WO2015067029A1 - 一种制备氮化硼单晶的装置及方法 - Google Patents

一种制备氮化硼单晶的装置及方法 Download PDF

Info

Publication number
WO2015067029A1
WO2015067029A1 PCT/CN2014/078078 CN2014078078W WO2015067029A1 WO 2015067029 A1 WO2015067029 A1 WO 2015067029A1 CN 2014078078 W CN2014078078 W CN 2014078078W WO 2015067029 A1 WO2015067029 A1 WO 2015067029A1
Authority
WO
WIPO (PCT)
Prior art keywords
boron nitride
single crystal
substrate
nitride single
reaction
Prior art date
Application number
PCT/CN2014/078078
Other languages
English (en)
French (fr)
Inventor
黄�俊
徐科
王建峰
任国强
Original Assignee
中国科学院苏州纳米技术与纳米仿生研究所
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 中国科学院苏州纳米技术与纳米仿生研究所 filed Critical 中国科学院苏州纳米技术与纳米仿生研究所
Publication of WO2015067029A1 publication Critical patent/WO2015067029A1/zh

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B25/00Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02Epitaxial-layer growth
    • C30B25/08Reaction chambers; Selection of materials therefor
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B25/00Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02Epitaxial-layer growth
    • C30B25/10Heating of the reaction chamber or the substrate
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B25/00Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02Epitaxial-layer growth
    • C30B25/16Controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B25/00Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02Epitaxial-layer growth
    • C30B25/18Epitaxial-layer growth characterised by the substrate
    • C30B25/183Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/40AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi

Definitions

  • the present invention relates to the field of semiconductor manufacturing technology, and in particular, to an apparatus and method for preparing a boron nitride single crystal. Background technique
  • h-BN hexagonal boron nitride
  • h-BN single crystals are mainly prepared by high temperature and high pressure liquid phase reaction, or by sintering Ni and h-BN powders in a crucible to a temperature of 1350-1600 ° C for sintering.
  • the h-BN single crystals prepared by these methods have a size of a few hundred micrometers at most, and the shape is very irregular, which is far from meeting the needs of related research and industrial development.
  • Device applications that truly implement h-BN must be able to produce high quality thin films using conventional thin film fabrication methods such as gas phase epitaxy. Summary of the invention
  • the technical problem to be solved by the present invention is to provide an apparatus and a method for preparing a boron nitride single crystal, which can grow a large-sized boron nitride single crystal on a large substrate by vapor phase epitaxy, and has a fast preparation speed and a growth apparatus. Simple, easy to use materials, low cost, and can be used for mass production.
  • the present invention provides an apparatus for preparing a boron nitride single crystal, comprising a reaction portion, a heating portion, and a support portion, wherein the substrate to be grown is placed in the reaction portion.
  • the heating portion surrounds the outer wall of the reaction portion, the reaction portion includes an inner wall made of polycrystalline crystal of corundum or boron nitride, and the heating portion is electrically coupled to induce induction at the support portion. Inductive current is applied to heat the substrate.
  • the outer wall of the reaction portion is a quartz tube
  • the heating portion is a coil wound around a position corresponding to the outer wall of the reaction portion and the support portion.
  • a method for preparing a boron nitride single crystal using the above apparatus comprising the following steps:
  • reaction gas is boron trichloride and ammonia gas.
  • step (2) further comprising: growing a buffer layer on the substrate: introducing an alternating current into the heating portion, heating the substrate to a first temperature by electromagnetic induction, and reacting the reaction gas and A carrier gas is introduced into the reaction portion to grow a boron nitride buffer layer on the substrate, and in the step (3), the boron nitride single crystal is grown on the buffer layer.
  • the first temperature is 900 ° C and the second temperature is 1600 ° C.
  • the second temperature is 900 to 1700 °C.
  • a step of heating the substrate to a third temperature and continuing to grow the boron nitride single crystal is further included.
  • the carrier gas is selected from one or more of hydrogen, nitrogen or argon.
  • the substrate is selected from the group consisting of silicon, sapphire, silicon carbide, and aluminum nitride.
  • the boron trichloride is prepared by reacting chlorine with boron.
  • the boron trichloride is prepared by reacting chlorine with boron.
  • the heating part passes the high-frequency alternating current, and the high-frequency alternating current generates a high-frequency changing magnetic field in the heating part, and the high-frequency changing magnetic field can induce an induced current in the supporting part. Since the support portion has a certain resistance, the presence of the induced current necessarily increases the temperature of the support portion, whereby the substrate can be heated, so that the substrate can be heated to 1600 ° C to obtain a boron nitride single crystal having a high lattice quality. .
  • a boron nitride single crystal can be grown on a large substrate, and a large-sized boron nitride single crystal can be prepared and grown at a high speed.
  • FIG. 1 is a schematic view showing the structure of an apparatus for preparing a boron nitride single crystal according to the present invention
  • FIG. 2 is a schematic view showing a method of preparing a boron nitride single crystal according to the present invention. detailed description
  • the apparatus 10 for preparing a boron nitride single crystal is a halide vapor phase epitaxy apparatus.
  • the apparatus 10 for preparing a boron nitride single crystal includes a reaction portion 1, a heating portion 2, and a support portion 3, and a substrate 4 to be grown is placed on a support portion 3 inside the reaction portion 1, and the heating portion 2 is surrounded
  • the outer wall 8 of the reaction portion 1 is a quartz tube for carrying the weight of the reactor 1 while preventing the reaction gas and the exhaust gas from leaking out.
  • the heating unit 2 is wound around a coil at a position corresponding to the quartz tube and the support portion 3, and the support portion 3 is a graphite holder.
  • the raw material used for preparing the boron nitride single crystal is boron trichloride and ammonia gas. Since the boron trichloride has a corrosive effect on quartz, the reaction portion 1 includes a corundum or nitriding. The inner wall 5 made of boron polycrystal is used to avoid corrosion of the reaction portion 1 by boron trichloride. Further, the reaction portion 1 includes an air inlet 6 and an air outlet 7, and the air inlet 6 is disposed opposite to the air outlet 7 to introduce a reaction gas into the reaction portion 1, and The exhaust gas remaining after the reaction is discharged from the reaction portion 1.
  • the heating unit 2 passes through a high frequency alternating current.
  • the high-frequency alternating current generates a magnetic field whose frequency changes at a high frequency in the heating portion 2, and a magnetic field whose high frequency changes can induce an induced current in the support portion 3. Since the support portion 3 has a certain electric resistance, the presence of an induced current inevitably raises the temperature of the support portion 3, whereby the substrate 4 can be heated.
  • the conventional gas phase epitaxy (outer wall heating) method has a growth temperature of up to 1200 ° C, and it is difficult to obtain a boron nitride single crystal of good quality.
  • the present invention utilizes electromagnetic induction to heat the substrate 4, and the substrate 4 can be heated to about 1600 ° C to obtain a high quality boron nitride single crystal.
  • the present invention also provides a method of preparing a boron nitride single crystal using the above apparatus, and Fig. 2 is a schematic view showing a method of preparing a boron nitride single crystal according to the present invention. Referring to Figure 2, the method includes the following steps:
  • Step S20 A substrate 4 is provided, and the substrate 4 is placed on the support portion 3 inside the reaction portion 1.
  • the substrate is selected from one of silicon, sapphire, silicon carbide, and aluminum nitride.
  • the inner wall of the reaction portion is made of corundum or boron nitride polycrystal to prevent corrosion of the reaction portion 1 by the subsequent reaction gas.
  • the support portion 3 is a graphite tray.
  • Step S22 introducing an alternating current into the heating unit 2, and using the electromagnetic induction to substrate 4 Heat to a second temperature.
  • the second temperature range is 900 to 1700 °C.
  • Step S23 A reaction gas and a carrier gas are introduced into the reaction portion 1 to grow a boron nitride single crystal on the substrate 4.
  • the reaction gas of the present invention is boron trichloride and ammonia gas, and boron trichloride and ammonia gas enter the reaction portion 4 from the gas inlet 6 and react to form a boron nitride single crystal and a hydrogen chloride gas, and the boron nitride A single crystal is grown on the substrate 4, and the hydrogen chloride gas is discharged as a tail gas from the gas outlet 7 to the reaction portion 1 with the carrier gas.
  • the heating unit 1 heats the substrate 4 by electromagnetic induction, and the substrate 4 can be heated to about 1600 °C to obtain a boron nitride single crystal having a high lattice quality.
  • step S23 after the reaction gas and the carrier gas are introduced into the reaction portion 1, the gas is kept for a while, and the holding time needs to be determined according to the thickness of the grown boron nitride single crystal, for example, 0.1-20 hours. .
  • the boron nitride single crystal prepared by the method for producing a boron nitride single crystal of the present invention has a size of up to 1 inch to 4 inches.
  • a buffer layer is grown on the substrate 4.
  • the specific steps are as follows: an alternating current is supplied to the heating unit 2, the substrate 4 is heated to a first temperature by electromagnetic induction, and a reaction gas and a carrier gas are introduced into the reaction portion 1 to be grown on the substrate 4. Boron nitride buffer layer.
  • the growth buffer layer is used to reconcile the lattice mismatch between the substrate 4 and the epitaxial film (i.e., boron nitride single crystal), to relieve the stress of the epitaxial film, and to make the epitaxial film grow better.
  • the boron nitride single crystal has different lattice quality, and the boron nitride single crystal formed at a high temperature has a good lattice quality but a lattice mismatch with the substrate, and the boron nitride single crystal grown at a low temperature
  • the lattice quality is not good but facilitates stress release between the substrate 4 and the epitaxial film. Therefore, the second temperature is higher than the first temperature to make the lattice quality of the boron nitride single crystal grown at the second temperature better.
  • the first temperature is different depending on the material of the substrate 4, and in the specific embodiment, the first temperature is 900 °C.
  • the gas is kept for a period of time, and the holding time needs to be determined according to the thickness of the grown boron nitride buffer layer, for example: 0-1 hour. If a buffer layer is grown on the substrate 4, the boron nitride single crystal in step S23 is grown on the buffer layer.
  • step S23 it may further comprise heating the substrate to a third temperature or more of the step temperature so that the grown boron nitride single crystal has a better lattice quality.
  • the boron trichloride may be prepared by reacting chlorine with boron or a commercially available product of boron trichloride.
  • the carrier gas is one or more of nitrogen, hydrogen or argon mixed in any ratio.
  • the boron nitride single crystal prepared by the method for producing a boron nitride single crystal of the present invention may have a size of from 1 inch to 4 inches.
  • boron nitride single crystal is prepared as follows:
  • the buffer layer is held at the first temperature for a number of times.
  • the thickness of the boron nitride buffer layer formed was 300 nm.
  • the sapphire substrate 4 is heated to a second temperature and held for a plurality of times to grow a boron nitride single crystal on the boron nitride buffer layer.
  • the second temperature is 1600 ° C
  • the thickness of the boron nitride single crystal is larger than ⁇
  • the thickness of the boron nitride single crystal is determined by the growth time.
  • Example 2 In the second embodiment, boron is used as a substrate, boron trichloride and ammonia are used as reaction gases, and nitrogen and hydrogen are used as carrier gases to grow a boron nitride single crystal.
  • the preparation method of the boron nitride single crystal is as follows:
  • the buffer layer is held at the first temperature for a number of times.
  • the thickness of the boron nitride buffer layer formed was 500 nm.
  • the silicon substrate 4 is heated to a second temperature and held for a time to grow a boron nitride single crystal on the boron nitride buffer layer.
  • the second temperature is 1200 ° C
  • the thickness of the boron nitride single crystal is about ⁇ ⁇
  • the thickness of the boron nitride single crystal is determined by the growth time.
  • the silicon substrate 4 is heated to a third temperature and held for a certain time to continue to grow the boron nitride single crystal on the boron nitride single crystal.
  • the third temperature is 1600 ° C
  • the thickness of the boron nitride single crystal grown in the present step is larger than ⁇
  • the thickness of the boron nitride single crystal is determined by the growth time.

Landscapes

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

Abstract

一种制备氮化硼单晶的设备,包括反应部(1)、加热部(2)及支撑部(3),待生长氮化硼单晶的衬底(4)放置在反应部(1)内部的支撑部(3)上,所述加热部(2)围绕所述反应部(1)的外壁(8),其特征在于,所述反应部(1)包括一由刚玉或氮化硼多晶制成的内壁(5),所述加热部(2)通有交流电,以在支撑部(3)诱导产生感应电流,对衬底(4)进行加热。制备氮化硼单晶的方法包括如下步骤(1)提供一衬底,所述衬底放置在反应部内部的支撑部上;(2)启动加热部,将衬底加热至一第二温度;(3)将反应气体及载气通入所述反应部中,以在衬底上生长氮化硼单晶;其中,所述反应气体为三氯化硼和氨气。

Description

一种制备氮化硼单晶的装置及方法 技术领域
本发明涉及半导体制造技术领域, 尤其涉及一种制备氮化硼 单晶的装置及方法。 背景技术
最近几年, 随着半导体产业的发展, 六方氮化硼 (h-BN) 单 晶的应用价值逐歩显露出来。 h-BN 单晶的应用价值体现在三个方 面: 一是用来制备紫外发光器件, 二是作为石墨烯 (gmphene) 电 子器件的衬底, 三是在材料科学前沿热点领域有重要的研究价值。 这些应用使得六方氮化硼 (h-BN) 单晶材料的制备研究日益受到 关注。
目前 h-BN 单晶主要是通过高温高压液相反应, 或者是用 Ni 和 h-BN 为粉末在坩埚中加热到 1350-1600°C进行烧结来制备。 但 是这些方法制备的 h-BN 单晶尺寸最大也就几百微米, 而且形状 很不规整, 远满足不了相关研究和产业发展的需要。 要真正实现 h-BN 的器件应用必须能够利用常规的薄膜制备手段 (如气相外 延) 实现其高质量薄膜的制备。 发明内容
本发明所要解决的技术问题是, 提供一种制备氮化硼单晶的 装置及方法, 其能够利用气相外延可以在较大衬底上生长大尺寸 氮化硼单晶、 制备速度快、 生长设备简单、 使用材料易得、 成本 较低、 可以用于大规模生产。
为了解决上述问题, 本发明提供了一种制备氮化硼单晶的装 置, 包括反应部、 加热部及支撑部, 待生长的衬底放置在反应部 内部的支撑部上, 所述加热部围绕所述反应部外壁, 所述反应部 包括一由刚玉或氮化硼多晶制成的内壁, 所述加热部通有交流电, 以在支撑部诱导产生感应电流, 对衬底进行加热。
进一歩, 所述反应部的外壁为石英管, 所述加热部为缠绕在 反应部外壁与支撑部对应位置的线圈。
一种采用上述的设备制备氮化硼单晶的方法, 包括如下歩骤:
( 1 ) 提供一衬底, 所述衬底放置在反应部内部的支撑部上;
(2 ) 在加热部中通入交流电, 利用电磁感应将衬底加热至一 ~ "温度;
( 3 ) 将反应气体及载气通入所述反应部中, 以在衬底上生长 氮化硼单晶;
其中, 所述反应气体为三氯化硼和氨气。
进一歩, 在歩骤 (2) 之前进一歩包括一在衬底上生长缓冲层 的歩骤: 在加热部中通入交流电, 利用电磁感应将衬底加热至一 第一温度, 将反应气体及载气通入所述反应部中, 以在衬底上生 长氮化硼缓冲层, 进一歩, 在歩骤 (3 ) 中, 所述氮化硼单晶生长 在缓冲层上。
进一歩, 当所述衬底为蓝宝石时, 所述第一温度为 900°C, 所 述第二温度为 1600°C。
进一歩, 所述第二温度为 900~1700°C。
进一歩, 当所述衬底为硅时, 在歩骤 (3 ) 之后, 还包括一将 衬底加热至一第三温度并继续生长氮化硼单晶的歩骤。
进一歩, 所述载气选自于氢气、 氮气或氩气中的一种或几种。 进一歩, 所述衬底选自于硅、 蓝宝石、 碳化硅及氮化铝中的 一种。
进一歩, 所述三氯化硼通过氯气与硼反应制备。
进一歩, 所述三氯化硼通过氯气与硼反应制备。 本发明的优点在于:
1、 三氯化硼和氨气作为反应气体以制备氮化硼单晶, 以氮化 硼多晶或刚玉作为反应部内壁的材料, 避免三氯化硼对反应部的 腐蚀。
2、 加热部通过高频交流电, 高频交流电在加热部内产生高频 变化的磁场, 高频变化的磁场可以在支撑部诱导产生感应电流。 由于支撑部具有一定的电阻, 所以感应电流的存在必然使支撑部 温度升高, 由此可以加热衬底, 使得可将衬底加热到 1600°C, 得 到晶格质量高的氮化硼单晶。
3、 使用气相外延技术, 可以在较大衬底上生长氮化硼单晶, 能够制备大尺寸的氮化硼单晶且生长速度快。
4、 生长设备简单, 用材料易得, 成本较低, 可以用于大规模 生产。 附图说明
图 1所示为本发明一种制备氮化硼单晶的装置的结构示意简 图;
图 2所示为本发明一种制备氮化硼单晶的方法的歩骤示意图。 具体实施方式
下面结合附图对本发明提供的一种制备氮化硼单晶的装置及 方法的具体实施方式做详细说明。
图 1所示为本发明一种制备氮化硼单晶的装置的结构示意图。 参见图 1, 在本具体实施方式中, 制备氮化硼单晶的装置 10为一 种卤化物气相外延装置。 所述一种制备氮化硼单晶的装置 10包括 反应部 1、 加热部 2及支撑部 3, 待生长的衬底 4放置在反应部 1 内部的支撑部 3上, 所述加热部 2围绕所述反应部 1的外壁 8。在 本具体实施方式中, 所述反应部 1的外壁 8为石英管, 所述石英 管用于承载反应器 1的重量, 同时防止反应气体及尾气外泄。 所 述加热部 2为缠绕在石英管与支撑部 3对应位置的线圈上, 所述 支撑部 3为石墨托。
在本发明中, 制备氮化硼单晶使用的原料使用的是三氯化硼 及氨气, 由于三氯化硼对石英有腐蚀作用, 所以, 所述反应部 1 包括一由刚玉或氮化硼多晶制成的内壁 5, 以避免三氯化硼对反应 部 1的腐蚀。进一歩,所述反应部 1包括一进气口 6及一出气口 7, 所述进气口 6与所述出气口 7相对设置, 以便将反应气体通入所 述反应部 1中, 并将反应后残余的尾气排出反应部 1。
所述加热部 2通过的是高频交流电。 高频交流电在加热部 2 内产生高频变化的磁场, 高频变化的磁场可以在支撑部 3中诱导 出感应电流。 由于支撑部 3具有一定的电阻, 所以感应电流的存 在必然使支撑部 3温度升高, 由此可以加热衬底 4。 一般传统的气 相外延 (外壁加热) 方法, 生长温度最高 1200°C, 难以获得质量 较好的氮化硼单晶。 本发明利用电磁感应来加热衬底 4, 可以将衬 底 4加热到 1600 °C左右, 从而能够得到高质量氮化硼单晶。 . 本发明还一种采用上述的设备制备氮化硼单晶的方法, 图 2 所示为本发明制备氮化硼单晶的方法的歩骤示意图。 参见图 2, 所 述方法包括如下歩骤:
歩骤 S20 : 提供一衬底 4, 所述衬底 4放置在反应部 1内部的 支撑部 3上。
所述衬底选自于硅、 蓝宝石、 碳化硅及氮化铝中的一种。 所 述反应部的内壁采用刚玉或氮化硼多晶制成, 以防止后续反应气 体对反应部 1的腐蚀, 在本具体实施方式中, 所述支撑部 3为石 墨托。
歩骤 S22 : 在加热部 2中通入交流电, 利用电磁感应将衬底 4 加热至一第二温度。 所述第二温度范围为 900~1700°C。
歩骤 S23 : 将反应气体及载气通入所述反应部 1中, 以在衬底 4上生长氮化硼单晶。
本发明所述反应气体为三氯化硼及氨气, 三氯化硼与氨气从 进气口 6进入反应部 4,并发生反应生成氮化硼单晶及氯化氢气体, 所述氮化硼单晶生长在衬底 4上, 所述氯化氢气体作为尾气随载 气从出气口 7排出反应部 1。 所述加热部 1利用电磁感应对衬底 4 进行加热, 可以将衬底 4加热到 1600 °C左右, 从而能够得到晶格 质量高的氮化硼单晶。
在歩骤 S23中, 向反应部 1中通入所述反应气体及载气后, 保温一段时间, 所述保温时间需要根据生长的氮化硼单晶的厚度 来确定, 例如: 0.1-20小时。 通过本发明制备氮化硼单晶的方法制 备的氮化硼单晶尺寸可达 1英寸到 4英寸。
进一歩, 在歩骤 S22之前进一歩包括一歩骤 S21 : 在衬底 4 上生长缓冲层。 具体歩骤如下: 在加热部 2中通入交流电, 利用 电磁感应将衬底 4加热至一第一温度, 将反应气体及载气通入所 述反应部 1中, 以在衬底 4上生长氮化硼缓冲层。 生长缓冲层是 为了调和衬底 4和外延膜 (即氮化硼单晶) 之间的晶格失配, 缓 解外延膜的应力, 使外延膜生长得更好。
在不同的温度下, 氮化硼单晶晶格质量不同, 高温下生成的 氮化硼单晶晶格质量好但是与衬底之间晶格失配, 而低温下生长 的氮化硼单晶晶格质量不好但是有利于衬底 4和外延膜之间的应 力释放。 所以, 所述第二温度高于所述第一温度, 以使第二温度 下生长的氮化硼单晶晶格质量更好。 根据衬底 4材料的不同, 所 述第一温度不同, 在本具体实施方式中, 所述第一温度为 900 °C。 向反应部 1中通入所述反应气体及载气后, 保温一段时间, 所述 保温时间需要根据生长的氮化硼缓冲层的厚度来确定, 例如: 0-1 小时。 若在衬底 4上生长缓冲层, 则歩骤 S23中的氮化硼单晶生 长在缓冲层上。
进一歩, 在歩骤 S23之后, 还可以包括加热衬底至一第三温 度或更多阶梯温度, 以便生长的氮化硼单晶晶格质量更好。
所述三氯化硼可以采用氯气与硼反应制备, 也可以为市售成 品三氯化硼。 所述载气为氮气、 氢气或氩气中的一种或几种以任 意比例混合。
通过本发明制备氮化硼单晶的方法制备的氮化硼单晶尺寸可 达 1英寸到 4英寸。
下面列以若干实施例进一歩阐述本发明。
实施例 1
在本实施例 1中, 以蓝宝石为衬底, 三氯化硼与氨气为反应 气体, 氮气和氢气为载气, 生长氮化硼单晶。 所述氮化硼单晶制 备方法如下:
( 1 ) 提供一蓝宝石衬底 4, 所述蓝宝石衬底 4放置在所述反 应部 1中的支撑部 3上;
(2 ) 在加热部 2中通入交流电, 利用电磁感应将蓝宝石衬底 4加热至一第一温度, 所述第一温度为 900°C ;
( 3 ) 将三氯化硼及氨气作为反应气体, 氮气及氢气作为载气 通过所述进气口 6通入所述反应部 1中, 以在蓝宝石衬底 4上生 长氮化硼单晶缓冲层, 在第一温度下保温若干时间。在本实施例 1 中, 生成的氮化硼缓冲层的厚度为 300nm。
(4 ) 将蓝宝石衬底 4加热至一第二温度并保温若干时间, 以 在氮化硼缓冲层上生长氮化硼单晶。 在本实施例 1中, 所述第二 温度为 1600°C, 所述氮化硼单晶的厚度大于 Ιμπι, 所述氮化硼单 晶的厚度由生长时间决定。
实施例 2 在本实施例 2中, 以硅为衬底, 三氯化硼与氨气为反应气体, 氮气和氢气为载气, 生长氮化硼单晶。 所述氮化硼单晶制备方法 如下:
( 1 ) 提供一硅衬底 4, 所述硅衬底 4放置在所述反应部 1中 的支撑部 3上;
(2 ) 在加热部 2中通入交流电, 利用电磁感应将硅衬底 3加 热至一第一温度, 所述第一温度为 900°C ;
( 3 ) 将三氯化硼及氨气作为反应气体, 氮气及氢气作为载气 通过所述进气口 6通入所述反应部 1中, 以在硅衬底 4上生长氮 化硼单晶缓冲层, 在第一温度下保温若干时间。 在本实施例 2中, 生成的氮化硼缓冲层的厚度为 500nm。
(4 ) 将硅衬底 4加热至一第二温度并保温若干时间, 以在氮 化硼缓冲层上生长氮化硼单晶。 在本实施例 2中, 所述第二温度 为 1200°C, 所述氮化硼单晶的厚度约为 Ιμπι, 所述氮化硼单晶的 厚度由生长时间决定。
( 5 ) 将硅衬底 4加热至一第三温度并保温若干时间, 以在氮 化硼单晶上继续生长氮化硼单晶。 在本实施例 2中, 所述第三温 度为 1600°C, 在本歩骤中生长的氮化硼单晶的厚度大于 Ιμπι, 所 述氮化硼单晶的厚度由生长时间决定。
以上所述仅是本发明的优选实施方式, 应当指出, 对于本技 术领域的普通技术人员, 在不脱离本发明原理的前提下, 还可以 做出若干改进和润饰, 这些改进和润饰也应视为本发明的保护范 围。

Claims

权 利 要 求 书
1.一种制备氮化硼单晶的装置,包括反应部、加热部及支撑部, 待生长氮化硼单晶的衬底放置在反应部内部的支撑部上, 所述加 热部围绕所述反应部外壁, 其特征在于, 所述反应部包括一由刚 玉或氮化硼多晶制成的内壁, 所述加热部通有交流电, 以在支撑 部诱导产生感应电流, 对衬底进行加热。
2.根据权利要求 1 所述的制备氮化硼单晶的装置, 其特征在 于, 所述反应部的外壁为石英管, 所述加热部为缠绕在反应部外 壁与支撑部对应位置的线圈。
3.—种采用权利要求 1所述的设备制备氮化硼单晶的方法,其 特征在于, 包括如下歩骤:
( 1 ) 提供一衬底, 所述衬底放置在反应部内部的支撑部上;
( 2 ) 在加热部中通入交流电, 利用电磁感应将衬底加热至一 ~ "温度;
( 3 ) 将反应气体及载气通入所述反应部中, 以在衬底上生长 氮化硼单晶;
其中, 所述反应气体为三氯化硼和氨气。
4.根据权利要求 3 所述的制备氮化硼单晶的方法, 其特征在 于, 在歩骤 (2 ) 之前进一歩包括一在衬底上生长缓冲层的歩骤: 在加热部中通入交流电, 利用电磁感应将衬底加热至一第一温度, 将反应气体及载气通入所述反应部中, 以在衬底上生长氮化硼缓 冲层, 进一歩, 在歩骤(3 ) 中, 所述氮化硼单晶生长在缓冲层上, 所述第二温度高于所述第一温度。
5.根据权利要求 4 所述的制备氮化硼单晶的方法, 其特征在 于, 当所述衬底为蓝宝石时, 所述第一温度为 900 °C, 所述第二温 度为 1600°C。
6.根据权利要求 3 所述的制备氮化硼单晶的方法, 其特征在 于, 所述第二温度为 900~1700 °C。
7.根据权利要求 3 所述的制备氮化硼单晶的方法, 其特征在 于, 当所述衬底为硅时, 在歩骤 (3 ) 之后, 还包括一将衬底加热 至一第三温度并继续生长氮化硼单晶的歩骤。
8.根据权利要求 3 所述的制备氮化硼单晶的方法, 其特征在 于, 所述载气选自于氢气、 氮气或氩气中的一种或几种。
9.根据权利要求 3 所述的制备氮化硼单晶的方法, 其特征在 于, 所述衬底选自于硅、 蓝宝石、 碳化硅及氮化铝中的一种。
10.根据权利要求 3所述的制备氮化硼单晶的方法, 其特征在 于, 所述三氯化硼通过氯气与硼反应制备。
PCT/CN2014/078078 2013-11-06 2014-05-22 一种制备氮化硼单晶的装置及方法 WO2015067029A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310543084.9A CN103541000B (zh) 2013-11-06 2013-11-06 一种制备氮化硼单晶的装置及方法
CN201310543084.9 2013-11-06

Publications (1)

Publication Number Publication Date
WO2015067029A1 true WO2015067029A1 (zh) 2015-05-14

Family

ID=49964829

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/078078 WO2015067029A1 (zh) 2013-11-06 2014-05-22 一种制备氮化硼单晶的装置及方法

Country Status (2)

Country Link
CN (1) CN103541000B (zh)
WO (1) WO2015067029A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103541000A (zh) * 2013-11-06 2014-01-29 中国科学院苏州纳米技术与纳米仿生研究所 一种制备氮化硼单晶的装置及方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111489858B (zh) * 2019-01-25 2021-12-31 清华大学 耐高温导线及应用该耐高温导线的探测器
CN113089091A (zh) * 2021-04-01 2021-07-09 北京化工大学 氮化硼模板及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101191202A (zh) * 2006-12-01 2008-06-04 甘志银 金属有机物化学气相沉积设备反应腔的加热系统
US20080132040A1 (en) * 2004-06-30 2008-06-05 Wang Nang Wang Deposition Technique for Producing High Quality Compound Semiconductor Materials
CN101230454A (zh) * 2007-12-28 2008-07-30 北京工业大学 一种立方氮化硼薄膜的制备方法
CN101323982A (zh) * 2008-07-16 2008-12-17 上海大学 一种高质量立方氮化硼薄膜的制备方法
US20110244694A1 (en) * 2010-03-30 2011-10-06 George Andrew Antonelli Depositing conformal boron nitride films
CN102330068A (zh) * 2011-10-21 2012-01-25 苏州明林光电科技有限公司 热解氮化硼板材的制备方法及该方法所用的气相沉积炉
CN102732861A (zh) * 2011-04-14 2012-10-17 北京北方微电子基地设备工艺研究中心有限责任公司 托盘及具有其的化学气相沉积设备
CN102796995A (zh) * 2012-08-27 2012-11-28 北京博宇半导体工艺器皿技术有限公司 制备热解氮化硼制品的气相沉积炉及方法
CN103074597A (zh) * 2012-12-26 2013-05-01 光达光电设备科技(嘉兴)有限公司 反应腔室
CN103541000A (zh) * 2013-11-06 2014-01-29 中国科学院苏州纳米技术与纳米仿生研究所 一种制备氮化硼单晶的装置及方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101086083B (zh) * 2007-06-08 2011-05-11 中国科学院苏州纳米技术与纳米仿生研究所 一种制备三族氮化物衬底的方法
CN103184514B (zh) * 2013-04-11 2016-07-06 中国科学院苏州纳米技术与纳米仿生研究所 晶体生长炉
CN103265303A (zh) * 2013-05-15 2013-08-28 西北工业大学 一种透波纤维增韧氮化硼陶瓷基透波复合材料的制备方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080132040A1 (en) * 2004-06-30 2008-06-05 Wang Nang Wang Deposition Technique for Producing High Quality Compound Semiconductor Materials
CN101191202A (zh) * 2006-12-01 2008-06-04 甘志银 金属有机物化学气相沉积设备反应腔的加热系统
CN101230454A (zh) * 2007-12-28 2008-07-30 北京工业大学 一种立方氮化硼薄膜的制备方法
CN101323982A (zh) * 2008-07-16 2008-12-17 上海大学 一种高质量立方氮化硼薄膜的制备方法
US20110244694A1 (en) * 2010-03-30 2011-10-06 George Andrew Antonelli Depositing conformal boron nitride films
CN102732861A (zh) * 2011-04-14 2012-10-17 北京北方微电子基地设备工艺研究中心有限责任公司 托盘及具有其的化学气相沉积设备
CN102330068A (zh) * 2011-10-21 2012-01-25 苏州明林光电科技有限公司 热解氮化硼板材的制备方法及该方法所用的气相沉积炉
CN102796995A (zh) * 2012-08-27 2012-11-28 北京博宇半导体工艺器皿技术有限公司 制备热解氮化硼制品的气相沉积炉及方法
CN103074597A (zh) * 2012-12-26 2013-05-01 光达光电设备科技(嘉兴)有限公司 反应腔室
CN103541000A (zh) * 2013-11-06 2014-01-29 中国科学院苏州纳米技术与纳米仿生研究所 一种制备氮化硼单晶的装置及方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103541000A (zh) * 2013-11-06 2014-01-29 中国科学院苏州纳米技术与纳米仿生研究所 一种制备氮化硼单晶的装置及方法

Also Published As

Publication number Publication date
CN103541000B (zh) 2016-09-07
CN103541000A (zh) 2014-01-29

Similar Documents

Publication Publication Date Title
Wang et al. High-temperature annealing induced evolution of strain in AlN epitaxial films grown on sapphire substrates
TWI660076B (zh) 碳化矽晶體及其製造方法
Zhang et al. High‐speed preparation of< 111>‐and< 110>‐oriented β‐SiC films by laser chemical vapor deposition
TW200534360A (en) Reduction of carrot defects in silicon carbide epitaxy
JP2008074662A (ja) 炭化珪素単結晶製造装置
CN107849730A (zh) 在单晶硅上生长外延3C‑SiC
WO2003085175A1 (fr) Cristal germe de monocristal de carbure de silicium et procede de production de lingot au moyen de celui-ci
JP2008110907A (ja) 炭化珪素単結晶インゴットの製造方法及び炭化珪素単結晶インゴット
Zhang et al. Preparation and characterization of AlN seeds for homogeneous growth
WO2015067029A1 (zh) 一种制备氮化硼单晶的装置及方法
Hu et al. Hydride vapor phase epitaxy for gallium nitride substrate
JP2008001569A (ja) 単結晶SiC及びその製造方法並びに単結晶SiCの製造装置
JP2017019679A (ja) 炭化珪素エピタキシャル基板
Sun et al. The fabrication of AlN by hydride vapor phase epitaxy
TW581831B (en) SiC single crystal and growth method thereof
JP5614387B2 (ja) 炭化珪素単結晶の製造方法、及び炭化珪素単結晶インゴット
CN102465337B (zh) 一种多片多源卧式氢化物气相外延生长系统
JP5761264B2 (ja) SiC基板の製造方法
JP4157326B2 (ja) 4h型炭化珪素単結晶インゴット及びウエハ
JP5333363B2 (ja) 炭化珪素単結晶育成用炭化珪素原料及びそれを用いた炭化珪素単結晶の製造方法
JP2014114169A (ja) 炭化珪素結晶の製造方法
JP2017154953A (ja) 炭化珪素単結晶製造装置
JPH02180796A (ja) 炭化珪素単結晶の製造方法
JP2011201755A (ja) 単結晶炭化珪素の製造方法
Gao et al. Research on the Key Problems in the Industrialization of SiC Substrate Materials

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: 14859725

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: 14859725

Country of ref document: EP

Kind code of ref document: A1