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Electronic Band Structure of Solids: Introduction To Solid State Physics
Electronic Band Structure of Solids: Introduction To Solid State Physics
Solids
Introduction to Solid State Physics
http://www.physics.udel.edu/~bnikolic/teaching/phys624/phys624.html
1
What are quantum numbers?
Quantum numbers label eigenenergies and eigenfunctions of a Hamiltonian
Bloch states have the property that their expectation values of r and k , follow
classical dynamics. The only change is that now n (k ) (band structure) must be
used: e
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.
n const (no interband transitions)
Limits of validity:
gap
2
(k ) eB gap
2
(k )
eEa = , hc = , gap (k ) n (k ) n (k )
F m F
h = gap , ? a
PHYS 624: Electronic Band Structure of Solids 3
What is the range of quantum numbers?
( 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
Sommerfeld: 2 2
hk
(k )
2m
Bloch: For a given band index n, n (k ) has
no simple explicit form. The only general
property is periodicity in the reciprocal space:
n (k G ) n (k )
PHYS 624: Electronic Band Structure of Solids 5
What is the velocity of electron?
V
Bloch: The wave function of an electron with band index n
and wave vector kis:
k (r ) e nk (r )
ikr
Sommerfeld Bloch
2 2
D( ) dk (k ) D( ) dk (k )
2 2
d d n
n B.Z .
1
D( )d
2 d
dS k
d k n (kk
) k kn ( ) k
D( )
3D
DOS: D( ) dr (r, )
k F kF
Points of Fermi
Surface in 1D
PHYS 624: Electronic Band Structure of Solids 11
Sommerfeld vs. Bloch: Fermi surface in 3D
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
the Fermi surface: for each n solve the equation n (k ) F in kvariable.
PURE
DOPPED
iGr
fG dr e f (r ); e iGr
dr 0
V pcell pcell pcell
(k ) (k G ) (k ) R eiRk
R
dk
R V pcell e iRk
(k )
BZ 2
3
Born-von Karman: f (r ) f (r N i ai )
3
mi 1
f (r ) f k e ikr
,k bi ; fk dr e ikr f (r ); eikr dr 0
k i 1 Ni Vcrystal crystal crystal
e ikR
N k ,0
3
R
R na , 0 n N i , N N1 N 2 N 3 ; k BZ
e
i i i
ikR
N R ,0 i 1
k
U (r ) U (r R ) U (r ) U G eiGr , G R 2 m
G
h2
H (r ) U (r ) (r ) (r ), (r ) Ck eikr
2
2m k
h2 k 2
k 2m
C k e ikr
k G
C U
k G e i ( k +G)r
k
C k e ikr
h2 2
k
k k G : e
ikr
Ck U G Ck-G 0, for all r
k 2m G
h2 k 2
Ck U G Ck-G 0, for all k k (k )
2m G
Potential acts to couple Ckwith its reciprocal space translation Ck G and the
problem decouples into N independent problems for each k within the first BZ.
G
6 G4 4 7 4 48
(r ) (r R )
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
ik U (r) nk (r) n (k )nk (r)
2
2. Each zone n is indexed by a k
2m vector and, therefore, has as
many energy levels as there
h2 are distinct k vector values
ik U (r) n,k (r) n (k )n,k (r)
2
3.
2m within the Brillouin zone, i.e.:
2m ik (k ) k G
2
k (r ) 0 (k )
2 0 0 0
2m
1 iGr
Counting of Quantum States:
k (r )
0
e
V
Extended Zone Scheme: FixG (i.e., the BZ) and then count k vectors within the
region corresponding to that zone.
Reduced Zone Scheme: Fix k in any zone and then, by changing G , count all
equivalent states in all BZ.
x x
: eiGx / 2 e iGx / 2 : cos : eiGx / 2 e iGx / 2 : sin
a a
PHYS 624: Electronic Band Structure of Solids 23
Free Bloch electrons at BZ boundary
1
G k U H k U (r )dr
V U G
2
2m
k k
2m
0 at BZ boundary Laue diffraction!
eikr ei (G+k)r
1 0
(k ) (k ) 4 U G
2 2
G 0 (k ) G 0 (k ) G0 (k ) 0
G 0
0
G
2
G' G '
G '
k G 0 (k ) G0 0 (k ) U G ; G 0 (k ) G0 0 (k ) U G
2 2 2
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.
2
2 4 2
S BZ b
2
, Scell a 2
a S cell
S BZ 4 2 2 2
S state , N N1 N 2
2 N 2 NS cell Scrystall
2 2 S BZ Sb
S Fermi N e S state 2 kF 0.798
a 2 2 a
S Fermi 2 N e S state S BZ k F 1.128
a
S BZ
S Fermi zN e S state z , for crystal with z-valence atoms
2
PHYS 624: Electronic Band Structure of Solids 27
Fermi surface in 2D for free Bloch electrons
0 (k ) 0 (k G)
2
(k ) (k G )
0 0
2
(k ) UG
2 4
1 (k ) 0 (k G ) k 0 (k ) k 0 (k G )
0
1
k (k ) 2 k 0 (k ) k 0 (k G) 2
2
0 (k ) 0 (k G)
2
2
UG
4
at the BZ boundary : 0 (k ) 0 (k G)
h2 h2 k
k (k ) k + k + G + G G 0
2m m 2
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.
Tight Binding approach is completely opposite to free Bloch electron: Ignore core
electron dynamics and treat only valence orbitals localized in ionic core potential.
Notation: x i ( x R i )
PHYS 624: Electronic Band Structure of Solids 33
One-dimensional case
ts t p
kl ( x) l x na
e ikx
Re kl ( x)
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!
Ri a Ri a
1 A, B 2 A, B
1A, B s px
3 3
1 A, B 1 A , B 1 A , B
2A, B s m px py
3 6 2
1 A, B 1 A, B 1 A, B
3A, B s px py
3 6 2
4A, B pzA, B
1 A 1 A
b ( onding )
i i i , i
B a ( ntibonding )
i iB
2 2
PHYS 624: Electronic Band Structure of Solids 39
Truncating the basis to a single orbital per atom
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))
1/ 2
(r ) R | Ta (r ) ( R | Ta
1
n
Rk
n
k
n
k r ) kn ( R 1r R 1a)
R | R a
1
R | Ta r Rr a, R | Ta
1 1 1
Plot (k ) 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 k
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 0 1
1/ 2
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.