US20160265137A1 - METHOD FOR GROWING BETA-Ga2O3-BASED SINGLE CRYSTAL FILM, AND CRYSTALLINE LAYERED STRUCTURE - Google Patents

METHOD FOR GROWING BETA-Ga2O3-BASED SINGLE CRYSTAL FILM, AND CRYSTALLINE LAYERED STRUCTURE Download PDF

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US20160265137A1
US20160265137A1 US15/025,956 US201415025956A US2016265137A1 US 20160265137 A1 US20160265137 A1 US 20160265137A1 US 201415025956 A US201415025956 A US 201415025956A US 2016265137 A1 US2016265137 A1 US 2016265137A1
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crystal film
gas
single crystal
growing
based single
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Ken Goto
Kohei Sasaki
Akinori Koukitu
Yoshinao Kumagai
Hisashi Murakami
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Tamura Corp
Tokyo University of Agriculture and Technology NUC
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Tamura Corp
Tokyo University of Agriculture and Technology NUC
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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
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/16—Controlling or regulating
    • C30B25/165—Controlling or regulating the flow of the reactive gases
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    • 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
    • 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
    • C23C16/44—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 method of coating
    • C23C16/448—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • 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
    • 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
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02414—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
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Definitions

  • the invention relates to a method for growing a ⁇ -Ga 2 O 3 -based single crystal film and a crystalline layered structure.
  • the MBE (Molecular Beam Epitaxy) method and the PLD (Pulsed Laser Deposition) method are known as a growth method of ⁇ -Ga 2 O 3 single crystal film (see, e.g., PTL 1 and PTL 2).
  • Other growth methods thereof, the sol-gel process, the MOCVD (Metal Organic Chemical Vapor Deposition) process and the mist CVD process are also known.
  • the MBE method is conducted, however, such that crystal is grown in a high vacuum chamber.
  • it is difficult to increase the diameter of a ⁇ -Ga 2 O 3 single crystal film.
  • a high-quality film can be generally obtained by increasing the growth temperature, a sufficient film growth rate is not obtained due to an increase in re-evaporation of source gases and it is thus not suitable for mass production.
  • the PLD method is not suitable for growing a film with a large area since a source (a raw material supply source to a substrate) is a point source which causes a growth rate to be different between a portion immediately above the source and other portions and in-plane distribution of film thickness is likely to be non-uniform. In addition, it takes long time to form a thick film due to a low film growth rate, hence, not suitable for mass production.
  • the MOCVD method and the mist CVD method it is relatively easy to increase a diameter but it is difficult to obtain single crystal films with high purity since impurities contained in the used materials are incorporated into the ⁇ -Ga 2 O 3 single crystal film during epitaxial growth.
  • a growth method of a ⁇ -Ga 2 O 3 -based single crystal film defined by [ 1 ] to [ 8 ] below will be provided.
  • a method for growing a ⁇ -Ga 2 O 3 -based single crystal film by HVPE method comprising a step of exposing a Ga 2 O 3 -based substrate to a gallium chloride-based gas and an oxygen-including gas and growing a ⁇ -Ga 2 O 3 -based single crystal film on a principal surface of the Ga 2 O 3 -based substrate at a growth temperature of not lower than 900° C.
  • a crystalline layered structure comprising:
  • a method for growing a ⁇ -Ga 2 O 3 -based single crystal film can be provided that allows a high-quality and large-diameter ⁇ -Ga 2 O 3 -based single crystal film to grow efficiently, as well as a crystalline layered structure having the ⁇ -Ga 2 O 3 -based single crystal film grown by the method.
  • FIG. 1 is a vertical cross-sectional view showing a crystalline layered structure in an embodiment.
  • FIG. 2 is a vertical cross-sectional view showing a vapor phase deposition system in the embodiment.
  • FIG. 3 is a graph showing a relation, based on calculation of thermal equilibrium, between a driving force for growth and a growth temperature of Ga 2 O 3 crystal in the case that a gallium chloride gas is only of a GaCl gas and a GaCl 3 gas, respectively.
  • FIG. 4 is a graph showing a relation, based on calculation of thermal equilibrium, between an atmosphere temperature and equilibrium partial pressures of GaCl gas, GaCl 2 gas, GaCl 3 gas and (GaCl 3 ) 2 gas which are obtained by reaction of Ga with Cl 2 .
  • FIG. 5 is a graph showing a relation, based on calculation of thermal equilibrium, between equilibrium partial pressure of GaCl and an O 2 /GaCl supplied partial pressure ratio when the atmosphere temperature during Ga 2 O 3 crystal growth is 1000° C.
  • FIG. 6 is a graph showing X-ray diffraction spectra obtained by 2 ⁇ - ⁇ scan on crystalline layered structure in each of which a Ga 2 O 3 single crystal film is epitaxially grown on a (010)-oriented principal surface of a Ga 2 O 3 substrate.
  • FIG. 7 is a graph showing an X-ray diffraction spectrum obtained by 2 ⁇ - ⁇ scan on a crystalline layered structure in which a Ga 2 O 3 single crystal film is epitaxially grown on a ( ⁇ 201)-oriented principal surface of a Ga 2 O 3 substrate at 1000° C.
  • FIG. 8 is a graph showing an X-ray diffraction spectrum obtained by 2 ⁇ - ⁇ scan on a crystalline layered structure in which a Ga 2 O 3 single crystal film is epitaxially grown on a (001)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • FIG. 9 is a graph showing an X-ray diffraction spectrum obtained by 2 ⁇ - ⁇ scan on a crystalline layered structure in which a Ga 2 O 3 single crystal film is epitaxially grown on a (101)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • FIG. 10A is a graph showing the concentration of impurities in the crystalline layered structure measured by secondary ion mass spectrometry (SIMS).
  • FIG. 10B is a graph showing the concentration of impurities in the crystalline layered structure measured by secondary ion mass spectrometry (SIMS).
  • FIG. 11A is a graph showing the carrier concentration profile in a depth direction of the crystalline layered structure in which a ⁇ -Ga 2 O 3 crystal film is epitaxially grown on a (001)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • FIG. 11B is a graph showing the voltage endurance characteristics of the crystalline layered structure in which a ⁇ -Ga 2 O 3 crystal film is epitaxially grown on a (001)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • FIG. 12 is a graph showing a carrier concentration profile in a depth direction of the crystalline layered structure in which a ⁇ -Ga 2 O 3 crystal film is epitaxially grown on a (010)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • FIG. 1 is a vertical cross-sectional view showing a crystalline layered structure 1 in an embodiment.
  • the crystalline layered structure 1 has a Ga 2 O 3 -based substrate 10 and a ⁇ -Ga 2 O 3 -based single crystal film 12 formed on a principal surface 11 of the Ga 2 O 3 -based substrate 10 by epitaxial crystal growth.
  • the Ga 2 O 3 -based substrate 10 is a substrate formed of a Ga 2 O 3 -based single crystal with a ⁇ -crystal structure.
  • the Ga 2 O 3 -based single crystal here means a Ga 2 O 3 single crystal or is a Ga 2 O 3 single crystal doped with an element such as Al or In, and may be, e.g., a (Ga x Al y In( 1-x-y )) 2 O 3 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x+y ⁇ 1) single crystal which is a Ga 2 O 3 single crystal doped with Al and In.
  • the band gap is widened by adding Al and is narrowed by adding In.
  • the Ga 2 O 3 -based substrate 10 may contain a conductive impurity such as Si.
  • the plane orientation of the principal surface 11 of the Ga 2 O 3 -based substrate 10 is, e.g., (010), ( ⁇ 201), (001) or (101).
  • a bulk crystal of a Ga 2 O 3 -based single crystal grown by, e.g., a melt-growth technique such as the FZ (Floating Zone) method or the EFG (Edge Defined Film Fed Growth) method is sliced and the surface thereof is then polished.
  • the ⁇ -Ga 2 O 3 -based single crystal film 12 is formed of a Ga 2 O 3 -based single crystal with a ⁇ -crystal structure in the same manner as the Ga 2 O 3 -based substrate 10 .
  • the ⁇ -Ga 2 O 3 -based single crystal film 12 may contain a conductive impurity such as Si.
  • a structure of a vapor phase deposition system used for growing the ⁇ -Ga 2 O 3 -based single crystal film 12 in the present embodiment will be described below as an example.
  • FIG. 2 is a vertical cross-sectional view showing a vapor phase deposition system 2 in the embodiment.
  • the vapor phase deposition system 2 is a vapor phase deposition system using HVPE (Halide Vapor Phase Epitaxy) technique, and has a reaction chamber 20 having a first gas introducing port 21 , a second gas introducing port 22 , a third gas introducing port 23 and an exhaust port 24 , and a first heating means 26 and a second heating means 27 which are placed around the reaction chamber 20 to heat predetermined regions in the reaction chamber 20 .
  • HVPE Hydrode Vapor Phase Epitaxy
  • the growth rate when using the HVPE technique is higher than that in the PLD method, etc.
  • in-plane distribution of film thickness is highly uniform and it is possible to grow a large-diameter film. Therefore, it is suitable for mass production of crystal.
  • the reaction chamber 20 has a source reaction region R 1 in which a reaction container 25 containing a Ga source is placed and a gallium source gas is produced, and a crystal growth region R 2 in which the Ga 2 O 3 -based substrate 10 is placed and the ⁇ -Ga 2 O 3 -based single crystal film 12 is grown thereon.
  • the reaction chamber 20 is formed of, e.g., quartz glass.
  • reaction container 25 is formed of, e.g., quartz glass and the Ga source contained in the reaction container 25 is metal gallium.
  • the first heating means 26 and the second heating means 27 are capable of respectively heating the source reaction region R 1 and the crystal growth region R 2 of the reaction chamber 20 .
  • the first heating means 26 and the second heating means 27 are, e.g., resistive heaters or radiation heaters.
  • the first gas introducing port 21 is a port for introducing a Cl-containing gas (Cl 2 gas or HCl gas) into the source reaction region R 1 of the reaction chamber 20 using an inert carrier gas (N 2 gas, Ar gas or He gas).
  • the second gas introducing port 22 is a port for introducing an oxygen-containing gas (O 2 gas or H 2 O gas, etc.) as an oxygen source gas and a chloride gas (e.g., silicon tetrachloride, etc.) used to add a dopant such as Si to the ⁇ -Ga 2 O 3 -based single crystal film 12 , into the crystal growth region R 2 of the reaction chamber 20 using an inert carrier gas (N 2 gas, Ar gas or He gas).
  • the third gas introducing port 23 is a port for introducing an inert carrier gas (N 2 gas, Ar gas or He gas) into the crystal growth region R 2 of the reaction chamber 20 .
  • a process of growing the ⁇ -Ga 2 O 3 -based single crystal film 12 in the present embodiment will be described below as an example.
  • the source reaction region R 1 of the reaction chamber 20 is heated by the first heating means 26 and an atmosphere temperature in the source reaction region R 1 is then maintained at a predetermined temperature.
  • a Cl-containing gas introduced through the first gas introducing port 21 using a carrier gas is reacted with the metal gallium in the reaction container 25 at the above-mentioned atmosphere temperature, thereby producing a gallium chloride gas.
  • the atmosphere temperature in the source reaction region R 1 here is preferably a temperature at which GaCl gas has the highest partial pressure among component gases of the gallium chloride gas produced by the reaction of the metal gallium in the reaction container 25 with the Cl-containing gas.
  • the gallium chloride gas here contains GaCl gas, GaCl 2 gas, GaCl 3 gas and (GaCl 3 ) 2 gas, etc.
  • the temperature at which a driving force for growth of Ga 2 O 3 crystal is maintained is the highest with the GaCl gas among the gases contained in the gallium chloride gas. Growth at a high temperature is effective to obtain a high-quality Ga 2 O 3 crystal with high purity. Therefore, for growing the ⁇ -Ga 2 O 3 -based single crystal film 12 , it is preferable to produce a gallium chloride gas in which a partial pressure of GaCl gas having a high driving force for growth at a high temperature is high.
  • FIG. 3 is a graph showing a relation, based on calculation of thermal equilibrium, between a driving force for growth and a growth temperature of Ga 2 O 3 crystal respectively when a gallium chloride gas consists of only a GaCl gas and consists of only a GaCl 3 gas.
  • the calculation conditions are as follows: a carrier gas is, e.g., an inert gas such as N 2 , a furnace pressure is 1 atom, the supplied partial pressures of GaCl gas and GaCl 3 gas are both 1 ⁇ 10 ⁇ 3 atom, and an O 2 /GaCl partial pressure ratio is 10.
  • the horizontal axis indicates a growth temperature (° C.) of Ga 2 O 3 crystal and the vertical axis indicates a driving force for crystal growth.
  • the Ga 2 O 3 crystal grows more efficiently with a larger driving force for crystal growth.
  • FIG. 3 shows that the maximum temperature at which the driving force for growth is maintained is higher when using the GaCl gas as a Ga source gas than when using the GaCl 3 gas.
  • FIG. 4 is a graph showing a relation, based on calculation of thermal equilibrium, between an atmosphere temperature during reaction and equilibrium partial pressures of GaCl gas, GaCl 2 gas, GaCl 3 gas and (GaCl 3 ) 2 gas which are obtained by reaction of Ga with Cl 2 .
  • the other calculation conditions are as follows: a carrier gas is, e.g., an inert gas such as N 2 , a furnace pressure is 1 atom and the supplied partial pressure of Cl 2 gas is 3 ⁇ 10 ⁇ 3 atom.
  • the horizontal axis indicates an atmosphere temperature (° C.) and the vertical axis indicates an equilibrium partial pressure (atm). It is shown that more gas is produced at a higher equilibrium partial pressure.
  • FIG. 4 shows that when reacting the metal gallium chloride with the Cl-containing gas at an atmosphere temperature of about not less than 300° C., the equilibrium partial pressure of GaCl gas particularly capable of increasing a driving force for growth of Ga 2 O 3 crystal is increased, i.e., a partial pressure ratio of the GaCl gas with respect to the gallium chloride gas becomes higher. Based on this, it is preferable that the metal gallium in the reaction container 25 be reacted with the Cl-containing gas in a state that the atmosphere temperature in the source reaction region R 1 is maintained at not less than 300° C. by using the first heating means 26 .
  • the partial pressure ratio of the GaCl gas is predominantly high (the equilibrium partial pressure of the GaCl gas is four orders of magnitude greater than the GaCl 2 gas and is eight orders of magnitude greater than the GaCl 3 gas) and the gases other than GaCl gas hardly contribute to the growth of Ga 2 O 3 crystal.
  • the metal gallium in the reaction container 25 be reacted with the Cl-containing gas in a state that the atmosphere temperature in the source reaction region R 1 is maintained at not more than 1000° C.
  • the gallium chloride gas produced in the source reaction region R 1 is mixed with the oxygen-containing gas introduced through the second gas introducing port 22 and the Ga 2 O 3 -based substrate 10 is exposed to the mixed gas, thereby epitaxially growing the ⁇ -Ga 2 O 3 -based single crystal film 12 on the Ga 2 O 3 -based substrate 10 .
  • pressure in the crystal growth region R 2 is maintained at, e.g., 1 atm.
  • a source gas of the additive element e.g., a chloride gas such as silicon tetrachloride (SiCl 4 )
  • SiCl 4 silicon tetrachloride
  • FIG. 5 is a graph showing a relation, based on calculation of thermal equilibrium, between an equilibrium partial pressure of GaCl and an O 2 /GaCl supplied partial pressure ratio when the atmosphere temperature during Ga 2 O 3 crystal growth is 1000° C.
  • a ratio of the supplied partial pressure of the O 2 gas to the supplied partial pressure of the GaCl gas is referred to as “O 2 /GaCl supplied partial pressure ratio”. It is calculated using the supplied partial pressure value of the GaCl gas fixed to 1 ⁇ 10 ⁇ 3 atom, a furnace pressure of 1 atom adjusted by using, e.g., an inert gas such as N 2 as a carrier gas, and various values of the O 2 gas supplied partial pressure.
  • the horizontal axis indicates the O 2 /GaCl supplied partial pressure ratio and the vertical axis indicates an equilibrium partial pressure (atm) of the GaCl gas. It is shown that the smaller the supplied partial pressure of the GaCl gas, the more the GaCl gas is consumed for growth of Ga 2 O 3 crystal, i.e., the Ga 2 O 3 crystal grows efficiently.
  • FIG. 5 shows that the equilibrium partial pressure of the GaCl gas sharply falls at the O 2 /GaCl supplied partial pressure ratio of not less than 0.5.
  • the ⁇ -Ga 2 O 3 -based single crystal film 12 is preferably grown in a state that a ratio of the supplied partial pressure of the O 2 gas to the supplied partial pressure of the GaCl gas in the crystal growth region R 2 is not less than 0.5.
  • FIG. 6 is a graph showing X-ray diffraction spectra obtained by 2 ⁇ - ⁇ scan on crystalline layered structures in each of which a Ga 2 O 3 single crystal film is epitaxially grown on a (010)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • the growth conditions are as follows: a furnace pressure is 1 atom, a carrier gas is N 2 gas, the GaCl supplied partial pressure is 5 ⁇ 10 ⁇ 4 atom, and the O 2 /GaCl supplied partial pressure ratio is 5.
  • the horizontal axis indicates an angle 2 ⁇ (degrees) formed between the incident direction and the reflected direction of X-ray and the vertical axis indicates diffraction intensity (arbitrary unit) of the X-ray.
  • FIG. 6 shows a spectrum from a ⁇ -Ga 2 O 3 substrate (without ⁇ -Ga 2 O 3 crystal film) and spectra from crystalline layered structures having ⁇ -Ga 2 O 3 crystal films respectively epitaxially grown at 800° C., 850° C., 900° C., 950° C., 1000° C. and 1050° C.
  • the ⁇ -Ga2O 3 crystal films of these crystalline layered structures have a thickness of about 300 to 1000 nm.
  • a ⁇ -Ga 2 O 3 single crystal film is obtained when a ⁇ -Ga 2 O 3 crystal film is grown at a growth temperature of not less than 900° C.
  • another Ga 2 O 3 -based substrate is used in place of the Ga 2 O 3 substrate or another Ga 2 O 3 -based crystal film is formed instead of the Ga 2 O 3 crystal film, evaluation results similar to those described above are obtained.
  • the ⁇ -Ga 2 O 3 -based single crystal film 12 is obtained by growing at a growth temperature of not less than 900° C.
  • FIG. 7 is a graph showing an X-ray diffraction spectrum obtained by 2 ⁇ - ⁇ scan on a crystalline layered structure in which a ⁇ -Ga 2 O 3 single crystal film is epitaxially grown on a ( ⁇ 201)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • the growth conditions for this ⁇ -Ga 2 O 3 single crystal film are as follows: a furnace pressure is 1 atom, a carrier gas is N 2 gas, the GaCl supplied partial pressure is 5 ⁇ 10 ⁇ 4 atom, the O 2 /GaCl supplied partial pressure ratio is 5 and the growth temperature is 1000° C.
  • FIG. 7 shows a spectrum from a ⁇ -Ga 2 O 3 substrate (without ⁇ -Ga 2 O 3 crystal film) having a ( ⁇ 201)-oriented principal surface and a spectrum from a crystalline layered structure having a ⁇ -Ga 2 O 3 crystal film epitaxially grown on the ⁇ -Ga 2 O 3 substrate at 1000° C.
  • the ⁇ -Ga 2 O 3 crystal film of this crystalline layered structure has a thickness of about 300 nm.
  • FIG. 8 is a graph showing an X-ray diffraction spectrum obtained by 2 ⁇ - ⁇ scan on a crystalline layered structure in which a Ga 2 O 3 single crystal film is epitaxially grown on a (001)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • the growth conditions for this ⁇ -Ga 2 O 3 single crystal film are as follows: a furnace pressure is 1 atom, a carrier gas is N 2 gas, the GaCl supplied partial pressure is 5 ⁇ 10 ⁇ 4 atom, the O 2 /GaCl supplied partial pressure ratio is 5 and the growth temperature is 1000° C.
  • FIG. 8 shows a spectrum from a ⁇ -Ga 2 O 3 substrate (without ⁇ -Ga 2 O 3 crystal film) having a (001)-oriented principal surface and a spectrum from a crystalline layered structure having a ⁇ -Ga 2 O 3 crystal film epitaxially grown on the ⁇ -Ga 2 O 3 substrate at 1000° C.
  • the ⁇ -Ga 2 O 3 crystal film of this crystalline layered structure has a thickness of about 6 ⁇ m.
  • FIG. 9 is a graph showing an X-ray diffraction spectrum obtained by 2 ⁇ - ⁇ scan on a crystalline layered structure in which a Ga 2 O 3 single crystal film is epitaxially grown on a (101)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • the growth conditions for this ⁇ -Ga 2 O 3 single crystal film are as follows: a furnace pressure is 1 atom, a carrier gas is N 2 gas, the GaCl supplied partial pressure is 5 ⁇ 10 ⁇ 4 atom, the O 2 /GaCl supplied partial pressure ratio is 5 and the growth temperature is 1000° C.
  • FIG. 9 shows a spectrum from a ⁇ -Ga 2 O 3 substrate (without ⁇ -Ga 2 O 3 crystal film) having a (101)-oriented principal surface and a spectrum from a crystalline layered structure having a ⁇ -Ga 2 O 3 crystal film epitaxially grown on the ⁇ -Ga 2 O 3 substrate at 1000° C.
  • the ⁇ -Ga 2 O 3 crystal film of this crystalline layered structure has a thickness of about 4 ⁇ m.
  • the horizontal axis indicates an angle 2 ⁇ (degrees) formed between the incident direction and the reflected direction of X-ray and the vertical axis indicates diffraction intensity (arbitrary unit) of the X-ray.
  • FIGS. 10A and 10B are graphs showing concentrations of impurities in the crystalline layered structure measured by secondary ion mass spectrometry (SIMS).
  • the horizontal axis indicates a depth ( ⁇ m) of the crystalline layered structure from a principal surface 13 of the ⁇ -Ga 2 O 3 single crystal film and the vertical axis indicates concentration (atoms/cm 3 ) of each impurity.
  • an interface between the ⁇ -Ga 2 O 3 substrate and the ⁇ -Ga 2 O 3 single crystal film is located at a depth of about 0.3 ⁇ m in the crystalline layered structure.
  • horizontal arrows on the right side in FIGS. 10A and 10B indicate the respective measurable lower limits of concentrations of the impurity elements.
  • the ⁇ -Ga 2 O 3 single crystal film of the crystalline layered structure used for the measurement is a film which is grown on the (010)-oriented principal surface of the ⁇ -Ga 2 O 3 substrate at a growth temperature of 1000° C.
  • FIG. 10A shows the concentrations of C, Sn, and Si in the crystalline layered structure and FIG. 10B shows the concentrations of H and Cl in the crystalline layered structure.
  • the concentration of each impurity element in the ⁇ -Ga 2 O 3 single crystal film is close to the measurable lower limit and is almost unchanged from the concentration in the Ga 2 O 3 substrate. This shows that the ⁇ -Ga 2 O 3 single crystal film is a highly pure film.
  • not more than about 5 ⁇ 10 16 (atoms/cm 3 ) of Cl is contained in the ⁇ -Ga 2 O 3 single crystal film.
  • the Ga 2 O 3 single crystal film is formed by the HVPE method using Cl-containing gas.
  • Cl-containing gas is not used to form a Ga 2 O 3 single crystal film when using a method other than the HVPE method, and the Ga 2 O 3 single crystal film does not contain Cl, or at least does not contain 1 ⁇ 10 16 (atoms/cm 3 ) or more of Cl.
  • FIG. 11A is a graph showing a carrier concentration profile in a depth direction of the crystalline layered structure in which a ⁇ -Ga 2 O 3 crystal film is epitaxially grown on a (001)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • the horizontal axis indicates a depth ( ⁇ m) from the surface of the ⁇ -Ga 2 O 3 crystal film and the vertical axis indicates a carrier concentration, i.e., a difference (cm ⁇ 3 ) between a donor concentration N d as a net donor concentration and an acceptor concentration N a .
  • a dotted curved line in the drawing is a theoretical curve showing a relation between the donor concentration and depletion layer thickness when relative permittivity of ⁇ -Ga 2 O 3 is 10 and built-in potential of ⁇ -Ga 2 O 3 in contact with Pt is 1.5V.
  • the procedure used to obtain the data shown in FIG. 11A is as follows. Firstly, an undoped ⁇ -Ga 2 O 3 crystal film having a thickness of about 15 ⁇ m is epitaxially grown on an Sn-doped n-type ⁇ -Ga 2 O 3 substrate having a (001)-oriented principal surface by the HVPE method. “Undoped” here means that intentional doping is not carried out, and it does not deny the presence of unintentional impurities.
  • the ⁇ -Ga 2 O 3 substrate is a 10 mm-square substrate having a thickness of 600 ⁇ m and has a carrier concentration of about 6 ⁇ 10 18 cm ⁇ 3 .
  • the growth conditions for this ⁇ -Ga 2 O 3 single crystal film are as follows: a furnace pressure is 1 atom, a carrier gas is N 2 gas, the GaCl supplied partial pressure is 5 ⁇ 10 ⁇ 4 atom, the O 2 /GaCl supplied partial pressure ratio is 5 and the growth temperature is 1000° C.
  • the surface of the undoped ⁇ -Ga 2 O 3 crystal film is polished 3 ⁇ m by CMP to flatten the surface.
  • a Schottky electrode is formed on the ⁇ -Ga 2 O 3 crystal film and an ohmic electrode on the ⁇ -Ga 2 O 3 substrate, and C-V measurement is conducted while changing bias voltage in a range of +0 to ⁇ 10V. Then, a carrier concentration profile in a depth direction is calculated based on the C-V measurement result.
  • the Schottky electrode here is an 800 ⁇ m-diameter circular electrode having a laminated structure in which a 15 nm-thick Pt film, a 5 nm-thick Ti film and a 250 nm-thick Au film are laminated in this order.
  • the ohmic electrode is a 10 mm-square electrode having a laminated structure in which a 50 nm-thick Ti film and a 300 nm-thick Au film are laminated in this order.
  • FIG. 11A no measurement point is present in a region shallower than 12 ⁇ m which is equal to the thickness of the ⁇ -Ga 2 O 3 crystal film, and all measurement points are 12 ⁇ m on the horizontal axis. This shows that the entire region of the ⁇ -Ga 2 O 3 crystal film is depleted in the bias voltage range of +0 to ⁇ 10V.
  • the entire region of the ⁇ -Ga 2 O 3 crystal film is naturally depleted at the bias voltage of 0. It is predicted that the residual carrier concentration in the ⁇ -Ga 2 O 3 crystal film is as very small as not more than 1 ⁇ 10 13 cm ⁇ 3 since the donor concentration is about 1 ⁇ 10 13 cm ⁇ 3 when the depletion layer thickness is 12 ⁇ m, based on the theoretical curve.
  • the residual carrier concentration in the ⁇ -Ga 2 O 3 crystal film is not more than 1 ⁇ 10 13 cm ⁇ 3 , for example, it is possible to control the carrier concentration in the ⁇ -Ga 2 O 3 crystal film in a range of 1 ⁇ 10 13 to 1 ⁇ 10 20 cm ⁇ 3 by doping a IV group element.
  • FIG. 11B is a graph showing voltage endurance characteristics of the above-mentioned crystalline layered structure.
  • the horizontal axis indicates applied voltage (V) and the vertical axis indicates current density (A/cm 2 ).
  • a dotted straight line in the drawing indicates the measurable lower limit value.
  • the procedure used to obtain the data shown in FIG. 11B is as follows. Firstly, the above-mentioned crystalline layered structure composed of a ⁇ -Ga 2 O 3 substrate and a ⁇ -Ga 2 O 3 crystal film is prepared.
  • a Schottky electrode is formed on the ⁇ -Ga 2 O 3 crystal film and an ohmic electrode on the ⁇ -Ga 2 O 3 substrate, and current density at an applied voltage of 1000V is measured.
  • the Schottky electrode here is a 200 ⁇ m-diameter circular electrode having a laminated structure in which a 15 nm-thick Pt film, a 5 nm-thick Ti film and a 250 nm-thick Au film are laminated in this order.
  • the ohmic electrode is a 10 mm-square electrode having a laminated structure in which a 50 nm-thick Ti film and a 300 nm-thick Au film are laminated in this order.
  • FIG. 11B shows that, even when voltage of 1000V is applied to the crystalline layered structure, leakage current is as very small as about 1 ⁇ 10 ⁇ 5 A/cm 2 and insulation breakdown does not occur. This result is considered to be due to that the ⁇ -Ga 2 O 3 crystal film is a high-quality crystal film with only few crystal defects and the donor concentration is low.
  • FIG. 12 is a graph showing a carrier concentration profile in a depth direction of the crystalline layered structure in which a ⁇ -Ga 2 O 3 crystal film is epitaxially grown on a (010)-oriented principal surface of a ⁇ -Ga 2 O 3 substrate.
  • the horizontal axis indicates a depth ( ⁇ m) from the surface of the ⁇ -Ga 2 O 3 crystal film and the vertical axis indicates a carrier concentration, i.e., a difference (cm ⁇ 3 ) between a donor concentration N d as a net donor concentration and an acceptor concentration N a .
  • a dotted curved line in the drawing is a theoretical curve showing a relation between the donor concentration and depletion layer thickness when relative permittivity of ⁇ -Ga 2 O 3 is 10 and built-in potential of ⁇ -Ga 2 O 3 in contact with Pt is 1.5V.
  • the procedure used to obtain the data shown in FIG. 12 is as follows. Firstly, an undoped ⁇ -Ga 2 O 3 crystal film having a thickness of about 0.9 ⁇ m is epitaxially grown on an Sn-doped n-type ⁇ -Ga 2 O 3 substrate having a (010)-oriented principal surface by the HVPE method.
  • the ⁇ -Ga 2 O 3 substrate is a 10 mm-square substrate having a thickness of 600 ⁇ m and has a carrier concentration of about 6 ⁇ 10 18 cm ⁇ 3 .
  • the growth conditions for this ⁇ -Ga 2 O 3 single crystal film are as follows: a furnace pressure is 1 atom, a carrier gas is N 2 gas, the GaCl supplied partial pressure is 5 ⁇ 10 ⁇ 4 atom, the O 2 /GaCl supplied partial pressure ratio is 5 and the growth temperature is 1000° C.
  • a Schottky electrode is formed on the undoped ⁇ -Ga 2 O 3 crystal film and an ohmic electrode on the ⁇ -Ga 2 O 3 substrate, and C-V measurement is conducted while changing bias voltage in a range of +0 to ⁇ 10V. Then, a carrier concentration profile in a depth direction is calculated based on the C-V measurement result.
  • the Schottky electrode here is a 400 ⁇ m-diameter circular electrode having a laminated structure in which a 15 nm-thick Pt film, a 5 nm-thick Ti film and a 250 nm-thick Au film are laminated in this order.
  • the ohmic electrode is a 10 mm-square electrode having a laminated structure in which a 50 nm-thick Ti film and a 300 nm-thick Au film are laminated in this order.
  • measurement points at a bias voltage of 0 are 0.85 ⁇ m on the horizontal axis (measurement points in a region deeper than 0.85 ⁇ m are measurement points when the bias voltage is close to 10V). It is predicted that the residual carrier concentration in the ⁇ -Ga 2 O 3 crystal film is as very small as not more than 3 ⁇ 10 15 cm ⁇ 3 since the donor concentration is about 2.3 ⁇ 10 15 cm ⁇ 3 when the depletion layer thickness is 0.85 ⁇ m, based on the theoretical curve.
  • the embodiment by controlling the conditions of producing the gallium source gas and the growth conditions for the ⁇ -Ga 2 O 3 -based single crystal film in the HVPE method, it is possible to efficiently grow a high-quality and large-diameter ⁇ -Ga 2 O 3 -based single crystal film.
  • the ⁇ -Ga 2 O 3 -based single crystal film has excellent crystal quality, it is possible to grow a good-quality crystal film on the ⁇ -Ga 2 O 3 -based single crystal film.
  • a high-quality semiconductor device can be manufactured by using the crystalline layered structure including the ⁇ -Ga 2 O 3 -based single crystal film in the present embodiment.
  • a method for efficiently growing a high-quality, large diameter ⁇ -Ga 2 O 3 -based single crystal film, and a crystalline layered structure having a ⁇ -Ga 2 O 3 -based single crystal film grown using this growing method are provided.

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