CN111254495A - Method for preparing terbium gallium garnet single crystal from polycrystalline raw material - Google Patents

Method for preparing terbium gallium garnet single crystal from polycrystalline raw material Download PDF

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CN111254495A
CN111254495A CN202010180146.4A CN202010180146A CN111254495A CN 111254495 A CN111254495 A CN 111254495A CN 202010180146 A CN202010180146 A CN 202010180146A CN 111254495 A CN111254495 A CN 111254495A
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raw material
crucible
polycrystalline raw
gallium garnet
polycrystalline
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侯田江
马晓
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Yangtze Optical Fibre and Cable Co Ltd
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Yangtze Optical Fibre and Cable Co Ltd
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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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a method for preparing terbium gallium garnet single crystals from polycrystalline raw materials, which comprises the following steps: (1) preparing raw materials: drying Ga2O3And Tb4O7The raw materials are mixed according to a preset proportion, and the mixture is uniformly mixed and then is loaded into a die to be pressed into a compact raw material block; (2) assembling the pulling furnace: the compact raw material block is loaded into a crucible arranged in a thermal field in a single crystal pulling furnace, an upper thermal field, a seed crystal rod and seed crystals are loaded, the top height of the crucible is calibrated by the tail end of the seed crystals, and the pulling furnace is assembled in a sealing way to form an oxygen-free atmosphere; (3) polycrystalline raw material synthesis: medium-frequency induction heating is adopted, and the power of the medium-frequency induction heating is controlled in a gradient manner, so that the compact raw material blocks are gradually sintered and finally melted from bottom to top and from outside to inside; (4) seed crystal descending: descending the seed crystal rod to enable the tail end of the seed crystal rod to be in contact with the liquid level of the polycrystalline raw material melt; (5) and (3) lifting and growing: seeding crystal growthGrowing the terbium gallium garnet crystal, and cooling and annealing to obtain the single crystal terbium gallium garnet crystal. The invention shortens the period, improves the production efficiency and can avoid the pollution of raw materials for many times.

Description

Method for preparing terbium gallium garnet single crystal from polycrystalline raw material
Technical Field
The invention belongs to the field of artificial crystals, and particularly relates to a method for preparing terbium gallium garnet single crystals from polycrystalline raw materials.
Background
At present, a pulling method is generally adopted for growing terbium gallium garnet single crystals by polycrystalline raw materials, and the pulling method relates to a plurality of process procedures such as raw material preparation, polycrystalline raw material synthesis, pulling growth, cooling annealing and the like. The whole process cycle of the terbium gallium garnet crystal is related to the size of the grown crystal, the larger the size is, the more raw materials are needed, and multiple feeding is often needed to meet the requirement of the grown raw materials. The common method for preparing the polycrystalline raw material is to press the mixed raw materials into blocks, then put the blocks into a container and sinter the blocks by a muffle furnace.
According to the preparation method of the polycrystalline raw material, the polycrystalline material after sintering is loose and easy to adhere to the inner wall of the container, and is easy to break in the process of taking out and transferring to the crucible, so that the density of the raw material is greatly reduced, the quality of the raw material added into the crucible each time is low, more times of feeding are needed, the growth period is long, and the efficiency is low; meanwhile, the transfer of raw materials can cause inevitable pollution of polycrystalline materials and influence the quality of crystals. In addition, muffle furnaces are not generally sealed to maintain an atmosphere, and gallium oxide components in the feedstock are more volatile at high temperatures, resulting in compositional drift and environmental pollution.
Disclosure of Invention
In view of the above drawbacks and needs of the prior art, the present invention provides a method for preparing a terbium gallium garnet single crystal from a polycrystalline raw material, which aims to solve the technical problems of contamination and inefficiency caused by transferring the sintered polycrystalline raw material into a crucible of a pulling furnace, which are required in the prior art, a small amount of times by directly completing sintering and melting of the polycrystalline raw material in the pulling furnace in which the terbium gallium garnet single crystal is grown.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing terbium gallium garnet single crystals from a polycrystalline raw material, comprising the steps of:
(1) preparing raw materials: drying Ga2O3And Tb4O7The raw materials are mixed according to a preset proportion, and the mixture is uniformly mixed and then is loaded into a die to be pressed into a compact raw material block;
(2) assembling the pulling furnace: filling the compact raw material blocks obtained in the step (1) into a crucible arranged in a temperature field in a single crystal pulling furnace, filling an upper temperature field, a seed crystal rod and seed crystals, calibrating the top height of the crucible by using the tail end of the seed crystals, and sealing and assembling the pulling furnace to form an oxygen-free atmosphere;
(3) polycrystalline raw material synthesis: medium-frequency induction heating is adopted, and the power of the medium-frequency induction heating is controlled in a gradient manner, so that the compact raw material blocks are gradually sintered and finally melted from bottom to top and from outside to inside;
(4) seed crystal descending: descending the seed crystal rod to enable the tail end of the seed crystal rod to be in contact with the liquid level of the polycrystalline raw material melt;
(5) and (3) lifting and growing: growing terbium gallium garnet crystal by seeding, and cooling and annealing to obtain the single crystal terbium gallium garnet crystal.
Preferably, the method for preparing terbium gallium garnet single crystals from polycrystalline raw materials comprises the specific process of the step (3) as follows:
the first stage is as follows: increasing the medium-frequency induction heating power to P1 so as to control the bottom of the crucible to be rapidly heated to the polycrystalline raw material sintering temperature, and enabling the central temperature of the bottom of the crucible to reach the polycrystalline raw material sintering temperature;
and a second stage: increasing the medium-frequency induction heating power from P1 to P2 so as to control the crucible to slowly raise the temperature, and increasing the medium-frequency induction heating power from P1 to P2 so that the overall temperature of the top area of the crucible reaches the sintering temperature of the sintered polycrystalline raw materials, wherein the stage lasts for more than 12 hours;
and a third stage: and increasing the medium-frequency induction heating power from P2 to P3 and maintaining P3 so as to control the crucible to rapidly heat up and preserve heat, so that the center temperature of the top of the crucible reaches the melting temperature of the polycrystalline raw material.
Preferably, the method for preparing the terbium gallium garnet single crystal from the polycrystalline raw material comprises the steps that the bottom of a crucible is a height region from the bottom of the crucible to the axial direction upward 0-5 mm, and the top of the crucible is a height region from the top of the crucible to the axial direction downward 10 +/-2 mm.
Preferably, in the method for preparing the terbium gallium garnet single crystal from the polycrystalline raw material, the sintering temperature of the polycrystalline raw material is 1300-1400 ℃, and the melting temperature of the polycrystalline raw material is 1700-1750 ℃.
Preferably, the method for preparing terbium gallium garnet single crystals from polycrystalline raw materials, wherein the step (4) further comprises: and (3) when the seed rod is lowered to enable the tail end of the seed rod to be in contact with the polycrystalline raw material melt liquid, obtaining the liquid level height by adopting a calibration method, and repeating the steps (1) to (4) until the liquid level height meets the process requirement when the liquid level height is lower than the liquid level height required by the process.
Preferably, in the method for preparing terbium gallium garnet single crystals from polycrystalline raw materials, the cross section shape of the compact raw material block in the step (1) is matched with the shape of the inner wall of a crucible in a pulling furnace for preparing terbium gallium garnet single crystals, the height of the compact raw material block is preferably higher than the height of the inner wall of the crucible, and the height of the compact raw material block is more preferably higher than the height of the inner wall of the crucible by 10-15 mm.
Preferably, in the method for preparing terbium gallium garnet single from polycrystalline raw materials, in the step (1), the compact raw material block is in a shoulder shape at the upper part, and is in a cylinder shape with the same diameter at the lower part, the diameter of the cylindrical cross section at the lower part of the block is smaller than the inner diameter of the crucible of the pulling furnace, and the difference is less than or equal to 5 mm.
Preferably, in the method for preparing terbium gallium garnet single crystals from polycrystalline raw materials, the step (1) of loading into the mold for pressing is carried out by pressing and molding by using an isostatic press under the pressure of more than or equal to 200 MPa.
Preferably, in the method for preparing terbium gallium garnet single crystals from polycrystalline raw materials, the step (2) of forming the oxygen-free atmosphere specifically comprises:
vacuuming and injecting N2And/or CO2As a protective atmosphere.
Preferably, in the method for preparing terbium gallium garnet single crystals from polycrystalline raw materials, the crucible pot top is 8-12 mm higher than the top of the medium-frequency induction coil during the assembly of the pulling furnace in the step (2).
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the density of polycrystalline raw materials sintered by the muffle furnace is smaller than that of initial lump materials, and the polycrystalline raw materials are transferred to an iridium crucible and are more likely to be crushed, so that the density of the raw materials is further reduced, so that the method for sintering the polycrystalline by directly adding the lump materials into the crucible has more raw materials added at one time, the crystal production period is obviously saved, and the production efficiency is improved;
(2) the method does not need to transfer crystal raw materials, and can avoid multiple raw material pollution;
(3) the method can sinter in atmosphere, reduce volatilization and reduce the deviation of crystal growth components;
(4) according to the method, due to the distribution of the thermal field in the crucible, the sintering process is from bottom to top, the sintering is carried out layer by layer, and the sintering is more sufficient after the temperature gradient process.
Drawings
FIG. 1 is a schematic view of a pulling furnace assembly provided by an embodiment;
FIG. 2 is a schematic diagram of the gradient power control of the IF power supply in the polycrystalline sintering and melting processes of the embodiment.
In all the drawings, the same reference numerals are used for representing the same elements or structures, wherein ① is an iraurita crucible, ② is an outer heat-insulating wall, ③ is an inner heat-insulating wall, ④ is a block raw material, ⑤ is heat-insulating sand, ⑥ is an iraurita rod, ⑦ is TGG <111> seed crystal, and ⑧ is a medium-frequency induction coil.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for preparing terbium gallium garnet single crystal from polycrystalline raw materials, which comprises the following steps:
(1) preparing raw materials: drying Ga2O3(99.999%) and Tb4O7(99.99%) the raw materials are mixed according to a preset proportion, and the mixture is uniformly mixed and then is put into a die to be pressed into a compact raw material block; the cross section shape of the compact raw material block is matched with the shape of the inner wall of a crucible in a pulling furnace for preparing terbium gallium garnet single crystals, the height of the compact raw material block is higher than the height of the inner wall of the crucible, preferably, the height of the compact raw material block is 10-15 mm higher than the height of the inner wall of the crucible, more preferably, the height of the compact raw material block is 10mm higher than the height of the inner wall of the crucible, and the volume of the compact raw material block after being melted does not exceed the. Preferably, the densified feedstock piecesThe upper part of the lump material is in a shoulder shape, the lower part of the lump material is in an equal-diameter cylinder shape, the diameter of the cylindrical cross section of the lower part of the lump material is smaller than the inner diameter of the crucible of the pulling furnace, and the difference value is smaller than or equal to 5 mm. The pressing in the mold is preferably carried out by pressing and molding by an isostatic press under the pressure of more than or equal to 200 MPa.
(2) Assembling the pulling furnace: loading the compact raw material block obtained in step (1) into a crucible installed in a thermal field in a single crystal pulling furnace, installing an upper thermal field, a seed rod and a seed crystal, calibrating the height of the top of the crucible with the end of the seed crystal, hermetically assembling the pulling furnace and forming an oxygen-free atmosphere, e.g., vacuumizing and injecting N2And/or CO2As a protective atmosphere; the top of the crucible pot is 8 mm-12 mm, preferably 10mm higher than the top of the medium-frequency induction coil.
(3) Polycrystalline raw material synthesis: medium-frequency induction heating is adopted, and the power of the medium-frequency induction heating is controlled in a gradient manner, so that the compact raw material blocks are gradually sintered and finally melted from bottom to top and from outside to inside; the specific process comprises the following steps:
the first stage is as follows: increasing the medium-frequency induction heating power to P1 so as to control the bottom of the crucible to be rapidly heated to the polycrystalline raw material sintering temperature, and enabling the central temperature of the bottom of the crucible to reach the polycrystalline raw material sintering temperature; p1 is preferably the power to maintain the temperature of the center of the bottom of the crucible at the sintering temperature of the sintered polycrystalline feedstock.
And a second stage: increasing the medium-frequency induction heating power from P1 to P2 so as to control the crucible to slowly raise the temperature, and increasing the medium-frequency induction heating power from P1 to P2 so that the overall temperature of the top area of the crucible reaches the sintering temperature of the sintered polycrystalline raw materials, wherein the stage lasts for more than 12 hours; p2 is preferably the power to maintain the temperature of the crucible top region at the sintering temperature of the polycrystalline feedstock.
And a third stage: and increasing the medium-frequency induction heating power from P2 to P3 and maintaining P3 so as to control the crucible to rapidly heat up and preserve heat, so that the center temperature of the top of the crucible reaches the melting temperature of the polycrystalline raw material. P3 is preferably the power to maintain the temperature of the region in the top of the crucible at the melting temperature of the polycrystalline feed material.
The bottom of the crucible is preferably selected to be a region with the height from the bottom of the crucible to the axial direction upward 0-5 mm, and the top of the crucible is preferably selected to be a region with the height from the top of the crucible to the axial direction downward 10 +/-2 mm. The sintering temperature of the polycrystalline raw material is 1300-1400 ℃, the preferred temperature is 1300 ℃, and the melting temperature of the polycrystalline raw material is 1700-1750 ℃.
(4) Seed crystal descending: and lowering the seed rod to enable the tail end of the seed rod to contact the liquid level of the polycrystalline raw material melt. Preferably, when the seed rod is lowered to enable the tail end of the seed rod to contact the polycrystalline raw material melt liquid, the liquid level height is obtained by adopting a calibration method, and when the liquid level height is lower than the liquid level height required by the process, the steps (1) to (4) are repeated until the liquid level height meets the process requirement.
(5) And (3) lifting and growing: growing terbium gallium garnet crystal by seeding, and obtaining single crystal terbium gallium garnet crystal by cooling and annealing
The method for preparing the terbium gallium garnet single crystal from the polycrystalline raw material avoids the process that the polycrystalline raw material sintered by the muffle furnace is repeatedly transferred to the pulling furnace in the traditional method, and directly sinters and melts the polycrystalline raw material in the pulling furnace.
The following are examples:
a method for preparing terbium gallium garnet single crystal from polycrystalline raw materials comprises the following steps:
(1) preparing raw materials: drying Ga2O3(99.999%) and Tb4O7(99.99%) the starting materials were dosed in a molar ratio Tb: Ga 3:5, and appropriately Ga-enriched2O3And putting the mixture into a mixing barrel, fully mixing the mixture for 12 to 16 hours by using a mixer, putting the fully mixed raw materials into a mould, and pressing the fully mixed raw materials into a compact block by using an isostatic press under the pressure of more than 200 MPa.
The compact raw material block is in a shape that the upper part is in a shoulder shape, namely the upper part is in a circular truncated cone shape, the diameter of the section of the upper part is smaller than that of the section of the lower part, the height of the circular truncated cone is 12mm, the lower part is in a cylindrical shape with the same diameter, and the diameter of the cylindrical section of the lower part of the block is 76mm (slightly smaller than the used crucible with the inner diameter of 80 mm).
(2) And (3) assembling the pulling furnace, namely, filling the compact raw material blocks obtained in the step (1) into a crucible arranged in a thermal field in the single crystal pulling furnace, wherein the thermal field is provided with an inner thermal insulation wall ③, thermal insulation sand ⑤ and an outer thermal insulation wall ② from inside to outside as shown in figure 1, and in order to add more raw materials as much as possible, the height of the block raw material ④ is 12mm higher than the top of the crucible ①.
Then adjusting a seed rod ⑥ and a seed crystal ⑦, calibrating the height H0 of the surface of the crucible by using the tail end of the seed crystal ⑦, installing an upper temperature field, cleaning a hearth and closing a furnace door.
Then, the hearth is vacuumized and filled with N2And CO2The furnace atmosphere is maintained.
(3) Polycrystalline raw material synthesis: medium-frequency induction heating is adopted, and the power of the medium-frequency induction heating is controlled in a gradient manner, so that the compact raw material blocks are gradually sintered and finally melted from bottom to top and from outside to inside; specifically, as shown in fig. 2:
the first stage is as follows: 0 to t1The time is 5h, the power is manually increased to a certain value P0 which is lower than the power corresponding to 1300 ℃ of bottom sintering, so as to reach the sintering point faster; then quickly heating the bottom of the crucible to 1300 ℃ by program sectional control, wherein the power is P1; the power value of P1 is 7500W (corresponding to the sintering temperature at the bottom of the crucible), and the program control is carried out;
and a second stage: t is t1～t2The time is 15h, the power is increased to P2 by program sectional control, the temperature of the axial-10 mm height area at the top of the crucible is slightly more than 1300 ℃, and the time from P1 to P2 is more than 12h, namely the power increasing rate is less than (P2-P1)/12h, and the higher the crucible is, the longer the time is, the enough sintering time of the upper raw material is ensured; through the power control process, the raw materials of each layer of the raw materials in the vertical direction in the crucible undergo the stage from uniform mixture → white polycrystalline material, and the raw materials are processed layer by layer from bottom to top, the polycrystalline raw materials at the bottom of the crucible are partially melted in the upper-layer sintering process, and the upper part of the crucible is collapsed and descended, so that the mixed materials exceeding the crucible are descended to the sintering area. The power value of P2 is 8500W (corresponding to the sintering temperature at the top of the crucible), and the program control is carried out;
and a third stage: t is t2～t3The time is 2h, the melting and heating stage is shown, P3 is all the melting power points of the polycrystalline material (i.e. the central temperature 1700-1750 ℃ at the position which is 10mm away from the top of the crucible), and the constant power is shownP3 after a certain time (i.e. t)3～t4The power is finely adjusted by observing the liquid level for the completion time of melting, until the material is completely melted), the upper polycrystalline material will be melted successively to form a complete melt. P3 power value was 12.5kW (corresponding to a melting temperature at which the top of the crucible was completely melted), program controlled;
(4) seed crystal descending: descending the seed crystal rod to enable the tail end of the seed crystal rod to be in contact with the liquid level of the polycrystalline raw material melt;
pulling down the seed crystal rod ⑥, when the tail end of the seed crystal ⑦ just contacts the liquid level, calibrating the liquid level height at this time to be H1, wherein the Delta H is (H1-H0) which is the distance between the liquid level and the top of the crucible, because the density of the raw material is far less than the density of the melt, the Delta H is more than or equal to H (H is 10mm shown in figure 1) after one-time feeding generally, when the Delta H is approximately equal to H, seeding growth can be started, and if the Delta H is far more than H, the secondary feeding amount needs to be checked again according to the liquid level height difference, and the steps (1) to (4) are repeated.
(5) And (3) lifting and growing: growing terbium gallium garnet crystal by seeding, and cooling and annealing to obtain the single crystal terbium gallium garnet crystal.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A method for preparing terbium gallium garnet single crystals from polycrystalline raw materials is characterized by comprising the following steps:
(1) preparing raw materials: drying Ga2O3And Tb4O7The raw materials are mixed according to a preset proportion, and the mixture is uniformly mixed and then is loaded into a die to be pressed into a compact raw material block;
(2) assembling the pulling furnace: filling the compact raw material blocks obtained in the step (1) into a crucible arranged in a temperature field in a single crystal pulling furnace, filling an upper temperature field, a seed crystal rod and seed crystals, calibrating the top height of the crucible by using the tail end of the seed crystals, and sealing and assembling the pulling furnace to form an oxygen-free atmosphere;
(3) polycrystalline raw material synthesis: medium-frequency induction heating is adopted, and the power of the medium-frequency induction heating is controlled in a gradient manner, so that the compact raw material blocks are gradually sintered and finally melted from bottom to top and from outside to inside;
(4) seed crystal descending: descending the seed crystal rod to enable the tail end of the seed crystal rod to be in contact with the liquid level of the polycrystalline raw material melt;
(5) and (3) lifting and growing: growing terbium gallium garnet crystal by seeding, and cooling and annealing to obtain the single crystal terbium gallium garnet crystal.
2. The method for preparing terbium gallium garnet single crystals from a polycrystalline raw material as claimed in claim 1, wherein the specific process of the step (3) comprises:
the first stage is as follows: increasing the medium-frequency induction heating power to P1 so as to control the bottom of the crucible to be rapidly heated to the polycrystalline raw material sintering temperature, and enabling the central temperature of the bottom of the crucible to reach the polycrystalline raw material sintering temperature;
and a second stage: increasing the medium-frequency induction heating power from P1 to P2 so as to control the crucible to slowly raise the temperature, and increasing the medium-frequency induction heating power from P1 to P2 so that the overall temperature of the top area of the crucible reaches the sintering temperature of the sintered polycrystalline raw materials, wherein the stage lasts for more than 12 hours;
and a third stage: and increasing the medium-frequency induction heating power from P2 to P3 and maintaining P3 so as to control the crucible to rapidly heat up and preserve heat, so that the center temperature of the top of the crucible reaches the melting temperature of the polycrystalline raw material.
3. The method for preparing terbium gallium garnet single crystals from a polycrystalline raw material as claimed in claim 2, wherein the bottom of the crucible is a region from the bottom of the crucible to a height of 0 to 5mm axially upward from the bottom, and the top of the crucible is a region from the top of the crucible to a height of 10 ± 2mm axially downward.
4. The method for preparing terbium gallium garnet sheets from a polycrystalline raw material as claimed in claim 2, wherein the sintering temperature of the polycrystalline raw material is between 1300 ℃ and 1400 ℃, and the melting temperature of the polycrystalline raw material is 1700 ℃ to 1750 ℃.
5. The method for preparing terbium gallium garnet sheets from a polycrystalline raw material as claimed in claim 1, wherein the step (4) further comprises: and (3) when the seed rod is lowered to enable the tail end of the seed rod to be in contact with the polycrystalline raw material melt liquid, obtaining the liquid level height by adopting a calibration method, and repeating the steps (1) to (4) until the liquid level height meets the process requirement when the liquid level height is lower than the liquid level height required by the process.
6. The method for preparing terbium gallium garnet single crystals from a polycrystalline raw material as claimed in claim 1, wherein the compact raw material block of step (1) has a cross-sectional shape matching the shape of the inner wall of the crucible in the pulling furnace for preparing terbium gallium garnet single crystals, preferably a height higher than the height of the inner wall of the crucible, more preferably a height higher than the height of the inner wall of the crucible by 10mm to 15 mm.
7. The method for preparing terbium gallium garnet sheet from a polycrystalline raw material according to claim 1, wherein the compact raw material block of the step (1) has a shape in which an upper portion is shoulder-shaped and a lower portion is a cylinder having a constant diameter, and the diameter of the cross section of the cylinder of the lower portion of the block is smaller than the inner diameter of the crucible of the pulling furnace by a difference of 5mm or less.
8. The method for preparing terbium gallium garnet sheet from a polycrystalline raw material as claimed in claim 1, wherein the mold-charging press of step (1) is press-formed using an isostatic press at a pressure of 200MPa or more.
9. The method for preparing terbium gallium garnet sheets from a polycrystalline raw material as claimed in claim 1, wherein said forming of the oxygen-free atmosphere of step (2) is specifically:
vacuuming and injecting N2And/or CO2As a protective atmosphere.
10. The method for preparing terbium gallium garnet sheet from a polycrystalline raw material as claimed in claim 1, wherein the step (2) of pulling the furnace is assembled such that the crucible top is 8mm to 12mm higher than the top of the medium frequency induction coil.
CN202010180146.4A 2020-03-16 2020-03-16 Method for preparing terbium gallium garnet single crystal from polycrystalline raw material Pending CN111254495A (en)

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WO2004065324A1 (en) * 2003-01-20 2004-08-05 Ube Industries, Ltd. Ceramic composite material for optical conversion and use thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114318537A (en) * 2021-12-31 2022-04-12 安徽科瑞思创晶体材料有限责任公司 Terbium gallium garnet crystal and growth method thereof

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