US3379502A - Single crystal phosphide production - Google Patents

Single crystal phosphide production Download PDF

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Publication number
US3379502A
US3379502A US487829A US48782965A US3379502A US 3379502 A US3379502 A US 3379502A US 487829 A US487829 A US 487829A US 48782965 A US48782965 A US 48782965A US 3379502 A US3379502 A US 3379502A
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United States
Prior art keywords
phosphide
reaction
metal
gallium
temperature
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Expired - Lifetime
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US487829A
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English (en)
Inventor
Addamiano Arrigo
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General Electric Co
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General Electric Co
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Publication date
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Priority to US487829A priority Critical patent/US3379502A/en
Priority to GB36142/66A priority patent/GB1089709A/en
Priority to NL6611421A priority patent/NL6611421A/xx
Priority to DE19661544193 priority patent/DE1544193A1/de
Priority to FR76445A priority patent/FR1492680A/fr
Priority to ES0331246A priority patent/ES331246A1/es
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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
    • 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
    • C30B29/44—Gallium phosphide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/06—Hydrogen phosphides
    • 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
    • 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
    • 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
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/06—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using as solvent a component of the crystal composition

Definitions

  • ABSTRACT OF THE DTSCLGSURE A method for the production of single crystal phosphides of gallium, aluminum or indium wherein a single continuous process is used to produce the phosphide and then to grow it into relatively large single crystals.
  • the metal desired in the phosphide is reacted with zinc phosphide to produce metal phosphide, and zinc and any residual zinc phosphide are removed from the location of the reaction by volatilization.
  • the metal desired in the phosphide is supplied in excess so that after volatilization of the zinc and zinc phosphide the reaction mixture can be taken to an elevated temperature for growth of the metal phosphide single crystals in a bath of the metal itself, thereby avoiding deleterious impurities.
  • the bath is then cooled and the excess metal removed such as by leaching.
  • This invention relates to a method for preparing single crystals of phosphides, and more particularly to the production of single crystal phosphides of the metals aluminum, gallium and indium.
  • Patent 3,008,805-Addamiano assigned to the assignee of the present invention.
  • that patent involves a method of reacting together in a neutral atmosphere at elevated temperatures gallium, aluminum or indium with zinc phosphide (Zn P or its equivalent ZnP to produce a phosphide of the selected metal according to the reaction Where Me is aluminum, gallium or indium. If stoichiometric amounts of the reactants are used, the metal is converted into the metal ph-osphide, and the by-product of the reaction, zinc, is removed from the reaction by vaporization.
  • Zn P or its equivalent ZnP zinc phosphide
  • phosphides in single crystal form are in demand for several applications including diodes, transistors, and electroluminescent devices.
  • the term single crystal herein refers to crystalline material in which at least one dimension of the crystal is greater than about 0.1 millimeters.
  • the various methods known in the art for producing these phosphides generally produce them in the form of powders, or as polycrystalline aggregates, so that the preparation of single crystals usually involves one or more additional steps. These additional steps are normally expen sive and time-consuming and may be accompanied by hazards due to the high dissociation pressures of the phosphides.
  • One of the known methods for growing relatively large single crystals of such phosphides involves sealing small or irregular crystals of the metal phosphide along with an excess of the selected metal into a suitable reaction vessel and heating the vessel to dissolve the crystals in the excess of metal. Disadvantages of this process include the apparent necessity of high temperature, high pressure reaction in small sealed containers or bombs as States Patent well as the unfavorable economics of conducting the reaction in this manner.
  • Another object of the invention is to provide such a process which is nonhazardous relative to the prior art and can be entirely programmed and automated.
  • Still another object is the provision of such a method in which it is not necessary to seal the reactants under vacuum in vitreous containers or in a high pressure vessel such as a bomb or autoclave.
  • the invention in one form provides a method for the preparation of single crystal phosphides of a metal selected from the group consisting of aluminum, gallium and indium wherein the phosphide is initially formed in a neutral atmosphere in a reaction chamber by reacting an excess of the selected metal with Zn P at a temperature in the range of 7001000 C. for a period of time sufiicient for the reaction to go essentially to completion.
  • the required time will, of course, depend on the amounts and particle sizes of the constituents, among other factors.
  • the reaction mixture is then raised to a temperature sufficient to eliminate any residual traces of free zinc by vaporization and of Zn P by sublimation, and then the reaction chamber is sealed at least moderately tightly, although a vacuumor gas-tight seal is not absolutely necessary.
  • the reaction mixture is then raised to a temperature sufficient to dissolve the formed selected metal phosphide in the excess of the selected metal. For example, with gallium as the selected metal, a temperature of 1250 C. should be sufiicient to reach temperature and phase equilibrium.
  • the reaction mixture can be stirred or rocked gently back and forth to enhance pro-gress towards equilibrium if desirable. Subsequently, the reaction mixture is cooled at a sufllciently slow rate such as about l10 C. per minute, or preferably 14 C.
  • gallium Although the melting point of gallium, 29.8 C., is far below that of zinc, 419.5 C., gallium has a very high boiling point of 2237 C. as compared to 906 C. for zinc and a sublimation temperature of about 1050 C. for Zn l This makes it possible to drive oil the zinc and Zn P while retaining gallium.
  • aluminum melts at 660 C. and boils at 2450 C., and the respective temperatures for indium are 156.2 C. and 2000 C.
  • an outer tube 1 of a material such as quartz is provided to separate the outer parts of the furnace, not shown, from the inner working parts.
  • the heating means may be provided either outside this outer tube 1, or at the reaction zone 3, which is a necked-down portion of an inner tube 2 of a material such as quartz, such as by the indicated resistance heating wires 5. If desired, heating means may be provided in both places to heat the entire furnace for the first part of the reaction and adjust the reaction zone to a higher temperature for the latter parts of the reaction.
  • the reaction mixture initially consisting essentially of an excess of the selected metal plus Zn P is placed in the reaction zone in a boat or other suitable vessel which might be made, for instance, of graphite, quartz or aluminum nitride.
  • a suitable gas such as argon can be passed through the inner tube 3 of the furnace to carry off zinc released and volatilized in the reaction, and later to remove the sublimated Zn P
  • plugs 6 may be pressed up against the suitably shaped shoulders of the necked-down portion 3, as indicated in dotted lines 7 for one of the plugs, to form a seal.
  • the purpose of making this seal is to prevent excessive volatilization of phosphorus coming from dissociation of the phosphide.
  • the seal may be only tight enough to prevent volatilization of such a great extent as would hamper the reaction.
  • It is preferable to control the furnace temperature profile to minimize vaporization losses of phosphorus by making the end portions of tube 1 hotter than the reaction zone 3.
  • the plugs can be kept in the furnace continuously provided they are of the right size and shape to allow gas flow around them before they are moved into the sealing position 7.
  • the ends of the plugs 6 and the mating surfaces of the necked-down portions 3 may, for example, be spherical, conical or flat, although spherical surfaces are preferred for greater ease of operation. Temperature sensing and controlling means as known in the art may be used for operation of the invention in such a furnace as this.
  • a mixture of 14 grams of gallium and 25.8 grams of Zn P was placed in a graphite boat in the reaction zone of a furnace such as described above.
  • the reaction was carried out at 900 C. for about fifteen hours in an atmosphere of flowing argon to produce about 2 grams of GaP.
  • about 12.6 grams of unreacted gallium were available for use as the solvent at the end of the reaction.
  • the temperature was then raised to about 1100 C. for a few minutes to vaporize any residual traces of unreacted zinc and sublime any Zn P remaining, these being carried from the reaction zone by the flowing argon gas.
  • the temperature was then brought to about 1250 C., the plugs 6 moved to the closing position, and the temperature kept at 1250 C.
  • the furnace was allowed to cool at a rate of from 14 C. per minute to about 900 C. at which temperature the electrical power input to the Cat 4 furnace'was turned off and the furnace was allowed to cool to room temperature.
  • the boat was taken out of the furnace and the GaP crystals were extracted from the excess gallium by removing the gallium first mechanically and then by attack with hydrochloric acid.
  • the crystals were well developed platelets, often of regular contour, hexagonally shaped, and as large as about 1-2 millimeters on a side (about 14 millimeters square), showing one shiny face, and, opposite to it, a relatively dull. one. This is an indication that the developed faces were (111) and (1T1) planes.
  • the preparation can incorporate a dopant such as ZnO, ZnS, CdS, or others known in the art along with the selected metal and Zn P in order to produce crystals having desirably controlled electrical and other physical properties.
  • a dopant such as ZnO, ZnS, CdS, or others known in the art along with the selected metal and Zn P in order to produce crystals having desirably controlled electrical and other physical properties.
  • metal being supplied in excess of stoichiometric amounts, eliminating by vaporization and carrying away from the reaction chamber the zinc produce by the reaction and excess zinc phosphide, and then essentially closing off said reaction chamber and raising the temperature to a. level and for a time sufficient to dissolve the formed selected metal phosphide crystals in the excess of said selected metal, then slowly cooling to a temperature at which substantially all of the selected metal phosphide has precipitated from the melt.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Luminescent Compositions (AREA)
US487829A 1965-09-16 1965-09-16 Single crystal phosphide production Expired - Lifetime US3379502A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US487829A US3379502A (en) 1965-09-16 1965-09-16 Single crystal phosphide production
GB36142/66A GB1089709A (en) 1965-09-16 1966-08-12 Improvements in single crystal phosphide production
NL6611421A NL6611421A (cs) 1965-09-16 1966-08-13
DE19661544193 DE1544193A1 (de) 1965-09-16 1966-09-02 Verfahren zur Herstellung von Einkristallphoshiden
FR76445A FR1492680A (fr) 1965-09-16 1966-09-15 Perfectionnements aux procédés d'élaboration des monocristaux de phosphure et produits obtenus
ES0331246A ES331246A1 (es) 1965-09-16 1966-09-15 Metodo para preparar monocristales de un fosfuro.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US487829A US3379502A (en) 1965-09-16 1965-09-16 Single crystal phosphide production

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US3379502A true US3379502A (en) 1968-04-23

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US (1) US3379502A (cs)
DE (1) DE1544193A1 (cs)
ES (1) ES331246A1 (cs)
GB (1) GB1089709A (cs)
NL (1) NL6611421A (cs)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115417390A (zh) * 2022-10-18 2022-12-02 太原理工大学 一种单晶紫磷的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871100A (en) * 1955-07-22 1959-01-27 Rca Corp Method of preparing indium phosphide
US2921905A (en) * 1956-08-08 1960-01-19 Westinghouse Electric Corp Method of preparing material for semiconductor applications
US3008805A (en) * 1959-06-09 1961-11-14 Gen Electric Preparation of metal phosphides
US3009780A (en) * 1959-06-22 1961-11-21 Monsanto Chemicals Process for the production of large single crystals of boron phosphide
GB949945A (en) * 1960-09-14 1964-02-19 Ass Elect Ind Improvements relating to the preparation of metal arsenides and/or phosphides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871100A (en) * 1955-07-22 1959-01-27 Rca Corp Method of preparing indium phosphide
US2921905A (en) * 1956-08-08 1960-01-19 Westinghouse Electric Corp Method of preparing material for semiconductor applications
US3008805A (en) * 1959-06-09 1961-11-14 Gen Electric Preparation of metal phosphides
US3009780A (en) * 1959-06-22 1961-11-21 Monsanto Chemicals Process for the production of large single crystals of boron phosphide
GB949945A (en) * 1960-09-14 1964-02-19 Ass Elect Ind Improvements relating to the preparation of metal arsenides and/or phosphides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115417390A (zh) * 2022-10-18 2022-12-02 太原理工大学 一种单晶紫磷的制备方法
CN115417390B (zh) * 2022-10-18 2023-07-28 太原理工大学 一种单晶紫磷的制备方法

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Publication number Publication date
NL6611421A (cs) 1967-03-17
GB1089709A (en) 1967-11-08
DE1544193A1 (de) 1971-01-28
ES331246A1 (es) 1967-08-01

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