WO2021068153A1 - Gallium oxide crystal growing method using cold crucible - Google Patents

Gallium oxide crystal growing method using cold crucible Download PDF

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WO2021068153A1
WO2021068153A1 PCT/CN2019/110321 CN2019110321W WO2021068153A1 WO 2021068153 A1 WO2021068153 A1 WO 2021068153A1 CN 2019110321 W CN2019110321 W CN 2019110321W WO 2021068153 A1 WO2021068153 A1 WO 2021068153A1
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crucible
water
melt
copper tube
cooled copper
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PCT/CN2019/110321
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French (fr)
Chinese (zh)
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唐慧丽
徐军
赵衡煜
何诺天
李东振
王东海
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南京同溧晶体材料研究院有限公司
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Priority to CN201980032816.3A priority Critical patent/CN112513342A/en
Priority to PCT/CN2019/110321 priority patent/WO2021068153A1/en
Publication of WO2021068153A1 publication Critical patent/WO2021068153A1/en

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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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger 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
    • C30B15/36—Single-crystal growth by pulling from a melt, e.g. Czochralski method characterised by the seed, e.g. its crystallographic orientation
    • 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
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
    • 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

Definitions

  • the invention relates to the field of chemistry, in particular to a method for growing a gallium oxide crystal cold crucible.
  • FETs field effect transistors
  • Schottky diodes Schottky diodes
  • gas sensors etc.
  • gallium oxide ultra-high voltage power devices have great application value in electromagnetic railguns and military radars.
  • Gallium oxide has five crystal structures of ⁇ , ⁇ , ⁇ , ⁇ and ⁇ , among which the ⁇ -type structure is the most stable, and the other phases are transformed into ⁇ phase when the temperature is higher than 850°C.
  • ⁇ -Ga 2 O 3 is a uniformly molten compound, which can be grown by the melt method to obtain ⁇ -Ga 2 O 3 bulk crystals.
  • the difficulty in growing gallium oxide crystals is that Ga 2 O 3 will undergo the following decomposition reactions in a high-temperature and oxygen-deficient growth atmosphere:
  • the present invention proposes a cold crucible growth method for gallium oxide crystals.
  • the invention provides a gallium oxide crystal cold crucible growth method, including the following steps:
  • the melt continues to generate heat under the action of the high-frequency induction coil, and the high-purity Ga 2 O 3 spherical raw material is poured into the melt to fully melt the newly-introduced high-purity Ga 2 O 3 spherical raw material.
  • the volume of the melt Further expand until the seed crystal and the melt are fully welded;
  • the high-purity Ga 2 O 3 spherical raw material is spherical particles with a diameter of 1 to 3 mm.
  • the heating frequency of the high-frequency induction coil is 0.5-2MHz, and the power is 50-200kw.
  • the cold crucible includes a crucible support column (1), a water-cooled copper tube crucible (2) arranged on the top of the crucible support column (1), and a high-frequency induction coil arranged around the outer side wall of the water-cooled copper tube crucible (2) (4); or the cold crucible includes a crucible support column (1), a water-cooled copper tube crucible (2), a zirconia ceramic crucible (3), a high-frequency induction coil (4); the water-cooled copper tube crucible (2) Fixed on the top of the crucible support column (1); the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on top of the refractory bricks (5); the high frequency The induction coil (4) is ringed on the outer side wall of the water-cooled copper tube crucible (2).
  • the diameter of the zirconia ceramic crucible is 40-160 mm, thereby reducing the amount of raw materials.
  • the invention also provides a cold crucible for growing gallium oxide crystals, comprising a crucible support column (1), a water-cooled copper tube crucible (2) arranged on the top of the crucible support column (1), and a water-cooled copper tube crucible ring (2) High-frequency induction coil (4) on the outer side wall; or, including crucible support column (1), water-cooled copper tube crucible (2), zirconia ceramic crucible (3), high-frequency induction coil (4);
  • the water-cooled copper tube crucible (2) is fixed on the top of the crucible support column (1); the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on the refractory bricks ( 5) The top; the high-frequency induction coil (4) is arranged around the outer side wall of the water-cooled copper tube crucible (2).
  • the method for growing gallium oxide crystals provided by the present invention is simple in process, no noble metal crucibles such as iridium and gold are needed, and the cold crucible melt shell formed by gallium oxide raw materials isolates the melt from the crucible, and greatly reduces the cost of crystal growth; graphite rods When ignited, the reaction product is CO 2 , which will not pollute the crystal; the normal-pressure air atmosphere is used to grow the crystal to inhibit the reaction from proceeding to the decomposition direction of gallium oxide, which effectively solves the problem of decomposition and volatilization during the growth process, and reduces the The pressure requirements of the equipment.
  • Figure 1 is a schematic diagram of the structure of a cold crucible used to grow gallium oxide crystals.
  • 1. Crucible support column; 2. Water-cooled copper tube crucible; 3. Zirconia ceramic crucible; 4. High frequency induction coil; 5.
  • Graphite rod 1.
  • the cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2) set on the top of the crucible support column (1), and a high-frequency induction coil (4) ringed on the outer side wall of the water-cooled copper tube crucible (2). ).
  • the water-cooled copper tube crucible is gradually lowered at a speed of 1 mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the cold crucible shell formed by the raw materials outside the melt is maintained constant.
  • the cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2), a zirconia ceramic crucible (3), and a high-frequency induction coil (4); the water-cooled copper tube crucible (2) is fixed on the crucible support column (1) Top; the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on top of the refractory bricks (5); the high-frequency induction coil (4) The ring is arranged on the outer side wall of the water-cooled copper tube crucible (2).
  • the water-cooled copper tube crucible is gradually lowered at a speed of 2.5mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the melt shell of the cold crucible formed by the raw materials outside the melt constant.
  • the cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2), a zirconia ceramic crucible (3), and a high-frequency induction coil (4); the water-cooled copper tube crucible (2) is fixed on the crucible support column (1) Top; the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on top of the refractory bricks (5); the high-frequency induction coil (4) The ring is arranged on the outer side wall of the water-cooled copper tube crucible (2).
  • the water-cooled copper tube crucible is gradually lowered at a speed of 0.5mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the melt shell of the cold crucible formed by the raw materials outside the melt constant.
  • the cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2) set on the top of the crucible support column (1), and a high-frequency induction coil (4) ringed on the outer side wall of the water-cooled copper tube crucible (2). ).
  • the water-cooled copper tube crucible is gradually lowered at a speed of 3mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the cold crucible shell formed by the raw materials outside the melt is maintained constant;
  • the temperature is slowly lowered and annealed, and cooled to room temperature to obtain a gallium oxide ( ⁇ -Ga 2 O 3 ) crystal.
  • the cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2) set on the top of the crucible support column (1), and a high-frequency induction coil (4) ringed on the outer side wall of the water-cooled copper tube crucible (2). ).
  • the water-cooled copper tube crucible is gradually lowered at a speed of 4mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the cold crucible shell formed by the raw material outside the melt is maintained constant;
  • the temperature is slowly lowered and annealed, and cooled to room temperature to obtain a gallium oxide ( ⁇ -Ga 2 O 3 ) crystal.

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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 present invention provides a gallium oxide crystal growing method using a cold crucible, comprising the following steps: placing β-Ga 2O 3 seed crystals and piling up high-purity Ga 2O 3 to form a raw material pile; starting a high-frequency induction generator power supply and inserting two graphite rods into the raw material pile; raising the heating power of the graphite rods until electric sparks are generated between the graphite rods so as to ignite the graphite rods to melt the surrounding spherical high-purity Ga 2O 3 raw material to form molten mass which continues to generate heat under the action of a high-frequency induction coil; adding the spherical high-purity Ga 2O 3 raw material into the molten mass to fully melt same so that the volume of the molten mass is further expanded until the seed crystal and the molten mass are in full contact with each other; gradually lowering a water-cooled copper tube crucible to enable the crystal to grow upward gradually from the seed crystal; and performing cooling and annealing. The method has a simple process and can greatly reduce the cost of crystal growth. The use of atmospheric air atmosphere to grow crystals not only effectively solves the problem of decomposition and volatilization during the growth process, but also lowers the pressure requirements of a device.

Description

一种氧化镓晶体冷坩埚生长方法Method for growing gallium oxide crystal cold crucible 技术领域Technical field
本发明涉及化学领域，特别涉及一种氧化镓晶体冷坩埚生长方法。The invention relates to the field of chemistry, in particular to a method for growing a gallium oxide crystal cold crucible.
背景技术Background technique
氧化镓(β-Ga 2O 3)晶体是一种超宽禁带半导体材料，具有禁带宽度大(Eg＝4.8～5.2eV)，吸收截止边短(～260nm)，击穿电场强度高(8MV/cm)，化学性能稳定，适合熔体法生长等优点。因此，β-Ga 2O 3成为高压、高功率器件和深紫外光电子器件的优选材料之一，可应用于场效应晶体管(FETs)、日盲紫外探测器、肖特基二极管、气体传感器等。近年来，氧化镓材料及器件的研究与应用呈现出显著的加速发展势头，成为当前德国、日本、美国等国家的研究热点和竞争重点。2016年1月，美国海军实验室设立了高效氧化镓薄膜外延项目，明确指出氧化镓超高压功率器件在电磁轨道炮、军用雷达等方面的具有重大应用价值。 Gallium oxide (β-Ga 2 O 3 ) crystal is an ultra-wide bandgap semiconductor material with a large forbidden band width (Eg=4.8～5.2eV), short absorption cut-off edge (～260nm), and high breakdown electric field strength ( 8MV/cm), stable chemical properties, suitable for melt growth and other advantages. Therefore, β-Ga 2 O 3 has become one of the preferred materials for high-voltage, high-power devices and deep ultraviolet optoelectronic devices, and can be applied to field effect transistors (FETs), solar-blind ultraviolet detectors, Schottky diodes, gas sensors, etc. In recent years, the research and application of gallium oxide materials and devices has shown a significant momentum of accelerated development, becoming the current research hotspot and competition focus in Germany, Japan, the United States and other countries. In January 2016, the U.S. Naval Laboratory established a high-efficiency gallium oxide thin film epitaxy project, which clearly pointed out that gallium oxide ultra-high voltage power devices have great application value in electromagnetic railguns and military radars.
氧化镓具有α、β、ε、δ和γ五种晶体结构，其中β型结构最稳定，温度高于850℃时其它相均转化为β相。β-Ga 2O 3为一致熔融化合物，能够采用熔体法生长获得β-Ga 2O 3体块晶体。生长氧化镓晶体的难点在于：在高温缺氧的生长气氛中Ga 2O 3会发生如下分解反应：
Figure PCTCN2019110321-appb-000001
Gallium oxide has five crystal structures of α, β, ε, δ and γ, among which the β-type structure is the most stable, and the other phases are transformed into β phase when the temperature is higher than 850°C. β-Ga 2 O 3 is a uniformly molten compound, which can be grown by the melt method to obtain β-Ga 2 O 3 bulk crystals. The difficulty in growing gallium oxide crystals is that Ga 2 O 3 will undergo the following decomposition reactions in a high-temperature and oxygen-deficient growth atmosphere:
Figure PCTCN2019110321-appb-000001
生成低价镓的氧化物和单质镓等产物；而镓会与铱金形成合金，造成贵金属损失；并且β-Ga 2O 3易产生挛晶、镶嵌结构、解理开裂、螺位错等缺陷。因此，获得大尺寸、高质量β-Ga 2O 3晶体极为困难。提拉法和导模法是目前生长大尺寸氧化镓晶体较为成功的方法。德国莱布尼茨晶体生长研究所采用提拉法成功生长出2英寸β-Ga 2O 3晶体，日本田村制作所(Tamura)和光波公司(Koha Co.,Ltd)采用导模法技术率先实现商品化2英寸β-Ga 2O 3基片，并试生长出6英寸晶体坯片。但这两种生长方法存在不足之处：提拉法和导模法生长β-Ga 2O 3晶体均采用铱金坩埚，而镓会对铱金坩埚内壁造成严重的腐蚀，铱金损耗量较大；为了抑制生长过程中Ga 2O 3的分解挥发，莱布尼茨晶体生长研究所采 用7bar高压CO 2气氛生长晶体，这对设备的耐压性提出了更加苛刻的要求。 Produce low-valent gallium oxides and elemental gallium and other products; gallium will form alloys with iridium and gold, causing loss of precious metals; and β-Ga 2 O 3 is prone to defects such as twin crystals, mosaic structures, cleavage cracks, screw dislocations, etc. . Therefore, it is extremely difficult to obtain large-size, high-quality β-Ga 2 O 3 crystals. The pulling method and the guided mode method are currently more successful methods for growing large-size gallium oxide crystals. The Leibniz Institute of Crystal Growth in Germany used the Czochralski method to successfully grow 2-inch β-Ga 2 O 3 crystals. Tamura and Koha Co., Ltd. took the lead in using guided mode technology. Commercialized a 2-inch β-Ga 2 O 3 substrate and tried to grow a 6-inch crystal blank. However, these two growth methods have shortcomings: the Czochralski method and the guided mode method both use iridium crucibles to grow β-Ga 2 O 3 crystals, and gallium will cause serious corrosion to the inner wall of the iridium crucible, and the loss of iridium is relatively high. Large; In order to suppress the decomposition and volatilization of Ga 2 O 3 during the growth process, the Leibniz Institute for Crystal Growth uses a 7bar high-pressure CO 2 atmosphere to grow crystals, which puts more stringent requirements on the pressure resistance of the equipment.
发明内容Summary of the invention
技术问题：针对现有技术的不足，本发明提出了一种氧化镓晶体冷坩埚生长方法。Technical problem: Aiming at the shortcomings of the prior art, the present invention proposes a cold crucible growth method for gallium oxide crystals.
技术方案：本发明提供的一种氧化镓晶体冷坩埚生长方法，包括以下步骤：Technical solution: The invention provides a gallium oxide crystal cold crucible growth method, including the following steps:
(1)在水冷铜管坩埚底部放置β-Ga 2O 3籽晶，在水冷铜管坩埚中堆积高纯Ga 2O 3圆球状原料形成原料堆；或者在水冷铜管坩埚内放置氧化锆陶瓷坩埚，在氧化锆陶瓷坩埚底部放置β-Ga 2O 3籽晶，在氧化锆陶瓷坩埚中堆积高纯Ga 2O 3圆球状原料形成原料堆； (1) Place β-Ga 2 O 3 seed crystals at the bottom of the water-cooled copper tube crucible, and pile high-purity Ga 2 O 3 spherical raw materials in the water-cooled copper tube crucible to form a raw material pile; or place zirconia ceramics in the water-cooled copper tube crucible In the crucible, β-Ga 2 O 3 seed crystals are placed at the bottom of the zirconia ceramic crucible, and high-purity Ga 2 O 3 spherical raw materials are stacked in the zirconia ceramic crucible to form a raw material pile;
(2)启动感应线圈的加热电源，将两根石墨棒插入原料堆中并保持两根石墨棒下端的初始间距为5～20mm；升高石墨棒的加热功率至石墨棒之间产生电火花，石墨棒起燃使周围的高纯Ga 2O 3圆球状原料熔融，形成熔体； (2) Start the heating power supply of the induction coil, insert two graphite rods into the raw material pile and keep the initial distance between the lower ends of the two graphite rods at 5-20mm; increase the heating power of the graphite rods until electric sparks are generated between the graphite rods, The graphite rod ignites to melt the surrounding high-purity Ga 2 O 3 spherical raw materials to form a melt;
(3)控制两根石墨棒下端的间距和石墨棒的加热功率，熔体体积不断增大，直到达到高纯Ga 2O 3圆球状原料启动熔体体积，收起石墨棒； (3) Control the distance between the lower ends of the two graphite rods and the heating power of the graphite rods, and the melt volume will continue to increase until it reaches the high-purity Ga 2 O 3 spherical raw material to start the melt volume, and the graphite rods are retracted;
(4)熔体在高频感应线圈的作用下持续发热，向熔体中投入高纯Ga 2O 3圆球状原料，使新投入的高纯Ga 2O 3圆球状原料充分熔化，熔体体积进一步扩大，直至籽晶与熔体充分熔接； (4) The melt continues to generate heat under the action of the high-frequency induction coil, and the high-purity Ga 2 O 3 spherical raw material is poured into the melt to fully melt the newly-introduced high-purity Ga 2 O 3 spherical raw material. The volume of the melt Further expand until the seed crystal and the melt are fully welded;
(5)熔体稳定30～60分钟后，将水冷铜管坩埚以0.5～5mm/h速度逐渐下降，晶体自籽晶处逐步向上结晶生长，此过程中熔体外部由原料形成的冷坩埚熔壳的位置保持不变；(5) After the melt is stable for 30-60 minutes, the water-cooled copper tube crucible is gradually lowered at a speed of 0.5-5mm/h, and the crystal gradually grows upward from the seed crystal. During this process, the cold crucible formed by the raw material outside the melt is melted The position of the shell remains unchanged;
(6)晶体生长结束后，缓慢降温退火，冷却至室温。(6) After the crystal growth is completed, slowly cool down and anneal, and cool to room temperature.
优选地，所述高纯Ga 2O 3圆球状原料为直径1～3mm的圆球颗粒。 Preferably, the high-purity Ga 2 O 3 spherical raw material is spherical particles with a diameter of 1 to 3 mm.
优选地，高频感应线圈的加热频率为0.5～2MHz，功率为50～200kw。Preferably, the heating frequency of the high-frequency induction coil is 0.5-2MHz, and the power is 50-200kw.
优选地，所述冷坩埚包括坩埚支撑柱(1)、设置于坩埚支撑柱(1)顶部的水冷铜管坩埚(2)、环设于水冷铜管坩埚(2)外侧壁的高频感应线圈(4)；或者所述冷坩埚包括坩埚支撑柱(1)、水冷铜管坩埚(2)、氧化锆陶瓷坩埚(3)、高频感应线圈(4)；所述水冷铜管坩埚(2)固定于坩埚支撑柱(1)顶部；所述水冷铜管坩埚(2)内设有耐火砖(5)，所述氧化锆陶瓷坩埚(3)置于耐火砖(5)顶部；所述高频感应线圈(4)环设于水冷铜管坩埚(2)外侧壁。Preferably, the cold crucible includes a crucible support column (1), a water-cooled copper tube crucible (2) arranged on the top of the crucible support column (1), and a high-frequency induction coil arranged around the outer side wall of the water-cooled copper tube crucible (2) (4); or the cold crucible includes a crucible support column (1), a water-cooled copper tube crucible (2), a zirconia ceramic crucible (3), a high-frequency induction coil (4); the water-cooled copper tube crucible (2) Fixed on the top of the crucible support column (1); the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on top of the refractory bricks (5); the high frequency The induction coil (4) is ringed on the outer side wall of the water-cooled copper tube crucible (2).
优选地，所述氧化锆陶瓷坩埚的直径为40～160mm，从而减少原料用量。Preferably, the diameter of the zirconia ceramic crucible is 40-160 mm, thereby reducing the amount of raw materials.
本发明还提供了一种用于生长氧化镓晶体的冷坩埚，包括坩埚支撑柱(1)、设置于坩埚支撑柱(1)顶部的水冷铜管坩埚(2)、环设于水冷铜管坩埚(2)外侧壁上的高频感应线圈(4)；或者，包括坩埚支撑柱(1)、水冷铜管坩埚(2)、氧化锆陶瓷坩埚(3)、高频感应线圈(4)；所述水冷铜管坩埚(2)固定于坩埚支撑柱(1)顶部；所述水冷铜管坩埚(2)内设有耐火砖(5)，所述氧化锆陶瓷坩埚(3)置于耐火砖(5)顶部；所述高频感应线圈(4)环设于水冷铜管坩埚(2)外侧壁。The invention also provides a cold crucible for growing gallium oxide crystals, comprising a crucible support column (1), a water-cooled copper tube crucible (2) arranged on the top of the crucible support column (1), and a water-cooled copper tube crucible ring (2) High-frequency induction coil (4) on the outer side wall; or, including crucible support column (1), water-cooled copper tube crucible (2), zirconia ceramic crucible (3), high-frequency induction coil (4); The water-cooled copper tube crucible (2) is fixed on the top of the crucible support column (1); the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on the refractory bricks ( 5) The top; the high-frequency induction coil (4) is arranged around the outer side wall of the water-cooled copper tube crucible (2).
有益效果：本发明提供的生长氧化镓晶体的方法工艺简单，无需使用铱金等贵金属坩埚，利用氧化镓原料形成的冷坩埚熔壳将熔体与坩埚隔离，大幅降低长晶成本；采用石墨棒引燃，其反应产物为CO 2，不会对晶体产生污染；采用常压空气气氛生长晶体，抑制反应向氧化镓的分解方向进行，有效解决了生长过程中的分解挥发问题，同时降低了对设备的耐压要求。 Beneficial effects: The method for growing gallium oxide crystals provided by the present invention is simple in process, no noble metal crucibles such as iridium and gold are needed, and the cold crucible melt shell formed by gallium oxide raw materials isolates the melt from the crucible, and greatly reduces the cost of crystal growth; graphite rods When ignited, the reaction product is CO 2 , which will not pollute the crystal; the normal-pressure air atmosphere is used to grow the crystal to inhibit the reaction from proceeding to the decomposition direction of gallium oxide, which effectively solves the problem of decomposition and volatilization during the growth process, and reduces the The pressure requirements of the equipment.
附图说明Description of the drawings
图1为用于生长氧化镓晶体的冷坩埚的结构示意图，图中：1.坩埚支撑柱；2.水冷铜管坩埚；3.氧化锆陶瓷坩埚；4.高频感应线圈；5.耐火砖；6.β-Ga 2O 3籽晶；7.氧化镓圆球状原料；8.石墨棒。 Figure 1 is a schematic diagram of the structure of a cold crucible used to grow gallium oxide crystals. In the figure: 1. Crucible support column; 2. Water-cooled copper tube crucible; 3. Zirconia ceramic crucible; 4. High frequency induction coil; 5. Refractory brick ; 6. β-Ga 2 O 3 seed crystal; 7. Gallium oxide spherical raw material; 8. Graphite rod.
具体实施方式Detailed ways
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。Further examples are given below to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and cannot be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the present invention. The scope of protection.
实施例1Example 1
使用的冷坩埚包括坩埚支撑柱(1)、设置于坩埚支撑柱(1)顶部的水冷铜管坩埚(2)、环设于水冷铜管坩埚(2)外侧壁上的高频感应线圈(4)。The cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2) set on the top of the crucible support column (1), and a high-frequency induction coil (4) ringed on the outer side wall of the water-cooled copper tube crucible (2). ).
(1)在水冷铜管坩埚底部放置β-Ga 2O 3籽晶，在坩埚内填入直径1～3mm高纯Ga 2O 3圆球状原料3kg，将石墨棒安装在夹具上作为引燃物。 (1) Place β-Ga 2 O 3 seed crystals at the bottom of the water-cooled copper tube crucible , fill the crucible with 3 kg of high-purity Ga 2 O 3 spherical raw materials with a diameter of 1 to 3 mm, and install the graphite rod on the fixture as an ignitor .
(2)启动感应线圈的加热电源，将两根石墨棒插入原料堆深度约为10mm，并保持石墨棒下端的初始间距约为10mm；感应线圈频率为1MHz，加热功率升高至100kw，石墨棒之间产生电火花使周围Ga 2O 3原料熔融，形成小熔池。 (2) Start the heating power supply of the induction coil, insert two graphite rods into the raw material pile to a depth of about 10mm, and keep the initial distance between the lower ends of the graphite rods about 10mm; the frequency of the induction coil is 1MHz, the heating power is increased to 100kw, the graphite rod An electric spark is generated between the surrounding Ga 2 O 3 raw materials to melt, forming a small molten pool.
(3)控制石磨棒下端的间距和加热功率，逐步拉开石墨棒增大熔体的体积，直到达到启动熔体体积收起石墨棒。(3) Control the spacing and heating power of the lower end of the stone grinding rod, and gradually pull the graphite rod apart to increase the volume of the melt until it reaches the start-up melt volume to retract the graphite rod.
(4)熔体在感应线圈的作用下持续发热，向熔体中投入高纯Ga 2O 3圆球颗粒料，使新投入的原料充分熔化，熔体体积进一步扩大，直至籽晶与熔体充分熔接。 (4) The melt continues to generate heat under the action of the induction coil, and high-purity Ga 2 O 3 pellets are put into the melt to fully melt the newly input raw materials, and the melt volume further expands until the seed crystal and the melt Fully welded.
(5)熔体稳定30分钟后，将水冷铜管坩埚以1mm/h速度逐渐下降，晶体自籽晶处逐步向上结晶生长，此过程中熔体外部由原料形成的冷坩埚熔壳的位置保持不变。(5) After the melt is stable for 30 minutes, the water-cooled copper tube crucible is gradually lowered at a speed of 1 mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the cold crucible shell formed by the raw materials outside the melt is maintained constant.
(6)晶体生长结束后，缓慢降温退火，冷却至室温，即得氧化镓(β-Ga 2O 3)晶体。 (6) After the crystal growth is completed, slowly cool down and anneal, and cool to room temperature to obtain a gallium oxide (β-Ga 2 O 3 ) crystal.
实施例2Example 2
使用的冷坩埚包括坩埚支撑柱(1)、水冷铜管坩埚(2)、氧化锆陶瓷坩埚(3)、高频感应线圈(4)；所述水冷铜管坩埚(2)固定于坩埚支撑柱(1)顶部；所述水冷铜管坩埚(2)内设有耐火砖(5)，所述氧化锆陶瓷坩埚(3)置于耐火砖(5)顶部；所述高频感应线圈(4)环设于水冷铜管坩埚(2)外侧壁上。The cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2), a zirconia ceramic crucible (3), and a high-frequency induction coil (4); the water-cooled copper tube crucible (2) is fixed on the crucible support column (1) Top; the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on top of the refractory bricks (5); the high-frequency induction coil (4) The ring is arranged on the outer side wall of the water-cooled copper tube crucible (2).
(1)水冷铜管坩埚内放置直径为160mm氧化锆陶瓷坩埚，将β-Ga 2O 3籽晶放置于氧化锆陶瓷底部，在坩埚内填入直径1～3mm高纯Ga 2O 3圆球状原料1.2kg，将石墨棒安装在夹具上作为引燃物。 (1) Place a zirconia ceramic crucible with a diameter of 160mm in the water-cooled copper tube crucible, place the β-Ga 2 O 3 seed crystal on the bottom of the zirconia ceramic, and fill the crucible with a spherical shape of high purity Ga 2 O 3 with a diameter of 1 to 3 mm The raw material is 1.2kg, and the graphite rod is installed on the fixture as an ignitor.
(2)启动感应线圈的加热电源，将两根石墨棒插入原料堆深度约为10mm，并保持石墨棒下端的初始间距约为10mm；感应线圈频率为0.5MHz，加热功率升高至80kw，石墨棒之间产生电火花使周围Ga 2O 3原料熔融，形成小熔池。 (2) Start the heating power supply of the induction coil, insert two graphite rods into the raw material pile to a depth of about 10mm, and keep the initial distance between the lower ends of the graphite rods about 10mm; the frequency of the induction coil is 0.5MHz, and the heating power is increased to 80kw. An electric spark is generated between the rods to melt the surrounding Ga 2 O 3 raw materials to form a small molten pool.
(3)控制石磨棒下端的间距和加热功率，逐步拉开石墨棒增大熔体的体积，直到达到启动熔体体积收起石墨棒。(3) Control the spacing and heating power of the lower end of the stone grinding rod, and gradually pull the graphite rod apart to increase the volume of the melt until it reaches the start-up melt volume to retract the graphite rod.
(4)熔体在感应线圈的作用下持续发热，向熔体中投入高纯Ga 2O 3圆球颗粒料，使新投入的原料充分熔化，熔体体积进一步扩大，直至籽晶与熔体充分熔接。 (4) The melt continues to generate heat under the action of the induction coil, and high-purity Ga 2 O 3 pellets are put into the melt to fully melt the newly input raw materials, and the melt volume further expands until the seed crystal and the melt Fully welded.
(5)熔体稳定45分钟后，将水冷铜管坩埚以2.5mm/h速度逐渐下降，晶体自籽晶处逐步向上结晶生长，此过程中熔体外部由原料形成的冷坩埚熔壳的位置保持不变。(5) After the melt is stable for 45 minutes, the water-cooled copper tube crucible is gradually lowered at a speed of 2.5mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the melt shell of the cold crucible formed by the raw materials outside the melt constant.
(6)晶体生长结束后，缓慢降温退火，冷却至室温，即得氧化镓(β-Ga 2O 3)晶体。 (6) After the crystal growth is completed, slowly cool down and anneal, and cool to room temperature to obtain a gallium oxide (β-Ga 2 O 3 ) crystal.
实施例3Example 3
使用的冷坩埚包括坩埚支撑柱(1)、水冷铜管坩埚(2)、氧化锆陶瓷坩埚(3)、高频感应线圈(4)；所述水冷铜管坩埚(2)固定于坩埚支撑柱(1)顶部；所述水冷铜管 坩埚(2)内设有耐火砖(5)，所述氧化锆陶瓷坩埚(3)置于耐火砖(5)顶部；所述高频感应线圈(4)环设于水冷铜管坩埚(2)外侧壁上。The cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2), a zirconia ceramic crucible (3), and a high-frequency induction coil (4); the water-cooled copper tube crucible (2) is fixed on the crucible support column (1) Top; the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on top of the refractory bricks (5); the high-frequency induction coil (4) The ring is arranged on the outer side wall of the water-cooled copper tube crucible (2).
(1)水冷铜管坩埚内放置直径为40mm氧化锆陶瓷坩埚，将β-Ga 2O 3籽晶放置于氧化锆陶瓷底部，在坩埚内填入直径1～3mm高纯Ga 2O 3圆球状原料300g，将石墨棒安装在夹具上作为引燃物。 (1) Place a zirconia ceramic crucible with a diameter of 40mm in the water-cooled copper tube crucible, place the β-Ga 2 O 3 seed crystal on the bottom of the zirconia ceramic, and fill the crucible with a spherical shape of high purity Ga 2 O 3 with a diameter of 1 to 3 mm The raw material is 300g, and the graphite rod is installed on the jig as an ignitor.
(2)启动感应线圈的加热电源，将两根石墨棒插入原料堆深度约为10mm，并保持石墨棒下端的初始间距约为5mm；感应线圈频率为0.5MHz，加热功率升高至50kw，石墨棒之间产生电火花使周围Ga 2O 3原料熔融，形成小熔池。 (2) Start the heating power supply of the induction coil, insert two graphite rods into the raw material pile to a depth of about 10mm, and keep the initial distance between the lower ends of the graphite rods about 5mm; the frequency of the induction coil is 0.5MHz, and the heating power is increased to 50kw. An electric spark is generated between the rods to melt the surrounding Ga 2 O 3 raw materials to form a small molten pool.
(3)控制石磨棒下端的间距和加热功率，逐步拉开石墨棒增大熔体的体积，直到达到启动熔体体积收起石墨棒。(3) Control the spacing and heating power of the lower end of the stone grinding rod, and gradually pull the graphite rod apart to increase the volume of the melt until it reaches the start-up melt volume to retract the graphite rod.
(4)熔体在感应线圈的作用下持续发热，向熔体中投入高纯Ga 2O 3圆球颗粒料，使新投入的原料充分熔化，熔体体积进一步扩大，直至籽晶与熔体充分熔接。 (4) The melt continues to generate heat under the action of the induction coil, and high-purity Ga 2 O 3 pellets are put into the melt to fully melt the newly input raw materials, and the melt volume further expands until the seed crystal and the melt Fully welded.
(5)熔体稳定30分钟后，将水冷铜管坩埚以0.5mm/h速度逐渐下降，晶体自籽晶处逐步向上结晶生长，此过程中熔体外部由原料形成的冷坩埚熔壳的位置保持不变。(5) After the melt is stable for 30 minutes, the water-cooled copper tube crucible is gradually lowered at a speed of 0.5mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the melt shell of the cold crucible formed by the raw materials outside the melt constant.
(6)晶体生长结束后，缓慢降温退火，冷却至室温，即得氧化镓(β-Ga 2O 3)晶体。 (6) After the crystal growth is completed, slowly cool down and anneal, and cool to room temperature to obtain a gallium oxide (β-Ga 2 O 3 ) crystal.
实施例4Example 4
使用的冷坩埚包括坩埚支撑柱(1)、设置于坩埚支撑柱(1)顶部的水冷铜管坩埚(2)、环设于水冷铜管坩埚(2)外侧壁上的高频感应线圈(4)。The cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2) set on the top of the crucible support column (1), and a high-frequency induction coil (4) ringed on the outer side wall of the water-cooled copper tube crucible (2). ).
(1)在水冷铜管坩埚底部放置β-Ga 2O 3籽晶，在坩埚内填入直径1～3mm高纯Ga 2O 3圆球状原料7.5kg，将石墨棒安装在夹具上作为引燃物。 (1) Place β-Ga 2 O 3 seed crystals at the bottom of the water-cooled copper tube crucible , fill the crucible with 7.5 kg of high-purity Ga 2 O 3 spherical raw materials with a diameter of 1 to 3 mm, and install the graphite rod on the fixture for ignition Things.
(2)启动感应线圈的加热电源，将两根石墨棒插入原料堆深度约为20mm，并保持石墨棒下端的初始间距约为20mm；感应线圈频率为2MHz，加热功率升高至200kw，石墨棒之间产生电火花使周围Ga 2O 3原料熔融，形成小熔池。 (2) Start the heating power supply of the induction coil, insert two graphite rods into the raw material pile to a depth of about 20mm, and keep the initial distance between the lower ends of the graphite rods about 20mm; the frequency of the induction coil is 2MHz, the heating power is increased to 200kw, and the graphite rods An electric spark is generated between the surrounding Ga 2 O 3 raw materials to melt, forming a small molten pool.
(3)控制石磨棒下端的间距和加热功率，逐步拉开石墨棒增大熔体的体积，直到达到启动熔体体积收起石墨棒。(3) Control the spacing and heating power of the lower end of the stone grinding rod, and gradually pull the graphite rod apart to increase the volume of the melt until it reaches the start-up melt volume to retract the graphite rod.
(4)熔体在感应线圈的作用下持续发热，向熔体中投入高纯Ga 2O 3圆球颗粒料，使新投入的原料充分熔化，熔体体积进一步扩大，直至籽晶与熔体充分熔接。 (4) The melt continues to generate heat under the action of the induction coil, and high-purity Ga 2 O 3 pellets are put into the melt to fully melt the newly input raw materials, and the melt volume further expands until the seed crystal and the melt Fully welded.
(5)熔体稳定60分钟后，将水冷铜管坩埚以3mm/h速度逐渐下降，晶体自籽晶处逐步向上结晶生长，此过程中熔体外部由原料形成的冷坩埚熔壳的位置保持不变；(5) After the melt is stable for 60 minutes, the water-cooled copper tube crucible is gradually lowered at a speed of 3mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the cold crucible shell formed by the raw materials outside the melt is maintained constant;
晶体生长结束后，缓慢降温退火，冷却至室温，即得氧化镓(β-Ga 2O 3)晶体。 After the crystal growth is completed, the temperature is slowly lowered and annealed, and cooled to room temperature to obtain a gallium oxide (β-Ga 2 O 3 ) crystal.
实施例5Example 5
使用的冷坩埚包括坩埚支撑柱(1)、设置于坩埚支撑柱(1)顶部的水冷铜管坩埚(2)、环设于水冷铜管坩埚(2)外侧壁上的高频感应线圈(4)。The cold crucible used includes a crucible support column (1), a water-cooled copper tube crucible (2) set on the top of the crucible support column (1), and a high-frequency induction coil (4) ringed on the outer side wall of the water-cooled copper tube crucible (2). ).
(1)在水冷铜管坩埚底部放置β-Ga 2O 3籽晶，在坩埚内填入直径1～3mm高纯Ga 2O 3圆球状原料7.5kg，将石墨棒安装在夹具上作为引燃物。 (1) Place β-Ga 2 O 3 seed crystals at the bottom of the water-cooled copper tube crucible , fill the crucible with 7.5 kg of high-purity Ga 2 O 3 spherical raw materials with a diameter of 1 to 3 mm, and install the graphite rod on the fixture for ignition Things.
(2)启动感应线圈的加热电源，将两根石墨棒插入原料堆深度约为5mm，并保持石墨棒下端的初始间距约为5mm；感应线圈频率为0.5MHz，加热功率升高至200kw，石墨棒之间产生电火花使周围Ga 2O 3原料熔融，形成小熔池。 (2) Start the heating power supply of the induction coil, insert two graphite rods into the raw material pile to a depth of about 5mm, and keep the initial distance between the lower ends of the graphite rods about 5mm; the frequency of the induction coil is 0.5MHz, and the heating power is increased to 200kw. An electric spark is generated between the rods to melt the surrounding Ga 2 O 3 raw materials to form a small molten pool.
(3)控制石磨棒下端的间距和加热功率，逐步拉开石墨棒增大熔体的体积，直到达到启动熔体体积收起石墨棒。(3) Control the spacing and heating power of the lower end of the stone grinding rod, and gradually pull the graphite rod apart to increase the volume of the melt until it reaches the start-up melt volume to retract the graphite rod.
(4)熔体在感应线圈的作用下持续发热，向熔体中投入高纯Ga 2O 3圆球颗粒料，使新投入的原料充分熔化，熔体体积进一步扩大，直至籽晶与熔体充分熔接。 (4) The melt continues to generate heat under the action of the induction coil, and high-purity Ga 2 O 3 pellets are put into the melt to fully melt the newly input raw materials, and the melt volume further expands until the seed crystal and the melt Fully welded.
(5)熔体稳定60分钟后，将水冷铜管坩埚以4mm/h速度逐渐下降，晶体自籽晶处逐步向上结晶生长，此过程中熔体外部由原料形成的冷坩埚熔壳的位置保持不变；(5) After the melt is stable for 60 minutes, the water-cooled copper tube crucible is gradually lowered at a speed of 4mm/h, and the crystals gradually crystallize upward from the seed crystal. During this process, the position of the cold crucible shell formed by the raw material outside the melt is maintained constant;
晶体生长结束后，缓慢降温退火，冷却至室温，即得氧化镓(β-Ga 2O 3)晶体。 After the crystal growth is completed, the temperature is slowly lowered and annealed, and cooled to room temperature to obtain a gallium oxide (β-Ga 2 O 3 ) crystal.

Claims (6)

  1. 一种氧化镓晶体冷坩埚生长方法，其特征在于：包括以下步骤：A method for growing gallium oxide crystals in a cold crucible is characterized in that it comprises the following steps:
    (1)在水冷铜管坩埚底部放置β-Ga 2O 3籽晶，在水冷铜管坩埚中堆积高纯Ga 2O 3圆球状原料形成原料堆；或者在水冷铜管坩埚内放置氧化锆陶瓷坩埚，在氧化锆陶瓷坩埚底部放置β-Ga 2O 3籽晶，在氧化锆陶瓷坩埚中堆积高纯Ga 2O 3圆球状原料形成原料堆； (1) Place β-Ga 2 O 3 seed crystals at the bottom of the water-cooled copper tube crucible, and pile high-purity Ga 2 O 3 spherical raw materials in the water-cooled copper tube crucible to form a raw material pile; or place zirconia ceramics in the water-cooled copper tube crucible In the crucible, β-Ga 2 O 3 seed crystals are placed at the bottom of the zirconia ceramic crucible, and high-purity Ga 2 O 3 spherical raw materials are stacked in the zirconia ceramic crucible to form a raw material pile;
    (2)启动高频感应线圈的加热电源，将两根石墨棒插入原料堆中并保持两根石墨棒下端的初始间距为5～20mm；升高石墨棒的加热功率至石墨棒之间产生电火花，石墨棒起燃使周围的高纯Ga 2O 3圆球状原料熔融，形成熔体； (2) Start the heating power supply of the high frequency induction coil, insert two graphite rods into the raw material pile and keep the initial distance between the lower ends of the two graphite rods at 5-20mm; increase the heating power of the graphite rods until electricity is generated between the graphite rods Sparks and graphite rods ignite to melt the surrounding high-purity Ga 2 O 3 spherical raw materials to form a melt;
    (3)控制两根石墨棒下端的间距和石墨棒的加热功率，熔体体积不断增大，直到达到高纯Ga 2O 3圆球状原料启动熔体体积，收起石墨棒； (3) Control the distance between the lower ends of the two graphite rods and the heating power of the graphite rods, and the melt volume will continue to increase until it reaches the high-purity Ga 2 O 3 spherical raw material to start the melt volume, and the graphite rods are retracted;
    (4)熔体在高频感应线圈的作用下持续发热，向熔体中投入高纯Ga 2O 3圆球状原料，使新投入的高纯Ga 2O 3圆球状原料充分熔化，熔体体积进一步扩大，直至籽晶与熔体充分熔接； (4) The melt continues to generate heat under the action of the high-frequency induction coil, and the high-purity Ga 2 O 3 spherical raw material is poured into the melt to fully melt the newly-introduced high-purity Ga 2 O 3 spherical raw material. The volume of the melt Further expand until the seed crystal and the melt are fully welded;
    (5)熔体稳定30～60分钟后，将水冷铜管坩埚以0.5～5mm/h速度逐渐下降，晶体自籽晶处逐步向上结晶生长，此过程中熔体外部由原料形成的冷坩埚熔壳的位置保持不变；(5) After the melt is stable for 30-60 minutes, the water-cooled copper tube crucible is gradually lowered at a speed of 0.5-5mm/h, and the crystal gradually grows upward from the seed crystal. During this process, the cold crucible formed by the raw material outside the melt is melted The position of the shell remains unchanged;
    (6)晶体生长结束后，缓慢降温退火，冷却至室温。(6) After the crystal growth is completed, slowly cool down and anneal, and cool to room temperature.
  2. 根据权利要求1所述的一种氧化镓晶体冷坩埚生长方法，其特征在于：所述高纯Ga 2O 3圆球状原料为直径1～3mm的圆球颗粒。 The method for growing a gallium oxide crystal cold crucible according to claim 1, wherein the high-purity Ga 2 O 3 spherical raw material is spherical particles with a diameter of 1 to 3 mm.
  3. 根据权利要求1所述的一种氧化镓晶体冷坩埚生长方法，其特征在于：高频感应线圈的加热频率为0.5～2MHz，功率为50～200kw。The method for growing a gallium oxide crystal cold crucible according to claim 1, wherein the heating frequency of the high-frequency induction coil is 0.5-2MHz, and the power is 50-200kw.
  4. 根据权利要求1所述的一种氧化镓晶体冷坩埚生长方法，其特征在于：所述冷坩埚包括坩埚支撑柱(1)、设置于坩埚支撑柱(1)顶部的水冷铜管坩埚(2)、环设于水冷铜管坩埚(2)外侧壁的高频感应线圈(4)；或者所述冷坩埚包括坩埚支撑柱(1)、水冷铜管坩埚(2)、氧化锆陶瓷坩埚(3)、高频感应线圈(4)；所述水冷铜管坩埚(2)固定于坩埚支撑柱(1)顶部；所述水冷铜管坩埚(2)内设有耐火砖(5)，所述氧化锆陶瓷坩埚(3)置于耐火砖(5)顶部；所述高频感应线圈(4)环设于水冷铜管坩埚(2)外侧壁。The method for growing a gallium oxide crystal cold crucible according to claim 1, wherein the cold crucible comprises a crucible support column (1), and a water-cooled copper tube crucible (2) arranged on top of the crucible support column (1) , A high-frequency induction coil (4) ringed on the outer side wall of the water-cooled copper tube crucible (2); or the cold crucible includes a crucible support column (1), a water-cooled copper tube crucible (2), and a zirconia ceramic crucible (3) , High-frequency induction coil (4); the water-cooled copper tube crucible (2) is fixed on the top of the crucible support column (1); the water-cooled copper tube crucible (2) is provided with refractory bricks (5), the zirconia The ceramic crucible (3) is placed on top of the refractory brick (5); the high-frequency induction coil (4) is ringed on the outer side wall of the water-cooled copper tube crucible (2).
  5. 根据权利要求4所述的一种氧化镓晶体冷坩埚生长方法，其特征在于：所述氧化锆 陶瓷坩埚的直径为40～160mm，从而减少原料用量。The method for growing a gallium oxide crystal cold crucible according to claim 4, wherein the diameter of the zirconia ceramic crucible is 40-160 mm, thereby reducing the amount of raw materials.
  6. 一种用于生长氧化镓晶体的冷坩埚，其特征在于：包括坩埚支撑柱(1)、设置于坩埚支撑柱(1)顶部的水冷铜管坩埚(2)、环设于水冷铜管坩埚(2)外侧壁的高频感应线圈(4)；或者，包括坩埚支撑柱(1)、水冷铜管坩埚(2)、氧化锆陶瓷坩埚(3)、高频感应线圈(4)；所述水冷铜管坩埚(2)固定于坩埚支撑柱(1)顶部；所述水冷铜管坩埚(2)内设有耐火砖(5)，所述氧化锆陶瓷坩埚(3)置于耐火砖(5)顶部；所述高频感应线圈(4)环设于水冷铜管坩埚(2)外侧壁。A cold crucible for growing gallium oxide crystals, characterized in that it comprises a crucible support column (1), a water-cooled copper tube crucible (2) arranged on the top of the crucible support column (1), and a water-cooled copper tube crucible ( 2) The high-frequency induction coil (4) on the outer side wall; or, including the crucible support column (1), the water-cooled copper tube crucible (2), the zirconia ceramic crucible (3), and the high-frequency induction coil (4); the water-cooled The copper tube crucible (2) is fixed on the top of the crucible support column (1); the water-cooled copper tube crucible (2) is provided with refractory bricks (5), and the zirconia ceramic crucible (3) is placed on the refractory bricks (5) The top; the high-frequency induction coil (4) is arranged around the outer side wall of the water-cooled copper tube crucible (2).
PCT/CN2019/110321 2019-10-10 2019-10-10 Gallium oxide crystal growing method using cold crucible WO2021068153A1 (en)

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