WO2019144804A1 - 晶体生长用坩埚以及释放碳化硅晶体热应力的方法 - Google Patents

晶体生长用坩埚以及释放碳化硅晶体热应力的方法 Download PDF

Info

Publication number
WO2019144804A1
WO2019144804A1 PCT/CN2019/071008 CN2019071008W WO2019144804A1 WO 2019144804 A1 WO2019144804 A1 WO 2019144804A1 CN 2019071008 W CN2019071008 W CN 2019071008W WO 2019144804 A1 WO2019144804 A1 WO 2019144804A1
Authority
WO
WIPO (PCT)
Prior art keywords
crucible
crystal
growth
splicing
silicon carbide
Prior art date
Application number
PCT/CN2019/071008
Other languages
English (en)
French (fr)
Inventor
高攀
忻隽
孔海宽
刘学超
郑燕青
施尔畏
Original Assignee
中国科学院上海硅酸盐研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院上海硅酸盐研究所 filed Critical 中国科学院上海硅酸盐研究所
Priority to US16/962,712 priority Critical patent/US11384451B2/en
Publication of WO2019144804A1 publication Critical patent/WO2019144804A1/zh

Links

Classifications

    • 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
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • 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
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/002—Crucibles or containers

Definitions

  • the invention belongs to the field of crystal growth and the field of silicon carbide materials, and particularly relates to a germanium for crystal growth and a method for releasing thermal stress in a crystal during the process of growing silicon carbide crystal by physical vapor transport.
  • Silicon carbide (SiC) single crystal materials have wide band gap, high thermal conductivity, high electron saturation migration rate, high breakdown electric field and other properties, and have obvious advantages compared with first generation semiconductor materials and second generation semiconductor materials. It is considered to be an ideal semiconductor material for manufacturing optoelectronic devices, high-frequency high-power devices, and power electronic devices, in white light illumination, optical storage, screen display, aerospace, high-temperature radiation environment, petroleum exploration, automation, radar and communication, and automotive electronics. It is widely used in other areas.
  • the most effective method for growing SiC crystals is physical vapor phase transport (PVT).
  • the entire growth chamber is mainly composed of a silicon carbide raw material region, a crystal growth region and a seed crystal region.
  • the main problem in the preparation of silicon carbide crystals by PVT method is that defects and stress accumulation regions are easily formed. Especially with the size requirement of SiC crystals reaching 4 inches and above, tiny thermal stresses are likely to cause crystal cracking, which greatly affects the yield of crystals. Therefore, how to reduce the thermal stress formed during the growth of silicon carbide crystals is crucial for the preparation of finished silicon carbide crystals.
  • the graphite crucibles used in the growth of silicon carbide crystals by PVT method are all three-high graphite, which are relatively expensive and are patented (CN201521114037.3, CN 201706886 U, CN 202688507 U) mentions that graphite crucibles with upper and lower spliced structure are used to reduce the cost by reusing part of the structural components, but the graphite component of the above-mentioned crucible growth zone is still a closed ring structure during crystal growth. The thermal stress accumulated in the silicon carbide crystal will not be fully and effectively released.
  • the inner wall of the crucible in the growth region of the SiC crystal growth process causes the thermal stress of the aggregation to be effectively released, which affects the problem of crystal yield.
  • the invention firstly designs a ring-shaped non-closed structure bismuth assembly, which is applied to a portion where the silicon carbide crystal growth region is in direct contact with the crystal side surface, which not only ensures the effective release of thermal stress accumulated in the silicon carbide crystal during crystal growth, and improves the crystal.
  • the yield while achieving a smaller portion of the bismuth component replacement, further reduces the cost of crystal preparation.
  • the invention provides a crucible for crystal growth, the crucible being a crucible in contact with a side of the prepared crystal, the crucible having a looped non-closed splice structure.
  • the crystal growth crucible has a ring-type non-closed splicing structure, so that the hoop crystal can be avoided, so that the thermal stress formed in the crystal during the crystal growth process is effectively released, the cracking rate of the crystal is lowered, and the yield of the crystal is improved.
  • the crucible is graphite crucible, silicon carbide crucible, or titanium carbide tantalum.
  • the splicing assembly of the crucible in direct contact with the side of the prepared crystal has a thickness of 1 mm or more, preferably 1 to 10 mm.
  • the raft is a single-layer structure, and each splicing component adopts a concave-convex mutual card splicing.
  • the crucible is a multi-layered nested structure, wherein at least the innermost layer is a ring-shaped non-closed splice structure, and the ring-shaped non-closed splice structure is a direct-fitting splicing and/or a embossed inter-card splicing.
  • the gap or tolerance of the splicing is controlled within 3 mm, preferably 0.1 to 1 mm.
  • the present invention provides a method for releasing thermal stress of a crystal during growth of a silicon carbide crystal, wherein a silicon carbide single crystal is deposited on the surface of the seed crystal by a physical vapor transport method, wherein the surface of the crystal is grown in the growth chamber.
  • the crucible to be contacted is any of the above crystal growth crucibles.
  • the ring type non-closed crucible structure can avoid the tightening of the crystal, so that the thermal stress formed in the silicon carbide crystal during the crystal growth process is effectively released, the cracking rate of the crystal is lowered, and the finished product of the silicon carbide crystal is improved. rate.
  • the degree of vacuum of the crystal growth furnace is drawn to 1.0 ⁇ 10 ⁇ 2 Pa or less, and the inert atmosphere is filled to a growth pressure of 6 to 40 Torr, and the growth temperature is 2000 to 2400 ° C.
  • the thermal stress formed by aggregation in the crystal during the crystal growth can be effectively released, the cracking rate of the crystal is lowered, and the yield of the crystal is improved.
  • FIG. 1 is a schematic diagram of a growth chamber structure of a SiC crystal grown by a physical vapor phase transfer (PVT) method; in the drawings, the parts represented by the respective numbers are listed as follows: 1.
  • the growth chamber chamber ⁇ component, and the dotted line indicates that it may be a multilayer or a single layer. Structure; 2, raw material zone ⁇ component; 3, seed crystal zone bonding seed crystal cap assembly; 4, SiC raw material; 5, SiC seed crystal; 6, growing crystal;
  • 2(1) is a schematic view showing an annular non-closed horizontal and vertical splicing structure of a growth chamber inner wall ⁇ assembly of a SiC crystal prepared by a PVT method;
  • Figure 2 (2) is a schematic view of the splicing single component of Figure 2 (1);
  • FIG. 3 is a top plan view of a growth zone graphite crucible assembly using vertical direct-fitting splicing
  • Example 4 is a crystal prepared in Examples and Comparative Examples: (top) crack-free crystals prepared in Example 1; (middle) crack-free crystals prepared in Example 2; (bottom) cracked crystals prepared in Comparative Example 1.
  • FIG. 1 is a schematic view showing the structure of a growth chamber in which a SiC crystal is grown by a physical vapor transport (PVT) method.
  • the growth chamber structure is mainly composed of a silicon carbide raw material region, a crystal growth region, and a seed crystal region.
  • the growth chamber structure includes: a raw material zone assembly 2, which is a high temperature zone for holding a crystal growth raw material (for example, SiC raw material) 4; a growth zone chamber ⁇ component 1 located above the raw material zone ⁇ assembly 2 And a cap assembly 3 that is placed over the material zone ⁇ assembly 2, and a seed crystal 5 is bonded to the side of the cap assembly 3 facing the crystal growth material.
  • a raw material zone assembly 2 which is a high temperature zone for holding a crystal growth raw material (for example, SiC raw material) 4
  • a growth zone chamber ⁇ component 1 located above the raw material zone ⁇ assembly 2
  • a cap assembly 3 that is placed over the material zone ⁇ assembly 2
  • a seed crystal 5 is bonded
  • the crystal growth raw material 4 is evaporated under high temperature conditions, and is naturally transported to the surface of the seed crystal 5 having a relatively low temperature, driven by a temperature gradient in the crucible, and finally formed in the growth chamber chamber ⁇ component 1 due to supersaturated condensation crystallization.
  • Crystal 6. In an example of growing a silicon carbide crystal by a PVT method, the vacuum of the growth chamber is evacuated to 1.0 ⁇ 10 ⁇ 2 Pa or less, and an inert gas (for example, argon gas or the like) is charged to a growth pressure of 6 to 40 Torr to a growth temperature of 2000 to ⁇ . At 2400 ° C, a silicon carbide single crystal is deposited on the surface of the seed crystal. After the growth is completed, the silicon carbide crystals are taken out by cooling.
  • an inert gas for example, argon gas or the like
  • the growth zone chamber ⁇ assembly 1 (also referred to as "crystal growth ⁇ ") is a ruthenium that is in contact with the prepared crystal side.
  • the growth zone chamber raft assembly 1 has a looped non-closed splicing structure.
  • Ring type non-closed splicing structure means that a plurality of splicing assemblies are spliced in the circumferential direction to form a cylindrical structure.
  • the ring-type non-closed splicing structure is movable when subjected to the force from the crystal, so that the crystal is not tightly held, so that the thermal stress formed in the crystal during the crystal growth process is effectively released, and the cracking rate of the crystal is lowered and the crystal is increased. The yield of the crystal.
  • the "growth chamber chamber assembly 1 has a looped non-closed splice structure" is understood to mean that the growth chamber chamber assembly 1 is at least partially a looped non-closed splice structure. More specifically, at least the direct contact of the growth zone chamber ⁇ assembly 1 with the side (typically the inner wall) of the prepared crystal is a ring-type non-closed splicing structure.
  • the growth zone chamber ⁇ assembly 1 is still formed as a whole to prevent the gas phase component from overflowing from the side.
  • the growth zone chamber jaw assembly 1 can be a longitudinal split type, an inner jacket type or a combination of a transverse type and a longitudinal type.
  • the growth zone chamber ⁇ assembly 1 may be of a longitudinal type splicing type (shown in Figure 3), a transverse type and a longitudinal type splicing type (shown in Figure 2 (1)) or both.
  • the growth zone chamber ⁇ assembly 1 may be a single layer structure or a multilayer (2 layers and above) nested structure.
  • the growth chamber chamber ⁇ assembly 1 When the growth chamber chamber ⁇ assembly 1 is a single-layer structure, the growth chamber chamber ⁇ assembly 1 is integrally formed into a ring-type non-closed splicing structure, and each splicing assembly adopts a concave-convex mutual card splicing (for example, as shown in FIG. 1). This prevents the gas phase component from escaping from the side.
  • the innermost layer is a ring-type non-closed splicing structure.
  • the splicing components of the innermost ring-type non-closed splicing structure may be combined by direct-fitting splicing, concave-convex mutual-card splicing, or two splicing methods.
  • Direct-fitting stitching means that the mating surface is formed into a flat surface (for example, as shown in FIG. 3).
  • the layers other than the innermost layer may be a ring-shaped non-closed splicing structure or a ring-shaped closed structure.
  • each splicing component may be combined by direct-fitting splicing, concave-convex mutual-card splicing, or two splicing methods.
  • the splicing of other layers is included in the direct splicing, it should be ensured that the growth chamber chamber ⁇ assembly 1 as a whole can still prevent the gas phase component from overflowing from the side.
  • the bonding faces between the splicing components of the other layers and the splicing components of the innermost layer may not be continuous in the radial direction.
  • the number of splicing components may be two or more, preferably 3 to 8.
  • the annular non-closed crucible assembly directly contacting the prepared crystal side surface may have a thickness of 1 mm or more.
  • the gap or tolerance of the splicing portion of each splicing assembly of the growth zone chamber ⁇ assembly 1 can be controlled within 2 mm, and is preferably 0.1 to 1 mm in order to prevent the gas phase component from overflowing from the assembly splicing seam.
  • the upper and lower ends of the growth chamber chamber assembly 1 may have an open structure.
  • the growth zone chamber ⁇ assembly 1 may have a top and bottom splicing structure and the like in addition to the ring type non-closed splicing structure.
  • the material of the growth zone chamber ⁇ assembly 1 may be graphite, and may also be silicon carbide germanium, titanium carbide tantalum or the like.
  • the material of the raw material region 2 ⁇ component 2 and the lid assembly may be graphite, and may also be silicon carbide germanium, titanium carbide tantalum or the like.
  • the outside of the growth chamber structure may also be surrounded by a heat insulating felt, such as a heat insulating carbon felt or the like.
  • the present invention Compared with the silicon carbide crystal prepared by the conventional ring-shaped closed jaw assembly, the present invention not only enables the thermal stress formed during the crystal growth process to be effectively released by adopting a ring-shaped non-closed spliced ruthenium assembly in the inner wall of the crystal growth region. It greatly reduces the cracking rate of the crystal, improves the yield of crystal growth, and at the same time realizes partial replacement of the splicing component, further reducing the preparation cost of the crystal.
  • the crystal growth enthalpy of the present invention is applied to the PVT method for growing a silicon carbide crystal as an example, but it should be understood that the crystal growth enthalpy of the present invention is not limited thereto, and is also applicable to growth of other crystals as long as the crystal needs to be released when growing the crystal.
  • the crystal thermal stress can be.
  • the graphite cap with the seed crystal adhered to the upper part, and the graphite crucible containing the silicon carbide raw material in the bottom material zone are placed in the thermal insulation carbon felt, wherein the growth chamber chamber graphite crucible assembly adopts the inner jacket 2 layer crucible structure.
  • the component in contact with the growing crystal in the chamber layer adopts a vertical direct-fitting splicing, as shown in FIG. 3, which is composed of 4 small pieces and spliced into a ring-shaped non-closed ⁇ inner sleeve, and the outer layer is closed by a conventional annular side ⁇ The structure is placed in the crystal growth furnace chamber.
  • the vacuum is pumped to 1.0 ⁇ 10 -2 Pa or less, heated by argon gas, grown to a growth pressure of 10 Torr, and grown at a temperature of 2080 ° C. After 120 h of growth, the program is cooled to room temperature and opened to obtain crack-free silicon carbide. Single crystal (Fig. 4 (top)), its side is smooth and ablated, indicating that the thermal stress in the crystal is effectively released.
  • the non-destructive splicing assembly can be reused, further reducing the cost of crystal preparation.
  • the graphite cap with the seed crystal adhered to the upper part and the graphite crucible containing the silicon carbide raw material in the bottom material area are placed in the heat insulating carbon felt, wherein the growth chamber chamber graphite crucible assembly adopts a single layer crucible structure.
  • the growth chamber chamber graphite crucible assembly adopts a single layer crucible structure.
  • a transverse type of concave-convex mutual card splicing as shown in Figure 2 (1)
  • a small number of small pieces are spliced into a ring-shaped non-closed ⁇ assembly. It is then placed in the crystal growth furnace chamber.
  • the vacuum is pumped to 1.0 ⁇ 10 -2 Pa or less, heated by argon gas, grown to a growth pressure of 20 Torr, and grown at a temperature of 2150 ° C. After 100 h of growth, the program is cooled to room temperature and opened to obtain crack-free silicon carbide. Single crystal (Fig. 4 (middle)), its side is smooth and ablated, indicating that the thermal stress in the crystal is effectively released.
  • the non-destructive splicing widget can be reused, which further reduces the cost of crystal preparation.
  • Embodiment 1 The only difference from Embodiment 1 is that the growth zone chamber graphite crucible assembly is combined with a ring-shaped closed crucible assembly, that is, a non-splicing manner. Specifically, as shown in FIG. 1 , first, a graphite cap with a seed crystal adhered to the upper portion, and a graphite crucible containing a silicon carbide raw material in a bottom material region are placed in the insulating carbon felt, wherein the growth chamber chamber graphite crucible assembly adopts a ring closure. The ⁇ component is combined in a non-splicing manner and placed in a crystal growth furnace chamber.
  • the vacuum was pumped to 1.0 ⁇ 10 -2 Pa or less, heated by argon gas, grown to a growth pressure of 10 Torr, and grown at a temperature of 2080 ° C. After 120 h of growth, the program was cooled to room temperature and opened to contact the crystal. The crucible assembly tightly clamps the silicon carbide crystal. After sawing the crucible assembly, cracks appear on the surface of the crystal (Fig. 4 (bottom)). The rough side indicates that the thermal stress in the crystal is not completely released.

Landscapes

  • 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

涉及晶体生长用坩埚以及释放碳化硅晶体热应力的方法，所述坩埚是与制备的晶体侧面相接触的坩埚，所述坩埚具有环式非闭合拼接结构。该晶体生长用坩埚具有环式非闭合拼接结构，因此可以避免紧箍晶体，从而使晶体生长过程中在晶体内聚集形成的热应力得到有效释放，降低晶体的开裂率，提高晶体的成品率。

Description

晶体生长用坩埚以及释放碳化硅晶体热应力的方法 技术领域
本发明属于晶体生长领域和碳化硅材料领域，具体涉及一种晶体生长用坩埚以及一种在物理气相传输法生长碳化硅晶体过程中释放晶体内热应力的方法。
 背景技术
碳化硅（SiC）单晶材料具有宽禁带、高热导率、高电子饱和迁移速率、高击穿电场等性质，与第一代半导体材料和第二代半导体材料相比有着明显的优越性，被认为是制造光电子器件、高频大功率器件、电力电子器件理想的半导体材料，在白光照明、光存储、屏幕显示、航天航空、高温辐射环境、石油勘探、自动化、雷达与通信、汽车电子化等方面有广泛应用。
目前生长SiC晶体最有效的方法是物理气相传输（PVT）法，整个生长室主要由碳化硅原料区、晶体生长区和籽晶区三部分组成。PVT法制备碳化硅晶体最主要问题是容易形成缺陷和应力聚集区，尤其随着SiC晶体的尺寸需求达到4英寸及以上，微小的热应力就容易导致晶体开裂，极大影响晶体的成品率。因此，如何降低碳化硅晶体生长过程中形成的热应力对于制备出碳化硅晶体成品是至关重要的。国内外专利（US 20160083865 A1、CN 200910243520.4、CN 201510994404.1）通常采用随炉退火或者取出晶体后二次热退火的方式来降低晶体中的热应力，但晶体生长过程中生长区的闭合圆环式石墨坩埚仍然与晶体侧面紧密接触，其热膨胀系数差异在晶体生长过程中所形成的内热应力将无法得到有效释放，导致晶体出炉就容易开裂。PVT法生长碳化硅晶体所采用的石墨坩埚都是三高式石墨，价格比较昂贵，在专利（CN201521114037.3、CN 201706886 U、CN 202688507 U）中都提到采用上下拼接式的结构的石墨坩埚，就是为了实现部分结构组件重复使用从而降低成本，但上述坩埚生长区的石墨组件仍是闭合圆环式结构，在晶体生长过程中碳化硅晶体内聚集的热应力将无法充分有效释放。
 技术问题
针对上述PVT法SiC晶体生长过程中生长区的坩埚内壁箍紧晶体导致聚集的热应力无法有效释放，影响晶体成品率的问题。本发明首次设计一种环式非闭合结构的坩埚组件，应用于碳化硅晶体生长区与晶体侧面直接接触的部位，不仅确保晶体生长时聚集在碳化硅晶体内的热应力得到有效释放，提高晶体成品率，同时实现坩埚组件更少部分更换进一步降低晶体的制备成本。
 技术解决方案
一方面，本发明提供一种晶体生长用坩埚，所述坩埚是与制备的晶体侧面相接触的坩埚，所述坩埚具有环式非闭合拼接结构。
该晶体生长用坩埚具有环式非闭合拼接结构，因此可以避免紧箍晶体，从而使晶体生长过程中在晶体内聚集形成的热应力得到有效释放，降低晶体的开裂率，提高晶体的成品率。
较佳地，所述坩埚为石墨坩埚、碳化硅坩埚、或碳化钛坩埚。
较佳地，所述坩埚中与制备的晶体侧面直接相接触的拼接组件的厚度为1mm以上，优选为1～10mm。
较佳地，所述坩埚为单层结构，且各拼接组件采用凹凸互卡式拼接。
较佳地，所述坩埚为多层嵌套结构，其中至少最内层为环式非闭合拼接结构，所述环式非闭合拼接结构为直接贴合式拼接和/或凹凸互卡式拼接。
较佳地，拼接处的缝隙或公差控制在3mm以内，优选为0.1～1mm。
另一方面，本发明提供一种碳化硅晶体生长过程中释放晶体热应力的方法，采用物理气相传输方法在籽晶表面沉积生长碳化硅单晶，其中在生长区腔室内与制备的晶体侧面相接触的坩埚采用上述任意一种晶体生长用坩埚。
本发明中，采用环式非闭合坩埚结构，可以避免紧箍晶体，从而使晶体生长过程中在碳化硅晶体内聚集形成的热应力得到有效释放，降低晶体的开裂率，提高碳化硅晶体的成品率。
较佳地，所述物理气相传输方法中，将晶体生长炉的真空度抽至1.0×10 -2Pa以下，充惰性气氛至生长压强6～40Torr，生长温度为2000～2400℃。
有益效果
根据本发明，可以使晶体生长过程中在晶体内聚集形成的热应力得到有效释放，降低晶体的开裂率，提高晶体的成品率。
 附图说明
图1 是物理气相传输（PVT）法生长SiC晶体的生长室结构示意图；附图中，各标号所代表的部件列表如下，1、生长区腔室坩埚组件，虚线表示可以为多层或单层结构；2、原料区坩埚组件；3、籽晶区的粘接籽晶的盖组件；4、SiC原料；5、SiC籽晶；6、生长的晶体；
图2(1)是PVT法制备SiC晶体的生长腔室内壁坩埚组件的环形非闭合横竖拼接结构示意图；
图2(2)是图2(1)的拼接单一部件示意图；
图3 是采用竖直型直接贴合式拼接的生长区石墨坩埚组件的俯视示意图；
图4是实施例和对比例制备的晶体：（上）实施例1制备的无裂纹晶体；（中）实施例2制备的无裂纹晶体；（下）对比例1制备的有裂纹晶体。
 本发明的最佳实施方式
以下通过下述实施方式和附图进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
图1 示出物理气相传输（PVT）法生长SiC晶体的生长室结构示意图。如图1所示，该生长室结构主要由碳化硅原料区、晶体生长区和籽晶区三部分组成。具体而言，该生长室结构包括：原料区坩埚组件2，其为高温区，用于盛放晶体生长原料（例如SiC原料）4；位于原料区坩埚组件2上方的生长区腔室坩埚组件1；以及盖于原料区坩埚组件2上的盖组件3，在盖组件3的朝向晶体生长原料一侧粘结有籽晶5。在高温条件下晶体生长原料4蒸发，在坩埚内的温度梯度驱动下，自然传输到温度相对较低的籽晶5表面，并由于超饱和凝结结晶，最终在生长区腔室坩埚组件1内形成晶体6。在采用PVT法生长碳化硅晶体的一个示例中，将生长室的真空度抽至1.0×10 -2Pa以下，充惰性气体（例如氩气等）至生长压强6～40Torr，至生长温度2000～2400℃，在籽晶表面沉积生长碳化硅单晶。生长完成后降温取出碳化硅晶体。
生长区腔室坩埚组件1（亦称“晶体生长用坩埚”）是与制备的晶体侧面相接触的坩埚。本发明一实施方式中，生长区腔室坩埚组件1具有环式非闭合拼接结构。
“环式非闭合拼接结构”是指由多个拼接组件在周向上拼接而形成筒状结构。该环式非闭合拼接结构在受到来自晶体的作用力时可活动，因而不会紧箍晶体，从而使晶体生长过程中在晶体内聚集形成的热应力得到有效释放，降低晶体的开裂率，提高晶体的成品率。
另外，“生长区腔室坩埚组件1具有环式非闭合拼接结构”应理解为生长区腔室坩埚组件1至少部分为环式非闭合拼接结构。更具体而言，生长区腔室坩埚组件1 的至少直接接触所制备的晶体的侧面（一般为内壁）为环式非闭合拼接结构。
同时，还应理解，生长区腔室坩埚组件1整体上仍形成为能够防止气相组分从侧面溢出的结构。
生长区腔室坩埚组件1可以是纵向型分体式、内外套式或横向型与纵向型组合式。
生长区腔室坩埚组件1可以采用纵向型拼接式（图3所示）、横向型与纵向型拼接式（图2(1)所示）或两者皆有。
生长区腔室坩埚组件1可为单层结构，也可为多层（2层及以上）嵌套结构。
生长区腔室坩埚组件1为单层结构时，生长区腔室坩埚组件1整体形成为环式非闭合拼接结构，各拼接组件采用凹凸互卡式拼接（例如如图1所示）。这样可以防止气相组分从侧面溢出。
生长区腔室坩埚组件1为多层嵌套结构时，至少最内层为环式非闭合拼接结构。最内层的环式非闭合拼接结构的各拼接组件可采用直接贴合式拼接、凹凸互卡式拼接、或两种拼接方式相组合。直接贴合式拼接是指贴合面形成为平面（例如如图3所示）。
除最内层以外的其它层可以是环式非闭合拼接结构，也可以是环式闭合结构。当其它层也是环式非闭合拼接结构时，各拼接组件可采用直接贴合式拼接、凹凸互卡式拼接、或两种拼接方式相组合。在其它层的拼接方式中含有直接贴合式拼接时，应保证生长区腔室坩埚组件1整体上仍能够防止气相组分从侧面溢出。例如，可使其它层的各拼接组件间的贴合面与最内层的各拼接组件间的贴合面不在径向上连续。
环式非闭合拼接结构中，拼接组件的个数可为两个以上，优选为3～8个。
与制备的晶体侧面直接相接触的环式非闭合坩埚组件，厚度可为1mm以上，为了避免石墨坩埚被气相组分腐蚀破坏同时尽量降低石墨坩埚对晶体侧面形成过大的挤压应力，更优选为1～10 mm。
生长区腔室坩埚组件1的各拼接组件的拼接处的缝隙或公差可控制在2mm以内，为了避免气相组分从组件拼接缝处溢出，优选为0.1～1mm。
生长区腔室坩埚组件1的上下端可为开口结构。生长区腔室坩埚组件1除具有环式非闭合拼接结构之外，还可以具有上下拼接结构等。
生长区腔室坩埚组件1的材质可为石墨，还可为碳化硅坩埚，碳化钛坩埚等。
原料区坩埚组件2、盖组件的材质可为石墨，还可为碳化硅坩埚，碳化钛坩埚等。
上述生长室结构的外部还可包围有保温毡，例如保温碳毡等。
与传统环式闭合坩埚组件箍紧制备的碳化硅晶体相比，本发明通过在晶体生长区腔室内壁采用环式非闭合拼接的坩埚组件，不仅使晶体生长过程中形成的热应力得到有效释放，大幅降低晶体的开裂率，提高晶体生长的成品率，同时实现拼接组件的部分更换，进一步降低晶体的制备成本。
上述以本发明的晶体生长用坩埚应用于PVT法生长碳化硅晶体为例，但应理解，本发明的晶体生长用坩埚不限于此，还可适用于生长其它晶体，只要生长该晶体时需要释放晶体热应力即可。
 本发明的实施方式
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。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例 1
如图1所示，首先将上部粘有籽晶的石墨盖，底部料区装有碳化硅原料的石墨坩埚置于保温碳毡中，其中生长区腔室石墨坩埚组件采用内外套2层坩埚结构，腔室内层与生长的晶体相接触的组件采用竖直型直接贴合式拼接，如图3所示由4小件拼接组合成环形非闭合坩埚内套，外层采用传统的环形侧面闭合坩埚结构，再放入晶体生长炉室中。真空度抽至1.0×10 -2 Pa以下，充氩气升温，至生长压强10Torr，生长温度2080℃的条件进行晶体生长，生长120h后，程序降温冷却至室温，开炉获得无裂纹的碳化硅单晶（图4（上）），其侧面光滑有烧蚀感，表明晶体内热应力得到有效释放。另外，无破坏的拼接组件可以重复使用，进一步降低了晶体的制备成本。
实施例 2
如图1所示，首先将上部粘有籽晶的石墨盖，底部料区装有碳化硅原料的石墨坩埚置于保温碳毡中，其中生长区腔室石墨坩埚组件采用单层坩埚结构，为防止气相组分从侧面溢出坩埚，须采用横向型凹凸互卡式拼接，如图2(1)所示由若干小件（如图2(2)所示）拼接组合成环形非闭合坩埚组件，再放入晶体生长炉室中。真空度抽至1.0×10 -2 Pa以下，充氩气升温，至生长压强20Torr，生长温度2150℃的条件进行晶体生长，生长100h后，程序降温冷却至室温，开炉获得无裂纹的碳化硅单晶（图4（中）），其侧面光滑有烧蚀感，表明晶体内热应力得到有效释放。另外，无破坏的拼接小组件可以重复使用，这进一步降低了晶体的制备成本。
对比例 1
与实施例1的不同之处仅在于采用生长区腔室石墨坩埚组件采用环形闭合坩埚组件即非拼接方式组合。具体而言，如图1所示，首先将上部粘有籽晶的石墨盖，底部料区装有碳化硅原料的石墨坩埚置于保温碳毡中，其中生长区腔室石墨坩埚组件采用环形闭合坩埚组件即非拼接方式组合，再放入晶体生长炉室中。真空度抽至1.0×10 -2 Pa以下，充氩气升温，至生长压强10Torr，生长温度2080℃的条件进行晶体生长，生长120h后，程序降温冷却至室温，开炉发现与晶体相接触的坩埚组件紧密箍紧碳化硅晶体，锯开坩埚组件后，晶体表面出现裂纹（图4（下）），其侧面比较粗糙表明晶体内热应力未完全释放。
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 (8)

  1. 一种晶体生长用坩埚，其特征在于，所述坩埚是与制备的晶体侧面相接触的坩埚，所述坩埚具有环式非闭合拼接结构。
  2. 根据权利要求1所述的晶体生长用坩埚，其特征在于，所述坩埚为石墨坩埚、碳化硅坩埚、或碳化钛坩埚。
  3. 根据权利要求1或2所述的晶体生长用坩埚，其特征在于，所述坩埚中与制备的晶体侧面直接相接触的拼接组件的厚度为1mm以上，优选为1～10mm。
  4. 根据权利要求1至3中任一项所述的晶体生长用坩埚，其特征在于，所述坩埚为单层结构，且各拼接组件采用凹凸互卡式拼接。
  5. 根据权利要求1至3中任一项所述的晶体生长用坩埚，其特征在于，所述坩埚为多层嵌套结构，其中至少最内层为环式非闭合拼接结构，所述环式非闭合拼接结构为直接贴合式拼接和/或凹凸互卡式拼接。
  6. 根据权利要求1至5中任一项所述的晶体生长用坩埚，其特征在于，拼接处的缝隙或公差控制在3mm以内，优选为0.1～1mm。
  7. 一种碳化硅晶体生长过程中释放晶体热应力的方法，其特征在于，采用物理气相传输方法在籽晶表面沉积生长碳化硅单晶，其中在生长区腔室内与制备的晶体侧面相接触的坩埚采用权利要求1至6中任一项所述的晶体生长用坩埚。
  8. 根据权利要求8所述的方法，其特征在于，所述物理气相传输方法中，将晶体生长炉的真空度抽至1.0×10 -2Pa以下，充惰性气氛至生长压强6～40Torr，生长温度为2000～2400℃。
PCT/CN2019/071008 2018-01-24 2019-01-09 晶体生长用坩埚以及释放碳化硅晶体热应力的方法 WO2019144804A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/962,712 US11384451B2 (en) 2018-01-24 2019-01-09 Crucible for crystal growth as well as method for releasing thermal stress in silicon carbide crystal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810069412.9A CN108149315B (zh) 2018-01-24 2018-01-24 晶体生长用坩埚以及释放碳化硅晶体热应力的方法
CN201810069412.9 2018-01-24

Publications (1)

Publication Number Publication Date
WO2019144804A1 true WO2019144804A1 (zh) 2019-08-01

Family

ID=62459016

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/071008 WO2019144804A1 (zh) 2018-01-24 2019-01-09 晶体生长用坩埚以及释放碳化硅晶体热应力的方法

Country Status (3)

Country Link
US (1) US11384451B2 (zh)
CN (1) CN108149315B (zh)
WO (1) WO2019144804A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT524250A1 (de) * 2020-09-28 2022-04-15 Ebner Ind Ofenbau Vorrichtung zum Züchten von Einkristallen, insbesondere von Einkristallen aus Siliziumcarbid

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108149315B (zh) * 2018-01-24 2020-10-23 中国科学院上海硅酸盐研究所 晶体生长用坩埚以及释放碳化硅晶体热应力的方法
CN108374197A (zh) * 2018-02-26 2018-08-07 西安理工大学 一种增加碳化硅晶体生长长度的石墨坩埚
CN115467016B (zh) * 2021-06-11 2023-11-07 中电化合物半导体有限公司 可释放碳化硅单晶生长应力的生长组件、设备及方法
CN114517333A (zh) * 2021-11-25 2022-05-20 安徽微芯长江半导体材料有限公司 一种用于SiC晶体生长的多用途石墨坩埚
CN114561694A (zh) * 2022-02-25 2022-05-31 浙江大学 一种制备低基平面位错碳化硅单晶的装置与方法
CN115537927B (zh) * 2022-12-01 2023-03-10 浙江晶越半导体有限公司 一种制备低基平面位错的碳化硅单晶晶锭生长系统及方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010101200A1 (ja) * 2009-03-06 2010-09-10 新日本製鐵株式会社 炭化珪素単結晶製造用坩堝、並びに炭化珪素単結晶の製造装置及び製造方法
CN103205803A (zh) * 2013-04-24 2013-07-17 哈尔滨奥瑞德光电技术股份有限公司 在蓝宝石单晶炉中应用的氧化锆保温结构
CN103215635A (zh) * 2013-04-27 2013-07-24 哈尔滨奥瑞德光电技术股份有限公司 一种蓝宝石单晶炉保温结构
CN104073878A (zh) * 2014-07-22 2014-10-01 南京理工宇龙新材料科技有限公司 一种蓝宝石晶体生长炉侧屏及其制备方法
CN204039545U (zh) * 2014-07-22 2014-12-24 南京理工宇龙新材料科技有限公司 一种蓝宝石晶体泡生法生长炉多温区保温侧屏
CN205774932U (zh) * 2016-06-02 2016-12-07 姜守振 一种应用在碳化硅单晶炉中的氧化锆保温结构
CN108149315A (zh) * 2018-01-24 2018-06-12 中国科学院上海硅酸盐研究所 晶体生长用坩埚以及释放碳化硅晶体热应力的方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4403955A (en) * 1982-02-22 1983-09-13 General Signal Corporation Receptacle for support of a melt containing crucible
JP3371120B2 (ja) * 1992-10-08 2003-01-27 アネルバ株式会社 電子銃の蒸着ルツボ
JP3508877B2 (ja) * 1994-08-09 2004-03-22 住友チタニウム株式会社 シリコン溶解装置
FR2804132B1 (fr) * 2000-01-20 2002-06-07 Lorraine Carbone Porte-creuset pour le tirage de monocristaux
WO2007038710A2 (en) * 2005-09-28 2007-04-05 Ii-Vi Incorporated Intra-cavity gettering of nitrogen in sic crystal growth
CN101495680A (zh) * 2006-06-23 2009-07-29 Rec斯坎沃佛股份有限公司 可重复使用的坩埚及其制造方法
JP2008222455A (ja) * 2007-03-08 2008-09-25 Ibiden Co Ltd シリコン単結晶引上用ルツボ
DE102009015236B4 (de) * 2009-04-01 2015-03-05 H.C. Starck Gmbh Tiegel und seine Verwendung
CN101984153B (zh) 2009-12-24 2013-03-20 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
CN201706886U (zh) 2010-03-04 2011-01-12 佛山通宝精密合金股份有限公司 一种用于感应加热的拼装式石墨坩埚
CN202688507U (zh) 2012-01-05 2013-01-23 上海东洋炭素有限公司 一种上下拼接的多晶石墨坩埚
CN203049085U (zh) * 2012-12-20 2013-07-10 海润光伏科技股份有限公司 直拉法生长单晶热场的石墨坩埚
US9322110B2 (en) * 2013-02-21 2016-04-26 Ii-Vi Incorporated Vanadium doped SiC single crystals and method thereof
CN203550555U (zh) * 2013-11-21 2014-04-16 郑州磐石新材料科技有限公司 拼砌组合式坩埚
US20160083865A1 (en) 2014-09-24 2016-03-24 Sumitomo Electric Industries, Ltd. Method for manufacturing silicon carbide single crystal
FR3029214B1 (fr) * 2014-12-02 2019-06-14 Commissariat A L'energie Atomique Et Aux Energies Alternatives Creuset reutilisable pour la fabrication de materiau cristallin.
CN105463574A (zh) 2015-12-28 2016-04-06 北京世纪金光半导体有限公司 一种防止碳化硅晶锭碎裂的方法
CN205241854U (zh) 2015-12-29 2016-05-18 中国科学院上海硅酸盐研究所 一种分体式碳化硅晶体生长用坩埚

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010101200A1 (ja) * 2009-03-06 2010-09-10 新日本製鐵株式会社 炭化珪素単結晶製造用坩堝、並びに炭化珪素単結晶の製造装置及び製造方法
CN103205803A (zh) * 2013-04-24 2013-07-17 哈尔滨奥瑞德光电技术股份有限公司 在蓝宝石单晶炉中应用的氧化锆保温结构
CN103215635A (zh) * 2013-04-27 2013-07-24 哈尔滨奥瑞德光电技术股份有限公司 一种蓝宝石单晶炉保温结构
CN104073878A (zh) * 2014-07-22 2014-10-01 南京理工宇龙新材料科技有限公司 一种蓝宝石晶体生长炉侧屏及其制备方法
CN204039545U (zh) * 2014-07-22 2014-12-24 南京理工宇龙新材料科技有限公司 一种蓝宝石晶体泡生法生长炉多温区保温侧屏
CN205774932U (zh) * 2016-06-02 2016-12-07 姜守振 一种应用在碳化硅单晶炉中的氧化锆保温结构
CN108149315A (zh) * 2018-01-24 2018-06-12 中国科学院上海硅酸盐研究所 晶体生长用坩埚以及释放碳化硅晶体热应力的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT524250A1 (de) * 2020-09-28 2022-04-15 Ebner Ind Ofenbau Vorrichtung zum Züchten von Einkristallen, insbesondere von Einkristallen aus Siliziumcarbid
AT524250B1 (de) * 2020-09-28 2022-07-15 Ebner Ind Ofenbau Vorrichtung zum Züchten von Einkristallen, insbesondere von Einkristallen aus Siliziumcarbid

Also Published As

Publication number Publication date
US20200354856A1 (en) 2020-11-12
CN108149315A (zh) 2018-06-12
US11384451B2 (en) 2022-07-12
CN108149315B (zh) 2020-10-23

Similar Documents

Publication Publication Date Title
WO2019144804A1 (zh) 晶体生长用坩埚以及释放碳化硅晶体热应力的方法
JP4622859B2 (ja) 半導体基板用熱処理治具および半導体基板の熱処理方法
KR102299654B1 (ko) 단결정 성장 퍼니스의 반사 스크린 및 단결정 성장 퍼니스
WO2019128524A1 (zh) 一种消除晶圆翘曲的方法及复合衬底
JP2012099848A (ja) 基板製造方法及び該方法によって得られた基板
JP4985625B2 (ja) 炭化珪素単結晶の製造方法
WO2020088233A1 (zh) 无需粘结籽晶的碳化硅单晶生长装置
CN108130593A (zh) 一种晶体生长炉用保温装置
CN110886014A (zh) 晶体生长装置
JPH1087394A (ja) 気相成長装置用サセプタ
JP5843725B2 (ja) 単結晶の製造方法
KR101619610B1 (ko) 대구경 단결정 성장장치 및 성장방법
US20140158042A1 (en) Apparatus for fabricating ingot
JP2012197190A (ja) 自立基板の製造方法、ＡｌＮ自立基板及びＩＩＩ族窒化物半導体デバイス
JP2000226299A (ja) 単結晶炭化珪素薄膜の製造方法および単結晶炭化珪素薄膜
KR20150076271A (ko) 물리적 체결을 이용한 대구경 단결정 성장장치 및 방법
JP6861557B2 (ja) 炭化珪素単結晶インゴットの製造装置及び炭化珪素単結晶インゴットの製造方法
US9171737B2 (en) Thermal oxide film formation method for silicon single crystal wafer
JP2016200254A (ja) 断熱構造体
JP2005132703A (ja) 炭化珪素基板の製造方法および炭化珪素基板
JP5545567B2 (ja) 単結晶ダイヤモンド成長用の基材及び単結晶ダイヤモンドの製造方法
JPH09263498A (ja) 炭化珪素単結晶の製造方法
JP6998634B1 (ja) ダイヤモンド形成用構造体、およびダイヤモンド形成用構造体の製造方法
WO2019022053A1 (ja) 単結晶の製造方法
JP2013256440A (ja) 窒化ガリウム基板の製造方法及び該製造方法により製造された窒化ガリウム基板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19743933

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19743933

Country of ref document: EP

Kind code of ref document: A1