CN114875490B - High-aluminum terbium aluminum gallium garnet magneto-optical crystal and preparation method and application thereof - Google Patents
High-aluminum terbium aluminum gallium garnet magneto-optical crystal and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 212
- 239000002223 garnet Substances 0.000 title claims abstract description 43
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000155 melt Substances 0.000 claims abstract description 25
- 238000010899 nucleation Methods 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 32
- 238000005245 sintering Methods 0.000 claims description 19
- 229910052733 gallium Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 12
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- FNCIDSNKNZQJTJ-UHFFFAOYSA-N alumane;terbium Chemical compound [AlH3].[Tb] FNCIDSNKNZQJTJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims description 2
- WVUAOWBLTAWACX-UHFFFAOYSA-N alumane;terbium Chemical compound [AlH3].[AlH3].[Tb] WVUAOWBLTAWACX-UHFFFAOYSA-N 0.000 claims 8
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- C30B27/00—Single-crystal growth under a protective fluid
- C30B27/02—Single-crystal growth under a protective fluid by pulling from a melt
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- 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
- G02F1/093—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 used as non-reciprocal devices, e.g. optical isolators, circulators
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
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Abstract
The invention relates to a high-aluminum terbium aluminum gallium garnet magneto-optical crystal and a preparation method and application thereof. The crystal has a molecular formula of Tb 3 Al x Ga 5‑x O 12 ,1.75≤x<5, abbreviated as TAGG, the crystal belongs to garnet structure. The high-alumina TAGG magneto-optical crystal is grown by a melt method, adopts a secondary seeding technology, grows to obtain large-size and high-quality single crystals, is superior to TGG crystals in magneto-optical, thermal, optical and other performances, and can be used for manufacturing high-efficiency magneto-optical devices.
Description
Technical Field
The invention relates to a preparation method and application of a novel magneto-optical crystal, in particular to a high-aluminum terbium aluminum gallium garnet crystal and a preparation method and application thereof, and belongs to the technical field of crystals and devices.
Background
The core of the nonreciprocal magneto-optical device based on Faraday magneto-optical effect is magneto-optical crystal, which has become one of the most commercialized crystals, and has very wide application in the fields of optical fiber communication, information processing, lasers, medicine and the like. In recent years, with the rapid development of optical communication technologies (such as terahertz communication) and high-power lasers, the application range of magneto-optical crystals is further expanded, and the requirements on crystal quality and performance are further improved.
In the 400-1100nm (excluding 470-500 nm) wave band, terbium Gallium Garnet (TGG) crystal is the most widely used magneto-optical crystal with highest commercialization degree at present due to its high Verdet constant, low absorption coefficient, high thermal conductivity, high laser damage threshold and excellent optical performance. TGG crystal mainly adopts a Czochralski method for growth, and the existing problems are mainly Ga in the growth process 2 O 3 Volatilization, spiral growth, difficulty in growing larger size high quality crystals, greatly limit the applications of TGG crystals, especially in high power applications, and severe light absorption causes crystal cracking. Terbium Aluminum Garnet (TAG) crystals and TGG crystals belong to a cubic crystal system structure, the application wave band is 400-1100nm, the Verdet constant is 1.3-1.5 times of that of the TGG crystals, compared with the TGG crystals, the performance of the TGG crystals is improved in all directions, the Terbium Aluminum Garnet (TAG) crystals are considered to be the best magneto-optical crystals of 400-1100nm, but TAP heterophases are generated at the temperature higher than 1850 ℃ due to the non-uniform melting characteristic, the growth is difficult, and large-size single crystals cannot be obtained. The prior art can only adopt a guided mode method and a floating zone method to obtain small-size crystals (see documents M.Geho, T.Sekijima, T.Fujii, journal of Crystal Growth,267,2004,188-193 and H.Liu, G.Zhan, G.Wu, C.Song, X.Wu, Q.Xu, X.Chen, X.Hu, N.Zhuang, J.Chen, cryst.Growth Des.,19,2019,1525-1531), and cannot meet the requirements of practical application.
The Terbium Aluminum Gallium Garnet (TAGG) mixed crystal combines the advantages of TGG and TAGG crystals, has consistent melting characteristics, can be grown by adopting a melt method, has obvious advantages in performance and cost compared with the TGG crystals, and is a potential magneto-optical material with excellent performance. CN102485975A discloses a method for pulling and growing terbium-doped gallium garnet (TGG) magneto-optical crystal, which comprises growing aluminum-doped TGG (Tb) 3 Ga 5-x Al x O 12 X=0 to 0.5), iron-doped TGG (Tb 3 Ga 5- x Fe x O 12 X=0 to 0.5) or doubly alloyed aluminum iron TGG (Tb 3 Ga 5-x-y Al x Fe y O 12 X+y=0 to 0.5) magneto-optical crystal, the crystal size is several times higher than the TAG crystal. In addition, the domestic state university further improves the aluminum content in the TAGG single crystal, but when the substitution ratio is only 34.2%, more defects appear in the crystal, and the crystal quality is not ideal (W.Zhang, F.Guo, J.Chen, journal of Crystal Growth,306,2007,195-199). In summary, TAGG crystals have excellent magneto-optical properties, but the aluminum content in TAGG crystals reported so far is low<35%) and when the aluminum content in the composition is further increased, the crystal growth is very difficult, and high aluminum TAGG single crystals (aluminum content more than 35%) are not reported at present. Therefore, the preparation of high-quality high-alumina TAGG crystals is a technical problem to be solved currently.
For this purpose, the present invention is proposed.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a high-aluminum TAGG magneto-optical crystal, and a preparation method and application thereof. Compared with TGG, the high-aluminum TAGG crystal greatly reduces the Ga content in the component and reduces Ga 2 O 3 The volatilization reduces the segregation of the melt components, is superior to TGG crystals in magneto-optical, thermal and optical properties, and can be used for manufacturing high-efficiency magneto-optical devices. The invention can prepare high-quality high-aluminum TAGG crystal, the key technical means is that the technology of secondary seeding is adopted, and the innovation of the seeding technology is an important factor for obtaining high-quality large-size TAGG crystal. For TAGG, when the aluminum content in the component is high, a large amount of TAP impurity phase exists in the crystal melt, so that the single crystal prepared by the conventional technology has poor crystallinity and cannot be used for magneto-optical devices. The invention provides a secondary seeding technology, which comprises the steps of firstly standing the lower end of TAGG seed crystal in a melt for 0.5-5 hours, inducing the melt in a crucible to be completely converted into garnet pure phase, and eliminating the interference of TAPG impurities on crystal growth; then the seed crystal is lifted off the liquid level of the melt, and then the secondary seeding is carried out, and the normal crystal growth procedure is carried out, thus obtaining the high-quality TAGG single crystalThe crystal has good transparency, no cracking and wrapping, and the prepared magneto-optical device has excellent performance.
The technical scheme of the invention is as follows:
a high-Al terbium AlGa garnet crystal with molecular formula of Tb 3 Al x Ga 5-x O 12 ,1.75≤x<5. The crystal belongs to a cubic system, the space group is Ia3d (230), al 3+ And Ga 3+ Co-located octahedral and tetrahedral sites.
The crystals according to the invention preferably have 3.ltoreq.x <5; further preferably x=3.5, 3.75, 4, 4.5.
According to the crystal of the present invention, preferably, the diameter of the high-alumina TAGG crystal is not less than 5mm, and more preferably, 20-100mm.
According to the crystal of the present invention, preferably, the high-alumina TAGG crystal has uniform melting characteristics, and can be used for single crystal growth by the Czochralski method.
According to the crystal disclosed by the invention, the transmittance of the high-aluminum TAGG crystal is preferably more than or equal to 80%.
According to the crystal of the present invention, preferably, the high alumina TAGG crystal has a Philippine constant>45rad m -1 T -1 @1064nm。
According to the invention, the high-aluminum TAGG crystal is grown by a melt method, and a secondary seeding technology is adopted. Firstly, placing TAGG seed crystal in melt to induce the melt to be completely converted into garnet pure phase, eliminating the interference of TAP impurity relative to crystal growth; then lifting the seed crystal off the melt level, then carrying out secondary seeding, and entering a normal crystal growth procedure.
According to the invention, preferably, the high-alumina TAGG crystal is grown by a melt pulling method, and the steps are as follows:
(1) Polycrystalline material synthesis
Weighing raw material Tb according to stoichiometric ratio 4 O 7 ，Ga 2 O 3 ，Al 2 O 3 And on the basis of this, ga 2 O 3 1% -3% excess of Ga in stoichiometric ratio 2 O 3 Mass, solid phase sintering method or liquid phase sintering method is adoptedSynthesizing polycrystal materials of TAGG garnet crystals by a method;
(2) Crystal growth
Placing the prepared polycrystalline material into an iridium crucible, loading into a pulling furnace, vacuumizing, filling protective gas, heating to melt the polycrystalline material, standing TAGG seed crystal in the melt after the melt is fully and uniformly mixed, then lifting the seed crystal to remove the liquid level of the melt, and then carrying out secondary seed sowing to start crystal growth; the pulling speed is 0.1-5mm/h, the rotating speed is 1-50rpm, when the crystal grows to the required size, the crystal is pulled off, and the temperature is reduced to the room temperature at the cooling speed of 5-100 ℃/h.
According to the process for preparing crystals of the present invention, preferably Tb in step (1) 4 O 7 ，Ga 2 O 3 ，Al 2 O 3 The purity of (3) was 99.999%.
According to the method for producing crystals of the present invention, preferably, the polycrystal material is synthesized in the step (1) by a solid phase sintering method.
According to the preparation method of the crystal, preferably, the sintering temperature of the solid-phase sintering method synthetic polycrystal material in the step (1) is 1300-1500 ℃ and the sintering time is 10-30 hours.
According to the preparation method of the crystal of the invention, ga is taken into consideration 2 O 3 In step (1) by an excess of 1% to 3%, preferably Ga, in the formulation 2 O 3 2% excess of Ga in stoichiometric ratio 2 O 3 Mass meter.
According to the method for producing a crystal of the present invention, preferably, the shielding gas charged in the step (2) is argon.
According to the method for producing a crystal of the present invention, preferably, the seed crystal used for the crystal growth in the step (2) is a <111> oriented seed crystal.
According to the method for producing crystals of the present invention, preferably, the crystal growth in step (2) is carried out by using the "secondary seeding" technique. Firstly, placing TAGG seed crystal in melt to induce the melt to be completely converted into garnet pure phase, eliminating the interference of TAP impurity relative to crystal growth; then lifting the seed crystal off the melt level, then carrying out secondary seeding, and entering a normal crystal growth procedure.
According to the method for producing a crystal of the present invention, it is preferable that the pulling rate at the time of growing the crystal in the step (2) is 0.5 to 2mm/h and the rotation speed is 10 to 20rpm.
According to the method for producing crystals of the present invention, it is preferable that the cooling rate at the time of growing the crystals in the step (2) is 40 to 60 ℃/h.
When the high-alumina TAGG garnet crystal is applied as a magneto-optical crystal, the grown crystal needs to be processed and polished for use.
The use of TAGG garnet crystals as magneto-optical crystals, including but not limited to any of the following:
application of TAGG garnet crystal as key material of magneto-optical isolator, and schematic diagram of magneto-optical isolator is shown in figure 1.
Use of a TAGG garnet crystal as a key material for magneto-optical modulators.
Use of a TAGG garnet crystal as a key material for magneto-optical switches.
Use of a TAGG garnet crystal as a key material for a magneto-optical circulator.
Use of a TAGG garnet crystal as a key material for a fiber optic current sensor.
The invention also provides a magneto-optical isolator, which comprises a Faraday magneto-optical device, wherein the Faraday magneto-optical device is the high-alumina TAGG crystal.
The invention is not described in detail and is in accordance with the prior art.
The technical principle and the excellent effect of the invention are as follows:
TAG crystals have a Verdet constant of about 1.3 to 1.5 times that of TGG crystals, but due to their non-uniform melting characteristics, large-size, high-quality crystals cannot be obtained, and cannot meet the requirements of applications. The high-alumina TAGG garnet crystal is used as a novel magneto-optical crystal, is mainly based on the TAGG crystal to optimize the components and the structure, overcomes the inconsistent melting habit, can adopt a melt method to grow large-size high-quality single crystals, and has optical, thermal and magneto-optical properties equivalent to the TAGG crystal.
In addition, compared with the commercial TGG crystal, the method has the following advantages: (1) reduce Ga 2 O 3 Volatilizing reduces the segregation of the melt components. (2) The high-aluminum TAGG crystal is consistently melted, can be grown by adopting a pulling method, has fewer iridium floats, and is easier to seed in high quality, thus obtaining high-quality single crystals. (3) Ga 2 O 3 Expensive, al 2 O 3 The cost is low, and the cost of crystal growth is greatly reduced. (4) The high-aluminum TAGG crystal combines the high-performance advantages of the TAGG crystal, and compared with the TGG crystal, the high-aluminum TAGG crystal has obviously improved magneto-optical performance, thermal performance, machining performance and the like.
The invention adopts the pulling method to grow the high-aluminum TAGG garnet crystal, has scientific and reasonable preparation method, can realize the growth of large-size and high-quality crystals, has short growth period and simple process, and is easy to realize industrial production.
Drawings
Fig. 1 is a schematic diagram of the magneto-optical isolator principle.
Fig. 2 is a photograph of a TAGG (x=3) crystal prepared in example 3.
Fig. 3 is a photograph of a sample after cutting and polishing of the TAGG (x=3) crystal prepared in example 3.
Fig. 4 is a photograph of a TAGG (x=3.75) crystal prepared in example 4.
Fig. 5 is a comparison of prepared TAGG (x=1.5, 3, 3.75) crystal powder XRD with standard diffraction spectra of TAG crystals.
Fig. 6 is a photograph of a TAGG (x=3.75) crystal prepared in comparative example 3.
Fig. 7 shows the field constants of the TAGG (x=3.75) crystal prepared in example 4 and the TGG (x=0) crystal prepared in comparative example 1 and the TGG (x=1.5) crystal prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are provided by the following detailed description and specific operations, and the scope of protection includes but is not limited to the following specific examples.
The TAGG garnet crystal is used as a key material of a magneto-optical isolator, and the schematic diagram of the magneto-optical isolator is shown in figure 1.
A laser, a polaroid 1, a Faraday rotor and a polaroid 2 are sequentially arranged along an optical path; the TAGG garnet crystal is mounted in a Faraday rotator.
Example 1: TAGG (x=1.75) crystal Tb 3 Al 1.75 Ga 3.25 O 12 Growth
(1) Solid phase sintering process to synthesize polycrystal material
Raw material Tb 4 O 7 ，Al 2 O 3 ，Ga 2 O 3 The purity of (2) was 99.99%. According to stoichiometric ratio Tb 3 Al 1.75 Ga 3.25 O 12 Weighing raw materials, taking Ga into account 2 O 3 Volatile decomposition of Ga during compounding 2 O 3 2wt.% excess, fully mixing the raw materials in a mixing barrel for 48h, pressing the uniformly mixed materials in a mould to form a cylinder, placing in a corundum crucible, and sintering at 1350 ℃ in a sintering furnace for 36h to obtain the polycrystalline material of TAGG (x=1.75)
(2) Czochralski crystal growth
Placing sintered polycrystalline material into iridium crucible (the crucible is placed in the prepared temperature field), centering, installing temperature field, and vacuumizing to 1×10 -4 Pa, filling argon to one atmosphere, adopting an intermediate frequency induction heating iridium crucible, heating to enable raw materials to be melted slowly, slightly overheating 10-20 ℃ to enable the raw materials to react for 0.5h, then adjusting the temperature, putting down a directional seed crystal to enable the seed crystal to stand in a melt for 1 h, then lifting the seed crystal, seeding again, and entering a diameter control program to carry out the stages of shouldering, isodiametric, ending and the like when the diameter of the seed crystal is contracted to 2-3 mm. Pulling speed is 2mm/h in the growth process, rotating speed is 10rpm, when the crystal grows to a set size, lifting off the crystal, cooling to room temperature at a cooling rate of 40 ℃/h, and discharging the crystal.
Example 2: TAGG (x=2) crystal Tb 3 Al 2 Ga 3 O 12 Growth
As described in example 1, the difference is that:
(1) Solid phase sintering process to synthesize polycrystal material
According to stoichiometric ratio Tb 3 Al 2 Ga 3 O 12 Weighing the raw materials to obtainTAGG (x=2) polymorphism.
(2) Czochralski crystal growth
The rotating speed in the growth process is 15rpm, and the cooling rate is 40 ℃/h.
Example 3: TAGG (x=3) crystal Tb 3 Al 3 Ga 2 O 12 Growth
As described in example 1, the difference is that:
(1) Solid phase sintering process to synthesize polycrystal material
According to stoichiometric ratio Tb 3 Al 3 Ga 2 O 12 And weighing the raw materials to obtain TAGG (x=3) polycrystal material.
(2) Czochralski crystal growth
The pulling speed is 1mm/h, the rotating speed is 30rpm, and the cooling rate is 40 ℃/h in the growing process.
Example 4: TAGG (x=3.75) crystal Tb 3 Al 3.75 Ga 1.25 O 12 Growth
As described in example 1, the difference is that:
(1) Solid phase sintering process to synthesize polycrystal material
According to stoichiometric ratio Tb 3 Al 3.75 Ga 1.25 O 12 The raw materials are weighed, and the TAGG (x=3.75) polycrystal material can be obtained.
(2) Czochralski crystal growth
The pulling speed is 1mm/h, the rotating speed is 10rpm, and the cooling rate is 40 ℃/h in the growing process.
Example 5: TAGG (x=4.5) crystal Tb 3 Al 4.5 Ga 0.5 O 12 Growth
As described in example 1, the difference is that:
(1) Solid phase sintering process to synthesize polycrystal material
According to stoichiometric ratio Tb 3 Al 4.5 Ga 0.5 O 12 The raw materials are weighed, and the TAGG (x=4.5) polycrystal material can be obtained.
(2) Czochralski crystal growth
The pulling speed in the growth process is 0.5mm/h, the rotating speed is 30rpm, and the cooling rate is 40 ℃/h.
Example 6: TAGG (x=4.9) crystal Tb 3 Al 4.9 Ga 0.1 O 12 Growth
As described in example 1, the difference is that:
(1) Solid phase sintering process to synthesize polycrystal material
According to stoichiometric ratio Tb 3 Al 4.9 Ga 0.1 O 12 The raw materials are weighed, and the TAGG (x=4.9) polycrystal material can be obtained.
(2) Czochralski crystal growth
The pulling speed in the growth process is 0.3mm/h, the rotating speed is 30rpm, and the cooling rate is 60 ℃/h.
Comparative example 1: pure TGG (x=0) crystal growth
As described in example 1, the difference is that: the components do not contain aluminum, and TGG crystals are grown by adopting a Czochralski method.
Comparative example 2: TAGG (x=1.5) crystal growth
As described in example 1, the difference is that: reducing the aluminum content in the crystal component, namely: x=1.5.
Comparative example 3: TAGG (x=3.75) crystal growth
As described in example 1, the difference is that: crystals are grown using conventional seeding techniques rather than "secondary seeding" techniques.
Test example 1
The crystal photograph of TAGG (x=3.75) obtained in example 4 is shown in fig. 4, and the crystal photograph of comparative example 3 is shown in fig. 6.
As can be seen from fig. 4 and 6, the appearance of the TAGG crystal is complete, no cracking exists, and the quality of the crystal is high by adopting the technique of 'secondary seeding'. The crystals obtained by the conventional seeding process in comparative example 3 were opaque polycrystalline. Therefore, the next process innovation is a key factor that high-aluminum TAGG crystals can realize large-size and high-quality crystal growth.
Test example 2
The magneto-optical properties of the TAGG (x=3.75) crystals prepared in example 4 and the TGG (x=0) crystals prepared in comparative example 1 and the TGG (x=1.5) crystals prepared in comparative example 2 are shown in fig. 7.
As can be seen from the comparison of FIG. 7, the Phillips constant of the high alumina TAGG crystals of the present invention is significantly better than that of the crystals of comparative examples 1 and 2. Therefore, the TAGG crystal of the invention has the aluminum content controlled within a certain range (high aluminum: 1.75 is less than or equal to x < 5), so as to prepare the TAGG crystal with excellent magneto-optical performance and important application prospect.
Claims (9)
1. A preparation method of a high-aluminum terbium aluminum gallium garnet crystal is characterized in that the molecular formula of the crystal is Tb 3 Al x Ga 5- x O 12 X is more than or equal to 3 and less than or equal to 3.75; the growth is carried out by a melt pulling method, firstly, high aluminum terbium aluminum gallium garnet crystal seed crystal is placed in a melt, the melt is induced to be completely converted into a phase of garnet Dan Chun, then the seed crystal is lifted off the liquid level of the melt, and then secondary seeding is carried out, and the crystal growth is started; pulling at 0.1-5mm/h and rotating at 1-50rpm, and cooling to room temperature at 5-100 deg.c/h.
2. The method for preparing high aluminum terbium aluminum gallium garnet crystal according to claim 1, wherein the diameter of the high aluminum terbium aluminum gallium garnet crystal is not less than 5 mm.
3. The method for preparing high-aluminum terbium aluminum gallium garnet crystal according to claim 1, wherein the high-aluminum terbium aluminum gallium garnet crystal has consistent melting characteristics, the transmittance of the high-aluminum terbium aluminum gallium garnet crystal is not less than 80%, and the Phillips constant of the high-aluminum terbium aluminum gallium garnet crystal>45 rad m -1 T -1 @1064 nm。
4. The method for preparing high aluminum terbium aluminum gallium garnet crystal according to claim 1, comprising the steps of:
(1) Polycrystalline material synthesis
Weighing raw material Tb according to stoichiometric ratio 4 O 7 ，Ga 2 O 3 ，Al 2 O 3 And on the basis of this, ga 2 O 3 In an excess of 1 to 3 wt.% to obtain Ga in stoichiometric ratio 2 O 3 Synthesizing polycrystal materials of the high-aluminum terbium aluminum gallium garnet crystal by a solid-phase sintering method or a liquid-phase method;
(2) Crystal growth
Putting the prepared polycrystalline material into an iridium crucible, loading the iridium crucible into a pulling furnace, vacuumizing, filling protective gas, heating to melt the polycrystalline material, after the melt is fully and uniformly mixed, standing a high-aluminum terbium aluminum gallium garnet crystal seed crystal in the melt, then lifting the seed crystal to remove the liquid level of the melt, and then carrying out secondary seeding to start crystal growth; pulling at 0.1-5mm/h and rotating at 1-50rpm, and cooling to room temperature at 5-100 deg.c/h.
5. The method for producing high-alumina terbium aluminum gallium garnet crystal according to claim 4, wherein Tb in step (1) 4 O 7 ，Ga 2 O 3 ，Al 2 O 3 The purity of (2) is 99.999%, and the solid-phase sintering method is adopted to synthesize the polycrystal material in the step (1).
6. The method for preparing high aluminum terbium aluminum gallium garnet crystal according to claim 5, wherein the sintering temperature of the solid phase sintering method synthetic polycrystal material in the step (1) is 1300-1500 ℃ and the sintering time is 10-30 hours.
7. The method of producing high aluminum terbium aluminum gallium garnet crystal according to claim 4, wherein the shielding gas filled in step (2) is argon, and the seed crystal used for crystal growth is a <111> oriented seed crystal.
8. The method for preparing high aluminum terbium aluminum gallium garnet crystal according to claim 4, wherein the pulling rate is 0.5-2mm/h and the rotation speed is 10-20rpm when the crystal is grown in the step (2).
9. The method for preparing high aluminum terbium aluminum gallium garnet crystal according to claim 4, wherein the cooling rate is 40-60 ℃/h when the crystal is grown in the step (2).
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