US3723599A - Technique for growth of single crystal gallium garnet - Google Patents

Technique for growth of single crystal gallium garnet Download PDF

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Publication number
US3723599A
US3723599A US00172751A US3723599DA US3723599A US 3723599 A US3723599 A US 3723599A US 00172751 A US00172751 A US 00172751A US 3723599D A US3723599D A US 3723599DA US 3723599 A US3723599 A US 3723599A
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technique
oxygen
growth
accordance
garnet
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US00172751A
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English (en)
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C Brandle
D Miller
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AT&T Corp
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Bell Telephone Laboratories Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/24—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates from liquids
    • H01F41/28—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates from liquids by liquid phase epitaxy
    • 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
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/28—Complex oxides with formula A3Me5O12 wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. garnets

Definitions

  • ABSTRACT Rare earth gallium garnet crystals evidencing low dislocation densities are obtained by the crystal pulling techniques utilizing an oxygen containing ambient wherein the partial pressure of oxygen ranges from about 3.8-19 millimeters of mercury.
  • such devices include a known magnetic garnet structure bearing an epitaxial film of a magnetic garnet.
  • a known magnetic garnet structure bearing an epitaxial film of a magnetic garnet.
  • workers in the art have continually sought to produce defectfree garnet substrates.
  • Studies of rare earth gallium garnet grown in accordance with such techniques have revealed that the grown materials evidence low dislocation densities. Nonetheless, small particle inclusions therein restrict the available surface area suitable for use in device applications.
  • this prior art deficiency has been successfully obviated by modifying the growth procedure.
  • This end has conveniently been attained by effecting rare earth gallium garnet growth in an oxidizing ambient wherein the partial pressure of oxygen is maintained within a critical prescribed range prior to and during growth of the desired crystal. Growth in the described manner has been found to result in the total elimination of the deleterious inclusions which have been attributed to the decomposition of the rare earth gallium garnet to yield gallium suboxide, rare earth sesquioxide, oxygen and a reduced rare earth gallium oxide.
  • FIG. 1 is a graphical representation on coordinates of growth time versus inclusion density showing the pregrowth conditions required to eliminate inclusions for stochiometric melts of gadolinium gallium garnet utilizing varying concentrations of oxygen;
  • FIG. 2 is a graphical representation on coordinates of growth time versus inclusion density showing the pregrowth conditions required to eliminate inclusions for melts of gadolinium gallium garnet containing 4 weight percent excess gadolinium oxide utilizing varying concentrations of oxygen;
  • FIG. 3 is a graphical representation on coordinates of growth time versus inclusion density showing the pregrowth conditions required to eliminate inclusions for melts of gadolinium gallium garnet containing 4 weight percent excess gallium oxide utilizing varying concentrations of oxygen.
  • the synthetic garnet materials here considered can be represented by the formula M Me Me 'O where M is one of the rare earth elements of atomic number between 62 and 71 or a mixture of these rare earth elements with each other, Me is gallium or scandium, Me is gallium and O is oxygen.
  • the formula for the rare earth garnet of interest is M Me Me 'O so indicating a molecular ratio of 3 parts of rare earth oxide to 5 parts of gallium oxide or gallium and scandium oxides.
  • the maintenance of this mol ratio known as the stochiometric ratio, yields satisfactory crystalline growth in accordance with this invention.
  • variations from the stochiometric ratio may be made without interfering with crystallization of the desired material.
  • excesses beyond stochiometry may be employed with respect to both gallium and the rare earth oxides, such excess varying up to 7 weight percent in each case. It has been determined that the use of excesses of either gallium or rare earth oxide beyond the noted limits results in the formation of a polycrystalline material which is of no value from a device standpoint.
  • defect-free rare earth gallium garnet can be grown utilizing a growth ambient containing oxygen and maintaining the melt in the oxygen ambient for a prescribed period of time prior to growth for the purpose of effecting oxidation of precipitates present therein.
  • the growth ambient may contain from 0.5 to 2.5 volume percent oxygen which corresponds with an oxygen partial pressure ranging from 3.8 to 19.0 millimeters of mercury.
  • the melt comprising the constituent components of the desired crystal is maintained in the oxygen ambient for a time period ranging from 1.5 to 10 hours, the shorter time period corresponding with the higher oxygen partial pressure and the longer time period corresponding with the lower oxygen pressure.
  • FIG. 1 is a graphical representation showing inclusion density as a function of growth time for stochiometric melts of gadolinium gallium garnet at varying oxygen partial pressures.
  • EXAMPLE 1 2 14.85 gramsof gadolinium oxide and 185.15 grams of gallium oxide, obtained from commercial sources, were weighed into an iridium crucible and heated to a temperature of approximately 1700C, the melting point of the mixture. Heat was effected by coupling the crucible with an RF induction heater. The crucible, together with its contents, was then permitted to attain a temperature of l750C at which point the charge was entirely liquid. Prior to the introduction of oxygen into the system, the melt was maintained in a neutral atmosphere, nitrogen, for one-half hour to insure a constant formation rate of the reduced compound.
  • Example 2 The procedure of Example 1 was repeated with the exception that the oxygen partial pressure was maintained at 0.5 percent by volume prior to and during growth, the pregrowth stage being conducted for 7 hours. It was observed that the inclusion density in the resultant grown crystal was zero.
  • Example 3 The procedure of Example 1 was repeated with the exception that the oxygen partial pressure was maintained at 1 volume percent prior to and during growth, the pregrowth stage lasting for 5 hours. The inclusion density of the resultant crystal was found to be zero.
  • Example 4 The procedure of Example 1 was repeated with the exception that the melt contained 4 weight percent excess gadolinium oxide, the pregrowth stage lasting for 2 hours. The resultant grown crystal evidenced an inclu' sion density of zero.
  • Example 5 The procedure of Example-2 was repeated with the exception that the melt contained 4 weight percent excess gadolinium oxide, the pregrowth stage lasting for 4 hours. The resultant grown crystal evidenced an inclusion density of zero.
  • Example 6 The procedure of Example 3 was repeated with the exception that the melt contained 4 weight percent excess gadolinium oxide, the pregrowth stage lasting for 4 hours. The resultant grown crystal evidenced an inclusion density of zero.
  • Example 7 The procedure of Example 1 was repeated ,with the exception that the melt contained 4 weight percent excess gallium oxide, the pregrowth stage lasting for 2.5 hours. The resultant grown crystal evidenced an inclusion density of zero.
  • Example 10 The procedure of Example 1 was repeated employing 70.59 grams of gadolinium oxide, 17.91 grams of scandium oxide and 36.50 grams of gallium oxide. The melt temperature was 1825C and it was elevated to l875C for 2 hours prior to growth. The resultant Gd Sc2Ga O12 crystal evidenced an inclusion density of zero.
  • melt comprises a stochiometric mixture of the constituent components of said garnet.
  • melt includes an excess of the constituent components of said garnet ranging up to 7 percent by weight.
  • said rare earth element is gadolinium.
  • melt comprises an excess of gallium oxide.
  • melt comprises an excess of gadolinium oxide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Soft Magnetic Materials (AREA)
US00172751A 1971-08-18 1971-08-18 Technique for growth of single crystal gallium garnet Expired - Lifetime US3723599A (en)

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US17275171A 1971-08-18 1971-08-18

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US (1) US3723599A (sv)
JP (1) JPS5246198B2 (sv)
BE (1) BE787642A (sv)
CA (1) CA954776A (sv)
DE (1) DE2240044C3 (sv)
FR (1) FR2149518B1 (sv)
GB (1) GB1394290A (sv)
IT (1) IT964946B (sv)
NL (1) NL146403B (sv)
SE (1) SE385437B (sv)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951729A (en) * 1973-01-16 1976-04-20 Hitachi, Ltd. Method for producing single crystals
US4040890A (en) * 1975-06-27 1977-08-09 Bell Telephone Laboratories, Incorporated Neodymium oxide doped yttrium aluminum garnet optical fiber
US4187139A (en) * 1973-02-14 1980-02-05 U.S. Philips Corporation Growth of single crystal bismuth silicon oxide
US4199396A (en) * 1976-06-24 1980-04-22 Union Carbide Corporation Method for producing single crystal gadolinium gallium garnet
US4302280A (en) * 1978-11-14 1981-11-24 Texas Instruments Incorporated Growing gadolinium gallium garnet with calcium ions
US4315832A (en) * 1979-03-05 1982-02-16 Hughes Aircraft Company Process for increasing laser crystal fluorescence yield by controlled atmosphere processing
US4323618A (en) * 1976-06-16 1982-04-06 U.S. Philips Corporation Single crystal of calcium-gallium germanium garnet and substrate manufactured from such a single crystal and having an epitaxially grown bubble domain film
US4350558A (en) * 1979-11-09 1982-09-21 Rhone-Poulenc Industries Process for the manufacture of polycrystalline garnet and corresponding monocrystals
US4350559A (en) * 1979-11-09 1982-09-21 Rhone-Poulenc Industries Process for the manufacture of polycrystalline garnet and corresponding monocrystal
US4534821A (en) * 1982-11-08 1985-08-13 Shin-Etsu Chemical Co., Ltd. Single crystal growing of rare earth-gallium garnet
US5691279A (en) * 1993-06-22 1997-11-25 The United States Of America As Represented By The Secretary Of The Army C-axis oriented high temperature superconductors deposited onto new compositions of garnet
US20060073978A1 (en) * 2003-02-06 2006-04-06 Brown University Method and apparatus for making continuous films of a single crystal material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5611679B2 (sv) * 1973-03-14 1981-03-16
GB2047113B (en) * 1979-04-12 1983-08-03 Union Carbide Corp Method for producing gadolinium gallium garnet

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3079240A (en) * 1960-05-13 1963-02-26 Bell Telephone Labor Inc Process of growing single crystals
US3272591A (en) * 1959-05-08 1966-09-13 Union Carbide Corp Production of single crystals from incongruently melting material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272591A (en) * 1959-05-08 1966-09-13 Union Carbide Corp Production of single crystals from incongruently melting material
US3079240A (en) * 1960-05-13 1963-02-26 Bell Telephone Labor Inc Process of growing single crystals

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Harrison, Research Vol. 12, 1959, pp. 395 403. *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951729A (en) * 1973-01-16 1976-04-20 Hitachi, Ltd. Method for producing single crystals
US4187139A (en) * 1973-02-14 1980-02-05 U.S. Philips Corporation Growth of single crystal bismuth silicon oxide
US4040890A (en) * 1975-06-27 1977-08-09 Bell Telephone Laboratories, Incorporated Neodymium oxide doped yttrium aluminum garnet optical fiber
US4323618A (en) * 1976-06-16 1982-04-06 U.S. Philips Corporation Single crystal of calcium-gallium germanium garnet and substrate manufactured from such a single crystal and having an epitaxially grown bubble domain film
US4199396A (en) * 1976-06-24 1980-04-22 Union Carbide Corporation Method for producing single crystal gadolinium gallium garnet
US4302280A (en) * 1978-11-14 1981-11-24 Texas Instruments Incorporated Growing gadolinium gallium garnet with calcium ions
US4315832A (en) * 1979-03-05 1982-02-16 Hughes Aircraft Company Process for increasing laser crystal fluorescence yield by controlled atmosphere processing
US4350558A (en) * 1979-11-09 1982-09-21 Rhone-Poulenc Industries Process for the manufacture of polycrystalline garnet and corresponding monocrystals
US4350559A (en) * 1979-11-09 1982-09-21 Rhone-Poulenc Industries Process for the manufacture of polycrystalline garnet and corresponding monocrystal
US4534821A (en) * 1982-11-08 1985-08-13 Shin-Etsu Chemical Co., Ltd. Single crystal growing of rare earth-gallium garnet
US5691279A (en) * 1993-06-22 1997-11-25 The United States Of America As Represented By The Secretary Of The Army C-axis oriented high temperature superconductors deposited onto new compositions of garnet
US20060073978A1 (en) * 2003-02-06 2006-04-06 Brown University Method and apparatus for making continuous films of a single crystal material

Also Published As

Publication number Publication date
NL146403B (nl) 1975-07-15
SE385437B (sv) 1976-07-05
CA954776A (en) 1974-09-17
NL7208408A (sv) 1973-02-20
GB1394290A (en) 1975-05-14
FR2149518A1 (sv) 1973-03-30
DE2240044C3 (de) 1975-01-02
DE2240044B2 (sv) 1974-05-09
BE787642A (fr) 1972-12-18
JPS5246198B2 (sv) 1977-11-22
FR2149518B1 (sv) 1975-09-12
DE2240044A1 (de) 1973-03-01
JPS4831200A (sv) 1973-04-24
IT964946B (it) 1974-01-31

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