IMPRS Block Course, 22.3. 26.3.

2013
Band structure of solids - a physicist point of view

Martin Wolf
Fritz-Haber-Institut of the Max-Planck-Society, Berlin, Germany

1. Electrons in solids: the free electron gas

2 Electronic band structure of periodic crystals

2.

3. Examples & angle-resolved photoemission

4. Surface states
 Introduction
Solid state physics - concepts
2

Structure of solid state materials

- model system: single crystals with periodic boundary conditions
- but defects play important role doping in semiconductors, optical materials
- alloys and amorphous solids technological relevance (steel, glass, ...)
Theoretical description of solids electron density of Si
- Schrdinger equation for electrons and nuclei
- BUT:
Maxwell
howequations
for ~1023 for electromagnetic
atoms / cm3 ! ? fields
+ Si + Si
Statistical
- physics and approximation
Born-Oppenheimer thermodynamics
distribution
Density functions
functional theoryfor electrons
(DFT): +
Si
(Fermions) andAll
Hohnberg+Kohn: phonons (Bosons)
physical observables
Solids are
are uniquely
q body
many y described
systemsby y ((r)
y ((electron)) density )
ab initio calculation
- electron-phonon of solid state properties
interaction EFermi
- exchange and correlation effects
- useful concept: single particle picture occupied
states
- however simple models (e.g. Drude model)
describe often already essential physics
 free electrons in solids
1. Electrons in solids: Overview
3

Ashcroft / Mermin
 free electrons in solids
1.1 Electrons in solids: Sommerfeld model
4

Effective one-electron potential: (rigid lattice)

V - Born-Oppenheimer approximation
- Single electron approximation

Sommerfeld model:
particle
particle in a box
box
 free electrons in solids
1.2 The free electron gas
5
Sommerfeld model in 1D

V
 free electrons in solids
1.3 Standing waves
6

D. Eigler (IBM): STM image of iron atoms on Cu(111)

 free electrons in solids
1.4 Sommerfeld model in 3D
7
Sommerfeld model in 3D

for periodic
boundary conditions !
 free electrons in solids
1.5 The density of states (DOS)
8

spin

EF

D E E dE
3
U n EF
5
0
 free electrons in solids
1.6 Fermi gas at T = 0
9

Fermi distribution: Density of states: Fermi sphere:

32
1 2m
D E E
2 2 2
f (E,
(E TT=0)
0)
2 2
EF kF
2m
 free electrons in solids
1.7 Fermi Dirac distribution
10

T = 5000 K
 band structure
2.1 Electronic band structure of solids
11

Effective one-electron potential:

- Born-Oppenheimer
B O h i approximation
i ti
- Single electron approximation
- Periodic p
potential
- Diffraction of electron waves
deviation from free electron
b d structure
band t t (band
(b d gaps,))
Reminder: Lattice planes and Miller Indexes Diffraction

12

Lattice planes: 3 lattice vectors ni i , i 1, 2,3 which do not fall on
a
n3a3
a straight line define a lattice plane, which is characterized
by 3 integers, the Miller indices hkl:

a3
1 1 1
h m , k m , l m , h, k , l Z a1
a2
n1 n2 n3 n1a1

n2 a2

The reciprocal lattice vector:

G hkl hg1 kg 2 lg 3 Ghkl

is perpendicular to the lattice

plane (hkl) and the distance
b t
between adjacent
dj t planes
l iis:

2
d hkl
G
dhkl
Reminder: Diffraction and Bragg law Diffraction

13

2
The Laue condition k G is equivalent to: 2k 0 sin G hkl
d hkl
This yields the Bragg law for diffraction 2d hkl sin

Bragg reflection
Ghkl at crystal planes hkl

2
k0 d hkl
G

Laue: Bragg:
Reminder: The reciprocal lattice Diffraction

3

F R
For i i , ni Z andd G hg1 kg 2 lg3 , h, k , l Z
n a
i 1

the condition G R 2 m , m Z requires: g i a j 2 ij

and therefore g j a k , a l , j k l

The resulting basis vectors of the reciprocal lattice are:

a2 a3 a3 a1 a1 a2
g1 2 , g 2 2 , g 3 2
a1 (a2 a3 ) a1 (a2 a3 ) a1 (a2 a3 )

Example: 2D - lattice Real space lattice Reciprocal lattice

units [m] units [m-1]

 Structure
Reminder: Wigner-Seitz cell
15

Goal: primitive unit cell Example:

(with minimum volume) construction in
2 dimensions 1/2
1/2
C4
C4

bcc C3 fcc
C3

C2 C2

The Wigner Seitz cell comprises all points closer to a certain lattice point
than to any other point of the Bravais lattice
The Wigner-Seitz cell reflects point group symmetry of the lattice
 Structure
Reminder: Brillouin zones
16

The first Brillouin zone is defined as the Wigner Seitz cell of the reciprocal lattice

bcc lattice fcc lattice hexagonal

lattice

4 4 4 4
arez arez arez crez
adir adir 3adir cdir

Note: The reciprocal lattice of the bcc lattice is the fcc lattice and vice versa.
 band structure
2.1 Electronic band structure of solids
17

Effective one-electron potential:

E(k) = k2/2m
- Born-Oppenheimer
B O h i approximation
i ti
- Single electron approximation
- Periodic p
potential
- Bragg reflexion at Brillouin zone
boundary standing waves
- Opening of band gaps
 Experimental observation by photoelectron spectroscopy

CourtesyofEliRotenberg ALS
 band structure
2.2 Origin of the band gap
19

band gap
 band structure
2.3 Bloch Theorem
20

U stationary
Use t ti S
Schrdinger
h di equation:
ti

for a periodic potential in a crystal: with lattice vector

This implies (non-degenerate wave functions):

Solution Bloch theorem:

The wave function in a periodic potential is given by a
a periodic function uk(r) modulated by a plane wave:
 band structure
2.4 Bloch Theorem
21
Translational symmetry

Bloch-wave:

Symmetry properties:
 band structure
2.5 Consequences of the Bloch Theorem
22

Th Bloch
The Bl h theorem
th yields
i ld ffor th
the wave ffunctions
ti and
d Eigenstates:
Ei t t

n (k) n (k G)

En (k) En (k G)

where the index n counts the Eigenstates En of electrons in the periodic potential.
B d structure
Band t t can be
b reduced
d d tto th
the 1
1. Brillouin
B ill i zone

Extended zone Reduced zone Repeated zone

scheme: scheme: scheme:

G
 band structure
2.6 Consequences of the Bloch Theorem
23
Extended
zone sheme

-G

Reduced
zone
o e sheme
s e e
 band structure
2.7 Nearly free electron approximation
24
 band structure
2.9 Tight binding approximation
25

HA i = Ei i
perturbation
p

k H k
E (k )
k k

ihm=n1
with

m=n1
 band structure
2.10 Tight binding approximation
26

px
x

px x

orbital i
ss-orbital
 band structure
2.11 Tight binding approximation
27

E2
Egap

E1
 band structure
2.12 Electronic band structure in 3D
28
 band structure
2.13 Tight binding approximation: Examples
29

1.BZ 2.BZ
 band structure
2.14 Tight binding approximation: Examples
30

Tight binding Bloch wave:

Band structure of Aluminium using 1 s, 3 p and 5 d basis set (j = 1 . . . 9) for tight binding calc.

from: D. A. Papaconstantopoulos, Handbook of the band structure of elemental solids,

Plenum Press (New York) 1986.
 band structure
3.1 Classification of solid state materials
31

EF

EF

kT
 band structure
3.2 Photoemission spectroscopy
32

e-

vertical
transition
 band structure
3.2 Photoemission spectroscopy
33

vertical
transition

Determination of band structure:

Assume free electron final state:

CourtesyofEliRotenberg ALS
 band structure
3.3 Band structure and density of states
35

V
 band structure
3.4 Examples of band structures
36

Egap

point
energy

K point

Fermi
level

Graphene
 surface states
4.1 Surface states
37

Broken
B k translational
t l ti l symmetry
t att surface
f can lead
l d tto solutions
l ti off
the Schrdinger equation which are localized at the surface.
Surface state exists in band gaps of the bulk projected band structure
andd ffrequently
tl di
disperse nearly
l parallel
ll l tto b
bulk
lk b
band
d edges
d
Surface states do not disperse normal to the surface

solid
lid vacuum 6
Cu(111) Evac
E
4
n=1

E - EF
sp-inverted
Evac Band gap
projected
2 n=0
band gap Surface
state
t t EF
0

z -2
2
surface 0.0 0.5 1.0
k|| (-1) M
 surface states
4.1 Surface states
38

Broken
B k translational
t l ti l symmetry
t att surface
f can lead
l d tto solutions
l ti off
the Schrdinger equation which are localized at the surface.
Surface state exists in band gaps of the bulk projected band structure
andd ffrequently
tl di
disperse nearly
l parallel
ll l tto b
bulk
lk b
band
d edges
d
Surface states do not disperse normal to the surface

6
Shockley state: Cu(111) Evac
- contribution of s/p-orbitals dominate
- delocalized parallel to surface 4
n=1

E - EF
-ppronounced dispersion
p
2 n=0
Tamm state EF
- contribution of d-orbitals dominate (or pz) 0
- more localized character
- small dispersion -2
0.0 0.5 1.0
Surface resonance: k|| (-1) M
- Resonant with bulk bands (& strong mixing)
- Penetration into the bulk (weak localization at surface)
 surface states
4.2 Surface states
39

Broken
B k translational
t l ti l symmetry
t att surface
f can lead
l d tto solutions
l ti off
the Schrdinger equation which are localized at the surface.
Example: two-band model for the Cu(111) surface

~e-z
 surface states
4.3 Surfacs states
40

Broken
B k translational
t l ti l symmetry
t att surface
f can lead
l d tto solutions
l ti off
the Schrdinger equation which are localized at the surface.
Example: two-band model for the Cu(111) & Cu(001) surface