US3647389A - Method of group iii-v semiconductor crystal growth using getter dried boric oxide encapsulant - Google Patents

Method of group iii-v semiconductor crystal growth using getter dried boric oxide encapsulant Download PDF

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Publication number
US3647389A
US3647389A US36367A US3647389DA US3647389A US 3647389 A US3647389 A US 3647389A US 36367 A US36367 A US 36367A US 3647389D A US3647389D A US 3647389DA US 3647389 A US3647389 A US 3647389A
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boric oxide
getter
gallium
growth
crystal growth
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US36367A
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Martin Eric Weiner
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AT&T Corp
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Bell Telephone Laboratories Inc
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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
    • C30B27/00—Single-crystal growth under a protective fluid
    • C30B27/02—Single-crystal growth under a protective fluid by pulling from a melt
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/06—Gettering
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/107—Melt

Definitions

  • the boric oxide is maintained for a time together with a getter substance under vacuum at a temperature at which both are molten.
  • some suitable getter substances are boron-palladium alloy, boron-platinum alloy and the pure metals or alloy combination of gallium, aluminum and silicon.
  • Field of the Invention The invention lies in the field of semiconductor crystal growth.
  • Boric oxide however is highly hygroscopic and even most high-purity materials contain sufficient quantities of water to cause the boric oxide to froth and spatter when melted.
  • a treatment has been developed to decrease the amount of water present in boric oxide to be used in crystal growth.
  • the material is subjected to a vacuum baking treatment in which the boric oxide is melted and maintained under vacuum at a temperature in excess of I,0O0 C. for times ranging from many hours to several days. Boric oxide produced by this rather extreme process has proven, generally, quite satisfactory for crystal growth and is widely used.
  • the liquid encapsulation technique as described above does not solve all of the crystal growth problems.
  • gallium arsenide under vacuum-baked boric oxide considerable bubbling is still observed and reaction products, which contaminate the crystal growth system, are produced.
  • arsenic is deposited over the inside of the vacuum chamber at times obscuring the viewing ports. Considerable effort has gone into an attempt to locate the source of these problems and effect improvements.
  • Volatile reaction products are substantially removed by the vacuum system and many solid and liquid reaction products and other impurities are dissolved in the getter substance.
  • This gettering step can also be incorporated in the vacuum baking procedure.
  • suitable getter substances are boron-palladium alloy, boron-platinum alloy, gallium aluminum, silicon or alloys of these latter three metals.
  • FIG. I is a plan view in section of a getter drying apparatus.
  • FIG. 2 is a plan view in section of a Czochralski crystal growth apparatus using the liquid encapsulation technique.
  • the proposed getter substance must be capable of reducing H (the high-temperature hydrated form of 8 0 at the drying temperature. Its oxide must be soluble in boric oxide and must be either volatile (hence removable by vacuum baking) or should not possess elements which would deleteriously contaminate the semiconductor melt.
  • the getter substance should be a liquid at the temperature at which drying is carried out so as to be capable of dissolving nonvolatile impurities. It is also advantageous that the getter substances be more dense than boric oxide since the simplest way to separate the getter substance from the boric oxide after drying is to melt the boric oxide and pour it oft" of the getter substance. Although this is not a strict requirement.
  • getter substances Considering these requirements as applied to the growth of gallium phosphide, gallium arsenide and mixed crystals thereof, a number of suitable getter substances have been found. Alloys of boron-platinum and boron-palladium possess a steep eutectic, melting in the neighborhood of 830 to 850 C. Alloys of these substances in the neighborhood of eutectic composition are suitable as getter substances.
  • the oxide produced by the reduction of water is boric oxide and thus does not introduce any new species into the boric oxide encapsulant.
  • the platinum or palladium are nonreacting in this system.
  • Gallium as a getter substance, introduces a new species into the boron oxide in that some gallium oxide remains after the drying treatment.
  • gallium is not a contaminant in the growth of gallium phosphide and gallium arsenide and the oxygen levels are reduced below the levels produced by the presence of H 0.
  • Oxygen is a deep trap in gallium arsenide and-an important dopant in gallium phosphide which must be carefully controlled.
  • Aluminum appearing just above gallium in the periodic table of the elements, is not an electrically active contaminant. It is thus an acceptable material. Also aluminum oxide is more stable than gallium oxide or boric oxide and, therefore, leads to even less oxygen contamination of the semiconductor melt.
  • the gettering process should take place at a temperature above which both the boric oxide and the getter substance are molten in order to promote the chemical drying process and the solution of other impurities in the getter substance.
  • the melting point of boric oxide is approximately 460 C. although because of its viscosity a preferred lower temperature for the gettering process is 600 C.
  • the temperature of the gettering process should be kept below l,500 C. because of excessive boric oxide evaporation above this temperature.
  • the drying process In order to remove the volatile reaction products. the drying process must take place under reduced pressure.
  • the time occupied by this process varies from about an hour to several days. 0ne reason for this large time variation is the variation of the viscosity of boric oxide with temperature.
  • the molten boric oxide is extremely viscous so that the pressure above the melt must be reduced slowly in order to avoid excessive frothing produced by the volatile reaction products.
  • the boric oxide is much less viscous and the pressure can be more rapidly reduced (within one hour or more preferably within 5 hours) to as low as the l micron level without causing excessive loss of boric oxide due to frothing.
  • Experiments which have been performed during the investigation of this process have generally taken place in the neighborhood of 900 to 1,100 C. Enough of the getter material must be used in order to react with all of the water in the boric oxide. However, much more than this quantity is generally employed since the speed of the reaction depends in part on the surface area of the molten getter substance.
  • FIG. 1 shows the elements of an exemplary getter drying apparatus.
  • the boric oxide 11 and the getter substance 12 are contained within a crucible 13 which is situated in a chamber 14, connected through an orifice 15 to a vacuum system 19.
  • the required treatment temperature is maintained by heating coils 16.
  • Fig. 2 shows some of the elements of a Czochralski crystal growing apparatus making use of the liquid encapsulation technique.
  • This is one of the many crystal growing techniques known in the art which can make use of liquid encapsulation where this proves advantageous.
  • the semiconductor melt 27 and the boron oxide encapsulant 21 are contained within a crucible 23 and maintained at the proper growing temperature by means of the heating element 26.
  • a rotating rod 29 with a seed crystal attached to its lowest end is lowered to make contact with the free surface 22 of the semiconductor melt 27 and initiate crystalization. It is then slowly raised pulling" crystal 28 from the melt through the encapsulant 21 which usually provides a coating over the crystal 28.
  • the pressure-regulating system 31 maintains the required overpressure of inert gas.
  • boric oxide can be produced by the disclosed process with less than 0.0] weight percent water. Water contents a factor 10 less than this and lower have been attained in boric oxide produced by a gettering process such as produced by an apparatus shown in FIG. 1.
  • Crystal growth'by an apparatus such as shown in FIG. 2 is greatly facilitated since the bubbling of the liquid encapsulant 21 is greatly reduced and the deposition of reaction products on the walls of the vacuum chamber 24 and the consequent obscuration of the viewing port 30 are greatly reduced.
  • the effects of the disclosed techniques can also be observed in the electrical properties of the pulled crystal 28. Exemplary crystals produced by this technique have shown such electrical improvements as increase of carrier mobility which can be traced to a lowering of the impurity content of the semiconductor material 28.
  • said getter substance consists essentially of at least one substance selected from the group consisting of gallium, boron-platinum alloy, boron-palladium alloy, aluminum and silicon.
US36367A 1970-05-11 1970-05-11 Method of group iii-v semiconductor crystal growth using getter dried boric oxide encapsulant Expired - Lifetime US3647389A (en)

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US (1) US3647389A (de)
JP (1) JPS5026422B1 (de)
BE (1) BE766750A (de)
CA (1) CA952413A (de)
CH (1) CH569514A5 (de)
DE (1) DE2122192C3 (de)
FR (1) FR2088484B1 (de)
GB (1) GB1311048A (de)
IT (1) IT942100B (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857679A (en) * 1973-02-05 1974-12-31 Univ Southern California Crystal grower
US3974002A (en) * 1974-06-10 1976-08-10 Bell Telephone Laboratories, Incorporated MBE growth: gettering contaminants and fabricating heterostructure junction lasers
US4196171A (en) * 1977-09-05 1980-04-01 Tokyo Shibaura Denki Kabushiki Kaisha Apparatus for making a single crystal of III-V compound semiconductive material
WO1981001016A1 (en) * 1979-10-12 1981-04-16 Western Electric Co Minimization of strain in single crystals
US4277303A (en) * 1978-08-07 1981-07-07 The Harshaw Chemical Company Getter for melt-grown scintillator ingot and method for growing the ingot
US4431476A (en) * 1981-01-17 1984-02-14 Tokyo Shibaura Denki Kabushiki Kaisha Method for manufacturing gallium phosphide single crystals
US4537652A (en) * 1983-06-10 1985-08-27 Sumitomo Electric Industries, Ltd. Process for preparing single crystal
US4704257A (en) * 1983-08-31 1987-11-03 Research Development Corporation Of Japan Apparatus for growing single crystals of dissociative compounds
US4721539A (en) * 1986-07-15 1988-01-26 The United States Of America As Represented By The United States Department Of Energy Large single crystal quaternary alloys of IB-IIIA-SE2 and methods of synthesizing the same
US4824520A (en) * 1987-03-19 1989-04-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Liquid encapsulated crystal growth
US5183767A (en) * 1991-02-14 1993-02-02 International Business Machines Corporation Method for internal gettering of oxygen in iii-v compound semiconductors
US5186784A (en) * 1989-06-20 1993-02-16 Texas Instruments Incorporated Process for improved doping of semiconductor crystals
US5272373A (en) * 1991-02-14 1993-12-21 International Business Machines Corporation Internal gettering of oxygen in III-V compound semiconductors
WO2010053960A1 (en) * 2008-11-07 2010-05-14 The Regents Of The University Of California Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-iii nitride crystals

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5914440B2 (ja) * 1981-09-18 1984-04-04 住友電気工業株式会社 ＣａＡｓ単結晶への硼素のド−ピング方法
US4637854A (en) * 1983-01-18 1987-01-20 Agency Of Industrial Science And Technology Method for producing GaAs single crystal

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Goetzherger et al.: Metal Precipitates in Silicon PN Junctions J. of Applied Physics Vol. 31 (1960), pp. 1821 1824 *
Mullin et al.: Liquid Encapsulation Techniques, J. Phys. Chem. Solids, Vol. 26 (1965), pp. 782 784 *
Pock: Glastechnische Berichte, Vol. 37 (1964), pp. 533 535 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857679A (en) * 1973-02-05 1974-12-31 Univ Southern California Crystal grower
US3974002A (en) * 1974-06-10 1976-08-10 Bell Telephone Laboratories, Incorporated MBE growth: gettering contaminants and fabricating heterostructure junction lasers
US4196171A (en) * 1977-09-05 1980-04-01 Tokyo Shibaura Denki Kabushiki Kaisha Apparatus for making a single crystal of III-V compound semiconductive material
US4277303A (en) * 1978-08-07 1981-07-07 The Harshaw Chemical Company Getter for melt-grown scintillator ingot and method for growing the ingot
WO1981001016A1 (en) * 1979-10-12 1981-04-16 Western Electric Co Minimization of strain in single crystals
US4299650A (en) * 1979-10-12 1981-11-10 Bell Telephone Laboratories, Incorporated Minimization of strain in single crystals
US4431476A (en) * 1981-01-17 1984-02-14 Tokyo Shibaura Denki Kabushiki Kaisha Method for manufacturing gallium phosphide single crystals
US4684515A (en) * 1983-06-10 1987-08-04 Sumitomo Electric Industries, Ltd. Single crystal article
US4537652A (en) * 1983-06-10 1985-08-27 Sumitomo Electric Industries, Ltd. Process for preparing single crystal
US4704257A (en) * 1983-08-31 1987-11-03 Research Development Corporation Of Japan Apparatus for growing single crystals of dissociative compounds
US4721539A (en) * 1986-07-15 1988-01-26 The United States Of America As Represented By The United States Department Of Energy Large single crystal quaternary alloys of IB-IIIA-SE2 and methods of synthesizing the same
US4824520A (en) * 1987-03-19 1989-04-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Liquid encapsulated crystal growth
US5186784A (en) * 1989-06-20 1993-02-16 Texas Instruments Incorporated Process for improved doping of semiconductor crystals
US5183767A (en) * 1991-02-14 1993-02-02 International Business Machines Corporation Method for internal gettering of oxygen in iii-v compound semiconductors
US5272373A (en) * 1991-02-14 1993-12-21 International Business Machines Corporation Internal gettering of oxygen in III-V compound semiconductors
WO2010053960A1 (en) * 2008-11-07 2010-05-14 The Regents Of The University Of California Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-iii nitride crystals
US20110223092A1 (en) * 2008-11-07 2011-09-15 The Regents Of The University Of California Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-iii nitride crystals
US8574525B2 (en) * 2008-11-07 2013-11-05 The Regents Of The University Of California Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-III nitride crystals

Also Published As

Publication number Publication date
IT942100B (it) 1973-03-20
DE2122192B2 (de) 1973-10-18
DE2122192A1 (de) 1971-11-25
DE2122192C3 (de) 1974-06-06
FR2088484A1 (de) 1972-01-07
FR2088484B1 (de) 1976-04-16
GB1311048A (en) 1973-03-21
JPS5026422B1 (de) 1975-09-01
CA952413A (en) 1974-08-06
CH569514A5 (de) 1975-11-28
BE766750A (fr) 1971-10-01

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