WO2021010237A1 - 酸化物半導体膜及び半導体装置 - Google Patents

酸化物半導体膜及び半導体装置 Download PDF

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WO2021010237A1
WO2021010237A1 PCT/JP2020/026642 JP2020026642W WO2021010237A1 WO 2021010237 A1 WO2021010237 A1 WO 2021010237A1 JP 2020026642 W JP2020026642 W JP 2020026642W WO 2021010237 A1 WO2021010237 A1 WO 2021010237A1
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film
oxide semiconductor
semiconductor layer
semiconductor film
oxide
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French (fr)
Japanese (ja)
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亮平 菅野
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Flosfia Inc
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Flosfia Inc
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Priority to JP2021532994A priority Critical patent/JPWO2021010237A1/ja
Priority to CN202080062724.2A priority patent/CN114342086A/zh
Publication of WO2021010237A1 publication Critical patent/WO2021010237A1/ja
Priority to US17/573,790 priority patent/US12107125B2/en
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    • 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
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • H10D30/471—High electron mobility transistors [HEMT] or high hole mobility transistors [HHMT]
    • H10D30/475—High electron mobility transistors [HEMT] or high hole mobility transistors [HHMT] having wider bandgap layer formed on top of lower bandgap active layer, e.g. undoped barrier HEMTs such as i-AlGaN/GaN HEMTs
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    • H10D30/64—Double-diffused metal-oxide semiconductor [DMOS] FETs
    • H10D30/66—Vertical DMOS [VDMOS] FETs
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    • H10D62/103—Constructional design considerations for preventing surface leakage or controlling electric field concentration for increasing or controlling the breakdown voltage of reverse-biased devices
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    • H10D62/106—Constructional design considerations for preventing surface leakage or controlling electric field concentration for increasing or controlling the breakdown voltage of reverse-biased devices by having particular doping profiles, shapes or arrangements of PN junctions; by having supplementary regions, e.g. junction termination extension [JTE]  having supplementary regions doped oppositely to or in rectifying contact with regions of the semiconductor bodies, e.g. guard rings with PN or Schottky junctions
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    • H10H20/833—Transparent materials

Definitions

  • the present invention relates to an oxide semiconductor film useful as a semiconductor and a semiconductor device and system using the oxide semiconductor film.
  • gallium oxide As a next-generation switching element capable of achieving high withstand voltage, low loss, and high heat resistance, semiconductor devices using gallium oxide (Ga 2 O 3 ) having a large bandgap are attracting attention, and are used for power semiconductor devices such as inverters. Expected to be applied. Moreover, it is expected to be applied as a light receiving / receiving device for LEDs, sensors, etc. due to its wide band gap. According to Non-Patent Document 1, the gallium oxide can control the bandgap by mixing indium and aluminum individually or in combination, and constitutes an extremely attractive material system as an InAlGaO-based semiconductor. ..
  • Non-Patent Document 2 and Patent Documents 1 and 2 mixed crystals of gallium oxide and aluminum oxide have been studied.
  • aluminum oxide has high insulating properties, is difficult to dope, and has a mobility of about 1 to 2 cm 2 / Vs at most, and it is difficult to obtain a mixed crystal of aluminum oxide and gallium oxide having excellent electrical characteristics. .. Therefore, a mixed crystal of aluminum oxide and gallium oxide, which is useful for semiconductor devices and has excellent electrical characteristics, has been desired.
  • An object of the present invention is to provide a novel and useful oxide semiconductor film having excellent semiconductor properties.
  • the present inventor is an oxide semiconductor film containing at least a metal oxide containing aluminum and gallium as a main component and having a mobility of 5 cm 2 / Vs or more.
  • the oxide semiconductor film thus obtained has excellent electrical characteristics and is useful for semiconductor devices, and can solve the above-mentioned conventional problems at once. I found that there is.
  • the present inventor completed the present invention by further studying after obtaining the above findings. That is, the present invention relates to the following invention.
  • the oxide semiconductor film of the present invention has good conductivity and is excellent in semiconductor characteristics.
  • FIG. It is a schematic block diagram of the film-forming apparatus used in an Example. It is a figure which shows the XRD measurement result in Example 1.
  • FIG. It is a figure which shows the XRD (X-ray Diffraction) measurement result in Example 2.
  • FIG. It is a figure which shows typically a preferable example of a Schottky barrier diode (SBD). It is a figure which shows typically a preferable example of a high electron mobility transistor (HEMT). It is a figure which shows typically a preferable example of a metal oxide film semiconductor field effect transistor (MOSFET). It is a figure which shows typically a preferable example of a junction field effect transistor (JFET).
  • SBD Schottky barrier diode
  • HEMT high electron mobility transistor
  • MOSFET metal oxide film semiconductor field effect transistor
  • JFET junction field effect transistor
  • IGBT insulated gate type bipolar transistor
  • LED light emitting element
  • LED light emitting element
  • LED light emitting element
  • power-source system typically a preferable example of a system apparatus.
  • power supply circuit diagram of a power supply device typically a preferable example of a power card.
  • the oxide semiconductor film of the present invention is an oxide semiconductor film containing at least a metal oxide containing aluminum and gallium as a main component, and is characterized by having a mobility of 5 cm 2 / Vs or more.
  • the "oxide semiconductor film” is not particularly limited as long as it is a film-like oxide semiconductor, and may be a crystalline film or an amorphous film. It may be a crystal film, a single crystal film, or a polycrystalline film. In the present invention, it is preferable that the oxide semiconductor film is a mixed crystal.
  • Metal oxide refers to those containing a metal element and oxygen.
  • the "main component” means that the metal oxide is contained in an atomic ratio of preferably 50% or more, more preferably 70% or more, still more preferably 90% or more with respect to all the components of the oxide semiconductor film. However, it means that it may be 100%.
  • the oxide semiconductor film preferably has a corundum structure.
  • the mobility refers to the mobility obtained by measuring the Hall effect, and in the embodiment of the present invention, the mobility is preferably 5 cm 2 / Vs or more, and the mobility is 5 cm 2 / Vs. The above is more preferable.
  • the carrier density of the oxide semiconductor film is not particularly limited, but in the embodiment of the present invention, it is preferably 1.0 ⁇ 10 16 / cm 3 or more and 1.0 ⁇ 10 20 / cm 3 or less. , 1.0 ⁇ 10 16 / cm 3 or more, more preferably 5.0 ⁇ 10 18 / cm 3 or less.
  • the oxide semiconductor film contains a dopant.
  • the dopant may be a p-type dopant or an n-type dopant, but in the embodiment of the present invention, the n-type dopant is preferable.
  • the n-type dopant include tin (Sn), germanium, silicon, titanium, zirconium, vanadium, niobium, and the like, and two or more of these elements.
  • the p-type dopant include Mg, H, Li, Na, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, Mn, Fe, Co, Ni, Pd, Cu, Ag, Au.
  • the p-type dopant is preferably a Group 1 metal or a Group 2 metal in the periodic table, more preferably a Group 2 metal, and most preferably magnesium (Mg). preferable.
  • the film thickness of the oxide semiconductor film is 500 nm or more because the effect of the semiconductor property of higher withstand voltage is exhibited.
  • the content of the aluminum is preferably 1 atomic% or more, more preferably 5 atomic% or more, and 15 atomic% or more with respect to the gallium. Most preferred.
  • the oxide semiconductor film having a band gap of 5.5 eV or more can be obtained.
  • the oxide semiconductor having more excellent electrical characteristics can be obtained even if the band gap is 5.5 eV or more.
  • the main surface of the oxide semiconductor film is the m-plane because it exhibits more excellent electrical characteristics.
  • the oxide semiconductor film preferably atomizes a first raw material solution containing at least aluminum to generate first atomized droplets, and further atomizes a second raw material solution containing at least gallium and dopant.
  • the second atomized droplet is generated (atomization step), and then the first atomized droplet is conveyed into the film forming chamber using the first carrier gas, and the second atomized droplet is transferred.
  • the first atomized droplet and the second atomized droplet are mixed in the film forming chamber, and the mixed atomized droplets are mixed.
  • the atomization step atomizes the raw material solution to obtain atomized droplets.
  • the atomized droplet may be a mist.
  • the atomization method is not particularly limited as long as the raw material solution can be atomized, and may be a known method, but in the present invention, the atomization method using ultrasonic waves is preferable.
  • Atomized droplets obtained using ultrasonic waves have a zero initial velocity and are preferable because they float in the air. For example, instead of spraying them like a spray, they float in space and are transported as a gas. It is very suitable because it is a possible atomized droplet and is not damaged by collision energy.
  • the size of the atomized droplet is not particularly limited and may be about several mm, but is preferably 50 ⁇ m or less, and more preferably 100 nm to 10 ⁇ m.
  • the first raw material solution is not particularly limited as long as it contains at least aluminum, and may contain an inorganic material or an organic material, but the present invention.
  • a solution in which aluminum is dissolved or dispersed in an organic solvent or water in the form of a complex or a salt can be preferably used as the first raw material solution.
  • the second raw material solution is not particularly limited as long as it contains at least gallium and the dopant, and may contain an inorganic material or an organic material, but the embodiment of the present invention.
  • a solution in which the gallium and the dopant are dissolved or dispersed in an organic solvent or water in the form of a complex or a salt can be preferably used as the second raw material solution.
  • the form of the complex include an acetylacetonate complex, a carbonyl complex, an ammine complex, and a hydride complex.
  • the salt form include organic metal salts (for example, metal acetate, metal oxalate, metal citrate, etc.), metal sulfide salts, nitrified metal salts, phosphor oxide metal salts, and metal halide metal salts (for example, metal chloride). Salts, metal bromide salts, metal iodide salts, etc.) and the like.
  • the solvent of the raw material solution is not particularly limited, and may be an inorganic solvent such as water, an organic solvent such as alcohol, or a mixed solution of an inorganic solvent and an organic solvent.
  • the solvent preferably contains water, and is also preferably a mixed solvent of water and acid. More specific examples of the water include pure water, ultra-pure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, fresh water, seawater, and the like. Ultra pure water is preferable.
  • the acid includes organic acids such as acetic acid, propionic acid, and butanoic acid; boron trifluoride, boron trifluoride etherate, boron trichloride, boron tribromide, and trifluoroacetic acid. , Trifluoromethanesulfonic acid, p-toluenesulfonic acid and the like.
  • the substrate is not particularly limited as long as it can support the oxide semiconductor film.
  • the material of the substrate is also not particularly limited as long as it does not interfere with the object of the present invention, and may be a known substrate, an organic compound, or an inorganic compound.
  • the shape of the substrate may be any shape and is effective for any shape, for example, plate-like, fibrous, rod-like, columnar, prismatic, such as a flat plate or a disk. Cylindrical, spiral, spherical, ring-shaped and the like can be mentioned, but in the present invention, a substrate is preferable.
  • the thickness of the substrate is not particularly limited in the present invention.
  • the substrate is not particularly limited as long as it does not interfere with the object of the present invention, and may be an insulator substrate, a semiconductor substrate, or a conductive substrate.
  • the substrate include a base substrate containing a substrate material having a corundum structure as a main component.
  • the "main component” means that the substrate material having the specific crystal structure has an atomic ratio of preferably 50% or more, more preferably 70% or more, still more preferably 90% with respect to all the components of the substrate material. It means that it is contained in% or more, and it means that it may be 100%.
  • the substrate material is not particularly limited and may be a known one as long as the object of the present invention is not impaired.
  • a sapphire substrate preferably an m-plane sapphire substrate
  • an ⁇ -type gallium oxide substrate preferably an m-plane ⁇ -type gallium oxide substrate
  • the like is preferable. Take as an example.
  • the substrate is a crystalline substrate, and it is also preferable that the substrate has an off angle of 0.2 ° to 12.0 °.
  • the mobility is 5 cm because gallium and aluminum are contained in the atomic ratio in the preferable range as described above and the carrier density is in the preferable range as described above. It is possible to realize the oxide semiconductor film having a band gap of 5.5 eV or more at 2 / Vs or more.
  • the carrier gas (including the first carrier gas and the second carrier gas) causes the atomized droplets (the first atomized droplet and the second atomized droplet) into the film forming chamber.
  • the type of carrier gas is not particularly limited as long as the object of the present invention is not impaired, and examples thereof include an inert gas such as oxygen, ozone, nitrogen and argon, and a reducing gas such as hydrogen gas and forming gas. In the present invention, it is preferable to use oxygen as the carrier gas. Further, the type of the carrier gas may be one type, but may be two or more types, and a diluted gas having a changed carrier gas concentration (for example, a 10-fold diluted gas or the like) may be further used.
  • the carrier gas may be supplied not only at one location but also at two or more locations.
  • the flow rate of the carrier gas is not particularly limited, but is preferably 0.01 to 20 L / min, and more preferably 1 to 10 L / min.
  • the flow rate of the diluting gas is preferably 0.001 to 2 L / min, more preferably 0.1 to 1 L / min.
  • the atomized droplet (a mixture of the first atomized droplet and the second atomized droplet) is thermally reacted in the vicinity of the substrate surface to form a part or all of the substrate surface.
  • the thermal reaction is not particularly limited as long as it is a thermal reaction in which a film is formed from the atomized droplets, and it may be sufficient if the atomized droplets react with heat, and reaction conditions and the like are also objects of the present invention. It is not particularly limited as long as it does not inhibit.
  • the thermal reaction is usually carried out at a temperature equal to or higher than the evaporation temperature of the solvent, but is preferably not too high or lower.
  • the thermal reaction is preferably carried out at a temperature of 750 ° C. or lower, more preferably at a temperature of 400 ° C. to 750 ° C.
  • the thermal reaction may be carried out under any atmosphere of vacuum, non-oxygen atmosphere, reducing gas atmosphere and oxygen atmosphere as long as the object of the present invention is not impaired, and the thermal reaction may be carried out under atmospheric pressure or atmospheric pressure. It may be carried out under either reduced pressure or reduced pressure, but in the present invention, it is preferably carried out in an oxygen atmosphere, preferably under atmospheric pressure, and in an oxygen atmosphere and under atmospheric pressure. It is more preferable to be carried out in.
  • the film thickness can be set by adjusting the film forming time, and in the present invention, the film thickness is preferably 500 nm or more.
  • a film may be formed on the substrate as it is, but a semiconductor layer having a composition different from that of the oxide semiconductor film (for example, n-type semiconductor layer, n + -type semiconductor layer, etc.) may be formed on the substrate.
  • a semiconductor layer having a composition different from that of the oxide semiconductor film for example, n-type semiconductor layer, n + -type semiconductor layer, etc.
  • the substrate A film may be formed on the film via another layer.
  • the semiconductor layer and the insulator layer include a semiconductor layer and an insulator layer containing the Group 9 metal and / or the Group 13 metal.
  • a semiconductor layer containing a corundum structure for example, a semiconductor layer containing a corundum structure, an insulator layer, a conductor layer, or the like can be mentioned as a preferable example.
  • the semiconductor layer containing the corundum structure include ⁇ -Fe 2 O 3 , ⁇ -Ga 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Ir 2 O 3 , ⁇ -In 2 O 3 , and the like. Examples include mixed crystals of.
  • the method of laminating the buffer layer including the corundum structure is not particularly limited, and may be the same as the laminating method described above.
  • the oxide semiconductor film obtained as described above can be used as a semiconductor layer in a semiconductor device. It is especially useful for power devices. Further, semiconductor devices are classified into horizontal elements (horizontal devices) in which electrodes are formed on one side of the semiconductor layer and vertical elements (vertical devices) in which electrodes are provided on both the front and back sides of the semiconductor layer. In the present invention, it can be suitably used for both horizontal and vertical devices, but it is particularly preferable to use it for vertical devices. Examples of the semiconductor device include a Schottky barrier diode (SBD), a metal semiconductor field effect transistor (MESFET), a high electron mobility transistor (HEMT), a metal oxide film semiconductor field effect transistor (MOSFET), and an electrostatic induction transistor (MSFET). SIT), junction field effect transistor (JFET), insulated gate bipolar transistor (IGBT), light emitting diode and the like.
  • SBD Schottky barrier diode
  • MESFET metal semiconductor field effect transistor
  • HEMT high electron mobility transistor
  • MOSFET metal oxide film semiconductor
  • FIG. 4 shows a Schottky barrier diode (SBD) including an n ⁇ type semiconductor layer 101a, an n + type semiconductor layer 101b, a p-type semiconductor layer 102, a metal layer 103, an insulator layer 104, a Schottky electrode 105a, and an ohmic electrode 105b.
  • SBD Schottky barrier diode
  • the metal layer 103 is made of a metal such as Al and covers the Schottky electrode 105a.
  • n-type semiconductor layer 121a with a wide bandgap an n-type semiconductor layer 121b with a narrow bandgap, an n + type semiconductor layer 121c, a p-type semiconductor layer 123, a gate electrode 125a, a source electrode 125b, a drain electrode 125c, and a substrate 129.
  • HEMT high electron mobility transistor
  • FIG. 6 shows an n ⁇ type semiconductor layer 131a, a first n + type semiconductor layer 131b, a second n + type semiconductor layer 131c, a p-type semiconductor layer 132, a p + type semiconductor layer 132a, a gate insulating film 134, and a gate electrode 135a.
  • a preferred example of a metal oxide semiconductor field effect transistor (MOSFET) including a source electrode 135b and a drain electrode 135c is shown.
  • the p + type semiconductor layer 132a may be a p-type semiconductor layer or may be the same as the p-type semiconductor layer 132.
  • FIG. 7 includes an n ⁇ type semiconductor layer 141a, a first n + type semiconductor layer 141b, a second n + type semiconductor layer 141c, a p-type semiconductor layer 142, a gate electrode 145a, a source electrode 145b, and a drain electrode 145c.
  • JFET junction electrode effect transistor
  • FIG. 8 shows an insulation provided with an n-type semiconductor layer 151, an n-type semiconductor layer 151a, an n + type semiconductor layer 151b, a p-type semiconductor layer 152, a gate insulating film 154, a gate electrode 155a, an emitter electrode 155b, and a collector electrode 155c.
  • a suitable example of a gated bipolar transistor (IGBT) is shown.
  • the semiconductor light emitting device of FIG. 9 includes an n-type semiconductor layer 161 on the second electrode 165b, and a light emitting layer 163 is laminated on the n-type semiconductor layer 161.
  • a p-type semiconductor layer 162 is laminated on the light emitting layer 163.
  • a translucent electrode 167 that transmits light generated by the light emitting layer 163 is provided on the p-type semiconductor layer 162, and a first electrode 165a is laminated on the translucent electrode 167.
  • the semiconductor light emitting device of FIG. 9 may be covered with a protective layer except for the electrode portion.
  • the material of the translucent electrode examples include a conductive material of an oxide containing indium (In) or titanium (Ti). More specifically, for example, In 2 O 3 , ZnO, SnO 2 , Ga 2 O 3 , TiO 2 , CeO 2, or a mixed crystal of two or more of these, or those doped with these can be mentioned.
  • a translucent electrode can be formed by providing these materials by a known method such as sputtering. Further, after the translucent electrode is formed, thermal annealing may be performed for the purpose of making the translucent electrode transparent.
  • the first electrode 165a is a positive electrode and the second electrode 165b is a negative electrode, and a current is passed through both of them to the p-type semiconductor layer 162, the light emitting layer 163, and the n-type semiconductor layer 161. As a result, the light emitting layer 163 emits light.
  • the materials of the first electrode 165a and the second electrode 165b include, for example, Al, Mo, Co, Zr, Sn, Nb, Fe, Cr, Ta, Ti, Au, Pt, V, Mn, Ni, Cu, Metals such as Hf, W, Ir, Zn, In, Pd, Nd or Ag or alloys thereof, metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO). Examples thereof include conductive films, organic conductive compounds such as polyaniline, polythiophene or polypyrrole, or mixtures thereof.
  • the film forming method of the electrode is not particularly limited, and is a wet method such as a printing method, a spray method, and a coating method, a physical method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, CVD, and plasma CVD. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material from chemical methods such as a method.
  • an n-type semiconductor layer 161 is laminated on a substrate 169, and an n-type semiconductor exposed by cutting out a part of a p-type semiconductor layer 162, a light emitting layer 163, and an n-type semiconductor layer 161.
  • the second electrode 165b is laminated on a part of the exposed surface of the semiconductor layer of the layer 161.
  • the semiconductor device of the present invention is suitably used as a power module, an inverter or a converter by using a known method, and further preferably used for a semiconductor system using a power supply device, for example. ..
  • the power supply device can be manufactured from the semiconductor device or as the semiconductor device by connecting to a wiring pattern or the like by a conventional method.
  • the power supply system 170 is configured by using the plurality of power supply devices 171 and 172 and the control circuit 173.
  • the power supply system can be used in the system apparatus 180 by combining the electronic circuit 181 and the power supply system 182.
  • An example of the power supply circuit diagram of the power supply device is shown in FIG. FIG.
  • FIG. 13 shows a power supply circuit of a power supply device including a power circuit and a control circuit.
  • the DC voltage is switched at a high frequency by an inverter 192 (composed of MOSFETs A to D), converted to AC, and then insulated and transformed by a transformer 193.
  • an inverter 192 composed of MOSFETs A to D
  • DCL195 smoothing coils L1 and L2
  • the voltage comparator 197 compares the output voltage with the reference voltage
  • the PWM control circuit 196 controls the inverter 192 and the rectifier MOSFET 194 so as to obtain a desired output voltage.
  • the semiconductor device is preferably a power card, includes a cooler and an insulating member, and the coolers are provided on both sides of the semiconductor layer at least via the insulating member. It is more preferable that heat dissipation layers are provided on both sides of the semiconductor layer, and that the cooler is provided on the outside of the heat dissipation layer at least via the insulating member.
  • FIG. 14 shows a power card which is one of the preferred embodiments of the present invention. The power card of FIG.
  • a double-sided cooling type power card 201 which includes a refrigerant tube 202, a spacer 203, an insulating plate (insulating spacer) 208, a sealing resin portion 209, a semiconductor chip 301a, and a metal heat transfer plate (protruding terminal).
  • the cross section in the thickness direction of the refrigerant tube 202 has a large number of flow paths 222 partitioned by a large number of partition walls 221 extending in the flow path direction at predetermined intervals from each other. According to such a suitable power card, higher heat dissipation can be realized and higher reliability can be satisfied.
  • the mist chemical vapor deposition (Mist Chemical Vapor Deposition) device (1) used in this embodiment will be described with reference to FIG.
  • the mist CVD apparatus (1) is a flow rate control valve (3a, 13a) for adjusting the flow rates of the carrier gas sources (2a, 12a) for supplying the carrier gas and the carrier gas sent out from the carrier gas sources (2a, 12a).
  • a substrate (10) is installed on the hot plate (8).
  • Mist generation source (4, 14), container (5, 15), ultrasonic oscillator (6, 16), supply pipe (9, 19) are provided.
  • the raw material solutions (4a, 14a) are the first raw material solution 4a and the second raw material solution 14a, and the mist of the first raw material solution and the mist of the second raw material solution are mixed in the film forming chamber 7. It is configured to.
  • the first raw material solution 4a obtained in 1 above was housed in the first mist source 4. Further, the second raw material solution 14a was housed in the second mist generation source 14. Next, as the substrate 10, an m-plane (having an off angle of 2 °) sapphire substrate was placed on the hot plate 8 and the hot plate 8 was operated to raise the temperature of the substrate to 650 ° C. Next, the first flow control valves 3a and 3b and the second flow control valves 13a and 13b are opened, respectively, and the first carrier gas sources 2a and 2b and the second carrier gas sources 12a, which are carrier gas sources, are opened.
  • the carrier gas , 12b respectively, supply the carrier gas into the film forming chamber 7, and after sufficiently replacing the atmosphere of the film forming chamber 7 with the carrier gas, the flow rate of the first carrier gas is set to 0.7 L / min, and the first The flow rate of the carrier gas (diluted) is adjusted to 0.5 L / min, the flow rate of the second carrier gas is adjusted to 1 L / min, and the flow rate of the second carrier gas (diluted) is adjusted to 0.5 L / min. Each was adjusted. Nitrogen was used as the carrier gas.
  • the ultrasonic transducer 6 is vibrated at 2.4 MHz, and the vibration is propagated to the raw material solution 4a through water 5a to atomize the first raw material solution 4a and cause the first mist 4b.
  • the ultrasonic oscillator 16 is vibrated at 2.4 MHz, and the vibration is propagated to the second raw material solution 14a through the water 15a to atomize the second raw material solution 14a and second. Mist 14b was generated.
  • the first mist 4b is introduced into the film forming chamber 7 by the carrier gas through the supply pipe 9, and the second mist 14b is produced by the carrier gas through the supply pipe 19.
  • the mist mixed in the film forming chamber 7 thermally reacted to form a film on the substrate 10.
  • the film forming time was 2 hours.
  • the film thickness of the obtained film was 750 nm.
  • the obtained membrane was a 2 O 3 membrane having a corundum structure (Al 0.11 Ga 0.89 ). It was.
  • the XRD measurement result is shown in FIG.
  • the Hall effect of the obtained ⁇ - (Al 0.11 Ga 0.89 ) 2 O 3 film was measured.
  • the carrier type was n-type and the carrier density was 1.37 ⁇ 10 18 (/ cm 3 ).
  • the mobility was 5.91 (cm 2 / V ⁇ s).
  • the obtained film had an m-plane as the main surface and had an off-angle in the a-axis direction.
  • Example 2 The film was formed in the same manner as in Example 1 except that the flow rate of the first carrier gas was 0.5 L / min and the film formation time was 3 hours.
  • the film thickness of the obtained film was 1310 nm.
  • the obtained membrane was identified using an X-ray diffractometer, the obtained membrane was a 2 O 3 membrane having a corundum structure (Al 0.15 Ga 0.85 ).
  • the XRD measurement result is shown in FIG.
  • the electrical characteristics of the obtained ⁇ - (Al 0.15 Ga 0.85 ) 2 O 3 film are the same as in Example 1, the carrier type is n-type, and the carrier density and mobility are the same as in Example 1. It was similar.
  • the bandgap of the obtained film was 5.5 eV.
  • the band gap was elastically scattered (zero energy loss) electron peaks and inelastically scattered (energy lost by the amount of interband excitation) using reflected electron energy loss spectroscopy (REELS). Calculated from the electron peak.
  • the obtained film had an m-plane as the main surface and had an off-angle in the a-axis direction.
  • the film formation time was set to 1 hour, and as the second raw material solution, a solution obtained by adding 2% hydrochloric acid to 0.05 mol / L of a gallium acetylacetonate aqueous solution was used, and the first carrier gas was used.
  • a film was formed in the same manner as in Example 1 except that the flow rate was 1.0 L / min.
  • the film thickness of the obtained film was 362 nm.
  • the obtained membrane was identified by using an X-ray diffractometer, the obtained membrane was a 2 O 3 membrane having a corundum structure (Al 0.20 Ga 0.80 ).
  • the band gap calculated in the same manner as in Example 2 was 5.8 eV.
  • the obtained film had an m-plane as the main surface and had an off-angle in the a-axis direction.
  • Test Example 2 The temperature of the substrate was 700 ° C., the film formation time was 1 hour, and as the second raw material solution, a solution obtained by adding 2% hydrochloric acid to 0.05 mol / L of a gallium acetylacetonate aqueous solution was used.
  • the film was formed in the same manner as in Example 1 except that the flow rate of the second carrier gas was 0.5 L / min.
  • the obtained membrane was identified by using an X-ray diffractometer, the obtained membrane was a 2 O 3 membrane having a corundum structure (Al 0.50 Ga 0.50 ).
  • the band gap calculated in the same manner as in Example 2 was 6.1 eV.
  • the obtained film had an m-plane as the main surface and had an off-angle in the a-axis direction.
  • the oxide semiconductor film of the present invention is useful as a semiconductor, and can be used in all fields such as semiconductors (for example, compound semiconductor electronic devices, etc.), electronic parts / electrical equipment parts, optical / electrophotographic related equipment, industrial parts, and the like. Since it has excellent semiconductor characteristics, it is particularly useful for semiconductor devices and the like.

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