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Introduction to Solid State Physics
http://www.physics.udel.edu/~bnikolic/teaching/phys624/phys624.html
Sommerfeld:
Bloch:
and
k -vector ( hk
is momentum)
The Crystal Momentum is not the Momentum of a Bloch electron: the rate of change of an
electron momentum is given by the total forces on the electron, but the rate of change of
electronic crystal momentum is:
dr
1 n (k )
v n (k ) nk v nk
;
dt
h k
d hk
e E(r, t ) v n (k ) B(r, t )
dt
where forces are exerted only by the external fields, and not by the periodic field of the lattice.
H classical n hk eA (r ) e (r )
B L k
2m
dp d ( hk )
H dr
H
,
v
dt
dt
r dt
p
p
A perfectly periodic ionic arrangement has zero resistance. Resistivity comes from
imperfections (example: a barrier induces a reflected and transmitted Bloch wave),
which control the mean-free path. This can be much larger than the lattice spacing.
A fully occupied band does not contribute to the current since the electrons cannot be
promoted to other empty states with higher k . The current is induced by
rearrangement of states near the Fermi energy in a partially occupied band.
Limits of validity:
2
2
gap
(k )
gap
(k )
eB
eEa =
, hc
=
, gap (k ) n (k ) n (k )
F
m
F
h = gap , ? a
Sommerfeld:
runs through all of
k-space consistent with the Born-von
Karman periodic boundary
conditions:
( x L, y , z ) ( x , y , z )
2
( x L, y , z ) ( x , y L , z ) k
nx , n y , nz nx , n y , nz 0, 1, 2, K
( x, y , z ) ( x , y , z L )
( x L, y , z ) ( x, y , z ) 0
( x L, y, z ) ( x, y L, z ) 0 k nx , n y , nz nx , n y , nz 1, 2, K
L
( x, y, z ) ( x, y, z L) 0
Bloch: For each n, k runs through all wave vectors in a single
primitive cell of the reciprocal lattice consistent with the Bornvon Karman periodic boundary conditions; n runs through an
infinite set of discrete values.
hk
(k )
2m
n (k G ) n (k )
PHYS 624: Electronic Band Structure of Solids
hk 1
v
m
h k
1 n (k )
v n (k )
h k
v v
h
dr (r ) mi (r )
*
1
(r )
e
V
k (r ) e nk (r )
ikr
D( )
dk (k ) D( )
dk (k )
2
2
d
n B.Z .
d k (k )
n
n B.Z .
D( )d
dS
n dk (k )
k n
Sn ( E )
1
dS k
2
d
d k n (kk
)
k kn ( ) k
D( )
k (0, 0, 0) max
k n (k ) 0 for k , , min
a
a
a
0 , 0, 0, saddle
k , 0, 0 , 0, ,
a
a
a
1D
3D
Local DOS: (r, ) ( r ) ( )
2
DOS: D( ) dr (r, )
PHYS 624: Electronic Band Structure of Solids
10
F
k F
(k ) F
kF
Points of Fermi
Surface in 1D
PHYS 624: Electronic Band Structure of Solids
11
For each partially filled band there will be a surface reciprocal space separating occupied
from the unoccupied levels the set of all such surfaces is known as the Fermi surface
and represents the generalization to Bloch electrons of the free electron Fermi sphere.
The parts of the Fermi surface arising from individual partially filled bands are branches of
kvariable.
n (k ) F in
the Fermi surface: for each n solve the equation
12
13
14
PURE
DOPPED
PHYS 624: Electronic Band Structure of Solids
15
I ( kin )
( kin )
16
17
f (r ) f (r R ) f (r ) f G eiGr
G
1
iGr
iGr
fG
d
r
e
f
(
r
);
e
dr 0
V pcell pcell
pcell
(k ) (k G ) (k ) R eiRk
R
dk
iRk
R V pcell
e
(k )
3
BZ 2
Born-von Karman:
f (r ) f k e
k
ikR
ikr
,k
i 1
N k ,0
e
k
ikR
mi
bi ;
Ni
N R ,0
fk
f (r ) f (r N i ai )
1
Vcrystal
na , 0 n
i 1
dr e ikr f (r );
crystal
eikr dr 0
crystal
N i , N N1 N 2 N 3 ; k BZ
18
h
2
H (r )
U (r ) (r ) (r ), (r ) Ck eikr
k
2m
h2 k 2
ikr
i ( k +G)r
ikr
C
e
C
U
e
C
e
k
k G
k
2m
k
k G
k
2 2
h
k
ikr
k k G : e
Ck U G Ck-G 0, for all r
k
G
2m
h2 k 2
Ck U G Ck-G 0, for all k k (k )
G
2m
19
i ( k G ) r
Ck G e e
G4 4 7 4 48
6
(r ) (r R )
iGr
ikr
H k G (r ) (k G ) k G (r )
1. k G (r ) k (r )
H k (r ) (k G ) k (r ) (k ) (k G )
h2
2
2.
ik U (r) nk (r) n (k )nk (r)
2m
h2
2
3.
ik U (r) n,k (r) n (k )n,k (r)
2m
N N1 N 2 N 3
20
h2 k 2
continuous spectrum with infinitely
n (k )
2m
n (k )= n (k + G ) does not mean that two electrons with wave vectors k and k G
nof(k )
have the same energy, but that any reciprocal lattice point can serve as the origin
.
U 0
21
2
0
2m ik (k )
2
h
2
0
0
k G
k (r ) 0 (k )
2m
1 iGr
0
k (r )
e
V
Extended Zone Scheme: FixG (i.e., the BZ) and then count
region corresponding to that zone.
Reduced Zone Scheme: Fix
equivalent states in all BZ.
, count all
22
x
a
x
a
23
k (G ) (G ) G k U G k
0
k
r G k (r )e
0
nk
ikr
Hk U G k
k0 (G ) k0 (H )
... O(U 3 )
1 i ( G k)r
e
V
1
i ( H+G+G )
G k U H k U G e
dr U G G,G-H U G-H
V G
G
1
G k U H k U (r )dr
2
V
U G
second order correction 0
0
(
G
)
G k
k (G + G )
PHYS 624: Electronic Band Structure of Solids
24
h 2
h
2
2
(G 0) (G )
k G + k G 2G k
2m
2m
0
k
0
k
G 0
1 0
(k ) G 0 (k ) G0 (k )
2
0
G 0
(k ) (k ) 4 U G
0
G
'
'
G'
G
G
k G 0 (k ) G0 0 (k ) U G ; G 0 (k ) G0 0 (k ) U G
2
2
2
25
In 1D model, there is always a gap at the Brillouin zone boundaries, even for an
arbitrarily weak potential.
In higher dimension, where the Brillouin zone boundary is a line (in 2D) or a surface
(in 3D), rather than just two points as here, appearance of an energy gap depends on
the strength of the periodic potential compared with the width of the unperturbed band.
26
S BZ
S state
4 2
2
2
b
, Scell a 2
S cell
a
S BZ
4 2
2 2
, N N1 N 2
2 N 2 NS cell Scrystall
S Fermi N e S state
2 2 S BZ
2
kF
a
2
Sb
0.798
2
a
S BZ
z
, for crystal with z-valence atoms
2
27
28
(k ) (k G )
2
0
k (k )
0 (k ) 0 (k G)
4
1
2
1
2 k 0 (k ) k 0 (k G) 2
UG
(k ) 0 (k G ) k 0 (k ) k 0 (k G )
0 (k ) 0 (k G)
4
UG
at the BZ boundary : 0 (k ) 0 (k G)
h2
h2 k
k (k ) k + k + G + G G 0
2m
m 2
29
Tight-binding approximation
Tight Binding approach is completely opposite to free Bloch electron: Ignore core
electron dynamics and treat only valence orbitals localized in ionic core potential.
There is another way to generate band gaps in the electronic DOS they naturally
emerge when perturbing around the atomic limit. As we bring more atoms together
or bring the atoms in the lattice closer together, bands form from mixing of the orbital
states. If the band broadening is small enough, gaps remain between the bands.
PHYS 624: Electronic Band Structure of Solids
30
31
32
Notation: x i ( x R i )
PHYS 624: Electronic Band Structure of Solids
33
One-dimensional case
Assuming that only nearest neighbor orbitals overlap:
34
One-dimensional examples:
s-orbital band vs. p-orbital band
tp 0
ts 0
ts t p
kl ( x)
ikx
e
l x na
Re kl ( x)
bandwidth: W 4dtl 2 ztl
PHYS 624: Electronic Band Structure of Solids
35
Wannier Functions
It would be advantageous to have at our disposal localized wave functions with vanishing
overlap i j ij : Construct Wannier functions as a Fourier transform of Bloch wave
functions!
36
Ri a
Ri a
37
r r
a, b
38
2
sp
Chemistry of Graphite:
hybridization, covalent
1 A, B
2 A, B
s
px
3
3
1 A, B 1 A , B 1 A , B
s m px
py
3
6
2
1 A, B 1 A, B 1 A, B
s
px
py
3
6
2
4A, B pzA, B
1A, B
2A, B
3A, B
b ( onding )
i
1 A
1 A
B
a ( ntibonding )
i i , i
i iB
2
2
39
The atomic
orbitals as well as the
atomic carbon x y functions form strong
bonding orbitals which are doubly occupied
and lie below the Fermi energy. They also
form strongly antibonding orbitals which are
high up and empty.
This leaves space on energy axis near the
Fermi level for
orbitals (they point
perpendicular to the direction of the bond
between them)
The
orbitals form two bands, one
bonding band lower in energy which is
doubly occupied, and one antibonding band
higher in energy which is unoccupied.
These two bands are not separated by a
gap, but have tendency to overlap by a
small amount leading to a semimetal.
kA
1
N
ikm
e
A (r m)
m
1
ikm
kB
e
B (r m)
N m
B (r ) A (r )
Bloch eigenstates:
kn kA kB
1
40
Diagonalize 2 x 2 Hamiltonian
kA H kA
kA H kB
H (k )
kB H kA
kB H kB
1
kA H kA eik ( m-m) dr A (r m) H A (r m )
N mm
kB H kB drB (r ) H B (r ) kA H kA dr A (r ) H A (r )
kA H kB dr A (r ) H B (r ) e ika dr A (r ) H B (r a) e ikb dr A (r ) H B (r b)
t
(k ) t 1 e ika e ikb
(k ) t 3 2 cos(ka) 2 cos(kb) 2 cos(k (a b))
PHYS 624: Electronic Band Structure of Solids
1/ 2
41
(r ) R | Ta (r ) ( R | Ta
n
Rk
n
k
n
k
R | Ta r Rr a, R | Ta
r ) kn ( R 1r R 1a)
R | R a
42
Plot
for some special directions in reciprocal space: there are three
directions of special symmetry which outline the irreducible wedge of the Brillouin
zone. Any other point
of the zone which is not in this wedge can be rotated into a
k-vector inside the wedge by a symmetry operation that leaves the crystal invariant.
along : (k ) t 5 4 cos 2
1/ 2
0 1
1/ 2
1/ 2
43
In the plane
perpendicular to atoms
44
45
Carbon Nanotubes
46
c na n a
3n2
2n1 n2
47
chk 2 m c h K 2 m 2n1 n2 3m
Conclusion:
The armchair CNT n1 n2 are metallic
The chiral CNT with 2n1 n2 3m
are moderate band-gap semiconductors.
48
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