CN114182339A - Method for growing rare earth doped yttrium iron garnet single crystal material - Google Patents
Method for growing rare earth doped yttrium iron garnet single crystal material Download PDFInfo
- Publication number
- CN114182339A CN114182339A CN202111274236.0A CN202111274236A CN114182339A CN 114182339 A CN114182339 A CN 114182339A CN 202111274236 A CN202111274236 A CN 202111274236A CN 114182339 A CN114182339 A CN 114182339A
- Authority
- CN
- China
- Prior art keywords
- iron garnet
- rare earth
- yttrium iron
- single crystal
- doped yttrium
- 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.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 144
- 239000002223 garnet Substances 0.000 title claims abstract description 54
- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title claims description 40
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract 2
- 238000001816 cooling Methods 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000004907 flux Effects 0.000 claims description 11
- -1 rare earth ion Chemical class 0.000 claims description 11
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 6
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052697 platinum Inorganic materials 0.000 abstract description 8
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000005291 magnetic effect Effects 0.000 description 8
- 230000005415 magnetization Effects 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000000411 transmission spectrum Methods 0.000 description 6
- 230000005389 magnetism Effects 0.000 description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical class [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000012856 weighed raw material Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 229910009493 Y3Fe5O12 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000002902 ferrimagnetic material Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
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
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
- C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
-
- 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
-
- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a method for growing rare earth doped yttrium iron garnet single crystals, belonging to the field of crystal growth and functional materials. The crystal has a typical garnet structure with the chemical formula RexY3‑xFe5O12Wherein rare earth ion (Re)3+) The content of x is more than or equal to 0.1 and less than or equal to 3. The invention adopts a top seed crystal method to grow the crystal, and the specific steps comprise: weighing the raw materials according to the stoichiometric ratio of each element, fully mixing the raw materials in a mixer, putting the mixed raw materials into a platinum crucible for melting, and introducing seed crystals for crystal growth to obtain the rare earth doped yttrium iron garnet crystal.
Description
Technical Field
The invention relates to a method for growing rare earth doped yttrium iron garnet single crystals by adopting a lead-free composite fluxing agent, belonging to the field of crystal growth and functional materials.
Background
The magneto-optical material has the characteristics of unique magneto-optical effect, magnetic performance, optical nonreciprocal property and the like in a near infrared band, has the characteristics of high transmittance, ultralow absorption, large Verdet constant and the like, and becomes a key core material of devices such as a magneto-optical isolator for optical communication and the like. With the arrival of the 5G information high-speed era, the capacity and the using amount of the magneto-optical isolator in China are increased year by year, but the core magneto-optical single crystal film material completely depends on import. Therefore, the development of magneto-optical single crystal materials which have the same performance as commercial magneto-optical single crystal films, have excellent magneto-optical effect and can realize large-size, high-uniformity and mass production is urgent.
The garnet type ferrite material has small absorption loss in near infrared band and stable physical and chemical properties, is an ideal magneto-optical material, and has a chemical molecular formula of RexY3-xFe5O12And Re represents a lanthanoid rare earth element. Wherein, yttrium iron garnet Y3Fe5O12The (YIG) crystal is a ferrimagnetic material with excellent performance and belongs to a cubic crystal system. The magnetism of YIG crystal is derived from Fe at a position and d position3+And O2Antiferromagnetic coupling by superexchange between ions. When c is nonmagnetic Y3+When the ion is substituted by rare earth ion, Re at c position3+Magnetization with Fe at d-and a-positions3+And the magnetization intensity obtained after coupling is coupled again, and the finally obtained net magnetization intensity is the saturation magnetization intensity of the rare earth doped YIG crystal. Therefore, the modified YIG single crystal material with excellent magneto-optical performance and appropriate magnetic properties such as temperature, wavelength and the like can be obtained by doping the rare earth ions. Aiming at the problems of small size, poor uniformity and the like existing in the existing rare earth ion doped YIG single crystal growth, the invention adopts a top seed crystal method to grow the single crystal material, has simple crystal growth process, is stable and reliable, can realize batch production, is expected to break the situation that magneto-optical materials for optical communication in China all depend on foreign import, and promotes the independent process in the optical communication field in China.
Disclosure of Invention
The invention aims to solve the problems of small size, poor uniformity and the like of rare earth ion doped yttrium iron garnet single crystal grown by a molten salt growth method.
A method for growing rare earth doped yttrium iron garnet single crystal material comprises the following steps:
1) obtaining mixed raw materials containing lanthanide oxide, yttrium oxide, iron oxide and composite fluxing agent;
the composite fluxing agent comprises a Z1 component, a Z2 component and a Z3 component; the Z1 component is selected from B2O3And/or H3BO3(ii) a The Z2 component is selected from BaCl2、BaF2At least one of BaO; the component Z3 is Bi2O3；
2) Growing the rare earth doped yttrium iron garnet single crystal material by a top seed crystal method.
Alternatively, in step 1) according to formula RexY3-xFe5O12Stoichiometric ratios of elements shown lanthanide oxides, yttrium oxides, iron oxides
Wherein Re is selected from at least one element of the lanthanide series;
0.1≤x≤3。
alternatively, 0.5 ≦ x ≦ 2.
Optionally, the composite fluxing agent in the step 1) comprises 6-8 molar parts of a Z1 component, 9-12 molar parts of a Z2 component and 1-2 molar parts of a Z3 component.
Optionally, the mass fraction of the composite fluxing agent system in the step 1) in the initial mixture is 76.94-80.91%.
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) introducing seed crystals for crystal growth under the condition that the temperature is 5-10 ℃ higher than the supersaturation temperature, wherein the supersaturation temperature is 1080-; 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 20-30 ℃/h to obtain the rare earth ion doped yttrium iron garnet crystal material.
Optionally, a platinum crucible is used in step (a).
It should be noted that bismuth oxide in the flux forms a bismuth simple substance at high temperature, and further forms an alloy with platinum, causing platinum corrosion, so that the bismuth oxide content and the crystal growth temperature need to be strictly controlled in the experimental process.
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 crystal growth furnace is a resistance heating element, and the heating element is a resistance wire or a silicon-carbon rod or a silicon-molybdenum rod.
Optionally, the temperature of the material melting in the step (a) is 1100-1200 ℃.
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 a magneto-optical single crystal material which contains the rare earth doped yttrium iron garnet single crystal material prepared by the method.
The application also provides the application of the magneto-optical single crystal material in optical communication devices.
Optionally, the magneto-optical single crystal material is applied to a magneto-optical isolator.
The application has the following beneficial effects:
the rare earth doped yttrium iron garnet single crystal material grown by the top seed crystal method is single crystal, has no inclusion, no crack and good uniformity, has excellent magnetics and magneto-optical characteristics, and can be applied to the field of optical communication such as magneto-optical isolators and the like. The invention is provided by containing Bi2O3The lead-free composite fluxing agent solves the problems ofThe method has the advantages of solving the problem of environmental pollution caused by a lead-containing fluxing agent system, greatly reducing the crystal growth temperature, reducing the energy consumption in the crystal growth process, along with simple, stable and reliable crystal growth process and realization of batch production.
In addition, nonmagnetic ions
Can replace twelve facial positions in a small amount
Ions, thereby further increasing the Faraday rotation angle of the rare earth doped yttrium iron garnet single crystal. The rare earth ion doped yttrium iron garnet single crystal has stable physical and chemical properties and excellent magnetic and magneto-optical properties. X-ray powder diffraction showed that the crystals had a typical garnet structure at room temperature. The Lambda950 ultraviolet visible near infrared spectrophotometer shows that the transmittance of the polished wafer is as high as 72.81 percent at 1550nm waveband; comprehensive physical property tester (PPMS) tests show that the saturation magnetization of the crystal is 9.42emu/g under a 600Oe magnetic field.
Drawings
FIG. 1 shows Dy grown by the top-seed method in example 13+Photograph of doped yttrium iron garnet crystal.
FIG. 2 shows Er grown by the top-seeded method in example 33+Photograph of doped yttrium iron garnet crystal.
FIG. 3 shows Dy in example 13+Powder diffraction pattern of doped yttrium iron garnet single crystal.
FIG. 4 shows Dy in example 13+Transmission spectrum of doped yttrium iron garnet single crystal.
FIG. 5 shows Dy in example 13+A hysteresis loop of a doped yttrium iron garnet single crystal.
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:
x-ray powder diffraction was measured 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 saturation magnetization was measured by using a comprehensive physical properties tester (Model 6000) of Quantum Design, USA.
Example 1 growth of Dy Using a Top-seeded method3+Doped yttrium iron garnet crystal:
(1) according to the chemical formula Dy2YFe5O12Dy was measured as the stoichiometric ratio of each element shown2O3、Fe2O3、Y2O3And a flux raw material, wherein the mass fraction of the composite flux in the mixed raw material is 73.55%. The composite fluxing agent comprises Z1 component B2O3Z2 component BaF2And Z3 component Bi2O3Wherein the molar ratio of the component Z1 to the component Z2 to the component Z3 is 6:9: 1. Putting the weighed raw materials into a mixer to be fully mixed for 24 hours to obtain mixed raw materials;
(2) putting the mixed raw materials into a platinum crucible for melting to obtain a melt; wherein the temperature of the material is 1130 ℃;
(3) cooling at the speed of 30-50 ℃/day, and searching for the accurate supersaturation temperature of the melt by using yttrium iron garnet seed crystals in the cooling process; taking the unmelted and non-growing temperature of the seed crystal for 3-5 days as the supersaturation temperature of the melt;
(4) introducing formal seed crystals at the supersaturation temperature of 1065 ℃ for crystal growth, wherein the direction of the seed crystals is [110] or [211 ]; the crystal rotation rate in the crystal growth process is 30rpm, and the cooling rate is 0.5 ℃/day;
(5) and (3) after the crystal growth is finished, annealing to room temperature at a cooling rate of 30 ℃/h to obtain the rare earth ion doped yttrium iron garnet crystal material (shown in figure 1), wherein the crystal size is 14mm multiplied by 10mm multiplied by 4 mm. The structure of the grown crystal is determined and the performance is characterized by performing performance test analysis on the grown crystal such as X-ray powder diffraction, transmission spectrum, magnetism and the like.
Example 2 Ho growth Using Top-seeded method3+Doped yttrium iron garnet crystal:
(1) according to the chemical formula Ho0.5Y2.5Fe5O12Stoichiometric ratio of the elements shown Ho2O3、Fe2O3、Y2O3And a flux raw material, wherein the mass fraction of the composite flux in the mixed raw material is 76.03%. The composite fluxing agent comprises Z1 component B2O3Z2 component BaF2And Z3 component Bi2O3Wherein the molar ratio of the component Z1 to the component Z2 to the component Z3 is 6:9: 1. Putting the weighed raw materials into a mixer to be fully mixed for 24 hours to obtain mixed raw materials;
(2) putting the mixed raw materials into a platinum crucible for melting to obtain a melt; wherein the temperature of the material is 1150 ℃;
(3) cooling at the speed of 50 ℃/day, and searching the accurate supersaturation temperature of the melt by using yttrium iron garnet seed crystals in the cooling process; taking the unmelted and non-growing temperature of the seed crystal for 3-5 days as the supersaturation temperature of the melt;
(4) introducing formal seed crystals for crystal growth at the supersaturation temperature of 1058 ℃, wherein the direction of the seed crystals is [110] or [211 ]; the crystal rotation rate in the crystal growth process is 30rpm, and the cooling rate is 1.5 ℃/day;
(5) and (3) after the crystal growth is finished, annealing to room temperature at a cooling rate of 30 ℃/h to obtain the rare earth ion doped yttrium iron garnet crystal material, wherein the crystal size is 22mm multiplied by 18mm multiplied by 4 mm. . The structure of the grown crystal is determined and the performance is characterized by performing performance test analysis on the grown crystal such as X-ray powder diffraction, transmission spectrum, magnetism and the like.
Example 3 growth of Er Using the Top-seeded method3+Doped yttrium iron garnet crystal:
(1) according to the chemical formula Er0.5Y2.5Fe5O12Er is a stoichiometric weight of each element shown2O3、Fe2O3、Y2O3And a flux raw material, wherein the mass fraction of the composite flux in the mixed raw material is 76.01%. The composite fluxing agent comprises Z1 component BaF2Z2 component B2O3And Z3 component Bi2O3Wherein the molar ratio of the component Z1 to the component Z2 to the component Z3 is 6:9: 1. Putting the weighed raw materials into a mixer to be fully mixed for 24 hours to obtain mixed raw materials;
(2) putting the mixed raw materials into a platinum crucible for melting to obtain a melt; wherein the temperature of the material is 1160 ℃;
(3) cooling at the speed of 30-50 ℃/day, and searching for the accurate supersaturation temperature of the melt by using yttrium iron garnet seed crystals in the cooling process; taking the unmelted and non-growing temperature of the seed crystal for 3-5 days as the supersaturation temperature of the melt;
(4) introducing formal seed crystals at the supersaturation temperature of 1049 ℃ to carry out crystal growth, wherein the direction of the seed crystals is [110] or [211 ]; the crystal rotation rate in the crystal growth process is 20rpm, and the cooling rate is 1 ℃/day;
(5) and (3) after the crystal growth is finished, annealing to room temperature at a cooling rate of 25 ℃/h to obtain the rare earth ion doped yttrium iron garnet crystal material (shown in figure 2), wherein the crystal size is 16mm multiplied by 5 mm. The structure of the grown crystal is determined and the performance is characterized by performing performance test analysis on the grown crystal such as X-ray powder diffraction, transmission spectrum, magnetism and the like.
Example 4 Dy obtained in example 1 was used3+Carrying out structure and performance tests on the doped yttrium iron garnet single crystal:
(a) the crystals were cut into small pieces and ground into powders for XRD powder diffraction testing. 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. 3).
(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 transmission spectrum showed a transmission as high as 72.81% at 1550nm (see FIG. 4).
(c) 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 9.42emu/g under a magnetic field of 600Oe (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 the crystal in 1550nm waveband is as high as 72.81%, the saturation magnetization of the crystal under a 600Oe magnetic field is 9.42emu/g, and the crystal has stable physical and chemical properties and is easy to process and store, so that the crystal is expected to be applied to optical communication devices such as a magneto-optical isolator and the like.
Comparative example 1
(1) According to the chemical formula Ho0.5Y2.5Fe5O12Stoichiometric ratio of the elements shown Ho2O3、Fe2O3、Y2O3And a flux raw material, wherein the mass fraction of the composite flux in the mixed raw material is 72%. The composite fluxing agent comprises Z1 component B2O3And Z2 component BaF2Wherein the molar ratio of the component Z1 to the component Z2 is 6: 9. Putting the weighed raw materials into a mixer to be fully mixed for 24 hours to obtain mixed raw materials;
(2) putting the mixed raw materials into a platinum crucible for melting to obtain a melt; wherein the temperature of the material is 1190 ℃;
(3) cooling at the rate of 40 ℃/day, and searching the accurate supersaturation temperature of the melt by using yttrium iron garnet seed crystals in the cooling process; taking the unmelted and non-growing temperature of the seed crystal for 3-5 days as the supersaturation temperature of the melt;
(4) introducing formal seed crystals at the supersaturation temperature of 1163 ℃ to carry out crystal growth, wherein the direction of the seed crystals is [110] or [211 ]; the crystal rotation rate in the crystal growth process is 30rpm, and the cooling rate is 0.5 ℃/day;
(5) and (3) after the crystal growth is finished, annealing to room temperature at a cooling rate of 30 ℃/h to obtain the rare earth ion doped yttrium iron garnet crystal material, wherein the crystal size is 12mm multiplied by 10mm multiplied by 4 mm. The structure of the grown crystal is determined and the performance is characterized by performing performance test analysis on the grown crystal such as X-ray powder diffraction, transmission spectrum, magnetism and the like.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for growing rare earth doped yttrium iron garnet single crystal material is characterized by comprising the following steps:
1) obtaining mixed raw materials containing lanthanide oxide, yttrium oxide, iron oxide and composite fluxing agent;
the composite fluxing agent comprises a Z1 component, a Z2 component and a Z3 component; the Z1 component is selected from B2O3And/or H3BO3(ii) a The Z2 component is selected from BaCl2、BaF2At least one of BaO; the component Z3 is Bi2O3；
2) Growing the rare earth doped yttrium iron garnet single crystal material by a top seed crystal method.
2. The method for growing a rare earth-doped yttrium iron garnet single crystal material according to claim 1, wherein the step 1) is performed according to a chemical formula RexY3-xFe5O12Weighing lanthanide oxide, yttrium oxide and iron oxide according to the stoichiometric ratio of the elements;
wherein Re is selected from at least one element of the lanthanide series; x is more than or equal to 0.1 and less than or equal to 3;
preferably, 0.5. ltoreq. x.ltoreq.2.
3. The method for growing a rare earth-doped yttrium iron garnet single crystal material according to claim 1, wherein the composite flux in the step 1) comprises 6-8 mol parts of Z1 component, 9-12 mol parts of Z2 component and 1-2 mol parts of Z3 component.
4. The method for growing the rare earth-doped yttrium iron garnet single crystal material as claimed in claim 1, wherein the mass fraction of the composite flux in the mixed raw materials in the step 1) is 76.94-80.91%.
5. The method for growing a rare earth-doped yttrium iron garnet single crystal material according to claim 1, wherein the step 2) comprises the following steps:
(a) putting the mixed raw materials into a crucible for melting to obtain a melt;
(b) introducing seed crystals for crystal growth under the condition that the temperature is 5-10 ℃ higher than the supersaturation temperature, wherein the supersaturation temperature is 1080-; 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 20-30 ℃/h to obtain the rare earth ion doped yttrium iron garnet crystal material.
6. The method for growing a rare earth-doped yttrium iron garnet single crystal material according to claim 5, wherein the temperature of the material in the step (a) is 1100-1200 ℃.
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 growing the rare earth-doped yttrium iron garnet single crystal material 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 unmelted and non-grown temperature of the yttrium iron garnet seed crystal in 3-5 days is taken as the supersaturation temperature of the melt in the cooling process.
9. A magneto-optical single crystal material comprising at least one of the rare earth doped yttrium iron garnet single crystal materials prepared according to the method of any one of claims 1 to 8.
10. Use of a magneto-optical single crystal material according to claim 9 in an optical communication device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111274236.0A CN114182339A (en) | 2021-10-29 | 2021-10-29 | Method for growing rare earth doped yttrium iron garnet single crystal material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111274236.0A CN114182339A (en) | 2021-10-29 | 2021-10-29 | Method for growing rare earth doped yttrium iron garnet single crystal material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114182339A true CN114182339A (en) | 2022-03-15 |
Family
ID=80601708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111274236.0A Pending CN114182339A (en) | 2021-10-29 | 2021-10-29 | Method for growing rare earth doped yttrium iron garnet single crystal material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114182339A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117934A (en) * | 1961-04-17 | 1964-01-14 | Bell Telephone Labor Inc | Garnet growth from barium oxide-boron oxide flux |
| JPS61186298A (en) * | 1985-02-15 | 1986-08-19 | Seiko Epson Corp | Production of single crystal |
| US4698820A (en) * | 1986-05-01 | 1987-10-06 | American Telephone And Telegraph Company, At&T Bell Laboratories | Magnetic device and method of manufacture |
| JP2017024960A (en) * | 2015-07-27 | 2017-02-02 | 住友金属鉱山株式会社 | Method for producing bismuth-substituted rare earth iron garnet crystal film and bismuth-substituted rare earth iron garnet crystal film |
| 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 |
-
2021
- 2021-10-29 CN CN202111274236.0A patent/CN114182339A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117934A (en) * | 1961-04-17 | 1964-01-14 | Bell Telephone Labor Inc | Garnet growth from barium oxide-boron oxide flux |
| JPS61186298A (en) * | 1985-02-15 | 1986-08-19 | Seiko Epson Corp | Production of single crystal |
| US4698820A (en) * | 1986-05-01 | 1987-10-06 | American Telephone And Telegraph Company, At&T Bell Laboratories | Magnetic device and method of manufacture |
| JP2017024960A (en) * | 2015-07-27 | 2017-02-02 | 住友金属鉱山株式会社 | Method for producing bismuth-substituted rare earth iron garnet crystal film and bismuth-substituted rare earth iron garnet crystal film |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Growth and characterization of cerium-substituted yttrium iron garnet single crystals for magneto-optical applications | |
| CN102011188B (en) | Method for growing RFeO3 photomagnetic function crystal by secondary melting method | |
| CN104073879B (en) | Bismuth displacement rare earth iron garnet single crystal and its manufacture method | |
| JP2004083390A (en) | Magnetic garnet material, faraday rotator, optical device, manufacturing method of bismuth substitution type rare earth iron garnet single crystal film, and single crystal film | |
| JPH0354198A (en) | Oxide garnet single crystal | |
| Ikesue et al. | Progress of magneto-optical ceramics | |
| Pal et al. | Nanocrystalline nickel-zinc ferrite prepared by the glass-ceramic route | |
| CN112095149B (en) | High-cerium-content scandium-doped gadolinium iron garnet magneto-optical crystal and preparation method and application thereof | |
| Shen et al. | The effect of terbium on the optical dispersion and magneto-optical properties of YIG crystals grown by flux-Bridgman method | |
| Damen et al. | Calcium gallium germanium garnet as a substrate for magnetic bubble application | |
| CN106149056A (en) | Rare earth alkaline earth borate and preparation method and application thereof | |
| CN114150365A (en) | Preparation method of large-size yttrium iron garnet single crystal | |
| CN114182339A (en) | Method for growing rare earth doped yttrium iron garnet single crystal material | |
| YANG et al. | High quality and large size yttrium iron garnet crystal grown by top seeded solution growth technique | |
| CN103866388B (en) | A kind of Emission in Cubic fluorite type niobic acid terbium calcium magneto-optical crystal and preparation method thereof | |
| Huang et al. | Growth and characterization of rare-earth iron garnet single crystals modified by bismuth and ytterbium substituted for yttrium | |
| Qing-Hui et al. | Magneto-optical and microwave properties of LuBiIG thin films prepared by liquid phase epitaxy method from lead-free flux | |
| US4499061A (en) | Strontium ferrite borate | |
| CN102268733A (en) | Magneto-optical crystal with rectangular hysteresis loop and high coercive field, and preparation method thereof | |
| CN110172734B (en) | Cubic phase doped cerium ferrite magneto-optical material and preparation method and application thereof | |
| JPS60255696A (en) | Production of bismuth-substituted magnetic garnet single crystal | |
| JPH09202697A (en) | Production of bismuth-substituted type garnet | |
| CN106521626A (en) | High terbium concentration borate and preparation method and application thereof | |
| Meisel et al. | Spin glass behaviour of CoGa compounds | |
| Huang et al. | Structural, Magnetic and Magneto‐Optical Properties of (YYbBi) 3Fe5O12 Single Crystal for High‐Performance Magneto‐Optical Applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220315 |