Crystals and Crystal

Growing

Why Single Crystals

What is a single crystal?
Single crystals cost a lot of money.
When and why is the cost justified?
Current semiconductor devices on an IC have
characteristic dimensions of micron.
What happens if grain size is on the scale of
microns?
What makes optical materials look translucent?
What happens when a weapons grade laser beam
hits an inhomogeneity in an optical component?

Applications of Single Crystals

For what applications are single crystals necessary?
1. Semiconductor optoelectronics (substrate materials)
Transistors, diodes, integrated circuits: Si, Ge, GaAs, InP
LEDs and lasers: GaAs, GaInAs, GaInP, GaAsP, GaP:N, ruby
Solar cells: Si, GaAs, GaInP/GaAs tandems
Microwave sources: GaAs
2. Non-glass optics (see previous lecture for transmission ranges): alkali
halides, alkaline earth halides, thallium halides, Ge, sapphire
3. Electromechanical transducers
Ultrasonic generators, sonar: ADP, KDP
Strain gauges: Si
Optical modulators: LiNbO3, BaTiO3, BaNaNiO3
Piezoelectric microphone sources: quartz
4. Radiation detectors: HgI2, NaI:Tl, CsI:Tl, LiI:Eu, Si, Ge, III-V, II-VI, PbS

5. Micromechanical devices: Si Utah Neural Array (SEM image)

6. Research: everything. Why?
7. Artificial gems: sapphire, ruby, TiO2, ZrO2
Why are they necessary for those applications? (Numbers correspond)
1. Electrical homogeneity on the length scale of the device; minimum
carrier scattering
2. Optical homogeneity on the length scale of the light being transmitted;
minimum light scattering
3. Mechanical strength and homogeneity; availability of processing
technology: nickel-based super alloy turbine blades
4. Purity; well-defined material
In all cases: optical, electronic or mechanical properties superior to nonsingle crystal competition.

Superconducting Ceramic Single

Crystals

Aps.org

Bulk Crystal Growth

Techniques

Technique
Melt:
Directional
Solidification

Examples
Elemental &
Compound
semiconductors: Si,
Ge, GaAs, InP

CuInSe2, MCT, CdTe,

Bridgman
(horizontal/vertic ZnSe, GaSe Oxidesal)
insulators: sapphire

Czochralski
("Cz")

Windows: sapphire
Scintillators: BGO,
CdWO4
NLO materials:
LiNbO3, CsLiB6O10
Alkali scintillatorsCsI:Tl
Halides: windowswide transmitting
filters

Advantages

Disadvantages

FAST
Large sizes possible

Often energy intensive

some materials
decompose before
melting

Reasonable Kef
Seeded: predetermined
orientation

Crucible can be a
problem

Always the technique of

choice

Dopants can be volatile

Contamination

Technique

Examples

Advantages

Disadvantages

Vapor

Physical vapor
transport
(evaporation &
condensation)

HgI2, CdS, ZnS, NH4X

Hg2Cl2, CdS
Molecular Organics!

Chemical vapor
deposition
(open flow)
Chemical vapor
transport
(closed system)

Refractories: SiC, PBN

Semiconductor
epitaxy!

Can be used with materials

that decompose or have
excessive vapor pressure
at melting point or with
destructive phase
transitions or extremely
high melting points or
which react with
containers.

TiO2, EuS, "halogen

lamps" SnO2, In2S3

Materials must have

reasonable vapor
pressure at
temperature where
surface kinetics is
adequate
Typically slow
Difficult to control

Very slow; batch

process

Solution/Flux
ADP, KDP,
Refractories
Hydrothermal quartz
Diamond: 1450 C, 742
kpsi, Ni flux
Proteins, Minerals,
Mo2C
High Tc
superconductors;
BiSrCaCuO
Mortons tablesalt

Large sizes possible

Potentially low cost, large
scale
Reduced temperature
less container
contamination
Can be inexpensive

Very slow
Temperature control
very important
Kef often very small
doping difficult

Digression on Segregation and

Purification
Electronic materials are only
interesting when doped
Carrier type: n
Dopant: P
Res:
1-20 ohms

Typical Numbers
On previous label, = 1-20 Ohm (presumably
1-20 -cm)
As you know: = 1/ = ne
For silicon at 10 -cm with n = 1700 cm2/V-sec
nP = 3.7x1014/cm3
nSi = 2.33 gm/cm3) x(6.02x1023 atoms/mole)
(28.068 gm/mole) = 4.997x10 22 atoms per
mole
nP / nSi = 7x10-9 = 7 ppb!
Background impurity level must be small on
this scale!

Segregation

Coefficient can be greater or less

than unity
Nutrient volume is finite
Causes major problems with dopant
uniformity
Can be resolved by adding dopant to
melts during growth
Only works for K>1!

Origin of Segregation: Binary Phase

Diagram

W. G. Pfann, Zone Melting

Using Segregation for Purification:

Normal Freezing

n.b.: exactly the same process is used

to grow large single crystals from the melt!

W. G. Pfann, Zone Melting

Impurity
Distribution after
Normal Freezing

W. G. Pfann, Zone Melting

Concept of Zone Refining

W. G. Pfann, Zone Melting

Molten zone of length l is passed through

ingot of length L
Also the process used to make float zone

Impurity
Distributio
n after
Single
Pass of
Zone
(Less efficient than
normal freezing)

W. G. Pfann, Zone Melting

Impurity
Distribution
from Multi-pass
Zone Refining
n.b.: k =
0.9524, l/L =
0.01

W. G. Pfann, Zone Melting

Take Away Lessons

Segregation of impurities/dopants is
a fact that you must deal with as an
aspect of materials preparation
Segregation can be used as part of
an elegant purification process
Zone refining can be very efective
for materials purification

Current Purification of Silicon

(Wikipedia)

Siemens process: high-purity silicon

rods are exposed to trichlorosilane at
1150 C. The trichlorosilane gas
decomposes and deposits additional
silicon onto the rods, enlarging them:
2 HSiCl3 Si + 2 HCl + SiCl4
Silicon produced from this and similar
processes is called polycrystalline silicon
. Polycrystalline silicon typically has
impurity levels of less than 10 9.

Czochralski
Growth

Synthesis may or may not be part of

growth
GaAs
preGa
Li H

may be pre-synthesized or a
measured quantity
As may be bubbled through
metal
synthesized from Li and H2 (or

D2)
Typical sizes: Si - 12" , 200 kg
charge; GaAs - 4"
We have grown from a 2 g melt of
isotopically pure K13C15N
www.people.seas.harvard.edu

Typical growth rates: cm/hr

Vertical Bridgman Technique

Melting point isotherm is directionally
translated through an ingot from a spatially
confined region.
Typically unseeded no seed necessary
Can be seeded: quality as high as
Czochralski
High yield: all starting material is recovered
as single crystal
Diameters to 22 inches; 40 cm2 square KDP
Used extensively for alkali halide
scintillators, transducers and windows