WO2024034512A1 - METHOD FOR GROWING β-GA2O3-BASED SINGLE CRYSTAL FILM - Google Patents

METHOD FOR GROWING β-GA2O3-BASED SINGLE CRYSTAL FILM Download PDF

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WO2024034512A1
WO2024034512A1 PCT/JP2023/028415 JP2023028415W WO2024034512A1 WO 2024034512 A1 WO2024034512 A1 WO 2024034512A1 JP 2023028415 W JP2023028415 W JP 2023028415W WO 2024034512 A1 WO2024034512 A1 WO 2024034512A1
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gas
single crystal
crystal film
hcl
gacl
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French (fr)
Japanese (ja)
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研太郎 江間
家弘 林
アムタ タンガラジャ
尚 村上
理紗 長野
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株式会社ノベルクリスタルテクノロジー
国立大学法人東京農工大学
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—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
    • 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
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H01L21/2003—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate
    • H01L21/2015—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate the substrate being of crystalline semiconductor material, e.g. lattice adaptation, heteroepitaxy

Definitions

  • the present invention relates to a method for growing a ⁇ -Ga 2 O 3 -based single crystal film.
  • Patent Document 1 a method for growing a ⁇ -Ga 2 O 3 -based single crystal film using the HVPE (Halide Vapor Phase Epitaxy) method is known (see Patent Document 1).
  • a Ga 2 O 3 -based substrate is exposed to a gallium chloride-based gas as a source gas for Ga and an oxygen-containing gas as a source gas for oxygen.
  • a ⁇ -Ga 2 O 3 -based single crystal film is grown on the main surface of the Ga 2 O 3 -based substrate.
  • An object of the present invention is to provide a method for growing a ⁇ -Ga 2 O 3 -based single crystal film that can grow a ⁇ -Ga 2 O 3 -based single crystal film at a high deposition rate while suppressing the occurrence of powder falling. It's about doing.
  • one embodiment of the present invention provides the following method for growing a ⁇ -Ga 2 O 3 -based single crystal film.
  • a method for growing a ⁇ -Ga 2 O 3- based single crystal film by HVPE in which a substrate is exposed to GaCl gas and an oxygen-containing gas as raw material gases, and a Cl-containing gas, and a film is grown on the main surface of the substrate.
  • a ⁇ -Ga 2 O 3 -based single crystal film comprising the step of growing a ⁇ -Ga 2 O 3-based single crystal film, wherein the Cl-containing gas is HCl gas, Cl 2 gas, or a mixed gas of HCl gas and Cl 2 gas. How to grow single crystal films.
  • a method for growing a ⁇ -Ga 2 O 3 -based single crystal film which can grow a ⁇ -Ga 2 O 3 -based single crystal film at a high deposition rate while suppressing the occurrence of powder falling. can do.
  • FIG. 1 is a vertical cross-sectional view of a crystal laminated structure according to an embodiment of the present invention.
  • FIG. 2 is a vertical sectional view of a vapor phase growth apparatus according to an embodiment of the present invention.
  • FIG. 3 is a table showing the relationship between the amount of HCl gas supplied and the state of the ⁇ -Ga 2 O 3 single crystal film.
  • Figure 4 shows the deposition rates of R HCl and ⁇ - Ga 2 O 3 single crystal films when the partial pressure P of GaCl gas is 1.3 ⁇ 10 ⁇ 3 atm and 2.7 ⁇ 10 ⁇ 3 atm. It is a graph showing the relationship between FIG. 5 is a graph showing preferred ranges of R HCl .
  • FIG. 6 is a graph showing the impurity concentration in the crystal laminated structure measured by secondary ion mass spectrometry (SIMS).
  • SIMS secondary ion mass spectrometry
  • FIG. 1 is a vertical cross-sectional view of a crystal laminated structure 1 according to an embodiment of the present invention.
  • the crystal laminated structure 1 has a substrate 10 and a ⁇ -Ga 2 O 3 -based single crystal film 12 formed on the main surface 11 of the substrate 10 by epitaxial crystal growth.
  • the ⁇ -Ga 2 O 3 -based single crystal film 12 is a film made of a Ga 2 O 3 -based single crystal having a ⁇ -type crystal structure.
  • the Ga 2 O 3 single crystal refers to a Ga 2 O 3 single crystal or a Ga 2 O 3 single crystal to which elements such as Al and In are added.
  • Al is added, the band gap is widened, and when In is added, the band gap is narrowed.
  • the ⁇ -Ga 2 O 3 single crystal film 12 may contain conductive impurities such as Si. Furthermore, since the ⁇ -Ga 2 O 3 -based single crystal film 12 is formed by the HVPE method using a gas containing Cl as a source gas, it contains Cl at a concentration of 1 ⁇ 10 15 cm ⁇ 3 or more.
  • the substrate 10 is a substrate that can be used as a base substrate for epitaxial growth of the ⁇ -Ga 2 O 3 single crystal film 12, such as a sapphire substrate or a Ga 2 O 3 single crystal substrate made of a Ga 2 O 3 single crystal. be.
  • the substrate 10 may contain conductivity type impurities.
  • FIG. 2 is a vertical sectional view of the vapor phase growth apparatus 2 according to the embodiment of the present invention.
  • the vapor phase growth apparatus 2 is a vapor phase growth apparatus for the HVPE (Halide Vapor Phase Epitaxy) method, and includes a first gas introduction port 21, a second gas introduction port 22, a third gas introduction port 23, and an exhaust gas It has a reactor 20 having a port 24 and a heating means 26 that is installed around the reactor 20 and heats the inside of the reactor 20.
  • HVPE Hydrode Vapor Phase Epitaxy
  • the reactor 20 includes a reaction vessel 25 containing a Ga raw material, a raw material reaction region R1 where a gallium raw material gas is generated, a substrate 10, and a reaction chamber 25 for forming a ⁇ -Ga 2 O 3 single crystal film 12. It has a crystal growth region R2 where growth is performed.
  • the reactor 20 is made of quartz glass, for example.
  • the reaction vessel 25 is, for example, quartz glass, and the Ga raw material contained in the reaction vessel 25 is metallic gallium.
  • the heating means 26 can heat the raw material reaction region R1 and the crystal growth region R2 of the reactor 20.
  • the heating means 26 is, for example, a resistance heating type or a radiation heating type heating device.
  • the first gas introduction port 21 supplies a Cl-containing gas such as Cl 2 gas or HCl gas to a raw material reaction region R1 of the reactor 20 using a carrier gas (N 2 gas, Ar gas, or He gas) that is an inert gas.
  • a carrier gas N 2 gas, Ar gas, or He gas
  • the second gas introduction port 22 uses an oxygen-containing gas such as O 2 gas or H 2 O gas, which is a raw material gas for oxygen, using a carrier gas (N 2 gas, Ar gas, or He gas), which is an inert gas.
  • This is a port for introducing into the crystal growth region R2 of the reactor 20.
  • the third gas introduction port 23 is provided with a Cl-containing gas, which is HCl gas, Cl 2 gas, or a mixed gas of HCl gas and Cl 2 gas, to suppress the occurrence of powder falling, and ⁇ -Ga 2 O 3- based single crystal.
  • a chloride gas for example, silicon tetrachloride, etc.
  • an inert carrier gas N 2 gas, Ar gas, or He gas. This is a port for introducing into the crystal growth region R2.
  • a carrier gas is used to contain Cl from the first gas introduction port 21.
  • a gas is introduced, and the metal gallium in the reaction vessel 25 is reacted with the Cl-containing gas at the above atmospheric temperature in the raw material reaction region R1 to generate GaCl gas.
  • GaCl gas which is the raw material gas for the ⁇ -Ga 2 O 3 -based single crystal film 12
  • Cl 2 gas that does not contain hydrogen
  • gallium chloride-based gases other than GaCl gas such as GaCl 2 gas, GaCl 3 gas, and (GaCl 3 ) 2 gas, are also produced. Since the partial pressure of GaCl gas is overwhelmingly high, gases other than GaCl gas hardly contribute to the growth of the Ga 2 O 3 single crystal.
  • the raw material reaction region R1 is heated.
  • GaCl gas, an oxygen-containing gas introduced from the second gas introduction port 22, and a Cl-containing gas such as HCl gas introduced from the third gas introduction port 23 are mixed, and the substrate 10 is added to the mixed gas.
  • a ⁇ -Ga 2 O 3 single crystal film 12 is epitaxially grown on the main surface 11 of the substrate 10 .
  • the pressure in the crystal growth region R2 in the furnace housing the reactor 20 is maintained at, for example, 1 atm.
  • ⁇ -Ga 2 O 3 single crystal film 12 containing additive elements such as Si, GaCl gas as a raw material gas, oxygen-containing gas, and HCl gas to suppress the occurrence of powder fall are used.
  • a raw material gas for an additive element for example, a chloride-based gas such as silicon tetrachloride (SiCl 4 )
  • SiCl 4 silicon tetrachloride
  • the Cl-containing gas for generating GaCl gas introduced into the raw material reaction region R1 from the first gas introduction port 21 is used in the crystal growth region in the process of forming the ⁇ -Ga 2 O 3 -based single crystal film 12.
  • the amount flowing into the crystal growth region R2 is the same as the amount of Cl-containing gas introduced from the third gas introduction port 23 into the crystal growth region R2 to suppress the occurrence of powder falling.
  • the amount is sufficiently small in comparison and can be ignored. That is, the Cl-containing gas for generating GaCl gas flowing from the raw material reaction region R1 to the crystal growth region R2 does not contribute to suppressing the occurrence of powder falling.
  • FIG. 3 is a table showing the relationship between the amount of HCl gas supplied and the state of the ⁇ -Ga 2 O 3 single crystal film 12 for suppressing the occurrence of powder falling.
  • FIG. 3 includes SEM (scanning electron microscopy) images of cross sections of a plurality of types of ⁇ -Ga 2 O 3 -based single crystal films 12 formed under conditions with different amounts of HCl gas supplied.
  • the ⁇ -Ga 2 O 3 single crystal film 12 included in the SEM observation image of FIG. 3 is a ⁇ -Ga 2 O 3 single crystal film formed on a sapphire substrate as the substrate 10.
  • GaCl gas which is a raw material gas, and oxygen-containing gas react in the gas phase
  • Ga oxide powder is generated in the gas phase and adheres to the substrate, that is, when powder falling occurs
  • the ⁇ -Ga 2 O 3 single crystal film 12 grows abnormally in three dimensions, and in the SEM image of its cross section, it is observed as a film with many voids and low density.
  • the partial pressure of GaCl gas P GaCl is 1.3 ⁇ 10 ⁇ 3 atm, 2.7 ⁇ 10 ⁇ 3 atm or 5.3 ⁇ 10 -3 atm, the deposition rate of the ⁇ -Ga 2 O 3 single crystal film 12 to suppress powder fall is such that HCl gas is not supplied during film formation. It was found that the film formation rate was significantly higher than that of the conventional method (less than 5 ⁇ m/h).
  • the relationship between the amount of HCl gas supplied and the state of the ⁇ -Ga 2 O 3 single crystal film 12 and the relationship between the amount of HCl gas supplied and the deposition rate of the ⁇ -Ga 2 O 3 single crystal film 12 are as follows: ⁇ The same holds true even when the -Ga 2 O 3 single crystal film 12 is a ⁇ -Ga 2 O 3 single crystal film other than the ⁇ -Ga 2 O 3 single crystal film. Further, even when using Cl 2 gas instead of HCl gas to suppress the occurrence of powder falling, the same results as those obtained when using HCl gas described above can be obtained.
  • the relationship between the amount of Cl 2 gas supplied and the state of the ⁇ -Ga 2 O 3 single crystal film 12 and the relationship between the amount of Cl 2 gas supplied and the deposition rate of the ⁇ -Ga 2 O 3 single crystal film 12 are as follows. , approximately the same as the relationship between the amount of HCl gas supplied and the state of the ⁇ -Ga 2 O 3 single crystal film 12 and the relationship between the amount of HCl gas supplied and the deposition rate of the ⁇ -Ga 2 O 3 single crystal film 12. It will be the same. Furthermore, the same applies even when a mixed gas of HCl gas and Cl 2 gas is used instead of HCl gas to suppress the occurrence of powder falling. However, when HCl gas is used, the effect of suppressing the occurrence of powder precipitation tends to be greater than when using Cl 2 gas or a mixed gas of HCl gas and Cl 2 gas.
  • FIG. 4 shows the formation of R HCl and ⁇ -Ga 2 O 3 single crystal film 12 when the partial pressure P GaCl of GaCl gas is 1.3 ⁇ 10 ⁇ 3 atm and 2.7 ⁇ 10 ⁇ 3 atm. It is a graph showing the relationship with speed.
  • FIG. 4 shows that the deposition rate of the ⁇ -Ga 2 O 3 single crystal film 12 decreases as R HCl increases, that is, the amount of HCl gas supplied during film deposition increases. That is, by supplying HCl gas during the formation of the ⁇ -Ga 2 O 3 -based single crystal film 12, abnormal growth of the ⁇ -Ga 2 O 3 -based single crystal film 12 due to the occurrence of powder precipitation can be suppressed. However, if the amount of HCl gas supplied is too large, the deposition rate of the ⁇ -Ga 2 O 3 -based single crystal film 12 will become low.
  • the lower limit of R HCl at which abnormal growth can be almost completely suppressed is set to 100%.
  • R HCl is approximately 150% or less.
  • FIG. 5 is a graph showing preferred ranges of R HCl .
  • the solid line R HCl 357.13 ⁇ P GaCl in FIG . This is an approximate straight line drawn based on the lower limit value of R HCl when abnormal growth is almost completely suppressed.
  • R Cl2 and R mix are preferably 187.57 ⁇ P GaCl or more, and 357.13 ⁇ More preferably, it is equal to or higher than P GaCl .
  • R Cl 2 or R mix is preferably 562.7 ⁇ P GaCl or less.
  • FIG. 6 is a graph showing the impurity concentration in the crystal laminated structure 1 measured by secondary ion mass spectrometry (SIMS).
  • the substrate 10 of the crystal laminated structure 1 according to FIG. 6 is a ⁇ -Ga 2 O 3 single-crystal substrate, and the ⁇ -Ga 2 O 3 -based single crystal film 12 is formed by using HCl gas to suppress the occurrence of powder falling. This is a deposited ⁇ -Ga 2 O 3 single crystal film.
  • the horizontal axis in FIG. 6 represents the depth ( ⁇ m) from the surface 13 of the ⁇ -Ga 2 O 3 single crystal film 12 of the crystal laminated structure 1, and the vertical axis represents the concentration of each impurity (cm ⁇ 3 ). .
  • the depth of the interface between the substrate 10 of the crystal laminated structure 1 and the ⁇ -Ga 2 O 3 single crystal film 12 is approximately 15 ⁇ m, and the impurity concentration shown in the graph of FIG . This is the concentration of impurities in the 3 -system single crystal film 12.
  • FIG. 6 shows the concentrations of H, C, Cl, N, and Si in the crystal laminated structure 1.
  • the concentrations of H, C, N, and Si in the ⁇ -Ga 2 O 3 single crystal film 12 are close to the measurable lower limit values
  • the concentrations in the ⁇ -Ga 2 O 3 single crystal film 12 are close to the measurable lower limit values.
  • the concentration is equivalent to that of a conventional growth method in which HCl gas is not supplied during the formation of a single crystal film. This shows that the ⁇ -Ga 2 O 3 -based single crystal film 12 is a highly pure film. Furthermore, from the concentration of H shown in FIG.
  • a method for growing a ⁇ -Ga 2 O 3 -based single crystal film which can grow the ⁇ -Ga 2 O 3 -based single crystal film at a high deposition rate while suppressing the occurrence of powder falling.
  • SYMBOLS 1 Crystal laminated structure, 10... Substrate, 11... Main surface, 12... ⁇ -Ga 2 O 3 system single crystal film, 2... Vapor phase growth apparatus, 20... Reactor, 21... First gas introduction port, 22...Second gas introduction port, 23...Third gas introduction port, 24...Exhaust port, 25...Reaction container, 26...Heating means

Abstract

Provided is a method for growing a β-Ga2O3-based single crystal film in which the β-Ga2O3-based single crystal film is grown by an HVPE process. This method for growing a β-Ga2O3-based single crystal film comprises a step for growing a β-Ga2O3-based single crystal film 12 on a main surface 11 of a substrate 10 by exposing the substrate 10 to a GaCl gas and an oxygen-containing gas, which are the starting gases, and a Cl-containing gas, wherein the Cl-containing gas is HCl gas, Cl2 gas, or a mixed gas of HCl gas and Cl2 gas.

Description

β－Ｇａ２Ｏ３系単結晶膜の成長方法Growth method of β-Ga2O3 single crystal film
　本発明は、β－Ｇａ２Ｏ３系単結晶膜（β－Ｇａ２Ｏ３－ｂａｓｅｄ　ｓｉｎｇｌｅ　ｃｒｙｓｔａｌ　ｆｉｌｍ）の成長方法に関する。 The present invention relates to a method for growing a β-Ga 2 O 3 -based single crystal film.
　従来、ＨＶＰＥ（Halide Vapor Phase Epitaxy）法によるβ－Ｇａ２Ｏ３系単結晶膜の成長方法が知られている（特許文献１を参照）。特許文献１に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法においては、Ｇａ２Ｏ３系基板をＧａの原料ガスとしての塩化ガリウム系ガス及び酸素の原料ガスである酸素含有ガスに曝し、Ｇａ２Ｏ３系基板の主面上にβ－Ｇａ２Ｏ３系単結晶膜を成長させる。 Conventionally, a method for growing a β-Ga 2 O 3 -based single crystal film using the HVPE (Halide Vapor Phase Epitaxy) method is known (see Patent Document 1). In the method for growing a β-Ga 2 O 3 -based single crystal film described in Patent Document 1, a Ga 2 O 3 -based substrate is exposed to a gallium chloride-based gas as a source gas for Ga and an oxygen-containing gas as a source gas for oxygen. A β-Ga 2 O 3 -based single crystal film is grown on the main surface of the Ga 2 O 3 -based substrate.
特開２０１５－９１７４０号公報JP2015-91740A
　しかしながら、特許文献１に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法などの、従来のＨＶＰＥ法によるβ－Ｇａ２Ｏ３系単結晶膜の成長方法によれば、β－Ｇａ２Ｏ３系単結晶膜の成膜速度を大きくすると、成膜中に原料ガスが気相反応することによりＧａ酸化物の粉が気相中で生成されて基板に付着する粉降りと呼ばれる現象が生じる。 However, according to a conventional method for growing a β-Ga 2 O 3 single crystal film using the HVPE method, such as the method for growing a β-Ga 2 O 3 single crystal film described in Patent Document 1, β-Ga 2 When the deposition rate of an O 3 -based single crystal film is increased, a phenomenon called powder falling occurs in which Ga oxide powder is generated in the gas phase and adheres to the substrate due to a gas phase reaction of the source gas during film deposition. arise.
　粉降りが生じると、基板に付着したＧａ酸化物の粉を起点とする、β－Ｇａ２Ｏ３系単結晶の三次元的な異常成長が生じ、エッチピットとして現れる結晶欠陥の密度が５×１０４ｃｍ－３以上に増加してしまう。このため、従来のＨＶＰＥ法によるβ－Ｇａ２Ｏ３系単結晶膜の成長方法によれば、粉降りの発生を抑えるために、成膜速度を５μｍ／ｈ未満に抑えなければならない。 When powder falls, three-dimensional abnormal growth of β-Ga 2 O 3 single crystals starts from the Ga oxide powder attached to the substrate, and the density of crystal defects appearing as etch pits increases by 5×. This increases to more than 10 4 cm -3 . Therefore, according to the conventional method for growing a β-Ga 2 O 3 -based single crystal film using the HVPE method, the film formation rate must be kept below 5 μm/h in order to suppress the occurrence of powder falling.
　本発明の目的は、粉降りの発生を抑えつつ高い成膜速度でβ－Ｇａ２Ｏ３系単結晶膜を成長させることのできる、β－Ｇａ２Ｏ３系単結晶膜の成長方法を提供することにある。 An object of the present invention is to provide a method for growing a β-Ga 2 O 3 -based single crystal film that can grow a β-Ga 2 O 3 -based single crystal film at a high deposition rate while suppressing the occurrence of powder falling. It's about doing.
　本発明の一態様は、上記目的を達成するために、下記のβ－Ｇａ２Ｏ３系単結晶膜の成長方法を提供する。 In order to achieve the above object, one embodiment of the present invention provides the following method for growing a β-Ga 2 O 3 -based single crystal film.
［１］ＨＶＰＥ法によるβ－Ｇａ２Ｏ３系単結晶膜の成長方法であって、基板を原料ガスであるＧａＣｌガス及び酸素含有ガス、並びにＣｌ含有ガスに曝し、前記基板の主面上にβ－Ｇａ２Ｏ３系単結晶膜を成長させる工程を含み、前記Ｃｌ含有ガスが、ＨＣｌガス、Ｃｌ２ガス、又はＨＣｌガスとＣｌ２ガスの混合ガスである、β－Ｇａ２Ｏ３系単結晶膜の成長方法。
［２］前記ＧａＣｌガスの分圧ＰＧａＣｌに対する前記Ｃｌ含有ガスの分圧の比の値であるＲが、１８７．５７×ＰＧａＣｌ以上である、上記［１］に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法。
［３］前記ＧａＣｌガスの分圧ＰＧａＣｌに対する前記Ｃｌ含有ガスの分圧の比の値であるＲが、３５７．１３×ＰＧａＣｌ以上である、上記［１］に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法。
［４］前記Ｒが、５６２．７×ＰＧａＣｌ以下である、上記［２］又は［３］に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法。 [1] A method for growing a β-Ga 2 O 3- based single crystal film by HVPE, in which a substrate is exposed to GaCl gas and an oxygen-containing gas as raw material gases, and a Cl-containing gas, and a film is grown on the main surface of the substrate. A β-Ga 2 O 3 -based single crystal film comprising the step of growing a β-Ga 2 O 3-based single crystal film, wherein the Cl-containing gas is HCl gas, Cl 2 gas, or a mixed gas of HCl gas and Cl 2 gas. How to grow single crystal films.
[2] β-Ga 2 O according to [1] above, wherein R, which is the ratio of the partial pressure of the Cl-containing gas to the partial pressure P GaCl of the GaCl gas, is 187.57×P GaCl or more. A method for growing a 3 -system single crystal film.
[3] β-Ga 2 O according to [1] above, wherein R, which is the ratio of the partial pressure of the Cl-containing gas to the partial pressure P GaCl of the GaCl gas, is 357.13×P GaCl or more. Growth method of 3 -system single crystal film.
[4] The method for growing a β-Ga 2 O 3 single crystal film according to [2] or [3] above, wherein the R is 562.7×P GaCl or less.
　本発明によれば、粉降りの発生を抑えつつ高い成膜速度でβ－Ｇａ２Ｏ３系単結晶膜を成長させることのできる、β－Ｇａ２Ｏ３系単結晶膜の成長方法を提供することができる。 According to the present invention, there is provided a method for growing a β-Ga 2 O 3 -based single crystal film, which can grow a β-Ga 2 O 3 -based single crystal film at a high deposition rate while suppressing the occurrence of powder falling. can do.
図１は、本発明の実施の形態に係る結晶積層構造体の垂直断面図である。FIG. 1 is a vertical cross-sectional view of a crystal laminated structure according to an embodiment of the present invention. 図２は、本発明の実施の形態に係る気相成長装置の垂直断面図である。FIG. 2 is a vertical sectional view of a vapor phase growth apparatus according to an embodiment of the present invention. 図３は、ＨＣｌガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜の状態の関係を示す表である。FIG. 3 is a table showing the relationship between the amount of HCl gas supplied and the state of the β-Ga 2 O 3 single crystal film. 図４は、ＧａＣｌガスの分圧ＰＧａＣｌが１．３×１０－３ａｔｍ、２．７×１０－３ａｔｍであるときのＲＨＣｌとβ－Ｇａ２Ｏ３系単結晶膜の成膜速度との関係を示すグラフである。Figure 4 shows the deposition rates of R HCl and β- Ga 2 O 3 single crystal films when the partial pressure P of GaCl gas is 1.3×10 −3 atm and 2.7×10 −3 atm. It is a graph showing the relationship between 図５は、ＲＨＣｌの好ましい範囲を示すグラフである。FIG. 5 is a graph showing preferred ranges of R HCl . 図６は、二次イオン質量分析法（ＳＩＭＳ）により測定した、結晶積層構造体中の不純物濃度を表すグラフである。FIG. 6 is a graph showing the impurity concentration in the crystal laminated structure measured by secondary ion mass spectrometry (SIMS).
（結晶積層構造体の構成）
　図１は、本発明の実施の形態に係る結晶積層構造体１の垂直断面図である。結晶積層構造体１は、基板１０と、基板１０の主面１１上にエピタキシャル結晶成長により形成されたβ－Ｇａ２Ｏ３系単結晶膜１２を有する。 (Configuration of crystal laminated structure)
FIG. 1 is a vertical cross-sectional view of a crystal laminated structure 1 according to an embodiment of the present invention. The crystal laminated structure 1 has a substrate 10 and a β-Ga 2 O 3 -based single crystal film 12 formed on the main surface 11 of the substrate 10 by epitaxial crystal growth.
　β－Ｇａ２Ｏ３系単結晶膜１２は、β型の結晶構造を有するＧａ２Ｏ３系単結晶からなる膜である。ここで、Ｇａ２Ｏ３系単結晶とは、Ｇａ２Ｏ３単結晶、又は、Ａｌ、Ｉｎ等の元素が添加されたＧａ２Ｏ３単結晶をいう。例えば、Ａｌ及びＩｎが添加されたＧａ２Ｏ３単結晶である（ＧａｘＡｌｙＩｎ（１－ｘ－ｙ））２Ｏ３（０＜ｘ≦１、０≦ｙ≦１、０＜ｘ＋ｙ≦１）単結晶であってもよい。Ａｌを添加した場合にはバンドギャップが広がり、Ｉｎを添加した場合にはバンドギャップが狭くなる。また、β－Ｇａ２Ｏ３系単結晶膜１２は、Ｓｉ等の導電型不純物を含んでもよい。また、β－Ｇａ２Ｏ３系単結晶膜１２は、Ｃｌが含まれるガスを原料ガスとして用いるＨＶＰＥ法により形成されるため、１×１０１５ｃｍ－３以上の濃度のＣｌを含む。 The β-Ga 2 O 3 -based single crystal film 12 is a film made of a Ga 2 O 3 -based single crystal having a β-type crystal structure. Here, the Ga 2 O 3 single crystal refers to a Ga 2 O 3 single crystal or a Ga 2 O 3 single crystal to which elements such as Al and In are added. For example, Ga 2 O 3 single crystal doped with Al and In (Ga x Al y In (1-x-y) ) 2 O 3 (0<x≦1, 0≦y≦1, 0<x+y ≦1) It may be a single crystal. When Al is added, the band gap is widened, and when In is added, the band gap is narrowed. Furthermore, the β-Ga 2 O 3 single crystal film 12 may contain conductive impurities such as Si. Furthermore, since the β-Ga 2 O 3 -based single crystal film 12 is formed by the HVPE method using a gas containing Cl as a source gas, it contains Cl at a concentration of 1×10 15 cm −3 or more.
　基板１０は、サファイア基板、Ｇａ２Ｏ３系単結晶からなるＧａ２Ｏ３系単結晶基板などの、β－Ｇａ２Ｏ３系単結晶膜１２のエピタキシャル成長の下地基板として用いることのできる基板である。基板１０は、導電型不純物を含んでいてもよい。 The substrate 10 is a substrate that can be used as a base substrate for epitaxial growth of the β-Ga 2 O 3 single crystal film 12, such as a sapphire substrate or a Ga 2 O 3 single crystal substrate made of a Ga 2 O 3 single crystal. be. The substrate 10 may contain conductivity type impurities.
（気相成長装置の構造）
　以下に、本実施の形態に係るβ－Ｇａ２Ｏ３系単結晶膜１２の成長に用いる気相成長装置の構造の一例について説明する。 (Structure of vapor phase growth apparatus)
An example of the structure of a vapor phase growth apparatus used for growing the β-Ga 2 O 3 single crystal film 12 according to this embodiment will be described below.
　図２は、本発明の実施の形態に係る気相成長装置２の垂直断面図である。気相成長装置２は、ＨＶＰＥ（Halide Vapor Phase Epitaxy）法用の気相成長装置であり、第１のガス導入ポート２１、第２のガス導入ポート２２、第３のガス導入ポート２３、及び排気ポート２４を有する反応炉２０と、反応炉２０の周囲に設置され、反応炉２０の内部を加熱する加熱手段２６を有する。 FIG. 2 is a vertical sectional view of the vapor phase growth apparatus 2 according to the embodiment of the present invention. The vapor phase growth apparatus 2 is a vapor phase growth apparatus for the HVPE (Halide Vapor Phase Epitaxy) method, and includes a first gas introduction port 21, a second gas introduction port 22, a third gas introduction port 23, and an exhaust gas It has a reactor 20 having a port 24 and a heating means 26 that is installed around the reactor 20 and heats the inside of the reactor 20.
　反応炉２０は、Ｇａ原料が収容された反応容器２５が配置され、ガリウムの原料ガスが生成される原料反応領域Ｒ１と、基板１０が配置され、β－Ｇａ２Ｏ３系単結晶膜１２の成長が行われる結晶成長領域Ｒ２を有する。反応炉２０は、例えば、石英ガラスからなる。 The reactor 20 includes a reaction vessel 25 containing a Ga raw material, a raw material reaction region R1 where a gallium raw material gas is generated, a substrate 10, and a reaction chamber 25 for forming a β-Ga 2 O 3 single crystal film 12. It has a crystal growth region R2 where growth is performed. The reactor 20 is made of quartz glass, for example.
　反応容器２５は、例えば、石英ガラスであり、反応容器２５に収容されるＧａ原料は金属ガリウムである。 The reaction vessel 25 is, for example, quartz glass, and the Ga raw material contained in the reaction vessel 25 is metallic gallium.
　加熱手段２６は、反応炉２０の原料反応領域Ｒ１と結晶成長領域Ｒ２を加熱することができる。加熱手段２６は、例えば、抵抗加熱式や輻射加熱式の加熱装置である。 The heating means 26 can heat the raw material reaction region R1 and the crystal growth region R2 of the reactor 20. The heating means 26 is, for example, a resistance heating type or a radiation heating type heating device.
　第１のガス導入ポート２１は、Ｃｌ２ガス又はＨＣｌガスであるＣｌ含有ガスを不活性ガスであるキャリアガス（Ｎ２ガス、Ａｒガス又はＨｅガス）を用いて反応炉２０の原料反応領域Ｒ１内に導入するためのポートである。第２のガス導入ポート２２は、酸素の原料ガスであるＯ２ガスやＨ２Ｏガス等の酸素含有ガスを不活性ガスであるキャリアガス（Ｎ２ガス、Ａｒガス又はＨｅガス）を用いて反応炉２０の結晶成長領域Ｒ２へ導入するためのポートである。第３のガス導入ポート２３は、粉降りの発生を抑えるためのＨＣｌガス、Ｃｌ２ガス、又はＨＣｌガスとＣｌ２ガスの混合ガスであるＣｌ含有ガス、及びβ－Ｇａ２Ｏ３系単結晶膜１２にＳｉ等のドーパントを添加するための塩化物系ガス（例えば、四塩化ケイ素等）を不活性ガスであるキャリアガス（Ｎ２ガス、Ａｒガス又はＨｅガス）を用いて反応炉２０の結晶成長領域Ｒ２へ導入するためのポートである。 The first gas introduction port 21 supplies a Cl-containing gas such as Cl 2 gas or HCl gas to a raw material reaction region R1 of the reactor 20 using a carrier gas (N 2 gas, Ar gas, or He gas) that is an inert gas. This is a port for introducing into The second gas introduction port 22 uses an oxygen-containing gas such as O 2 gas or H 2 O gas, which is a raw material gas for oxygen, using a carrier gas (N 2 gas, Ar gas, or He gas), which is an inert gas. This is a port for introducing into the crystal growth region R2 of the reactor 20. The third gas introduction port 23 is provided with a Cl-containing gas, which is HCl gas, Cl 2 gas, or a mixed gas of HCl gas and Cl 2 gas, to suppress the occurrence of powder falling, and β-Ga 2 O 3- based single crystal. A chloride gas (for example, silicon tetrachloride, etc.) for adding a dopant such as Si to the film 12 is added to the reactor 20 using an inert carrier gas (N 2 gas, Ar gas, or He gas). This is a port for introducing into the crystal growth region R2.
（β－Ｇａ２Ｏ３系単結晶膜の成長）
　以下に、本実施の形態に係るβ－Ｇａ２Ｏ３系単結晶膜１２の成長工程の一例について説明する。 (Growth of β-Ga 2 O 3 -based single crystal film)
An example of the growth process of the β-Ga 2 O 3 -based single crystal film 12 according to the present embodiment will be described below.
　まず、加熱手段２６を用いて反応炉２０の原料反応領域Ｒ１の雰囲気温度を所定の温度、例えば５００～９００℃に保った状態で、第１のガス導入ポート２１からキャリアガスを用いてＣｌ含有ガスを導入し、原料反応領域Ｒ１において、上記の雰囲気温度下で反応容器２５内の金属ガリウムとＣｌ含有ガスを反応させ、ＧａＣｌガスを生成する。 First, while maintaining the atmospheric temperature of the raw material reaction region R1 of the reactor 20 at a predetermined temperature, for example, 500 to 900°C using the heating means 26, a carrier gas is used to contain Cl from the first gas introduction port 21. A gas is introduced, and the metal gallium in the reaction vessel 25 is reacted with the Cl-containing gas at the above atmospheric temperature in the raw material reaction region R1 to generate GaCl gas.
　なお、β－Ｇａ２Ｏ３系単結晶膜１２の原料ガスであるＧａＣｌガスの生成においては、水素を含まないＣｌ２ガスをＣｌ含有ガスとして用いることが好ましい。 Note that in the generation of GaCl gas, which is the raw material gas for the β-Ga 2 O 3 -based single crystal film 12, it is preferable to use Cl 2 gas that does not contain hydrogen as the Cl-containing gas.
　また、金属ガリウムとＣｌ含有ガスの反応から、ＧａＣｌガス以外の塩化ガリウム系ガスであるＧａＣｌ２ガス、ＧａＣｌ３ガス、及び（ＧａＣｌ３）２ガスも生成されるが、これらの塩化ガリウム系ガスのうちでＧａＣｌガスの分圧が圧倒的に高くなるため、ＧａＣｌガス以外のガスはＧａ２Ｏ３系単結晶の成長にほとんど寄与しない。 In addition, from the reaction of metallic gallium and Cl-containing gas, gallium chloride-based gases other than GaCl gas, such as GaCl 2 gas, GaCl 3 gas, and (GaCl 3 ) 2 gas, are also produced. Since the partial pressure of GaCl gas is overwhelmingly high, gases other than GaCl gas hardly contribute to the growth of the Ga 2 O 3 single crystal.
　次に、加熱手段２６を用いて反応炉２０の結晶成長領域Ｒ２の雰囲気温度を所定の温度、例えば８００～１１００℃に保った状態で、結晶成長領域Ｒ２において、原料反応領域Ｒ１で生成されたＧａＣｌガスと、第２のガス導入ポート２２から導入された酸素含有ガスと、第３のガス導入ポート２３から導入されたＨＣｌガス等のＣｌ含有ガスとを混合させ、その混合ガスに基板１０を曝し、基板１０の主面１１上にβ－Ｇａ２Ｏ３系単結晶膜１２をエピタキシャル成長させる。このとき、反応炉２０を収容する炉内の結晶成長領域Ｒ２における圧力を、例えば、１ａｔｍに保つ。 Next, while maintaining the atmospheric temperature of the crystal growth region R2 of the reactor 20 at a predetermined temperature, for example, 800 to 1100° C., using the heating means 26, in the crystal growth region R2, the raw material reaction region R1 is heated. GaCl gas, an oxygen-containing gas introduced from the second gas introduction port 22, and a Cl-containing gas such as HCl gas introduced from the third gas introduction port 23 are mixed, and the substrate 10 is added to the mixed gas. Then, a β-Ga 2 O 3 single crystal film 12 is epitaxially grown on the main surface 11 of the substrate 10 . At this time, the pressure in the crystal growth region R2 in the furnace housing the reactor 20 is maintained at, for example, 1 atm.
　ここで、Ｓｉ等の添加元素を含むβ－Ｇａ２Ｏ３系単結晶膜１２を形成する場合には、原料ガスであるＧａＣｌガス、酸素含有ガス、及び粉降りの発生を抑える為のＨＣｌガス等のＣｌ含有ガスに加えて、第３のガス導入ポート２３より、添加元素の原料ガス（例えば、四塩化ケイ素（ＳｉＣｌ４）等の塩化物系ガス）も結晶成長領域Ｒ２に導入する。 Here, when forming the β-Ga 2 O 3 single crystal film 12 containing additive elements such as Si, GaCl gas as a raw material gas, oxygen-containing gas, and HCl gas to suppress the occurrence of powder fall are used. In addition to the Cl-containing gases, a raw material gas for an additive element (for example, a chloride-based gas such as silicon tetrachloride (SiCl 4 )) is also introduced into the crystal growth region R2 from the third gas introduction port 23.
　なお、β－Ｇａ２Ｏ３系単結晶膜１２を成長させる際は、酸素含有ガスとして水素を含まないＯ２ガスを用いることが好ましい。 Note that when growing the β-Ga 2 O 3 based single crystal film 12, it is preferable to use O 2 gas that does not contain hydrogen as the oxygen-containing gas.
　第１のガス導入ポート２１から原料反応領域Ｒ１内に導入された、ＧａＣｌガスを生成するためのＣｌ含有ガスが、β－Ｇａ２Ｏ３系単結晶膜１２を成膜する工程において結晶成長領域Ｒ２へ流れ込む可能性があるが、その結晶成長領域Ｒ２へ流れ込む量は、第３のガス導入ポート２３から結晶成長領域Ｒ２に導入される、粉降りの発生を抑えるためのＣｌ含有ガスの量と比較して十分に少なく、無視できる量である。すなわち、原料反応領域Ｒ１から結晶成長領域Ｒ２へ流れ込むＧａＣｌガスを生成するためのＣｌ含有ガスは、粉降りの発生の抑制に寄与しない。 The Cl-containing gas for generating GaCl gas introduced into the raw material reaction region R1 from the first gas introduction port 21 is used in the crystal growth region in the process of forming the β-Ga 2 O 3 -based single crystal film 12. However, the amount flowing into the crystal growth region R2 is the same as the amount of Cl-containing gas introduced from the third gas introduction port 23 into the crystal growth region R2 to suppress the occurrence of powder falling. The amount is sufficiently small in comparison and can be ignored. That is, the Cl-containing gas for generating GaCl gas flowing from the raw material reaction region R1 to the crystal growth region R2 does not contribute to suppressing the occurrence of powder falling.
　図３は、粉降りの発生を抑制するためのＨＣｌガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜１２の状態の関係を示す表である。図３には、ＨＣｌガスの供給量が異なる条件で成膜された複数種のβ－Ｇａ２Ｏ３系単結晶膜１２の断面のＳＥＭ（走査電子顕微鏡）観察画像が含まれている。図３のＳＥＭ観察画像に含まれるβ－Ｇａ２Ｏ３系単結晶膜１２は、いずれも基板１０としてのサファイア基板上に成膜されたβ－Ｇａ２Ｏ３単結晶膜である。 FIG. 3 is a table showing the relationship between the amount of HCl gas supplied and the state of the β-Ga 2 O 3 single crystal film 12 for suppressing the occurrence of powder falling. FIG. 3 includes SEM (scanning electron microscopy) images of cross sections of a plurality of types of β-Ga 2 O 3 -based single crystal films 12 formed under conditions with different amounts of HCl gas supplied. The β-Ga 2 O 3 single crystal film 12 included in the SEM observation image of FIG. 3 is a β-Ga 2 O 3 single crystal film formed on a sapphire substrate as the substrate 10.
　図３に含まれるＲＨＣｌは、反応炉２０内のＧａＣｌガスの分圧ＰＧａＣｌに対するＨＣｌガスの分圧ＰＨＣｌの比の値である。すなわち、ＲＨＣｌ＝ＰＨＣｌ／ＰＧａＣｌである。 R HCl included in FIG. 3 is a value of the ratio of the partial pressure of HCl gas P HCl to the partial pressure P GaCl of GaCl gas in the reactor 20. That is, R HCl = P HCl /P GaCl .
　ＨＶＰＥ法による成膜中に原料ガスであるＧａＣｌガスと酸素含有ガスが気相反応することによりＧａ酸化物の粉が気相中で生成されて基板に付着する現象、すなわち粉降りが発生すると、β－Ｇａ２Ｏ３系単結晶膜１２が三次元的に異常成長し、その断面のＳＥＭ観察画像では空隙が多く密度の低いような膜として観察される。 During film formation by the HVPE method, when GaCl gas, which is a raw material gas, and oxygen-containing gas react in the gas phase, Ga oxide powder is generated in the gas phase and adheres to the substrate, that is, when powder falling occurs, The β-Ga 2 O 3 single crystal film 12 grows abnormally in three dimensions, and in the SEM image of its cross section, it is observed as a film with many voids and low density.
　図３によれば、ＲＨＣｌ＝０、すなわちβ－Ｇａ２Ｏ３系単結晶膜１２の成膜の際にＨＣｌガスを供給しない場合は、β－Ｇａ２Ｏ３系単結晶膜１２が粉降りにより異常成長している。 According to FIG. 3, when R HCl = 0, that is, when HCl gas is not supplied during the formation of the β-Ga 2 O 3 -based single crystal film 12, the β-Ga 2 O 3 -based single crystal film 12 becomes a powder. Abnormal growth due to rain.
　また、図３によれば、ＧａＣｌガスの分圧ＰＧａＣｌが１．３×１０－３ａｔｍであるときには、ＲＨＣｌがおよそ０．２５以上でβ－Ｇａ２Ｏ３系単結晶膜１２の異常成長が効果的に抑えられ、ＲＨＣｌがおよそ０．５０以上でほぼ完全に抑えられることがわかる。また、ＧａＣｌガスの分圧ＰＧａＣｌが２．７×１０－３ａｔｍであるときには、ＲＨＣｌがおよそ０．５０以上でβ－Ｇａ２Ｏ３系単結晶膜１２の異常成長が効果的に抑えられ、ＲＨＣｌがおよそ１．０以上でほぼ完全に抑えられることがわかる。 Further, according to FIG. 3, when the partial pressure P GaCl of GaCl gas is 1.3×10 −3 atm, abnormality in the β-Ga 2 O 3 single crystal film 12 occurs when R HCl is approximately 0.25 or more. It can be seen that growth is effectively suppressed and almost completely suppressed when R HCl is approximately 0.50 or higher. Furthermore, when the partial pressure P GaCl of the GaCl gas is 2.7×10 −3 atm, the abnormal growth of the β-Ga 2 O 3 single crystal film 12 is effectively suppressed when the R HCl is approximately 0.50 or more. It can be seen that R HCl is almost completely suppressed when it is approximately 1.0 or more.
　さらに、ＧａＣｌガスの分圧ＰＧａＣｌが５．３×１０－３ａｔｍであるときには、ＲＨＣｌがおよそ１．０以上でβ－Ｇａ２Ｏ３系単結晶膜１２の異常成長が効果的に抑えられ、ＲＨＣｌがおよそ２．０以上でほぼ完全に抑えられることが確認されている。 Furthermore, when the partial pressure P GaCl of the GaCl gas is 5.3×10 −3 atm, abnormal growth of the β-Ga 2 O 3 single crystal film 12 is effectively suppressed when R HCl is approximately 1.0 or more. It has been confirmed that R HCl can be almost completely suppressed at approximately 2.0 or higher.
　これらの結果から、β－Ｇａ２Ｏ３系単結晶膜１２の成膜の際にＨＣｌガスを供給することにより、粉降りの発生によるβ－Ｇａ２Ｏ３系単結晶膜１２の異常成長を抑えることができ、また、ＨＣｌガスの供給量を増やす、すなわちＲＨＣｌを増加させることにより、より効果的に異常成長が抑えられることがわかった。ＨＣｌガスの供給により粉降りの発生が抑えられるのは、ＨＣｌガスが気相中で生成されるＧａ酸化物の粉を分解するためであると考えられる。 From these results, it is possible to prevent the abnormal growth of the β-Ga 2 O 3 single crystal film 12 due to the occurrence of powder by supplying HCl gas during the formation of the β-Ga 2 O 3 single crystal film 12. It has also been found that abnormal growth can be suppressed more effectively by increasing the amount of HCl gas supplied, that is, by increasing R HCl . The reason why the supply of HCl gas suppresses the occurrence of powder falling is considered to be because HCl gas decomposes Ga oxide powder generated in the gas phase.
　また、異常成長がほぼ完全に抑えられるときのＲＨＣｌの下限値を１００％としたときに、ＲＨＣｌをおよそ５０％以上とすることにより、ある程度効果的に異常成長を抑えられることがわかった。 In addition, when the lower limit of R HCl at which abnormal growth is almost completely suppressed is 100%, it was found that abnormal growth can be suppressed to some extent effectively by increasing R HCl to approximately 50% or more. .
　また、β－Ｇａ２Ｏ３系単結晶膜１２の成膜の際にＨＣｌガスを供給することにより、ＧａＣｌガスの分圧ＰＧａＣｌが１．３×１０－３ａｔｍ、２．７×１０－３ａｔｍ、５．３×１０－３ａｔｍのいずれである場合にも、粉降りを抑えるためのβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度が、成膜時にＨＣｌガスを供給しない従来の方法における成膜速度（５μｍ／ｈ未満）よりも格段に大きくなることがわかった。 In addition, by supplying HCl gas during the formation of the β-Ga 2 O 3 single crystal film 12, the partial pressure of GaCl gas P GaCl is 1.3×10 −3 atm, 2.7×10 − 3 atm or 5.3×10 -3 atm, the deposition rate of the β-Ga 2 O 3 single crystal film 12 to suppress powder fall is such that HCl gas is not supplied during film formation. It was found that the film formation rate was significantly higher than that of the conventional method (less than 5 μm/h).
　なお、ＨＣｌガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜１２の状態の関係及びＨＣｌガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度の関係は、β－Ｇａ２Ｏ３系単結晶膜１２がβ－Ｇａ２Ｏ３単結晶膜以外のβ－Ｇａ２Ｏ３系単結晶膜である場合にも同様に成り立つ。また、粉降りの発生を抑えるためにＨＣｌガスの代わりにＣｌ２ガスを用いる場合であっても、上記のＨＣｌガスを用いる場合の結果と同様の結果が得られる。すなわち、Ｃｌ２ガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜１２の状態の関係及びＣｌ２ガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度の関係は、上記のＨＣｌガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜１２の状態の関係及びＨＣｌガスの供給量とβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度の関係とほぼ同じになる。さらに、粉降りの発生を抑えるためにＨＣｌガスの代わりにＨＣｌガスとＣｌ２ガスの混合ガスを用いる場合であっても同様である。ただし、ＨＣｌガスを用いる場合、Ｃｌ２ガスやＨＣｌガスとＣｌ２ガスの混合ガスを用いる場合よりも粉降りの発生を抑制する効果が大きくなる傾向がある。 The relationship between the amount of HCl gas supplied and the state of the β-Ga 2 O 3 single crystal film 12 and the relationship between the amount of HCl gas supplied and the deposition rate of the β-Ga 2 O 3 single crystal film 12 are as follows: β The same holds true even when the -Ga 2 O 3 single crystal film 12 is a β-Ga 2 O 3 single crystal film other than the β-Ga 2 O 3 single crystal film. Further, even when using Cl 2 gas instead of HCl gas to suppress the occurrence of powder falling, the same results as those obtained when using HCl gas described above can be obtained. That is, the relationship between the amount of Cl 2 gas supplied and the state of the β-Ga 2 O 3 single crystal film 12 and the relationship between the amount of Cl 2 gas supplied and the deposition rate of the β-Ga 2 O 3 single crystal film 12 are as follows. , approximately the same as the relationship between the amount of HCl gas supplied and the state of the β-Ga 2 O 3 single crystal film 12 and the relationship between the amount of HCl gas supplied and the deposition rate of the β-Ga 2 O 3 single crystal film 12. It will be the same. Furthermore, the same applies even when a mixed gas of HCl gas and Cl 2 gas is used instead of HCl gas to suppress the occurrence of powder falling. However, when HCl gas is used, the effect of suppressing the occurrence of powder precipitation tends to be greater than when using Cl 2 gas or a mixed gas of HCl gas and Cl 2 gas.
　図４は、ＧａＣｌガスの分圧ＰＧａＣｌが１．３×１０－３ａｔｍ、２．７×１０－３ａｔｍであるときのＲＨＣｌとβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度との関係を示すグラフである。 FIG. 4 shows the formation of R HCl and β-Ga 2 O 3 single crystal film 12 when the partial pressure P GaCl of GaCl gas is 1.3×10 −3 atm and 2.7×10 −3 atm. It is a graph showing the relationship with speed.
　図４は、ＲＨＣｌが大きい、すなわち成膜時のＨＣｌガスの供給量が大きいほど、β－Ｇａ２Ｏ３系単結晶膜１２の成膜速度が低下することを示している。すなわち、β－Ｇａ２Ｏ３系単結晶膜１２の成膜の際にＨＣｌガスを供給することにより、粉降りの発生によるβ－Ｇａ２Ｏ３系単結晶膜１２の異常成長を抑えることができるが、ＨＣｌガスの供給量が大きすぎると、β－Ｇａ２Ｏ３系単結晶膜１２の成膜速度が小さくなってしまう。 FIG. 4 shows that the deposition rate of the β-Ga 2 O 3 single crystal film 12 decreases as R HCl increases, that is, the amount of HCl gas supplied during film deposition increases. That is, by supplying HCl gas during the formation of the β-Ga 2 O 3 -based single crystal film 12, abnormal growth of the β-Ga 2 O 3 -based single crystal film 12 due to the occurrence of powder precipitation can be suppressed. However, if the amount of HCl gas supplied is too large, the deposition rate of the β-Ga 2 O 3 -based single crystal film 12 will become low.
　ＨＣｌガスの供給量の増加に伴うβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度の低下を抑えるためには、異常成長がほぼ完全に抑えられるときのＲＨＣｌの下限値を１００％としたときに、ＲＨＣｌをおよそ１５０％以下とすることが好ましい。 In order to suppress the decrease in the deposition rate of the β-Ga 2 O 3 -based single crystal film 12 due to an increase in the supply amount of HCl gas, the lower limit of R HCl at which abnormal growth can be almost completely suppressed is set to 100%. Preferably, R HCl is approximately 150% or less.
　図５は、ＲＨＣｌの好ましい範囲を示すグラフである。図５の実線ＲＨＣｌ＝３５７．１３×ＰＧａＣｌは、ＧａＣｌガスの分圧ＰＧａＣｌが１．３×１０－３ａｔｍ、２．７×１０－３ａｔｍ、５．３×１０－３ａｔｍであるときの、異常成長がほぼ完全に抑えられるときのＲＨＣｌの下限値に基づいて引かれた近似直線である。 FIG. 5 is a graph showing preferred ranges of R HCl . The solid line R HCl = 357.13×P GaCl in FIG . This is an approximate straight line drawn based on the lower limit value of R HCl when abnormal growth is almost completely suppressed.
　図５の下側の点線ＲＨＣｌ＝１８７．５７×ＰＧａＣｌは、実線ＲＨＣｌ＝３５７．１３×ＰＧａＣｌのＲＨＣｌを５０％にした直線である。また、図５の上側の点線ＲＨＣｌ＝５６２．７×ＰＧａＣｌは、実線ＲＨＣｌ＝３５７．１３×ＰＧａＣｌのＲＨＣｌを１５０％にした直線である。 The dotted line R HCl =187.57×P GaCl on the lower side of FIG. 5 is a straight line with the R HCl of the solid line R HCl =357.13×P GaCl set to 50%. Further, the dotted line R HCl =562.7×P GaCl on the upper side of FIG. 5 is a straight line with R HCl of the solid line R HCl =357.13×P GaCl set to 150%.
　このため、粉降りの発生によるβ－Ｇａ２Ｏ３系単結晶膜１２の異常成長を抑えるためには、ＲＨＣｌが１８７．５７×ＰＧａＣｌ以上、すなわちＰＧａＣｌとＲＨＣｌをプロットした点が図５の点線ＲＨＣｌ＝１８７．５７×ＰＧａＣｌの線上又は上側に位置することが好ましく、ＲＨＣｌが３５７．１３×ＰＧａＣｌ以上、すなわちＰＧａＣｌとＲＨＣｌをプロットした点が図５の実線ＲＨＣｌ＝３５７．１３×ＰＧａＣｌの線上又は上側に位置することがより好ましい。 Therefore, in order to suppress the abnormal growth of the β-Ga 2 O 3 single crystal film 12 due to the occurrence of powder falling, R HCl must be 187.57×P GaCl or more, that is, the point where P GaCl and R HCl are plotted is It is preferable that the dotted line R HCl = 187.57×P GaCl in FIG. 5 be located on or above the line , and the solid line in FIG . It is more preferable that R HCl =357.13×P be located on or above the line of GaCl .
　また、ＨＣｌガスの供給量の増加に伴うβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度の低下を抑えるためには、ＲＨＣｌが５６２．７×ＰＧａＣｌ以下、すなわちＰＧａＣｌとＲＨＣｌをプロットした点が図５の点線ＲＨＣｌ＝５６２．７×ＰＧａＣｌの線上又は下側に位置することが好ましい。 In addition, in order to suppress the decrease in the deposition rate of the β-Ga 2 O 3 series single crystal film 12 due to an increase in the supply amount of HCl gas, it is necessary to set R HCl to 562.7×P GaCl or less, that is, P GaCl and R It is preferable that the point where HCl is plotted is located on or below the dotted line R HCl =562.7×P GaCl in FIG.
　上述のように、粉降りの発生を抑えるためにＨＣｌガスの代わりにＣｌ２ガスやＨＣｌガスとＣｌ２ガスの混合ガスを用いる場合であっても、上記のＨＣｌガスを用いる場合の結果と同様の結果が得られるため、ＰＧａＣｌに対するＣｌ２ガスの分圧ＰＣｌ２の比の値ＲＣｌ２やＰＧａＣｌに対するＣｌ２ガスとＣｌ２ガスの混合ガスの分圧Ｐｍｉｘの比の値Ｒｍｉｘの好ましい値は、ＲＨＣｌの好ましい値と同様である。すなわち、粉降りの発生によるβ－Ｇａ２Ｏ３系単結晶膜１２の異常成長を抑えるためには、ＲＣｌ２やＲｍｉｘが１８７．５７×ＰＧａＣｌ以上であることが好ましく、３５７．１３×ＰＧａＣｌ以上であることがより好ましい。また、Ｃｌ２ガスやＨＣｌガスとＣｌ２ガスの混合ガスの供給量の増加に伴うβ－Ｇａ２Ｏ３系単結晶膜１２の成膜速度の低下を抑えるためには、ＲＣｌ２やＲｍｉｘが５６２．７×ＰＧａＣｌ以下であることが好ましい。 As mentioned above, even when using Cl 2 gas or a mixed gas of HCl gas and Cl 2 gas instead of HCl gas to suppress the occurrence of powder falling, the same result as when using HCl gas described above is obtained. Since the result is obtained, the value of the ratio of the partial pressure P Cl2 of Cl 2 gas to P GaCl , the value R mix of the partial pressure P mix of the mixed gas of Cl 2 gas and Cl 2 gas to P Cl2 and P GaCl , Preferred values are similar to those for R HCl . That is, in order to suppress abnormal growth of the β-Ga 2 O 3 single crystal film 12 due to occurrence of powder falling, R Cl2 and R mix are preferably 187.57×P GaCl or more, and 357.13× More preferably, it is equal to or higher than P GaCl . In addition, in order to suppress the decrease in the deposition rate of the β-Ga 2 O 3 -based single crystal film 12 due to an increase in the supply amount of Cl 2 gas or a mixed gas of HCl gas and Cl 2 gas, R Cl 2 or R mix is preferably 562.7×P GaCl or less.
　また、粉降りはβ－Ｇａ２Ｏ３系単結晶膜１２の成膜中に原料ガスが気相反応することにより生じる現象であるため、上記のＨＣｌガスなどのＣｌ含有ガスにより粉降りの発生を抑制する効果は、基板の材料に依らず同様に得られる。例えば、図３～５に示される結果は、基板１０としてサファイア基板を用いた実験により得られたものであるが、基板１０としてサファイア基板の代わりにβ－Ｇａ２Ｏ３系単結晶などの他の材料からなる基板を用いた場合であっても、同様の結果が得られる。 In addition, since powder falling is a phenomenon caused by a gas phase reaction of the raw material gas during the formation of the β-Ga 2 O 3 single crystal film 12, powder falling may occur due to Cl-containing gas such as the HCl gas mentioned above. The effect of suppressing this can be obtained in the same way regardless of the material of the substrate. For example, the results shown in FIGS. 3 to 5 were obtained through experiments using a sapphire substrate as the substrate 10, but instead of the sapphire substrate, other materials such as β-Ga 2 O 3 single crystal were used as the substrate 10. Similar results can be obtained even when using a substrate made of a material of
　図６は、二次イオン質量分析法（ＳＩＭＳ）により測定した、結晶積層構造体１中の不純物濃度を表すグラフである。図６に係る結晶積層構造体１の基板１０はβ－Ｇａ２Ｏ３単結晶基板であり、β－Ｇａ２Ｏ３系単結晶膜１２は粉降りの発生を抑えるためにＨＣｌガスを用いて成膜されたβ－Ｇａ２Ｏ３単結晶膜である。 FIG. 6 is a graph showing the impurity concentration in the crystal laminated structure 1 measured by secondary ion mass spectrometry (SIMS). The substrate 10 of the crystal laminated structure 1 according to FIG. 6 is a β-Ga 2 O 3 single-crystal substrate, and the β-Ga 2 O 3 -based single crystal film 12 is formed by using HCl gas to suppress the occurrence of powder falling. This is a deposited β-Ga 2 O 3 single crystal film.
　図６の横軸は結晶積層構造体１のβ－Ｇａ２Ｏ３系単結晶膜１２の表面１３からの深さ（μｍ）を表し、縦軸は各不純物の濃度（ｃｍ－３）を表す。なお、結晶積層構造体１の基板１０とβ－Ｇａ２Ｏ３系単結晶膜１２の界面の深さはおよそ１５μｍであり、図６のグラフに示される不純物の濃度は、β－Ｇａ２Ｏ３系単結晶膜１２中の不純物の濃度である。 The horizontal axis in FIG. 6 represents the depth (μm) from the surface 13 of the β-Ga 2 O 3 single crystal film 12 of the crystal laminated structure 1, and the vertical axis represents the concentration of each impurity (cm −3 ). . The depth of the interface between the substrate 10 of the crystal laminated structure 1 and the β-Ga 2 O 3 single crystal film 12 is approximately 15 μm, and the impurity concentration shown in the graph of FIG . This is the concentration of impurities in the 3 -system single crystal film 12.
　図６は、Ｈ、Ｃ、Ｃｌ、Ｎ、Ｓｉの結晶積層構造体１中の濃度を表す。図６によれば、Ｈ、Ｃ、Ｎ、Ｓｉについては、β－Ｇａ２Ｏ３系単結晶膜１２中の濃度が測定可能な下限値に近く、Ｃｌについては、β－Ｇａ２Ｏ３系単結晶膜の成膜の際にＨＣｌガスを供給しない従来の成長手法と同等の濃度である。このことは、β－Ｇａ２Ｏ３系単結晶膜１２が純度の高い膜であることを示している。また、図６に示されるＨの濃度から、β－Ｇａ２Ｏ３系単結晶膜１２の成膜時に供給されるＨＣｌに由来するＨのβ－Ｇａ２Ｏ３系単結晶膜１２への混入がないことが確認された。また、図６に示されるＳｉの濃度から、石英からなる反応炉２０からβ－Ｇａ２Ｏ３系単結晶膜１２へのＳｉの混入がないことが確認された。 FIG. 6 shows the concentrations of H, C, Cl, N, and Si in the crystal laminated structure 1. According to FIG. 6, the concentrations of H, C, N, and Si in the β-Ga 2 O 3 single crystal film 12 are close to the measurable lower limit values, and for Cl, the concentrations in the β-Ga 2 O 3 single crystal film 12 are close to the measurable lower limit values. The concentration is equivalent to that of a conventional growth method in which HCl gas is not supplied during the formation of a single crystal film. This shows that the β-Ga 2 O 3 -based single crystal film 12 is a highly pure film. Furthermore, from the concentration of H shown in FIG. 6, it can be seen that H derived from HCl supplied during the formation of the β-Ga 2 O 3 -based single crystal film 12 is mixed into the β-Ga 2 O 3 -based single crystal film 12. It was confirmed that there was no Further, from the Si concentration shown in FIG. 6, it was confirmed that no Si was mixed into the β-Ga 2 O 3 single crystal film 12 from the quartz reactor 20.
　図６によれば、β－Ｇａ２Ｏ３系単結晶膜１２中におよそ１．５×１０１６（ｃｍ－３）以下のＣｌが含まれている。これは、β－Ｇａ２Ｏ３系単結晶膜１２がＣｌ含有ガスを用いるＨＶＰＥ法により形成されることに起因する。通常、ＨＶＰＥ法以外の方法によりβ－Ｇａ２Ｏ３系単結晶膜を形成する場合には、Ｃｌ含有ガスを用いないため、β－Ｇａ２Ｏ３系単結晶膜中にＣｌが含まれることはなく、少なくとも、１×１０１５ｃｍ－３以上のＣｌが含まれることはない。 According to FIG. 6, approximately 1.5×10 16 (cm −3 ) or less of Cl is contained in the β-Ga 2 O 3 single crystal film 12. This is because the β-Ga 2 O 3 single crystal film 12 is formed by the HVPE method using a Cl-containing gas. Normally, when forming a β-Ga 2 O 3 single-crystal film by a method other than the HVPE method, Cl-containing gas is not used, so Cl is not included in the β-Ga 2 O 3 -based single crystal film. At least, it does not contain more than 1×10 15 cm −3 of Cl.
（実施の形態の効果）
　上記本発明の実施の形態によれば、β－Ｇａ２Ｏ３系単結晶膜の成膜の際にＨＣｌガス、Ｃｌ２ガス、又はＨＣｌガスとＣｌ２ガスの混合ガスを供給することにより、粉降りの発生を抑えつつ高い成膜速度でβ－Ｇａ２Ｏ３系単結晶膜を成長させることができる。 (Effects of embodiment)
According to the embodiment of the present invention, by supplying HCl gas, Cl 2 gas, or a mixed gas of HCl gas and Cl 2 gas when forming a β-Ga 2 O 3 -based single crystal film, A β-Ga 2 O 3 -based single crystal film can be grown at a high deposition rate while suppressing the occurrence of powder falling.
　以上、本発明の実施の形態を説明したが、本発明は、上記実施の形態に限定されず、発明の主旨を逸脱しない範囲内において種々変形実施が可能である。また、発明の主旨を逸脱しない範囲内において上記実施の形態の構成要素を任意に組み合わせることができる。また、上記に記載した実施の形態は特許請求の範囲に係る発明を限定するものではない。また、実施の形態の中で説明した特徴の組合せの全てが発明の課題を解決するための手段に必須であるとは限らない点に留意すべきである。 Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the invention. Furthermore, the constituent elements of the embodiments described above can be arbitrarily combined without departing from the spirit of the invention. Furthermore, the embodiments described above do not limit the claimed invention. Furthermore, it should be noted that not all combinations of features described in the embodiments are essential for solving the problems of the invention.
　粉降りの発生を抑えつつ高い成膜速度でβ－Ｇａ２Ｏ３系単結晶膜を成長させることのできる、β－Ｇａ２Ｏ３系単結晶膜の成長方法を提供する。 Provided is a method for growing a β-Ga 2 O 3 -based single crystal film, which can grow the β-Ga 2 O 3 -based single crystal film at a high deposition rate while suppressing the occurrence of powder falling.
１…結晶積層構造体、　１０…基板、　１１…主面、　１２…β－Ｇａ２Ｏ３系単結晶膜、　２…気相成長装置、　２０…反応炉、　２１…第１のガス導入ポート、　２２…第２のガス導入ポート、　２３…第３のガス導入ポート、　２４…排気ポート、　２５…反応容器、　２６…加熱手段 DESCRIPTION OF SYMBOLS 1... Crystal laminated structure, 10... Substrate, 11... Main surface, 12... β-Ga 2 O 3 system single crystal film, 2... Vapor phase growth apparatus, 20... Reactor, 21... First gas introduction port, 22...Second gas introduction port, 23...Third gas introduction port, 24...Exhaust port, 25...Reaction container, 26...Heating means

Claims (4)

  1. 　ＨＶＰＥ法によるβ－Ｇａ２Ｏ３系単結晶膜の成長方法であって、
    　基板を原料ガスであるＧａＣｌガス及び酸素含有ガス、並びにＣｌ含有ガスに曝し、前記基板の主面上にβ－Ｇａ２Ｏ３系単結晶膜を成長させる工程を含み、
    　前記Ｃｌ含有ガスが、ＨＣｌガス、Ｃｌ２ガス、又はＨＣｌガスとＣｌ２ガスの混合ガスである、
    　β－Ｇａ２Ｏ３系単結晶膜の成長方法。     A method for growing a β-Ga 2 O 3 single crystal film by HVPE method, the method comprising:
    A step of exposing the substrate to GaCl gas and oxygen-containing gas, which are source gases, and Cl-containing gas, and growing a β-Ga 2 O 3 -based single crystal film on the main surface of the substrate,
    The Cl-containing gas is HCl gas, Cl 2 gas, or a mixed gas of HCl gas and Cl 2 gas,
    A method for growing a β-Ga 2 O 3 single crystal film.
  2. 　前記ＧａＣｌガスの分圧ＰＧａＣｌに対する前記Ｃｌ含有ガスの分圧の比の値であるＲが、１８７．５７×ＰＧａＣｌ以上である、
    　請求項１に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法。     R, which is the ratio of the partial pressure of the Cl-containing gas to the partial pressure P GaCl of the GaCl gas, is 187.57×P GaCl or more;
    The method for growing a β-Ga 2 O 3 single crystal film according to claim 1.
  3. 　前記ＧａＣｌガスの分圧ＰＧａＣｌに対する前記Ｃｌ含有ガスの分圧の比の値であるＲが、３５７．１３×ＰＧａＣｌ以上である、
    　請求項１に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法。     R, which is the ratio of the partial pressure of the Cl-containing gas to the partial pressure P GaCl of the GaCl gas, is 357.13×P GaCl or more;
    The method for growing a β-Ga 2 O 3 single crystal film according to claim 1.
  4. 　前記Ｒが、５６２．７×ＰＧａＣｌ以下である、
    　請求項２又は３に記載のβ－Ｇａ２Ｏ３系単結晶膜の成長方法。     The R is 562.7×P GaCl or less,
    The method for growing a β-Ga 2 O 3 single crystal film according to claim 2 or 3.
PCT/JP2023/028415 2022-08-10 2023-08-03 METHOD FOR GROWING β-GA2O3-BASED SINGLE CRYSTAL FILM WO2024034512A1 (en)

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