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=
For T 0,
f(E) = 1 for E < E
F
f(E) = 0 for E > E
F
E/k
B
in units of 10
4
K
f(E)
~k
B
T
24
25
Leads to condition for
allowed k-values next
two pages
Free Electron Theory
Periodic boundary conditions (box, side L) to count states
) , , ( ) , , ( z y x z y L x = +
is travelling wave solution
) (
.
) (
z k y k x k i
r ik
k
z y x
e e r
+ +
= =
provided that k
x
= 0, 2/L, 4/L .... 2n/L, where n is a positive or
negative integer
Proof:
1 0 1 2 sin 2 cos = + = + n i n
) (
2
exp ) ( exp L x
L
n
i L x ik
x
+ = +
n i
L
nx
i
2 exp
2
exp =
x ik
L
nx i
x
exp
2
exp = =
26
27
Counting of States (important, needed to evaluate e.g. the
density of states, Fermi energy and other key properties)
Allowed values of k are thus k
x
= 0, 2/L, 4/L .... 2n/L
In one dimension, one allowed value of k for range of k of 2/L
Substituting into Schrdinger equation gives
r ik
k
e r
.
) ( =
2
2
2 2 2
2
2
) (
2
k
m
k k k
m
E
z y x k
= + + =
Parabolic dispersion of free particle with mass m
Corresponds to
with ,
2
2
k p
m
p
E = =
p is termed the crystal momentum, and k the wavevector
Dispersion Relation
28
Density of States
The Fermi energy and Fermi surface
Key properties of metals
29
30
Need to determine number of states in k-space up to a given
energy (the Fermi energy)
One allowed wavevector in volume element of k-space of (2/L)
3
Volume of sphere in k-space up to energy E, wavevector k is
Then calculate number of available states from E = 0 to E
F
, and
hence derive expression for density of states
3
3
4
F
k
+ the Pauli exclusion principle
Number of states,
Fermi wavevector
and Fermi energy
31
( )
3 2
2
2
3
2
n
m
E
F
=
Values of T
F
, k
F
, E
F
,
v
F
for sodium and
their significance
(37000K, 0.96x10
10
m
-1
,
3.2eV, 1.07x10
6
m/sec)
32
33
Topic 2 summary
1. Electrons are Fermions and obey Fermi-Dirac statistics and
the Pauli exclusion principle
2. States up to E
F
filled, above E
F
empty
3. Form of the density of states proportional to E
1/2
4. Expressions and quantitative values for E
F
, k
F
, v
F
(these are
important!)
Topic 3: Conductivity
Drude theory of conductivity based on free electron model
Ion cores ignored, periodic lattice ignored, effective mass
Zero frequency approximation, Ohms Law
Displacement of Fermi sphere by electric field and
scattering processes
Phonon and defect scattering, Matthiesens rule
34
Deduce velocity
Define mobility
Deduce current density,
conductivity and Ohms
Law
m
ne
m
e
ne j
2
v
=
=
=
35
Newtons 2
nd
Law
Include scattering
scattering time
d.c conditions , B = 0
( )
( ) B E e
dt
dk
B E e
dt
d
m
x v
x v
v
+ =
+ =
( ) B E e
dt
d
m x v
v v
+ =
E e
m
=
v
Fermi sea of electrons in
applied electric field, and
scattering processes
For derivation of
displacement in k-
space see next slide
36
So displacement of Fermi sea by
electric field is very small
Scattering counters acceleration of
electrons by electric field
Motion of electrons in electric field and
scattering: change in wavevector
Alternatively:
37
eE mv
k
m
E e
v
D
= =
=
5 x 10
8
smaller than k
F
For metals two scattering
mechanisms are important
1. Lattice scattering - phonons
2. Imperfections (defects)
impurity atoms, vacancies,
lattice defects
Scattering collisions which are
important are those which relax
momentum gained from E-field
Scattering must be across Fermi
sea
i.e. large k, small E
38
Phonon scattering
Fermi energy ~ 3 eV
Phonons have maximum energy
~50 meV
Scattering must be to an empty
state
Thus only electrons close to Fermi
surface can be scattered
Must conserve energy and
momentum
Collisions which relax momentum
gained in applied electric field lead
to resistance
Must be across Fermi sea:
Large k small E
39
Situation is similar for defect scattering
However, in this case collisions are elastic, but still with large
momentum change as for phonons
It is again scattering with large k which is effective in leading
to resistance (as for phonon scattering)
For phonons scattering is inelastic, but energy change is
negligible
For phonons (conservation of energy and wavevector):
el
f ph
el
i
el
f ph
el
i
E E
k k k
= +
= +
Combination of two types of scattering
Phonon scattering is temperature dependent
Scattering by imperfections is temperature independent
Matthiesens rule (additive combination of contributions from
phonon and defect scattering)
40
Scattering of electrons is not by
ions
Instead by impurities and defects
Electrons propagate freely in periodic
structure (see Bragg scattering later)
Mean free path l
B
> 1m or more
l
B
>> interatomic spacing, so
collisions not with ions
41
Additional point (important)
Topic 3: Summary
Theory of conductivity based on free electron model
Ion cores ignored, periodic lattice ignored. Electrons treated with
effective mass
Displacement of Fermi sphere by electric field and scattering
processes
Phonon and defect scattering. Contributions are additive.
Matthiesens rule
Scattering processes which relax momentum across the Fermi sea
are the important ones (in opposite direction to acceleration by field)
Scattering is not by the ions of the lattice.
42
43
Topic 4: Electrons in periodic lattice, nearly
free electron model
Many experimental observations are not explained by free electron
theory, including:
1. Existence of bands, band gaps
2. Existence of non-metals
3. Effective mass
4. Colours of metals
5. High frequency conductivity
6. Existence of holes
7. Nature of the Hall effect
The periodic lattice is all important in explaining these and other
phenomena
44
Periodic lattice gives rise to
Bragg diffraction of electron
waves
45
o
a a
k
n n
90
2 sin 2
2
=
= = =
1
= =
is zero at zone boundary, corresponds to standing wave
Continuing last slide
51
To summarise Topic 4
Bragg diffraction defines edge of Brillouin zone.
Group velocity at Bragg condition (at zone boundary)
is zero
Bragg diffraction, and hence band gaps, occurs for
waves (k-values) in synchronism with lattice
periodicity
General condition for Bragg diffraction,
G is reciprocal lattice vector
G k =
52
Nobel Prize in Physics 2009; Strong relevance to Solid State
Physics
Charles K Kao, Optical fibres, Basis of internet data transmission
Combines semiconductor laser
sources, modulators, detectors,
knowledge of optical absorption
mechanisms in solids
53
Willard S. Boyle and George E. Smith, Charge Coupled Device Detectors
Digital imaging device in cameras, fax
machines, scanners, telescopes and
many other types of modern
instrumentation. Based on silicon
integrated circuit technology and field
effect transistors
Readout of information
from each pixel
54
Key Points of Topics 1-4
1. Existence of bands and band gaps vital to explain key properties of
electrons in solids
2. Band region of allowed electron states in E(k) space
3. Band gap - region of forbidden states, no allowed states
4. Explains distinction between metals, semiconductors and insulators
5. Fermi-Dirac distribution function. States filled up to Fermi wavevector
6. Behaviour of Fermi sphere under applied electric field, small
perturbation
7. Scattering mechanisms. Scattering is not by ions of lattice.
8. Bragg scattering gives rise to band gaps
9. Bragg condition defines k-vectors at which Bragg scattering occurs
10. Treatment of k-vectors for which waves in synchronism with lattice
provides insight into origin of band gaps
11. General condition for Bragg diffraction
12. Outer shell electrons provide dominant contribution to conduction (see
periodic table)
G k =
55
Atomic configuration of sodium:
1s
2
, 2s
2
, 2p
6
, 3s
1
n = 1, 2 shells tightly bound and give rise to lower energy
valence bands. Do not contribute to conduction.
3s electron is weakly bound and leads to conduction. Half
filled band
56
Topic 5: Introduction to Brillouin zones, half-filled
and filled bands
Number of states in a band
Monovalent atoms metallic
Insulators: can only occur for even number of valence electrons
Group II elements, nevertheless are metallic.
Concept of overlapping bands
57
Each unit cell contributes one value
of k to each Brillouin zone, and
hence to each band
Including spin, 2N states per band
If one atom per unit cell
(monovalent), then band half filled
alkali, noble metals
Insulators can only occur for even
number of valence electrons per
primitive cell (e.g. C, Si, Ge, which
are 4 valent, plus have 2 atoms per
primitive cell)
Group II elements could be
insulators, but bands overlap, so
metals, but relatively poor metals
(also see Hall effect where there is
hole conduction)
Counting of states and filling of bands
Periodic boundary conditions
(following from pages 26, 27)
k = 0, 2/L, 4/L .... 2n/L
L is length of chain of atoms, n is an
integer
If N is number of atoms, the lattice
constant a is equal to L/N
Total number of states between /a
is N
More strictly, N is number of primitive
unit cells in chain
58
Conduction in half-filled
and filled bands
I
II
IV
Note also:
Transition metals
Noble metals
59
Alkali metals and noble metals have one outer shell
electron: partially filled band and hence metal
Group IV: semiconductors, insulators, 4 outer shell
filled bands
Group II: even number of outer shell electrons, but
overlapping bands. Hence metallic.
60
61
How bands can overlap
And thus overlapping bands
i.e. energy in second band
less than that in first
in
E
c
< E
b
for
m
k
E
g
2
2 2
<
E
c
can be less than E
b
for:
:
62
Overlapping bands: energy of state in second band lower than in first
Consequence: some of states in second band filled before
uppermost states in first
Leads to two partially filled bands
Electrons and holes anomalous Hall coefficient
63
Summary, Topic 5
Total number of states in 1D chain, using periodic boundary conditions =
N, where N is number of atoms. Given by total number of allowed k-
values.
Each unit cell contributes one value of k to each Brillouin zone, and hence
to each band. Including spin gives 2N states per band
Monovalent atoms with one atom per unit cell (alkali and noble metals),
band half filled, expect metallic
Insulators: can only occur for even number of valence electrons per
primitive cell e.g. C, Si, Ge 4 valence electrons plus 2 atoms per primitive
cell
But group II elements, the alkaline earths (metals) have even number of
electrons, expected to be insulators, but are metallic.
Overlapping bands. Can only occur in 2 and 3D. Simple proof for 2D.
64
Summary of Bragg diffraction, Brillouin zones
1. Bragg condition defines edges of Brillouin zones
2. For one dimension, simple proof of condition k = /a (page 45)
3. In general
4. Can also be understood in terms of mixing of particular values of
k by Fourier components of periodic lattice potential (page 49)
(Kittel pages 34-36 for rigorous treatment)
5. Dependence of band gaps on atomic number, differing roles of
inner and outer shells.
G k =
65
Topic 6: Construction and Properties of Brillouin Zones
Use generalised Bragg condition to construct Brillouin Zones
Definition and properties of Brillouin Zones
Consequences for Fermi surfaces
Different zone schemes
Essential steps to understand shapes of Fermi surfaces of
real metals (and hence conduction properties)
66
Bragg Diffraction:
67
G = 2/a in 1D
In 1D, re-
derivation of
Braggs Law
68
Geometrical constructions
to obtain Brillouin Zones
Also see next slide
Perpendicular
bisectors
of G
1
Hook and Hall
(p334)
69
Construction of Brillouin Zones for Square Lattice
70
Definition of
Brillouin zones
71
1. Generalised Bragg condition
2. defines boundaries of Brillouin zones . k lies
on perpendicular bisector of G.
3. Construction of 1
st
, 2
nd,
3
rd
zones
4. If Fermi surface is sufficiently large that it crosses
Brillouin zone boundaries, then shape of Fermi surface
will be strongly modified.
2
. 2 G G k =
72
By reciprocal lattice translation
(2/a), can translate points in
higher zones into first zone
Reduced
zone scheme
Hook and Hall
(p116-118)
Also see Hook and Hall
p39 for physical
discussion
Translation vector
73
Repeated, reduced and
extended zone
schemes
Rely on reciprocal lattice
translations
One Brillouin zone one
band in extended zone
scheme
74
( ) ) (k G k = +
using
Shapes of Fermi surface resulting from Brillouin Zone structure
Superimpose Fermi circle
on Brillouin Zones
Additional
mechanism for
occurrence of
partially filled bands
Complicated shapes
of Fermi surfaces
75
Summary: Topic 6
Generalised Bragg Condition:
Brillouin zone boundaries defined by intersection of k with perpendicular
bisectors of reciprocal lattice vectors G
Reciprocal lattice vector in 1D G = 2x/a
Generalise to 3D
First Brillouin Zone is the set of points in reciprocal space that can be reached
from origin without crossing any Bragg plane
Generalise to 2
nd
, nth zones
All Brillouin Zones have the same volume
Basis of reduced, repeated and extended zones. Approximate
proof and consequences.
2
. 2 G G k =
) ( ) ( k G k = +
76
Topic 7: Fermi Surfaces in Metals, Their Forms and
Their Measurement
Topic 6 has introduced effect of periodic potential and of
Brillouin zones on shapes of Fermi surface
Topic 7 is concerned with the shapes of Fermi surfaces in real
metals, and the role of the crystal lattice potential and its
periodicity
Will discuss silicon band structure
in next lecture - download
77
Band must intersect Brillouin Zone boundary
at right angles (2D picture, also holds in 3D)
(as for band at zone boundary in 1D)
78
Real Fermi surfaces
e.g. copper, silver , gold
fcc lattice in real space
bcc lattice in reciprocal space
Belly, neck and dogs bone
orbits
Distortion of Fermi surfaces by
periodic potential at Brillouin
zone boundaries (as in 2D on
previous slide)
Fermi surface in copper
Alkali metals e.g. Na, K Fermi surface lies
inside 1
st
Brillouin zone, and is only very
slightly distorted
Repeated zone scheme
79
Origin of neck orbits:
Energy of band lowered as it approaches zone boundary
So states at higher k may be populated
Thus spherical Fermi surface distorted
Dogs Bone
Hole-like constant energy surface: easily visualised in
extended zone scheme
Other ways to produce holes??
80
Intermediate summary:
1. Periodic potential produces gaps at zone
boundary
2. Fermi surface intersects zone boundary at
right angles
3. Crystal potential rounds out sharp corners in
Fermi surface
4. Total volume enclosed by Fermi surface
depends only on electron density
independent of details of potential
81
Soft X-ray emission
Method to measure conduction electron
distribution in solids
1. Only outer shell electrons contribute
2. All inner shells are filled, and play no role e.g.
In Na 1s, 2s, 2p shells filled (p55)
3. Can measure energy distribution of conduction
electrons by soft x-ray emission
4. Use high energy electron bombardment to
create hole in one of inner shells
5. Conduction electron falls into hole. X-ray
photon emitted
6. Distribution of emitted x-rays gives measure of
conduction electron distribution
Related topics due to conduction electrons: plasmons,
plasma reflectivity see later in course. Determine Fermi
energy from plasma frequency.
82
Soft x-ray emission
spectrum
0 E
F
83
Summary Topic 7
1. Periodic potential produces gaps at boundaries
2. Fermi surface must intersect zone boundary at right angles
3. Crystal potential rounds out sharp corners in Fermi surface
4. Total volume enclosed by Fermi surface depends only on number
of electrons why. Independent of potential
5. All Brillouin zones have same volume
6. Copper, silver, gold, belly, neck and dogs bone orbits
7. Alkali metals much simpler
8. Soft X-Ray emission measures electron distribution of occupied
bands in solids. Complementary to conductivity, Hall effect,
plasma reflectivity
84
Topic 8: Tight Binding Model
1. Levels sharp in isolated atoms
2. When atoms brought together, Pauli principle does not allow
energies of electrons on different atoms to be the same.
3. For N atoms, bands formed to accommodate 2N electrons
band contains 2N states
4. Tight binding since electrons assumed to be associated
initially with individual atoms
5. Shape of different bands different, since orbital leading to
different bands are different and have different overlap
85
Why?
See Rosenberg book
The band structure of silicon as a real example
Atomic levels
broaden into bands
The band at 0 eV is
the valence band
The next band to
higher energy is the
conduction band
Derive from
outermost electron
states in atomic Si
87
Summary: Topic 8
1. Tight binding model is alternative approach to understand band
formation (intuitive approach starting from atomic orbitals)
2. Degeneracy of levels lifted due to wavefunction overlap
3. Predicts 2N states per band as does periodic potential model
88
Topic 9: Effective Mass, Electrons and Holes
We have shown in previous topics that electrons and holes are
not scattered by the ions of the crystal lattice (except at the
Bragg condition)
However the ions and the periodic potential do lead to a
measurable change in the properties of the charge carriers: they
lead to effective masses which are not equal to the free electron
mass
We also introduce the concept of holes in this topic
89
Derivation of
expression for
effective mass
At zone
boundary v
g
= ??
90
Variation of
effective mass
with E and k
m*/m
e
k
91
See diagram on
previous page
92
Electrons and
holes in
electric field
93
Examples holes in
semiconductors
Partially filled bands in
metals: group II elements
See Hall effect, cyclotron
resonance to determine
sign of charge carriers
Also note large range of
effective masses
94
Pictorial
representation of
motion of empty states
(holes) in electric field
Supplement
Filled band: no current
Remove one electron
Current is minus that
carried by one electron i.e.
-(-e)v = +ev
95
Summary Topic 9
1. Derivation of expression for effective mass for charge carrier
in energy band.
2. Variation of m
*
with k across Brillouin zone
3. Concept of holes, positive mass, positive charge particle.
4. Empty electron state in otherwise filled band
5. Charge transport by electrons and holes
6. Large range of effective masses
=
2
2
2 *
dk
E d
m