
2 2
1
| |
2
3
2
2
2
1
2
3
2
2
2
1
n
a
c
ck f
n
a
n n n
a
k k k k k to al proportion is f
= =
+ + = + + = =
t
t t

where, n is the distance in abstract number space from the origin (0,0,0)
To the point (n
1
,n
2
n
3
)
The number of modes between f and (f+df) is the number of points
in number space with radii between n and (n+dn) multiplied by
(1) 1/8 and (2) by 2
,

The first factor arises because modes with positive and negative n
correspond to the same modes, so take n
1,
n
2,
n
3,
> 0
The second factor arises because there are two modes with
perpendicular polarization (directions of oscillation of E) for each value
of f
Since the density of points is 1 (one point per unit volume) in
number space, the number of modes between f and (f+df) is the
number of points dN in number space in the positive octant of a shell
The volume of a complete shell is the area of the shell multiplied by
its thickness, 4t n
2
dn
The number of modes with associated radii in number space
between n and (n+dn) is, therefore, dN = (2)(1/8)4t n
2
dn = t n
2
dn
Density of EM Modes, 2
Density of EM and Electron States
2
3
3
2 2
8 )
2
( )
2
(
2
and
2
,
2
f
c
a
c
a
f
c
a
df
dn
n
df
dN
c
a
df
dn
f
c
a
n So
n
a
c
f
t t t = = =
= =
=
df
dn
n
df
dn
dn
dN
df
dN
2
t = =
The density of EM states is the
number of modes per unit frequency:
This may be expressed in terms of f
once n and dn/df are so expressed:

2
3
8
f
c df
dN t
=
This is density of modes in a volume a
3

For a unit volume, the density of states is:
The density of electron states is the
number of modes per unit frequency:
2 3
2 / 3 3
2 / 1 2 / 1
2 / 3
0
2 / 1
0 0
2
2 / 1
0
2 / 1
0
2 / 1
2 / 1
0
2
0
2
2
) 2 (
,
2
)
1
(
2
1
) (
)
1
(
2
1
2
and, , ) (
), ( for solving and , But,
t
t
t t
t

m a
C CE E
E
EE E
E
dE
dn
n
dE
dN
dE
EE
dE
E
E
dn
E
E
n
E n n E E
dE
dn
n
dE
dn
dn
dN
dE
dN
= = =
= =
= =
=
=
= =

2 / 1
2 / 3
0
2
E
E dE
dN t
=
Velocity Distribution
Find the velocity distribution the probability per
unit velocity of finding a state with velocity v
2 2
2 / 3
2
2 / 3
2 / 1
2 / 1 2
2 / 1
2 / 1 2
2
) (
) (
2
) )(
2
( ) (
,
2 2
1
E
and for s expression need So
) ( ,
2
1
v v
m
C v g
dv v g dv v
m
C mvdv v
m
C dE CE dE E g
mvdv dE v
m
E mv
dE E
dE CE dE E g mv E
=
= = = =
= = =
= =
Electron Density per unit Energy
The density of states dN/dE is often
written g(E)
The number of electrons per unit energy,
N(E) also depends upon the probability
that a given state is occupied, F(E). It is,
N(E) = g(E)F(E)
Fermi-Dirac Distribution Function
We introduce the probability distribution
function, F(E), which describes the
probability that a state with energy E is
occupied
For electrons this function is the Fermi-Dirac
Distribution Function
At T = 0

<
>
=
F
F
E E
E E
E f
for , 1
for , 0
) (
Fermi-Dirac Distribution Function
At T > 0 K
1
1
) (
/ ) (
+
=
T k E E
B F
e
E f
Free Electron Models
Classical Model:
Metal is an array of positive
ions with electrons that are
free to roam through the
ionic array
Electrons are treated as an ideal
neutral gas, and their total
energy depends on the
temperature and applied field
In the absence of an electrical
field, electrons move with
randomly distributed thermal
velocities
When an electric field is
applied, electrons acquire a net
drift velocity in the direction
opposite to the field
Quantum Mechanical
Model:
Electrons are in a potential
well with infinite barriers:
They do not leave metal,
but free to roam inside
Electron energy levels are
discrete (quantized) and
well defined, so average
energy of electron is not
equal to (3/2)k
B
T
Electrons occupy energy
levels according to Paulis
exclusion principle
energy when electric field is
applied
Consequences for Metal Theories
At T = 0 K

N is the electron density, i.e. the number of electrons per
unit volume of metal
Calculations show that

Thermal energy at room temperature:
k
B
T ~ 0.025 eV k
B
T << E
F
(0)
( )
3 / 2
2
2
3
2
) 0 ( t N
m
E
e
F

=
eV 10 5 ~ ) 0 (
F
E
Consequences for Metal Theories
Only electrons occupying levels close to the Fermi
Energy will participate in the conduction, since
only these electrons can be excited into the higher
energy states by the electric field
From QM point of view, energy supplied by the
electric field excites electrons into higher lying
energy levels

Temperature Dependence of
Metals Resistivity
Lets introduce the Fermi
velocity:

Then:
F
e
v
l
m
n q
=
= =
t
t
o

2
1
e
F
F F F
m
E
v mv E
2
,
2
1
2
= =
l n q
mv
mv
l n q
e
F
F
e
2
2
=
=

o
Conductivity of Metals
There is still a problem, since according to our definition of
the free mean path, the conductivity is temperature
independent

QM resolves the problem:
Electrons inside the metal have de Broglie wavelength:

But wave in a crystal lattice undergoes Bragg scattering when the
condition, 2dsinu = n, is satisfied. If > 2d, Bragg scattering cannot
occur at any angle. In copper,
F
= 4.65 A, while, d = 2.09 A. So Bragg
scattering cannot occur.
F
mv
nl q
2
= o

A 5 3 ~
2
= =
F e F
F
E m
h
p
h

Conductivity of Metals
Thus, the scattering mechanism is not collisions of electrons with ions, but
rather scattering of electron wave from deviations form perfection in the crystal
that may arise from imperfections in the lattice or vibrations of the ions in the
lattice
In a high quality metal the latter mechanism dominates
When the atoms vibrate the lattice is no longer ideal and presents an effective
cross sectional area for scattering of tr
2,
where r is the amplitude of vibration.
The electron mean free path l is inversely proportional to the scattering cross
section

But the energy of a vibrating atom, E ~ r
2
~ kT
So l ~ 1/T

Hence as is found experimentally
2
1
r
l
t
=
T mv
nl e
F
1
~
2
= o