1

Lecture contents

• Solid state physics review

– Approximations
– Bloch theorem
– k-vector
– Brillouin zone
– Tight-binding model

NNSE 618 Lecture #3

 Few concepts from Solid State Physics 2

1. Adiabatic approximation
When valence and core ectrons are separated, general Schrödinger equation for a
condensed medium without spin

= H L + He

H( R, r )  E( R, r )
• Mass of ions >1000 (for most
semiconductors >102 times greater than
mass of electrons
( R, r )   (r, R)( R)
• Ion velocities >100 times slower
• Electrons adjust ‘instantaneously” to the
positions of atoms
H L ( R)  EL ( R)
• Separate ion and electron motion
(accuracy ~m/M)
H e (r , R)  Ee (r , R)

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Few concepts from Solid State Physics
2. Phonons
Hamiltonian for lattice motion (harmonic oscillations) :
Phonon dispersion

 
pl2 relation in GaAs
 U 0 Rl0  Rm0   Cl ,m ul  um   U anhar
1
HL  
2

l 2M l l ,m l ,m 2

Displacements show up as plane waves with weak

interaction via anharmonicity:

uk ,  u0eikr it
Energy in a mode:

 1
E k ,     nk ,    
 2
Equilibrium distribution (Bose Einstein):

1
n( ) 
  
exp   1
 kT 
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Few concepts from Solid State Physics
3. One-electron (mean-field) approximation
Schrödinger equation for the electrons (no spin):

V (r )  V
i
e i e e

Introduce one-electron states, i :  (r , R)   i (ri , R)

i

H ei 
pi2
2m l
 
 V ri  Rl0  Ve ph  Vee
Small perturbation
One-electron Schrödinger equation (each state can
accommodate up to 2 electrons):
 p2 
  V r  (r )  E (r ) V(r) has periodicity of the crystal
 2m 
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Translational symmetry: Bloch theorem
One-electron Schrödinger equation (each state can accommodate up to 2 electrons):

 p2 
  V r  (r )  E (r )
 2m 
If V(r) is a periodic function:

V (r )  V (r  R) R  m1a1  m2 a2  m3a3
The solution is :
From:
 k ( r )  e uk ( r )
ikr
• Linearity of the Schrödinger
where uk (r) is a periodic function: equation
• Fourier theorem *
uk (r )  uk (r  R)
uk might be not a single valence electron
Important : function but is close to linear combination of
2 2
valence electron wavefunctions
 k ( r )   k ( r  R)
Quasi-wavevector k is analogous to a
wavevector for free electrons (V=const)
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Reciprocal space (1D)

Wavefunction of an electron in crystal :  k ( r )  e uk ( r )

ikr

1D free electrons “band structure” is:

 2k 2
E
2m

k’ k’-b

 k ' ( r )  e uk ' ( r )  e
ik 'r ikr
e ibr

u k ' ( r )  e uk ( r )
ikr

periodic function
2
1D reciprocal lattice vector : b  m (Bloch function)
a0

 
First Brillouin zone:  k
a0 a0
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Bloch theorem: consequences

• Introduced k-vector quantum number for

 p2 
periodic potential   V r  (r )  E (r )
• Momentum is not conserved (not a quantum
 2 m 
number), however quasi-momentum is  k (r )  eikr uk (r )
conserved
• k-vector can be considered to lie in the first
Brillouin zone
 2  1 
2

• Solution with periodic boundary conditions     k   V ( r )  u k ( r )  Ek u k ( r )
 2m  i  
gives eigen-functions un,k for a given k which
forms orthogonal basis (compare with Fourier uk (r )  uk (r  R)
expansion)
un,k (r ), En,k
• n –values enumerate bands
• Electron occupying level with wavevector k in
1
the band n has velocity vn (k )   k En (k )


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Reciprocal space: 3D

b  m1b1  m2b2  m3b3 b1  2

a2  a3 
, b2 , b3  ...
a1  a2   a3
Diamond structure Zinc-blende structure

Basis of an FCC structure

a1 
a0
0,1,1 First Brillouin zone:
2
a2  0 1,0,1
a
2
a3  0 1,1,0 
a
2

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Tight-binding model
V(x) 2
a0
H cryst    2   V0 (r  R)
2m R

What do we know?
• Formation of energy band
• Width depends mainly on interaction of the closest neighbors
• Wavefunctions are renormalized

Start with valence state: H at 0 (r )  E0 0 (r )

Consider crystal Hamiltonian as

atomic + perturbation : H cryst  H at  V

Solution in the form :    CR 0 (r  R); R  ma0 ; m  0,1...

R
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Tight-binding model: solution
   CR 0 (r  R)
R

 dr

CR  N 1 2eikR

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Tight-binding model: solution

  (r ) | V |  (r  R) e
0 0
ikR

Solution for band constructed from a E k  E0  R

single atomic orbital (s-band):
  (r ) |  (r  R) e
R
0 0
ikR

When overlap is negligible:  0 (r ) |  0 (r  R)   ( R)

Transfer integrals :  0 (r ) | V |  0 (r  R)  

Diagonal element:  0 (r ) | V |  0 (r )  

S-band: Ek  E0      ( R)eikR
R
Over nearest neibors
Width of a 1D S-band = 2

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Tight-binding model: s-band in FCC crystal

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Tight-binding model: effective mass

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Atomic states: electron in central-symmetric field
n=2
m=0 m = 1, Re m = 1, Im
Z2 me 4
En  
n   l 2 2 2
l=0

l=1

If we want them real or

symmetrical in space:
n=3  px 
1
 1,1  1, 1 
2

l=2  py 
i
1,1  1, 1 
2
 pz  1, 0
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Tight-binding model: LCAO

Need to include:
   e ikR 0 (r  R)  (k , r )     ml (r  Rlj )
ikRlj
>1 atoms in unit cell Cml e
>1 atomic orbitals R ml j

For diamond or zinc-blende structures:

l = 1,2 (two atoms in unit cell)
m = 1, …4 (s, px, py, pz)

1 secular equation: E

R
at  Ek  ( R)  VR e ikR  0

8 secular equations:

  
 ik R  R 
   e lj l ' j '  ml (r  Rlj ) | H |  m'l ' (r  Rl ' j ' )   Ek  mm' ll ' 
Cm'l ' (k )  0
m ',l '    
 j , j ' 

Major difficulties are in calculation of 3D atomic overlap integrals: Vss , Vsps , Vpps , Vpp

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Molecular orbitals for diamond or zinc-blende

structures (Si, Ge GaAs, InP….)

V = matrix element of interection Hamiltonian

From Yu and Cordona, 2001 NNSE 618 Lecture #3

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LCAO for diamond or zinc-blende structures

Atomic overlap integrals:

Vsss , Vsps , Vpps , Vpp

Four crystal overlap integrals

(calculating sums for 4 nearest neighbors)
Vss  4Vsss
4Vsps
Vsp 
3
4V pps 8V pp
Vxx  
3 3
4V pps 4V pp
Vxy  
3 3
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LCAO for diamond or zinc-blende structures
Molecular orbitals are extended to crystal  only nearest neibours
interact
At k = 0 (G-point), the s-p overlap integrals cancel out leading to
wavefunctions constructed from pure s or p states.

As a result:
E s  (0)  E sat  Vss
E p  (0)  E at
p  V xx

In the G-point:

Bottom of the C.B. is

“made” from s-orbitals

Top of the V.B. is “made”

from p-orbitals

NNSE 618 Lecture #3