[go: up one dir, main page]

US3079240A - Process of growing single crystals - Google Patents

Process of growing single crystals Download PDF

Info

Publication number
US3079240A
US3079240A US28862A US2886260A US3079240A US 3079240 A US3079240 A US 3079240A US 28862 A US28862 A US 28862A US 2886260 A US2886260 A US 2886260A US 3079240 A US3079240 A US 3079240A
Authority
US
United States
Prior art keywords
flux
garnet
yttrium
range
ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US28862A
Other languages
English (en)
Inventor
Joseph P Remeika
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AT&T Corp
Original Assignee
Bell Telephone Laboratories Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bell Telephone Laboratories Inc filed Critical Bell Telephone Laboratories Inc
Priority to US28862A priority Critical patent/US3079240A/en
Priority to GB17162/61A priority patent/GB912799A/en
Priority to BE603732A priority patent/BE603732A/fr
Priority to FR861711A priority patent/FR1289841A/fr
Application granted granted Critical
Publication of US3079240A publication Critical patent/US3079240A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C04B35/2641—Compositions containing one or more ferrites of the group comprising rare earth metals and one or more ferrites of the group comprising alkali metals, alkaline earth metals or lead
    • 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
    • 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
    • C04B35/2683—Other ferrites containing alkaline earth metals or lead
    • 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
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • 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
    • Y10S117/917—Magnetic

Definitions

  • This invention relates to a method of growing single crystals of synthetic garnet, orthoferrites and ferrites in a flux comprising lead oxide and boron oxide.
  • the synthetic garnet materials considered here can be represented by the formulas M3Me5012 or M ME (MCO4) 3 where O is oxygen, Me is a trivalent metal and M is yttrium or one of the rare earth elements of atomic number between 62 and 71 or a mixture of these rare earth elements with each other or with yttrium.
  • Me may be trivalent iron or trivalent iron mixed in part with at least one of the elements of gallium, aluminum, scandium, chromium or cobalt.
  • the orthoferrites consider-ed can be represented by the formula XFeO there Fe is iron, 0 is oxygen and X may be yttrium, lanthanum, praseodymium, neodymium, or one of the rare earth elements of atomic number between 62 and 71.
  • Magnetic spinels prepared from the combined lead oxide-boron oxide flux include: magnesium, nickel, cobalt, aluminum, zinc and cadmium ferrites.
  • Nonmagnetic spinels prepared include magnesium aluminum and magnesium gallium.
  • ferrites are produced by mixing oxides of selected metals and heating the mixture to a given temperature at which a reaction between the oxides takes place. The mixture is then cooled, ground, and pressed into a suitable shaped and sintered.
  • garnets are termed garnets," because they possess the cubic structure of the mineral garnets such as grossularite, Ca Al (SiO As is well known in the art, single crystals of ferrimagnetic material show enhancement of certain magnetic properties associated with the polycrystalline material.
  • the resonance lines of single crystal materials are much narrower than those found in the polycrystalline material, this property forming the basis for the types of microwave devices described in copending application Serial Number 778,352, filed December 5, 1958, now U.S. Patent No. 3,016,495, and Serial Number 774,172, filed November 17, 1958, now U.S. Patent No. 3,013,229.
  • a convenient prior art method of producing such single crystals consisted of combining the reactants in proper proportions with a flux consisting of lead oxide, heating the mixture to form a homogeneous liquid, and forming the single crystals from a molten bath by standard crystallization procedures. This technique is discussed in detail in copending application Serial Number 655,955, filed April 30, 1957, now U.S. Patent No. 2,957,- 827.
  • the present invention embodies the same general procedures as the aforementioned crystal growing methods with the exception of the flux employed.
  • the present inventive method utilizes a fiux initially comprising lead
  • the use of such a flux is advan-' oxide and boron oxide. tageous in several respects, the most important being the increased solubility of constituent materials which permits the process to be operated at lower temperatures than the prior art. yield and crystal size.
  • each procedure is considered individually- GARNETS
  • borate formation is the most important considera-j tion in determining a maximum boron content. It has been found that use of a ratio of born oxide to lead oxide of greater than about 1 to 9 results in formation of borates resulting in increased difiiculty of separation of this material from the desired crystal.
  • the lower temperature limit of the system during crystal lization in the yttrium iron garnet and gadolinium iron garnet systems is determined by the observed re-solution of these materials in the solvent at temperatures substan tially lower than about 1000 C., although this limit is determined by a most favorable flux composition and is to this re-solution observed at temperatures below this minimum it is necessary in the growth of garnet structures in this system to remove all the liquid portion of the flux ,at about this temperature. It is possible to avoid resolution by rapid quench of the flux from this minimum temperature to a complete solidification, so permitting-acid separation where desirable. This re-solution phenomenon is common to the use of the orthodox lead oxide flux.v
  • Optimum cooling rates over the crystallization range of from about 1300 C. to 1000 C. are determined by the usual criteria, the faster the rate of cooling, the greater the number of nucleation centers with a consequent decrease in crystal size, and vice versa. Cooling rates may vary from as low as 2 C. per hour or lower to as high as 10 C. per hour. It is generally desirable to cool as slowly as possible to secure the largest possible crystal Further advantages include increase in cooling rates'are used, it is desirable from an economicstandpoint to more rap-idly cool from the initial high temperature of 1300 C. down to the temperature at which nucleation is first observed. For the usual situation, using the preferred 1 to 10 flux and a nutrient concentration close to the preferred value, this initial nucleation occurs at 1215 C.
  • the formula for yttrium iron garnet is Y Fe O so indicating a molecular ratio of threeparts of yttrium oxide to five parts of iron oxide (weight ratio of 6.8280).
  • the optimum observed weight ratio of starting ingredients, however, on which the above figures are based, is 8.021110.
  • This excess of iron oxide is necessary to keep the yttrium iron garnet in equilibrium over the crystallization range. Operation with the ratio indicated by the stoichiometric material-s results in a decrease of yield of the order of 30 percent.
  • the use of an excess of yttrium oxide'results in the formation of yttrium orthoferrite and yttrium borates as the stable phase and virtually no yttrium iron garnet is produced.
  • the absolute limit at one end of the range corresponds with the stoichiometric ratio of yttrium orthoferrite, i.e., 11.0 yttrium to 8.0 iron.
  • the preferred range is of the order of from 7.9 yttrium to 11.1 iron, to 8.1 yttrium to 10.9 iron.
  • the boron to lead ratio in the flux and also the preferred ranges discussed are suitable.
  • the maximum temperature of 1300 C. is the same for the various reasons described.
  • the gross nutrient to flux ratio is approximately the same as the for yttrium iron garnet.
  • the preferred range is of the order of from 0.5;1.1 to
  • garnet materials which have been prepared by this method include; yttrium gallium garnet, gadolinium gallium garnet, erbium iron garnet, ytterbiunuand all of the rare earth iron garnets from samarium to lutecium.
  • Other substitutions including partial substitution of up to 50 percent gallium for iron have been made in the yttrium iron garnet system. All conditions discussed above are suitably used in the growth of any of the rare earth garnets;
  • a mixture of the starting materials is weighed into a cubic centimeter platinum crucible and sealed with a platinum lid.
  • the crucible is next placed into a horizontal globar furnace with a silicon carbide mufiie and a mullite floor plate.
  • the furnace may be pre heated to 1300 C.
  • the crucible, together with its contents, is then permitted to attain a temperature of 1300 C. and is maintained at this temperature for a period of eight hours.
  • For charges of the order of 500 grams it has been found helpful to stir the mixture and so assure complete solution. Without stirring, in a charge of this size, it is observed that stratification of the nutrient materials occurs at the top of the melt which is caused by the large dilferences in densities of nutrient and flux.
  • Controlled cooling at the rate of 2 per hour from the maximum of 1300" C. is then commenced by a controlled energization of the furnace. This program is continued until the re-solution temperature is reached. At this point, the crucible is removed from the furnace and the still liquid portion is poured off. After pouring off the liquid, the crystals still in the crucible are permitted to cool. This is tantamount to an air quench, cooling taking of the order of one hour to reach the ambient temperature.
  • the crucible is then immersed in a vessel containing a. dilute solution of nitric acid and Water, of the order of 50 percent by volume.
  • the acid cleaning procedure is con-- tinued until all flux residue has been removed from the crystals.
  • acid cleaning at room temperature takes of the order of three hours, although this is variable, being dependent on the amount of residue, the size of the charge and the number of clusters. It is found expeditious to carry out the acid cleaning at temperatures approximating the boiling point of the acid solution.
  • the acid solution is poured off, the crucible removed from the container and the crystals washed in three successive rinses of boiling distilled water. Following the water washing, the crystals are dried by air-drying at room temperature.
  • the resultant crystals were chemically analyzed and magnetic measurements were made on the washed product. These measurements, not considered to be within the scope of this disclosure, were in conformity with observed magnetic properties on other specimens of these compositions.
  • the orthoferrite system has a much greater temperature range of stability than does the garnet system. It has, therefore, been found unnecessary to use other than stoichiometric amounts of star-ting ingredients, so indicat- Table I Flux composition Crystal Starting ingredients Yield size Ex (gms) Product (grns.) maximum PbO B203 dimensions (gins) (gms.) (0111s.)
  • the increase in crystal size, by weight is of the order of five times, crystals of yttrium orthoferrite of rectangular configuration, l X 1 x 2 centimerers being obtained in the combined flux, as compared with /2 x /2 x 1 centimeter in the Pb0 flux.
  • orthoferrites based on lanthanum, praseodymium, and neodymium are somewhat small er than the other orthoferrites, the same increase in crystal size being realized, however, by use of the combined flux.
  • Orthoferrites which have been produced in the combined flux are: yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium. All of these materials are transparent with the exception of praseodymium and neodymium.
  • These materials may be modified by inclusion of small amounts of additional ingredients, such as in the yttrium iron garnet system.
  • additional ingredients such as in the yttrium iron garnet system.
  • the combined flux is uniquely suitable for addition of aluminum as a modifying ingredient.
  • modification may be carried out, for example, for the purpose of improving light transmission.
  • the domain boundaries move for applied fields of less than 1 oersted, however, approximately 50 oersteds are required to magnetize the crystals to saturation. When saturated, crystals as large as 0.2 X 0.2 x 0.1 inch remain single domains. Fields of approximately 2500 oersteds are then required to reverse the first magnetization on the single domain crystals.
  • the preferred flux composition for the orthoferrites and also the spinels is at the ratio of 1 to 20.
  • the range of 1:18 to 1:22 is considered to define the exclusive useful operating flux compositional range for this system.
  • Use of appreciably greater ratios results in borate formation with the attendant difiiculty of separation of final product, as discussed above in connecion with the garnet system.
  • Use of appreciably lesser ratios simply results in decreased solubility and so puts a further limit on yield. It is estiing equal molecular amounts of rare earth oxide and Fe 0
  • the preferred gross nutrient to flux ratio is 1 to 3, with a preferred range encompassed by the ratio limits of 1:2.8 to 1:3.2.
  • the procedure employed for growth of orthoferrite crystals is similar to that discussed above for the garnet system. However, there are slight variations as follows: after mixing the starting ingredients in a platinum crucible the procedure for garnet growth is repeated until the cooling step is reached. At this point, cooling is continued until complete crystallization of the entire contents of the crucible, which generally occurs at 850 C. for the orthoferrites. When attaining this temperature the input to the furnace is cut cit and cooling continued at a rate determined by the specific apparatus employed, for example, 50 C. per hour. When entire contents reach the ambient temperature it is necessary to separate nutrient from flux.
  • X may be yttrium, lanthanum, praseodymium, neodymium or one of the rare earth elements of atomic number between 62 and 71 and O is oxygen.
  • Z was cobalt, chromium, gallium or aluminum.
  • These materials are known as rare earth co'baltiates, rare earth orthochromites, rare earth gallates and rare earth aluminates.
  • cobaltia-tes the other X20 compounds are transparent, generally evidencing no coloration whatsoever except for the orthochromates which are greenish.
  • SPINEL FERRITES Single crystalline magnetic spinel ferrites have been crystallized in the prior art from a lead oxide flux.
  • the advantage of using a lead oxide-boron oxide flux here is the same as for the ortho-ferrites. Solubility is increased by the order of a factor of three, so resulting in a concomitant increase in yield.
  • the method of growing single crystals of a material selected from the group consisting of synthetic garnets, spinel ferrites and orthoferrites which comprises heating the constituent components of said material together with a mixture of lead oxide and boron oxide, the weight ratio of P130 to B 0 being in the range of 9:1 to 14:1 for garnet growth and in the range of 18:1 to 22:1 for orthoferrite and spinel ferrite growth, the gross nutrient to flux ratio being in the range of 121.8 to 1:2.2 for garnet growth, 1:2.8 to 1:32 for ortho'ferrites, and 1:2 to 1:5 for spinel ferrites, and slowly cooling the resultant melt whereby said material precipitates from the melt in crystals.
  • a material selected from the group consisting of synthetic garnets, spinel ferrites and orthoferrites which comprises heating the constituent components of said material together with a mixture of lead oxide and boron oxide, the weight ratio of P130 to B 0 being in the range of 9:1 to 14:1 for garnet growth and in the range

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Compounds Of Iron (AREA)
  • Magnetic Ceramics (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US28862A 1960-05-13 1960-05-13 Process of growing single crystals Expired - Lifetime US3079240A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US28862A US3079240A (en) 1960-05-13 1960-05-13 Process of growing single crystals
GB17162/61A GB912799A (en) 1960-05-13 1961-05-11 Improvements in or relating to the growth of single crystals of synthetic garnets, ferrites and orthoferrites
BE603732A BE603732A (fr) 1960-05-13 1961-05-12 Procédé d'obtention de monocristaux de ferrites, orthoferrites et grenats synthétiques
FR861711A FR1289841A (fr) 1960-05-13 1961-05-13 Procédé de croissance de monocristaux

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US28862A US3079240A (en) 1960-05-13 1960-05-13 Process of growing single crystals

Publications (1)

Publication Number Publication Date
US3079240A true US3079240A (en) 1963-02-26

Family

ID=21845926

Family Applications (1)

Application Number Title Priority Date Filing Date
US28862A Expired - Lifetime US3079240A (en) 1960-05-13 1960-05-13 Process of growing single crystals

Country Status (4)

Country Link
US (1) US3079240A (fr)
BE (1) BE603732A (fr)
FR (1) FR1289841A (fr)
GB (1) GB912799A (fr)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149910A (en) * 1962-06-04 1964-09-22 Tauber Arthur Method of growing single crystals
US3150925A (en) * 1961-04-20 1964-09-29 Richard J Gambino Method of growing single crystals
US3162603A (en) * 1963-02-01 1964-12-22 Jack A Kohn Method of growing iridium substituted single crystal using bismuth oxide flux
US3224843A (en) * 1960-06-30 1965-12-21 Owens Corning Fiberglass Corp Separation of crystals from a boric anhydride matrix
US3226183A (en) * 1961-06-12 1965-12-28 Bertaut Erwin Felix Preparation of monocrystals of rare earth manganites
US3305301A (en) * 1963-04-03 1967-02-21 Bell Telephone Labor Inc Process for the growth of ordered lithium ferrite
US3356929A (en) * 1964-07-01 1967-12-05 Bell Telephone Labor Inc Microwave devices utilizing eu-fe garnet containing ga
US3370963A (en) * 1965-03-24 1968-02-27 Bell Telephone Labor Inc Growth of divalent metal aluminates
US3386799A (en) * 1965-11-16 1968-06-04 Bell Telephone Labor Inc Growth of yttrium iron garnet
DE1272800B (de) * 1963-10-04 1968-07-11 Western Electric Co Verfahren zur Zuechtung von Granat-Kristallen
US3404966A (en) * 1964-09-04 1968-10-08 Northeru Electric Company Ltd Melting a ferrous ion containing ferrimagnetic oxide in a ferric ion crucible
US3438723A (en) * 1963-08-26 1969-04-15 Sprague Electric Co Method of preparing +2 valent metal yttrium and rare earth ferrites
US3486937A (en) * 1967-03-24 1969-12-30 Perkin Elmer Corp Method of growing a single crystal film of a ferrimagnetic material
US3516839A (en) * 1967-09-01 1970-06-23 Gen Electric Transparent magnesia-alumina spinel and method
US3645788A (en) * 1970-03-04 1972-02-29 North American Rockwell Method of forming multiple-layer structures including magnetic domains
US3723599A (en) * 1971-08-18 1973-03-27 Bell Telephone Labor Inc Technique for growth of single crystal gallium garnet
US3946124A (en) * 1970-03-04 1976-03-23 Rockwell International Corporation Method of forming a composite structure
US4013501A (en) * 1976-05-27 1977-03-22 Bell Telephone Laboratories, Incorporated Growth of neodymium doped yttrium aluminum garnet crystals
US4199396A (en) * 1976-06-24 1980-04-22 Union Carbide Corporation Method for producing single crystal gadolinium gallium garnet
US4273609A (en) * 1978-10-25 1981-06-16 Sperry Corporation Rinse melt for LPE crystals
US20050022720A1 (en) * 2003-07-31 2005-02-03 Kolis Joseph W. Acentric orthorhombic lanthanide borate crystals, method for making, and applications thereof
US20050022721A1 (en) * 2003-07-31 2005-02-03 Kolis Joseph W. Acentric, rhombohedral lanthanide borate crystals, method for making, and applications thereof
CN110137346A (zh) * 2019-06-18 2019-08-16 西安工业大学 一种锰掺杂铁酸钬HoMnxFe1-xO3磁电材料的制备方法
CN112267146A (zh) * 2020-10-13 2021-01-26 上海应用技术大学 一种采用复合助熔剂生长钇铁石榴石晶体的方法
CN112851348A (zh) * 2021-01-11 2021-05-28 西南科技大学 掺钕钇铁石榴石基陶瓷固化体的制备方法
CN115287759A (zh) * 2022-08-04 2022-11-04 西南应用磁学研究所(中国电子科技集团公司第九研究所) 一种生长大尺寸尖晶石型NiZn铁氧体单晶材料的方法
CN119143186A (zh) * 2024-11-20 2024-12-17 山东建筑大学 一种Au和Co共掺杂的铁酸钬气敏材料及其应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957827A (en) * 1957-04-30 1960-10-25 Bell Telephone Labor Inc Method of making single crystal garnets
US3011868A (en) * 1959-09-15 1961-12-05 Robert E Moore Method of making synthetic mica

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957827A (en) * 1957-04-30 1960-10-25 Bell Telephone Labor Inc Method of making single crystal garnets
US3011868A (en) * 1959-09-15 1961-12-05 Robert E Moore Method of making synthetic mica

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3224843A (en) * 1960-06-30 1965-12-21 Owens Corning Fiberglass Corp Separation of crystals from a boric anhydride matrix
US3150925A (en) * 1961-04-20 1964-09-29 Richard J Gambino Method of growing single crystals
US3226183A (en) * 1961-06-12 1965-12-28 Bertaut Erwin Felix Preparation of monocrystals of rare earth manganites
US3149910A (en) * 1962-06-04 1964-09-22 Tauber Arthur Method of growing single crystals
US3162603A (en) * 1963-02-01 1964-12-22 Jack A Kohn Method of growing iridium substituted single crystal using bismuth oxide flux
US3305301A (en) * 1963-04-03 1967-02-21 Bell Telephone Labor Inc Process for the growth of ordered lithium ferrite
US3438723A (en) * 1963-08-26 1969-04-15 Sprague Electric Co Method of preparing +2 valent metal yttrium and rare earth ferrites
DE1272800B (de) * 1963-10-04 1968-07-11 Western Electric Co Verfahren zur Zuechtung von Granat-Kristallen
US3356929A (en) * 1964-07-01 1967-12-05 Bell Telephone Labor Inc Microwave devices utilizing eu-fe garnet containing ga
US3404966A (en) * 1964-09-04 1968-10-08 Northeru Electric Company Ltd Melting a ferrous ion containing ferrimagnetic oxide in a ferric ion crucible
US3370963A (en) * 1965-03-24 1968-02-27 Bell Telephone Labor Inc Growth of divalent metal aluminates
US3386799A (en) * 1965-11-16 1968-06-04 Bell Telephone Labor Inc Growth of yttrium iron garnet
US3486937A (en) * 1967-03-24 1969-12-30 Perkin Elmer Corp Method of growing a single crystal film of a ferrimagnetic material
US3516839A (en) * 1967-09-01 1970-06-23 Gen Electric Transparent magnesia-alumina spinel and method
US3645788A (en) * 1970-03-04 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
US3723599A (en) * 1971-08-18 1973-03-27 Bell Telephone Labor Inc Technique for growth of single crystal gallium garnet
US4013501A (en) * 1976-05-27 1977-03-22 Bell Telephone Laboratories, Incorporated Growth of neodymium doped yttrium aluminum garnet crystals
US4199396A (en) * 1976-06-24 1980-04-22 Union Carbide Corporation Method for producing single crystal gadolinium gallium garnet
US4273609A (en) * 1978-10-25 1981-06-16 Sperry Corporation Rinse melt for LPE crystals
US20050022721A1 (en) * 2003-07-31 2005-02-03 Kolis Joseph W. Acentric, rhombohedral lanthanide borate crystals, method for making, and applications thereof
US20050022720A1 (en) * 2003-07-31 2005-02-03 Kolis Joseph W. Acentric orthorhombic lanthanide borate crystals, method for making, and applications thereof
CN110137346A (zh) * 2019-06-18 2019-08-16 西安工业大学 一种锰掺杂铁酸钬HoMnxFe1-xO3磁电材料的制备方法
CN110137346B (zh) * 2019-06-18 2023-04-18 西安工业大学 一种锰掺杂铁酸钬HoMnxFe1-xO3磁电材料的制备方法
CN112267146A (zh) * 2020-10-13 2021-01-26 上海应用技术大学 一种采用复合助熔剂生长钇铁石榴石晶体的方法
CN112851348A (zh) * 2021-01-11 2021-05-28 西南科技大学 掺钕钇铁石榴石基陶瓷固化体的制备方法
CN115287759A (zh) * 2022-08-04 2022-11-04 西南应用磁学研究所(中国电子科技集团公司第九研究所) 一种生长大尺寸尖晶石型NiZn铁氧体单晶材料的方法
CN115287759B (zh) * 2022-08-04 2024-01-16 西南应用磁学研究所(中国电子科技集团公司第九研究所) 一种生长大尺寸尖晶石型NiZn铁氧体单晶材料的方法
CN119143186A (zh) * 2024-11-20 2024-12-17 山东建筑大学 一种Au和Co共掺杂的铁酸钬气敏材料及其应用

Also Published As

Publication number Publication date
BE603732A (fr) 1961-09-01
FR1289841A (fr) 1962-04-06
GB912799A (en) 1962-12-12

Similar Documents

Publication Publication Date Title
US3079240A (en) Process of growing single crystals
SAVAGE et al. Growth and properties of single crystals of hexagonal ferrites
US2957827A (en) Method of making single crystal garnets
Korczak et al. Liquid encapsulated Czochralski growth of silver thiogallate
Van Uitert et al. Garnets for bubble domain devices
GB1156199A (en) Improvements in or relating to Dielectric Materials with a Stable Dielectric Constant at High Temperature
US3281363A (en) Bismuth-containing garnets and their preparation
US3117934A (en) Garnet growth from barium oxide-boron oxide flux
US3057677A (en) Yttrium and rare earth borates
US3050407A (en) Single crystal garnets
Chen et al. Phase diagram and single crystal growth of (La, Sr) 2CuO4 from CuO solution
US5466388A (en) Material for magnetostatic-wave devices
US4499061A (en) Strontium ferrite borate
US3370963A (en) Growth of divalent metal aluminates
Zhang et al. Phases transition, component variation and valence of Tb element during terbium gallium garnet polycrystalline synthesization
JPH034518B2 (fr)
Wanklyn et al. Flux growth of rare earth silicates and aluminosilicates
US3305301A (en) Process for the growth of ordered lithium ferrite
US5043231A (en) Gadolinium-lutetium-gallium garnet crystal, process for its production and substrate for magneto-optical device made thereof
JPH09328396A (ja) 磁気光学素子の基板用ガーネット結晶及びその製造法
Quon et al. Effect of volatilization loss in flux crystallization of YFeO3 OR Y3FeO12
US3075831A (en) Growth of single crystals of corundum and gallium oxide
US3051656A (en) Method of preparing magnetic garnet crystals
US3386799A (en) Growth of yttrium iron garnet
US3380919A (en) Preparation of ferromagnetic nimno