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WO2012079439A1 - 物理气相传输法生长碳化硅单晶及碳化硅单晶的原位退火工艺 - Google Patents

物理气相传输法生长碳化硅单晶及碳化硅单晶的原位退火工艺 Download PDF

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WO2012079439A1
WO2012079439A1 PCT/CN2011/082107 CN2011082107W WO2012079439A1 WO 2012079439 A1 WO2012079439 A1 WO 2012079439A1 CN 2011082107 W CN2011082107 W CN 2011082107W WO 2012079439 A1 WO2012079439 A1 WO 2012079439A1
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Prior art keywords
growth
crystal
growth chamber
silicon carbide
temperature
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English (en)
French (fr)
Inventor
陈小龙
王波
李龙远
彭同华
刘春俊
王文军
王刚
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Tankeblue Semiconductor Co Ltd
Institute of Physics of CAS
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Tankeblue Semiconductor Co Ltd
Institute of Physics of CAS
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Priority to US13/994,306 priority Critical patent/US9340898B2/en
Priority to JP2013513548A priority patent/JP5450895B2/ja
Priority to EP20110848136 priority patent/EP2653591A4/en
Publication of WO2012079439A1 publication Critical patent/WO2012079439A1/zh
Anticipated expiration legal-status Critical
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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
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/002—Controlling or regulating
    • 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
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C30B23/06—Heating of the deposition chamber, the substrate or the materials to be evaporated
    • 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
    • C30B29/36—Carbides
    • 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
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment

Definitions

  • the invention is mainly applied to the field of crystal growth and post-growth treatment, in particular A process for growing a silicon carbide single crystal by a physical vapor phase transfer method and an in-situ annealing process of a silicon carbide single crystal after the growth.
  • the wide bandgap semiconductor material represented by silicon carbide and gallium nitride is the third generation of wide bandgap semiconductors after silicon and gallium arsenide.
  • silicon carbide has great advantages in terms of operating temperature, radiation resistance, and breakdown voltage.
  • silicon carbide has the advantages of high thermal conductivity, high breakdown field strength, high saturation electron drift rate and high bonding energy. Its excellent performance can meet the high temperature, high frequency and high performance of modern electronic technology. Power and new requirements for radiation resistance are considered to be one of the most promising materials in the field of semiconductor materials.
  • Due to the similar lattice constant and thermal expansion coefficient of hexagonal silicon carbide and gallium nitride it also becomes a high-brightness light-emitting diode.
  • the most effective method for growing silicon carbide crystals is the physical vapor transport method (Journal of Crystal Growth 43 (1978) 209-212).
  • the typical growth chamber structure is shown in Figure 1.
  • the crucible consists of an upper cover and a lower crucible, the upper cover for the seed crystal and the lower crucible for the silicon carbide feed.
  • the sidewalls and the upper and lower sides are high temperature resistant insulation materials, and the insulation material is usually graphite felt.
  • the side wall of the insulation layer is a quartz sleeve water-cooling device. Due to the large radiant heat of the insulation layer, the flow rate of the cooling water is required to be large. Outside the water cooling device is an induction coil heater.
  • the C plane is usually used as a growth plane for SiC crystal growth.
  • the temperature of the SiC material is higher and the temperature of the seed crystal is lower.
  • the SiC raw material at high temperature is sublimated into gas phase substances (mainly Si, Si 2 C, SiC 2 ), and these gas phase materials are transported to the lower temperature seed crystals to form SiC crystals.
  • gas phase substances mainly Si, Si 2 C, SiC 2
  • the use of this process to grow silicon carbide crystals, the proper temperature field distribution in the growth chamber is a key condition for obtaining high quality crystals.
  • the growth process of silicon carbide crystals can be roughly divided into three stages, the initial stage of crystal growth (ie, the length of the growth phase), the middle and early stages of crystal growth (ie, the stage of diameter expansion) and the middle and late stages of crystal growth (ie, the equal diameter growth stage).
  • the axial temperature gradient in the growth chamber should be controlled to be relatively small, so that the growth interface temperature is relatively high, so that the spiral growth center in the initial stage of growth is minimized, and the high-quality initial length is achieved.
  • the axial temperature gradient in the growth chamber should be controlled relatively small, and the radial temperature gradient control is relatively large, and the diameter expansion process in the first half of the single crystal growth is completed.
  • the axial temperature gradient in the growth chamber should be controlled relatively large, and the radial temperature gradient control is relatively small to achieve high quality single crystal equal diameter growth process.
  • the temperature field distribution in the growth chamber needs to be adjusted in real time throughout the crystal growth process.
  • the temperature field distribution in the growth chamber is mainly designed by the size and shape of the heat dissipation holes of the insulation material when the furnace is installed, thereby realizing the temperature field distribution in the growth chamber. Since the size and shape of the heat-dissipating holes of the insulating material are statically constant during the growth process, the temperature field distribution in the growth chamber is also statically constant throughout the crystal growth process.
  • the invention provides a The process of growing silicon carbide single crystal by physical vapor transport method and the in-situ annealing process of silicon carbide single crystal after growth.
  • the crystal growth process adjusts the temperature field distribution of the growth chamber in real time by regulating the position of the upper insulation layer of the growth chamber, so that the temperature field distribution inside the growth chamber is regulated in real time according to the process requirements throughout the crystal growth process. Since the temperature field distribution in the growth chamber is controlled in real time, it helps to greatly improve the crystal quality and yield.
  • the inert gas pressure in the growth chamber is increased, and the temperature gradient in the growth chamber is decreased, so that the in-situ annealing of the silicon carbide crystal is performed under a small temperature gradient, which is helpful. Reduce the internal stress between the crystal and the lid and the silicon carbide crystal, thereby reducing the breakage rate in the subsequent processing and improving the subsequent processing yield of the silicon carbide crystal.
  • the process for growing a silicon carbide single crystal by the physical vapor transport method of the present invention comprises:
  • an automatic transmission device is used to control the position of the insulation layer, and the relative position of the insulation layer in the furnace body is recorded; during the growth process, the relative position of the insulation layer is adjusted by the automatic transmission device according to the process requirements, so that the growth chamber is grown.
  • the temperature field distribution reaches the desired temperature field distribution.
  • the insulating layer material includes high temperature resistant graphite, solid graphite felt and/or soft graphite felt.
  • the insulating layer structure comprises a columnar insulating layer, a truncated insulating layer and/or a tapered insulating layer.
  • the automatic transmission device includes an automatic ascending and automatic descending function, and each of the functional running speed and the running displacement is continuously adjustable within a certain range.
  • the running speed is preferably 0.01 mm / h - 50 mm / h
  • the running displacement is preferably 0-600mm.
  • the automatic transmission includes a stop function, and the duration of the function is continuously adjustable within a certain range.
  • the stop function duration is preferred 0-100h.
  • the crystal growth rate can reach 0.1 mm / h - 4 mm / h.
  • the crystal dislocation density is less than 10 3 /cm 2 .
  • the temperature field distribution in the growth chamber is achieved by designing the size and shape of the heat dissipation holes of the insulation material during the furnace installation to achieve the temperature field distribution in the growth chamber. Since the size and shape of the heat-dissipating holes of the insulating material are statically unchanged during the growth process, the temperature field distribution in the growth chamber is also statically constant throughout the crystal growth process. However, this statically constant temperature field distribution in the growth chamber is not conducive to the growth of large-sized, high-quality silicon carbide crystals. In the early stage of crystal growth, it is desirable to have as few spiral growth centers as possible, which requires a relatively high growth interface temperature, which in turn requires a relatively small axial temperature gradient in the growth chamber.
  • crystal growth In the early and middle stages of crystal growth, crystal growth is expected to occur, which requires a relatively small axial temperature gradient and a relatively large radial temperature gradient. In the middle and late stages of crystal growth, it is expected that crystals can grow at a relatively fast velocity, which requires a relatively large axial temperature gradient and a relatively small radial temperature gradient.
  • an automatic transmission device is used to control the relative position of the insulation layer in the furnace.
  • the relative position of the thermal insulation layer is controlled in real time by an automatic transmission according to the needs of the growth process, thereby obtaining a desired temperature field distribution.
  • the automatic transmission has automatic rising, automatic lowering and stopping functions, and the running speed, running displacement and duration of various functions are continuously adjustable within a certain range to meet the needs of the actual growth process. Since the temperature field distribution in the growth chamber can be adjusted according to the actual process requirements, the diameter of the crystal single crystal region can be ensured, the density of micropipes and dislocation defects in the crystal can be reduced, and the crystal growth rate and crystal quality can be improved.
  • the crystal dislocation density grown by this method can be less than 10 3 /cm 2 , and the crystal growth rate can be continuously adjusted in the range of 0.1 mm / h - 4 mm / h.
  • the in-situ annealing process steps of the present invention include:
  • the inert gas pressure in the growth chamber is slowly increased, and the temperature of the growth chamber is slowly increased to reduce the temperature gradient in the growth chamber, and the temperature in the growth chamber is maintained at the temperature during the growth process;
  • the pressure of the inert gas in the growth chamber is gradually raised to 10,000 Pa or more, preferably 50,000 Pa or more.
  • the slower growth of the growth chamber reduces the temperature gradient within the growth chamber comprising slowly lowering the insulation layer to bring the insulation layer closer to the growth chamber.
  • maintaining the temperature in the growth chamber at the temperature during growth includes real-time regulation of the heating power source.
  • the growth chamber has a temperature gradient of less than 10 ° C /cm, preferably less than 5 ° C / cm. .
  • the inert gas includes argon or helium.
  • the silicon carbide crystal has a size of 2-8 inches.
  • the crystalline form of the silicon carbide crystal is 4H-SiC, 15R-SiC and/or 6H-SiC.
  • the silicon carbide crystal comprises a conductive type and/or a semi-insulating silicon carbide crystal.
  • the silicon carbide crystal after the growth has a large internal stress.
  • the presence of this internal stress will cause the crystal to rupture during subsequent processing, thereby directly reducing the crystal yield.
  • the crystal In order to eliminate the internal stress in the silicon carbide crystal after the end of growth, the crystal needs to be annealed in situ.
  • the growth chamber requires a certain temperature gradient and a low inert gas pressure (generally 1,000Pa-10,000Pa),
  • the silicon carbide vapor phase material is transported from the high temperature raw material region to the low temperature seed crystal region to be crystallized into silicon carbide crystals.
  • the temperature gradient in the growth chamber is required to be as small as possible in order to sufficiently release the stress inside the crystal.
  • the insulating layer is slowly lowered to bring the thermal insulation layer close to the growth chamber, so as to strengthen the growth chamber, thereby reducing the temperature gradient in the growth chamber; and slowly increasing the inert gas pressure in the growth chamber (at least 10,000Pa or more, preferably 50,000Pa Above) to prevent further crystals from decomposing and evaporating.
  • slowly increasing the pressure of the inert gas in the growth chamber can result in a decrease in the overall temperature in the growth chamber; on the other hand, strengthening the insulation of the growth chamber can result in an increase in the overall temperature in the growth chamber.
  • the temperature during growth is about 10-40. Hours so that the internal stress in the crystal is sufficiently released. Subsequently, the growth chamber temperature is slowly lowered from the growth temperature to room temperature, and the cooling time is about 20-50. Hours.
  • the purpose of slow cooling is to avoid introducing new internal stresses during the cooling process.
  • the slow cooling phase can be set to stage cooling according to the process requirements.
  • the above-mentioned in-situ annealing process of the silicon carbide crystal can largely eliminate the internal stress of the crystal, thereby reducing the breakage rate of the crystal in the subsequent processing and improving the yield of the crystal. Moreover, the in-situ annealing process reduces the internal stress of the silicon carbide crystal after the growth, and improves the yield of the silicon carbide crystal in the subsequent processing steps.
  • FIG. 1 is a schematic view showing the structure of a growth chamber for growing a silicon carbide crystal by a physical vapor phase transfer method
  • Figure 2 is a schematic view of the initial stage of crystal growth after adding an insulating layer
  • Figure 3 is a schematic diagram of the rising thermal insulation layer in the middle and the middle of the crystal growth to a preset position
  • Figure 4 is a schematic view of the thermal insulation layer 8 in the middle and late stages of crystal growth away from the growth chamber;
  • Figure 5 is a schematic view of the growth chamber during in-situ annealing after the end of crystal growth
  • Fig. 6 and Fig. 7 show that the insulating layer 8 has a cylindrical shape and a conical shape, respectively.
  • figure 1 It is a schematic diagram of the structure of a crystal growth chamber heated by an induction coil commonly used in growing silicon carbide crystals, wherein reference numeral 1 denotes an insulating material; 2 denotes a double-layer water-cooled quartz tube; and 3 denotes an induction coil; Indicates a silicon carbide raw material; 5 denotes a graphite growth chamber; 6 denotes a silicon carbide vapor phase material; and 7 denotes a grown silicon carbide crystal.
  • reference numeral 1 denotes an insulating material
  • 2 denotes a double-layer water-cooled quartz tube
  • 3 denotes an induction coil
  • 5 denotes a graphite growth chamber
  • 6 denotes a silicon carbide vapor phase material
  • 7 denotes a grown silicon carbide crystal.
  • the graphite growth chamber is made of three high graphite.
  • the heat preservation material on the side of the growth chamber and the upper and lower insulation materials are processed by high temperature resistant graphite felt.
  • the upper part of the growth chamber has no insulation material and functions as a heat dissipation hole.
  • the entire insulation material together with the growth chamber is sealed in a water-cooled quartz tube sleeve, and the insulation material and the water-cooled quartz tube have a sufficiently wide distance to prevent the thermal insulation material from damaging the inner wall of the quartz tube too much to damage the quartz sleeve.
  • the outer side of the quartz sleeve is an induction coil heating device.
  • Fig. 2 is a schematic view showing the addition of the insulating layer 8 at the initial stage of crystal growth. Except for the addition of the truncated insulation layer 8, the same as in Figure 1. Insulation 8 It is also made of high temperature resistant graphite material. The design of the upper and lower layers of the insulation layer 8 matches the size of the vent holes left in the upper part of the growth chamber. In the early stage of crystal growth, the insulation layer 8 It is located in the upper heat dissipation hole of the growth chamber, so that the growth chamber can obtain a relatively small temperature gradient, a high growth interface temperature, and a high quality initial lengthening process.
  • Figure 3 is a schematic diagram of the thermal insulation layer 8 after the initial growth of crystal growth.
  • insulation layer 8 Slowly rise to a preset position at a certain speed, so that a relatively small axial temperature gradient and a relatively large radial temperature gradient are obtained in the growth chamber to complete the diameter-increased growth process of the silicon carbide crystal.
  • Figure 4 is a schematic view of the insulative layer 8 in the middle and late stages of crystal growth away from the growth chamber.
  • insulation layer 8 Keep away from the growth chamber at a certain speed, so that a relatively large axial temperature gradient is obtained in the growth chamber, and the equal diameter growth process of the silicon carbide single crystal is completed at a faster growth rate.
  • the growth method can ensure the diameter of the crystal single crystal region, reduce the density of microtubules and dislocation defects in the crystal, and increase the crystal growth rate and crystal quality.
  • the crystal dislocation density grown by this method can be less than 10 3 /cm 2 , and the crystal growth rate can be continuously adjusted in the range of 0.1 mm / h - 4 mm / h.
  • FIG. 5 is a schematic illustration of the growth chamber during in-situ annealing after the end of crystal growth.
  • the in-situ annealing process can largely eliminate the internal stress of the crystal, thereby reducing the breakage rate of the crystal in the subsequent processing and improving the yield of the crystal.
  • the physical vapor transport method grows 2 inches of 6H semi-insulating silicon carbide crystals.
  • the furnace When the furnace is installed, it is a round-shaped insulation layer. 8 Located in the upper vent of the growth chamber.
  • the inert gas in the growth chamber is a flowing atmosphere, and the pressure is maintained at about 8000 Pa.
  • the insulating layer 8 Under the action of the automatic transmission, it is 10 mm away from the growth chamber at a speed of 0.5 mm / h, and the insulation layer 8 stays at this position for 20 hours to complete the diameter expansion process in the middle and the middle of the crystal.
  • the insulation layer 8 Again, under the action of the automatic transmission, the speed is increased by 30mm and 50mm at 1mm / h and 10mm / h respectively. In hours, the rapid equal diameter growth in the middle and late stages of the crystal is completed. In the above crystal growth process, the stability of the growth interface temperature should be controlled, and the heating power supply can be adjusted if necessary. After the crystal growth is completed, the crystal is annealed in situ. Use 10h The inert gas pressure in the growth chamber is slowly increased from 8,000 Pa to 50,000 Pa, while the insulation layer 8 is lowered by 50 mm at a speed of 25 mm / h and 5 mm / h, respectively. 40mm.
  • the insulation layer 8 is again lowered into the vents in the upper part of the growth chamber.
  • the growth temperature should be kept constant, and the heating power can be adjusted if necessary. Then keep the growth temperature 10 After an hour, the growth chamber temperature was then lowered from room temperature to room temperature over 30 hours.
  • a 3 inch 4H conductive silicon carbide crystal was grown by physical vapor transport. When the furnace is installed, it is a round-shaped insulation layer. 8 Located in the upper vent of the growth chamber. The inert gas in the growth chamber is a flowing atmosphere, and the pressure is maintained at about 5,000 Pa. After the crystal is grown for 5 hours, after the initial phase of the crystal is completed, the insulating layer 8 Under the action of the automatic transmission, it is 10 mm away from the growth chamber at a speed of 0.4 mm / h, and the insulation layer 8 stays at this position for 40 hours to complete the diameter expansion process in the middle and the middle of the crystal.
  • the insulation layer 8 Again, under the action of the automatic transmission, the speed is increased by 30mm and 50mm at 1mm / h and 10mm / h respectively. In hours, the rapid equal diameter growth in the middle and late stages of the crystal is completed. In the above crystal growth process, the stability of the growth interface temperature should be controlled, and the heating power supply can be adjusted if necessary. After the crystal growth is completed, the crystal is annealed in situ. Use 10h Increase the inert gas pressure in the growth chamber from 5,000Pa to 30,000Pa, while the insulation layer 8 drops 50mm at 25mm / h and 5mm / h respectively. 40mm. The insulation layer 8 is again lowered into the vents in the upper part of the growth chamber.
  • the growth temperature should be kept constant, and the heating power can be adjusted if necessary. Then keep the growth temperature 20 After an hour, the growth chamber temperature was then lowered from room temperature to room temperature over 40 hours.
  • a 4 inch 4H conductive silicon carbide crystal was grown by physical vapor transport. When the furnace is installed, it is a round-shaped insulation layer. 8 Located in the upper vent of the growth chamber. The inert gas in the growth chamber is a flowing atmosphere, and the pressure is maintained at about 3,000 Pa. After the crystal is grown for 10 hours, after the initial phase of the crystal is completed, the insulating layer 8 Under the action of the automatic transmission, it is 10 mm away from the growth chamber at a speed of 0.3 mm / h, and the insulation layer 8 stays at this position for 50 hours to complete the diameter expansion process in the middle and the middle of the crystal.
  • the insulation layer 8 Again, under the action of the automatic transmission, the speed is increased by 30mm and 50mm at 0.5mm / h and 10mm / h respectively. In hours, the rapid equal diameter growth in the middle and late stages of the crystal is completed. In the above crystal growth process, the stability of the growth interface temperature should be controlled, and the heating power supply can be adjusted if necessary. After the crystal growth is completed, the crystal is annealed in situ. 8h The inert gas pressure in the growth chamber is slowly increased from 3,000 Pa to 30,000 Pa, while the insulation layer 8 is lowered by 25 mm at a speed of 25 mm / h and 6.7 mm / h, respectively. And 40mm.
  • the insulation layer 8 is again lowered into the vents in the upper part of the growth chamber.
  • the growth temperature should be kept constant, and the heating power can be adjusted if necessary. Then keep the growth temperature 25 After an hour, the growth chamber temperature was then lowered from room temperature to room temperature over 50 hours.
  • a 6-inch 6H conductive silicon carbide crystal was grown by physical vapor transport.
  • Cylindrical insulation layer when furnace is installed 8 Located in the upper vent of the growth chamber.
  • the inert gas in the growth chamber is a flowing atmosphere, and the pressure is maintained at about 2,500 Pa.
  • the insulating layer 8 Under the action of the automatic transmission, it is 10 mm away from the growth chamber at a speed of 0.2 mm / h, and the insulation layer 8 stays at this position for 65 hours to complete the diameter expansion process in the middle and the middle of the crystal.
  • the insulation layer 8 Again, under the action of the automatic transmission, the speed is increased by 30mm and 50mm at 0.5mm / h and 10mm / h respectively. In hours, the rapid equal diameter growth in the middle and late stages of the crystal is completed. In the above crystal growth process, the stability of the growth interface temperature should be controlled, and the heating power supply can be adjusted if necessary. After the crystal growth is completed, the crystal is annealed in situ. With 6h The inert gas pressure in the growth chamber is slowly increased from 2,500 Pa to 30,000 Pa, while the insulation layer 8 is lowered by 50 mm at a speed of 25 mm / h and 10 mm / h, respectively. 40mm.
  • the insulation layer 8 is again lowered into the vents in the upper part of the growth chamber.
  • the growth temperature should be kept constant, and the heating power can be adjusted if necessary. Then keep the growth temperature 35 After an hour, the growth chamber temperature was then lowered from room temperature to room temperature over 60 hours.

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Abstract

本发明提供了一种物理气相传输法生长碳化硅单晶的工艺以及生长结束后碳化硅单晶的原位退火工艺。具体来说，通过调控生长室上部保温层的位置达到实时动态调控生长室的温场分布，从而在整个晶体生长过程中根据工艺需要对生长室内部的温场分布进行实时调控。由于生长室内的温场分布实时可控，有助于大幅度提高晶体质量和产率。碳化硅单晶生长结束后，升高生长室内惰性气体压力，同时减小生长室内温度梯度，使得碳化硅晶体原位退火在小温度梯度下进行，有助于降低晶体与坩埚盖之间以及碳化硅晶体内部应力，从而降低后续加工过程中的破损率，提高碳化硅晶体后续加工成品率。

Description

物理气相传输法生长碳化硅单晶及碳化硅单晶的原位退火工艺
技术领域
本发明主要应用于晶体生长及生长结束后处理领域，具体来说 涉及 一种物理气相传输法生长碳化硅单晶的工艺以及生长结束后碳化硅单晶的原位退火工艺 。
背景技术
在信息技术迅猛发展的今天，半导体技术的革新扮演着越来越重要的角色。以碳化硅、氮化镓为代表的宽禁带半导体材料，是继硅、砷化镓之后的第三代宽禁带半导体。与硅和砷化镓为代表的传统半导体材料相比，碳化硅在工作温度、抗辐射、耐击穿电压等性能方面具有很大优势。作为目前发展最成熟的宽带隙半导体材料，碳化硅具有高热导率、高击穿场强、高饱和电子漂移速率和高键合能等优点，其优异性能可以满足现代电子技术对高温、高频、高功率以及抗辐射的新要求，因而被看作是半导体材料领域最有前景的材料之一。此外，由于六方碳化硅与氮化镓相近的晶格常数及热膨胀系数，因此也成为制造高亮度发光二极管 (HB-LED) 的理想衬底材料。
目前生长碳化硅晶体最有效的方法是物理气相传输法（ journal of crystal growth 43 (1978) 209-212 ），典型的生长室结构如图 1 所示。坩埚由上部的盖和下部的埚组成，上部的盖用于粘籽晶，下部的埚用于装碳化硅原料。坩埚侧壁及上下是耐高温的保温材料，保温材料通常是石墨毡。保温层侧壁是石英套水冷装置，由于保温层辐射热量较大，要求冷却水流速较大。水冷装置外是感应线圈加热器。通常采用 C 面作为生长面进行 SiC 晶体生长。通过调节保温毡散热孔形状和大小，使得 SiC 原料处温度较高，而籽晶处温度较低。处于高温处的 SiC 原料升华分解成气相物质（主要为 Si, Si2C ， SiC2 ），这些气相物质输运到温度较低的籽晶处，结晶生成 SiC 晶体。采用这种工艺生长碳化硅晶体，生长室内合适的温场分布是获得高质量晶体的关键条件。碳化硅晶体生长过程大致可分为三个阶段，晶体生长初期（即接长阶段），晶体生长初中期（即扩径生长阶段）及晶体生长中后期（即等径生长阶段）。在单晶生长初期，生长室内轴向温度梯度应控制相对较小，使得生长界面温度相对较高，进而使得生长初期螺旋生长中心尽量少，实现 高质量初期接长。在单晶生长初中期，生长室内轴向温度梯度应控制相对较小，径向温度梯度控制相对较大，完成单晶生长初中期的扩径生长过程。在单晶生长中后期，生长室内轴向温度梯度应控制相对较大，径向温度梯度控制相对较小，实现高质量单晶等径生长过程。由上所述可见，要获得高质量碳化硅晶体，在整个晶体生长过程中生长室内的温场分布需要实时调整。然而在目前的碳化硅晶体生长工艺中，生长室内的温场分布主要通过装炉时，设计保温材料的散热孔大小和形状，实现生长室内的温场分布。由于该保温材料的散热孔大小和形状在生长过程中是静态不变的，因此生长室内的温场分布在整个晶体生长过程中也是静态不变的。
由于碳化硅晶体生长过程在非平衡状态下进行，生长结束后的碳化硅晶体具有较大的内应力。该内应力的存在将导致晶体在后续加工过程中破裂，从而直接降低晶体成品率。晶体在加工过程中的破裂现象在大尺寸晶体（ 3 英寸 以上）加工过程中尤其明显。如何优化原位退火工艺（即晶体生长结束后在炉中直接退火的过程）以及二次退火工艺（即晶体从炉中取出后的再次退火过程），消除碳化硅晶体内应力，从而提高碳化硅晶体成品率成为碳化硅晶体生长领域一个亟待解决的关键技术问题。
发明内容
本发明提供了一种 物理气相传输法生长碳化硅单晶的工艺以及生长结束后碳化硅单晶的原位退火工艺。该晶体生长工艺通过调控生长室上部保温层的位置达到实时动态调控生长室的温场分布，从而在整个晶体生长过程中根据工艺需要对生长室内部的温场分布进行实时调控。由于生长室内的温场分布实时可控，有助于大幅度提高晶体质量和产率。碳化硅单晶生长结束后，升高生长室内惰性气体压力，同时减小生长室内温度梯度，使得碳化硅晶体原位退火在小温度梯度下进行，有助于 降低晶体与坩埚盖之间以及碳化硅晶体内部应力，从而降低后续加工过程中的破损率，提高碳化硅晶体后续加工成品率。
为 实现上述目的， 本发明物理气相传输法生长碳化硅单晶的工艺包括：
生长装炉时，用一种自动传动装置控制保温层的位置，并记录该保温层在炉体内的相对位置；生长过程中，根据工艺需要利用自动传动装置调节保温层的相对位置，使生长室内温场分布达到期望的温场分布。
进一步，保温层材质包括耐高温石墨、固态石墨毡和 / 或软石墨毡。
更进一步，保温层结构包括柱状保温层、圆台状保温层和 / 或锥状保温层。
更进一步，所述自动传动装置包括自动上升、自动下降功能，并且每一种功能运行速度、运行位移在一定范围内连续可调。所述运行速度优选 0.01mm /h-50mm/h 、运行位移优选 0-600mm 。
更进一步，所述自动传动装置包括停止功能，该功能持续时间在一定范围内连续可调。所述停止功能持续时间优选 0-100h 。
更进一步，晶体生长速度可达 0.1mm /h-4mm/h 。
更进一步，晶体位错密度小于 103/cm2 。
目前的碳化硅晶体生长工艺，生长室内的温场分布是在装炉时，通过设计保温材料的散热孔大小和形状，实现生长室内的温场分布。由于该保温材料的散热孔大小和形状在生长过程中静态不变，因此生长室内的温场分布在整个晶体生长过程中也是静态不变的。然而，生长室内这种静态不变的温场分布不利于生长大尺寸、高质量碳化硅晶体。在晶体生长初期，期望螺旋生长中心尽量少，这就要求生长界面温度相对较高，进而要求生长室内轴向温度梯度相对较小。晶体生长初中期，期望晶体扩径生长，这就要求相对较小的轴向温度梯度和相对较大的径向温度梯度。晶体生长中后期，期望晶体能以较快的速度等径生长，这就要求相对较大的轴向温度梯度和相对较小的径向温度梯度。
为实现生长室内温场分布的实时调控，采用一种自动传动装置控制保温层在炉内的相对位置。在晶体生长过程中，根据生长工艺的需要，利用自动传动装置实时控制保温层的相对位置，从而获得期望的温场分布。该自动传动装置具有自动上升、自动下降及停止功能，而且各种功能的运行速度、运行位移以及持续时间在一定范围内均连续可调，以满足实际生长工艺的需要。由于生长室内的温场分布可以根据实际工艺需要进行调控，因此可保证晶体单晶区直径尺寸，减少晶体中微管和位错缺陷密度，提高晶体生长速度和结晶质量。利用该方法生长的晶体位错密度可小于 103/cm2 ，晶体生长速度在 0.1mm /h-4mm/h 范围内连续可调。
为实现上述目的，本发明原位退火工艺步骤包括：
1 ）碳化硅单晶生长结束后，缓慢升高生长室内惰性气体压力，同时缓慢加强生长室的保温减小生长室内温度梯度，整个过程中生长室内温度维持在生长时的温度；
2 ）保持生长时温度约 10-40 小时；
3 ）将生长室内温度由生长温度缓慢降低至室温，缓慢降温时间约 20-50 小时。
进一步，缓慢升高生长室内惰性气体压力至 10,000Pa 以上，优选 50,000Pa 以上。
更进一步，所述缓慢加强生长室的保温减小生长室内温度梯度包括缓慢下降保温层，使保温层靠近生长室。
更进一步，所述生长室内温度维持在生长时的温度包括实时调控加热电源功率。
更进一步， 所述生长室内温度梯度小于 10 ℃ /cm ，优选小于 5 ℃ /cm 。。
更进一步，所述惰性气体包括氩气或氦气。
更进一步，所述碳化硅晶体尺寸为 2-8英寸。
更进一步，所述碳化硅晶体晶型为 4H-SiC 、 15R-SiC 和 / 或 6H-SiC 。
更进一步，所述碳化硅晶体包括导电型和 / 或半绝缘型碳化硅晶体。
由于碳化硅晶体生长过程在非平衡状态下进行，生长结束后的碳化硅晶体具有较大的内应力。该内应力的存在将导致晶体在后续加工过程中破裂，从而直接降低晶体成品率。为消除生长结束后碳化硅晶体中的内应力，需对晶体进行原位退火。
碳化硅晶体生长过程中，生长室内需要一定的温度梯度以及较低的惰性气体压力（一般 1,000Pa-10,000Pa ） , 使得碳化硅气相物质由高温原料区传输至低温籽晶区，结晶成碳化硅晶体。然而，生长结束后对晶体进行原位退火过程中，要求生长室内温度梯度尽量小，以便充分释放晶体内部的应力。为了解决生长时温度梯度和退火时温度梯度的不同要求，需要对生长室内的温度梯度进行动态调控。晶体生长结束后，进行原位退火时，缓慢下降保温层，使保温层靠近生长室，以便加强生长室的保温，从而减小生长室内温度梯度；同时缓慢升高生长室内惰性气体压力（至少 10,000Pa 以上，优选 50,000Pa 以上），以防止生长完的晶体进一步分解、蒸发。一方面，缓慢升高生长室内惰性气体压力可导致生长室内整体温度降低；另一方面，加强生长室的保温可导致生长室内整体温度升高。在整个调控过程中，需注意两方面的协调性，以保持生长室内的温度不变，如需要可实时调控加热电源功率，以免在原位退火的晶体中引入新的内应力。
待升高生长室内惰性气体压力和减小生长室内温度梯度后，保持生长时温度约 10-40 小时，以便晶体中的内应力得到充分的释放。随后，将生长室内温度由生长温度缓慢降低至室温，降温时间约 20-50 小时。缓慢降温的目的是避免在降温的过程中再次引入新的内应力。该缓慢降温阶段可以根据工艺需要设为分段降温。
上述碳化硅晶体原位退火工艺可很大程度上消除晶体内应力，从而降低晶体在后续加工过程中的破损率，提高了晶体的成品率。而且，该原位退火工艺降低了生长结束后的碳化硅晶体的内应力，提高了碳化硅晶体在后续加工步骤中的成品率。
附图说明
图 1 是物理气相传输法生长碳化硅晶体的生长室结构示意图；
图 2 是晶体生长初期加保温层后的示意图；
图 3 是晶体生长初中期上升保温层至预设位置后的示意图；
图 4 是晶体生长中后期保温层 8 远离生长室后的示意图；
图 5 是晶体生长结束后原位退火时生长室的示意图；
图 6 、图 7示出保温层 8 形状分别是圆柱状和圆锥状。
具体实施方式
以下参照附图，对物理气相传输法生长碳化硅单晶的工艺以及生长结束后碳化硅单晶的原位退火工艺作详细说明。图 1 是目前生长碳化硅晶体普遍使用的感应线圈加热的晶体生长室结构示意图，其中标号 1 表示保温材料；标号 2 表示双层水冷石英管；标号 3 表示感应线圈；标号 4 表示碳化硅原料；标号 5 表示石墨生长室；标号 6 表示碳化硅气相物质；标号 7 表示生长的碳化硅晶体。在图 1 中，石墨生长室由三高石墨加工而成，生长室侧面及上下的保温材料都是用耐高温石墨毡加工而成，生长室的上部有一块区域没有保温材料，起散热孔作用。整个保温材料连同生长室都被密封在装有水冷的石英管套筒内，且保温材料与水冷石英管之间有足够宽的距离，以免保温材料对石英管内壁辐射热太大而损坏石英套筒；石英套筒外侧则是感应线圈加热装置。
图 2 是晶体生长初期加保温层 8 后的示意图。除了增加圆台状保温层 8 外，其余同图 1 。保温层 8 也是由耐高温石墨材料加工而成，保温层 8 上下面处的设计与生长室上部留有的散热孔尺寸相匹配。在晶体生长初期，保温层 8 位于生长室上部散热孔内，以便生长室内获得相对较小的温度梯度，较高的生长界面温度，实现高质量初期接长过程。
图 3 是晶体生长初中期上升保温层 8 后的示意图。在晶体生长初中期，保温层 8 以一定速度缓慢上升至预设位置，以便生长室内获得相对较小的轴向温度梯度和相对较大的径向温度梯度，完成碳化硅晶体的扩径生长过程。
图 4 是晶体生长中后期保温层 8 远离生长室后的示意图。在晶体生长中后期，保温层 8 以一定速度远离生长室，以便生长室内获得相对较大的轴向温度梯度，以较快的生长速度完成碳化硅单晶的等径生长过程。
由于生长室内的温场分布可根据实际工艺需要进行调控，因此该生长方法可保证晶体单晶区直径尺寸，减少晶体中微管和位错缺陷密度，提高晶体生长速度和结晶质量。利用该方法生长的晶体位错密度可小于 103/cm2 ，晶体生长速度在 0.1mm /h-4mm/h 范围内连续可调。
晶体内部产生应力的因素有很多，通常认为晶体生长温度梯度是产生应力的主要原因；单晶边缘的多晶或其它缺陷、晶体与坩埚盖热膨胀系数不匹配及晶体内部掺杂不均等都会造成晶体内部产生应力。
正如背景技术所提到的，为实现碳化硅晶体生长，生长室内需要一定的温度梯度以使碳化硅气相物质由高温原料区传输至低温籽晶区，结晶成碳化硅晶体。该温度梯度将导致晶体生长过程中产生内应力。为消除晶体中的内应力，降低晶体在后续加工过程中的破损率，需对晶体进行原位退火。但是，生长室的温度梯度不利于原位退火消除晶体内应力。为了减小生长室内的温度梯度，可下降保温层 8 。图 5 是晶体生长结束后原位退火时生长室的示意图。
该原位退火工艺可很大程度上消除晶体内应力，从而降低晶体在后续加工过程中的破损率，提高了晶体的成品率。
实施例 1
物理气相传输法生长 2 英寸 6H 半绝缘碳化硅晶体。装炉时，呈圆台状保温层 8 位于生长室上部散热孔内。生长室内惰性气体采用流动气氛，压力维持在 8000Pa 左右。待晶体生长 2 小时，完成晶体初期接长阶段后，保温层 8 在自动传动装置的作用下以 0.5mm /h 速度远离生长室 10mm ，保温层 8 在此位置停留 20 小时，完成晶体初中期的扩径生长过程。随后，保温层 8 再次在自动传动装置的作用下分别以 1mm /h 和 10mm /h 速度上升 30mm 和 50mm ，上升完毕后停留 80 小时，完成晶体中后期的快速等径生长。在上述晶体生长过程中，应控制生长界面温度的稳定性，如需要可调整加热电源功率。晶体生长结束后，对晶体进行原位退火。用 10h 将生长室内的惰性气体压力由 8,000Pa 缓慢增至 50,000Pa ，同时保温层 8 分别以 25mm /h 和 5mm /h 的速度下降 50mm 和 40mm 。保温层 8 再次降至生长室上部的散热孔内。在上述晶体原位退火过程中，应保持生长温度不变，如需要可调整加热电源功率。然后保持生长温度 10 小时，随后用 30 小时使生长室内温度由生长温度降至室温。
实施例 2
物理气相传输法生长 3 英寸 4H 导电碳化硅晶体。装炉时，呈圆台状保温层 8 位于生长室上部散热孔内。生长室内惰性气体采用流动气氛，压力维持在 5000Pa 左右。待晶体生长 5 小时，完成晶体初期接长阶段后，保温层 8 在自动传动装置的作用下以 0.4mm /h 速度远离生长室 10mm ，保温层 8 在此位置停留 40 小时，完成晶体初中期的扩径生长过程。随后，保温层 8 再次在自动传动装置的作用下分别以 1mm /h 和 10mm /h 速度上升 30mm 和 50mm ，上升完毕后停留 80 小时，完成晶体中后期的快速等径生长。在上述晶体生长过程中，应控制生长界面温度的稳定性，如需要可调整加热电源功率。晶体生长结束后，对晶体进行原位退火。用 10h 将生长室内的惰性气体压力由 5,000Pa 缓慢增至 30,000Pa ，同时保温层 8 分别以 25mm /h 和 5mm /h 的速度下降 50mm 和 40mm 。保温层 8 再次降至生长室上部的散热孔内。在上述晶体原位退火过程中，应保持生长温度不变，如需要可调整加热电源功率。然后保持生长温度 20 小时，随后用 40 小时使生长室内温度由生长温度降至室温。
实施例 3
物理气相传输法生长 4 英寸 4H 导电碳化硅晶体。装炉时，呈圆台状保温层 8 位于生长室上部散热孔内。生长室内惰性气体采用流动气氛，压力维持在 3,000Pa 左右。待晶体生长 10 小时，完成晶体初期接长阶段后，保温层 8 在自动传动装置的作用下以 0.3mm /h 速度远离生长室 10mm ，保温层 8 在此位置停留 50 小时，完成晶体初中期的扩径生长过程。随后，保温层 8 再次在自动传动装置的作用下分别以 0.5mm /h 和 10mm /h 速度上升 30mm 和 50mm ，上升完毕后停留 80 小时，完成晶体中后期的快速等径生长。在上述晶体生长过程中，应控制生长界面温度的稳定性，如需要可调整加热电源功率。晶体生长结束后，对晶体进行原位退火。用 8h 将生长室内的惰性气体压力由 3,000Pa 缓慢增至 30,000Pa ，同时保温层 8 分别以 25mm /h 和 6.7mm /h 的速度下降 50mm 和 40mm 。保温层 8 再次降至生长室上部的散热孔内。在上述晶体原位退火过程中，应保持生长温度不变，如需要可调整加热电源功率。然后保持生长温度 25 小时，随后用 50 小时使生长室内温度由生长温度降至室温。
实施例 4
物理气相传输法生长 6 英寸 6H 导电碳化硅晶体。装炉时，呈圆柱状保温层 8 位于生长室上部散热孔内。生长室内惰性气体采用流动气氛，压力维持在 2,500Pa 左右。待晶体生长 15 小时，完成晶体初期接长阶段后，保温层 8 在自动传动装置的作用下以 0.2mm /h 速度远离生长室 10mm ，保温层 8 在此位置停留 65 小时，完成晶体初中期的扩径生长过程。随后，保温层 8 再次在自动传动装置的作用下分别以 0.5mm /h 和 10mm /h 速度上升 30mm 和 50mm ，上升完毕后停留 85 小时，完成晶体中后期的快速等径生长。在上述晶体生长过程中，应控制生长界面温度的稳定性，如需要可调整加热电源功率。晶体生长结束后，对晶体进行原位退火。用 6h 将生长室内的惰性气体压力由 2,500Pa 缓慢增至 30,000Pa ，同时保温层 8 分别以 25mm /h 和 10mm /h 的速度下降 50mm 和 40mm 。保温层 8 再次降至生长室上部的散热孔内。在上述晶体原位退火过程中，应保持生长温度不变，如需要可调整加热电源功率。然后保持生长温度 35 小时，随后用 60 小时使生长室内温度由生长温度降至室温。
应该指出，上述的具体实施方式只是对本发明进行详细说明，它不应是对本发明的限制。对于本领域的技术人员而言，在不偏离权利要求的宗旨和范围时，可以有多种形式和细节的变化。

Claims (20)

  1. 一种物理气相传输法生长碳化硅单晶的工艺，该工艺通过调控生长室上部保温层的位置达到实时动态调控生长室的温场分布，从而在整个晶体生长过程中根据工艺需要对生长室内部的温场分布进行实时调控，该工艺包括：
    生长装炉时，利用自动传动装置控制保温层的位置，并记录该保温层在炉体内的相对位置；生长过程中，根据工艺需要利用自动传动装置调节保温层的相对位置，使生长室内温场分布达到期望的温场分布。
  2. 权利要求 1 所述的生长工艺，保温层材质包括耐高温石墨、固态石墨毡、软石墨毡或其组合。
  3. 如权利要求 1 所述的生长工艺，保温层结构包括柱状保温层、圆台状保温层、锥状保温层或其组合。
  4. 如权利要求1所述的生长工艺，所述自动传动装置具有自动上升、自动下降功能，并且每一种功能运行速度、运行位移在一定范围内连续可调。
  5. 如权利要求4所述的生长工艺，所述自动传动装置具有自动上升、自动下降功能，并且每一种功能运行速度在0.01mm/h-50mm/h、运行位移在0-600mm范围内连续可调。
  6. 如权利要求1所述的生长工艺，所述自动传动装置具有停止功能，该功能持续时间在一定范围内连续可调。
  7. 如权利要求6所述的生长工艺，所述自动传动装置具有停止功能，该功能持续时间在0-100h范围内连续可调。
  8. 如权利要求1所述的生长工艺，晶体生长速度可达0.1mm/h-4mm/h。
  9. 如权利要求1所述的生长工艺，晶体位错密度小于103/cm2。
  10. 一种生长结束后碳化硅单晶的原位退火工艺，该工艺步骤包括：
    1）碳化硅单晶生长结束后，缓慢升高生长室内惰性气体压力，同时缓慢加强生长室的保温减小生长室内温度梯度，整个过程中生长室内温度维持在生长时的温度；
    2）保持生长时温度约10-40小时；
    3）将生长室内温度由生长温度缓慢降低至室温，缓慢降温时间约20-50小时。
  11. 如权利要求10所述的原位退火工艺，缓慢升高生长室内惰性气体压力至10,000Pa以上。
  12. 如权利要求11所述的原位退火工艺，缓慢升高生长室内惰性气体压力至50,000Pa以上。
  13. 如权利要求10所述的原位退火工艺，所述缓慢加强生长室的保温减小生长室内温度梯度包括缓慢下降保温层，使保温层靠近生长室。
  14. 如权利要求10所述的原位退火工艺，所述生长室内温度维持在生长时的温度包括实时调控加热电源功率。
  15. 如权利要求10所述的原位退火工艺，所述生长室内温度梯度小于10℃/cm。
  16. 如权利要求15所述的原位退火工艺，所述生长室内温度梯度小于5℃/cm。
  17. 如权利要求10所述的原位退火工艺，所述惰性气体包括氩气或氦气。
  18. 如权利要求10所述的原位退火工艺，所述碳化硅晶体尺寸为2-8英寸。
  19. 如权利要求10所述的原位退火工艺，所述碳化硅晶体晶型为4H-SiC、15R-SiC、6H-SiC或其组合。
  20. 如权利要求10所述的原位退火工艺，所述碳化硅晶体包括导电型和/或半绝缘型碳化硅晶体。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014034504A (ja) * 2012-08-10 2014-02-24 Toyota Central R&D Labs Inc 昇華性単結晶の製造方法
CN110777427A (zh) * 2018-07-25 2020-02-11 昭和电工株式会社 晶体生长装置
CN111304745A (zh) * 2018-12-12 2020-06-19 Skc株式会社 晶锭的制备装置以及碳化硅单晶锭的制备方法
CN114645326A (zh) * 2020-12-18 2022-06-21 中国科学院上海硅酸盐研究所 一种InTeI单晶体的制备方法

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8860040B2 (en) 2012-09-11 2014-10-14 Dow Corning Corporation High voltage power semiconductor devices on SiC
CN102817083A (zh) * 2012-09-21 2012-12-12 上海应用技术学院 SiC晶片的退火方法
US9738991B2 (en) 2013-02-05 2017-08-22 Dow Corning Corporation Method for growing a SiC crystal by vapor deposition onto a seed crystal provided on a supporting shelf which permits thermal expansion
US9797064B2 (en) 2013-02-05 2017-10-24 Dow Corning Corporation Method for growing a SiC crystal by vapor deposition onto a seed crystal provided on a support shelf which permits thermal expansion
US9279192B2 (en) 2014-07-29 2016-03-08 Dow Corning Corporation Method for manufacturing SiC wafer fit for integration with power device manufacturing technology
CN105463573A (zh) * 2015-12-22 2016-04-06 中国电子科技集团公司第二研究所 降低碳化硅晶体杂质并获得高纯半绝缘碳化硅晶体的方法
CN105696082A (zh) * 2016-04-19 2016-06-22 北京世纪金光半导体有限公司 一种pvt法生长碳化硅单晶时随炉退火的方法
US20170321345A1 (en) * 2016-05-06 2017-11-09 Ii-Vi Incorporated Large Diameter Silicon Carbide Single Crystals and Apparatus and Method of Manufacture Thereof
CN106222739A (zh) * 2016-09-13 2016-12-14 山东省科学院能源研究所 一种改善物理气相传输法晶体生长炉温度场分布的装置
CN106480504B (zh) * 2016-12-09 2018-10-12 河北同光晶体有限公司 一种降低大直径SiC单晶内应力的炉后退火方法
CN106637410B (zh) * 2016-12-30 2019-03-26 珠海鼎泰芯源晶体有限公司 坩埚装置
US10793972B1 (en) 2017-07-11 2020-10-06 Ii-Vi Delaware, Inc. High quality silicon carbide crystals and method of making the same
CN107541785A (zh) * 2017-09-12 2018-01-05 中国电子科技集团公司第四十六研究所 一种氮化铝晶体的原位退火工艺
CN107557872A (zh) * 2017-10-30 2018-01-09 中国电子科技集团公司第四十六研究所 一种大尺寸碳化硅晶体原位热处理方法
CN108103575A (zh) * 2017-11-14 2018-06-01 山东天岳先进材料科技有限公司 一种低应力碳化硅单晶的制备方法及其装置
CN107904661B (zh) * 2017-12-07 2021-04-27 北京华进创威电子有限公司 一种低应力氮化铝晶体的生长方法
JP6881365B2 (ja) * 2018-03-16 2021-06-02 信越半導体株式会社 炭化珪素単結晶の製造方法及び製造装置
CN109554761B (zh) * 2018-11-26 2021-04-20 国宏中宇科技发展有限公司 一种碳化硅晶体电阻法退火用温控系统及方法
CN110592672B (zh) * 2018-12-14 2020-09-18 北京天科合达半导体股份有限公司 一种低基面位错密度的碳化硅晶体生长方法
CN110284199B (zh) * 2019-07-16 2021-03-16 中国科学院上海硅酸盐研究所 一种晶体原位碳化退火装置及方法
CN110306238B (zh) * 2019-07-16 2021-05-04 安徽微芯长江半导体材料有限公司 一种晶体生长装置及晶体生长方法
CN110904501B (zh) * 2019-11-13 2022-03-29 安徽微芯长江半导体材料有限公司 晶体生长用籽晶下置式装置
KR102192518B1 (ko) * 2020-07-14 2020-12-17 에스케이씨 주식회사 웨이퍼 및 웨이퍼의 제조방법
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CN116815319B (zh) * 2023-06-27 2024-08-16 通威微电子有限公司 碳化硅晶体生长方法和长晶装置
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CN117966254B (zh) * 2023-12-29 2025-07-15 中国科学院物理研究所 一种基于机器学习的精确控温方法
CN118880445B (zh) * 2024-07-16 2025-11-04 中国科学院物理研究所 用于pvt法生长大尺寸单晶的装置和方法
CN119800509A (zh) * 2025-01-02 2025-04-11 山西天成半导体材料有限公司 一种碳化硅晶体生长炉及晶体生长方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11278985A (ja) * 1998-03-26 1999-10-12 Toyota Central Res & Dev Lab Inc 単結晶の製造方法
US5968261A (en) * 1995-09-05 1999-10-19 Northrop Grumman Corporation Method for growing large silicon carbide single crystals
US6451112B1 (en) * 1999-10-15 2002-09-17 Denso Corporation Method and apparatus for fabricating high quality single crystal
CN1554808A (zh) * 2003-12-24 2004-12-15 山东大学 一种生长具有半导体特性的大直径6H-SiC单晶的装置和方法
KR20050033393A (ko) * 2003-10-06 2005-04-12 신병철 승화법을 이용한 단결정 성장 장치의 탄화규소 단열재
JP2007076928A (ja) * 2005-09-12 2007-03-29 Matsushita Electric Ind Co Ltd 単結晶の製造装置及び製造方法
US7767022B1 (en) * 2006-04-19 2010-08-03 Ii-Vi Incorporated Method of annealing a sublimation grown crystal
CN101984153A (zh) * 2009-12-24 2011-03-09 新疆天科合达蓝光半导体有限公司 一种降低碳化硅晶体应力的退火工艺

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2123745U (zh) * 1991-11-19 1992-12-02 樊爱民 一种改进的盐浴炉
JP3216322B2 (ja) * 1993-04-12 2001-10-09 住友金属鉱山株式会社 単結晶育成装置
JP3003027B2 (ja) * 1997-06-25 2000-01-24 日本ピラー工業株式会社 単結晶ＳｉＣおよびその製造方法
DE19842109A1 (de) * 1998-09-08 2000-03-09 Forschungsverbund Berlin Ev Züchtungsapparatur zum Züchten von SiC-Einkristallen
JP3926281B2 (ja) * 2003-03-06 2007-06-06 株式会社豊田中央研究所 ＳｉＣ単結晶の製造方法
US7294324B2 (en) * 2004-09-21 2007-11-13 Cree, Inc. Low basal plane dislocation bulk grown SiC wafers
CN2743375Y (zh) * 2004-09-22 2005-11-30 中国科学院半导体研究所 竖直式离子注入碳化硅高温退火装置
CN2730890Y (zh) * 2004-09-22 2005-10-05 中国科学院半导体研究所 水平式离子注入碳化硅高温退火装置
CN1249271C (zh) * 2004-12-15 2006-04-05 中国科学院上海光学精密机械研究所 砷化镓单晶的生长方法
JP4473769B2 (ja) * 2005-04-14 2010-06-02 新日本製鐵株式会社 炭化珪素単結晶の焼鈍方法
US7344596B2 (en) * 2005-08-25 2008-03-18 Crystal Systems, Inc. System and method for crystal growing
US8361227B2 (en) * 2006-09-26 2013-01-29 Ii-Vi Incorporated Silicon carbide single crystals with low boron content
CN100400723C (zh) * 2006-05-29 2008-07-09 中国科学院物理研究所 一种碳化硅单晶生长后的热处理方法
JP5517930B2 (ja) * 2007-06-27 2014-06-11 トゥー‐シックス・インコーポレイテッド ゆがみ及び反りの少ないＳｉＣ基質の製造
JP4992647B2 (ja) * 2007-10-05 2012-08-08 住友電気工業株式会社 窒化アルミニウム結晶の成長方法および結晶成長装置
JP2010076954A (ja) * 2008-09-24 2010-04-08 Bridgestone Corp ＳｉＣ単結晶製造方法、ＳｉＣ単結晶製造用反応容器、ＳｉＣ単結晶製造装置
JP5402798B2 (ja) * 2010-04-06 2014-01-29 新日鐵住金株式会社 炭化珪素単結晶インゴットの製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5968261A (en) * 1995-09-05 1999-10-19 Northrop Grumman Corporation Method for growing large silicon carbide single crystals
JPH11278985A (ja) * 1998-03-26 1999-10-12 Toyota Central Res & Dev Lab Inc 単結晶の製造方法
US6451112B1 (en) * 1999-10-15 2002-09-17 Denso Corporation Method and apparatus for fabricating high quality single crystal
KR20050033393A (ko) * 2003-10-06 2005-04-12 신병철 승화법을 이용한 단결정 성장 장치의 탄화규소 단열재
CN1554808A (zh) * 2003-12-24 2004-12-15 山东大学 一种生长具有半导体特性的大直径6H-SiC单晶的装置和方法
JP2007076928A (ja) * 2005-09-12 2007-03-29 Matsushita Electric Ind Co Ltd 単結晶の製造装置及び製造方法
US7767022B1 (en) * 2006-04-19 2010-08-03 Ii-Vi Incorporated Method of annealing a sublimation grown crystal
CN101984153A (zh) * 2009-12-24 2011-03-09 新疆天科合达蓝光半导体有限公司 一种降低碳化硅晶体应力的退火工艺

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF CRYSTAL GROWTH, vol. 43, 1978, pages 209 - 212
See also references of EP2653591A4

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014034504A (ja) * 2012-08-10 2014-02-24 Toyota Central R&D Labs Inc 昇華性単結晶の製造方法
CN110777427A (zh) * 2018-07-25 2020-02-11 昭和电工株式会社 晶体生长装置
US11105016B2 (en) 2018-07-25 2021-08-31 Showa Denko K.K. Crystal growth apparatus with controlled center position of heating
CN110777427B (zh) * 2018-07-25 2021-11-19 昭和电工株式会社 晶体生长装置
CN111304745A (zh) * 2018-12-12 2020-06-19 Skc株式会社 晶锭的制备装置以及碳化硅单晶锭的制备方法
US11078599B2 (en) 2018-12-12 2021-08-03 Skc Co., Ltd. Apparatus for producing an ingot comprising a crucible body with a lid assembly having a movable core member and method for producing silicon carbide ingot using the apparatus
CN111304745B (zh) * 2018-12-12 2021-12-03 赛尼克公司 晶锭的制备装置以及碳化硅单晶锭的制备方法
CN114645326A (zh) * 2020-12-18 2022-06-21 中国科学院上海硅酸盐研究所 一种InTeI单晶体的制备方法
CN114645326B (zh) * 2020-12-18 2024-02-06 中国科学院上海硅酸盐研究所 一种InTeI单晶体的制备方法

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