CN114875490A - 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 218
- 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 16
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 239000000155 melt Substances 0.000 claims abstract description 26
- 238000010899 nucleation Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 38
- 238000005245 sintering Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- FNCIDSNKNZQJTJ-UHFFFAOYSA-N alumane;terbium Chemical compound [AlH3].[Tb] FNCIDSNKNZQJTJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000013307 optical fiber Substances 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 3
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 11
- 230000002194 synthesizing effect Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- 238000004891 communication Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UYVZCGGFTICJMW-UHFFFAOYSA-N [Ir].[Au] Chemical compound [Ir].[Au] UYVZCGGFTICJMW-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006698 induction 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
- 239000000203 mixture 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
-
- 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
Abstract
The invention relates to a high-aluminum terbium aluminum gallium garnet magneto-optical crystal and a preparation method and application thereof. The molecular formula of the crystal is Tb 3 Al x Ga 5‑x O 12 ,1.75≤x<5, abbreviated as TAGG, the crystal belongs to the garnet structure. The high-aluminum TAGG magneto-optical crystal grows by a melt method, adopts a secondary seeding technology to grow and obtain a large-size and high-quality single crystal, is superior to a TGG crystal in magneto-optical, thermal, optical and other properties, and can be used for manufacturing a high-efficiency magneto-optical device.
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, belonging to the technical field of crystals and devices.
Background
The non-reciprocal magneto-optical device based on Faraday magneto-optical effect has wide application in the fields of optical fiber communication, information processing, laser, medicine and the like, and the core of the non-reciprocal magneto-optical device is a magneto-optical crystal, so that the magneto-optical crystal becomes one of the crystals with the highest commercialization degree. In recent years, with the rapid development of optical communication technology (such as terahertz communication) and high-power lasers, the application range of magneto-optical crystals is further expanded, and the requirements on the quality and performance of the crystals are further improved.
In the 400-1100nm (excluding 470-500nm) waveband, the Terbium Gallium Garnet (TGG) crystal is a magneto-optical crystal which is most widely applied and has the highest commercialization degree at present due to high Verdet constant, low absorption coefficient, high thermal conductivity, high laser damage threshold and excellent optical performance. The TGG crystal is mainly grown by a Czochralski method, and the existing problem is that Ga is mainly grown in the growth process 2 O 3 Volatilization and spiral growth are difficult to grow crystals with larger size and high quality, which limits the application of TGG crystals to a great extent, especially in the aspect of high power application, and the crystals crack due to serious light absorption. The Terbium Aluminum Garnet (TAG) crystal and the TGG crystal belong to a cubic crystal system structure, the application waveband is 400-plus 1100nm, the Verdet constant is 1.3-1.5 times of that of the TGG crystal, compared with the TGG crystal, the performance is improved in all aspects, and the crystal is considered to be the best magneto-optical crystal of 400-plus 1100nm, but due to the non-uniform melting characteristic, TAP impurity phase appears at the temperature higher than 1850 ℃, the crystal is difficult to grow, and a large-size single crystal cannot be obtained. The prior art can only adopt a mode-guiding 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-.
The Terbium Aluminum Gallium Garnet (TAGG) mixed crystal combines the advantages of both TGG and TAG crystals, has consistent melting characteristics, can grow the crystals by adopting a melt method, has obvious advantages in the aspects of performance and cost compared with the TGG crystals, and is a potential magneto-optical material with excellent performance. CN102485975A discloses a pulling growth method of Terbium Gallium Garnet (TGG) -doped magneto-optical crystal, which comprises growing aluminum-doped TGG (Tb) 3 Ga 5-x Al x O 12 X is 0-0.5), iron-doped TGG (Tb) 3 Ga 5- x Fe x O 12 ，x0-0.5) or double-doped aluminum iron TGG (Tb) 3 Ga 5-x-y Al x Fe y O 12 And x + y is 0-0.5) magneto-optical crystal, and the crystal size is several times larger than that of the TAG crystal. In addition, domestic fuzhou university further increases the aluminum content in the TAGG single Crystal, but when the substitution ratio is only 34.2%, more defects appear inside 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, the TAGG crystal has excellent magneto-optical characteristics, but the currently reported TAGG crystal has a lower aluminum content (<35%), when the aluminum content in the components is further increased, the crystal growth is very difficult, and no high-aluminum TAGG single crystal (the aluminum content is more than 35%) is reported at present. Therefore, the preparation of high-quality high-aluminum TAGG crystal is a technical problem to be solved at present.
The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects 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 content of Ga in the components and reduces Ga 2 O 3 Volatilization reduces the segregation of melt components, is superior to TGG crystal in the aspects of magneto-optic, thermal, optical and other properties, and can be used for manufacturing high-efficiency magneto-optic devices. The invention can prepare high-quality high-aluminum TAGG crystal, the key technical means is to adopt a secondary seeding technology, and the innovation of the seeding technology is an important factor for obtaining the high-quality large-size TAGG crystal. For TAGG, when the aluminum content in the composition is high, a large amount of TAP impurity phase exists in the crystal melt, so that the single crystal prepared by the conventional seed technology has poor crystallinity and cannot be used in magneto-optical devices. The 'secondary seeding' technology provided by the invention is characterized in that the lower end of TAGG seed crystal is placed in a melt for 0.5-5 hours to induce the melt in a crucible to be completely converted into a garnet pure phase, so that the interference of TAP impurities on the crystal growth is eliminated; and then, extracting seed crystals from the liquid level of the melt, then performing secondary seeding, and entering a normal crystal growth procedure to obtain high-quality TAGG single crystals, wherein the obtained crystals have good transparency and are free of cracks and inclusions, and the prepared magneto-optical device has excellent performance.
The technical scheme of the invention is as follows:
a high-Al terbium Al gallium 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 crystal system, and the space group is Ia3d (230), Al 3+ And Ga 3+ Octahedral and tetrahedral sites.
The crystal according to the present invention, preferably, 3. ltoreq. x < 5; further, x is preferably 3.5, 3.75, 4, or 4.5.
According to the crystal of the invention, the diameter of the high-aluminum TAGG crystal is preferably more than or equal to 5mm, and more preferably 20-100 mm.
According to the crystal of the invention, preferably, the high-aluminum TAGG crystal has consistent melting characteristics, and can be subjected to single crystal growth by a pulling method.
According to the crystal of the invention, the light transmittance of the high-aluminum TAGG crystal is preferably more than or equal to 80%.
The crystal according to the invention, preferably, the high-alumina TAGG crystal has a Phillips 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, standing a TAGG seed crystal in a melt to induce the melt to be completely converted into a garnet pure phase, and eliminating the interference of TAP impurities on the crystal growth; then the seed crystal is lifted off the liquid level of the melt, and then secondary seeding is carried out, and the normal crystal growth procedure is entered.
According to the present invention, preferably, the high aluminum TAGG crystal is grown by a melt pulling method, which includes the following steps:
(1) polycrystalline material synthesis
Weighing Tb as raw material 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 Ga in a stoichiometric excess of 1% to 3% 2 O 3 The mass meter synthesizes a polycrystal material of the TAGG garnet crystal by adopting a solid-phase sintering method or a liquid-phase method;
(2) crystal growth
Putting the prepared polycrystalline material into an iraurita crucible, putting the iraurita crucible into a pulling furnace, vacuumizing, filling protective gas, heating to melt the polycrystalline material, standing the TAGG seed crystal in the melt after the melt is fully mixed uniformly, pulling the seed crystal off the liquid level of the melt, and then performing secondary seeding 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 out, and the temperature is reduced to the room temperature at the cooling rate of 5-100 ℃/h.
According to the production method of the crystal of the present invention, preferably, Tb in step (1) 4 O 7 ，Ga 2 O 3 ，Al 2 O 3 The purity of (D) was 99.999%.
According to the method for producing a crystal of the present invention, it is preferable that the polycrystalline material is synthesized in step (1) by a solid phase sintering method.
According to the preparation method of the crystal, the sintering temperature for synthesizing the polycrystalline material by the solid phase sintering method in the step (1) is 1300-1500 ℃, and the sintering time is 10-30 hours.
According to the method for producing a crystal of the present invention, Ga is considered 2 O 3 By the step (1) of adding an excess of 1% to 3% to the batch, preferably, Ga 2 O 3 Ga in a 2% excess, obtained in stoichiometric ratio 2 O 3 And (4) measuring the mass.
According to the method for producing a crystal of the present invention, it is preferable that the protective gas charged in the step (2) is argon.
According to the method for preparing the crystal of the present invention, it is preferable that the seed crystal used for the crystal growth in the step (2) is a <111> oriented seed crystal.
According to the preparation method of the crystal, preferably, the crystal growth in the step (2) is seeded by a 'secondary seeding' technology. Firstly, standing a TAGG seed crystal in a melt to induce the melt to be completely converted into a garnet pure phase, and eliminating the interference of TAP impurities on the crystal growth; then the seed crystal is lifted off the liquid level of the melt, and then secondary seeding is carried out, and the normal crystal growth procedure is entered.
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 20 rpm.
According to the method for preparing the crystal of the present invention, it is preferable that the cooling rate is 40 to 60 ℃/h when the crystal is grown in the step (2).
When the high-aluminum TAGG garnet crystal is used as a magneto-optical crystal, the grown crystal needs to be processed and polished for use.
The application of the TAGG garnet crystal as a magneto-optical crystal includes, but is not limited to, any one of the following:
the TAGG garnet crystal is applied as a key material of a magneto-optical isolator, and the principle diagram of the magneto-optical isolator is shown in figure 1.
The application of TAGG garnet crystal as key material of magneto-optical modulator.
The TAGG garnet crystal is used as a key material of a magneto-optical switch.
The TAGG garnet crystal is used as a key material of a magneto-optical circulator.
The TAGG garnet crystal is applied as a key material of 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-aluminum TAGG crystal.
The invention has not been described in detail, but is in accordance with the state of the art.
The technical principle and the excellent effects of the invention are as follows:
the Verdet constant of the TAG crystal is about 1.3-1.5 times of that of the TGG crystal, but because of the non-uniform melting characteristic, the TAG crystal cannot obtain a large-size and high-quality crystal and cannot meet the application. The high-aluminum TAGG garnet crystal is used as a novel magneto-optical crystal, is optimized in components and structure mainly based on the TAG crystal, overcomes the non-uniform melting habit, can be used for large-size high-quality single crystal growth by adopting a melt method, and has optical, thermal and magneto-optical properties equivalent to those of the TAG crystal.
In addition, compared with the commercial TGG crystal, the following advantages are provided: firstly, Ga is reduced 2 O 3 Volatilization reduces the segregation of melt components. ② high-aluminum TAGG crystal is uniformly melted, and can be fed by adopting pulling methodThe growth is carried out, the amount of the iridium gold floating objects is less, the high-quality seeding is easier, and the high-quality single crystal is obtained. ③ Ga 2 O 3 High price, Al 2 O 3 The price is low, and the cost of crystal growth is greatly reduced. The high-aluminum TAGG crystal combines the advantage of high performance of the TAG crystal, and compared with the TGG crystal, the magneto-optical performance, the thermal performance, the machining performance and the like are obviously improved.
The method adopts a 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 principle of a magneto-optical isolator.
Fig. 2 is a photograph of a crystal of TAGG (x ═ 3) prepared in example 3.
Fig. 3 is a photograph of a sample after crystal cutting and polishing of TAGG (x ═ 3) prepared in example 3.
Fig. 4 is a photograph of a crystal of TAGG (x ═ 3.75) prepared in example 4.
Figure 5 is a comparison of the prepared TAGG (x ═ 1.5, 3, 3.75) crystal powder XRD against the TAG crystal standard diffraction spectrum.
Fig. 6 is a photograph of a crystal of TAGG (x ═ 3.75) prepared in comparative example 3.
Fig. 7 shows the feld constants of the crystal of TAGG (x ═ 3.75) obtained in example 4, the crystal of TGG (x ═ 0) obtained in comparative example 1, and the crystal of TGG (x ═ 1.5) obtained in comparative example 2.
Detailed Description
The present invention is further illustrated below with reference to examples, which are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation procedures are given, 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 principle diagram of the magneto-optical isolator is shown in figure 1.
A laser, a polaroid 1, a Faraday rotor and a polaroid 2 are arranged along an optical path in sequence; the TAGG garnet crystal was mounted in a Faraday rotor.
Example 1: crystal Tb of TAGG (x ═ 1.75) 3 Al 1.75 Ga 3.25 O 12 Growth of
(1) Solid phase sintering method for synthesizing polycrystal material
Raw material Tb 4 O 7 ，Al 2 O 3 ，Ga 2 O 3 The purity of (2) was 99.99%. In stoichiometric ratio Tb 3 Al 1.75 Ga 3.25 O 12 Weighing raw materials, taking Ga into account 2 O 3 Volatilizing and decomposing of (1), Ga in compounding 2 O 3 2 wt.% excessive, putting the raw materials into a mixing barrel for fully mixing, wherein the mixing time is 48h, putting the uniformly mixed materials into a die for pressing into a cylinder, putting the cylinder into a corundum crucible, and sintering the cylinder for 36h at 1350 ℃ in a sintering furnace to obtain the polycrystal material TAGG (x is 1.75)
(2) Czochralski crystal growth
Putting the sintered polycrystal material into an iraurita crucible (the crucible is already placed in a prepared temperature field), centering, filling the temperature field, and vacuumizing to 1 × 10 -4 And Pa, introducing argon to atmospheric pressure, heating the iraurita crucible by adopting medium-frequency induction, raising the temperature by a program to slowly melt the raw materials, slightly overheating at 10-20 ℃ to fully react the raw materials for 0.5h, then adjusting the temperature, putting down the oriented seed crystal, standing the seed crystal in the melt for 1 h, then taking out the seed crystal, sowing the seed crystal again, and entering a diameter control program to carry out shoulder putting, diameter equalizing, tail ending and other stages when the diameter of the seed crystal is contracted to 2-3 mm. And in the growth process, the pulling speed is 2mm/h, the rotating speed is 10rpm, when the crystal grows to a set size, the crystal is pulled off, the temperature is reduced to room temperature at the cooling rate of 40 ℃/h, and the crystal is discharged.
Example 2: crystal Tb of TAGG (x ═ 2) 3 Al 2 Ga 3 O 12 Growth of the seed
As described in example 1, except that:
(1) solid phase sintering method for synthesizing polycrystal material
In stoichiometric ratio Tb 3 Al 2 Ga 3 O 12 Weighing the raw materials to obtain the TAGG (x is 2) polycrystal material.
(2) Czochralski crystal growth
The rotating speed is 15rpm in the growth process, and the cooling rate is 40 ℃/h.
Example 3: crystal Tb of TAGG (x ═ 3) 3 Al 3 Ga 2 O 12 Growth of the seed
As described in example 1, except that:
(1) solid phase sintering method for synthesizing polycrystal material
In stoichiometric ratio Tb 3 Al 3 Ga 2 O 12 Weighing the raw materials to obtain the TAGG (x is 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 growth process.
Example 4: crystal Tb of TAGG (x ═ 3.75) 3 Al 3.75 Ga 1.25 O 12 Growth of
As described in example 1, except that:
(1) solid phase sintering method for synthesizing polycrystal material
In stoichiometric ratio Tb 3 Al 3.75 Ga 1.25 O 12 Weighing the raw materials to obtain the TAGG (x is 3.75) polycrystal material.
(2) Czochralski crystal growth
The pulling speed is 1mm/h, the rotating speed is 10rpm, and the cooling rate is 40 ℃/h in the growth process.
Example 5: crystal Tb of TAGG (x ═ 4.5) 3 Al 4.5 Ga 0.5 O 12 Growth of
As described in example 1, except that:
(1) solid phase sintering method for synthesizing polycrystal material
In stoichiometric ratio Tb 3 Al 4.5 Ga 0.5 O 12 Weighing the raw materials to obtain the TAGG (x is 4.5) polycrystal material.
(2) Czochralski crystal growth
The pulling speed is 0.5mm/h, the rotating speed is 30rpm, and the cooling rate is 40 ℃/h in the growth process.
Example 6: crystal Tb of TAGG (x ═ 4.9) 3 Al 4.9 Ga 0.1 O 12 Growth of
As described in example 1, except that:
(1) solid phase sintering method for synthesizing polycrystal material
In stoichiometric ratio Tb 3 Al 4.9 Ga 0.1 O 12 Weighing the raw materials to obtain the TAGG (x is 4.9) polycrystal material.
(2) Czochralski crystal growth
The pulling speed is 0.3mm/h, the rotating speed is 30rpm, and the cooling rate is 60 ℃/h in the growth process.
Comparative example 1: pure TGG (x ═ 0) crystal growth
As described in example 1, except that: the components do not contain aluminum, and a Czochralski method is adopted to grow TGG crystals.
Comparative example 2: crystal growth of TAGG (x ═ 1.5)
As described in example 1, except that: reducing the aluminum content in the crystal component, namely: x is 1.5.
Comparative example 3: crystal growth of TAGG (x ═ 3.75)
As described in example 1, except that: the crystal is grown by adopting a conventional seeding process instead of a secondary seeding technology.
Test example 1
A crystal photograph of TAGG (x ═ 3.75) obtained in example 4 is shown in fig. 4, and a crystal photograph of comparative example 3 is shown in fig. 6.
As can be seen from the figures 4 and 6, the TAGG crystal adopting the secondary seeding technology has complete appearance, no cracking and high crystal quality. The crystal obtained by the conventional seeding process in comparative example 3 was an opaque polycrystal. Therefore, the next technological innovation is a key factor for realizing the growth of large-size and high-quality high-aluminum TAGG crystals.
Test example 2
The magneto-optical properties of the crystal of TAGG (x ═ 3.75) obtained in example 4, the crystal of TGG (x ═ 0) obtained in comparative example 1, and the crystal of TGG (x ═ 1.5) obtained in comparative example 2 are shown in fig. 7.
As can be seen from the comparison of FIG. 7, the Phillid constant of the high-alumina TAGG crystal of the present invention is significantly superior to that of the crystals of comparative examples 1 and 2. Therefore, the TAGG crystal of the invention has excellent magneto-optical performance and important application prospect only by controlling the aluminum content in a certain range (x is more than or equal to 1.75 and less than 5 of high aluminum).
Claims (10)
1. A high-Al terbium Al gallium garnet crystal is characterized in that the molecular formula of the crystal is Tb 3 Al x Ga 5-x O 12 ,1.75≤x<5。
2. The high-aluminum terbium aluminum gallium garnet crystal according to claim 1, characterized in that x is 3. ltoreq. x < 5.
3. The 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;
preferably, the high aluminum terbium aluminum gallium garnet crystal has consistent melting characteristics;
preferably, the transmittance of the high-aluminum terbium aluminum gallium garnet crystal is more than or equal to 80 percent;
preferably, the high-aluminum terbium aluminum gallium garnet crystal has a Phillid constant>45rad m -1 T -1 @1064nm。
4. A method of preparing the high-aluminum terbium aluminum gallium garnet crystal of claim 1 comprising: the crystal seed crystal of high aluminum terbium aluminum gallium garnet is placed in the melt statically to induce the melt to be completely converted into garnet pure phase, then the crystal seed is lifted off the melt liquid surface, and then secondary seeding is carried out to enter a normal crystal growth procedure.
5. The method for preparing a high-aluminum terbium aluminum gallium garnet crystal according to claim 4, wherein the melt method is a melt pulling method comprising the following steps:
(1) polycrystalline material synthesis
Weighing Tb as raw material 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 Ga in an excess of 1 to 3% by weight, obtained in stoichiometric ratio 2 O 3 The mass meter synthesizes a polycrystal material of the high-aluminum terbium aluminum gallium garnet crystal by adopting a solid-phase sintering method or a liquid-phase method;
(2) crystal growth
Putting the prepared polycrystalline material into an iraurita crucible, putting the iraurita crucible into a pulling furnace, vacuumizing, filling protective gas, heating to melt the polycrystalline material, standing a high-aluminum terbium aluminum gallium garnet crystal seed crystal in a melt after the melt is fully mixed uniformly, then pulling the seed crystal off the liquid level of the melt, and then performing secondary seeding 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 out, and the temperature is reduced to the room temperature at the cooling rate of 5-100 ℃/h.
6. The method for preparing a high-aluminum terbium aluminum gallium garnet crystal according to claim 5, wherein Tb in step (1) 4 O 7 ，Ga 2 O 3 ，Al 2 O 3 The purity of (A) is 99.999%;
preferably, the polycrystalline material is synthesized in step (1) by a solid-phase sintering method.
7. The method for preparing a terbium aluminum gallium garnet crystal with high aluminum content according to claim 5, wherein the sintering temperature of the polycrystalline material synthesized by the solid phase sintering method in the step (1) is 1300-1500 ℃, and the sintering time is 10-30 hours.
8. The method for preparing a high-aluminum terbium aluminum gallium garnet crystal according to claim 5, wherein the protective gas charged in the step (2) is argon;
preferably, the seed crystal used for the crystal growth in the step (2) is a <111> oriented seed crystal;
preferably, the pulling speed is 0.5-2mm/h and the rotating speed is 10-20rpm when the crystal is grown in the step (2);
preferably, the temperature reduction rate is 40-60 ℃/h when the crystal is grown in the step (2).
9. A use of the high-aluminum terbium aluminum gallium garnet crystal of claim 1 in the following fields:
use as a device material for magneto-optical isolators;
use as a device material for magneto-optical modulators;
use as a device material for a magneto-optical switch;
use as a device material for magneto-optical circulators;
the material is applied to optical fiber current sensor devices.
10. A magneto-optical isolator comprising a faraday magneto-optical device, wherein said faraday magneto-optical device is a high aluminum terbium aluminum gallium garnet crystal of claim 1.
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