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
Resistance or RF heating Melt contained in quartz or Si3N4 crucible Chamber under Argon Si melts 1421C
Viewport

Puller

Seed Crystal

Melt

Heaters

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
Furnace tube Heater Pull Molten Pull Crystal Molten zone Polycrystal

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 C <0.03 <0.3 <50 <0.1 <0.03 <0.03 <0.03 <0.3 <0.03 <0.03 <0.1

Impurity concentration of Nb as reported by Giebovsky and Semenov

N H Si Al K Ca Na P S

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 Stock
Melt Stock

RF Coil

RF Coil

Melt

Seed
Single Crystal

Offset

Floating Zone RF
No practical advantage over EB heating Diameter of Xtal can be made larger by offsetting 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

Molten Metal

Radiation Cooling Single Crystal Selector Water Cooled Chill

Ceramic Mold

Uses columnar seed grain Single crystal selector (pigtail) Ceramic mold maintained at ~Tm Directional solidification from chill to top of blade Side entry gate/runner 15 Kg is considered a large pour

Columnar Grain Seed Crystal

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. 2. 3. 4. Handbook of Semiconductor Silicon Technology, W.C. OMara, R. B. Herring, L. P. Hunt, Noyes Publications, Norwich, NY, (1980). Moment, R. L., J. Nucl. Mater. 20, (1966), pp 341. Schulze, K. K. Preparation and Characterization of Ultra-High Purity Niobium, JOM, May, 1981, pp 334. 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. 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. 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. Naramoto, H., Kamada, K., Growth of Niobium Single Crystals by a Pedestal Method, J. of Crystal Growth, 24/25, (1974), pp. 531-536.

5.

6. 7.

References
8. 9. 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. Singh, J., Electronic and Optoelectronic Properties of Semiconductor Structures, Cambridge University Press, 0521182379X, Chapter 1, Structural Properties of Semiconductors, Cambridge, UK, (2003). Lawley, A., Crystal Growing, Vacuum Metallurgy, ed. By O. Winkler, R. Bakish, Elsevier Publishing Co., Amsterdam, (1971), pp 633-642. 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. Ford, T., Single Crystal Blades, Aircraft Engr. & Aerospace Tech., V. 69, No. 6, (1997), pp. 564-566. 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.

10. 11. 12. 13.