WO2020199843A1 - 用于在超临界流体中生长材料的装置和材料的生长方法 - Google Patents

用于在超临界流体中生长材料的装置和材料的生长方法 Download PDF

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WO2020199843A1
WO2020199843A1 PCT/CN2020/078000 CN2020078000W WO2020199843A1 WO 2020199843 A1 WO2020199843 A1 WO 2020199843A1 CN 2020078000 W CN2020078000 W CN 2020078000W WO 2020199843 A1 WO2020199843 A1 WO 2020199843A1
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container
pressure
growth
supercritical fluid
heating
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PCT/CN2020/078000
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English (en)
French (fr)
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乔焜
郑革
高明哲
吴小平
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上海玺唐半导体科技有限公司
四川航空工业川西机器有限责任公司
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Publication of WO2020199843A1 publication Critical patent/WO2020199843A1/zh

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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
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes

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  • the present invention relates to a technology for growing materials in a supercritical fluid, in particular to a device for growing materials in a supercritical fluid and a method for growing materials, and particularly to a device and a method for preparing gallium nitride single crystals using an ammothermal method. method.
  • the third-generation semiconductor material is a wide-gap semiconductor material represented by gallium nitride (GaN), silicon carbide (SiC), diamond, and zinc oxide. Its band gap energy can reach 3.3 ⁇ 5.5eV, which is different from the traditional first-generation semiconductor material.
  • the third-generation semiconductor materials Compared with semiconductor materials silicon (Si) and germanium (Ge), second-generation semiconductor materials gallium arsenide (GaAs) and indium phosphide (InP), the third-generation semiconductor materials have large band gaps, high breakdown electric fields, The unique properties of large thermal conductivity, high electronic saturation drift speed, low dielectric constant, etc., make it show great application potential in optoelectronic devices, power electronics, radio frequency microwave devices, lasers and detectors, and are semiconductors in the world The focus of field research. my country's research work on gallium nitride (GaN) and silicon carbide (SiC) materials and devices is relatively late.
  • GaN gallium nitride
  • SiC silicon carbide
  • gallium nitride single crystals include hydride vapor phase epitaxy, high-pressure nitrogen solution method, ammonia thermal method, Na flux method, etc., but the single crystal growth technology is currently immature and has not yet reached wide application.
  • the ammonia thermal method is easy to obtain single crystals of larger size, and has the potential for mass production of gallium nitride single crystals.
  • Both the hydrothermal method and the ammonia thermal method belong to the solvothermal method, which refers to the solvent crystal manufacturing method in the supercritical state or the subcritical state, or the coexistence of the two states.
  • solvothermal method refers to the solvent crystal manufacturing method in the supercritical state or the subcritical state, or the coexistence of the two states.
  • hydrothermal method When water is used as the solvent, it is called hydrothermal method.
  • ammothermal When it is a solvent, it is called ammothermal.
  • Supercritical fluid is a substance that exceeds the critical temperature and critical pressure of the fluid.
  • the critical temperature and critical pressure are the highest temperature and highest pressure at which the substance can exist in a gas-liquid balance.
  • the material to be grown is placed inside the reactor.
  • the reactor is also provided with solid or liquid that forms a supercritical fluid under high temperature and high pressure. During the growth of the material, the reactor is heated and pressurized to exceed the critical temperature and critical pressure, so that solids and/or liquids are converted into supercritical fluids.
  • the interior of the reactor also includes a partition with through holes, and the partition divides the interior of the reactor into an upper half and a lower half.
  • the partition divides the interior of the reactor into an upper half and a lower half.
  • one of the upper half and the lower half is equipped with a seed crystal, and the other is equipped with a polycrystalline culture material.
  • the supercritical pressure is formed in the reactor under high temperature and high pressure.
  • the fluid solid or liquid is usually a supercritical ammonia fluid solution, and the supercritical ammonia fluid solution usually includes a mineralizer to increase the solubility of the polycrystalline culture medium.
  • the maximum reaction temperature can reach 650° C. or higher, and the maximum reaction pressure can reach 200 MPa.
  • the diameter of the high-pressure reactor that can meet the above-mentioned high temperature, high pressure and high corrosion resistance is limited. The diameter of the autoclave directly determines the maximum size of the gallium nitride single crystal prepared. In this factor, the manufacture of a larger size gallium nitride single crystal is restricted.
  • Hot isostatic pressing is a technology for processing products in a closed ultra-high pressure vessel under the combined action of high temperature and high pressure. Usually, nitrogen or argon is used as the pressure transmission medium to form a high temperature zone through electric heating technology. Hot isostatic pressing technology currently has four major applications: powder compaction sintering, casting densification treatment, diffusion joining and immersion carbonization.
  • the diameter of the hot zone of the hot isostatic pressing device is generally 150 mm to 800 mm, and the diameter of the hot zone of larger specifications can be 800 mm to 1600 mm, or even up to 2000 mm.
  • the present invention was made in view of the above-mentioned state of the prior art.
  • the purpose of the present invention is to provide a device for growing a material in a supercritical fluid and a material growth method, so that the material can reach a larger growth size.
  • an apparatus for growing materials in a supercritical fluid which is characterized by comprising a first container, a second container and a heating component,
  • the inner cavity of the first container contains one or more second containers,
  • the heating component is arranged in the inner cavity of the first container and used to heat the second container, and the material to be grown can be arranged to grow in the second container,
  • Both the first container and the second container can be filled with a medium for transferring pressure.
  • the difference between the pressure in the first container and the pressure in the second container The value is smaller than the difference between the pressure in the second container and the standard atmospheric pressure.
  • the first container includes an inner cylinder, a pre-stressed steel wire winding layer and an end cap, the pre-stressed steel wire winding layer surrounds the outer circumference of the inner cylinder, and the work used in the first container
  • the medium is gas.
  • the inner cylinder is always in a state of compressive stress and compressive strain
  • the end cover is a floating structure
  • the axial force received by the end cover is transmitted to the frame for bearing.
  • the size range of the second container covers the range of 1 inch to 80 inches in diameter.
  • the second container is made of stainless steel or iron-based alloy.
  • the heating member is configured to surround the outer peripheral wall of the second container.
  • the heating component includes a first heating belt and a second heating belt that can be independently controlled in temperature from each other, and the first heating belt and the second heating belt are disposed in the second container. Different positions on the axis.
  • the material is gallium nitride crystal
  • the supercritical fluid is a supercritical ammonia fluid solution
  • the first container uses a reaction container of a hot isostatic pressing device
  • a partition with a through hole is provided in the second container, and the partition divides the second container into an upper half and a lower half in the axial direction.
  • a method for growing a material in a supercritical fluid characterized in that the growth of the material uses the device according to the present invention
  • the pressure in the first container is always greater than the pressure in the second container.
  • the difference between the pressure in the first container minus the pressure in the second container is less than 200 MPa.
  • a method for growing a material in a supercritical fluid characterized in that the growth of the material uses the device of the present invention
  • the seed crystal is arranged in the upper half, the polycrystalline culture medium is arranged in the lower half, and the mineralizer used can make the polycrystalline culture medium in the supercritical fluid under the temperature and pressure of crystal growth.
  • the temperature and pressure of the first container and the second container are lowered.
  • the device according to the present invention is easy to manufacture and enables the grown material to reach a large size.
  • Fig. 1 shows a schematic diagram of an apparatus for growing a material in a supercritical fluid according to an embodiment of the present invention.
  • Fig. 2 shows a schematic diagram of an apparatus for growing materials in a supercritical fluid according to an embodiment of the present invention.
  • Fig. 3 shows a schematic diagram of an axial cross-sectional view of a first container according to an embodiment of the present invention.
  • Fig. 4 is a cross-sectional view taken along a-a line in Fig. 3.
  • Fig. 5 shows a schematic diagram of an outer frame of an ultra-high pressure vessel according to an embodiment of the present invention.
  • the present invention improves the hot isostatic pressing equipment and is used for crystal growth applications.
  • the device according to the present invention can grow, for example, 12 inches or more in diameter.
  • Gallium nitride single crystal crystal; in addition, multiple single crystal growth containers can be placed in the hot isostatic pressing equipment at the same time to increase the number of gallium nitride single crystal crystals generated in the same growth cycle, and realize the production of gallium nitride single crystal crystal Batching.
  • the diameter of the second container of the hot isostatic pressing equipment can cover 1 inch to 80 inches under the condition that the working temperature is not more than 800 °C and the pressure is not more than 200 MPa. The range of inches.
  • the device and processing method for processing materials in a supercritical fluid according to the present invention will be described with reference to FIGS. 1 to 5.
  • the axial direction A referred to in the present invention is parallel to the direction indicated by arrow A in FIG. 1
  • the radial direction R referred to in the present invention is parallel to the direction indicated by arrow R in FIG. 1.
  • the apparatus for processing materials in a supercritical fluid includes a first container 10 and a second container 20, and heating components H provided in the inner cavity of the first container 10 and the outer periphery of the second container 20.
  • the pressure that the first container 10 can bear is, for example, about 200 MPa, and the first container 10 is, for example, an ultra-high pressure container of a hot isostatic pressing device.
  • the maximum temperature that the first container 10 can bear is 800° C.
  • the maximum pressure that the first container 10 can bear is 200 MPa.
  • the structure of the first container 10 adopts the pre-stressed steel wire winding technology, that is, the inner surface (especially the dangerous point) of the inner cylinder 11 described below will neither appear tensile stress nor tensile strain under various conditions.
  • the first container 10 includes an inner cylinder 11, the inner cylinder 11 has end caps 13 at both ends in the axial direction A, the end cap 13 is a floating structure, the axial force of the end cap 13 will be It is passed to the following rack 31 to receive it.
  • the outer circumference of the inner cylinder 11 is surrounded by a prestressed steel wire winding layer 12, and the inner cylinder 11 is always in a state of compressive stress and compressive strain.
  • the prestressed steel wire winding technology can fully ensure the service life and safety of the inner cylinder 11. Even if the steel wire breaks, the first container 10 will enter the unexploded first leak failure mode, which means that after part of the steel wire is damaged, the inner cylinder 11 has already reached the yield limit, causing leakage without the risk of explosion.
  • the inner cavity of the first container 10 is provided with a heating part H. Since in the application of single crystal growth, there is usually a temperature difference between the polycrystalline culture material and the seed crystal, the heating part H includes a first heating zone H1 and a first heating zone H1 that are spaced apart in the axial direction A and whose temperature can be independently controlled.
  • the heating components H are looped around the outer circumference of the second container 20 to uniformly heat the upper and lower parts of the second container 20, respectively.
  • the heating element H may not form a complete loop; the first heating belt H1 and the second heating belt H2 may also be arranged in the axial direction A without being spaced apart.
  • a cooling layer (not shown in the figure) may be provided on the outer peripheral side and/or the inner peripheral side of the wall of the first container 10, preferably , The cooling layer is provided on the outer peripheral side of the wall of the first container 10.
  • a circulating cooling liquid may circulate in the cooling layer.
  • the interior of the first container 10 is filled with an inert gas, such as nitrogen or argon, as a pressure transmission medium.
  • an inert gas such as nitrogen or argon
  • the second container 20 located inside the heating part H does not need to have its own heating part.
  • a partition 21 with a through hole is provided in the second container 20.
  • the partition 21 divides the interior of the reactor into an upper half and a lower half in the axial direction A, and the upper half and/or the lower half are respectively used for accommodating seeds Crystal and/or polycrystalline culture material.
  • the second container 20 is also used to contain a supercritical ammonia fluid solution containing a mineralizer.
  • the first container 10 When the device is working, the first container 10 has a first pressure P1, and the second container 20 has a second pressure P2.
  • the second container 20 is filled with mineralizer, seed crystals and polycrystalline culture material and then sealed. Generally, both the first pressure P1 and the second pressure P2 can reach more than 100 MPa.
  • the pressure difference ⁇ P is less than the difference between the first pressure P1 and the atmospheric pressure.
  • the internal and external pressure difference of the second container 20 placed in the first container 10 is less than the internal and external pressure difference of the second container 20 originally placed under atmospheric pressure.
  • the radial size of the second container 20 can be set to be larger according to the target size of the gallium nitride single crystal; without being restricted by the radial size of the second container 20, the diameter of the gallium nitride single crystal can be changed from the original 2 inches increases to, for example, 12 inches or more.
  • the second pressure P2 can be controlled to be always less than the first pressure P1 when the device is working.
  • the external pressure of the second container 20 is stronger than the internal pressure, only ordinary sealing elements can be used to make the second container 20 well sealed with the supercritical ammonia fluid solution in it.
  • the nitrogen or argon in the first container 10 entering the second container 20 it will not adversely affect the growth of the gallium nitride single crystal.
  • the inner cavity of the second container 20 and the inner cavity of the first container 10 are respectively provided with pressure sensors, and the first pressure P1 and the second pressure P2 are controlled in real time during the entire growth process of the gallium nitride single crystal. , So that the second pressure P2 is always less than the first pressure P1. Under such pressure control, the cost of the sealing element of the second container 20 can be reduced.
  • the pressure that the sealing element needs to bear is P1-P2.
  • the difference between the first pressure P1 and the second pressure P2 cannot be too large, otherwise the wall of the second container 20 will be adversely affected.
  • the difference between the first pressure P1 and the second pressure P2 is greater than 10 MPa and less than 20 MPa, and more preferably, the difference between the first pressure P1 and the second pressure P2 is greater than 10 MPa and less than 15 MPa.
  • the temperature in the upper region in the axial direction A is high, and the temperature in the lower region is low.
  • the growth of crystals uses the temperature difference of the solution.
  • a seed crystal is set in the upper half of the second container 20, and a polycrystalline culture medium is set in the lower half.
  • the mineralizer used is crystallized
  • the growth temperature and pressure conditions can make the polycrystalline culture medium have a negative solubility coefficient in the supercritical fluid.
  • mineralizers that can be selected include but are not limited to ammonium fluoride, ammonium chloride, ammonium iodide, ammonium bromide, and transition metal halides to improve the solubility of the polycrystalline culture medium.
  • the diameter of the second container 20 can cover 1 inch to 80 inches without considering the pressure bearing problem of the second container 20 Range.
  • the material for the second container 20 according to the present invention may not only need to use a nickel-based alloy with higher material strength, but also use other materials to make the second container 20, such as but not Limited to the use of iron-based alloys, stainless steel, non-ferrous metal alloys, ceramic materials, carbon fiber, platinum (Pt), iridium (Ir), copper (Au), silver (Ag), osmium (Os) and other precious metal simple substances.
  • one first container 10 can contain one or more second containers 20.
  • the heating component may be a set of heating components capable of surrounding the plurality of second containers 20, or may be a set of heating components capable of surrounding each second container 20 respectively.
  • the first step is to charge the second container 20.
  • a partition 21 and solid substances including seed crystals, polycrystalline culture materials and mineralizers
  • the seed crystals are placed in the second container 20.
  • the upper half of the polycrystalline culture medium is placed in the lower half, and the mineralizer is for example ammonium fluoride.
  • the liquid ammonia is injected into the second container 20 through the liquid ammonia injection system and then sealed and packaged. When injecting liquid ammonia, it is required to avoid the mixing of oxygen and water and other oxygen-containing compounds.
  • the second container 20 is placed in the first container 10 so that the second container 20 is placed corresponding to the heating component.
  • the end cap 13 of the first container 10 is closed.
  • the rack 31 (refer to FIG. 5) can be used.
  • the rack 31 is arranged on the rail seat 32 and can reciprocate along the rail seat 32 .
  • the first container 10 and the second container 20 are simultaneously cooled down to the specified temperature and pressure. This process still needs to be controlled so that the first pressure P1 inside the first container 10 is always greater than the second pressure P2 inside the second container 20.
  • the corresponding pipe fittings and sensor connecting wires are removed, and the second container 20 is moved out of the first container 10.
  • the ammonia in the second container 20 is released into water. Open the second container 20 and take out the gallium nitride crystal.
  • the heating method of the first container 10 is internal heating, and the structure of the first container 10 and the heating components will not adversely affect each other.
  • the heating method of the second container 20 is external heating, and the heating component inside the first container 10 is used to heat the second container 20 to ensure that the internal environment of the second container 20 is pure and pollution-free.
  • the first container 10 can be up to several meters in size and can withstand the same order of pressure as the pressure of the second container 20; and the first container 10 also has a larger diameter to accommodate the second container 20. Under such conditions, the pressure difference between the inside and outside of the second container 20 is small, and the second container 20 may have a larger diameter.
  • the second container 20 can be made of, for example, a common alloy. Compared with the nickel-based alloy used in the prior art to make the second container 20, the material of the common alloy is The cost is lower and the manufacturing process is simpler.

Abstract

一种用于在超临界流体中生长材料的装置和材料的生长方法。用于在超临界流体中生长材料的装置包括第一容器、第二容器和加热部件，所述第二容器被容纳于所述第一容器的内腔，所述加热部件设置于所述第一容器的内腔并用于给所述第二容器加热，待生长的材料能够被设置在所述第二容器内生长，所述第一容器和所述第二容器均能够填充用于传递压力的介质，使所述第一容器内的压强与所述第二容器内的压强的差值小于所述第二容器内的压强与标准大气压的差值。上述装置的制作成本低且能使生长的材料达到较大的尺寸。

Description

用于在超临界流体中生长材料的装置和材料的生长方法
相关申请的引用
本发明要求2019年3月29日在中国提交的，名称为“用于在超临界流体中生长材料的装置和材料的生长方法”、申请号为201910250202.4的发明专利申请的优先权，该申请的全部内容通过引用并入本文。
技术领域
本发明涉及用于在超临界流体中生长材料的技术，尤其涉及用于在超临界流体中生长材料的装置和材料的生长方法，且特别涉及使用氨热法制备氮化镓单晶的装置和方法。
背景技术
第三代半导体材料是以氮化镓(GaN)、碳化硅(SiC)、金刚石、氧化锌为代表的宽禁带半导体材料，其带隙能可达3.3～5.5eV,与传统的第一代半导体材料硅(Si)和锗(Ge)、第二代半导体材料砷化镓(GaAs)和磷化铟(InP)等相比，第三代半导体材料具有禁带宽度大、击穿电场高、热导率大、电子饱和漂移速度高、介电常数小等独特的性能，使其在光电子器件、电力电子、射频微波器件、激光器和探测器等方面展现出巨大的应用潜力，是世界各国半导体领域研究的热点。我国开展氮化镓(GaN)和碳化硅(SiC)材料及器件方面的研究工作比较晚，在科技部等预研项目的支持下，取得了一定的成果，逐步缩小了与国外先进技术的差距，在一些领域已取得了应用，但是研究的成果主要还停留在实验室阶段，器件性能距离国外的报道还有很大差距。
氮化镓单晶的生长方法有氢化物气相外延法、高压氮气溶液法、氨热法、Na助熔剂法等，但是单晶生长技术目前并不成熟，还未达到广泛应用。上述 方法之中氨热法易于获得较大尺寸的单晶，有批量化生产氮化镓单晶的潜力。
水热法和氨热法均属于溶剂热法，是指在超临界状态或亚临界状态，或两种状态共存状态下的溶剂结晶制造方法，以水为溶剂时称为水热法，以氨为溶剂时称为氨热法。
超临界流体是超过该流体的临界温度和临界压力的物质，临界温度和临界压力是物质能气液平衡地存在的最高温度和最高压力。在使用超临界流体生长材料时，待生长的材料被置于反应釜的内部。反应釜内还设有在高温高压下形成超临界流体的固体或液体。在材料的生长过程中，反应釜被加热加压至超过临界温度和临界压力，使固体和/或液体转化成超临界流体。
在一些例如晶体生长的应用中，反应釜的内部还包括设有通孔的隔板，隔板将反应釜内部分隔成上半部和下半部。例如氨热法使氮化镓单晶生长的应用中，上半部和下半部中的一者设有籽晶、另一者设有多晶培养料，反应釜内在高温高压下形成超临界流体的固体或液体通常是超临界的氨流体溶液，通常该超临界的氨流体溶液包括矿化剂以增加多晶培养料的溶解度。
例如氨热法制备氮化镓单晶的应用中，最高反应温度可达650℃或更高，最高反应压强可达200MPa。在此温度和压力条件下，通常需要使用能够承受高温高压的镍基合金材料，例如Inconel 625，718等，来制造高压反应釜，且需要在镍基合金内部设置贵金属内衬抵抗氨流体溶液的腐蚀性。但是由于受限于镍基合金材料的加工能力，能够制造满足上述耐高温高压高腐蚀的高压反应釜的直径是有限的。高压反应釜的直径直接决定了所制备的氮化镓单晶的最大尺寸，在这一因素上，制造更大尺寸的氮化镓单晶受到了限制。
热等静压技术是一种在密闭的超高压容器内、在高温和高压的共同作用下对制品进行处理的技术，通常以氮气或氩气为传压介质，通过电加热技术形成高温区。热等静压技术目前主要有粉末致密烧结、铸件致密化处理、扩 散连接和浸渍碳化四大工艺应用。
热等静压装置的热区直径一般为150mm至800mm，较大规格的热区直径可以是800mm至1600mm、甚至是达到2000mm。
发明内容
鉴于上述现有技术的状态而做出本发明。本发明的目的在于提供一种用于在超临界流体中生长材料的装置和材料的生长方法，使得材料能达到较大的生长尺寸。
根据本发明的第一方面，提供一种用于在超临界流体中生长材料的装置，其特征在于，包括第一容器、第二容器和加热部件，
所述第一容器的内腔容纳有一个或多个所述第二容器，
所述加热部件设置于所述第一容器的内腔并用于给所述第二容器加热，待生长的材料能够被设置在所述第二容器内生长，
所述第一容器和所述第二容器均能够填充用于传递压力的介质，在所述材料的生长过程中，使所述第一容器内的压强与所述第二容器内的压强的差值小于所述第二容器内的压强与标准大气压的差值。
在至少一个实施方式中，所述第一容器包括内筒、预应力钢丝缠绕层和端盖，所述预应力钢丝缠绕层环绕在所述内筒的外周，所述第一容器内使用的工作介质为气体。
在至少一个实施方式中，所述内筒始终处于压应力和压应变状态，所述端盖为浮动式结构，所述端盖所受的轴向力传递给机架来承受。
在至少一个实施方式中，在所述第二容器工作温度不大于800℃、压力不大于200MPa的条件下，第二容器尺寸范围覆盖直径1英寸至80英寸的范围。
在至少一个实施方式中，所述第二容器由不锈钢或铁基合金制成。
在至少一个实施方式中，所述加热部件被构造为环绕所述第二容器的外周壁。
在至少一个实施方式中，所述加热部件包括能够彼此被独立控制温度的第一加热带和第二加热带，所述第一加热带和所述第二加热带设置于所述第二容器的轴向上的不同位置。
在至少一个实施方式中，所述材料为氮化镓晶体，所述超临界流体为超临界氨流体溶液，所述第一容器使用热等静压设备的反应容器，
所述第二容器内设有具有通孔的隔板，所述隔板在轴向上将所述第二容器分隔成上半部和下半部。
根据本发明的第二方面，提供一种用于在超临界流体中生长材料的方法，其特征在于，所述材料的生长使用根据本发明所述的装置，
在所述材料的生长过程中，所述第一容器内的压强始终大于所述第二容器内的压强。
在至少一个实施方式中，所述第一容器内的压强减去所述第二容器内的压强的差值小于200MPa。
根据本发明的第三方面，提供一种用于在超临界流体中生长材料的方法，其特征在于，所述材料的生长使用本发明所述的装置，
籽晶设置于所述上半部，多晶培养料设置于所述下半部，所使用的矿化剂在结晶生长的温度和压力下能够使所述多晶培养料在所述超临界流体里具有负的溶解度系数，
待所述氮化镓晶体生长至直径至少大于等于2英寸后，使所述第一容器和所述第二容器降温降压。
根据本发明的装置便于制作且能使生长的材料达到大的尺寸。
附图说明
图1示出了根据本发明的一个实施方式的用于在超临界流体中生长材料的装置的示意图。
图2示出了根据本发明的一个实施方式的用于在超临界流体中生长材料的装置的示意图。
图3示出了根据本发明的一个实施方式的第一容器的轴向剖视的示意图。
图4是图3的a-a向的剖视图。
图5示出了根据本发明的一个实施方式的超高压容器的外部机座示意图。
附图标记说明：
10第一容器；11内筒；12预应力钢丝缠绕层；13端盖；
20第二容器；21隔板；
31机架；32导轨座；
P1第一压强；P2第二压强。
具体实施方式
下面参照附图描述本发明的示例性实施方式。应当理解，这些具体的说明仅用于示教本领域技术人员如何实施本发明，而不用于穷举本发明的所有可行的方式，也不用于限制本发明的范围。
本发明对热等静压设备进行改进、并用于晶体生长的应用，例如结合氨热法生长氮化镓单晶的技术，根据本发明的装置能够生长出直径为例如12英寸甚至更大规格的氮化镓单晶晶体；此外，在热等静压设备中可以同时放置多个单晶生长容器，以增加同一生长周期中氮化镓单晶晶体生成数量，使氮化镓单晶晶体生产实现批量化。根据本发明的装置所包括的热等静压设备，在工作温度不大于800℃、压强不大于200MPa的条件下，热等静压设备的用 以容纳的第二容器直径能够覆盖1英寸至80英寸的范围。
以制备氮化镓单晶的装置和氮化镓单晶的制备方法为例，参照图1至图5介绍根据本发明的用于在超临界流体中处理材料的装置和处理方法。若非特别说明，本发明所称的轴向A与图1中箭头A所指方向平行、本发明所称的径向R与图1中箭头R所指方向平行。
参照图1，根据本发明的用于在超临界流体中处理材料的装置包括第一容器10和第二容器20以及设置于第一容器10内腔、第二容器20的外周的加热部件H。第一容器10能够承受的压强例如约为200MPa，第一容器10例如是热等静压设备的超高压容器。
在本实施方式中，第一容器10能够承载的最高温度为800℃、能够承载的最大压强为200MPa。
所述第一容器10的构造采用预应力钢丝缠绕技术，即各种状态下使下述内筒11的内表面(尤其是危险点)既不出现拉应力也不出现拉应变。
参照图3和图4，第一容器10包括内筒11，内筒11在轴向A上的两端具有端盖13，端盖13为浮动式结构，端盖13所受的轴向力将传递给下述的机架31来承受。内筒11的外周环绕有预应力钢丝缠绕层12，内筒11始终处于压应力和压应变状态，预应力钢丝缠绕技术可以充分保证内筒11的使用寿命及安全性。即使钢丝发生断裂，第一容器10将进入未爆先漏失效模式，表现为部分钢丝破坏后，内筒11早已达到屈服极限，产生泄漏，而无爆炸危险。
第一容器10的内腔设有加热部件H。由于在单晶生长的应用中，多晶培养料和籽晶之间通常需要有温度差，因此加热部件H包括在轴向A上间隔开的、能够被独立控制温度的第一加热带H1和第二加热带H2。
加热部件H(第一加热带H1和第二加热带H2)呈环形地套装在第二容器20的外周以分别对第二容器20的上部和下部均匀加热。在其他实施方式中，加热部件H也可以不形成完整的环形；第一加热带H1和第二加热带H2也可以 在轴向A上不间隔开地排列。
为了使第一容器10内部的高温不影响第一容器10的加强结构，在第一容器10的壁的外周侧和/或内周侧还可以设置冷却层(图中未示出)，优选地，冷却层设置在第一容器10的壁的外周侧。冷却层内例如可以流通有可循环的冷却液。
第一容器10内部充有惰性气体，例如氮气或氩气，作为传压介质。
位于加热部件H内侧的第二容器20则不需要自带加热部件。第二容器20内设置具有通孔的隔板21，隔板21将反应釜内部在轴向A上分隔成上半部和下半部，上半部和/或下半部分别用于容纳籽晶和/或多晶培养料。另外，第二容器20还用于容纳含有矿化剂的超临界氨流体溶液。
装置工作时，第一容器10内部具有第一压强P1，第二容器20内部具有第二压强P2，第二容器20内外的压强差ΔP等于第一压强P1与第二压强P2的差值，即压强差ΔP＝|P1-P2|。第二容器20内部充装矿化剂、籽晶和多晶培养料后密封。通常，第一压强P1和第二压强P2均可以达到100MPa以上。显然，压强差ΔP小于第一压强P1与大气压的差值，换言之，置于第一容器10内的第二容器20的内外压差小于原先置于大气压下的第二容器20的内外压差。且通过设置合理的第一压强P1，可以使第二容器20内外的压强非常接近，于是第二容器20的壁所需承受的压力很小，从而克服了第二容器20的直径受限的情况。第二容器20的径向尺寸可以根据氮化镓单晶的目标尺寸而设置得较大；在不受第二容器20径向尺寸限制的情况下，氮化镓单晶的直径可以由原先的2英寸增加到例如12英寸甚至更大。
考虑到第二容器20的密封问题，优选地，在装置工作时可以控制使第二压强P2始终小于第一压强P1。在这样的环境下，由于第二容器20外部压强大于内部压强，因此可以只使用普通的密封元件，便可以使第二容器20良好地密封其内的超临界氨流体溶液。至于第一容器10内的氮气或氩气进入第二容 器20则不会对氮化镓单晶的生长造成不良影响。在本实施方式中，第二容器20的内腔和第一容器10的内腔分别设有压力传感器，在氮化镓单晶生长的整个过程中，实时控制第一压强P1和第二压强P2，使第二压强P2始终小于第一压强P1。在这样的压强控制下，第二容器20的密封元件的成本可以被降低，例如，密封元件需要承受的压强为P1-P2。
应当理解，第一压强P1减去第二压强P2的差值不能太大，否则也会对第二容器20的壁造成不良影响。优选地，第一压强P1减去第二压强P2的差值大于10MPa而小于20MPa，更优选地，第一压强P1减去第二压强P2的差值大于10MPa而小于15MPa。
值得说明的是，由于气体受热上升的作用，在第一容器10内部，轴向A上靠上的区域温度高、靠下的区域温度低。而晶体的生长利用了溶液的温差，在溶液上热下冷的情况下，在第二容器20的上半部设置籽晶、下半部设置多晶培养料，所使用的矿化剂在结晶生长的温度和压力条件下可以使多晶培养料在超临界流体里具有负的溶解度系数。根据结晶生长的温度和压力，可以选用的矿化剂包括但不限于氟化铵、氯化铵、碘化铵、溴化铵以及过渡金属卤化物，以提高多晶培养料的溶解度。
以上，使用常规的用于生长氮化镓单晶的反应釜的结构和材料，在不需要考虑第二容器20的压力承载问题的情况下，第二容器20的直径可覆盖1英寸至80英寸的范围。
由于第二容器20内外压力差较小，根据本发明的第二容器20的制作材料可以不仅仅需要使用材料强度较高的镍基合金，也可使用其他材料制作第二容器20，例如但不限于使用铁基合金，不锈钢，有色金属合金，陶瓷材料，碳纤维，铂(Pt)，铱(Ir)、铜(Au)、银(Ag)、锇(Os)等贵金属单质。
由于第一容器10的直径可以达到数米，而应用中的氮化镓单晶通常只需要数英寸，因此一个第一容器10内可以容纳一个或多个第二容器20。例如， 参照图2，在第一容器10内设有三个第二容器20。对于容纳多个第二容器20的第一容器10，加热部件可以是一套能够包围多个第二容器20的加热部件，也可以是能够分别包围每个第二容器20的多套加热部件。
接下来，以氮化镓单晶的制备为例，介绍使用第一容器10生长氮化镓单晶的步骤。
首先是对第二容器20进行装料，在第二容器20内放入隔板21和固体物质(包括籽晶、多晶培养料和矿化剂)，其中，籽晶放置在第二容器20的上半部、多晶培养料放置在下半部，矿化剂使用例如氟化铵。通过液氨注入系统向第二容器20内注入液氨后密封封装。注入液氨时要求避免氧气和水等含氧化合物的混入。
然后将第二容器20放置到第一容器10内，使第二容器20与加热部件相对应地放置。将第一容器10的端盖13闭合。
由于第一容器10的体积和质量较大，在开闭第一容器10的过程中，可以借助机架31(参照图5)，机架31设置于导轨座32并能沿导轨座32往复运动。
之后向第一容器10内腔注入氮气，第一容器10加压升温至合适的温度和压强后保温保压。这一过程中，同时控制第二容器20内的压强，使第一容器10内部的第一压强P1始终大于第二容器20内的第二压强P2。
保温保压步骤完成后，第一容器10和第二容器20同时进行降温降压至指定的温度和压强。这一过程仍需控制使第一容器10内部的第一压强P1始终大于第二容器20内的第二压强P2。
之后移去相应管件及传感器连接线，将第二容器20移出第一容器10。待第二容器20冷却到室温后，将第二容器20内的氨释放到水中。打开第二容器20，取出氮化镓晶体。
下面简单说明本发明的上述实施方式的部分有益效果。
(i)第一容器10的加热方式为内加热，第一容器10的结构和加热部件互相不会发生不良影响。
(ii)第二容器20的加热方式为外加热，使用第一容器10内部的加热部件对第二容器20进行加热，保证第二容器20内部环境的纯净无污染。
(iii)第一容器10尺寸可达数米且能承受与第二容器20的压力同样数量级的压力；且第一容器10也具有较大的直径以容纳第二容器20。在这样的条件下，第二容器20的内外压差较小，第二容器20可以具有较大的直径。
(iv)由于第二容器20的内外压差较小，第二容器20比如可以由普通合金制成，相比于现有技术中使用镍基合金制作第二容器20而言，普通合金的材料成本更低，制作工艺更简单。
(v)在晶体生长过程中控制压强，使第一容器10内的第一压强P1始终大于第二容器20内的第二压强P2，从而可以降低第二容器20的密封元件的成本，普通的密封元件便可以预防第二容器20内的气体或液体泄漏至第一容器10中。
(vi)利用第一容器10内上部温度高、下部温度低的温度环境，使用具有负的溶解度系数的矿化剂，能提高多晶培养料的溶解度。
应当理解，上述实施方式仅是示例性的，不用于限制本发明。本领域技术人员可以在本发明的教导下对上述实施方式做出各种变型和改变，而不脱离本发明的范围。

Claims (11)

  1. 一种用于在超临界流体中生长材料的装置，其特征在于，包括第一容器(10)、第二容器(20)和加热部件(H)，
    所述第一容器(10)的内腔容纳有一个或多个所述第二容器(20)，
    所述加热部件(H)设置于所述第一容器(10)的内腔并用于给所述第二容器(20)加热，待生长的材料能够被设置在所述第二容器(20)内生长，
    所述第一容器(10)和所述第二容器(20)均能够填充用于传递压力的介质，在所述材料的生长过程中，使所述第一容器(10)内的压强与所述第二容器(20)内的压强的差值小于所述第二容器(20)内的压强与标准大气压的差值。
  2. 根据权利要求1所述的装置，其特征在于，所述第一容器(10)包括内筒(11)、预应力钢丝缠绕层(12)和端盖(13)，所述预应力钢丝缠绕层(12)环绕在所述内筒(11)的外周，所述第一容器(10)内使用的工作介质为气体。
  3. 根据权利要求2所述的装置，其特征在于，所述内筒(11)始终处于压应力和压应变状态，所述端盖(13)为浮动式结构，所述端盖(13)所受的轴向力传递给机架(31)来承受。
  4. 根据权利要求1所述的装置，其特征在于，在所述第二容器(20)工作温度不大于800℃、压力不大于200MPa的条件下，所述第二容器(20)尺寸范围覆盖直径1英寸至80英寸的范围。
  5. 根据权利要求1所述的装置，其特征在于，所述第二容器(20)由不锈钢或铁基合金制成。
  6. 根据权利要求1所述的装置，其特征在于，所述加热部件(H)被构造为环绕所述第二容器(20)的外周壁。
  7. 根据权利要求1所述的装置，其特征在于，所述加热部件(H)包括能够彼此被独立控制温度的第一加热带(H1)和第二加热带(H2)，所述第 一加热带(H1)和所述第二加热带(H2)设置于所述第二容器(20)的轴向上的不同位置。
  8. 根据权利要求1至7中任一项所述的装置，其特征在于，所述材料为氮化镓晶体，所述超临界流体为超临界氨流体溶液，所述第一容器(10)使用热等静压设备的反应容器，
    所述第二容器(20)内设有具有通孔的隔板(21)，所述隔板(21)在轴向上将所述第二容器(20)分隔成上半部和下半部。
  9. 一种用于在超临界流体中生长材料的方法，其特征在于，所述材料的生长使用根据权利要求1至8中任一项所述的装置，
    在所述材料的生长过程中，所述第一容器(10)内的压强始终大于所述第二容器(20)内的压强。
  10. 根据权利要求9所述的方法，其特征在于，所述第一容器(10)内的压强减去所述第二容器(20)内的压强的差值小于200MPa。
  11. 一种用于在超临界流体中生长材料的方法，其特征在于，所述材料的生长使用根据权利要求8所述的装置，
    籽晶设置于所述上半部，多晶培养料设置于所述下半部，所使用的矿化剂在结晶生长的温度和压力下能够使所述多晶培养料在所述超临界流体里具有负的溶解度系数，
    待所述氮化镓晶体生长至直径至少大于等于2英寸后，使所述第一容器(10)和所述第二容器(20)降温降压。
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CN111020708A (zh) * 2019-12-16 2020-04-17 上海玺唐半导体科技有限公司 热等静压晶体生长装置
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