Crystal Growth Techniques

Ron Graham
October 31, 2006
 Agenda

Summarize current techniques

Discuss advantages/disadvantages
Propose hybrid method
 Basic Methods
Czochralski (CZ)
Bridgman (and variations)
Various floating zone methods
EB drip melting
Strain annealing
Other methods
 Czochralski

Czochralski (CZ) typically used for Si

Can grow boules to 300 mm with
400 mm being introduced
Uses seed crystal
Pulls boule out of the melt
 Czochralski Puller

Seed
Resistance or RF heating View-
Crystal
port
Melt contained in quartz or
Si3N4 crucible
Chamber under Argon Melt
Heaters

Si melts 1421C
 Czochralski
Growth speed is 12 mm/min
Crucible introduces oxygen contamination
Feed material form is unconstrained
Axial resistivity uniformity is poor
Heat up/cool down times are long
Materials of construction are issue Nb Tm =
2477C
Ingot weight can reach 400 kg
 Czochralski
Modification is a Tri-arc furnace
Melting accomplished by 3 arcs
Rotating, water-cooled Cu crucible
Melt conducted under vacuum
Reportedly can melt to 3000C
 Bridgman Technique
Vertical or horizontal
Uses a crucible
Requires seed crystal
Directional solidification
Precise temperature gradient required
 Bridgman Technique
Molten
Furnace tube zone
Heater Polycrystal

Pull Molten Pull Crystal

Seed Crystal Seed

Bridgman Technique

solid-liquid interface

Carefully controlled
temperature gradient
required.

Temperature TM
 Bridgman Technique

Growth rates of about 1 mm/hr

Crucibles usually used one time
Used for small Nb crystals 10 x 4060 mm
Requires only tip of seed to be molten
Can reach 200 mm for Si and GaAs crystals
 Floating Zone Techniques

Electron beam floating zone (EBFZ)

RF floating zone
 EB Floating Zone
Actual experience with refractory alloys
including Nb, Ta, Mo, Re, and W
Vacuum melting chamber, annular EB gun
Crystal rotator and translator
No crucible
0.550 mm/min growth rates
EB Floating Zone Melt stock (anode)

W filament cathode

Liquid metal Focusing electrodes

 EB Floating Zone

Zone refining is added benefit

Diameters up to 110 mm reported for Nb
Diameters limited by surface tension/runout
EB heating penetration limited
Does not seem practical for 300 mm
 EB Floating Zone
O <0.03
C <0.3
N <50
Impurity concentration
H <0.1
of Nb as reported by Si <0.03
Giebovsky and Semenov Al <0.03
K <0.03
Ca <0.3
Na <0.03
P <0.03
S <0.1
ppm
 EB Floating Zone
Modified pedestal technique reported for Nb
Used annular EB gun
Nb feedstock is rotating pedestal
Melt top of pedestal and touch seed to it
Pull non-rotating seed up off the pedestal
1.5 x 30 - 50 mm length
After Naramota and Kamada
 Floating Zone RF
Melt
Melt Stock
Stock
RF Coil RF Coil

Melt
Seed
Offset

Single Crystal
 Floating Zone RF
No practical advantage over EB heating
Diameter of Xtal can be made larger by off-
setting bottom pull rod from melt stock
Requires multiple passes to achieve crystal
Molten zone stability critical
Surface tension
Cohesion
Levitation
 EB Vertical Drip Melting
Well known technology
Can readily make large-grain ingots to 400 mm
Rotating melt-stock, vertically oriented above
water-cooled copper crucible
Multiple EB guns at 30 axis to melt stock
Bottom withdrawal of ingot
Excellent refining and purification
 EB Vertical Drip Melting
Single grain (with surrounding equiaxed grains)
demonstrated on small diameter
Large grains 150 x 220 mm possible
Not a robust process at this time
Limited by perturbations such as thermal gradients,
vibrations, fluid flow, nucleation off crucible wall
EB Vertical
Drip Melting
EB Vertical Drip Melting
A reminder of how refractory
metals solidify
These are the nuclei for new grains
Dendrites are easily disturbed and
broken off
If they dont re-dissolve they form
new grains
There can only be one dendrite in
a single crystal
Single Crystal Turbine Blades
Radiation
Heating Uses columnar seed grain
Single crystal selector (pigtail)
Molten
Metal Ceramic mold maintained at ~Tm
Directional solidification from chill
Radiation
to top of blade
Cooling
Ceramic Mold

Single
Side entry gate/runner
Crystal
Selector

Columnar Grain
15 Kg is considered a large pour
Water Cooled Seed Crystal
Chill
 Strain Annealing
Relies on principal of critical grain growth
Low strains = low dislocation density
Insufficient nucleation sites for new grains
Strain to ~ 35%, anneal
Results in large grains
Single grains to 5 mm2
Impractical for our purposes
 Other methods
Epitaxial growth - thin film only, very slow growth
rate
Variations of Bridgman technique using IR heat
lamps (so called image or mirror furnaces)
Levitation melting
 One Proposal
EBFZ on tubular melt stock
May be able to produce a single crystal tube
Thin wall contains molten zone
Surface tension may be able to support molten
metal column
Benefits of zone refining
Tube could be hydroformed to cavity shape
EB Floating Zone on Tube
Tubular melt stock
 References
1. Handbook of Semiconductor Silicon Technology, W.C. OMara, R. B. Herring, L. P.
Hunt, Noyes Publications, Norwich, NY, (1980).
2. Moment, R. L., J. Nucl. Mater. 20, (1966), pp 341.
3. Schulze, K. K. Preparation and Characterization of Ultra-High Purity Niobium, JOM,
May, 1981, pp 334.
4. Giebovsky, V.G., Semenov, V.N., Growing Single Crystals of High-Purity Refractory
Metals by Electron-Beam Zone Melting, High Temp. Materials and Processes, V. 14,
No. 2, (1995) pp. 121130.
5. Yudin, I.A., Elotin, A.V., Usage of EB Floating Zone Melting for Production of
Rhenium Alloys Wire, Rhenium and Rhenium Alloys, ed. By B. D. Bryskin, TMS,
(1997), pp. 805 808.
6. Liu, J., Zee, R.H. Growth of molybdenum-based alloy single crystals using electron
beam zone melting, J. of Crystal Growth, 163 (1996) pp. 259265.
7. Naramoto, H., Kamada, K., Growth of Niobium Single Crystals by a Pedestal
Method, J. of Crystal Growth, 24/25, (1974), pp. 531-536.
 References
8. Chen, H. et. Al., Growth of lead molybdate crystals by vertical Bridgman method,
Bull. Mater. Sci, Vol. 28, No. 6, Indian Academy of Sciences, (2005), pp. 555-560.
9. Singh, J., Electronic and Optoelectronic Properties of Semiconductor Structures,
Cambridge University Press, 0521182379X, Chapter 1, Structural Properties of
Semiconductors, Cambridge, UK, (2003).
10. Lawley, A., Crystal Growing, Vacuum Metallurgy, ed. By O. Winkler, R. Bakish,
Elsevier Publishing Co., Amsterdam, (1971), pp 633-642.
11. Yang, X.L., Lee, P.D., DSouza, N., Stray Grain Formation in the Seed Region of
Single-Crystal Turbine Blades, JOM, (May, 2005), pp. 40-44.
12. Ford, T., Single Crystal Blades, Aircraft Engr. & Aerospace Tech., V. 69, No. 6,
(1997), pp. 564-566.
13. M. Gell, D. N. Duhl, and A. F. Giamel, The Development of Single Crystal Superalloy
Turbine Blades, Superalloys 1980: Proceedings of the Fourth International
Symposium on Superalloys, edited by J. K. Tien, AIME/ASM, Metals Park, Ohio,
1980, pp 205-214.