Lecture 3

Semiconductor alloys
Heterostructures
Bandgap engineering
Quantum structures

ELEC-E3140 Semiconductor physics

 Outline
Semiconductor alloys
Heterostructures
Bandgap engineering
Quantum structures

ELEC-E3140 Semiconductor physics

 Alloying

• Semiconductor materials
can be mixed to form
semiconductor alloys.
• Alloying is a way to modify
the bandstructure
• Solid solutions of the
elementary compounds
can form binary alloys
(e.g., Si+Ge -> SixGe1-x)
• Solid solutions of the
binary compounds can
form ternary or quaternary
alloys

SixGe1-x

ELEC-E3140 Semiconductor physics

III-V Nitrides

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 Random ternary alloy

Example: a ternary compound

AxB1-xC
• x atoms of the element A
• 1-x atoms of element B
• A and B atoms randomly
mixed in group III sublattice
• all group V lattice sites
occupied by element C

InxGa1-xAs

Random alloy

ELEC-E3140 Semiconductor physics

 Random alloy

Example: a ternary compound

ACyD1-y
• y atoms of element C
• 1-y atoms of element D
• C and D atoms randomly
mixed in group V sublattice
• all group III lattice sites
occupied by element A

GaAsyP1-y

Random alloy

ELEC-E3140 Semiconductor physics

 Ordered alloy

Example: a ternary compound

Ga0.5In0.5P
• can be random alloy
• but can also form periodic
structure by alternating
layers of GaP and InP
• fabrication conditions
dictate which one is formed

Ga0.5In0.5P

Ordered alloy

ELEC-E3140 Semiconductor physics

Quaternary InGaAsP alloy
InxGa(1-x)AsyP(1-y)
Eg and a can be set independently by changing x and y

In0.53Ga0.47As

ELEC-E3140 Semiconductor physics

 Lattice constant of alloys
The lattice constant of ternary and quaternary alloys can be
approximated by the Vegard’s law.

Ternary alloy (e.g.: InxGa1-xAs)

a Ax B(1 x)C  xa AC  (1  x)aBC

Quaternary alloy (e.g.: InxGa1-xAsyP1-y)

a Ax B(1 x)C y D(1 y)  xya AC  x(1  y)a AD  (1  x) ya BC  (1  x)(1  y)aBD

The Vegard law applies as well to the dielectric constant

ELEC-E3140 Semiconductor physics

 Miscibility gap

• In some alloys thermodynamics

does not predict the existence of a
completely random alloy.
AxB1-xCyD1-y
AD
• Such alloys form immiscible
BD solutions. A miscibility gap exists in
T1
the phase diagram.
y
• Immiscibility increases with
T2 increasing difference in the covalent
radii of atoms trying to occupy the
same lattice sites.
AC BC •The gap usually becomes smaller for
x
higher growth temperatures.

ELEC-E3140 Semiconductor physics

 Bandgap energy for ternary alloys
Ax B(1 x )C
Eg  (1  x) EgBC  xE gAC  bABC x(1  x)

Bowing factor

Bowing in the
bandgap arises from
increasing disorder
due to alloying !

ELEC-E3140 Semiconductor physics

 Bandgap energy for quaternary alloys
 AC D 
x(1  x) yE g x 1 x x   (1  y) E g x 1 x ( x)   y (1  y ) xE g y 1 y  y   (1  x) E g y 1 y ( x) 
A B C A B D BC D
   
E g x (1 x) y (1 y ) 
A B C D
x(1  x)  y (1  y )

ELEC-E3140 Semiconductor physics

 Direct and indirect bandgap

AlGaAs

AlxGa1-xAs has a direct bandgap for x < 0.45

ELEC-E3140 Semiconductor physics

 AlGaAs band gaps
Example. The band gaps of Al0.3Ga0.7As and Al0.6Ga0.4As.

Direct band gap

Indirect band gap

ELEC-E3140 Semiconductor physics

Bandgap energy of alloys

ELEC-E3140 Semiconductor physics

 Outline
Semiconductor alloys
Heterostructures
Bandgap engineering
Quantum structures

ELEC-E3140 Semiconductor physics

 Heterostuctures
• In a heterostructure two (or more) different semiconductors are placed
on top of each other
• But how do the energy bands of different materials align?
• Two material parameters might
have something to do with this:
• Electron affinity: the change
in energy when an electron
is added to a neutral atom
• Ionisation energy: electron is
removed from a neutral
atom

• Neither one does not give the

answer accurately, it must be
determined experimentally.

ELEC-E3140 Semiconductor physics

 Band alignment

If we know the band discontinuity between A and B ECAB

and between B and C EC
BC
Electron affinity rule

=> Discontinuity between A and C:

ECAC  ECAB  ECBC

Most common case GaAs/Al(Ga)As:

EC 60 65
 ...
EV 40 35

ELEC-E3140 Semiconductor physics

 Types of alignment
The heterostructure can be
• Type I structure if the band gap of the smaller band gap material aligns
“inside” the larger band gap.
• Type III structure if the band gap of the smaller band gap material aligns
completely “outside” the larger band gap.
• Type II structure if neither one is the case
The heterostructure is called double heterojunction (DHJ) when (typically)
the smaller band gap material is sandwiched between larger band gap
materials, e.g. AlGaAs/GaAs/AlGaAs.

ELEC-E3140 Semiconductor physics

 Lattice matching
A crystalline layer can be
grown by epitaxy on a
crystalline substrate with the
same lattice constant.
Available substrates, e.g.:
• Si, Ge
• GaAs, InP, GaP
• InAs, InSb, GaSb
• SiC, sapphire (for GaN)

Homoepitaxy: GaAs on
GaAs

Heteroepitaxy: AlAs on
GaAs (aAlAs = 5.6605Å,
aGaAs= 5.653Å)
ELEC-E3140 Semiconductor physics
InGaAs and InGaAsP alloys
InxGa(1-x)AsyP(1-y)
Eg and a can be set independently by changing x and y

InxGa(1-x)As
Lattice-matches InP for x = 0.53

In0.53Ga0.47As

ELEC-E3140 Semiconductor physics

 Lattice mismatch and pseudomorphic materials

• The lattice mismatch is defined as:

a a  a0
 f
a a
• Lattice mismatch generates
strain in the grown layer
(the substrate is typically much thicker):
a > a0: compressive strain
a < a0 : tensile strain

• A coherently strained crystal is called pseudomorphic, since it takes

on the morphology or form, in this case the lattice constant, of the
substrate.

ELEC-E3140 Semiconductor physics

 Compressive and tensile stress
In pseudomorphic crystal the lattice constant parallel to surface is the
same in all the layers!

Compressive (a > a0) :

• the perpendicular lattice

constant will grow

Tensile (a < a0):

• the perpendicular lattice

constant will shrink

ELEC-E3140 Semiconductor physics

 Strain in a (001)-oriented epitaxial film

The substrate is typically much thicker than the epitaxial layer

 only the epitaxial layer is strained!

ad1  a0 d0
a parallel   a0  1  f  a (if d0  d1 )
d1  d0

Strained growth places stress upon the epitaxial layer in the x and
y directions. The stress components in the x and y directions are
equal and force lattice constants in both of the parallel directions
to be equal. For this biaxial strain one can write:

f xx  f yy  f

ELEC-E3140 Semiconductor physics

 Strain in a (001)-oriented epitaxial film
Strain in the z-direction (growth direction) can be determined by
writing Hooke’s law in terms of elastic stiffness constants for a
pseudomorphic crystal:
 S xx   c11 c12 c12  f xx 
     c12 and c11 are elastic constants
 S yy    c12 c11 c12  f yy  of the epitaxial layer
 S   c12 c12 c11 
 zz 
f 
 zz 
Because the z-component of the stress Szz is zero, one
gets for the strain in the z-direction:
2c12
S zz  c12 f xx  c12 f yy  c11 f zz  0  f zz   f
c11
 2c12 
a perpendicular  1  f zz  a  1  f  a  1   ST f  a
 c11 

ELEC-E3140 Semiconductor physics

 ELEC-E3140
Semiconductor physics

Lecture quiz 2

Time: 5 minutes
 Critical thickness

• Below critical thickness hc the minimum energy state of the

bilayer system is achieved by strain

• Above the critical thickness: relaxation by dislocations

• The critical thickness is dependent upon the amount of lattice

mismatch and material properties as well as the type of
dislocations

a a2
• Matthews & Blakeslee model: hc  
2 a / a 2 a

ELEC-E3140 Semiconductor physics

 Critical thickness

Remember:
Pseudomorphic layers
must have a thickness
less than hc !

For a 1% lattice mismatch, the critical thickness is a few

hundred ångströms.

ELEC-E3140 Semiconductor physics

 Critical thickness

For the case of misfit dislocations forming

at the interface, it holds:

Poisson ratio:
 vPR    hc 2  
a0 1   ln    1
 4    a0   vPR  c12 /  c11  c12 
hc 
2 2 f 1  vPR 

• The use of strained semiconductors removes the restrictions of lattice-

matching and allows band-engineering !!

ELEC-E3140 Semiconductor physics

 Semiconductors for electronics

Electronics:
• by far most common is silicon
High-speed electronics:
• most compatable to Si is SiGe
• III-Vs: GaAs, InGaAs

High-power electronics:
• SiC (600 V)
• SiC or GaN (1200 V)

ELEC-E3140 Semiconductor physics

 Semiconductors for optoelectronics

UV: GaN, AlGaN

Blue, green: GaN, InGaN

Yellow, red: GaAsP, AlGaInP

Near infrared region (0.8-1.0 mm): GaAs, AlGaAs, InGaAs

Communication wavelengths (1.3-1.7 mm): InP, InGaAsP

Far infrared (> 2 mm): GaSb, InSb, InAs

ELEC-E3140 Semiconductor physics

 Outline
Semiconductor alloys
Heterostructures
Bandgap engineering
Quantum structures

ELEC-E3140 Semiconductor physics

 Bandgap engineering

Bandgaps and band structure of semiconductors can be

engineered by two main means
• Alloying
• Strain
In addition, heterostructures can used. In heterostructures a
new way to modify the energy bands emerges
• Quantum structures

ELEC-E3140 Semiconductor physics

 Bandstructure changes due to biaxial strain

• Changes in bandgaps
• Changes in conduction band effective masses
• Changes in valence bandstructure (the heavy-hole and
light-hole states will be splitted, for tensile strain the light-hole is
expected to be above the heavy-hole state, while for
compressive strain the reverse is expected)

Electrical and optical

properties will be changed!

ELEC-E3140 Semiconductor physics

 Effect of biaxial strain on bands

• Heavy-hole and light-hole states will be splitted due to strain

For a (001)-oriented film: • Esh and Ehy are shear and

hydrostatic components of the
1
Eg HH  Ego  Esh  Ehy change in the band energies
2 from the unstrained position Ego
1 • a and b are material
Eg LH  Ego  Esh  Ehy deformation potentials
2
• c12 and c11 are elastic
Esh  2b  c11  2c12  / c11  f constants of the
Ehy  2a  c11  c12  / c11  f epitaxial layer

ELEC-E3140 Semiconductor physics

 Valence band
Separation of LH and HH bands.

Tensile Unstrained Compressive

cb

Eg smaller Eg larger
LH
vb HH HH
HH
LH

LH

ELEC-E3140 Semiconductor physics

 Outline
Semiconductor alloys
Heterostructures
Bandgap engineering
Quantum structures

ELEC-E3140 Semiconductor physics

 Quantum well
z
y
x
InP
InAs0.65P0.35 (5nm)
Lz

InP Ly Cross-sectional TEM image of

a GaInNAs QW grown on GaAs.

Lx
• Quantum well: a thin semiconductor layer (Lz<20nm) embedded
between two semiconductors with larger bandgap.
• Electrons and holes trapped in the well are free to move in the x-y
plane, but are strongly confined in the z-direction = 2D electron gas.

ELEC-E3140 Semiconductor physics

Quantum well

ELEC-E3140 Semiconductor physics

 Energy levels for electrons

e4 (ℓ=4)
EC
e3 (ℓ=3)
e2 (ℓ=2)
e1 (ℓ=1)
EC
Eg,1 Eg,2 Lz

In the infinite well approximation,

the energy levels are given by:
EV  2 2 2
Ee 
Lz
2me L2z
z  (k  k )
2 2 2

E  EC  Ee 
Electron x y

energy: 2me

ELEC-E3140 Semiconductor physics

 Energy levels for holes
E
EV hh1 (ℓ=1)
lh1 (ℓ=1)
EC hh2 (ℓ=2)
lh2 (ℓ=2)

Eg,1 Eg,2 Lz

In the infinite well approximation,

the energy levels are given by:
EV
 2 2 2  2 2 2
Lz Ehh   2
Elh   2
2 m L 2 mlh Lz
z
 (k x  k y )
2 2 2 hh z
Heavy hole E  EV  Ehh  
energy: 2mhh

ELEC-E3140 Semiconductor physics

Electron and hole energy subbands

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Valence bandstructure in a QW

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 Finite barriers in QWs

When barriers are considered as finite, we can derive equations to solve

 tanF
W I 2m* E

H 2 K  2

 cot F
W I 
2m* V0  E 
H 2 K   2

The energy values are smaller than with infinite barriers.

ELEC-E3140 Semiconductor physics

GaAs/AlGaAs QW

Three QW
states

Wavefunction
in the lowest
state

ELEC-E3140 Semiconductor physics

 Quantum well structures

Quantum well structure can be

• single quantum well (QW/SQW)
• multi quantum well (MQW)
• superlattice (SL) MQW/SL
QW

Wide barriers => multiquantum well ~ separate QWs

Narrow barriers => superlattice ~ energy subbands over the
structure

ELEC-E3140 Semiconductor physics

Superlattice

Second band

First band

ELEC-E3140 Semiconductor physics

ELEC-E3140 Semiconductor physics
 Quantum wires

z
y
x
InP
InAs0.65P0.35
Lz
Lx
InP Ly (110) cross-section TEM picture of
stacked InAs QWires in InAlAs
matrix lattice matched to InP.

• Quantum wire: 1D quantum system

• Electrons and holes trapped in the wires are free to move only
along the y-direction

ELEC-E3140 Semiconductor physics

 Quantum dots
Bulk semiconductor Quantum Well (QW) Quantum Dot

A B A
Energy
Energy Energy s-state

conduction band
Ec y
Band edge
valence band Eh
x
x x
Density of Density of Density of
states states states

Energy Energy
Energy
ELEC-E3140 Semiconductor physics