CN114250515B - Calcium-magnesium-zirconium doped gadolinium gallium garnet crystal, preparation method, application and temperature field thereof - Google Patents
Calcium-magnesium-zirconium doped gadolinium gallium garnet crystal, preparation method, application and temperature field thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 142
- ZPDRQAVGXHVGTB-UHFFFAOYSA-N gallium;gadolinium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Gd+3] ZPDRQAVGXHVGTB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- CCRAOWWOICDIGI-UHFFFAOYSA-N [Zr].[Ca].[Mg] Chemical compound [Zr].[Ca].[Mg] CCRAOWWOICDIGI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000004576 sand Substances 0.000 claims abstract description 18
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims abstract description 17
- 239000002223 garnet Substances 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 27
- 239000000155 melt Substances 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 13
- 239000011575 calcium Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 208000034699 Vitreous floaters Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/14—Heating of the melt or the crystallised materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on magneto-optical elements, e.g. exhibiting Faraday effect
Abstract
The invention discloses a calcium-magnesium-zirconium doped gadolinium gallium garnet crystal, a preparation method thereof and a temperature field. The calcium-magnesium-zirconium doped gadolinium gallium garnet crystal provided by the invention is a cubic garnet phase, wherein Gd in dodecahedron 3+ The (0.106 nm) portion is covered with a cation Ca having a larger ionic radius 2+ (0.112 nm) substitution; ga in octahedra 3+ The (0.062 nm) portion is bound by a cation Mg having a larger ionic radius 2+ (0.072 nm) and Zr 4+ (0.075 nm) substitution, with unit cell parameters ofThe mismatching rate of the material and the Bi-doped RIG series film is less than 0.05%, so that the growth of the Bi-doped RIG series film can be better assisted. The preparation method comprises regulating growth atmosphere and inhibiting Ga 2 O 3 Is volatilized, and is matched with the process adjustment of a pulling method, thereby avoiding the problems of spiral growth and crystal cracking. The temperature field for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal comprises a concentrically nested zirconia inner cylinder, a zirconia sand heat-insulating layer and an alumina outer cylinder; the temperature field is arranged in the lifting furnace.
Description
Technical Field
The invention belongs to the field of crystals and optical devices, and particularly relates to a calcium-magnesium-zirconium doped gadolinium gallium garnet crystal, a preparation method thereof and a temperature field.
Background
The magneto-optical device is one of the core and key devices in a laser communication system, the Bi-doped rare earth iron garnet epitaxial film is a key raw material of the magneto-optical device, the performance of the magneto-optical device is directly dependent on the quality of a substrate monocrystal, the magneto-optical monocrystal film material commonly used at present takes a Gadolinium Gallium Garnet (GGG) crystal substrate as a growth substrate, but the lattice constant of the Gadolinium Gallium Garnet (GGG) crystal is small, the lattice constants of the substrate and the Bi-doped RIG film are not matched, and the mismatching rate of the gadolinium gallium garnet and the Bi-doped RIG film exceeds 0.05 percent, so that the growth of the crystal is not favored. Only if the mismatch rate is not more than 0.05%, the growth of the crystal is facilitated.
SGGG crystals are uniform molten compounds having a melting point of about 1730 ℃ and are commonly encountered in the growth of single crystals by the czochralski method 2 O 3 Causing strong liquid flow effect and interface turnover, leading to outstanding problems such as spiral growth and crystal cracking, thereby bringing great difficulty to the growth of crystals.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a calcium-magnesium-zirconium doped gadolinium-gallium garnet crystal, a preparation method thereof and a temperature field thereof, and aims to prepare the lattice constant of the gadolinium-gallium garnet crystal by micro-doping calcium-magnesium-zirconium elements so as to be matched with a Bi-doped RIG series film, reduce the mismatching rate with the Bi-doped RIG series film, and thereby facilitate the growth of the Bi-doped RIG series film, and solve the technical problems that the mismatching rate of the existing gadolinium-gallium garnet and the Bi-doped RIG series film exceeds 0.05 percent and is unfavorable for the growth of the crystal.
In order to achieve the above object, according to one aspect of the present invention, there is provided a calcium-magnesium-zirconium doped gadolinium gallium garnet crystal having the formula:
Gd 3-x Ca x Ga 5-x-2y Mg y Zr x+y O 12
wherein x is more than or equal to 0.35 and less than or equal to 0.4,0.25, and y is more than or equal to 0.3; is a cubic garnet phase, wherein Gd in dodecahedron 3+ By cations Ca 2+ Substitution of Ga in octahedra 3+ Is coated with Mg 2+ And Zr (Zr) 4+ And (3) substitution.
Preferably, the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal has unit cell parameters of
Preferably, the mismatching rate of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal and the Bi-doped RIG series film is less than 0.05 percent.
Preferably, the calcium magnesium zirconium doped gadolinium gallium garnet crystal has x=0.35 and y=0.3, or x=0.4 and y=0.25.
According to another aspect of the invention, there is provided a method for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal, comprising the steps of:
(1) Preparing a polycrystalline raw material: weighing raw materials required by crystal growth according to the stoichiometric ratio of the molecular formula of the calcium-magnesium-zirconium doped gadolinium-gallium garnet magneto-optical crystal, uniformly mixing in a mixer, tabletting by an isostatic press, and sintering at high temperature in a muffle furnace; wherein Ga 2 O 3 An excess of 1-4wt%;
(2) Single crystal growth: and adding the polycrystalline raw material into an iridium crucible, placing the iridium crucible in a temperature field, and growing SGGG monocrystal by adopting a melt pulling method to obtain the calcium-magnesium-zirconium doped gadolinium-gallium garnet crystal.
Preferably, the preparation method of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal is characterized in that the step (2) is characterized in that the crystal growth atmosphere is controlled as follows: filling the mixture with 50-70 v/v% CO 2 Is an inert gas of (a).
Preferably, the pulling speed of the step (2) is 0.8-2mm/h, the crystal transformation speed is regulated within 5-10rpm, when the crystal grows to the required size, the crystal is pulled to be separated from the surface of the melt by 1-15mm, and then the crystal is annealed to room temperature in stages, wherein the cooling speed is 5-30 ℃/h.
Preferably, in the preparation method of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal, the raw materials required by crystal growth in the step (1) are subjected to drying treatment.
According to another aspect of the invention, there is provided the use of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal for the manufacture of Bi-doped rare earth iron garnet epitaxial films.
According to another aspect of the invention, a temperature field for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal is provided, which comprises a zirconium oxide inner cylinder, a zirconium oxide sand heat-insulating layer and an aluminum oxide outer cylinder which are nested concentrically; the temperature field is arranged in the lifting furnace.
The diameter of the inner cavity of the inner cylinder is 80-120 mm, the thickness of the wall of the inner cylinder is 20-30 mm, and the heat conductivity is 0.23-0.35W/(m.k); the thickness of the zirconia sand heat-insulating layer is between 30 and 50 mm; the diameter of the inner cavity of the outer cylinder is 160-200 mm, the wall thickness of the inner cylinder is 20-30 mm, and the thermal conductivity is 0.4-0.6W/(m.k).
Preferably, the zirconium oxide sand heat insulation layer uses 50-100 mesh zirconium oxide sand in the temperature field of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal.
In general, the above technical solutions conceived by the present invention, compared with the prior art, enable the following beneficial effects to be obtained:
the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal provided by the invention is a cubic garnet phase, wherein Gd in dodecahedron 3+ The (0.106 nm) portion is covered with a cation Ca having a larger ionic radius 2+ (0.112 nm) substitution; ga in octahedra 3+ The (0.062 nm) portion is bound by a cation Mg having a larger ionic radius 2+ (0.072 nm) and Zr 4+ (0.075 nm) substitution, with unit cell parameters ofThe mismatching rate of the material and the Bi-doped RIG series film is less than 0.05%, so that the growth of the Bi-doped RIG series film can be better assisted.
The preparation method of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal provided by the invention can inhibit Ga by adjusting the growth atmosphere 2 O 3 The volatilization of the crystal is matched with the process adjustment of a pulling method, the problems of liquid flow effect and interface overturning are overcome, the problems of spiral growth and crystal cracking are avoided, and the high-quality complete calcium-magnesium-zirconium doped gadolinium-gallium garnet crystal is prepared.
The temperature field for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal provided by the invention can realize good heat preservation and power control effects, and can generate a temperature gradient at a growth interface so that the crystal is easy to grow.
Drawings
FIG. 1 is a schematic diagram of a temperature field structure for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal provided by the invention;
fig. 2 is a schematic diagram of a thermal field inner cylinder structure for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a thermal field outer barrel structure for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to an embodiment of the present invention; .
The same reference numbers are used throughout the drawings to reference like elements or structures, wherein: 1 is an inner cylinder, 2 is a zirconia sand heat-insulating layer, and 3 is an outer cylinder.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The calcium-magnesium-zirconium doped gadolinium gallium garnet crystal provided by the invention has the molecular formula as follows:
Gd 3-x Ca x Ga 5-x-2y Mg y Zr x+y O 12
wherein 0.35.ltoreq.x.ltoreq. 0.4,0.25.ltoreq.y.ltoreq.0.3, preferably x=0.35 and y=0.3, or x=0.4 and y=0.25.
Is a cubic garnet phase, wherein Gd in dodecahedron 3+ The (0.106 nm) portion is covered with a cation Ca having a larger ionic radius 2+ (0.112 nm) substitution; ga in octahedra 3+ The (0.062 nm) portion is bound by a cation Mg having a larger ionic radius 2+ (0.072 nm) and Zr 4+ (0.075 nm) substitution, with unit cell parameters ofThe mismatch rate with the Bi-doped RIG series film is less than 0.05 percent.
Since Bi has a large atomic radius and is incorporated into a crystal to increase the lattice constant of the product, a substrate having a large lattice constant is required to be used to increase the amount of Bi incorporated, and a part of Sc is used to replace Ga in GGG crystals, so that not only can the lattice constant be increased, but also high-quality crystals can be grown more easily, but also the lattice constant can be increased in such a manner that the raw material of Sc is expensive, gd in GGG is replaced with Ca, and Mg and Zr are replaced with Ga, and therefore, the substrate is more suitable as a substrate for a Bi-incorporated RIG-based iron garnet film.
The lattice parameters of the substrate should be as small as possible with the lattice constant of the Bi-doped iron garnet film being grown. Bi-doped iron garnet thin film generally has a lattice constant ofIn order to reduce the mismatch ratio with Bi-doped RIG-based thin films, it is necessary to control the cell parameters to +.>Although Ca 2+ And Mg (magnesium) 2+ The doping of (2) can improve the unit cell parameters, however, if too much doping causes uneven components, the growth is difficult and easy to crack, and Ca needs to be controlled 2+ And Mg (magnesium) 2+ The respective doping amounts are in the proper ranges.
Further, how to solve various problems occurring in the SGGG single crystal growth process, such as a given lattice constant, an external shape, a size, and cracking, by adjusting process parameters and optimizing conditions such as a temperature field structure, has become a key for growing high quality substrate single crystals.
The preparation method of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal provided by the invention comprises the following steps:
(1) Preparing a polycrystalline raw material: weighing raw materials required by crystal growth according to the stoichiometric ratio of the molecular formula of the calcium-magnesium-zirconium doped gadolinium-gallium garnet magneto-optical crystal, uniformly mixing in a mixer, tabletting by an isostatic press, and sintering at high temperature in a muffle furnace; wherein Ga2O3 is in an excess of 1-4wt%, preferably in an excess of 3%.
The raw material required by the crystal growth is gadolinium oxide Gd 2 O 3 (99.999 percent), gallium oxide Ga 2 O 3 (99.999%), calcium oxide CaO (99.99%), magnesium oxide MgO (99.99%) and zirconium oxide ZrO 2 (99.99%) of the raw materials were prepared according to the formula Gd 3- x Ca x Ga 5-x-2y Mg y Zr x+y O 12 (x is more than or equal to 0.35 and less than or equal to 0.4,0.25, y is more than or equal to 0.3); due to Ga 2 O 3 Can volatilize at high temperature, and Ga is added to the composition to reduce the deviation of components 2 O 3 A suitable excess is 1-4wt%. Ga 2 O 3 Easily dissociable from the melt, which results in inexpensive raw material components and hence impurities, a certain proportion of excess is required, whereas too much excess on the one hand tends to form other impurity compounds and on the other hand Ga 2 O 3 The volatilization can cause strong liquid flow effect and section turnover, so that the problems of spiral growth and crystal cracking are more serious, and Ga is controlled 2 O 3 Excessive 1-4wt% and regulating atmosphere to inhibit Ga 2 O 3 Volatilizing to inhibit the generation of impurity compound, overcome spiral growth and crystal cracking, and obtain crystal with higher purity and better quality. Generally Ga 2 O 3 The excess ranges within 4wt% without significant differences, and excessive excess may form a heterogeneous phase.
Preferably, the raw materials required for crystal growth are subjected to drying treatment.
(2) Single crystal growth: adding the polycrystalline raw material into an iridium crucible, placing the iridium crucible in a temperature field, and growing SGGG monocrystal by adopting a melt pulling method to obtain calcium-magnesium-zirconium doped gadolinium gallium garnet crystal (SGGG crystal); the crystal growth atmosphere is controlled as follows: charging with a mixture containing 50v/v% CO 2 Inert gas of (2), e.g. 50% CO 2 +50％N 2 The method comprises the steps of carrying out a first treatment on the surface of the The pulling speed is 0.8-2mm/h, the crystal transformation speed is regulated within 5-10rpm, when the crystal grows to the required size, the crystal is pulled to be separated from the surface of the melt by 1-15mm, and then the crystal is annealed to room temperature in stages, and the cooling speed is 5-30 ℃/h.
The preparation of the multi-metal doped Ga series crystal generally needs to adopt a platinum crucible or an iridium crucible with stable properties, while the preparation temperature of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal is higher, and the iridium crucible needs to be adopted. The growth atmosphere of the invention adopts CO 2 Inhibition of Ga 2 O 3 Volatilize to match Ga 2 O 3 Excessive and other raw material proportions, and grows high-purity calciumMagnesium-zirconium doped gadolinium gallium garnet crystal. CO 2 High content is for Ga 2 O 3 The volatilization control effect of the catalyst is better, but the crucible is more easily oxidized to form iridium oxide floaters, thereby affecting the crystal seeding growth and CO 2 If the content is too low, ga 2 O 3 The volatilization can be more obvious by naked eyes, so the volatilization can be greatly inhibited by controlling the volatilization at 50-70 v/v percent, and the floating objects are not easy to produce.
Controlling Ga 2 O 3 The liquid flow effect of the method is mainly achieved by adjusting the atmosphere and secondarily adjusting the crystal transformation speed during crystal seeding, and under the crystal growth atmosphere provided by the invention, the crystal transformation speed and the pulling speed are controlled, so that spiral growth and crystal cracking can be well avoided.
The temperature field for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal is shown in fig. 1, and comprises a concentric nested zirconia inner cylinder (shown in fig. 2), a zirconia sand heat-insulating layer and an alumina outer cylinder (shown in fig. 3); the temperature field is arranged in the lifting furnace.
The diameter of the inner cavity of the inner cylinder is 80-120 mm, the thickness of the wall of the inner cylinder is 20-30 mm, and the heat conductivity is 0.23-0.35W/(m.k); the thickness of the zirconia sand heat-insulating layer is between 30 and 50mm, and the zirconia sand heat-insulating condition of 50 to 100 meshes is good; the diameter of the inner cavity of the outer cylinder is 160-200 mm, the wall thickness of the inner cylinder is 20-30 mm, and the thermal conductivity is 0.4-0.6W/(m.k);
the design of the inner sleeve and the outer sleeve not only can realize good heat preservation and power control effects, but also can generate temperature gradient at a growth interface, so that crystals are easy to grow. The selection of the good inner and outer sleeve sizes and the material heat conduction performance needs to be tested and searched according to specific conditions.
The following are examples:
the temperature field for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal adopted in the embodiment is shown in fig. 1, and comprises a concentric nested zirconia inner cylinder (shown in fig. 2), a zirconia sand heat-insulating layer and an alumina outer cylinder (shown in fig. 3); the temperature field is arranged in the lifting furnace.
The diameter of the inner cavity of the inner cylinder is 100mm, the thickness of the wall of the inner cylinder is 25mm, the heat conductivity is 0.23-0.35W/(m.k), and the temperature resistance is 2200 ℃; the thickness of the zirconia sand heat-insulating layer is 40mm, and the zirconia sand heat-insulating condition of 50-100 meshes is good; the diameter of the inner cavity of the outer cylinder is 180mm, the thickness of the inner cylinder wall is 25mm, the temperature resistance is 1700 ℃, and the thermal conductivity is 0.4-0.6W/(m.k).
Example 1
The preparation method of the calcium-magnesium-zirconium doped gadolinium gallium garnet SGGG crystal comprises the following specific preparation steps:
(1) Synthesizing a polycrystalline raw material: according to Gd 3-x Ca x Ga 5-x-2y Mg y Zr x+y O 12 The stoichiometric ratio of (x=0.35, y=0.3) accurately weighs Gd with purity greater than 99.99% 2 O 3 、Ga 2 O 3 CaO, mgO and ZrO 2 Raw materials are weighed, put into a clean mixing barrel after the raw materials are weighed, mixed for 24 hours in a mixer, then put into a rubber mold customized according to the size of a crucible, and pressed and molded under 200Mpa by using an isostatic press. Placing the pressed corundum crucible into a muffle furnace, and calcining at 1300 ℃ for 12-18h by adopting a high-temperature sintering mode. The content of the high-purity Gd is more than 99.99 percent 2 O 3 、Ga 2 O 3 CaO, mgO and ZrO 2 The waste water is required to be removed in an oven before use.
(2) With dimensions phi 80 x 80mm 3 The synthesized SGGG polycrystalline raw material is added into the iridium crucible in a pulling furnace in batches as a container for crystal growth, a temperature field formed by matching and combining a zirconia inner cylinder, zirconia sand and an alumina outer cylinder is adopted, the liquid level position is controlled to be about 10-20mm away from the top of the crucible, the SGGG after annealing is arranged as seed crystal, and the temperature field for heat preservation is placed; the top of the crucible is leveled with the coil, vacuumized and introduced with 50% CO 2 +50％N 2 Maintaining the furnace at a positive pressure; the crystal growth adopts a JPG software automatic control system, and the dimension and shape data of the crystal to be grown, such as the dimension and length of each stage, etc. are input.
(3) In the heating process, proper power is adjusted according to experience, and the temperature is slightly higher than the melting point of the crystal by 30-50 ℃ so as to uniformly melt the raw materials. After the melt is kept at the constant temperature for a period of time, the SGGG seed crystal with the direction of <111> is lowered to the position above the liquid level to preheat the seed crystal, then the seed crystal is lowered to be contacted with the melt, the rotation speed of the crystal is regulated to be 10rpm, and the temperature is kept for 60 minutes;
(4) After the quality change is stable, starting to lift and automatically grow crystals, adjusting the pulling speed to be 0.8-2mm/h, setting the rotating speed to be 10rpm in the process of shouldering growth, and gradually reducing the pulling speed from 2mm/h to 1.5mm/h; when the length of the crystal reaches 20mm, namely the crystal enters an equal diameter state, the pulling speed is stabilized to 1.5mm/h, and as the length of the crystal is lengthened, the step rotating speed is gradually reduced from 10rpm to 5rpm, and the step pulling speed is gradually reduced from 1.5mm/h to 0.8mm/h until the crystal grows to the required length.
When the crystal grows to the end, the crystal is pulled out to be separated from the liquid level, then three sections of step speeds are set, the temperature is slowly reduced to the room temperature, and the crystal is taken out.
The crystal grown in this example has a well-ordered shape, a uniform distribution of elements, and a lattice constant of the crystalMeets the requirement of Bi-doped RIG series film.
Example 2
The preparation method of the calcium-magnesium-zirconium doped gadolinium gallium garnet SGGG crystal comprises the following specific steps:
(1) Synthesizing a polycrystalline raw material: according to Gd 3-x Ca x Ga 5-x-2y Mg y Zr x+y O 12 The stoichiometric ratio of (x=0.4, y=0.25) accurately weighs Gd with purity greater than 99.99% 2 O 3 、Ga 2 O 3 CaO, mgO and ZrO 2 Raw materials are weighed, put into a clean mixing barrel after the raw materials are weighed, mixed for 24 hours in a mixer, then put into a rubber mold customized according to the size of a crucible, and pressed and molded under 200Mpa by using an isostatic press. Placing the pressed corundum crucible into a muffle furnace, and calcining at 1300 ℃ for 12-18h by adopting a high-temperature sintering mode. The content of the high-purity Gd is more than 99.99 percent 2 O 3 、Ga 2 O 3 CaO, mgO and ZrO 2 The waste water is required to be removed in an oven before use.
(2) With dimensions phi 80 x 80mm 3 The synthesized SGGG polycrystalline raw material is added into the iridium crucible in a pulling furnace in batches as a container for crystal growth, a temperature field formed by matching and combining a zirconia inner cylinder, zirconia sand and an alumina outer cylinder is adopted, the liquid level position is controlled to be about 10-20mm away from the top of the crucible, the SGGG after annealing is arranged as seed crystal, and the temperature field for heat preservation is placed; the top of the crucible is leveled with the coil, vacuumized and introduced with 70% CO 2 +30％N 2 Maintaining the furnace at a positive pressure; the crystal growth adopts a JPG software automatic control system, and the dimension and shape data of the crystal to be grown, such as the dimension and length of each stage, etc. are input.
(3) In the heating process, proper power is adjusted according to experience, and the temperature is slightly higher than the melting point of the crystal by 30-50 ℃ so as to uniformly melt the raw materials. After the melt is kept at the constant temperature for a period of time, the SGGG seed crystal with the direction of <111> is lowered to the position above the liquid level to preheat the seed crystal, then the seed crystal is lowered to be contacted with the melt, the rotation speed of the crystal is regulated to be 10rpm, and the temperature is kept for 60 minutes;
(4) After the quality change is stable, starting to lift and automatically grow crystals, adjusting the pulling speed to be 0.8-2mm/h, setting the rotating speed to be 10rpm in the process of shouldering growth, and gradually reducing the pulling speed from 2mm/h to 1.5mm/h; when the crystal length reaches 20rpm, namely, the crystal enters an equal diameter state, the pulling speed is stabilized to 1.5mm/h, and as the crystal length is lengthened, the step rotating speed is gradually reduced from 10rpm to 5rpm, and the step pulling speed is gradually reduced from 1.5mm/h to 0.8mm/h until the crystal grows to the required length.
When the crystal grows to the end, the crystal is pulled out to be separated from the liquid level, then three sections of step speeds are set, the temperature is slowly reduced to the room temperature, and the crystal is taken out.
The crystal grown in this example has a well-ordered shape, a uniform distribution of elements, and a lattice constant of the crystalMeets the requirement of Bi-doped RIG series film.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal is characterized by comprising the following steps of:
(1) Preparing a polycrystalline raw material: weighing raw materials required by crystal growth according to the stoichiometric ratio of the molecular formula of the calcium-magnesium-zirconium doped gadolinium-gallium garnet magneto-optical crystal, uniformly mixing in a mixer, tabletting by an isostatic press, and sintering at high temperature in a muffle furnace; wherein Ga 2 O 3 An excess of 1-4wt%;
(2) Single crystal growth: adding the polycrystalline raw material into an iridium crucible, placing the iridium crucible in a temperature field, and growing SGGG monocrystal by adopting a melt pulling method to obtain the calcium-magnesium-zirconium doped gadolinium-gallium garnet crystal; the crystal growth atmosphere is controlled as follows: filling the mixture with 50-70 v/v% CO 2 Is regulated within 5-10 rpm;
the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal has the molecular formula as follows:
Gd 3-x Ca x Ga 5-x-2y Mg y Zr x+y O 12
wherein x is more than or equal to 0.35 and less than or equal to 0.4,0.25, and y is more than or equal to 0.3; is a cubic garnet phase, wherein Gd in dodecahedron 3+ By cations Ca 2+ Substitution of Ga in octahedra 3+ Is coated with Mg 2+ And Zr (Zr) 4+ And (3) substitution.
2. The method for preparing calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to claim 1, wherein the pulling speed of step (2) is 0.8-2mm/h, when the crystal grows to a required size, the crystal is pulled to be separated from the surface of the melt by 1-15mm, and then the crystal is annealed to room temperature in a staged manner, and the cooling speed is 5-30 ℃/h.
3. The method for preparing a calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to claim 1, wherein the unit cell parameters of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal are as follows
4. The method for preparing a calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to claim 1 or 3, wherein the mismatching rate of the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal and the Bi-doped RIG series film is less than 0.05 percent.
5. The method of preparing a calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to claim 1, wherein x=0.35 and y=0.3, or x=0.4 and y=0.25.
6. The method for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to claim 1, wherein a temperature field for preparing the calcium-magnesium-zirconium doped gadolinium gallium garnet crystal is applied, and the temperature field is applied and comprises a zirconium oxide inner cylinder, a zirconium oxide sand heat-insulating layer and an aluminum oxide outer cylinder which are concentrically nested; the temperature field is arranged in the lifting furnace;
the diameter of the inner cavity of the inner cylinder is 80-120 mm, the thickness of the wall of the inner cylinder is 20-30 mm, and the heat conductivity is 0.23-0.35W/(m.k); the thickness of the zirconia sand heat-insulating layer is between 30 and 50 mm; the diameter of the inner cavity of the outer cylinder is 160-200 mm, the wall thickness of the inner cylinder is 20-30 mm, and the thermal conductivity is 0.4-0.6W/(m.k).
7. The method for preparing calcium-magnesium-zirconium doped gadolinium gallium garnet crystal according to claim 6, wherein the zirconia sand heat-insulating layer uses 50-100 mesh zirconia sand.
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| CN106087037A (en) * | 2016-08-30 | 2016-11-09 | 成都晶九科技有限公司 | Crystal pull growth furnace temperature field structure and pulling growth technique thereof |
| JP2017105668A (en) * | 2015-12-09 | 2017-06-15 | 住友金属鉱山株式会社 | RAISING METHOD OF CaMgZr-SUBSTITUTED GADOLINIUM GALLIUM GARNET SINGLE CRYSTAL |
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| CN106087037A (en) * | 2016-08-30 | 2016-11-09 | 成都晶九科技有限公司 | Crystal pull growth furnace temperature field structure and pulling growth technique thereof |
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