BULK CRYSTAL GROWTH and LIQUID PHASE EPITAXY

Lecture-3, 2B 1700, 2B1823 - Advanced Semiconductor Materials

Bulk crystal growth techniques

• Need for bulk crytals
• Horizontal/Vertical Bridgman technique
• Liquid Encapsulated Czochralski technique
• Dopant distribution
• Wafer specification

Liquid Phase Epitaxy

• Various epitaxial techniques
• Liquid phase epitaxy
• Growth procedure and reactors
• LPE phase diagrams

Sebastian Lourdudoss, KTH

NEED
• Device structure:
Several epitaxial layers often with different compositions and/or
doping on a substrate

Layer 3
Epitaxial
Layer 2
growth
Layer 1
Substrate
Bulk
growth

• Epitaxy (from Greek: epi = upon; taxis= ordered):

Growth of a crystal on a substrate with the same crystallographic structure as
the substrate
=> Monocrystalline substrate needed to grow epitaxial layers
• Homoepitaxy: e.g., InP/InP
Heteroepitaxy: e.g., InGaAs/InP

Sebastian Lourdudoss, KTH

Requirements:
1) Wafers with least defects and dislocations
(if present can propagate into the
epitaxial layers)
2) Wafers of ultimate purity
(electrically active impurity atoms < 10
parts per billion atomic)
3) Wafers with controlled electrically active
dopant atoms

Sebastian Lourdudoss, KTH

Practical Difficulties with certain Vap. Pr.
III-V semiconductors Compound M.Pt. at M.pt.
(oC) (atm)
1) In general, high melting points InSb 525 4x10-8
GaSb 712 1x10-6
=> Crucibles normally silica InAs 943 0.33
(silica becomes soft at 1100 - GaAs 1238 1.0
1200 oC) graphite or InP 1062 27.5
GaP 1465 32
pyrolytic boron nitride (PBN)
2) Vapour pressures high at m.pt. HgSe 799
HgTe 670 12.5
for InP, GaP and GaAs ( low for CdSe 1239 0.3
InSb, GaSb and InAs) CdTe 1092 0.65
ZnSe 1526 0.5
3) Decomposition near the ZnTe 1300 0.6
melting point
Ge 960
=> loss of one of the elements Si 1420
=> defects From “Compound Semiconductor Devices,
(Remedy = Evacuated and Structures and Processing, Ed. K.A.Jackson,
Willey-VCH, Weinheim, 1998.
closed systems)

Sebastian Lourdudoss, KTH

Phase diagram for the Ga-As
system

Sebastian Lourdudoss, KTH

BRIDGMAN TECHNIQUE

• Growth on the seed from a

melt ( Tseed < T melt)
• Hot wall
• Growth in evacuated and
sealed containers
=> purity higher
• Easy to control the
vapour pressure
• Low vapour pressure
system only

Sebastian Lourdudoss, KTH

 LIQUID ENCAPSULATED CZOCHRALSKI (LEC)
METHOD

• Cold wall system

• High pressure with inert gas / active gas
• Encapsulant (B2O3) hinders vapour escape from
the melt + wets the growing surface
• Normally higher dislocation density than in
Bridgman technique (because of thermal
non-uniformity)
• Contamination from the surrounding material
(e.g. carbon from graphite parts)

• Low pressure LEC ( Dissociation pressure < 2 atm)

• High pressure LEC (Dissociation pressure > 2 atm)
=> inert gas or active gas used

Sebastian Lourdudoss, KTH

Czochralski Growth Method

Sebastian Lourdudoss, KTH

Sebastian Lourdudoss, KTH
 Dopants

ke , Effective distribution
coefficient = Cs /Cl where
Cl = concentration in the
melt far from the interface
(weight/1g melt)
C k
k = s
= 0

C k + (1 − k )e
e − vδ
D
l 0 0

v = crystal growth rate

δ = diffusion barrier width
D = diff. coeff. of dopant in
the melt

k0, eqm. Distribution coefficient = Cs /Cli

Cli = concentration in the melt at the interface (weight/1g melt)
Cs = concentration in the solid (weight/1g solid)

Sebastian Lourdudoss, KTH

Equilibrium segregation coefficients for dopants
in silicon and GaAs

Sebastian Lourdudoss, KTH

Dopant concentration in the solid Cs :

k −1
  0
M 
C = k C 1 −
s 0 0 M 
 0

where k0, eqm. distribution coefficient

= Cs /Cl (Cl is the concn. in the melt),
C0 = Initial concentration in the melt and
M/M0 = Fraction of the melt solidified

Sebastian Lourdudoss, KTH

Sebastian Lourdudoss, KTH
Orientation flat, index flat, G-type, J-type

Sebastian Lourdudoss, KTH

Dovetail groove and V-groove

Sebastian Lourdudoss, KTH

Sebastian Lourdudoss, KTH
Sebastian Lourdudoss, KTH
 SEVERAL EPITAXIAL TECHNIQUES

• Liquid Phase Epitaxy (LPE)

- Semiconductor solid from a liquid solution
- An equilibrium process using liquidus - solidus
equilibrium
• Vapour Phase Epitaxy (VPE)
- Semiconductor solid from gas sources
- A special case of Chemical Vapour Deposition (CVD)
• Molecular Beam Epitaxy (MBE)
- Semiconductor solid from atomic or molecular beams
- Beams arrive directly on the growth surface without
any prior interferance or interaction (feasible in an
ultra high vacuum environment)

Sebastian Lourdudoss, KTH

 Liquid Phase Epitaxy

Observations:
1) III-V comounds decompose before reaching their melting points (melting
points are very high)
This means normally ∆Hfusion/∆H0formation > 1
AlSb 0.848 GaAs 1.26
GaSb 1.48 InAs 1.35
InSb 1.43

NaCl 0.07 KF 0.05

2) High vapour pressure of V species at the congruent melting point

Remedy:
• Dissolve V species (solutes) in III species (solvents)
• Use solidus ⇔ liquidus equilibrium to carry out epitaxy

THIS IS LPE!

Implication:
• Growth predicted by thermodynamics almost accurately

Sebastian Lourdudoss, KTH

Liquid Phase Epitaxy reactors

Sebastian Lourdudoss, KTH

LPE PHASE DIAGRAMS

Sebastian Lourdudoss, KTH

Doping of InGaAsP lattice
matched to InP with LPE

Sebastian Lourdudoss, KTH

 Regrowth by LPE

p-quaternary
contact layer

p-InP
Active layer cladding layer

n-InP

p-InP

n-InP
substrate

Sebastian Lourdudoss, KTH

ADVANTAGES OF LPE

• Simple
• Inexpensive
• Rather non-hazardous
• Suitable for selective growth
• Al and Sb compounds possible

=> Highly suitable for simple structures

DISADVATAGES OF LPE

• Too simple to grow quantum structures

• Thickness control and composition control difficult
• Redissolution of the grown material
• High growth temperatures for certain compounds
(e.g. GaAs at ~ 800-900 oC but InP at ~ 600 oC)
• Fe doping (for semi-insulation) difficult because of low
distribution coefficient
Sebastian Lourdudoss, KTH