US3429740A - Growing garnet on non-garnet single crystal - Google Patents

Growing garnet on non-garnet single crystal Download PDF

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US3429740A
US3429740A US489930A US3429740DA US3429740A US 3429740 A US3429740 A US 3429740A US 489930 A US489930 A US 489930A US 3429740D A US3429740D A US 3429740DA US 3429740 A US3429740 A US 3429740A
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garnet
single crystal
substrate
crystal
mgo
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US489930A
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Jack E Mee
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Boeing North American Inc
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North American Rockwell Corp
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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
    • H01F41/22—Heat treatment; Thermal decomposition; Chemical vapour deposition
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2675—Other ferrites containing rare earth metals, e.g. rare earth ferrite garnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
    • H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
    • H01F10/18—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being compounds
    • H01F10/20—Ferrites
    • H01F10/24—Garnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/26—Thin magnetic films, e.g. of one-domain structure characterised by the substrate or intermediate layers
    • H01F10/28—Thin magnetic films, e.g. of one-domain structure characterised by the substrate or intermediate layers characterised by the composition of the substrate

Definitions

  • Crystals with the garnet structure have become important technologically and scientifically in recent years. Many of the crystals have magnetic properties which make them useful for device purposes. For example, thin crystals of certain of the magnetic garnets are transparent and display a magneto-optic eifect when polarized light impinges on the crystal. Such magneto-optic etfect can be used for display purposes. Scientifically, this effect can be used to study magnetic domain structures, electronic absorption spectra, etc. Even non-magnetic garnets have useful device properties, e.g., Y Al O may be used as a laser host material.
  • Single crystal garnets are grown by Verneuil, hydrothermal and flux techniques. Commercially they are usually grown by the flux techniques wherein the garnet is grown from a molten salt solution. These methods are not adaptable to growing high quality, thin single crystal garnet films.
  • the characterizing feature of this invention is a cornposite of single crystal garnet on a single crystal substrate which is not within the garnet class.
  • the epitaxial single crystal garnet film may be grown by a chemical vapor deposition process on large areas.
  • Garnet is defined herein as a solid material having the formula ⁇ M [M (M 0 where M is defined herein as at least one element selected from the class consisting of Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Ym, Yb, Lu, Ca and Bi; M is defined herein as at least one element selected from the class consisting of Fe, In, Sc, Mg, Zr, Sb, Al and Ga; and M is defined herein as at least one element selected from the class consisting of Fe, Al, Ga, Si, Ge and V. Particularly preferred because of their magnetic properties are the rare earth iron garnets.
  • this class of garnet materials are Y Fe O and Gd Fe O while the preferred non-magnetic garnet is Y Al O
  • the notations represent sites in the garnet material designated 0, a, and d sites respectively. Elements known to exist in these sites in the garnets are listed below and designated as to their oxidation state:
  • Garnets may be defined as pure, mixed or substituted. Typical examples of pure garnets are Y Fe O and Tb Fe O Examples of mixed garnets include where x may have a maximum value of 0.5, 1.3, 2, 1.4, 0.35 respectively for the preceding examples.
  • La, Pr and Nd exist in mixed garnets, they do not exist in pure garnets such as La Fe O Pr Fe O and Nd Fe O
  • a garnet with any other type of substitution is called a substitution garnet, for example, ⁇ Y [F62] (Fe Al 0 and 3x x [FEZ] 3-x x) l2-
  • Other Fe containing garnets include Sm Fe O It is an object of this invention to provide single crystal garnet crystallographically bonded to a single crystal nongarnet structure.
  • Another object of this invention is to provide a composition having a large area of single crystal garnet on a non-garnet substrate.
  • Still another object of this invention is to provide a process for producing single crystal garnet on single crystal non-garnet substrates in large quantities.
  • FIGURE 1 is a representation of an apparatus used in growing single crystal garnet on a single crystal nongarnet substrate.
  • the apparatus of the present invention comprises a chamber 1, including inlet means 2 for injecting gases into one end of the chamber 1, and an exhaust 5 at the other end of the chamber.
  • the chamber is surrounded by heater elements 6, 7 and 8 for controlling the temperature at locations within the chamber.
  • Supported inside chamber 1 are a plurality of spaced crucibles 10 and 11.
  • the crucibles are spaced to be within the area heated by respective heater elements.
  • Also within the chamber is a quartz holder 13 on which substrates or seed crystals 12 are supported.
  • substrate and crystals are used interchangeably herein.
  • the crystals are located in chamber 1 so that they are exposed to a mixture of gases flowing from inlets 2 and 14.
  • Inlet 2 is connected to a source (not shown) of inert carrier gases such as helium and argon.
  • Inlet 14 is connected to a source (not shown) of gases such as oxygen and water vapor, carbon dioxide and hydrogen.
  • the substrates 12 on which the garnet crystal material is deposited or grown are comprised of single crystal nongarnet type materials.
  • the substrate material selected is MgO, although other substrate materials, for example, MgAl O lit-A and other materials having the formula Me'Mei'O, may also be utilized in producing the structure.
  • Me may be Li, Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd and Me" may be Al, Cr, Mn, Fe, Ti.
  • the substrates 12 may be prepared by cleaving optical grade MgO along a ⁇ 100 ⁇ cleavage plane or by cutting the MgO in the plane of desired configuration along its other crystal faces.
  • the substrates are ground flat to produce a crystal having a selected size and a selected crystallographic plane and chemically polished in an acid etch solution.
  • the substrates 12 are supported on the holder 13 inside chamber 1 and a garnet layer may be deposited as described in detail hereinafter.
  • the source materials 15 and 16 for producing the garnet deposit on the substrates 12 are placed in containers and 11 and heated to vaporization by heater elements 6 and 7 respectively.
  • Metal halides used as source materials are placed inside containers 10 and 11.
  • the halides include those of the metallic elements Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca and Bi in one container, and Fe, In, Sc, Mg, Zr, Sb, Al, Ga, Si, Ge and V in the other. When heated, the solid metal halides slowly vaporize.
  • the above described gases are emitted through inlets 2 and 14.
  • the plurality of gases including a source of available oxygen and the source material vapors react at the heated surface of the substrate to epitaxially deposit single crystal garnet on the non-garnet substrates.
  • the composition may be removed and placed in other environments, for example, a conventional vacuum deposition chamber (not shown) for further processing, depending upon the particular use intended for the composition.
  • a conventional vacuum deposition chamber not shown
  • the corresponding halides of iron and of the desired rare earth metals are selected.
  • the halides of yttrium, gadolinium and iron will be utilized.
  • the choice of particular halide, such as chloride, bromide, iodide or fluoride will be determined by its decomposition temperature and other factors known to those skilled in the art.
  • Example I A substrate material, MgO, is prepared by cleaving the crystal along a ⁇ 100 ⁇ cleavage plane into approximately 18 mm. x 12 mm. dimensions. After cleaving, the substrate is mechanically ground flat on a series of metallographic papers to the 4/0 size. They are then chemically polished in a concentrated H PO etching solution heated to 125 C. for minutes. After the etching the substrates are given a thorough hot water rinse.
  • a quartz or alumina cylindrical shaped apparatus of FIGURE 1 having a 54 mm. ID. is utilized as the deposition chamber.
  • a quartz or alumina holder is used to support the MgO crystal in the middle of the chamber.
  • Quartz or alumina crucibles 10 and 11 contain source materials 15 and 16. The crucibles are each carefully located in the chamber with each source material having individually controlled electrical heater elements 6 and 7.
  • the source materials are the metal halides FeBr and YC1
  • the temperature for the FeBr is held at 700 C. and the YCl is held at 1150 C. to give sufficient vapor pressures for the two reactants.
  • the crystal is maintained at 1150 C.
  • argon at 1 ft. /hr. is passed through inlet 2 and carries the FeBr and YCl vapors to the MgO crystal.
  • Oxygen at 1 ftfi/hr. is bubbled through water at room temperature and brought into the reaction area just in front of the MgO crystal through the opening provided by a 10 mm. ID. Vycor or alumina tube at one end of the chamber, shown in FIGURE 1 as opening 14.
  • the H 0, 0 FeBr and YCl vapors react in the area of the MgO crystal.
  • the reaction is continued for one hour, then the furnaces and the substrate are permitted to cool for approximately two hours.
  • the garnet film formed is approximately five microns thick over an area of 18 mm. x 12 mm.
  • the film displays the characteristics ferromagnetic properties of yttrium iron garnet and is identified by X-ray diffraction techniques.
  • the reaction to form the garnet layer can be represented as follows:
  • Example II The process and apparatus as described in connection with Example I is utilized in this example except that AlCl at C. and YCl at 1150 C. are used in place of the source materials described therein. Instead of oxygen, argon is bubbled through water to produce an H O vapor.
  • the reaction to form the garnet layer can be represented as follows:
  • Example IV The process and apparatus as described in connection with Example I is utilized in this example, except that GdI at -1000 C. is used in place of the YCl
  • the reaction to form the garnet layer can be represented as follows:
  • Example VI The process and apparatus as described in Example V except that a ⁇ 111 ⁇ MgO plane is used rather than a ⁇ 110 ⁇ plane.
  • Example VII (110) or (111) MgO seed fi 'am I FB zm 19mm.) goat.)
  • a composite comprising a monocrystalline substrate of non-garnet material and an epitaxial film of single crystal garnet material on said substrate, said substrate being selected from the class consisting of MgO, rat-A1 and MeMe" O wherein Me is selected from the class consisting of Li, Mg, Mn, Fe, Co, Ni, Cu, Zn and Cd and wherein Me is selected from the class consisting of A1, Cr, Mn, Fe and Ti.
  • a composite according to claim 1 wherein said single crystal garnet material is selected from the class consisting Of Y3F5O12, Gd3F5O12 and Y3Al50 2.
  • said substrate comprises MgO having a deposition surface
  • said halides include an iron halide and at least one rare-earth metal halide selected from the class consisting of gadolinium and yttrium halides.
  • halides include a yttrium halide and an aluminum halide.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Thin Magnetic Films (AREA)
  • Compounds Of Iron (AREA)
US489930A 1965-09-24 1965-09-24 Growing garnet on non-garnet single crystal Expired - Lifetime US3429740A (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3486937A (en) * 1967-03-24 1969-12-30 Perkin Elmer Corp Method of growing a single crystal film of a ferrimagnetic material
US3607390A (en) * 1969-09-29 1971-09-21 Ibm Single crystal ferrimagnetic films
US3615168A (en) * 1969-08-12 1971-10-26 Bell Telephone Labor Inc Growth of crystalline rare earth iron garnets and orthoferrites by vapor transport
US3617381A (en) * 1968-07-30 1971-11-02 Rca Corp Method of epitaxially growing single crystal films of metal oxides
US3645787A (en) * 1970-01-06 1972-02-29 North American Rockwell Method of forming multiple layer structures including magnetic domains
US3645788A (en) * 1970-03-04 1972-02-29 North American Rockwell Method of forming multiple-layer structures including magnetic domains
US3753814A (en) * 1970-12-28 1973-08-21 North American Rockwell Confinement of bubble domains in film-substrate structures
US3837911A (en) * 1971-04-12 1974-09-24 Bell Telephone Labor Inc Magnetic devices utilizing garnet epitaxial materials and method of production
US3849193A (en) * 1971-05-25 1974-11-19 Commissariat Energie Atomique Method of preparation of single crystal films
US3864165A (en) * 1970-09-08 1975-02-04 Westinghouse Electric Corp Fabrication of ferrite film for microwave applications
US3946124A (en) * 1970-03-04 1976-03-23 Rockwell International Corporation Method of forming a composite structure
US3982049A (en) * 1969-06-16 1976-09-21 Rockwell International Corporation Method for producing single crystal films
US4001793A (en) * 1973-07-02 1977-01-04 Rockwell International Corporation Magnetic bubble domain composite with hard bubble suppression
FR2354809A1 (fr) * 1976-06-16 1978-01-13 Philips Nv Monocristal de grenat de calcium-gallium-germanium, ainsi que substrat forme par un tel monocristal et muni d'une couche a bulles magnetiques formee par voie d'epitaxie
KR20150032825A (ko) * 2013-09-20 2015-03-30 스카이워크스 솔루션즈, 인코포레이티드 공진-미만 무선 주파수 순환기들 및 격리기들과 관련된 재료들, 장치들 및 방법들
US20160226120A1 (en) * 2011-06-06 2016-08-04 Skyworks Solutions, Inc. Rare earth reduced garnet systems and related microwave applications
US9829728B2 (en) 2015-11-19 2017-11-28 Massachusetts Institute Of Technology Method for forming magneto-optical films for integrated photonic devices

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5981570A (ja) * 1982-11-01 1984-05-11 Hitachi Ltd 光方式磁界測定装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3131082A (en) * 1962-02-01 1964-04-28 Gen Electric Rare earth-iron garnet preparation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3131082A (en) * 1962-02-01 1964-04-28 Gen Electric Rare earth-iron garnet preparation

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3486937A (en) * 1967-03-24 1969-12-30 Perkin Elmer Corp Method of growing a single crystal film of a ferrimagnetic material
US3617381A (en) * 1968-07-30 1971-11-02 Rca Corp Method of epitaxially growing single crystal films of metal oxides
US3982049A (en) * 1969-06-16 1976-09-21 Rockwell International Corporation Method for producing single crystal films
US3615168A (en) * 1969-08-12 1971-10-26 Bell Telephone Labor Inc Growth of crystalline rare earth iron garnets and orthoferrites by vapor transport
US3607390A (en) * 1969-09-29 1971-09-21 Ibm Single crystal ferrimagnetic films
US3645787A (en) * 1970-01-06 1972-02-29 North American Rockwell Method of forming multiple layer structures including magnetic domains
US3946124A (en) * 1970-03-04 1976-03-23 Rockwell International Corporation Method of forming a composite structure
US3645788A (en) * 1970-03-04 1972-02-29 North American Rockwell Method of forming multiple-layer structures including magnetic domains
US3864165A (en) * 1970-09-08 1975-02-04 Westinghouse Electric Corp Fabrication of ferrite film for microwave applications
US3753814A (en) * 1970-12-28 1973-08-21 North American Rockwell Confinement of bubble domains in film-substrate structures
US3837911A (en) * 1971-04-12 1974-09-24 Bell Telephone Labor Inc Magnetic devices utilizing garnet epitaxial materials and method of production
US3849193A (en) * 1971-05-25 1974-11-19 Commissariat Energie Atomique Method of preparation of single crystal films
US4001793A (en) * 1973-07-02 1977-01-04 Rockwell International Corporation Magnetic bubble domain composite with hard bubble suppression
FR2354809A1 (fr) * 1976-06-16 1978-01-13 Philips Nv Monocristal de grenat de calcium-gallium-germanium, ainsi que substrat forme par un tel monocristal et muni d'une couche a bulles magnetiques formee par voie d'epitaxie
US20160226120A1 (en) * 2011-06-06 2016-08-04 Skyworks Solutions, Inc. Rare earth reduced garnet systems and related microwave applications
US10230146B2 (en) * 2011-06-06 2019-03-12 Skyworks Solutions, Inc. Rare earth reduced garnet systems and related microwave applications
KR20150032825A (ko) * 2013-09-20 2015-03-30 스카이워크스 솔루션즈, 인코포레이티드 공진-미만 무선 주파수 순환기들 및 격리기들과 관련된 재료들, 장치들 및 방법들
US20150130550A1 (en) * 2013-09-20 2015-05-14 Skyworks Solutions, Inc. Materials, devices and methods related to below-resonance radio-frequency circulators and isolators
US9552917B2 (en) * 2013-09-20 2017-01-24 Skyworks Solutions, Inc. Materials, devices and methods related to below-resonance radio-frequency circulators and isolators
US20170133141A1 (en) * 2013-09-20 2017-05-11 Skyworks Solutions, Inc. Devices and methods for below-resonance radio-frequency applications
US9829728B2 (en) 2015-11-19 2017-11-28 Massachusetts Institute Of Technology Method for forming magneto-optical films for integrated photonic devices

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DE1646789B2 (de) 1975-02-13
GB1137950A (en) 1968-12-27
DE1646789A1 (de) 1971-09-16
NL6613458A (enrdf_load_stackoverflow) 1967-03-28
DE1646789C3 (de) 1975-09-25

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