Chapter 2 Semiconductor Electronic Structure

Reading after class

 Neaman, 1. The Crystal Structure of Solids (pp1-20); 3. Introduction to the
Quantum Theory of Solids (pp. 58-91)
 Jasprit Singh, 2. Properties of semiconductors: electronic states: 2.1-2.8
(pp53-81)
 Kasap, 3.1 Review of Semiconductor Concepts and Energy Bands (pp.179-
184); 3.4 Direct and Indirect Bandgap Semiconductors: E–k Diagrams
(pp.194-197)
 Matter
Positive Ion + Electrons (outer shell)
↓
Nucleus + Electrons
↓
Collection of atoms →
Electronic structure of an isolated atom: Energy levels

Electron
orbitals
←Vacuum level

2
−  2 + U = E
2m

Energy Levels:
Coupled atoms: Splitting of energy levels

Electron Electron
orbitals orbitals
←Vacuum level
Electronic structure of coupled atoms: band formation

Conduction Band

CB

VB

Valence Band

bringing together isolated silicon atoms

 1D crystal
Free space: free electron model E = (ћk)²/2m
Solid: why metal, insulators, or semiconductor?
1D crystal

V(x)

V0

E
ΔE
Kronig-Penny Model

1234567 …
Number of wells
 1D infinite potential well
 2
2
Eigen equation − = E
2m x 2 n=3

 n z 
Eigen function  = An sin  
 L  n=2

 n 
2 2

Eigen energy En =  
n=1
x
2m  L  0 L

What about a finite potential well?

→ Boundary condition/Continuity condition
 1 =  2  1 =  2
 
 1  2  1  1 1  2
 x = x  m x = m x
 1 2

if the mass becomes different

p = –iћ = mv
 Reflection and transmission at a potential step

2
 2 1 1 2  2 2
2
− + V ( x) 1 = E 1 − + V ( x) 2 = E 2
2m x 2
I
E
T 2m x 2

 1 = Ae + Be
ik1 x − ik1 x
V  2 = Ceik2 x + De−ik2 x , D = 0
R
k12 =
2mE x 2m ( E − V )
2 0 k22 = 2
Region I Region II

Boundary condition at x = 0:
A + B = C B k1 − k2
= and
C
=
2k1
 A k1 + k2 A k1 + k2
k1 ( A − B) = k2C
( k1 m ) B ( k1 − k2 )
2 2

Reflection coefficient R= =
( k1 m ) A ( k1 + k2 )
2 2

( k2 m ) C
2
4k1k2
Transmission coefficient T= =
( k1 m ) A ( k1 + k2 )
2 2

Note that T + R = 1
 Bloch’s Theorem
The Schrodinger’s equation for electron motion V(x)
x

2 2
H ( x) = E ( x) H = − + V ( x)
2m x 2
a
where V(x+a) = V(x)
Solution: ψk(x) = eikx uk(x) Bloch function

envelope function unit cell function uk(x+a) = uk (x)

Free space: Ek = (ћk)²/2m, ψk(x) = eikx
In crystal: Hψk (x) = Ek ψk (x) → E~k relation  Electronic Bandstructure

 2
2  2
 2 ikx
 − 2m x 2 +V ( x)  k ( x) = Ek k ( x) → − 2m x 2 e uk ( x)  =  Ek − V ( x)  e uk ( x)
ikx

 
ikx  2
2
k 2 ikx 2 2
e uk ( x ) − 2ike uk ( x ) − e ikx
u ( x ) =  E − V ( x )  e ikx
uk ( x )
x 2m x 2 k k
2m 2m
 2
2
   2 2
k 
−  u ( x )+2ik u ( x )  =  E − − V ( x )  uk ( x)
2m  x 2 k
x
k k
  2m 
 E-k diagram in the first Brillouin zone
ik x 2
 k  ( x ) = e uk  ( x ) k − m=k reduced wavevector
a
2  
= eikx e
i
a
mx
uk  ( x ) − k the first Brillouin zone
a a
2
i mx
 k ( x) = eikxuk ( x) uk ( x)=e a
uk ' ( x )
2 2
i m( x+a ) i mx
i 2 m
uk ( x +a) = e a
uk  ( x ) = e e a
uk  ( x ) = uk ( x )

φ(x)

a
 Krönig-Penny Model
Without the knowledge of V(x), can we get most of the features?
2
 2    2 2
k   k ( x)=eikxuk ( x)
−  u ( x )+2ik u ( x )  =  E − − V ( x )  uk ( x)
2m  x 2 k
x
k k
  2m 

2   2   2   2 = 2mE
u ( x)+2ik u ( x) −  k −  2   u ( x) = 0
x 2
x       2 = 2m( E − V0 ) = 2 − 2mV

uI = ( Ae x + Be − x ) e −ikx
Trial solution

uII = ( Ce  x + De −  x ) e −ikx
Continuity condition
uI (0) = uII (0) uI (a − b) = uII (−b)
duI duII duI duII
= =
dx x =0 dx x =0 dx x = a −b dx x =− b

E-k relation:
sin  a
cos ka = P + cos  a P = maV0b 2

a
 (a) P → ∞, or bV0 is large

2
n
2

sin  a = 0;  a =  n ; En =   → Infinite potential well

2m  a 
(b) P → 0, or bV0 is small
2
cos ka = cos  a; ka =  a; E = k2 → Free electron model
2m
sin  a
3 P + cos  a
(c) P=
R.H.S. a
2

L.H.S. between
+1 and –1

a

E-k relation:
sin  a
(L.H.S.) cos ka = P + cos  a (R.H.S.) P = maV0b 2
 = 2mE
a
Origin of energy bands
Every band in the Krönig-Penney Model has a finite well discrete level as
its “parent”! For N wells, each band contains N states

Periodic nuclear
3
potential P
sin  a
+ cos  a
(c) P = a
2 R.H.S.
+ + + +
L.H.S. between
+1 and –1
Electronic wavefunctions overlap and their energies form bands
a

Shallower
E-k relation:potentials give bigger overlaps.
sin  a bonding-antibonding splitting of2each multiply
(L.H.S.) cos ka = P
Greater overlap creates greater+ cos  a (R.H.S.) P = maV0b  = 2mE
 a
degenerate level, creating wider bandwidths
Origin of energy gaps
– At the boundary of an allowed band
coska =1; k = nπ/a, n = 0, 1,  2, … d
– Bragg reflection of waves from a linear chain
of atoms: 2a = nλ θ
– Free electron model is invalid due to the strong
reflection from the atoms 2dsinθ = nλ with θ = π/2

– The incident and reflected waves form standing waves as follows

x  x Charge piles up at ion positions,
 +  ei x a + e−i x a = 2 cos  +  cos 2
2

a a lowering the potential energy

x  x Charge piles up between ions,
 −  ei x a − e−i x a = 2i sin  −  sin 2
2

a a raising the potential energy

• The reduced zone scheme (red) gives the same information as the extended zone
scheme (as is true in general)
• Discontinuities at the BZ edges, at k = (nπ/a) Because of the periodicity of E(k).

The first BZ E = (ħ2k2)/(2m0)

 Formation of energy bands from atomic levels bands
• The outermost electronic levels (in the valence Electrons are in
free space
shell) are all either s-type or p-type
IV Semiconductors
C ls22s22p2
Si 1s22s22p63s23p2
Ge ls22s22p63s23p63d104s24p2
III-V Semiconductors
Ga ls22s22p63s23p63d104s24p1
As ls22s22p63s23p63d104s24p3
etc.

• The outermost electronic levels of the atoms

make energy bandstructure of a semiconductor
• The central cell character of the Bloch functions
is described by s- and p-type functions
• Electronic states in allowed bands are Bloch
states, i.e., plane wave states (~eik•r)
 Metal Semiconductor

Work function eϕ

Electron affinity eχ

1
f (E) =
1 + e ( E − EF ) k BT
 Bravais lattice (review)
• An infinite array of discrete points with an arrangement and orientation that
appears exactly the same, from whichever of the points the array is viewed.
• A set of points in space which forms a periodic structure.
Triclinic Monoclinic Orthorhombic Tetragonal Rhombohedral Hexagonal Cubic

Primitive

Base-Centered

Body-Centered

Face-Centered
 Crystal Structure: Bravais lattice with a basis (review)
• Basis: A crystal is produced by attaching a basis to every lattice point. The basis
is the physical unit consisting of one or more atoms.

A useful crystal structure viewer: http://www.dawgsdk.org/crystal/en/library/

• Tetrahedron covalent bond and its schematic 2D representation
Concepts of bands, electron and hole

Hole Conduction
electron

• (Conduction) electron, (valence) hole

• Energy band formation
• Conduction band/Electron band
• Valence band/Hole band
• Forbidden gap
• Bandgap energy
• Classification of
solids by conductivity
• Conductor/Metal
• Semiconductor
• Insulator
• Classification of
Semiconductors
• Elemental
• Compound
• Alloy
 Band diagram for complete k-vectors
Direct gap

• Important high symmetry points, a = 5.65Å

2/a = 0.565nm
– Γ point: kx = ky = kz = 0
– X point: kx = 2π/a ; ky = kz = 0
– L point: kx = ky = kz = π/a

The values and notations of certain important k-points are shown in the figure.
Most semiconductors have bandedges of allowed bands at one of these points.
 Indirect gap

2/a
a = 5.43Å
= 0.543nm
8/a
 Miller indices (review)
(hkl): A planes denoted by integers taken from
reciprocal intercepts, e.g. (100),(010), etc.
(hkl ): A plane that intercepts the negative side of the
axis (100) .
{hkl}: Planes of equivalent symmetry, such as {100} for
(100),(010), etc. in cubic symmetry. U
[hkl]: A crystal direction, e.g. [100] for +x-axis.
K
<hkl>: Full set of equivalent directions, e.g. <100> for
[100], [010] etc.
[hklm]: A plane in a hexagonal lattice (such as wurtzite)
with intercepts on the a1, a2, a3, and z-axis.
• Show that separation between the planes (hkl) for a cubic lattice with sides a is
a
d ( hkl ) =
(h 2
+k +l
2
)
2 12

• Example: use of Miller indices

In the old times (up to the 150 mm wafer diameter era), wafers had flats,
and the flats told you:
- The orientation of the wafer: {100} or {111};
- The doping type of the wafer: n- or p-type;
- The primary flat is usually at the face of {110}.
 Concept of effective mass
• In free space • In Crystal
p= k Electron momentum p= k Crystal momentum
2
E=
2
k Electron energy E ~ k relation Bandstructure
2m
2  k (r )=eik r uk (r )
k= Propagation vector

 de Broglie wavelength F =Fint +Fext
(– e) E
E
dp
E = Fext
dt

0 k

What is the mass of electron in crystal?

 1 dE dk dk
• The work δE is done by the force F as F  vg  t =  E → F = =
vg dk dt dt
d E 1 dE dE
The group velocity vg = ;  = → vg = k
dk dk dk
dvg 1 d 2 E 1 d 2 E dk 1 d 2 E 1 1 d 2E
= = 2
= 2 2
F → *
= 2 m* – effective mass
dt dkdt dk dt dk m dk 2
E

Eg

• The E-k relation is no longer free-electron like due to the periodic potential of
the crystal
• The mass of electrons in a solid is different from that of the rest mass, denoted
as effective mass
 Concept of hole
External electrical field k vector of electron ↑
At the edge of the band, what will happen on electron?
– Jump to the next band?
– Stay within the band
Nothing has happened – Pauli’s Exclusion Principle
>0
t<
E εx Field
The total current carried by a filled band
N
kn
I =  ( −e ) * = 0
n =1 m
A completely filled band has a pair of
electrons at each energy, with –kx and +kx.
Thus, no net flow of charges and null –K
kx
total current! K K
−
2 2
 External electric field (εx along x) All electrons move along +kx
Initially unoccupied state k = 0 The next state k+ → unoccupied
() All electrons occupying states move in the band
(☺) One virtual particle emptying a state moves in the band
>0
t< E εx

–K
kx
K K
−
2 2
Total current carried by the band with electron missing in the jth state:
N
kn kj N kn kj
I =  ( −e ) * = ( e ) * +  ( − e ) * = e *
n =1, n  j m m n =1 m m
i.e. I band = I occupied
(electron )
= I unoccupied
(hole)

Only incompletely occupied band can carry current!

Hole  empty state  vacant state  unoccupied state; a hole carries +e
 Semiconductor with full VB & empty CB: { Total wavevector Σk = 0 or
Crystal momentum p = Σћk = 0
1e missing in VB Δp = –ћke
Taking 1e away:
1h acquired in VB Δp = ћkh }→ – ke = kh in VB
2 2 2
ke2 kh
− = E = → mh = –me for VB; m is inversely proportional to d2E/dk2
2me 2mh
mhvh = ћkh = –ћke = –meve → vh = ve Equal velocity for h and the missing e in VB

Conduction band Valence Band Missing electron:

E E
dk e
= −e ( E + v e  B )
dt
ke kh kh dk h
= e ( E + vh  B )
k k dt

A hole acts in applied

electric and magnetic fields
Valence Band
as if it has a positive
Conduction Band
charge +e
Electron’s band diagram Holes’ band diagram
 Photon absorption: generate 1h in VB and 1e in CB simultaneously
Electron picture: VB → CB
e
Current of an e-h pair in applied
CB → VB
h electric field: j = je + jh
Hole picture:
Q je
Conventional band diagram: ε ve
e
vh
Consider e in CB & h in VB only h
P jh
ke = kh ћω = Ee + Eh + Eg
Conduction band Valence Band Electron band
E E E
Q

ћω
ke(VB) ke(CB) kh(CB) kh(VB) ke, kh
k k k
P

Valence Band Conduction Band Hole band

Electron’s band diagram Holes’ band diagram Conventional band diagram
 Simplified band diagram
• Near-bandedge electrons can be described by a simple effective mass pictures
2
k2 CB: Conduction Band
Bottom of the conduction band Ee = EC + *
2me VB: Valence Band
m*e : effective mass of electron
( k − km ) HH: Heavy Hole Band
2 2

Ee = EC + LH: Light Hole Band

2me*
2 2
SO: Split-Off Band
Top of the valence band k Δ = Split-Off Energy
Eh = EV −
m*h : effective masse of hole 2mh*

E CB E
CB
CB
EC
Eg Direct bandgap Indirect bandgap
0E 0
V
x k km k
VB Δ Δ
HH
HH
LH LH
SO SO
Bandedge diagram E-k diagram
Band diagrams of some important semiconductors
Si Ge InP InAs GaAs AlAs

Si Ge InP InAs GaAs AlAs

Eg 1.124 0.664 1.344 0.354 1.424 2.153
 Some important properties of Si and GaAs

Semi-Empirical
Varshni Equation
 Semiconductor alloys
Other than elemental and compound semiconductors, semiconductor alloys also
exist and are extremely useful. For example,
Binary alloy
Si1-xGex: Alloy of x molar fraction of Ge atoms and (1-x) molar
fraction of Si atoms arranged randomly
Ternary alloy
AlxGa1-xAs: Alloy of two compound semiconductors AlAs and
GaAs with x fraction of AlAs and (1-x) fraction of GaAs
InxGa1-xAs: x InAs and (1-x) GaAs
Quaternary alloy
In1-xGaxAsyP1-y: (1-x)y InAs, (1-x)(1-y) InP, x(1-y) GaP, and xy GaAs

Question:
For an alloy made from two semiconductors (whether elemental or
compound), how do its properties differ from those of its constituents?
• Vegard’s Law (linear interpolation rule)
The lattice constant of an alloy of an alloy is a weighted sum of the
lattice constants of each of its constituents, and the weight assigned to
each constituent is equal to its molar fraction in the alloy.
Example:
Binary alloy:
aSixGe1−x = x aSi + (1- x) aGe
Ternary alloy:
aAlxGa1−x As = x aAlAs + (1- x) aGaAs
Quaternary alloy:
aIn1−xGax Asy P1− y = (1- x) y aInAs + (1- x)(1- y) aInP + x(1- y) aGaP + xy aGaAs

What about other material parameters, e.g. dielectric constants, effective

masses, band gaps, etc.? If you do not know any better ， the linear
interpolation rule can be a good first approximation.
However, it does not always work very well for quantities other than the
lattice constant.
• Bandgap energy
The band gap of AlxGa1-xAs at the  point is given more accurately by,

Eg ( )[Al xGa1− x As] = xEg ( )[AlAs] + (1 − x) Eg ( )[GaAs] − cx(1 − x)

where c=0.438eV (at 300K) is called the bowing parameter

Be careful about the optical property change: the AlxGa1-xAs alloy is direct gap
for small x but indirect gap for large x.
• Effective mass
The linear interpolation rule works better if the inverse effective masses are
averaged.

Example:
The electron effective mass me* for GaxIn1-xAs
1 1 1− x
*
= * + *
me [Ga x In1− x As] me [GaAs] me [ InAs]

where all effective masses are at the -point in the conduction band.

• For the dielectric constants, and refractive indices, the linear rule can be
hopelessly wrong, especially if the wavelength at which these are desired is
close to the band gap of any one of the constituents in the alloy.
 Density of states (DOS)
ρ(k)dk: number of states ρ(E)dE: number of states
ρ(k) ρ(E)
between k ~ k+dk per between E ~ E+dE per
k-space
unit volume unit volume
E kz

CB
k

VB k 0
kx ky

“Particle in a box”
Vout=∞ Zero boundary condition
z
k  2 L = N  2
k x = nx Lx
Vin= 0 k y = n y Ly
0 y 0 L
k z = nz Lz
x Standing wave solution  k ( x)= sin kx
Volume between No. of states between Volume occupied by
k ~ k+dk k ~ k+dk one state in k-space
4 k 2 dk (1 8 )
2 ( Lx ) ( Ly ) ( Lz )
Lx ) ( Ly ) ( Lz )
4πk2dk(1/8)
(
kz dk
E kz  Ly
 Lz
CB k k  Lx
ky − a + a
VBkx k
kx ky

Lx =Ly =Lz =1mm

4 k dk (1 8 )
2
k x min =  1mm = 103  m −1
 (k )dk =  2 Lx Ly Lz
( Lx ) ( Ly ) ( Lz ) a = 5Å
k x max =  5Å = 2 109  m −1
k2
 (k )=  (k )dk = ( E )dE
 2

2 2 32 0 a L
k 2m
E = EC +  (E) = e
E − EC kmax = 2 2a
2me  2 3
• For electron wave expressed in propagation wave form  (r ) = Aeik r
i( kx L + k y y + kz z ) i( k y y +kz z )
Cyclic boundary  ( L, y , z ) =  (0, y , z ) Ae = Ae e ik x L
=1
condition (particle ( x, L, z ) = ( x, 0, z ) 2 2 2
k =  n k =  n k =  nz
conservation)  ( x, y, L) =  ( x, y, 0) x
L
x y
L
y z
L
kz dk
…

z kz

… k
0 y
ky
x kx ky
kx 2π/L
Volume between No. of states between Volume occupied by
k ~ k+dk k ~ k+dk one state in k-space
4 k 2 dk
2 ( 2 Lx ) ( 2 Ly ) ( 2 Lz )
( 2 Lx ) ( 2 Ly ) ( 2 Lz )
4πk2dk

4 k 2 dk k2
 (k )dk =  2 Lx Ly Lz  (k )=
( 2 Lx ) ( 2 Ly ) ( 2 Lz ) 2
  (2me )3 2 E
 E − EC for E  E C E ρe(E)
e ( E ) =  2 2 3
for E  E C E E
0
 C
Eg
 (2mh ) 32 EV
 EV − E for E  E V
 h ( E ) =  2 2 3
for E  E V ρh(E)
0 k

Density of states
2 2 2
• DOS for a more complicated example, E (k ) = E + k 2
+ k 2
+ k 2
c x y z
e.g. non-isotropic but parabolic 2m x 2m y 2mz
*
(2mDOS )3 2 1
e ( E ) = E − E , where m *
= ( m m m ) 3
2 2 3
C DOS x y z

• Considering normalization, let Lx= Ly = Lz = 1

4 k 2 dk dk x dk y dk z dk x dk y dk z
 ( E )dE = 2 
( 2 )
3
= 2   ( E − E (k ))
( 2 )
3  f ( E )  ( E )dE  2  
2  2  2
f (E)

• 2D semiconductor
2 kdk dk x dk y dk x dk y
 2 D ( E )dE = 2 
( 2 )
2
= 2   ( E − E ( k ))
( 2 )
2  f ( E )  2 D ( E )dE  2   
2 2
f (E)
 2D Density of states
kz
E E

0
a = 5Å
L 3D
bulk

= 20Å EC
kmax = a
2
 2
 
k z min = Ez min =   k
Lz 2me  Lz  dk
k
2 ky
 q 
2 2
k 2
k 2
k 2 2
k
2 2 2 k+dk
Eq =   +Eq = E − EC = + x
+ y
kx z
k
2me  Lz  2me 2me 2me 2me
Area between No. of states between Area occupied by one
k|| ~ k|| +dk|| k|| ~ k|| +dk|| state in k|| -space
2 k dk (1 4 )
2 k dk (1 4 ) 2 ( Lx ) ( Ly )
( Lx ) ( Ly )
2 k dk (1 4 )
2 2 2
k k k
 2D (k )dk =  2 Lx Ly = E = dE = dk
( Lx ) ( Ly )  2me me
dk k me me
 2D (k )dk = 2D (k )dk =  2D ( E )dE  ( E ) =  ( k ) = =
dE  2 k  2
2D 2D
 2D Density of states
kz
E E
3D
QW
3D
bulk

9Eq=1

4Eq=1 dk
k
Eq=1 ky
k+dk
EC k|| EC me 2me 3me
ρ(E) kx k
 2 Lz  2 Lz  2 Lz
2
 q 
2
k2 2
k2 2
E (k ) = EC + +Eq E = Eq =   k 2 = k 2 + kq2
2me 2me 2me  Lz 
k 2 = k x2 + k y2
k qme  2D me
 2D (k ) =  2D ( E ) = → 3D = kq =  Lz
  2
Lz  2 Lz
12
2me3 2 2me3 2 2me3 2 2
  qme
 bulk
( E =EC +Eq ) = E − EC = Eq =   = 2
3D
 2 3
 2 3
2 3
2me  Lz   Lz
 Summary
• Electronic structure of isolated atom
• Bloch theorem
• Kronig-Penny model
• Origin of bands / bandgaps
• Effective mass
• Holes
• E-k diagram
• Band structures of semiconductors
• Vegard’s Law
• Density of states (DOS)