WO2005001907A1 - THE METHOD OF PREPARING COMPOSITE SUBSTRATE MATERIALS OF Ϝ-LiAlO2 /α-Al2O3 - Google Patents

THE METHOD OF PREPARING COMPOSITE SUBSTRATE MATERIALS OF Ϝ-LiAlO2 /α-Al2O3 Download PDF

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WO2005001907A1
WO2005001907A1 PCT/CN2004/000303 CN2004000303W WO2005001907A1 WO 2005001907 A1 WO2005001907 A1 WO 2005001907A1 CN 2004000303 W CN2004000303 W CN 2004000303W WO 2005001907 A1 WO2005001907 A1 WO 2005001907A1
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lia10
composite substrate
lialo2
al2o3
platinum
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Jun Xu
Haili Wang
Shengming Zhou
Weiqiao Yang
Guanliang Peng
Guoqing Zhou
Chengyong Jiang
Ci Song
Yin Hang
Jiliang Si
Guangjun Zhao
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Shanghai Institute Of Optics And Fine Mechanics Chinese Academy Of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • 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
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/20—Aluminium oxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/0242—Crystalline insulating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides

Definitions

  • the invention relates to a method for preparing a ⁇ -LiA10 2 / a -A1 2 0 3 composite substrate material.
  • the ⁇ -LiA10 2 / a-A1 2 0 3 composite substrate material is mainly used for epitaxial growth of InN-GaN-based blue light semiconductors.
  • the III-nitride semiconductor material InN-GaN has excellent characteristics, such as stable physical and chemical properties, high thermal conductivity and high electron saturation speed, and the optical transition probability of direct band gap materials is an order of magnitude higher than that of indirect band gaps.
  • Gap InN-GaN-based semiconductors have shown broad application prospects in short-wavelength light-emitting diodes, lasers and ultraviolet detectors, and high-temperature electronic devices. Because the melting point of industrial nN-GaN is relatively high; the saturation vapor pressure of N 2 is large, and the preparation of InN- GaN bulk single crystals is very difficult. Therefore, InN-GaN is generally grown on a heterogeneous substrate by epitaxial technology.
  • White sapphire crystal ( ⁇ - ⁇ 1 2 0 3 ) is easy to prepare, cheap, and has good high temperature stability.
  • ⁇ - ⁇ 1 2 0 3 is currently the most commonly used InN-GaN epitaxial substrate material (see Jpn. J. Appl. Phys., Vol. 36, 1997, p. 1568).
  • Lithium aluminate ( ⁇ -LiA10 2 ) is an InN-GaN epitaxial substrate material that has only attracted attention in recent years. Due to its relatively small lattice mismatch with the GaN epitaxial film, only 1.4%, which makes it into A fairly ideal GaN epitaxial substrate material (see US patent USP6218280, Kryliouk Olga, Anderson Tim, Chai Bruce, "Method and apparatus for producing group-II nitrides',).
  • the technical problem to be solved by the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a method for preparing a ⁇ -LiA10 2 / ⁇ -A1 2 0 3 composite substrate material for growing a high-quality InN-GaN thin film epitaxial growth.
  • the preparation method of the composite substrate material ( ⁇ -LiA10 2 / ⁇ - ⁇ 1 ⁇ ) of the present invention uses the vapor phase transport equilibrium (Vapor Transport Equilibration, VTE for short) technology to diffuse lithium ions in a high-temperature, lithium-rich atmosphere. so that ⁇ Li 2 0 and ⁇ - ⁇ 1 2 0 3 solid-phase reaction, preparing a coating layer ⁇ - LiA10 2 - A1A composite substrate material ( ⁇ - LiA10 2 / ⁇ - ⁇ 1 2 0 3).
  • the method for preparing the ⁇ -LiA10 2 / a ⁇ 1 2 0 3 composite substrate material of the present invention, including the specific process flow is as follows:
  • the resistance furnace can also be replaced by a silicon carbon rod furnace or a silicon molybdenum furnace.
  • the present invention Compared with the previous substrates (a-A1 2 0 3 and Y- LiA10 2 ), the present invention has the advantages of overcoming the large lattice mismatch of the previous ⁇ -A1 ⁇ substrate and difficulty in obtaining large-size high-quality LiA10 2 Problems such as single crystal substrates can be used for epitaxial growth of high-quality industrial nN-GaN thin films.
  • FIG. 1 is a schematic diagram of a gas phase transport equilibrium experimental device. detailed description
  • FIG. 1 A schematic diagram of an experimental device for preparing a composite substrate material Y- LiA10 2 / ⁇ -A1 2 0 3 by using the vapor phase transfer equilibrium (VTE) technology used in the present invention is shown in Fig. 1.
  • VTE vapor phase transfer equilibrium
  • Vapor transport level ning (VTE) technique is a mass transfer process, so the crucible should ensure sufficient Li 2 0 supply, secondly, balancing the gas phase is to rely Li 2 0 steady stream LiA10 2 and Li 2 0 mixture from It is maintained by volatilization in the block, in order to prevent the equilibrium damage caused by the depletion of Li 2 0 on the surface of the mixed block, the mixed block should have a porous structure. In order to maximize the volatile surface of Li 2 0.
  • White sapphire ( ⁇ - ⁇ 1 2 0 3 ) wafer is placed in or suspended in a closed platinum crucible, and then the closed platinum crucible is placed in an electric furnace (silicon carbon rod furnace or silicon molybdenum rod furnace) and heated to a predetermined equilibrium The temperature and temperature are maintained for a certain period of time to carry out equilibrium vapor diffusion.
  • the equilibrium temperature should be selected as high as possible, generally 1000 ⁇ 1400 ° C.
  • VTE composite substrate material equilibrium vapor transport
  • a double-sided polished or single-sided polished sapphire ⁇ - ⁇ 1 2 0 3 wafer is placed or suspended on a platinum wire, and a crucible covered with LiAlO ⁇ n Li 2 0 mixed powder 7 and thermocouple 8 is added. Cover the crucible with a platinum lid. 9 Close it and place it in a resistance furnace.
  • ⁇ 3> The temperature is raised to about 1000 to 1400 ° C, and the temperature is maintained for 20 to 100 hours. Li 2 0 diffuses into the ⁇ - ⁇ 1 2 03 wafer. Thus, a LiA10 2 / a- ⁇ 1 2 0 3 composite substrate material was obtained.
  • the present invention relates to a substrate prior - comparison ( ⁇ 1 2 0 3 and ⁇ - LiA10 2), to overcome the prior LiA10 2 single crystal ⁇ - ⁇ 1 2 0 3 substrate lattice mismatch degree is difficult to obtain large size and high quality Problems such as substrates can be used for epitaxial growth of high-quality InN-GaN thin films.

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

Abstract

A method of preparing composite substrate materials of -Ϝ-LiAlO2/α-Al2O3 comprise the steps of: laying LiAlO2 and Li2O mixed mass with pore in the platinum pot; on the platinum wire, laying or hanging the sapphire α-Al2O3 wafer that have been polished at single or both sides, putting the pot lid to cover LiAlO2 and Li2O mixed powders and thermocouple, sealing the top of pot with the platinum cover, then placing it in the resistance furnace; heating the resistance furnace up to about 1000-1400°C and maintaining the temperature for 20-100 hours, then the Li2O will diffuse into the α-Al2O3 wafer, and Ϝ-LiAlO2/α-Al2O3 composite substrate materials can be obtained after lowering the temperature. The present invention overcomes the problems that the mismatching level of α-Al2O3 crystal lattice and the difficulty of achieving the big size and high quality LiAlO2 single crystal substrate and or so, and can be used in epitaxial growing of the high quality InN-GaN film.

Description

y-LiA102/ a -A1203复合衬底材料的制备方法 技术领域 Method for preparing y-LiA10 2 / a -A1 2 0 3 composite substrate material
本发明涉及一种 γ- LiA102/ a -A1203复合衬底材料的制备方法。 γ- LiA102/ a - A1203复合衬底材料主要用作 InN- GaN基蓝光半导体外延生 长。 The invention relates to a method for preparing a γ-LiA10 2 / a -A1 2 0 3 composite substrate material. The γ-LiA10 2 / a-A1 2 0 3 composite substrate material is mainly used for epitaxial growth of InN-GaN-based blue light semiconductors.
背景技术 Background technique
III族氮化物半导体材料 InN- GaN具有优异的特性， 如稳定的物理和 化学性质、 高热导和高电子饱和速度、 直接带隙材料的光跃迁几率比间 接带隙的高一个数量级， 因此， 宽带隙 InN- GaN基半导体在短波长发光 二极管、 激光器和紫外探测器以及高温电子器件方面显示出广阔的应用 前景。 由于工 nN- GaN熔点比较高； N2饱和蒸汽压较大， InN- GaN体单晶 制备十分困难， 因此 InN- GaN—般是在异质衬底上用外延技术生长的。 The III-nitride semiconductor material InN-GaN has excellent characteristics, such as stable physical and chemical properties, high thermal conductivity and high electron saturation speed, and the optical transition probability of direct band gap materials is an order of magnitude higher than that of indirect band gaps. Gap InN-GaN-based semiconductors have shown broad application prospects in short-wavelength light-emitting diodes, lasers and ultraviolet detectors, and high-temperature electronic devices. Because the melting point of industrial nN-GaN is relatively high; the saturation vapor pressure of N 2 is large, and the preparation of InN- GaN bulk single crystals is very difficult. Therefore, InN-GaN is generally grown on a heterogeneous substrate by epitaxial technology.
白宝石晶体（α -Α1203)， 易于制备， 价格便宜，且具有良好的高温稳 定性等特点， α - Α1203是目前最常用的 InN-GaN外延衬底材料（参见 Jpn. J. Appl. Phys.，第 36卷， 1997年， 第 1568页）。 White sapphire crystal (α-Α1 2 0 3 ) is easy to prepare, cheap, and has good high temperature stability. Α-Α1 2 0 3 is currently the most commonly used InN-GaN epitaxial substrate material (see Jpn. J. Appl. Phys., Vol. 36, 1997, p. 1568).
铝酸锂（γ- LiA102)是近几年才受到重视的 InN- GaN外延衬底材料， 由于其与 GaN外延膜的晶格失配度相当小， 只有 1. 4%, 这使它成为一种 相当理想的 GaN外延衬底材料（参见美国专利 USP6218280，Kryliouk Olga, Anderson Tim, Chai Bruce, "Method and apparatus for producing group - ΠΙ nitrides ', )。 Lithium aluminate (γ-LiA10 2 ) is an InN-GaN epitaxial substrate material that has only attracted attention in recent years. Due to its relatively small lattice mismatch with the GaN epitaxial film, only 1.4%, which makes it into A fairly ideal GaN epitaxial substrate material (see US patent USP6218280, Kryliouk Olga, Anderson Tim, Chai Bruce, "Method and apparatus for producing group-II nitrides',).
在先衬底（α - Α1Λ和 γ- LiA102)存在的显著缺点是： （1) 用 a - A1203 作衬底， a 和 GaN之间的晶格失配度高达 14%，使制备的 GaN薄膜 具有较高的位错密度和大量的点缺陷； （2)由于 LiA102熔体在高温下容 易发生非化学计量比挥发， 晶体生长困难， 难以获得大尺寸、 高质量的 LiA102单晶体， 而且， 衬底的加工过程造成了大量的原材料的浪费。 ' 发明内容 The significant disadvantages of previous substrates (α-Α1Λ and γ-LiA10 2 ) are: (1) Using a-A1 2 0 3 as the substrate, the lattice mismatch between a and GaN is as high as 14%, so that The prepared GaN thin film has a high dislocation density and a large number of point defects; (2) LiA10 2 melt is prone to non-stoichiometric volatilization at high temperatures, crystal growth is difficult, and it is difficult to obtain large-size, high-quality LiA10 2 single crystal, and the processing of the substrate caused a large amount of waste of raw materials. '' Summary of the Invention
本发明要解决的技术问题在于克服上述现有技术的不足， 提供一种 用于生长高质量 InN- GaN薄膜外延生长的 γ- LiA102/ α - A1203复合衬底材 料的制备方法。 The technical problem to be solved by the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a method for preparing a γ-LiA10 2 / α-A1 2 0 3 composite substrate material for growing a high-quality InN-GaN thin film epitaxial growth.
本发明的复合衬底材料 (γ- LiA102/ α -Α1Λ)的制备方法是利用气相 传输平衡（Vapor Transport Equilibration, 简称 VTE)技术， 在高温、 富锂的气氛中， 通过锂离子的扩散， 使 Li20和 α -Α1203发生固相反应, 制备具有 γ- LiA102覆盖层的 α - A1A复合衬底材料 (γ- LiA102/ α - Α1203)。 The preparation method of the composite substrate material (γ-LiA10 2 / α-Α1Λ) of the present invention uses the vapor phase transport equilibrium (Vapor Transport Equilibration, VTE for short) technology to diffuse lithium ions in a high-temperature, lithium-rich atmosphere. so that α Li 2 0 and α -Α1 2 0 3 solid-phase reaction, preparing a coating layer γ- LiA10 2 - A1A composite substrate material (γ- LiA10 2 / α - Α1 2 0 3).
本发明的 γ- LiA102/ a Α1203复合衬底材料的制备方法， 包括具体工 艺流程如下： The method for preparing the γ-LiA10 2 / a Α1 2 0 3 composite substrate material of the present invention, including the specific process flow is as follows:
<1>在铂金坩埚内， 放置有带气孔的 LiA102和 Li20混合料块；<1> In the platinum crucible, a mixed block of LiA10 2 and Li 2 0 with air holes is placed;
〈2〉将双面抛光或单面抛光的蓝宝石 a -A1203晶片置于或悬于铂金 丝上， 加上覆盖有 LiA10^B Li2(^t合粉料和热电偶的坩埚盖，坩埚顶部 加铂金盖密闭， 置于电阻炉中； <2> Place the double-side polished or single-side polished sapphire a-A1 2 0 3 wafer on or hang from platinum wire, and add the crucible cover covered with LiA10 ^ B Li 2 (^ t powder and thermocouple) The top of the crucible is sealed with a platinum lid and placed in a resistance furnace;
〈3〉该电阻炉加热升温至 1000~1400°C左右，恒温 20〜： L00小时， Li20 扩散到 a - Α1Λ晶片中， 降温后可得到 LiA102/ -Α1203复合衬底材料。 所述的 LiA102和 Li20 混合料块的重量比的选取范围是<3> The resistance furnace heating to about 1000 ~ 1400 ° C, the thermostat 20~: L00 hours, Li 2 0 diffusion to a - Α1Λ wafer, obtained after cooling LiA10 2 -Α1 2 0 3 composite substrate material / . The selection range of the weight ratio of the LiA10 2 and Li 2 0 mixed blocks is
[LiA102] / [Li20] = (0~95)： (100-5)。 [LiA10 2 ] / [Li 2 0] = (0 ~ 95): (100-5).
所述的电阻炉也可用硅碳棒炉或硅钼 #炉代替。  The resistance furnace can also be replaced by a silicon carbon rod furnace or a silicon molybdenum furnace.
本发明与在先衬底（a - A1203和 Y-LiA102)相比， 其优点是： 克服了在 先 α -Α1Λ衬底晶格失配度大和难以获得大尺寸高质量 LiA102单晶衬底 等问题， 可用于生长高质量工 nN-GaN薄膜外延生长。 Compared with the previous substrates (a-A1 2 0 3 and Y- LiA10 2 ), the present invention has the advantages of overcoming the large lattice mismatch of the previous α-A1 Λ substrate and difficulty in obtaining large-size high-quality LiA10 2 Problems such as single crystal substrates can be used for epitaxial growth of high-quality industrial nN-GaN thin films.
附图说明 BRIEF DESCRIPTION OF THE DRAWINGS
图 1是气相传输平衡实验装置示意图。 具体实施方式 FIG. 1 is a schematic diagram of a gas phase transport equilibrium experimental device. detailed description
本发明所用的气相传输平衡 (VTE)技术制备复合衬底材料 Y-LiA102/ α - A1203的实验装置示意图见图 1，铂金坩埚 1内，放置有带气孔 2的一 定配比的 LiA102和 Li20混合料块 3， 料块 3上部是铂金丝 4， 双面抛光 或单面抛光的蓝宝石 α -Α1203晶片 5置于铂金丝 4上， 料块 3上部有铂 金片 6和 LiA102和 Li20混合粉料 7覆盖，热电偶 8插入粉料 7中，坩祸 1顶部加铂金盖 9密闭。 A schematic diagram of an experimental device for preparing a composite substrate material Y- LiA10 2 / α-A1 2 0 3 by using the vapor phase transfer equilibrium (VTE) technology used in the present invention is shown in Fig. 1. A certain ratio of air holes 2 is placed in a platinum crucible 1. LiA10 2 and Li 2 0 mixed block 3, the upper part of block 3 is platinum wire 4, sapphire α-A1 2 0 3 polished on both sides or single side is placed on platinum wire 4, and platinum is placed on top of block 3 Sheet 6 and LiA10 2 and Li 2 0 mixed powder 7 are covered, thermocouple 8 is inserted into powder 7, and platinum lid 9 is added to the top of Crucible 1 to seal it.
气相传输平寧 (VTE)技术是一种质量传输过程，因此坩埚内应保证有 足够的 Li20供应量，其次，气相的平衡是依靠 Li20源源不断地从 LiA102 和 Li20混合料块中挥发来维持的，为防止混合料块表面 Li20耗尽造成的 平衡破坏， 应使混合料块具有多孔结构。 以尽量增加 Li20的挥发表面。 Vapor transport level ning (VTE) technique is a mass transfer process, so the crucible should ensure sufficient Li 2 0 supply, secondly, balancing the gas phase is to rely Li 2 0 steady stream LiA10 2 and Li 2 0 mixture from It is maintained by volatilization in the block, in order to prevent the equilibrium damage caused by the depletion of Li 2 0 on the surface of the mixed block, the mixed block should have a porous structure. In order to maximize the volatile surface of Li 2 0.
白宝石（ α -Α1203)晶片置于_或悬于密闭的铂金坩埚内，然后将密闭的 铂金坩埚放入电炉（硅碳棒炉或硅钼棒炉）内，加热到预定的平衡温度， 保温一定的时间进行气相平衡扩散，为了加快扩散过程和.结构调整过程， 应选取尽可能高的平衡温度， 一般选取 1000〜1400°C。 White sapphire (α-Α1 2 0 3 ) wafer is placed in or suspended in a closed platinum crucible, and then the closed platinum crucible is placed in an electric furnace (silicon carbon rod furnace or silicon molybdenum rod furnace) and heated to a predetermined equilibrium The temperature and temperature are maintained for a certain period of time to carry out equilibrium vapor diffusion. In order to speed up the diffusion process and the structural adjustment process, the equilibrium temperature should be selected as high as possible, generally 1000 ~ 1400 ° C.
本发明的气相传输平衡（VTE)技术制备复合衬底材料 γ- LiA102/ α - Α1203的具体 艺流程如下： Techniques for preparing the composite substrate material equilibrium vapor transport (VTE) of the present invention γ- LiA10 2 / α - particularly process flow Α1 2 0 3 as follows:
<1>在铂金坩埚 1内， 放置有带气孔 2的 LiA102和 Li20混合料块 3， 选取 [LiA102] / [Li20] = (0~95)： (100〜5)重量比。 <1> In the platinum crucible 1, LiA10 2 and Li 2 0 mixed block 3 with air holes 2 are placed. Select [LiA10 2 ] / [Li 2 0] = (0 ~ 95): (100 ~ 5) weight ratio.
<2〉将双面抛光或单面抛光的蓝宝石 α -Α1203晶片， 置于或悬于铂金 丝上，加上覆盖有 LiAlO^n Li20混合粉料 7和热电偶 8的坩埚盖，坩埚 顶部加铂金盖 .9密闭， 置于电阻炉中。 <2> A double-sided polished or single-sided polished sapphire α-Α1 2 0 3 wafer is placed or suspended on a platinum wire, and a crucible covered with LiAlO ^ n Li 2 0 mixed powder 7 and thermocouple 8 is added. Cover the crucible with a platinum lid. 9 Close it and place it in a resistance furnace.
<3>加热升温至 1000〜1400°C左右， 恒温 20~100小时， Li20扩散到 α - Α1203晶片中。 从而得到了 LiA102/ a - Α1203复合衬底材料。 <3> The temperature is raised to about 1000 to 1400 ° C, and the temperature is maintained for 20 to 100 hours. Li 2 0 diffuses into the α-Α1 2 03 wafer. Thus, a LiA10 2 / a-Α1 2 0 3 composite substrate material was obtained.
下面是用上述的气相传输平衡实验装置和具体的工艺流程制备 Y-LiA102/ a - A1203复合衬底材料的具体实施例。 The following is prepared using the above-mentioned vapor transmission equilibrium experimental device and specific process flow A specific embodiment of the Y-LiA10 2 / a-A1 2 0 3 composite substrate material.
在 Φ 100x80mm的鉑金坩埚内， 放置有带气孔的 LiA102和 Li20混合 料块， 选取[1^八102] / [1^20] =75 : 25重量比。将双面抛光或单面抛光的蓝 宝石 a - A1203晶片， 置于或悬于铂金丝上， 加上覆盖有 LiA102和 Li20混 合粉料和热电偶的坩埚盖， 坩埚顶部加铂金盖密闭， 置于电阻炉中。 加 热电阻炉升温至 1150°C ， 恒温 100小时， Li20扩散到 - A1203晶片中。 从而得到了 γ- LiA102/ a -A1203复合衬底材料。 该复合衬底可用于生长高 质量 InN- GaN薄膜外延生长。 In a platinum crucible of Φ 100x80mm, a mixed block of LiA10 2 and Li 2 0 with air holes was placed, and a weight ratio of [1 ^ eight 10 2 ] / [1 ^ 2 0] = 75 : 25 was selected. Single-sided or double-sided polished sapphire polishing a - A1 2 0 3 of the wafer, was placed on a platinum or gold suspended, plus covered with LiA10 2 and Li 2 0 mixed powder crucible lid and thermocouple, top of the crucible plus The platinum lid was sealed and placed in a resistance furnace. The heating resistance furnace was heated up to 1150 ° C and kept at a constant temperature for 100 hours. Li 2 0 diffused into the -A1 2 03 wafer. Thus, a γ-LiA10 2 / a -A1 2 0 3 composite substrate material was obtained. The composite substrate can be used for epitaxial growth of high-quality InN-GaN thin films.
工业实用性 Industrial applicability
本发明与在先衬底（ - Α1203和 γ- LiA102)相比， 克服了在先 α -Α1203 衬底晶格失配度大和难以获得大尺寸高质量 LiA102单晶衬底等问题， 可 用于生长高质量 InN- GaN薄膜外延生长。 The present invention relates to a substrate prior - comparison (Α1 2 0 3 and γ- LiA10 2), to overcome the prior LiA10 2 single crystal α -Α1 2 0 3 substrate lattice mismatch degree is difficult to obtain large size and high quality Problems such as substrates can be used for epitaxial growth of high-quality InN-GaN thin films.

Claims

权 利 要 求 Rights request
1 一种 γ- LiA102/ a - A1203复合衬底材料的制备方法， 其特征在于包 括如下具体步骤： 1 A method for preparing a γ-LiA10 2 / a-A1 2 0 3 composite substrate material, which is characterized by including the following specific steps:
①在铂金坩埚内， 放置有带气孔的 LiA102和 Li20混合料块；① In the platinum crucible, a mixed block of LiA10 2 and Li 2 0 with air holes is placed;
②将双面抛光或单面抛光的蓝宝石 a -A1203晶片置于或悬于铂金丝 上， 加上覆盖有 LiA102和 Li20混合粉料和热电偶的坩埚盖，坩埚顶部加 铂金盖密闭， 置于电阻炉中； ② Place the double-side polished or single-side polished sapphire a-A1 2 0 3 wafers on or suspended from platinum wire, and cover the crucible cover covered with LiA10 2 and Li 2 0 mixed powder and thermocouple. The platinum lid is sealed and placed in a resistance furnace;
③该电阻炉加热升温至 1000〜1400°C， 恒温 20~100小时， Li20扩散 到 a - A1 晶片中， 降温后可得到 LiA102/ a - A1203复合衬底材料。 ③ The resistance furnace is heated up to 1000 ~ 1400 ° C and maintained at a constant temperature for 20 ~ 100 hours. Li 2 0 diffuses into the a-A1 wafer. After the temperature is lowered, a LiA10 2 / a-A1 2 0 3 composite substrate material can be obtained.
2、根据权利要求 1所述的 y_LiA102/ a - A1203复合衬底材料的制备方 法， 其特征在于所述的 LiA102和 Li20.混合料块（3) 的重量比的选取范 围是 [LiA102] / [Li2O;K0〜95)： (100-5)。 2. The y claim 1 _LiA10 2 / a claim - A1 2 0 3 Preparation of a composite substrate material, wherein said weight LiA10 2 and Li 2 0. mix block (3) ratio The selection range is [LiA10 2 ] / [Li 2 O; K0 ~ 95): (100-5).
3、根据权利要求 1或 2所述的 γ- LiA102/ a - A1203复合衬底材料的制 备方法， 其特征在于所述的电阻炉也可用硅碳棒炉或硅钼棒炉代替。 3. The method for preparing a γ-LiA10 2 / a-A1 2 0 3 composite substrate material according to claim 1 or 2, characterized in that the resistance furnace can also be replaced by a silicon carbon rod furnace or a silicon molybdenum rod furnace. .
PCT/CN2004/000303 2003-06-27 2004-04-02 THE METHOD OF PREPARING COMPOSITE SUBSTRATE MATERIALS OF Ϝ-LiAlO2 /α-Al2O3 WO2005001907A1 (en)

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7326477B2 (en) 2003-09-23 2008-02-05 Saint-Gobain Ceramics & Plastics, Inc. Spinel boules, wafers, and methods for fabricating same
US7045223B2 (en) 2003-09-23 2006-05-16 Saint-Gobain Ceramics & Plastics, Inc. Spinel articles and methods for forming same
CN1322176C (en) * 2004-09-28 2007-06-20 中国科学院上海光学精密机械研究所 Preparation for single-crystal thin film covering layer substrate with r-LiALO2
CN1322175C (en) * 2004-09-28 2007-06-20 中国科学院上海光学精密机械研究所 Preparation for r-Li ALO2 single-crystal thin-film covering layer substrate by pulsing laser deposition
CN1308499C (en) * 2005-02-23 2007-04-04 中国科学院上海光学精密机械研究所 Process for preparing titanium doped lithium aluminate wafer
US7919815B1 (en) 2005-02-24 2011-04-05 Saint-Gobain Ceramics & Plastics, Inc. Spinel wafers and methods of preparation
CN100457630C (en) * 2006-12-18 2009-02-04 天津理工大学 Prepn process of lithium aluminate substrate material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704266A (en) * 1985-06-20 1987-11-03 Sumitomo Chemical Company, Limited Method for producing lithium aluminate powders
US5625202A (en) * 1995-06-08 1997-04-29 University Of Central Florida Modified wurtzite structure oxide compounds as substrates for III-V nitride compound semiconductor epitaxial thin film growth
CN1189545A (en) * 1997-01-30 1998-08-05 中国科学院上海光学精密机械研究所 Verticle temp gradient process for growing crystal of lithium aluminate and gallium aluminate
CN1399308A (en) * 2002-05-31 2003-02-26 南京大学 Prepn of composite ZnAl2O4/alpha-Al2O3 Substrate and growth of GaN film on ZnAl2O4 substrate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704266A (en) * 1985-06-20 1987-11-03 Sumitomo Chemical Company, Limited Method for producing lithium aluminate powders
US5625202A (en) * 1995-06-08 1997-04-29 University Of Central Florida Modified wurtzite structure oxide compounds as substrates for III-V nitride compound semiconductor epitaxial thin film growth
CN1189545A (en) * 1997-01-30 1998-08-05 中国科学院上海光学精密机械研究所 Verticle temp gradient process for growing crystal of lithium aluminate and gallium aluminate
CN1399308A (en) * 2002-05-31 2003-02-26 南京大学 Prepn of composite ZnAl2O4/alpha-Al2O3 Substrate and growth of GaN film on ZnAl2O4 substrate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHAOXIA, B. ET AL.: "Preparation of ZnAL2O4/alpha-AL2O3composite substrate And growth of GaN thin film", SCIENCE IN CHINA (SERIES A), vol. 32, no. 10, October 2002 (2002-10-01) *

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