US3819421A - Method for the manufacture of dislocation-free, single-crystal gallium arsenide rod - Google Patents

Method for the manufacture of dislocation-free, single-crystal gallium arsenide rod Download PDF

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Publication number
US3819421A
US3819421A US00334935A US33493573A US3819421A US 3819421 A US3819421 A US 3819421A US 00334935 A US00334935 A US 00334935A US 33493573 A US33493573 A US 33493573A US 3819421 A US3819421 A US 3819421A
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Prior art keywords
crystal
gallium arsenide
vessel
tube
arsenic
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Expired - Lifetime
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US00334935A
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English (en)
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H Merkel
H Wolf
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Siemens AG
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Siemens AG
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/30—Mechanisms for rotating or moving either the melt or the crystal
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/42—Gallium arsenide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10S117/906—Special atmosphere other than vacuum or inert
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10—Apparatus
    • Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1032—Seed pulling
    • Y10T117/1064—Seed pulling including a fully-sealed or vacuum-maintained crystallization chamber [e.g., ampoule]

Definitions

  • the melt temperature is controlled to initially draw a 23/301 252/6.2'3 GA narrow-neck and then decreased until a crystal of [51] Int. Cl B01 l7/ld the desired diameter is being drawn
  • dislocations present in the seed crystal continue to grow in the crystal and are further augmented by dislocations which are newly formed at the interface between the seed and the crystal.
  • New dislocations are also incorporated into the crystal by excessive separa tion rates, i.e., a large increase of the diameter over a short axial distance.
  • the apparatus which they described has a number of disadvantages.
  • the cover makes observation of the crystal difficult, and is the source of defects such as contamination.
  • the present invention provides such a method in which single crystal gallium arsenide rods which are free from dislocations can be produced with a simple and inexpensive apparatus.
  • the gallium arsenide crystals are drawn within an enclosed quartz tube, from a gallium arsenide melt in a graphite crucible which is inductively heated.
  • the mounting of the seed crystal, the changing of the height and the rotation of the seed crystal are achieved by means of magnetic coupling in the manner described in German Pat. No. 1,044,769.
  • the temperature within the quartz tube is controlled so that over a distance of about 3 cm the crystal is reduced to a diameter as small as possible and then is gradually increased to a desired diameter.
  • the area over the gallium arsenide crucible Prior to sealing the drawing vessel, i.e., the quartz tube, the area over the gallium arsenide crucible is charged with an inert gas or an inert gas mixture at a pressure of0.2 to 0.8 kg/cm (0.2 to 0.8 X l0 N/m
  • the charging gas is selected to have a thermal conductivity of 0.18 mW cmK' at 300 K and 0.3 mW cml( at l,500 K.
  • the arsenic addition is proportioned so that the partial pressure of the arsenic during the drawing process is 0.8 to 1.5 kg/cm (0.8 to 1.5 X 10 N/m
  • a seed crystal diameter of between 2 and 10 mm. is used.
  • the gases and/or gas mixtures with the low heat conductivity mentioned above will preferably be krypton and zenon although a mixture of these gases or mixtures of one of these gases with argon and in some circumstances with nitrogen can also be used.
  • the thermal shielding provided by these gases or gas mixtures provides an axial temperature gradient at the transition between solid and liquid and a radial heat flow in the crystal and in the melt which are very small. As a consequence, the transition zone between the solid and liquid phase is perfectly flat.
  • the apparatus disclosed for practicing this method is much simpler than that described by Steinemann and Zimmerli. In addition, the introduction of impurities which result from the lid and radiation shield of graphite at the growing crystal is prevented.
  • FIG. 1 is a cross section view, partially in schematic form, of a typical apparatus for performing the crystal growing method of the present invention.
  • FIG. 2 is a diagram illustrating the temperature dependence of the thermal conductivity of several gases.
  • gallium arsenide used in the present invention.
  • gallium arsenide has an arsenic vapor pressure of l kglcm
  • arsenic vapor pressure in the range of 0.8 to 1.5 kg/cm preferably 1.3 kg/cm
  • the vessel will preferably be of fused quartz. During the drawing operation the lowest temperature of the vessel wall must be maintained at at least 680 C.
  • the crucible from which the GaAs crystal is to be pulled, is filled or charged with Stoichiometrically structured, mostly in polycrystalline form, gallium arsenide which has been synthesized from the gallium and arsenic elements using well known methods. It should be noted, that it is also possible to perform the synthesis of the gallium arsenide in the drawing apparatus itself. To perform this synthesis, the required amount of gallium, accurately weighed, and which has been freed of oxide layers by a prior heat treatment, is placed in the crucible.
  • a sufficient amount of Oxygen-free arsenic to form a stoichiometrically composed GaAs melt in the crucible is then deposited in the lower part of the drawing vessel along with enough excess arsenic to maintain an arsenic vapor pressure of 1.3 kg/cm with the minimum temperature of the vessel wall at 680 C.
  • the apparatus for pulling of a dislocation-free singlecrystal gallium arsenide rod in accordance with the method of the present invention is shown in FIG. 1.
  • the vessel 1 in which the pulling is accomplished comprises a transparent fused quartz member having a length of 60 cm and an inside diameter of 4.5 cm. After each drawing operation, the vessel is cut at the point indicated as 2 on the figure to permit access to the pulling mechanism in the rod.
  • the vessel will be useable a number of times [at least 20 times] having been made longer than is necessary for a single pulling operation.
  • a guide tube 32 is attached to the top of the vessel 1 and is perfectly aligned along the axis of the vessel.
  • the pulling mechanism comprises a drawing tube made of quartz glass which slips over the guide tube 32.
  • Both guide tube 32 and the inside of tube 31 are carefully ground to provide a closely aligned fit between the two surfaces.
  • Four segments of magnetic steel 33 are secured to the tube 31 at its outside at 3. These interact with the magnets 15 mounted outside the tube 1. in the manner described in the above referenced German patent, to pull and rotate the drawing tube 31.
  • Secured to the base of the tube 31 is the mount 4 for the seed crystal.
  • a graphite crucible 8 in which the gallium arsenide melt is deposited.
  • the entire crucible can be enclosed in fused quartz, or inserts of fused quartz, boron nitrite, aluminum nitrite, aluminum oxide or other suitable pure materials may be placed inside of the crucible and should be fit thereto as closely as possible.
  • the seed crystal mount 4 is composed of graphite or boron nitrite and is secured to the lower end of tube 31 with a quartz splint.
  • the seed crystal 6 will preferably be 6 cm long and will have a (111) orientation; its lower half will be cylindrical and have a diameter of 4 mm and its upper half will be ground as a prism with a cross section of 4 mm by 4 mm.
  • the prismatic portion of the seed crystal will be inserted very accurately into a corresponding shaped opening in the seed crystal mount 4. Eight screws made of graphite or boron nitrite will hold the seed crystal 6 in place in the crystal mount 4.
  • the crucible 8 is formed by drilling a cylindrical graphite block, preferably one with a diameter of 4 cm and a height of 5 cm, to form a hole which is 4 cm deep and of a diameter such as to leave a wall thickness of 4 mm. With these dimensions the crucible will hold a little more than 60 grams of gallium arsenide melt. The remaining portion of the graphite block interacts with a high frequency magnetic field provided by coils outside the vessel to inductively heat the melt in the manner described in the above referenced German patent. The coils 13 which provide the high frequency field to the crucible 8 are water cooled in a manner described in the reference. Secured to the bottom of the vessel 1 is a graphite quartz socket 9 used to support the crucible 8.
  • the vessel 1 Prior to beginning the drawing operation the vessel 1 will be cut in two sections at the line 2.
  • the crucible 8 will be filled with 60 grams of gallium arsenide in the form of polycrystalline rods of suitable length.
  • the crucible 8 is then placed on the quartz socket 9 in the lower part of the vessel 1.
  • the required excess arsenic For the present example 2.7 grams of arsenic would be used.
  • the two halves of vessel 1 are then fused together, in exact vertical alignment with the end of the finally etched seed crystal placed carefully on the gallium arsenide rods located in the crucible 8.
  • the vessel 1 is then evacuated by an evacuation stub 7 located at the top of the vessel.
  • the portion of the vessel 1 above the crucible 8 is then heated for 1 hour at 620 C.
  • the vessel is cooled under a vacuum and a mixture of krypton and xenon gas admitted until a pressure of 0.5 kg/cm is reached in the vessel.
  • the vessel 1 is then sealed by closing off the evacuation tube 7 and is now ready for the drawing operation.
  • the vessel 1 is then placed in a furnace installation which comprises a resistance furnace 11 extending over most of the upper secton of the vessel 1, a short resistance furnace 12, the induction heating coils 13, and a lower resistance furnace 14, which heats the base of the vessel 1.
  • the resistance furnace 11 may, for example comprise a slotted Megapyr tube. This resistance furnace l1 heats the vessel down to the area near the crucible.
  • the short furnace 12 which has its heater windings arranged in a slanted or stair-like ceramic body to facilitate viewing the crystal as it is being drawn.
  • the gallium arsenide is heated to its melting point by the inductive heating of the graphite crucible 8, with coils 13, which are coupled to a high frequency generator in a manner known in the art.
  • the entire vessel is brought to a temperature of approximately 650 C. by means of the resistance furnaces ll, 12 and 14 causing all the excess arsenic which was deposited in the portion 10 of the vessel to evaporate.
  • the temperature of the furnaces 11 and 12 is then increased to 700 C. and that of furnace 14 to 680 C.
  • the gallium arsenide in the crucible 8 is then melted by the high frequency inductive heating described above.
  • the temperature of the gallium arsenide melt is controlled by means of a radiation pyrometer in a manner well known in the art.
  • the seed crystal When temperatures have stabilized, and the gallium arsenide is melted, the seed crystal is dipped into the melt and after temperature equilibrium is established, the pulling process is started.
  • the magnets 15 are used to rotate the pulling tube 31 at a rotation speed of about rpm.
  • the temperature of the melt is maintained at a level such as to cause the growing crystal to have a diameter which is decreased down to about 1 mm. This comprises the narrow-neck, and is then drawn out for approximately 15 to 20 mm.
  • the neck of the crystal is free of dislocations.
  • the dislocations will have traveled, following the direction of their growth, toward the lateral boundary of the narrow-neck and will have disappeared.
  • the temperature of the gallium arsenide melt is then reduced slowly so that the crystal gradually becomes thicker again.
  • the drawing is continued with a constant pulling velocity of about 2 cm per hour at a rotation speed of 20 rpm. In this manner, a dislocation-free cylindrical crystal of 15 mm diameter with a length of 9-10 cm is formed.
  • the graph of FIG. 2 illustrates the conductivity of various gases over a range of temperatures and is helpful in selecting the gas or gases to be used in the drawing vessel.
  • gallium arsenide crystals which are essentially free of dislocations, have improved purity and quality and are suited, due to their high crystal perfection, for the manufacture of semiconductor devices with optimum properties, for example, light emitting diodes, opto-electronic coupling elements, injection lasers.
  • substrate crystals for epitaxial deposition with other compound semiconductors and mixed crystals such as, for instance, Ga(As,P) and as seed crystals for the drawing of, for example, gallium arsenide single-crystals by the protective-melt method has been shown.
  • a method for drawing a dislocation-free, singlecrystal gallium arsenide rod in a drawing apparatus comprising a closed quartz tube having at its bottom portion means to inductively heat a graphite crucible which is filled with gallium arsenide and placed in the bottom of the tube and means to support, pull and rotate a seed crystal comprising the steps of:
  • said inert gas comprises one of the group consisting of krypton, xenon and a mixture of krypton and xenon.
  • drawing apparatus further includes heating means surrounding the quartz tube and further including the step of heating said tube to maintain it at a temperature above that at which arsenic will precipitate on the walls ofthe tube.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
US00334935A 1972-03-01 1973-02-22 Method for the manufacture of dislocation-free, single-crystal gallium arsenide rod Expired - Lifetime US3819421A (en)

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Application Number Priority Date Filing Date Title
DE19722209869 DE2209869B1 (de) 1972-03-01 1972-03-01 Verfahren zur herstellung eines versetzungsfreien einkristallinen galliumarsenidstabes

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US (1) US3819421A (de)
JP (1) JPS48102569A (de)
BE (1) BE795938A (de)
CH (1) CH591893A5 (de)
DE (1) DE2209869B1 (de)
GB (1) GB1408215A (de)
NL (1) NL7301465A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028058A (en) * 1974-04-30 1977-06-07 Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh Device for making monocrystalline gallium arsenide
US4776971A (en) * 1985-05-29 1988-10-11 Montedison S.P.A. Gallium arsenide single crystals with low dislocation density and high purity
US5578284A (en) * 1995-06-07 1996-11-26 Memc Electronic Materials, Inc. Silicon single crystal having eliminated dislocation in its neck
US5779790A (en) * 1996-03-15 1998-07-14 Shin-Etsu Handotai Co., Ltd. Method of manufacturing a silicon monocrystal
US5997641A (en) * 1996-12-06 1999-12-07 Komatsu Electronic Metals Co., Ltd. Seed-crystal holder for single-crystal pulling devices with magnetic field applied thereto
WO2019223326A1 (zh) * 2018-05-23 2019-11-28 中国科学院金属研究所 一种激光辅助加热生长大尺寸晶体的方法及专用设备

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2962363A (en) * 1957-07-09 1960-11-29 Pacific Semiconductors Inc Crystal pulling apparatus and method
US3344071A (en) * 1963-09-25 1967-09-26 Texas Instruments Inc High resistivity chromium doped gallium arsenide and process of making same
US3488157A (en) * 1964-07-03 1970-01-06 Wacker Chemie Gmbh Apparatus for manufacturing,purifying and/or doping mono- or polycrystalline semi-conductor compounds
US3507625A (en) * 1966-01-10 1970-04-21 Philips Corp Apparatus for producing binary crystalline compounds
US3627499A (en) * 1968-01-18 1971-12-14 Philips Corp Method of manufacturing a crystalline compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2962363A (en) * 1957-07-09 1960-11-29 Pacific Semiconductors Inc Crystal pulling apparatus and method
US3344071A (en) * 1963-09-25 1967-09-26 Texas Instruments Inc High resistivity chromium doped gallium arsenide and process of making same
US3488157A (en) * 1964-07-03 1970-01-06 Wacker Chemie Gmbh Apparatus for manufacturing,purifying and/or doping mono- or polycrystalline semi-conductor compounds
US3507625A (en) * 1966-01-10 1970-04-21 Philips Corp Apparatus for producing binary crystalline compounds
US3627499A (en) * 1968-01-18 1971-12-14 Philips Corp Method of manufacturing a crystalline compound

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028058A (en) * 1974-04-30 1977-06-07 Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh Device for making monocrystalline gallium arsenide
US4776971A (en) * 1985-05-29 1988-10-11 Montedison S.P.A. Gallium arsenide single crystals with low dislocation density and high purity
US5578284A (en) * 1995-06-07 1996-11-26 Memc Electronic Materials, Inc. Silicon single crystal having eliminated dislocation in its neck
US5628823A (en) * 1995-06-07 1997-05-13 Memc Electronic Materials, Inc. Process for eliminating dislocations in the neck of a silicon single crystal
US5779790A (en) * 1996-03-15 1998-07-14 Shin-Etsu Handotai Co., Ltd. Method of manufacturing a silicon monocrystal
US5997641A (en) * 1996-12-06 1999-12-07 Komatsu Electronic Metals Co., Ltd. Seed-crystal holder for single-crystal pulling devices with magnetic field applied thereto
WO2019223326A1 (zh) * 2018-05-23 2019-11-28 中国科学院金属研究所 一种激光辅助加热生长大尺寸晶体的方法及专用设备

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Publication number Publication date
JPS48102569A (de) 1973-12-22
NL7301465A (de) 1973-09-04
DE2209869C2 (de) 1974-01-24
BE795938A (fr) 1973-08-27
CH591893A5 (de) 1977-10-14
DE2209869B1 (de) 1973-06-20
GB1408215A (en) 1975-10-01

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