WO2020217564A1 - 半導体膜 - Google Patents

半導体膜 Download PDF

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WO2020217564A1
WO2020217564A1 PCT/JP2019/035514 JP2019035514W WO2020217564A1 WO 2020217564 A1 WO2020217564 A1 WO 2020217564A1 JP 2019035514 W JP2019035514 W JP 2019035514W WO 2020217564 A1 WO2020217564 A1 WO 2020217564A1
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semiconductor film
film
substrate
layer
plane
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French (fr)
Japanese (ja)
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守道 渡邊
福井　宏史
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to EP19925779.1A priority Critical patent/EP3960915A4/en
Priority to JP2020538744A priority patent/JP6784871B1/ja
Priority to CN201980093713.8A priority patent/CN113677834A/zh
Publication of WO2020217564A1 publication Critical patent/WO2020217564A1/ja
Priority to US17/450,706 priority patent/US20220029022A1/en
Anticipated expiration legal-status Critical
Priority to US19/019,799 priority patent/US20250159937A1/en
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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
    • C23C16/44—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
    • C23C16/4486—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 producing an aerosol and subsequent evaporation of the droplets or particles
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/029—Graded interfaces
    • 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
    • C30B25/14—Feed and outlet means for the gases; Modifying the flow of the reactive gases
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/40—Crystalline structures
    • H10D62/405—Orientations of crystalline planes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6755—Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate

Definitions

  • the present invention relates to a semiconductor film, more particularly ⁇ -Ga 2 O 3 based semiconductor film.
  • gallium oxide (Ga 2 O 3 ) has been attracting attention as a material for semiconductors.
  • Gallium oxide is known to have five crystal forms of ⁇ , ⁇ , ⁇ , ⁇ and ⁇ .
  • ⁇ -Ga 2 O 3 which is a metastable phase has a band gap of 5.3 eV. It is very large and is expected as a material for power semiconductors.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2014-72533 describes a semiconductor provided with a base substrate having a corundum-type crystal structure, a semiconductor layer having a corundum-type crystal structure, and an insulating film having a corundum-type crystal structure.
  • the apparatus is disclosed, and an example in which an ⁇ -Ga 2 O 3 film is formed as a semiconductor layer on a sapphire substrate is described.
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2016-25256
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2016-25256 contains an n-type semiconductor layer containing a crystalline oxide semiconductor having a corundum structure as a main component and an inorganic compound having a hexagonal crystal structure as a main component.
  • a semiconductor device including a p-type semiconductor layer and an electrode is disclosed.
  • Patent Document 2 on a c-plane sapphire substrate, the alpha-Ga 2 O 3 film having a corundum structure metastable phase as an n-type semiconductor layer, hexagonal as p-type semiconductor layer crystal structure It is disclosed that a diode is produced by forming an ⁇ -Rh 2 O 3 film having.
  • ⁇ -Ga 2 O 3 is a metastable phase
  • a single crystal substrate has not been put into practical use, and it is generally formed by heteroepitaxial growth on a sapphire substrate or the like.
  • stress is applied to the semiconductor film due to the difference in lattice constant with sapphire, and a large number of crystal defects may be formed or the semiconductor film may be warped.
  • Non-Patent Document 1 Applied Physics Express, vol.9, pages 071101-1 to 071101-4
  • a buffer layer between sapphire and ⁇ -Ga 2 O 3 Al x , Ga 1-x
  • x 0.2 ⁇ 0.9
  • example edge dislocation and screw dislocation is respectively becomes 3 ⁇ 10 8 / cm 2 and 6 ⁇ 10 8 / cm 2 is It is shown.
  • the dielectric breakdown electric field characteristics are affected by the number of crystal defects, so further reduction of crystal defects is desired.
  • the semiconductor film has a large warp, cracks are likely to occur and there is a risk of breakage during handling. That is, when a functional layer is formed on a semiconductor film having a large warp by a film forming method such as mist CVD, the film thickness and film quality may be distributed. Therefore, a semiconductor film having a small warp is desired.
  • the ⁇ -Ga 2 O 3 film is a so-called mosaic crystal in which a region (domain) in which tilt (inclination of the crystal axis in the growth direction) and twist (rotation of the crystal axis in the surface surface) are slightly different exists.
  • the film formation temperature is relatively low because the ⁇ -Ga 2 O 3 layer is a metastable phase.
  • the presence of grain boundaries between domains may reduce the dielectric breakdown electric field characteristics, so suppression of domain formation is also desired.
  • ⁇ -Ga 2 O 3 system the X-ray rocking curve half width of the (104) plane in at least one surface of the semiconductor film is set to be lower than or equal 500Arcsec, crystal defects significantly less alpha-Ga to obtain a finding that can provide 2 O 3 based semiconductor film.
  • an object of the present invention is to provide a crystal defect is significantly less ⁇ -Ga 2 O 3 based semiconductor film.
  • it is a semiconductor film having a corundum type crystal structure composed of ⁇ -Ga 2 O 3 or ⁇ -Ga 2 O 3 system solid solution, and is on at least one surface of the semiconductor film (104).
  • a semiconductor film having a surface X-ray locking curve half-price width of 500 arcsec or less is provided.
  • the semiconductor film of the present invention has a corundum-type crystal structure composed of an ⁇ -Ga 2 O 3 or ⁇ -Ga 2 O 3 system solid solution.
  • ⁇ -Ga 2 O 3 belongs to a trigonal crystal group and has a corundum-type crystal structure.
  • the ⁇ -Ga 2 O 3 system solid solution is a solid solution of other components in ⁇ -Ga 2 O 3 , and the corundum type crystal structure is maintained.
  • At least one of the surface (104) plane of the X-ray rocking curve (hereinafter, referred XRC FWHM) is not less 500arcsec less, preferably 150arcsec less, It is more preferably 100 arcsec or less, further preferably 50 arcsec or less, and particularly preferably 40 arcsec or less. That is, as a method for evaluating crystal defects and domains, a method is known in which X-ray locking curve (XRC) measurement of the (006) plane or the (104) plane is performed and the evaluation is performed in the half width.
  • XRC X-ray locking curve
  • XRC full width at half maximum reflects the amount of warpage in addition to crystal defects and domains.
  • the XRC full width at half maximum of the (104) plane is a region where various defects such as through-blade dislocations and penetrating spiral dislocations, tilt (tilt of the crystal axis in the growth direction) and twist (rotation of the crystal axis in the surface surface) are different ( Since it reflects all the mosaic properties of the domain) and the warped state, it is suitable as an evaluation method for semiconductor films. Therefore, when the XRC range width is within the above range, there are few crystal defects, the mosaic property is small (the domain is small), and the warp is also small, and as a result, on the surface (or inside) of such a semiconductor film.
  • At least one surface means at least one of two main surfaces (that is, a film surface or a plate surface) of the semiconductor film facing each other, regardless of the front surface or the back surface. The purpose.
  • the "surface” means an outer surface of an object, regardless of whether or not it is exposed to the outside (for example, in contact with or bonded to another object). May be).
  • the "front surface” shall mean the surface facing the "back surface”.
  • the surface of the ⁇ -Ga 2 O 3 based semiconductor film can be performed using the measurement of XRC profile, typical XRD apparatus (104) plane.
  • XRC profile typical XRD apparatus (104) plane.
  • a Bruker-AXS D8-DISCOVER is used as the XRD apparatus, 2 ⁇ , ⁇ , ⁇ , and ⁇ are adjusted so that the peak of the (104) plane of ⁇ -Ga 2 O 3 appears.
  • the tube voltage is 40 kV
  • the tube current is 40 mA
  • the collimator diameter is 0.5 mm
  • the anti-scattering slit is 3 mm
  • the range of ⁇ 15.5 to 19.5 °
  • the ⁇ step width is 0.005 °
  • the counting time is 0.5.
  • the measurement may be performed under the condition of seconds.
  • This measurement is preferably performed after converting CuK ⁇ rays into parallel monochromatic light with a Ge (022) asymmetric reflection monochromator. Then, the full width at half maximum in the XRC profile of the (104) plane is determined by performing a peak search after smoothing the profile using XRD analysis software (manufactured by Bruker-AXS, "LEPTOS” Ver4.03). Can be done.
  • the XRC half width of the (006) plane on at least one surface of the semiconductor film of the present invention is also small, preferably 50 arcsec or less, and more preferably 40 arcsec or less. There is no problem even if the XRC half width of the (006) plane is the same as the half width peculiar to the X-ray source used for the measurement, but in reality, it is preferably 30 arcsec or more.
  • the XRC full width at half maximum of the (006) plane reflects information on penetrating spiral dislocations, tilts and warpages.
  • the XRC full width at half maximum is within the above range, there are few crystal defects, the mosaic property is small (there are few domains), and the warp is also small, and as a result, on the surface (or inside) of such a semiconductor film. ), Crystal defects do not propagate inside the functional layer, and a high-quality functional layer having excellent characteristics such as higher dielectric breakdown electric field characteristics can be obtained.
  • ⁇ -Ga 2 O 3 based semiconductor film can be performed using the measurement is also typical XRD apparatus XRC profile (006) plane.
  • the measurement conditions are such that 2 ⁇ , ⁇ , ⁇ , and ⁇ are adjusted so that the peak of the (006) plane of ⁇ -Ga 2 O 3 appears.
  • one surface of the semiconductor film (hereinafter, referred to as front surface) for XRC FWHM of (104) plane in the (FWHM-T), the main semiconductor film FWHM-B / FWHM-T, which is the ratio of the full width at half maximum (FWHM-B) of the (104) plane on the front surface facing the front surface (hereinafter referred to as the back surface), has a relationship of FWHM-B / FWHM-T> 1. It is preferable to be in.
  • the film-forming side The XRC half-price width of the surface of the film may be smaller than the XRC half-price width of the surface adjacent to the film-forming substrate.
  • the XRC full width at half maximum reflects various defects and mosaic properties
  • the above relationship indicates that the quality of the front surface is improved rather than that of the back surface.
  • it means that crystal defects and mosaic properties were reduced during the film formation of the semiconductor film.
  • the FWHM-B / FWHM-T is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.3 or more, and particularly preferably 1.7 or more.
  • the upper limit of FWHM-B / FWHM-T is not particularly limited, but is, for example, 5.0 or less.
  • the back surface of the semiconductor film refers to the surface facing the surface (front surface) on the side where the XRC half width is small, but is typically used for film formation of the semiconductor film. Refers to the surface on the side adjacent to (or adjacent to) the underlying substrate.
  • the measurement of XRC profile (104) plane in ⁇ -Ga 2 O 3 based semiconductor film deposition base substrate for the adjacent surface is self-supporting surface of the film-forming side in the case of the semiconductor film ( It can be carried out in the same way as the front surface).
  • a support substrate hereinafter referred to as a first support substrate
  • a different support substrate hereinafter referred to as a second support substrate
  • the first support substrate is removed from the semiconductor film by peeling, grinding and polishing to remove the back surface of the semiconductor film.
  • the second support substrate and the joining and bonding method are not particularly limited as long as the semiconductor film can be supported without causing warpage of the semiconductor film.
  • a single crystal substrate such as sapphire or a substrate made of a material having a thermal expansion characteristic close to that of the semiconductor film such as a Cu—Mo composite material can be used.
  • an adhesive such as brazing, soldering, solid phase bonding, or epoxy can be used.
  • the method for removing the first support substrate is not particularly limited as long as it does not affect the quality of the semiconductor film.
  • the first support substrate when the first support substrate is removed by grinding and polishing, a altered layer due to processing is introduced into the semiconductor film, which may affect the XRC profile. Therefore, it is desirable to remove the work-altered layer introduced into the semiconductor film by CMP or ion milling after removing the support substrate. Further, as long as the XRC profile of the semiconductor film can be obtained, it is not necessary to remove all the first support substrates. That is, by making the first support substrate thin (for example, about 1 ⁇ m in thickness), X-rays can pass through the first support substrate to obtain an XRC profile of a semiconductor film.
  • ⁇ -Ga 2 O 3 based semiconductor film of the present invention preferably has a crystal defect density of the at least one surface is 1.0 ⁇ 10 6 / cm 2 or less, more preferably 1.0 ⁇ 10 5 / It is cm 2 or less, more preferably 4.0 ⁇ 10 3 / cm 2 or less, and particularly preferably 1.0 ⁇ 10 3 / cm 2 or less.
  • Such a semiconductor film having a remarkably low crystal defect density has excellent dielectric breakdown electric field characteristics and is suitable for use in power semiconductors.
  • the functional layer is formed on (or inside) such a surface, a high-quality functional layer having excellent characteristics such as high dielectric breakdown electric field characteristics can be obtained.
  • the lower limit of the crystal defect density is not particularly limited, and a lower limit is preferable.
  • the crystal defect refers to a through-blade dislocation, a through-spiral dislocation, a through-mixed dislocation, and a basal plane dislocation
  • the crystal defect density is the total of each dislocation density.
  • the basal plane dislocation is a problem when the semiconductor film has an off-angle, and is not a problem because the surface of the semiconductor film is not exposed when there is no off-angle.
  • the penetrating blade dislocations are 3 ⁇ 10 4 / cm 2
  • the penetrating spiral dislocations are 6 ⁇ 10 4 / cm 2
  • the penetrating mixed dislocations are 4 ⁇ 10 4 / cm 2
  • the crystal defect density is 1.3. It becomes ⁇ 10 5 / cm 2 .
  • crystal defect density of the ⁇ -Ga 2 O 3 based semiconductor film can be evaluated by a plane TEM observation (plan view), or cross-sectional TEM observation.
  • plane TEM observation plane view
  • cross-sectional TEM observation when the plane TEM observation of the surface of the semiconductor film is carried out, it can be carried out by using a general transmission electron microscope.
  • TEM observation may be performed at an accelerating voltage of 300 kV.
  • the test piece used for TEM observation is preferably one in which a sample is cut out so as to include one surface of the semiconductor film so that a measurement field of view of 50 ⁇ m ⁇ 50 ⁇ m can be observed.
  • the crystal defect density can be evaluated from the planar TEM image of the surface of the test piece thus obtained.
  • the semiconductor film of the present invention contains ⁇ -Ga 2 O 3 , Cr 2 O 3 , Fe 2 O 3 , Ti 2 O 3 , V 2 O 3 , Ir 2 O 3 , Rh 2 O 3 , and In 2 O 3. It can be composed of an ⁇ -Ga 2 O 3 system solid solution in which one or more components selected from the group consisting of Al 2 O 3 are solid-dissolved. All of these components have a corundum-type crystal structure and have relatively close lattice constants to each other. Therefore, the metal atoms of these components easily replace Ga atoms in the solid solution. Further, by dissolving these components in solid solution, it becomes possible to control the band gap, electrical characteristics, and / or lattice constant of the semiconductor film. The solid solution amount of these components can be appropriately changed according to the desired characteristics.
  • the semiconductor film can contain a Group 14 element as a dopant at a ratio of 1.0 ⁇ 10 16 to 1.0 ⁇ 10 21 / cm 3 .
  • the Group 14 element is the Group 14 element according to the periodic table formulated by the IUPAC (International Union of Pure and Applied Chemistry). Specifically, carbon (C), silicon (Si), and germanium (Ge). ), Tin (Sn) and lead (Pb).
  • the amount of dopant can be appropriately changed according to the desired characteristics, but is preferably 1.0 ⁇ 10 16 to 1.0 ⁇ 10 21 / cm 3 , and more preferably 1.0 ⁇ 10 17 to 1.0. ⁇ 10 19 / cm 3 .
  • these dopants are uniformly distributed in the film, and the concentrations of one front surface (front surface) and the opposite surface (back surface) are about the same. That is, it is preferable that the semiconductor film uniformly contains the Group 14 element as the dopant in the above ratio.
  • the semiconductor film is an alignment film oriented in a specific plane orientation, for example, a c-axis alignment film.
  • the orientation of the semiconductor film can be investigated by using a known method, but it can be investigated by performing reverse pole figure orientation mapping using, for example, an electron backscatter diffraction device (EBSD).
  • EBSD electron backscatter diffraction device
  • the thickness of the semiconductor film may be appropriately adjusted from the viewpoint of cost and required characteristics. That is, if it is too thick, it takes time to form a film, so it is preferable that the film is not extremely thick from the viewpoint of cost. Further, when a device that requires a particularly high dielectric strength is manufactured, a thick film is preferable. On the other hand, when manufacturing a device that requires conductivity in the vertical direction (thickness direction), a thin film is preferable. In this way, the film thickness may be appropriately adjusted according to the desired characteristics, but the thickness of the semiconductor film is typically 0.3 ⁇ m or more, more typically 0.3 to 50 ⁇ m, or 0.5. It is ⁇ 20 ⁇ m, or 0.5-10 ⁇ m.
  • a thick film may be used, for example, 50 ⁇ m or more, or 100 ⁇ m or more, and there is no particular upper limit unless there is a cost limitation.
  • the semiconductor film has an area of preferably 20 cm 2 or more, more preferably 70 cm 2 or more, and further preferably 170 cm 2 or more on one side thereof.
  • the upper limit of the size of the semiconductor film is not particularly limited, but is typically 700 cm 2 or less on one side.
  • the semiconductor film may be in the form of a self-supporting film of the film alone, or may be formed on a support substrate.
  • a substrate having a corundum structure and oriented in two axes of the c-axis and the a-axis (biaxially oriented substrate) is preferable.
  • a biaxially oriented substrate having a corundum structure as the support substrate, it is possible to serve as a seed crystal (base substrate for film formation) for heteroepitaxial growth of the semiconductor film.
  • the biaxially oriented substrate may be a polycrystal, a mosaic crystal (a set of crystals whose crystal orientations are slightly deviated), or a single crystal.
  • the main components of the support substrate are ⁇ -Al 2 O 3 , ⁇ -Cr 2 O 3 , ⁇ -Fe 2 O 3 , ⁇ -Ti 2 O 3 , ⁇ -V 2 O 3 , and ⁇ -Rh 2 O 3.
  • a solid solution containing two or more kinds selected from the group consisting of 3 is preferable, and a solid solution of ⁇ -Cr 2 O 3 or ⁇ -Cr 2 O 3 and a dissimilar material is particularly preferable.
  • corundum having sapphire, on corundum single crystal such as Cr 2 O 3 the a-axis length and / or c-axis length larger than the sapphire
  • a composite base substrate having an orientation layer made of a material having a type crystal structure can also be used.
  • the alignment layer is a material selected from the group consisting of ⁇ -Cr 2 O 3 , ⁇ -Fe 2 O 3 , ⁇ -Ti 2 O 3 , ⁇ -V 2 O 3 , and ⁇ -Rh 2 O 3.
  • ⁇ -Al 2 O 3 , ⁇ -Cr 2 O 3 , ⁇ -Fe 2 O 3 , ⁇ -Ti 2 O 3 , ⁇ -V 2 O 3 , and ⁇ -Rh 2 O 3 selected from the group. It is preferable to contain a solid solution containing two or more of them.
  • the semiconductor film formed on the film-forming substrate may be separated and reprinted on another support substrate.
  • the material of the other support substrate is not particularly limited, but a suitable material may be selected from the viewpoint of material physical properties.
  • a metal substrate such as Cu, a ceramic substrate such as SiC or AlN, or the like is preferable.
  • a support substrate having such a coefficient of thermal expansion By using a support substrate having such a coefficient of thermal expansion, the difference in thermal expansion from the semiconductor film can be reduced, and as a result, cracks and peeling of the semiconductor film due to thermal stress can be suppressed.
  • An example of such a support substrate is a substrate made of a Cu—Mo composite material.
  • the composite ratio of Cu and Mo can be appropriately selected in consideration of the coefficient of thermal expansion matching with the semiconductor film, the thermal conductivity, the conductivity and the like.
  • ⁇ -Cr 2 O 3 or a biaxially oriented substrate composed of a solid solution of ⁇ -Cr 2 O 3 and a dissimilar material, or ⁇ -Cr 2 O 3 or ⁇ -Cr 2 any of the composite substrate having O 3 and an alignment layer formed of a solid solution of different materials are preferred.
  • the semiconductor film of the present invention has extremely few crystal defects and can exhibit high dielectric breakdown electric field characteristics.
  • a technique for obtaining a semiconductor film having such a low crystal defect density has not been conventionally known.
  • a substrate in which (Al x , Ga 1-x ) 2 O 3 layer (x 0.2 to 0.9) is introduced as a buffer layer between sapphire and ⁇ -Ga 2 O 3 layer.
  • the formation of the ⁇ -Ga 2 O 3 layer using, the resulting ⁇ -Ga 2 O 3 layer, the density of the edge dislocation and screw dislocation respectively 3 ⁇ 10 8 / Cm 2 and 6 ⁇ 10 8 / cm 2 .
  • Manufacturing method a semiconductor film of a semiconductor film, ⁇ -Ga 2 O 3, or ⁇ -Ga 2 O 3 based semiconductor film having the corundum crystalline structure composed of a solid solution, (104) in at least one surface side of the X
  • the production method is not particularly limited as long as the film can be formed so that the half price width of the line locking curve is 500 arcsec or less.
  • a biaxially oriented substrate composed of a solid solution of ⁇ -Cr 2 O 3 or ⁇ -Cr 2 O 3 and a dissimilar material, or ⁇ -Cr 2 O 3 or ⁇ -Cr 2 O It is preferable to use any of the composite base substrates having an orientation layer composed of a solid solution of 3 and a different material as the base substrate for film formation.
  • a method for manufacturing a semiconductor film will be described in the order of (1) manufacturing of a composite substrate and (2) formation of a semiconductor film.
  • a sapphire substrate is prepared, (b) a predetermined orientation precursor layer is prepared, and (c) the orientation precursor layer is heat-treated on the sapphire substrate. It can be preferably produced by converting at least a portion near the sapphire substrate into an alignment layer and, if desired, performing processing such as (d) grinding or polishing to expose the surface of the alignment layer.
  • This alignment precursor layer becomes an alignment layer by heat treatment, and is a material having a corundum-type crystal structure whose a-axis length and / or c-axis length is larger than sapphire, or a-axis length and / or c-axis by heat treatment described later.
  • the orientation precursor layer may contain trace components in addition to the material having a corundum-type crystal structure. According to such a manufacturing method, the growth of the alignment layer can be promoted by using the sapphire substrate as a seed crystal. That is, the high crystallinity and crystal orientation orientation peculiar to a single crystal of a sapphire substrate are inherited by the alignment layer.
  • a sapphire substrate is prepared.
  • the sapphire substrate used may have any orientation plane. That is, it may have a-plane, c-plane, r-plane, and m-plane, and may have a predetermined off-angle with respect to these planes.
  • c-plane sapphire since it is c-axis oriented with respect to the surface, it is possible to easily heteroepitaxially grow an oriented layer oriented c-axis on it.
  • a sapphire substrate to which a dopant has been added in order to adjust the electrical characteristics.
  • dopants can be used as such dopants.
  • orientation precursor layer A material having a corundum-type crystal structure whose a-axis length and / or c-axis length is larger than sapphire, or a corundum-type crystal structure whose a-axis length and / or c-axis length is larger than sapphire by heat treatment.
  • An orientation precursor layer containing the material to be used is prepared.
  • the method for forming the orientation precursor layer is not particularly limited, and a known method can be adopted.
  • Examples of methods for forming an orientation precursor layer include AD (aerosol deposition) method, sol-gel method, hydrothermal method, sputtering method, thin-film deposition method, various CVD (chemical vapor deposition) methods, PLD method, and CVT (chemical vapor deposition) method. Methods such as the vapor phase transport method and the sublimation method can be mentioned.
  • Examples of the CVD method include a thermal CVD method, a plasma CVD method, a mist CVD method, an MO (organic metal) CVD method, and the like.
  • a method may be used in which a molded product of the orientation precursor is prepared in advance and the molded product is placed on a sapphire substrate.
  • Such a molded product can be produced by molding the material of the orientation precursor by a method such as tape molding or press molding. Further, it is also possible to use a method in which a polycrystal prepared in advance by various CVD methods or sintering is used as the orientation precursor layer and placed on a sapphire substrate.
  • a method of directly forming the orientation precursor layer by using an aerosol deposition (AD) method, various CVD methods, or a sputtering method is preferable.
  • AD aerosol deposition
  • various CVD methods various CVD methods
  • a sputtering method it becomes possible to form a dense orientation precursor layer in a relatively short time, and it becomes easy to cause heteroepitaxial growth using a sapphire substrate as a seed crystal.
  • the AD method does not require a high vacuum process and has a relatively high film formation rate, and is therefore preferable in terms of manufacturing cost.
  • the sputtering method it is possible to form a film using a target made of the same material as the orientation precursor layer, but it is also possible to use a reactive sputtering method in which a metal target is used to form a film in an oxygen atmosphere. it can.
  • a method of placing the molded product prepared in advance on sapphire is also preferable as a simple method, but since the orientation precursor layer is not dense, a process of densification is required in the heat treatment step described later.
  • the method using a polycrystalline body prepared in advance as the orientation precursor layer requires two steps, a step of preparing the polycrystalline body and a step of heat treatment on the sapphire substrate.
  • the AD method is a technology in which fine particles and fine particle raw materials are mixed with gas to form an aerosol, and this aerosol is jetted at high speed from a nozzle to collide with a substrate to form a film, which is said to be able to form a densified film at room temperature. It has characteristics.
  • FIG. 1 shows an example of a film forming apparatus (aerosol deposition (AD) apparatus) used in such an AD method.
  • the film forming apparatus 20 shown in FIG. 1 is configured as an apparatus used in the AD method of injecting raw material powder onto a substrate in an atmosphere of atmospheric pressure lower than atmospheric pressure.
  • the film forming apparatus 20 includes an aerosol generation unit 22 that generates an aerosol of a raw material powder containing a raw material component, and a film forming unit 30 that injects the raw material powder onto a sapphire substrate 21 to form a film containing the raw material component.
  • the aerosol generation unit 22 includes an aerosol generation chamber 23 that stores raw material powder and receives a carrier gas supply from a gas cylinder (not shown) to generate an aerosol, and a raw material supply pipe 24 that supplies the generated aerosol to the film forming unit 30.
  • the aerosol generation chamber 23 and the aerosol in the aerosol are provided with a vibration exciter 25 that vibrates at a frequency of 10 to 100 Hz.
  • the film-forming unit 30 has a film-forming chamber 32 that injects aerosols onto the sapphire substrate 21, a substrate holder 34 that is arranged inside the film-forming chamber 32 and fixes the sapphire substrate 21, and a substrate holder 34 on the X-axis-Y-axis. It is equipped with an XY stage 33 that moves in a direction. Further, the film forming section 30 includes an injection nozzle 36 having a slit 37 formed at the tip thereof to inject aerosol into the sapphire substrate 21, and a vacuum pump 38 for reducing the pressure in the film forming chamber 32.
  • the AD method can control the film thickness, film quality, etc. depending on the film forming conditions.
  • the form of the AD film is easily affected by the collision rate of the raw material powder with the substrate, the particle size of the raw material powder, the aggregated state of the raw material powder in the aerosol, the injection amount per unit time, and the like.
  • the collision speed of the raw material powder with the substrate is affected by the differential pressure between the film forming chamber 32 and the injection nozzle 36, the opening area of the injection nozzle, and the like. If appropriate conditions are not used, the coating may become a powder or pores, so it is necessary to control these factors appropriately.
  • the raw material powder of the orientation precursor can be molded to prepare the molded product.
  • the orientation precursor layer is a press molded body.
  • the press-molded product can be produced by press-molding the raw material powder of the orientation precursor based on a known method.
  • the raw material powder is placed in a mold, preferably 100 to 400 kgf / cm 2 , more preferably 150. It may be produced by pressing at a pressure of about 300 kgf / cm 2 .
  • the molding method is not particularly limited, and in addition to press molding, tape molding, casting molding, extrusion molding, a doctor blade method, and any combination thereof can be used.
  • additives such as a binder, a plasticizer, a dispersant, and a dispersion medium are appropriately added to the raw material powder to form a slurry, and the slurry is passed through a narrow slit-shaped discharge port to form a sheet. It is preferable to discharge and mold.
  • the thickness of the molded product formed into a sheet is not limited, but is preferably 5 to 500 ⁇ m from the viewpoint of handling. Further, when a thick orientation precursor layer is required, a large number of these sheet molded products may be stacked and used as a desired thickness.
  • the portion near the sapphire substrate becomes an orientation layer by the subsequent heat treatment on the sapphire substrate.
  • the molded product may contain trace components such as a sintering aid in addition to the material having or bringing about a corundum-type crystal structure.
  • (C) Heat treatment of the alignment precursor layer on the sapphire substrate The sapphire substrate on which the alignment precursor layer is formed is heat-treated at a temperature of 1000 ° C. or higher. By this heat treatment, at least a portion of the alignment precursor layer near the sapphire substrate can be converted into a dense alignment layer. Further, this heat treatment makes it possible to grow the oriented layer heteroepitaxially. That is, by forming the alignment layer with a material having a corundum-type crystal structure, heteroepitaxial growth occurs in which the material having a corundum-type crystal structure grows as a seed crystal using a sapphire substrate during heat treatment. At that time, the crystals are rearranged, and the crystals are arranged according to the crystal plane of the sapphire substrate.
  • the crystal axes of the sapphire substrate and the alignment layer can be aligned.
  • the sapphire substrate and the alignment layer can both be oriented in the c-axis with respect to the surface of the base substrate.
  • this heat treatment makes it possible to form a gradient composition region in a part of the alignment layer. That is, during the heat treatment, a reaction occurs at the interface between the sapphire substrate and the alignment precursor layer, and the Al component in the sapphire substrate diffuses into the alignment precursor layer and / or the component in the alignment precursor layer is in the sapphire substrate. Diffuses into a sapphire composition region composed of a solid solution containing ⁇ -Al 2 O 3 .
  • the orientation precursor layer is in a non-oriented state at the time of its production, that is, it is an amorphous or non-oriented polycrystal, and it is preferable to cause crystal rearrangement using sapphire as a seed crystal during this heat treatment step. By doing so, the crystal defects reaching the surface of the alignment layer can be effectively reduced. The reason for this is not clear, but it is thought that the rearrangement of the crystal structure of the solid-phase orientation precursor layer once formed using sapphire as a seed may be effective in eliminating crystal defects.
  • the heat treatment is not particularly limited as long as a corundum-type crystal structure is obtained and heteroepitaxial growth using a sapphire substrate as a seed occurs, and the heat treatment can be carried out in a known heat treatment furnace such as a tube furnace or a hot plate. Further, in addition to these heat treatments under normal pressure (pressless), pressure heat treatments such as hot press and HIP, and combinations of normal pressure heat treatments and pressure heat treatments can also be used.
  • the heat treatment conditions can be appropriately selected depending on the material used for the alignment layer.
  • the heat treatment atmosphere can be selected from atmospheric, vacuum, nitrogen and inert gas atmospheres.
  • the preferred heat treatment temperature also varies depending on the material used for the alignment layer, but is preferably 1000 to 2000 ° C, more preferably 1200 to 2000 ° C, for example.
  • the heat treatment temperature and holding time are related to the thickness of the alignment layer generated by heteroepitaxial growth and the thickness of the inclined composition region formed by diffusion with the sapphire substrate, and are related to the type of material, the target alignment layer, and the thickness of the inclined composition region. It can be adjusted as appropriate depending on the size. However, when a prefabricated molded product is used as an orientation precursor layer, it is necessary to sinter and densify it during heat treatment, and atmospheric firing at high temperature, hot pressing, HIP, or a combination thereof is preferable. ..
  • the surface pressure is preferably 50 kgf / cm 2 or more, more preferably 100 kgf / cm 2 or more, particularly preferably 200 kgf / cm 2 or more, the upper limit is not particularly limited.
  • the firing temperature is also not particularly limited as long as sintering, densification, and heteroepitaxial growth occur, but is preferably 1000 ° C. or higher, more preferably 1200 ° C. or higher, further preferably 1400 ° C. or higher, and particularly preferably 1600 ° C. or higher.
  • the firing atmosphere can also be selected from atmosphere, vacuum, nitrogen and an inert gas atmosphere.
  • the firing jig such as a mold, those made of graphite or alumina can be used.
  • an oriented precursor layer or a surface layer having poor orientation or no orientation may exist or remain.
  • the surface derived from the alignment precursor layer is subjected to processing such as grinding or polishing to expose the surface of the alignment layer.
  • processing such as grinding or polishing to expose the surface of the alignment layer.
  • a material having excellent orientation is exposed on the surface of the alignment layer, so that the semiconductor layer can be effectively epitaxially grown on the material.
  • the method for removing the orientation precursor layer and the surface layer is not particularly limited, and examples thereof include a method for grinding and polishing and a method for ion beam milling. Polishing of the surface of the alignment layer is preferably performed by lapping using abrasive grains or chemical mechanical polishing (CMP).
  • a semiconductor film is formed on the alignment layer of the obtained composite substrate.
  • a semiconductor film forming method as long as a semiconductor film having the characteristics specified in the present invention is obtained, in other words, the half width of the X-ray locking curve of the (104) plane on at least one surface of the semiconductor film is 500 arcsec or less.
  • a known method is possible. However, any one of mist CVD method, HVPE method, MBE method, MOCVD method, hydrothermal method and sputtering method is preferable, and mist CVD method, hydrothermal method or HVPE method is particularly preferable. Among these methods, the HVPE method will be described below.
  • the HVPE method (halide vapor deposition method) is a type of CVD and is a method applicable to film formation of compound semiconductors such as Ga 2 O 3 and GaN.
  • the Ga raw material and the halide are reacted to generate gallium halide gas, which is supplied onto the base substrate for film formation.
  • O 2 gas is supplied onto the film-forming substrate, and the gallium halide gas reacts with the O 2 gas to grow Ga 2 O 3 on the film-forming substrate. It is a method that enables high-speed and thick film growth and has a wide range of achievements in industry, and examples of film formation of ⁇ -Ga 2 O 3 as well as ⁇ -Ga 2 O 3 have been reported.
  • FIG. 2 shows an example of a vapor phase growth apparatus using the HVPE method.
  • the vapor phase growth apparatus 40 using the HVPE method includes a reaction furnace 50, a susceptor 58 on which a film-forming substrate 56 is placed, an oxygen raw material supply source 51, a carrier gas supply source 52, and a Ga raw material supply source 53.
  • a heater 54 and a gas discharge unit 57 are provided.
  • An arbitrary reaction furnace that does not react with the raw material is applied to the reaction furnace 50, for example, a quartz tube. Any heater capable of heating up to at least 700 ° C. (preferably 900 ° C. or higher) is applied to the heater 54, for example, a resistance heating type heater.
  • a metal Ga 55 is placed inside the Ga raw material supply source 53, and a halogen gas or a hydrogen halide gas, for example, HCl is supplied.
  • the halogen gas or halogenated gas is preferably Cl 2 or HCl.
  • the supplied halogen gas or halogenated gas reacts with the metal Ga55 to generate gallium halide gas, which is supplied to the film-forming base substrate 56.
  • the gallium halide gas preferably contains GaCl and / or GaCl 3 .
  • the oxygen raw material supply source 51 can supply an oxygen source selected from the group consisting of O 2 , H 2 O and N 2 O, but O 2 is preferable. These oxygen raw material gases are supplied to the film-forming substrate 56 at the same time as the gallium halide gas.
  • the Ga raw material and the oxygen raw material gas may be supplied together with a carrier gas such as N 2 or a rare gas.
  • the gas discharge unit 57 may be connected to a vacuum pump such as a diffusion pump or a rotary pump, for example, and controls not only the discharge of unreacted gas in the reaction furnace 50 but also the inside of the reaction furnace 50 under reduced pressure. You may. This can suppress the gas phase reaction and improve the growth rate distribution.
  • a vacuum pump such as a diffusion pump or a rotary pump, for example, and controls not only the discharge of unreacted gas in the reaction furnace 50 but also the inside of the reaction furnace 50 under reduced pressure. You may. This can suppress the gas phase reaction and improve the growth rate distribution.
  • ⁇ -Ga 2 O 3 is formed on the film-forming base substrate 56 by heating the film-forming base substrate 56 to a predetermined temperature using the heater 54 and simultaneously supplying the gallium halide gas and the oxygen raw material gas. Will be done.
  • the film forming temperature is not particularly limited as long as ⁇ -Ga 2 O 3 is formed, but is typically 250 ° C to 900 ° C, for example.
  • the partial pressure of the Ga raw material gas and the oxygen raw material gas is also not particularly limited.
  • the partial pressure of the Ga raw material gas may be in the range of 0.05 kPa or more and 10 kPa or less
  • the partial pressure of the oxygen raw material gas may be in the range of 0.25 kPa or more and 50 kPa or less.
  • ⁇ -Ga 2 O 3 system semiconductor film containing a Group 14 element as a dopant or when forming a mixed crystal film with ⁇ -Ga 2 O 3 containing an oxide of In or Al. May supply these halides and the like by providing a separate supply source, or may mix and supply the halides from the Ga raw material supply source 53. Further, a material containing a Group 14 element, In, Al or the like may be placed in the same place as the metal Ga55, reacted with a halogen gas or a hydrogen halide gas, and supplied as a halide. Similar to gallium halide, those halide gases supplied to the base substrate 56 for film formation react with the oxygen raw material gas to form oxides, which are incorporated into the ⁇ -Ga 2 O 3 system semiconductor film.
  • a single-layer structure film can be formed by keeping the supply amount of Ga raw material, oxygen raw material, etc. constant and appropriately controlling the film forming conditions. In this way, a semiconductor film having an extremely small X-ray locking curve full width at half maximum of 500 arcsec or less on the surface (104) can be formed on the composite substrate.
  • the semiconductor film of the present invention has extremely small warpage after being formed on the film-forming substrate or when separated from the film-forming substrate to form a self-standing film.
  • a biaxially oriented substrate composed of a solid solution of ⁇ -Cr 2 O 3 or ⁇ -Cr 2 O 3 and a different material, or ⁇ -Cr 2 O 3 or ⁇ -Cr.
  • the amount of warpage can be particularly reduced.
  • the amount of warpage when a 2-inch size semiconductor film is produced can be 30 ⁇ m or less, more preferably 20 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • the semiconductor film of the present invention can be a film having a small mosaic property.
  • the ⁇ -Ga 2 O 3 film formed on the conventional sapphire substrate may be an aggregate (mosaic crystal) of domains having slightly different crystal orientations. The cause of this is not clear, but it can be mentioned that the film formation temperature is relatively low because ⁇ -Ga 2 O 3 is a metastable phase. Since the film formation temperature is low, it is difficult for the adsorbed components to migrate on the substrate surface, and step flow growth is difficult. For this reason, the growth mode of island-like growth (three-dimensional growth) tends to be dominant.
  • the base substrate for film formation there may be a lattice mismatch between the semiconductor film and the sapphire, and the crystal orientation directions of the island-shaped growth portions (domains) may be slightly different from each other. For this reason, the domains do not meet completely and tend to form mosaic crystals.
  • the semiconductor film of the present invention in particular as film formation base substrate, ⁇ -Cr 2 O 3, or ⁇ -Cr 2 O 3 and single crystal substrate composed of a solid solution of different materials, or ⁇ -Cr 2 O 3
  • the film formation temperature is, for example, 600 ° C. or higher, preferably 700 ° C. or higher, more preferably 800 ° C. or higher, and further preferably 900 ° C. or higher.
  • known methods such as XRC measurement, EBSD measurement, and TEM can be used, but the evaluation in the XRC half width as described above is particularly preferable.
  • the obtained semiconductor film can be formed as it is or divided into semiconductor elements.
  • the semiconductor film may be peeled off from the composite substrate to form a single film.
  • a peeling layer may be provided in advance on the alignment layer surface (deposition surface) of the composite base substrate.
  • Examples of such a release layer include those provided with a C injection layer and an H injection layer on the surface of the composite substrate. Further, C or H may be injected into the film at the initial stage of film formation of the semiconductor film to provide a release layer on the semiconductor film side.
  • a support substrate (mounting substrate) different from the composite substrate is adhered and bonded to the surface of the semiconductor film formed on the composite substrate (that is, the surface opposite to the composite substrate), and then the semiconductor film is formed. It is also possible to peel off the composite substrate from the substrate.
  • a support substrate (mounting substrate) a substrate having a coefficient of thermal expansion at 25 to 400 ° C. of 6 to 13 ppm / K, for example, a substrate made of a Cu—Mo composite material can be used.
  • known methods such as brazing, soldering, and solid phase bonding can be mentioned.
  • an electrode such as an ohmic electrode or a Schottky electrode, or another layer such as an adhesive layer may be provided between the semiconductor film and the support substrate.
  • Example 1 A commercially available Cr 2 O 3 single crystal (size 8 mm ⁇ 8 mm, thickness 0.5 mm, c-plane, no off-angle) (hereinafter referred to as Cr 2 O 3 substrate) is used as the base substrate for film formation, and is as follows. Then, an ⁇ -Ga 2 O 3 film (semiconductor film) was formed.
  • FIG. 3 schematically shows the mist CVD device 61 used in this example.
  • the mist CVD apparatus 61 includes a dilution gas source 62a, a carrier gas source 62b, a flow rate control valve 63b, a mist generation source 64, a container 65, an ultrasonic vibrator 66, a quartz tube 67, a heater 68, a susceptor 70, and an exhaust port 71.
  • a substrate 69 is placed on the susceptor 70.
  • the flow rate control valve 63a is configured to be able to adjust the flow rate of the dilution gas sent out from the dilution gas source 62a, while the flow rate control valve 63b is configured to be able to adjust the flow rate of the carrier gas sent out from the carrier gas source 62b.
  • the raw material solution 64a is contained in the mist generation source 64, while water 65a is contained in the container 65.
  • the ultrasonic transducer 66 is attached to the bottom surface of the container 65.
  • the quartz tube 67 forms a film forming chamber, and a heater 68 is installed in the peripheral portion of the quartz tube 67.
  • the susceptor 70 is made of quartz, and the surface on which the substrate 69 is placed is inclined from the horizontal plane.
  • the flow rate of the dilution gas was adjusted to 0.5 L / min and the flow rate of the carrier gas was adjusted to 1 L / min, respectively.
  • Nitrogen gas was used as the dilution gas and the carrier gas.
  • the ultrasonic transducer 66 was vibrated at 2.4 MHz, and the vibration was propagated to the raw material solution 64a through water 65a to mist the raw material solution 64a to generate mist 64b.
  • This mist 64b is introduced into the quartz tube 67, which is a film forming chamber, by a diluent gas and a carrier gas, reacts in the quartz tube 67, and forms a film on the substrate 69 by a CVD reaction on the surface of the substrate 69. It was. In this way, a crystalline semiconductor film (semiconductor layer) was obtained.
  • the film formation time was 60 minutes.
  • EBSD Film surface on the film formation side composed of Ga oxide by SEM (Hitachi High-Technologies Corporation, SU-5000) equipped with an electron backscatter diffraction device (EBSD) (Nordlys Nano manufactured by Oxford Instruments). Inverse pole map orientation mapping was performed with a field of view of 500 ⁇ m ⁇ 500 ⁇ m. The conditions for this EBSD measurement were as follows.
  • the Ga oxide film has a corundum-type crystal structure with c-axis orientation in the normal direction of the substrate and biaxial orientation with in-plane orientation. From these, it was shown that an alignment film made of ⁇ -Ga 2 O 3 was formed.
  • a Ge (022) asymmetric reflection monochromator was used to convert CuK ⁇ rays into parallel monochromatic light.
  • the full width at half maximum (FWHM) of the obtained (104) plane XRC profile shall be peak-searched after smoothing the profile using XRD analysis software (Made by Bruker-AXS, "LEPTOS” Ver4.03).
  • XRD analysis software Mode by Bruker-AXS, "LEPTOS” Ver4.03
  • Example 2 Formation of ⁇ -Ga 2 O 3 film in the same manner as in Example 1 except that the raw material solution in (1b) above was prepared as follows and the film formation time in (1d) above was set to 130 minutes. And various evaluations were performed. The results were as shown in Table 1.
  • Example 3 The ⁇ -Ga 2 O 3 film was formed in the same manner as in Example 1 except that the temperature inside the quartz tube 67 was set to 460 ° C. in the above (1c) and the film formation time in the above (1d) was set to 200 minutes. Formation and various evaluations were performed. The results were as shown in Table 1.
  • Example 4 In the above (1b'), tin (II) chloride dihydrate was added so that the atomic ratio of tin to gallium was 5.0 ⁇ 10-6, and in the above (1c), the temperature inside the quartz tube 67 was adjusted. The formation of the ⁇ -Ga 2 O 3 film and various evaluations were carried out in the same manner as in Example 2 except that the temperature was set to 460 ° C. and the film formation time was set to 110 minutes in (1d) above. The results were as shown in Table 1.
  • Example 5 A composite substrate prepared as follows was used as the substrate for film formation, and tin (II) chloride dihydration was used so that the atomic ratio of tin to gallium was 0.7 in (1b') above.
  • the formation of the ⁇ -Ga 2 O 3 film and various evaluations were carried out in the same manner as in Example 2 except that the substance was added and the film formation time was set to 280 minutes in the above (1d). The results were as shown in Table 1.
  • the AD film formation conditions were as follows. That is, the carrier gas was N 2, and a ceramic nozzle having a slit having a long side of 5 mm and a short side of 0.3 mm was used.
  • the scanning conditions of the nozzle are 0.5 mm / s, movement of 55 mm perpendicular to the long side of the slit and in the forward direction, movement of 5 mm in the direction of the long side of the slit, and vertical and return to the long side of the slit. Repeated scanning of moving 55 mm in the direction, moving 5 mm in the long side direction of the slit and in the direction opposite to the initial position, and when moving 55 mm from the initial position in the long side direction of the slit, scan in the opposite direction.
  • the cycle of returning to the initial position was set as one cycle, and this was repeated for 500 cycles.
  • the set pressure of the transport gas was adjusted to 0.06 MPa
  • the flow rate was adjusted to 6 L / min
  • the pressure in the chamber was adjusted to 100 Pa or less.
  • the thickness of the AD film (alignment precursor layer) formed in this manner was about 100 ⁇ m.
  • Cr, O and Al are detected in a range from the Cr oxide layer to a depth of 30 ⁇ m, and a Cr—Al oxide layer (gradient composition layer) having a thickness of about 30 ⁇ m is detected between the Cr oxide layer and the sapphire substrate.
  • a Cr—Al oxide layer gradient composition layer
  • the ratio of Cr and Al was different in the Cr—Al oxide layer, the Al concentration was high on the sapphire substrate side, and the Al concentration was low on the side close to the Cr oxide layer.
  • the Cr oxide layer is a layer having a biaxially oriented corundum-type crystal structure oriented in the c-axis direction in the substrate normal direction and also in the in-plane direction. .. From these, it was shown that the front surface of the substrate was formed with an orientation layer made of ⁇ -Cr 2 O 3 . Based on the above results, the manufacturing process of the composite base substrate is schematically shown in FIGS. 5 (a) to 5 (d).
  • (D3) XRD XRD in-plane measurement of the front surface of the substrate was performed using a multifunctional high-resolution X-ray diffraction (XRD) apparatus (D8 DISCOVER, manufactured by Bruker AXS Co., Ltd.). Specifically, after adjusting the Z-axis according to the height of the substrate surface, the (11-20) plane is adjusted with Chi, Phi, ⁇ , and 2 ⁇ to set the shaft under the following conditions. 2 ⁇ - ⁇ measurement was performed.
  • XRD X-ray diffraction
  • the a-axis length of the alignment layer was 4.961 ⁇ .
  • Example 6 Except that tin (II) chloride dihydrate was added so that the atomic ratio of tin to gallium was 0.2 in (1b') above, and the film formation time was 600 minutes in (1d) above.
  • the formation of the ⁇ -Ga 2 O 3 film and various evaluations were carried out in the same manner as in Example 5. The results were as shown in Table 1.

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