Quantum Theory of Solids

• Schrodinger’s
Schrodinger s wave equation in spherical coordinates
• Energy bands
 E-k relationship

 Carriers in semiconductors ((electrons,, holes))

 Effective mass

 Semiconductor,
S i d t insulator,
i l t metals t l
 Direct vs. indirect bandgap

• Density of states
• Fermi
Fermi-Dirac
Dirac probability function

1
 Schrodinger’s Wave Equation
• Schrodinger wave eq. in 1D (x-coordinate):

• Schrodinger wave eq. in 3D, for H (Z = 1): F = -dV(x)/dx( )

F of e- & nucleus  V =  (1/40)[e2/(x2 + y2 + z2)½]
=> such V(x,
V(x yy, z) can
can’tt lead to separable equation,
equation
  f(x)g(y)h(z)
=>> spherical di t r, ,
h i l coordinates:  
x = rsincos ↓
i  i  V = - (1/4
y = rsinsin (1/4 0)[e)[ 2/r]
/]
z = rcos  = R(r)()()
x, y, z: -  
r: 0  , : 0  : 0  2 2
 Wave Functions and Energy Levels
• n,l,m(r,,) = Rn,l(r)l,m()m()
n: principal quantum number = 1, 2, 3, …
l angular
l: l momentum quantum number b = 0,0 1,
1 2,..,
2 n-1 1
m: magnetic quantum number = 0, 1, 2, ..., l
• E quantized
ti d = - (me )/(32 202ħ2)(1/n
( 4)/(32 )(1/ 2) = -13.6 V/ 2
13 6 eV/n
spin
Z
1
2
3
4
5
6
7
8
9
10 3
 Energy Bands - H H: 1s1
• Isolated
I l t d H atom:
t discrete
di t energy level
l l
E = - (me4)/(32202ħ2)(1/n2) = -13.6 eV/n2
• H atoms
t close
l together:
t th energy bands
b d
||2

-13.6 eV

V = - (1/4 )[ 2/r]
(1/4 0)[e /] (almost continuous
* past example, bcc: within band)
a = 5A

r0
4
 Energy Bands - Si
• Isolated Si atom: energy levels T = 0K
• Si atoms
t close
l together:
t th energy bands
b d
Si: 1s22s22p
p63s23p
p2 Eg: bandgap

 51022 cm-3 N atoms

5
 Potential Function in Crystal
• Isolated atom:
Z=1 V(r) = - (1/40)(Ze2/r) r -1
E = -13.6eV/n2
• Many atoms in 1D lattice:

6
 Kronig-Penney
g y Model
• Approximate V(x) by Kronig-Penney Model
V(x)
( ) = 0 in regioin
g I
= V0 in region II

* Block theorem: for periodic V(x)

(1) , u(x) is a periodic function with period (a+b)
pput ((1)) into wave equation
q + pperiodic B.C. => find allowable E
k    E, find E vs. k
=>
with
7
 E vs. k (Free Electron)
* free e- : V0 = 0
=> P’ = 0
> cos a = cos ka
=>
 = k

=> ,

consistent
(previous
chapter)
8
E vs. k (Electron in Crystal)
* e- in crystal: V0  0, P’  0
P’  0
P

-1  f(a) = cos ka  1
k    E, E = cos ka
find E vs. k

ka
0 
a = 

9
* Example: Find the forbidden bandgap at ka =  assume P’ = 8 and a = 4.5 A
, (2)

1st ka =  ,
2nd ka = 
try and error in (2)

E2
E1

a = 
ka
0  10
 Reduced-Zone Representation
= cos (ka + 2n) = cos (ka – 2n)
* Plot E vs.
vs k within –(/a)
(/a) < k < (/a),
(/a) i.e.  < ka < 
i e –

A’

B’

11
 Electrical Conduction - Bond Model
• Conduction electron (or hole): electron breaks loose and
a conduction electron (or hole, carry positive charge) is created

T = 0K T > 0K

12
 Electrical Conduction - T = 0K
Energy Band Model C.B.

• Valence band (V.B.):

(V B ): highest filled band
• Conduction band (C.B.): lowest empty band
V.B.
• Eg: bandgap N atoms
Si: 1s22s22p63s23p2

T = 0K T > 0K T > 0K
13
 Holes, Drift Current
• Holes: like positive charges occupy empty states

-
• Drift current: apply E, F = qE +
(A/ 2)
Jdrf = -qnvdn + qpvdp (A/cm
n: electron density (cm-3)
p: hole density (cm-33) Jn
vdn, vdp: drift velocity (cm/s) vdn
14
 Effective Mass
• Electron (or hole) in lattice: not free electron (or hole)
- Fint due to V(r) Ftotal = (Fint + Fext) = ma
F = -dV(x)/dx Fext = m*a
- Fext = qE m* : effective mass
* For free electron: => m* = ?

15
 Effective Mass
* For electron (or hole) in the bottom (or top)
of conduction (or valence) band:
parabolic approximation

, T > 0K

m* depends on C1 ,
C1 depends on V(r)
off atoms
t (Si,
(Si Ge,
G …))

Fext = -eE = mn*a

(for electrons)
= eE = mp*a
(for holes)
16
Energy Band - Semiconductors
C.B.

V.B.
T = 0K
T > 0K
• Semiconductor at T > 0 K:
- some electrons
l in
i C.B.
C B andd
some holes in V.B.
(current flow when E applied)
- Eg ~ 1 eV (1.1 eV for Si)
* S
Semiconductor
i d t att T = 0 K:
K
- C.B. totally full and V.B.
totally empty
(no current even E applied)
17
Energy
gy Band - Insulators
• Insulator:
- totally
ll filled
fill d bands
b d andd
totally empty bands
(conductivity very small)
- Eg is large: > 3.5 eV
(5 5 eV for C,
(5.5 C 9 eV for SiO2)

* Fermi-Dirac probability function

18
 Energy
gy Band - Metals
• Metal:
- partially
i ll filled
fill d band
b d
- overlapping allowed bands

19
Energy
gy Band in 3D Crystal
y
• e- traveling in different direction see different
V(r) => different E vs. k
in different direction
* Direct bandgap: GaAs
* Indirect bandgap: Si, Ge

same k
different k

20
 Density of States
• Energy band: a collection of energy states (n, l, m, s)
• Density of states: the number of states in a small range of energy E

* Electrons move relatively freely in C.B. but confined to the crystal

=> consider
id an free
f electron
l in
i 3D infinite
i fi i potential
i l well
ll
for

elsewhere
21
 Density of States (Free Electron)
* 1D infinite potential well:
k = (na, n = 1, 2, ..

* Extend to 3D infinite potential well: nx , ny , nz : positive integers > 0

(nx , ny , nz)
(kx , ky , kz)
* 1D: distance between 2 quantum states
i k space (kx)
in

* 3D: volume of single quantum state Vk

in k space (kx , ky , kz)
Vk = (/a)3
22
 Density of States (Free Electron)
* In k space, number of quantum states between
k and k + dk of volume a3: (n, l, m, s)
(n, l, m)
(kx , ky , kz)
(2: two spin states allowed for each quantum state)

* In E space, number of quantum states between

E and E + dE of volume a3:

* Density of state per unit energy per unit volume:

23
 Densityy of States (Semiconductors)
* Electrons and holes are confined within the semiconductor crystal

Free electron

* Density of allowed energy states in C.B.

CB

(mn*: density of state effective mass of electron)

24
 Densityy of States (Semiconductors)
* Density of allowed energy states in V.B.

0.0259 eV
(mp*: density of state effective mass of hole)
Si :
1.1 eV
* Example: Find the number of quantum states
in Si between Ec and Ec + kT at T = 300 K

1022 cm-3
Si density: 5510
ni = 1.51010 cm-3
 Nd = 1014~1018 cm-3
25
 Statistical Mechanics
• f(E):
f(E) probability
b bili off a quantum state at energy E occupied i d by
b a particle
i l
(statistical behavior of large number of particles)
- Maxwell-Boltzmann
M ll B lt probability
b bilit function
f ti fM(E)
fM(E) = A–1 e–E/kT
- Bose-Einstein
Bose Einstein probability function
fB(E) = 1 / (Ae E/kT – 1) fF(E)
- Fermi
Fermi-Dirac
Dirac probability function Fermi level
fF(E) = 1 / [e (E-EF)/kT + 1], EF: Fermi energy
particle number of particle allowed example
in each quantum state
fM distinguishable no limit low pressure gas molecules
fB indistinguishable no limit photons
fF indistinguishable one electrons in a crystal
(
(uncertainty
i (Pauli
(P li exclusion
l i principle)
i i l )
principle) (n, l, m, s)
26
 Fermi-Dirac Probability
y Function
* g(E): number of quantum states per unit volume per unit energy
* fF(E): probability of quantum state at energy E being occupied
* N(E): number of particles per unit volume per unit energy
=> N(E)
( ) = g(
g(E)f
) F((E))
find electron concentration in C.B.
hole concentration in V.B.

27
 Fermi-Dirac Probability Function
* T = 0 K:
EF
EF

* T > 0 K:
EF
EF

fF(E = EF) = 1/2

28
 Fermi-Dirac Probability
y Function
* Example: at T = 300K find the probability an energy lever 3kT
above EF is occupied
p byy an electron

300K

3kT

29
Boltzmann Approximation
Si : 1.1 eV EF

N(E) = g(E)fF(E)

top of conduction band

n g c ( E ) f F ( E )dE
Ec
Ev
p g v ( E )[1  f F ( E )]dE
bottom of valence band

• For (E - EF) >> kT: e.g. 3kT

fM(E) = A–1 e–E/kT = 4.74%

< 5%
error
= 4.98%

Boltzmann approximation
30