CN114150365A - Preparation method of large-size yttrium iron garnet single crystal - Google Patents
Preparation method of large-size yttrium iron garnet single crystal Download PDFInfo
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- CN114150365A CN114150365A CN202111271504.3A CN202111271504A CN114150365A CN 114150365 A CN114150365 A CN 114150365A CN 202111271504 A CN202111271504 A CN 202111271504A CN 114150365 A CN114150365 A CN 114150365A
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- 239000013078 crystal Substances 0.000 title claims abstract description 123
- 239000002223 garnet Substances 0.000 title claims abstract description 60
- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 22
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 229910009493 Y3Fe5O12 Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical group F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims description 2
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 7
- 239000011162 core material Substances 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000000411 transmission spectrum Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005350 ferromagnetic resonance Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
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- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 239000012856 weighed raw material Substances 0.000 description 1
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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
- 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
-
- 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
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- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a preparation method of a large-size yttrium iron garnet single crystal, which comprises the following steps: 1) obtaining a mixed raw material containing yttrium oxide, iron oxide and composite fluxing agent; the composite fluxing agent contains Bi2O3(ii) a 2) And growing by a top seed crystal method to obtain the yttrium iron garnet single crystal material. The crystal has excellent magnetic characteristics and stable physical and chemical properties, is a core material of an isolator, a circulator, a phase shifter and a filter, and has a wide application market in the field of 5G communication. The invention is provided by containing Bi2O3The composite fluxing agent greatly reduces the crystal growth temperature, obtains large-size yttrium iron garnet single crystals with the size of 50mm multiplied by 42mm multiplied by 11mm and the weight of 74.72g, has good crystal uniformity and no cracking or inclusion, and the crystal quality completely meets the application of microwave and magneto-optical devices.
Description
Technical Field
The invention relates to a large-size yttrium iron garnet single crystal material and a preparation method thereof, belonging to the field of crystal growth and functional materials.
Background
Garnet ferrite single crystals are core materials of microwave and magneto-optical devices, and have wide application markets in the fields of aerospace, electronic information, mobile communication and the like. The microwave and magneto-optical ferrite device mainly relates to devices such as an isolator, a circulator, a phase shifter, a filter and the like, has the most important characteristics of nonreciprocal transmission, ferromagnetic resonance, electrically controllable characteristics and the like, and is a key core device for realizing the functions of isolation, phase shift, switching, modulation, amplification and the like of microwave transmission in a microwave system. With the increasing application requirements, the development of high power, high temperature stability and low loss materials has become a key technical problem for improving the performance of devices.
Among the gyromagnetic materials, garnet-type, spinel-type, and hexagonal magnetoplumbite-type materials are the most widely used materials in microwave ferrites. The garnet ferrite has the characteristics of narrow ferromagnetic resonance line width delta H, low dielectric loss, small magnetocrystalline anisotropy and the like, and becomes a preferred key core material of a device. The chemical formula of the garnet type ferrite structure is Re3Fe5O12Wherein Y is3Fe5O12Is the most representative garnet-type microwave and magneto-optical material. In recent years, with the development of consumer technologies such as electronic information and mobile communication, higher demands have been made on garnet-type microwave ferrite materials, and small line width and high dielectric constant garnet materials have become one of the hot spots in the field of microwave ferrite research, in addition to the need to pay attention to microwave magnetic loss. Therefore, the development and growth of garnet single crystal materials with large size, narrow line width and high dielectric constant have great application value.
Disclosure of Invention
The invention aims to find a preparation process capable of realizing the growth of a large-size yttrium iron garnet single crystal, so as to solve the problems of small size, poor uniformity and the like of the yttrium iron garnet single crystal grown by a molten salt growth method, and provide a new thought for the growth of the large-size yttrium iron garnet single crystal.
In order to solve the above-mentioned problem that the yttrium iron garnet single crystal is difficult to grow by the molten salt method, the present inventors have conducted intensive research and study on a flux system for yttrium iron garnet single crystal growth.
A preparation method of a large-size yttrium iron garnet single crystal comprises the following steps:
1) obtaining a mixed raw material containing yttrium oxide, iron oxide and composite fluxing agent;
the composite flux contains Bi2O3；
2) And growing by a top seed crystal method to obtain the yttrium iron garnet single crystal material.
Optionally, said step 1) is according to formula Y3Fe5O12Yttrium oxide and iron oxide were weighed out in the stoichiometric ratios of the elements shown.
Optionally, the composite flux comprises a Z1 component, a Z2 component, and a Z3 component; the Z1 component is selected from PbF2、PbO、Pb3O4At least one of; the Z2 component is selected from B2O3And/or H3BO3(ii) a The component Z3 is Bi2O3；
Alternatively, 4-6 molar parts of the Z1 component, 2-3 molar parts of the Z2 component and 1-2 molar parts of the Z3 component.
Optionally, the mass fraction of the composite fluxing agent in the mixed raw materials in the step 1) is 68.25-73.78%.
Optionally, the step 2) specifically includes the following steps:
(a) putting the mixed raw materials into a crucible for melting to obtain a melt;
(b) reducing the melt to saturation temperature, introducing seed crystals for crystal growth; the crystal rotation rate in the crystal growth process is 20-30 rpm, and the cooling rate is 0.25-2 ℃/day;
(c) and after the crystal growth is finished, annealing to room temperature at a cooling rate of 50-60 ℃/h to obtain the yttrium iron garnet crystal material.
Optionally, a platinum crucible is used in step (a).
It should be noted that bismuth oxide can form an alloy with platinum at high temperature, which can cause damage to the platinum pot. Therefore, the content of bismuth oxide needs to be strictly controlled in the experimental process, and the corrosion of bismuth oxide to the platinum crucible can be effectively reduced or even avoided.
Optionally, in the step (a), the weighed raw materials are placed in a mixer to be fully mixed for 24 hours, so as to obtain a mixed raw material.
Optionally, the temperature of the material melting in the step (a) is 1000-1100 ℃.
Optionally, the temperature is kept for 48-72 hours in the material melting process in the step (a).
Optionally, the seed crystal is introduced in step (b) by suspending a yttrium iron garnet seed crystal in the center of the melt level;
optionally, the seed crystal direction in the step (b) is a [110] or [211] direction.
Optionally, the determination method of the supersaturation temperature in the step (b) is to cool at a rate of 30-50 ℃/day, and the temperature of the yttrium iron garnet seed crystal which is not melted and does not grow for 3-5 days is used as the supersaturation temperature of the melt in the cooling process.
The application also provides the application of the single crystal material prepared by the method in microwave devices or magneto-optical devices.
Optionally, the microwave device or the magneto-optical device comprises a circulator, a filter, an isolator.
The crystal growth furnace adopted by the invention is a resistance heating element, and the heating element is a resistance wire or a silicon-carbon rod or a silicon-molybdenum rod.
The application has the following beneficial effects:
the invention is provided by containing Bi2O3The composite fluxing agent greatly reduces the crystal growth temperature, obtains large-size yttrium iron garnet single crystals with the size of 50mm multiplied by 42mm multiplied by 11mm and the weight of 74.72g, has good crystal uniformity and no cracking or inclusion, and the crystal quality completely meets the application of microwave and magneto-optical devices. Bismuth oxide is added into a traditional lead oxide and boron oxide fluxing agent system in a certain proportion, so that the growth temperature of the yttrium iron garnet crystal is greatly reduced, the energy consumption in the crystal growth process is reduced, and the crystal growth cost is reduced. On the other hand, although the nonmagnetic ion Bi3+ 
Radius of greater than Y3+ 
Ionic radius of (B), but Bi3+Can realize the pair Y3Fe5O12Middle dodecahedron position Y3+The dielectric constant and the Curie temperature of the material can be effectively improved by replacing ions by a small amount.
The yttrium iron garnet single crystal disclosed by the invention is stable in structure and excellent in magnetic property. X-ray powder diffraction indicates that the crystal has a typical yttrium iron garnet structure at room temperature; the Lambda950 ultraviolet visible near-infrared spectrophotometer shows that the transmittance of the polished wafer is 76.24% at the wavelength of 1200-2300 nm; the dielectric temperature spectrum shows that the dielectric constant at room temperature is 25; the comprehensive physical property tester (PPMS) tests show that the saturation magnetization of the crystal is 25.43 emu/g.
Drawings
FIG. 1 is a yttrium iron garnet single crystal material grown by the top-seed method in example 1.
FIG. 2 is a powder diffraction pattern of the yttrium iron garnet single crystal grown in example 1.
FIG. 3 is a transmission spectrum of the yttrium iron garnet single crystal grown in example 1.
FIG. 4 is a dielectric temperature spectrum of the yttrium iron garnet single crystal grown in example 1.
FIG. 5 is a hysteresis loop of the yttrium iron garnet single crystal grown in example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
In the examples, the test conditions are as follows, unless otherwise specified:
the X-ray powder diffraction spectrum was obtained using a japanese X-ray diffractometer (Rigaku diffractometer, MiniFlex 600); the transmittance was measured using an ultraviolet-visible near-infrared spectrophotometer (Lambda950) manufactured by Perkin Elmer; the dielectric temperature spectrum is measured by an Alpha-A broadband dielectric/impedance analyzer of Novocontrol company in Germany; the saturation magnetization was measured by using a comprehensive physical properties tester (Model 6000) of Quantum Design, USA.
Example 1 large size yttrium iron garnet crystals were grown using a top-seeded method:
starting material Y2O3、Fe2O3And weighing the composite fluxing agent according to the stoichiometric ratio to obtain an initial mixture, wherein the mass fraction of the composite fluxing agent in the mixed raw materials is 73.78%. Wherein the composite fluxing agent comprises Z1 component PbF2Z2 component B2O3And Z3 component Bi2O3And the molar ratio of the component Z1, the component Z2 and the component Z3 is 6:2: 1.
And (3) fully mixing the initial mixture in a mixer for 24 hours, putting the obtained mixed raw material into a platinum crucible, and placing the platinum crucible into a crystal growth furnace at 1050 ℃ for constant temperature 48 hours for melting. Adopting yttrium iron garnet seed crystals to search the supersaturation temperature of the melt, introducing formal seed crystals at 990 ℃, and then slowly cooling for growth; the crystal rotation rate is 30rpm, and the cooling rate is 1 ℃/day; and after the growth is finished, taking the crystal out of the liquid level, cooling and annealing to room temperature at the speed of 50 ℃/h, and finally obtaining the yttrium iron garnet crystal material, wherein the grown single crystal is a poly-crystal with exposed (110) and (211) natural growth surfaces (see figure 1), and the crystal size is 50mm multiplied by 42mm multiplied by 11 mm. The crystal has good quality, no fluxing agent inclusion and good uniformity. The structure is determined and the performance is represented by testing and analyzing the performance of the grown crystal such as X-ray powder diffraction, transmission spectrum, magnetic performance, electrical performance and the like.
Example 2 growth of large size yttrium iron garnet crystals using top seed crystal method:
starting material Y2O3、Fe2O3And weighing the composite fluxing agent according to the stoichiometric ratio to obtain an initial mixture, wherein the mass fraction of the composite fluxing agent in the mixed raw materials is 68.25 percent. Wherein the composite fluxing agent comprises Z1 component PbF2Z2 component B2O3And Z3 component Bi2O3And the molar ratio of the component Z1, the component Z2 and the component Z3 is 4:2: 1.
The initial mixture was put into a blender and mixed thoroughly for 24 hours, and the resulting mixed raw material was put into a platinum crucible and placed in a crystal growth furnace at 1100 ℃ for melting at a constant temperature for 48 hours. Adopting yttrium iron garnet seed crystals to search the supersaturation temperature of the melt, introducing formal seed crystals at the supersaturation temperature of 1040 ℃, and then slowly cooling for growth; the crystal rotation rate is 30rpm, and the cooling rate is 0.25 ℃/day; and after the growth is finished, the crystal is taken out of the liquid level, the temperature is reduced and the crystal is annealed to the room temperature at 50 ℃/h, and the yttrium iron garnet crystal material is finally obtained, wherein the grown single crystal is a poly-crystal with exposed (110) and (211) natural growth surfaces, and the size of the crystal is 19mm multiplied by 5 mm. The crystal has good quality, no fluxing agent inclusion and good component uniformity. The structure of the grown crystal is determined and the performance of the crystal is represented by testing and analyzing the performance of X-ray powder diffraction, transmission spectrum, magnetic performance, electrical performance and the like of the grown crystal.
Example 3 the yttrium iron garnet single crystal obtained in example 1 was subjected to structural and performance tests:
(a) the crystals were cut into small pieces, ground and pulverized into powder for XRD powder diffraction test. The powder diffraction pattern of the yttrium iron garnet single crystal indicates a typical garnet-type structure at room temperature, belonging to the cubic system (see fig. 2).
(b) The obtained yttrium iron garnet single crystal is sliced in the (110) or (211) direction and then subjected to double-sided fine polishing. The transmittance was measured using an ultraviolet visible near infrared spectrophotometer (Lambda 950). The transmittance spectrum shows that the transmittance is as high as 76.24% in the 1200-2300nm wave band (see figure 3).
(c) The obtained yttrium iron garnet single crystal is sliced in the (110) or (211) direction, and then double-side polished and gold-plated. The prepared sample is used for testing the dielectric temperature spectrum. The dielectric temperature spectrum of the yttrium iron garnet single crystal was measured at a temperature of from-30 ℃ to 300 ℃. The dielectric thermogram showed that the yttrium iron garnet single crystal had a dielectric constant of 25 at room temperature (see FIG. 4).
(d) The obtained yttrium iron garnet single crystal was ground into powder for magnetic property test. The hysteresis loop was measured by a comprehensive physical property tester, and the result showed that the saturation magnetization of the crystal was 25.43emu/g (see FIG. 5).
As can be seen from the above examples, the yttrium iron garnet single crystal has a typical garnet structure and belongs to the cubic system; the transmittance of 1200-2300nm waveband is up to 76.24%, the dielectric constant at room temperature is 25, the saturation magnetization is 25.43emu/g, and the crystal has stable physicochemical properties and is easy to process and store, so that the crystal is expected to be applied to devices such as isolators, circulators, phase shifters, filters and the like.
Comparative example 1
Starting material Y2O3、Fe2O3And weighing the composite fluxing agent according to the stoichiometric ratio to obtain an initial mixture, wherein the mass fraction of the composite fluxing agent in the mixed raw materials is 68.58%. Wherein the composite fluxing agent comprises Z1 component PbF2And Z2 component B2O3And the molar ratio of the component Z1 to the component Z2 is 6: 2.
And (3) fully mixing the initial mixture in a mixer for 24 hours, putting the obtained mixed raw materials into a platinum crucible, and placing the platinum crucible in a crystal growth furnace at 1150 ℃ for melting for 72 hours at constant temperature. Adopting yttrium iron garnet seed crystals to search the supersaturation temperature of the melt, introducing formal seed crystals at 1080 ℃, and then slowly cooling for growth; the crystal rotation rate is 30rpm, and the cooling rate is 2 ℃/day; and after the growth is finished, taking the crystal out of the liquid level, cooling and annealing to room temperature at the speed of 50 ℃/h to finally obtain the yttrium iron garnet crystal material, wherein the grown single crystal is a poly-crystal with exposed (110) and (211) natural growth surfaces, and the size of the crystal is 9mm multiplied by 10mm multiplied by 4 mm. The crystal has good quality, no fluxing agent inclusion and good uniformity. The structure is determined and the performance is represented by testing and analyzing the performance of the grown crystal such as X-ray powder diffraction, transmission spectrum, magnetic performance, electrical performance and the like.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a large-size yttrium iron garnet single crystal is characterized by comprising the following steps:
1) obtaining a mixed raw material containing yttrium oxide, iron oxide and composite fluxing agent;
the composite fluxing agent contains Bi2O3；
2) And growing by a top seed crystal method to obtain the yttrium iron garnet single crystal material.
2. The method for preparing a large-sized yttrium-iron-garnet single crystal according to claim 1, wherein the step 1) is performed according to formula Y3Fe5O12Yttrium oxide and iron oxide were weighed out in the stoichiometric ratios of the elements shown.
3. The method for preparing a large-sized yttrium iron garnet single crystal according to claim 1, wherein the composite flux in the step 1) comprises a Z1 component, a Z2 component and a Z3 component; the Z1 component is selected from PbF2、PbO、Pb3O4At least one of; the Z2 component is selected from B2O3And/or H3BO3(ii) a The component Z3 is Bi2O3；
Preferably, the composite fluxing agent comprises 4-6 molar parts of the Z1 component, 2-3 molar parts of the Z2 component and 1-2 molar parts of the Z3 component.
4. The method for preparing a large-size yttrium iron garnet single crystal according to claim 1, wherein the mass fraction of the composite flux in the mixed raw materials in the step 1) is 68.25-73.78%.
5. The method for preparing a large-size yttrium iron garnet single crystal according to claim 1, wherein the step 2) specifically comprises the following steps:
(a) putting the mixed raw materials into a platinum crucible for melting to obtain a melt;
(b) reducing the temperature of the melt to a supersaturation temperature 990-1040 ℃; introducing seed crystals for crystal growth; the crystal rotation rate in the crystal growth process is 20-30 rpm, and the cooling rate is 0.25-2 ℃/day;
(c) and after the crystal growth is finished, annealing to room temperature at a cooling rate of 50-60 ℃/h to obtain the yttrium iron garnet single crystal material.
6. The method for growing the large-size yttrium iron garnet single crystal material according to claim 5, wherein the temperature of the material in the step (a) is 1000-1100 ℃.
7. The method of preparing a large-sized yttrium iron garnet single crystal according to claim 5, wherein the seed crystal is introduced in the step (b) by suspending the yttrium iron garnet seed crystal in the center of the melt surface;
preferably, the seed crystal direction in the step (b) is a [110] or [211] direction.
8. The method for preparing a large-size yttrium iron garnet single crystal according to claim 5, wherein the supersaturation temperature in the step (b) is determined by cooling at a rate of 30-50 ℃/day, and the temperature at which the yttrium iron garnet seed crystal does not melt and grow for 3-5 days is used as the supersaturation temperature of the melt in the cooling process.
9. A single crystal material, characterized in that it is an yttrium iron garnet single crystal material prepared according to the method of any one of claims 1 to 8.
10. Use of the single crystal material of claim 9 in a microwave device or a magneto-optical device.
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| CN115491748A (en) * | 2022-11-01 | 2022-12-20 | 安徽科瑞思创晶体材料有限责任公司 | Bismuth yttrium-doped iron garnet, crystal growth method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329184A (en) * | 2000-06-06 | 2002-01-02 | 株式会社东金 | Bismuth-substituted garnets thick film material and producing method thereof |
| CN1878892A (en) * | 2003-12-11 | 2006-12-13 | 金裕坤 | Method for preparing garnet single crystal and garnet single crystal prepared thereby |
| CN101061263A (en) * | 2004-11-19 | 2007-10-24 | Tdk株式会社 | Magnetic garnet single crystal, optical device using same and method for producing single crystal |
| CN104073879A (en) * | 2013-03-28 | 2014-10-01 | 株式会社Granopt | Bismuth-replacement RIG (rare earth iron garnet) monocrystal and manufacturing method thereof |
| CN110820045A (en) * | 2019-12-11 | 2020-02-21 | 上海应用技术大学 | Preparation method of rare earth garnet single crystal |
| CN110904506A (en) * | 2019-12-04 | 2020-03-24 | 上海应用技术大学 | Preparation method of rare earth replacement yttrium iron garnet crystal |
| CN112267146A (en) * | 2020-10-13 | 2021-01-26 | 上海应用技术大学 | Method for growing yttrium iron garnet crystal by adopting composite fluxing agent |
-
2021
- 2021-10-29 CN CN202111271504.3A patent/CN114150365A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329184A (en) * | 2000-06-06 | 2002-01-02 | 株式会社东金 | Bismuth-substituted garnets thick film material and producing method thereof |
| CN1878892A (en) * | 2003-12-11 | 2006-12-13 | 金裕坤 | Method for preparing garnet single crystal and garnet single crystal prepared thereby |
| CN101061263A (en) * | 2004-11-19 | 2007-10-24 | Tdk株式会社 | Magnetic garnet single crystal, optical device using same and method for producing single crystal |
| CN104073879A (en) * | 2013-03-28 | 2014-10-01 | 株式会社Granopt | Bismuth-replacement RIG (rare earth iron garnet) monocrystal and manufacturing method thereof |
| CN110904506A (en) * | 2019-12-04 | 2020-03-24 | 上海应用技术大学 | Preparation method of rare earth replacement yttrium iron garnet crystal |
| CN110820045A (en) * | 2019-12-11 | 2020-02-21 | 上海应用技术大学 | Preparation method of rare earth garnet single crystal |
| CN112267146A (en) * | 2020-10-13 | 2021-01-26 | 上海应用技术大学 | Method for growing yttrium iron garnet crystal by adopting composite fluxing agent |
Non-Patent Citations (1)
| Title |
|---|
| 徐孝贞等: "Y3-xBixFe5O12的晶体生长", 《物理学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115491748A (en) * | 2022-11-01 | 2022-12-20 | 安徽科瑞思创晶体材料有限责任公司 | Bismuth yttrium-doped iron garnet, crystal growth method and application thereof |
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