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WO2019098294A1 - Procédé de formation de film semi-conducteur d'oxyde de type p - Google Patents

Procédé de formation de film semi-conducteur d'oxyde de type p Download PDF

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Publication number
WO2019098294A1
WO2019098294A1 PCT/JP2018/042345 JP2018042345W WO2019098294A1 WO 2019098294 A1 WO2019098294 A1 WO 2019098294A1 JP 2018042345 W JP2018042345 W JP 2018042345W WO 2019098294 A1 WO2019098294 A1 WO 2019098294A1
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Prior art keywords
film
type
metal
oxide semiconductor
metal oxide
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Japanese (ja)
Inventor
勲 ▲高▼橋
時宜 松田
四戸　孝
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Flosfia Inc
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Flosfia Inc
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C30B23/06—Heating of the deposition chamber, the substrate or the materials to be evaporated
    • 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

Definitions

  • the present invention relates to a method for forming a p-type oxide semiconductor.
  • a semiconductor device using gallium oxide (Ga 2 O 3 ) with a large band gap has attracted attention as a next-generation switching element capable of achieving high withstand voltage, low loss, and high heat resistance, and is used for power semiconductor devices such as inverters. Application is expected. Moreover, application as a light emitting and receiving device such as an LED or a sensor is also expected from a wide band gap.
  • the gallium oxide can be band gap controlled by mixing crystal with indium or aluminum respectively or in combination, and constitutes an extremely attractive material family as an InAlGaO-based semiconductor. .
  • Patent Document 1 a ⁇ -Ga 2 O 3 based crystal is subjected to FZ method using MgO (p-type dopant source). It is described that when formed, a substrate exhibiting p-type conductivity is obtained. Further, Patent Document 2 describes that a p-type semiconductor is formed by ion-implanting a p-type dopant into an ⁇ - (Al x Ga 1 -x ) 2 O 3 single crystal film formed by MBE. .
  • Non-patent Document 2 it is difficult to realize the production of p-type semiconductors (Non-patent Document 2), and it has not been reported that these methods succeeded in producing p-type semiconductors. Therefore, a viable p-type oxide semiconductor and a method for producing the same have been desired.
  • Non-Patent Document 3 and Non-Patent Document 4 for example, using Rh 2 O 3 or ZnRh 2 O 4 as a p-type semiconductor has been studied, but Rh 2 O 3 There is a problem that the concentration of the raw material becomes particularly thin at the time of film formation, which affects the film formation, and it was difficult to prepare a Rh 2 O 3 single crystal even using an organic solvent. Also, there is a problem that even if the Hall effect measurement is performed, the p type is not determined and the measurement itself can not be performed, and the measurement value of the Hall coefficient is, for example, 0.2 cm 3 / C) There was only the following, and it was not enough to use it. In addition, since ZnRh 2 O 4 has a low mobility and a narrow band gap, there is a problem that it can not be used for an LED or a power device, and these were not necessarily satisfactory.
  • Patent Document 3 describes that delafossite, oxychalcogenide or the like is used as a p-type semiconductor.
  • these semiconductors have mobility of about 1 cm 2 / V ⁇ s or less, have poor electrical characteristics, and have pn junctions with n-type next-generation oxide semiconductors such as ⁇ -Ga 2 O 3. There was also a problem that did not work well.
  • Ir 2 O 3 is conventionally known.
  • Patent Document 4 describes using Ir 2 O 3 as an iridium catalyst.
  • Patent Document 5 describes that Ir 2 O 3 is used as a dielectric.
  • Patent Document 6 describes using Ir 2 O 3 for the electrode.
  • Ir 2 O 3 is conventionally known.
  • Patent Document 4 describes using Ir 2 O 3 as an iridium catalyst.
  • Patent Document 5 describes that Ir 2 O 3 is used as a dielectric.
  • Patent Document 6 describes using Ir 2 O 3 for the electrode.
  • Ir 2 O 3 for the electrode.
  • JP 2005-340308 A JP, 2013-58637, A JP, 2016-25256, A Unexamined-Japanese-Patent No. 9-25255 JP-A-8-227793 Japanese Patent Application Laid-Open No. 11-21687
  • An object of the present invention is to provide a method capable of industrially advantageously forming a p-type oxide semiconductor film excellent in semiconductor characteristics.
  • the present inventors used metal oxide gas as a raw material for forming a p-type oxide semiconductor film, so that the film thickness is 50 nm or more even though it is not amorphous.
  • metal oxide gas as a raw material for forming a p-type oxide semiconductor film, so that the film thickness is 50 nm or more even though it is not amorphous.
  • a p-type oxide semiconductor film having a surface roughness of 10 nm or less can be formed, and such a p-type oxide semiconductor film can solve the aforementioned conventional problems at once. Found out.
  • the present invention relates to the following inventions.
  • the metal oxide gas contains a d-block metal of the periodic table or a periodic group 13 metal.
  • the metal oxide gas contains a periodic table group 9 metal or a group 13 metal.
  • [4] The method for forming a p-type oxide semiconductor film according to any one of the above [1] to [3], wherein the metal oxide gas contains at least iridium.
  • [5] The p-type oxide semiconductor film according to any one of the above [1] to [4], wherein the metal oxide gas is obtained by sublimation of a solid of the metal oxide gas by heating. Formation method.
  • [6] The method for forming a p-type oxide semiconductor film according to any one of the above [1] to [5], wherein the formation of the p-type oxide semiconductor film is performed under atmospheric pressure.
  • [7] The method for forming a p-type oxide semiconductor film according to any one of the above [1] to [6], wherein the formation of the p-type oxide semiconductor film is performed by crystal growth.
  • [8] The method for forming a p-type oxide semiconductor film according to the above [7], wherein the crystal growth is performed on a substrate having a corundum structure.
  • a method for forming a metal oxide film which is a method for forming a metal oxide film, comprising forming a metal oxide film, the metal oxide gas containing a periodic table group 9 and / or periodic table group 13 metal in an oxygen atmosphere
  • the method for forming a p-type oxide semiconductor film of the present invention can industrially advantageously form a p-type oxide semiconductor film excellent in semiconductor characteristics.
  • the method for forming a p-type oxide semiconductor film of the present invention is a method for forming a p-type oxide semiconductor film, characterized in that a metal oxide gas is used as a raw material for forming the p-type oxide semiconductor film.
  • a metal oxide gas is used as a raw material for forming the p-type oxide semiconductor film.
  • a solid substance (such as powder) of metal oxide gas is sublimated (sublimation step), and then the resulting metal oxide gas is used to grow crystals on a substrate having a corundum structure. (Crystal growth process).
  • a metal oxide gas is obtained by subliming a solid substance (for example, powder or the like) of the metal oxide gas into a gaseous state.
  • the metal oxide gas include metal oxides of metals contained in a gaseous p-type oxide semiconductor film, and the valence of the metal oxide does not hinder the object of the present invention. It is not particularly limited, and may be monovalent or divalent. It may be trivalent or tetravalent.
  • the metal oxide preferably contains the d block metal of the periodic table or the periodic table group 13 metal, and more preferably includes the periodic table group 9 metal or the group 13 metal. preferable.
  • the metal oxide may be iridium, and a metal of Group 2 of the periodic table, a metal of Group 9 other than iridium, or a metal of Group 13 It is also preferable to contain.
  • a preferable metal oxide as described above one having a band gap of 2.4 eV or more can be obtained, so that a wider band gap and more excellent electric characteristics can be exhibited in the p-type oxide semiconductor. it can.
  • Period table means the periodic table defined by International Union of Pure and Applied Chemistry (IUPAC).
  • D block refers to an element having electrons that satisfy 3d, 4d, 5d and 6d orbitals.
  • Examples of the d-block metal include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper.
  • Cu zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), laurenthium (Lr), razarhodium (Rf), dubnium (Db), seaborgium (Sg), boli Beam (Bh), hassium (Hs), meitnerium (Mt), darmstadtium (Ds), roentgenium (Rg), including Copernicium (Cn) and two or more metals thereof.
  • group 2 metal may be any group 2 metal of the periodic table, and examples of the group 2 metal include beryllium (Be), magnesium (Mg), calcium (Ca), and strontium Sr), barium (Ba), or two or more of these metals, and the like.
  • the “group 9 metal” may be a group 9 metal of the periodic table, and such a group 9 metal includes, for example, iridium (Ir), cobalt (Co), rhodium (Rh) or these And the like.
  • the “group 13 metal” is not particularly limited as long as it is a group 13 metal of the periodic table, and examples of the group 13 metal include aluminum (Al), gallium (Ga), indium (In), and the like. Although thallium (Tl) or two or more of these metals and the like can be mentioned, in the present invention, one or more selected from aluminum (Al), gallium (Ga) and indium (In) are preferable.
  • the p-type oxide semiconductor film contains a metal oxide containing iridium as a main component
  • IrO 2 gas as the metal oxide gas.
  • a heating means is mentioned as a sublimation means.
  • the heating temperature is not particularly limited, but is preferably 600 ° C. to 1200 ° C., more preferably 800 ° C. to 1000 ° C.
  • the metal oxide gas obtained by sublimation is preferably transported to the substrate by the carrier gas.
  • 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 oxygen, ozone, inert gases such as nitrogen and argon, and reducing gases such as hydrogen gas and forming gas.
  • oxygen it is preferable to use oxygen as a carrier gas.
  • a carrier gas in which oxygen is used air, oxygen gas, ozone gas etc. are mentioned, for example, Especially oxygen gas and / or ozone gas are preferred.
  • one kind of carrier gas may be used, it may be two or more kinds, and a dilution gas (for example, 10-fold dilution gas etc.) in which the carrier gas concentration is changed may be used as the second carrier gas. You may use further.
  • the carrier gas may be supplied not only to one place, but also to two or more places.
  • the flow rate of the carrier gas is not particularly limited, but is preferably 0.01 to 20 L / min and more preferably 0.1 to 10 L / min.
  • the substrate is not particularly limited as long as it can support the p-type oxide semiconductor film, but preferably has a corundum structure.
  • the material of the substrate may be a known substrate, may be an organic compound, or may be an inorganic compound.
  • a metal oxide having a corundum structure such as sapphire or ⁇ -type gallium oxide can be mentioned as a preferable example.
  • the shape of the substrate may be any shape, and is effective for any shape, for example, plate-like such as flat plate or disc, fiber-like, rod-like, cylindrical, prismatic, Although cylindrical shape, helical shape, spherical shape, ring shape etc. are mentioned, a substrate is preferable in the present invention.
  • the thickness of the substrate is not particularly limited in the present invention.
  • the substrate is not particularly limited as long as it has a plate shape and serves as a support for the p-type oxide semiconductor film.
  • the substrate may be an insulator substrate, a semiconductor substrate, or a conductive substrate, but the substrate is preferably an insulator substrate and has a metal film on the surface. It is also preferred that it is a substrate.
  • the substrate preferably includes, for example, a substrate having a corundum structure.
  • the substrate material is not particularly limited as long as it has a corundum structure, and may be known.
  • the substrate having the corundum structure examples include a base substrate mainly composed of a substrate material having a corundum structure, and more specifically, for example, a sapphire substrate (preferably c-plane sapphire substrate) or an ⁇ -type A gallium oxide substrate etc. are mentioned.
  • “main component” means that the substrate material having the above-mentioned specific crystal structure is, in atomic ratio, preferably 50% or more, more preferably 70% or more, still more preferably 90% to all components of the substrate material. It means that% or more is included, and it may mean that it may be 100%.
  • crystal growth process In the crystal growth step, the metal oxide gas is crystal-grown near the surface of the substrate, and a film is formed on part or all of the surface of the substrate.
  • the crystal growth temperature is preferably lower than the heating temperature of the sublimation process, more preferably 900 ° C. or less, and most preferably 500 ° C. to 900 ° C.
  • crystal growth may be performed under any atmosphere of vacuum, non-oxygen atmosphere, reducing gas atmosphere and oxidizing atmosphere, as long as the object of the present invention is not hindered. Although it may be carried out under any conditions of reduced pressure and reduced pressure, in the present invention, it is preferable to be carried out under an oxidizing atmosphere, preferably under atmospheric pressure, preferably under an oxidizing atmosphere and under atmospheric pressure.
  • the “oxidative atmosphere” is not particularly limited as long as it is an atmosphere in which crystals or mixed crystals of metal oxides can be formed, and it may be any oxygen or oxygen-containing compound, for example, a carrier gas containing oxygen.
  • An oxidizing atmosphere may be used by using or using an oxidizing agent.
  • the film thickness can be set by adjusting the film formation time. In the present invention, it is preferably 50 nm or more, more preferably 100 nm or more, and most preferably 1.0 ⁇ m or more.
  • the upper limit of the film thickness is not particularly limited, but is preferably 1 mm, and more preferably 100 ⁇ m.
  • the metal oxide gas may be added to a p-type dopant to be subjected to this step, and the metal oxide having the corundum structure may be p-type doped.
  • the p-type dopant for example, Mg, H, Li, Na, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, Mn, Fe, Co, Ni, Pd, Cu, Ag, Au And Zn, Cd, Hg, Tl, Pb, N, P and the like, and two or more of these elements and the like.
  • the p-type dopant is preferably a Group 1 metal or a Group 2 metal of the periodic table, more preferably a Group 2 metal, and most preferably magnesium (Mg). preferable.
  • the p-type oxide semiconductor film obtained in this step may be annealed.
  • the metal oxide gas may be obtained, for example, by evaporating and optionally oxidizing a liquid substance (for example, mist or the like) of a precursor of the metal oxide gas.
  • a liquid substance for example, mist or the like
  • the liquid substance (for example, mist or the like) of the precursor of the metal oxide gas is preferably a mist obtained by atomizing or dropletizing the raw material solution.
  • the method for forming a p-type oxide semiconductor film of the present invention it is obtained by evaporating and optionally oxidizing a liquid substance (for example, mist etc.) of a precursor of metal oxide gas
  • a method for forming a p-type oxide semiconductor film when using a metal oxide is described in more detail.
  • a raw material solution containing a precursor of the metal oxide gas is atomized or formed into droplets using a two-zone film forming apparatus shown in FIG.
  • the obtained mist or droplets are evaporated or optionally oxidized (evaporation step), and then the obtained metal oxide gas is used to grow crystals on a substrate having a corundum structure (Crystal growth step).
  • the substrate and the crystal growth step may be the same as the substrate and crystal growth step in the method for forming a p-type oxide semiconductor film using the solid substance of the metal oxide gas described above.
  • the raw material solution is atomized or formed into droplets.
  • the means for atomizing or dropletizing the raw material solution is not particularly limited as long as it can atomize or drop the raw material solution, and may be a known means, but in the present invention, ultrasonic waves are used.
  • the atomizing means or dropletizing means used is preferred.
  • the mist or droplet obtained by using ultrasonic waves is preferable because it has an initial velocity of zero and floats in the air, and for example, it can be transported as a gas floating in a space rather than being sprayed like a spray. It is very suitable because it is a mist which is not damaged by collision energy.
  • the droplet size is not particularly limited, and may be about several mm, but preferably 50 ⁇ m or less, and more preferably 100 nm to 10 ⁇ m.
  • the raw material solution contains a precursor of the metal oxide gas, and is not particularly limited as long as atomization or dropletization is possible, and may contain an inorganic material or an organic material. It may be.
  • the raw material solution contains a metal or a compound thereof contained in the p-type oxide semiconductor film.
  • the raw material solution one in which the metal contained in the p-type oxide semiconductor film is dissolved or dispersed in the form of a complex or a salt in an organic solvent or water can be suitably used.
  • the form of the complex include acetylacetonato complex, carbonyl complex, ammine complex, hydride complex and the like.
  • salt form examples include organic metal salts (eg, metal acetate, metal oxalate, metal citric acid, etc.), metal sulfides, metal nitrates, metal phosphates, metal halides (eg metal chlorides) And metal bromides, metal iodides and the like).
  • additives such as hydrohalic acid and an oxidizing agent
  • hydrohalic acid examples include hydrobromic acid, hydrochloric acid, hydroiodic acid and the like, but hydrobromic acid or hydroiodic acid is preferable among them because a better film can be obtained.
  • oxidizing agent examples include hydrogen peroxide (H 2 O 2 ), sodium peroxide (Na 2 O 2 ), barium peroxide (BaO 2 ), benzoyl peroxide (C 6 H 5 CO) 2 O 2 and the like.
  • the raw material solution may contain a dopant. Doping can be favorably performed by including the dopant in the raw material solution.
  • the dopant is not particularly limited as long as the object of the present invention is not impaired.
  • the dopant for example, Mg, H, Li, Na, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, Mn, Fe, Co, Ni, Pd, Cu, Ag, Au, Zn And p-type dopants such as Cd, Hg, Tl, Pb, N, P and the like.
  • the concentration of the dopant may generally be about 1 ⁇ 10 16 / cm 3 to 1 ⁇ 10 22 / cm 3 , and the concentration of the dopant may be low, for example, about 1 ⁇ 10 17 / cm 3 or less. May. Furthermore, in the present invention, the dopant may be contained at a high concentration of about 1 ⁇ 10 20 / cm 3 or more.
  • 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 solvent of an inorganic solvent and an organic solvent.
  • the solvent preferably contains water, and more preferably water or a mixed solvent of water and an alcohol.
  • the metal oxide gas is obtained by evaporating and optionally oxidizing a liquid substance (for example, mist or the like) of the precursor of the metal oxide gas.
  • the metal oxide gas may be the same as the metal oxide gas in the sublimation process.
  • a heating means is mentioned, for example.
  • the heating temperature in the evaporation means may be the same as the heating temperature in the sublimation means.
  • the metal oxide gas obtained by evaporation is preferably transported to the substrate by the carrier gas.
  • 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 oxygen, ozone, inert gases such as nitrogen and argon, and reducing gases such as hydrogen gas and forming gas.
  • oxygen gas and / or ozone gas are preferred.
  • the precursor of the metal oxide gas can be more suitably oxidized by using oxygen gas and / or ozone gas as the carrier gas.
  • one kind of carrier gas may be used, it may be two or more kinds, and a dilution gas (for example, 10-fold dilution gas etc.) in which the carrier gas concentration is changed may be used as the second carrier gas. You may use further.
  • the carrier gas may be supplied not only to one place, but also to two or more places.
  • the flow rate of the carrier gas is not particularly limited, but is preferably 0.01 L / min to 20 L / min and more preferably 0.1 to 10 L / min.
  • the p-type oxide semiconductor film obtained as described above is suitably used as a p-type semiconductor layer using a known means.
  • the p-type oxide semiconductor film is formed by using, as the metal oxide gas, a substance obtained by sublimation of a solid substance (for example, powder) of the metal oxide gas.
  • the above-described p-type oxide semiconductor film can be formed more favorably, and for example, a p-type oxide semiconductor film having a surface roughness of 5 nm or less and excellent in surface smoothness can be obtained, which is preferable.
  • a film may be formed as it is on the substrate, but a semiconductor layer different from the p-type semiconductor layer (for example, n-type semiconductor layer, n + -type semiconductor layer, n ⁇ -type semiconductor) may be formed on the substrate After laminating other layers such as a layer or the like), an insulator layer (including a semi-insulator layer), a buffer layer and the like, a film may be formed on the substrate via the other layer.
  • a semiconductor layer and an insulator layer the semiconductor layer containing the said 13th group metal, an insulator layer, etc. are mentioned, for example.
  • a semiconductor layer including a corundum structure, an insulator layer, a conductor layer, and the like can be given as preferable examples.
  • the semiconductor layer containing the corundum structure include ⁇ -Fe 2 O 3 , ⁇ -Ga 2 O 3 , and ⁇ -Al 2 O 3 .
  • the means for laminating the buffer layer is not particularly limited, and may be the same as the means for forming the p-type oxide semiconductor.
  • the method for manufacturing a semiconductor device includes the step of laminating at least a p-type semiconductor layer and an n-type semiconductor layer.
  • the means for forming the n-type semiconductor layer is not particularly limited and may be a known means, but in the present invention, the mist CVD method is preferable.
  • the n-type semiconductor layer preferably contains an oxide semiconductor as a main component, and an oxide semiconductor containing a metal of Group 13 of the periodic table (for example, Al, Ga, In, Tl, etc.) as a main component. More preferable.
  • the n-type semiconductor layer preferably contains a crystalline oxide semiconductor as a main component, more preferably contains a crystalline oxide semiconductor containing Ga, and has a corundum structure and contains Ga. Most preferably, a crystalline oxide semiconductor is used as the main component.
  • a pn junction is formed favorably even when the lattice constant difference between the oxide semiconductor which is the main component of the n-type semiconductor and the p-type oxide semiconductor is 1.0% or less. It is preferable that the content is 0.3% or less.
  • the “lattice constant difference” is a value obtained by subtracting the lattice constant of the p-type oxide semiconductor from the lattice constant of the oxide semiconductor which is the main component of the n-type semiconductor, It is defined as a value (%) obtained by multiplying the absolute value of the value divided by the lattice constant by 100.
  • the lattice constant difference is 1.0% or less
  • the p-type oxide semiconductor has a corundum structure
  • the oxide semiconductor which is the main component of the n-type semiconductor also has a corundum structure
  • the p-type oxide semiconductor is a single crystal or mixed crystal of Ir 2 O 3
  • the oxide semiconductor that is the main component of the n-type semiconductor is a single oxide of Ga 2 O 3 .
  • the case of a crystal or mixed crystal may, for example, be mentioned.
  • the main component means that the oxide semiconductor is contained in an atomic ratio, preferably 50% or more, more preferably 70% or more, still more preferably 90% or more to all components of the n-type semiconductor layer Meaning that it may be 100%.
  • the p-type oxide semiconductor may be single crystal or polycrystal.
  • the p-type oxide semiconductor film obtained by the above preferable formation method is industrially useful and has excellent electrical characteristics. More specifically, the mobility is usually 1.0 cm 2 / V ⁇ s or more.
  • the mobility refers to the mobility obtained by Hall effect measurement, and in the present invention, the mobility is preferably 3.0 cm 2 / Vs or more.
  • the p-type oxide semiconductor film preferably has a carrier density of 8.0 ⁇ 10 20 / cm 3 or more.
  • the carrier density refers to the carrier density in the semiconductor film obtained by Hall effect measurement.
  • the lower limit of the carrier density is not particularly limited, but is preferably about 1.0 ⁇ 10 15 / cm 3 or more, and more preferably about 1.0 ⁇ 10 17 / cm 3 or more.
  • the carrier density is in the range of 1.0 ⁇ 10 16 / cm 3 to 1.0 ⁇ 10 20 / cm 3 by adjusting the kind and amount of dopant or the mixed crystal material and the content thereof. It can be easily controlled.
  • the p-type oxide semiconductor film obtained as described above can be used for a semiconductor device as a p-type semiconductor layer, and is particularly useful for power devices.
  • a semiconductor device By using the p-type oxide semiconductor film for a semiconductor device, roughness scattering can be suppressed, and the channel mobility of the semiconductor device can be made excellent.
  • Semiconductor devices are classified into horizontal devices (horizontal devices) in which electrodes are formed on one side of the semiconductor layer and vertical devices (vertical devices) each having electrodes on the front and back sides of the semiconductor layer.
  • horizontal devices horizontal devices
  • vertical devices vertical devices each having electrodes on the front and back sides of the semiconductor layer.
  • it can be used suitably also as a horizontal type device and a vertical type device, it is preferred to use for a vertical type device especially.
  • SBD Schottky barrier diode
  • MESFET metal semiconductor field effect transistor
  • HEMT high electron mobility transistor
  • MOSFET metal oxide semiconductor field effect transistor
  • SIT electrostatic induction transistor
  • JFET junction field effect transistor
  • IGBT insulated gate bipolar transistor
  • Example 1 Film Forming Apparatus
  • the film forming apparatus 1 of FIG. 1 is provided with a quartz cylinder 2 connected to a carrier gas supply source, and a raw material installation stand 4 made of quartz in the quartz cylinder 2.
  • Raw material 5 is placed.
  • a heater 3 is cylindrically provided outside the quartz cylinder 2 around the raw material installation stand, and is configured to be able to heat the raw material 5.
  • a quartz substrate table is installed as a susceptor 7 at the back of the quartz tube 2 and the installation position is adjusted so that the susceptor 7 is within the crystal growth temperature.
  • IrO 2 powder as the raw material 5 was placed on the raw material installation stand 4, and a sapphire substrate was placed on the susceptor 7 as the substrate 6. Next, the temperature of the heater 3 is raised to 850 ° C., and the IrO 2 powder placed on the raw material installation table 4 is heated to sublime the IrO 2 powder, thereby making gaseous iridium oxide Generated.
  • the carrier gas is supplied from the carrier gas supply source into the quartz cylinder 2, and the above 2.
  • the metal oxide gas (gaseous iridium oxide) generated in the above was supplied to the substrate 6 through the quartz cylinder 2.
  • the flow rate of the carrier gas was 1.0 L / min, and oxygen was used as the carrier gas.
  • the metal oxide gas reacted near the surface of the substrate 6 under atmospheric pressure to form a film on the substrate.
  • the film formation time was 60 minutes, and the film thickness was 220 nm.
  • the substrate temperature at the time of film formation was 600.degree.
  • the films obtained in the above were subjected to film identification using an X-ray diffraction apparatus, and the obtained film was an ⁇ -Ir 2 O 3 film.
  • the result of XRD is shown in FIG.
  • Hall effect measurement was performed on the obtained ⁇ -Ir 2 O 3 film, it was found that the F value is 0.998, the carrier type is “p”, and the semiconductor is a p-type semiconductor.
  • the carrier concentration was 1.05 ⁇ 10 22 (/ cm 3 ), and the mobility was 3.12 (cm 2 / V ⁇ s).
  • AFM atomic force microscope
  • the surface roughness (Ra) is 3.5 nm, and it can be seen that the surface smoothness is very excellent.
  • the surface roughness (Ra) was calculated based on JIS B0601 using a surface shape measurement result for an area of 90 ⁇ m square by an atomic force microscope (AFM).
  • the mist CVD apparatus used in this comparative example will be described with reference to FIG.
  • the mist CVD apparatus 19 comprises a susceptor 21 for mounting the substrate 20, a carrier gas supply means 22a for supplying a carrier gas, and a flow rate control valve 23a for adjusting the flow rate of the carrier gas delivered from the carrier gas supply means 22a.
  • the susceptor 21 is made of quartz, and the surface on which the substrate 20 is placed is inclined from the horizontal surface.
  • the ultrasonic transducer was vibrated, and the vibration was propagated to the raw material solution 24 a through the water 25 to atomize the raw material solution 24 a to generate mist.
  • the mist was conveyed by the carrier gas to the supply pipe 27 and thermally reacted in the vicinity of the surface of the substrate 20 at 750 ° C. under atmospheric pressure to form a film on the substrate 20.
  • the film thickness was 280 nm.
  • the films obtained in the above were subjected to film identification using an X-ray diffraction apparatus, and the obtained film was an ⁇ -Ir 2 O 3 film.
  • the result of XRD is shown in FIG.
  • Hall effect measurement was performed on the obtained ⁇ -Ir 2 O 3 film, it was found that the F value is 0.998, the carrier type is “p”, and the semiconductor is a p-type semiconductor.
  • the carrier concentration was 2.97 ⁇ 10 21 (/ cm 3 ), and the mobility was 0.38 (cm 2 / V ⁇ s).
  • the surface roughness (Ra) was 302 nm.
  • the surface roughness (Ra) was calculated based on JIS B0601 using a surface shape measurement result for an area of 90 ⁇ m square by an atomic force microscope (AFM).
  • Example 2 and Comparative Example 2 Films were obtained in the same manner as in Example 1 and Comparative Example 1 except that the film formation time was increased, and they were referred to as Example 2 and Comparative Example 2, respectively. And about the obtained film
  • the p-type oxide semiconductor film obtained by the forming method of the present invention is industrially useful because it is excellent in film quality such as surface smoothness and crystallinity. It can be seen that the electrical characteristics such as mobility are also excellent.
  • Example 3 A p-type oxide semiconductor film was obtained in the same manner as in Example 1 except that the film formation time was 2 hours. Next, an n ⁇ -type semiconductor layer was stacked over the p-type oxide semiconductor film. In the lamination of the n-type semiconductor layer, gallium bromide (gallium concentration 0.1 mol / L) is mixed with ultrapure water, hydrobromic acid is added to a volume ratio of 20%, and an aqueous solution is prepared. The film was formed in the same manner as in Comparative Example 1 except that this was used as a raw material solution, the temperature of the heater was 420 ° C., and the film forming time was 30 minutes. The film was an ⁇ -Ga 2 O 3 film.
  • gallium bromide gallium concentration 0.1 mol / L
  • hydrobromic acid is added to a volume ratio of 20%
  • an aqueous solution is prepared.
  • the film was formed in the same manner as in Comparative Example 1 except that this was used as a raw material solution, the temperature
  • n + -type semiconductor layer was stacked on the obtained n ⁇ -type semiconductor layer.
  • gallium bromide gallium concentration 0.1 mol / L
  • hydrobromic acid is added to a volume ratio of 10% to prepare an aqueous solution
  • a film was formed in the same manner as in Comparative Example 1 except that 1% of germanium oxide was added to prepare a raw material solution, the temperature of the heater was set to 390 ° C., and the film forming time was set to 30 minutes. It was done by doing.
  • a Ti film was formed by sputtering on the n + -type semiconductor layer of the obtained laminate, and then photolithography and etching were performed to fabricate a pn diode. An IV measurement was performed on the obtained pn diode. The results are shown in FIG. As apparent from FIG. 7, the p-type oxide semiconductor film of the present invention, for example, has a good PN junction together with a high voltage and low loss n-type semiconductor (for example, gallium oxide etc.) having high breakdown electric field strength. It turns out that it can be realized.
  • a high voltage and low loss n-type semiconductor for example, gallium oxide etc.
  • Example 4 Film Forming Apparatus
  • the film forming apparatus 10 of FIG. 8 is provided with a quartz cylinder 2 connected to a carrier gas supply source, and a raw material installation stand 4 made of quartz in the quartz cylinder 2.
  • Raw material 5 is placed.
  • a heater (raw material side) 3a and a heater (substrate side) 3b are respectively provided cylindrically on the outside of the quartz cylinder 2 around the raw material installation stand so that the raw material 5 can be heated.
  • a quartz substrate table is installed as a susceptor 7 at the back of the quartz tube 2 and the installation position is adjusted so that the susceptor 7 is within the crystal growth temperature.
  • IrO 2 powder as the raw material 5 was placed on the raw material installation stand 4, and a sapphire substrate was placed on the susceptor 7 as the substrate 6.
  • the temperature of the heater (raw material side) 3a is raised to 850 ° C.
  • the IrO 2 powder placed on the raw material installation table 4 is heated to sublime the IrO 2 powder, thereby forming a gaseous state.
  • the temperature of the heater (substrate side) 3 b was increased to 350 ° C.
  • the carrier gas is supplied from the carrier gas supply source into the quartz cylinder 2 while maintaining the temperature of the heater (raw material side) 3a at 850 ° C. and the temperature of the heater (substrate side) at 350 ° C. Above 2.
  • the metal oxide gas (gaseous iridium oxide) generated in the above was supplied to the substrate 6 through the quartz cylinder 2.
  • the carrier gas flow rate was 2.0 L / min, and oxygen was used as the carrier gas.
  • the metal oxide gas reacted near the surface of the substrate 6 under atmospheric pressure to form a film on the substrate.
  • the film formation time was 90 minutes.
  • the film obtained by the above was subjected to film identification using an X-ray diffractometer, and the obtained film was an ⁇ -Ir 2 O 3 film.
  • the result of XRD is shown in FIG.
  • the film surface is observed using an atomic force microscope (AFM)
  • AFM atomic force microscope
  • the surface roughness (Ra) is 0.161 nm and the surface smoothness is very excellent.
  • the surface roughness (Ra) was calculated based on JIS B0601 using a surface shape measurement result for an area of 90 ⁇ m square by an atomic force microscope (AFM).
  • Example 5 In the same manner as in Example 4, except that the temperature of the heater (substrate side) was 250.degree. C., the flow rate of the carrier gas was 4.0 L / min, and the film formation time was 120 minutes, p Type oxide semiconductor film was obtained. About the obtained film, when the film was identified using an X-ray diffractometer, the obtained film was an ⁇ -Ir 2 O 3 film. Moreover, the film
  • Example 6 Film Forming Apparatus
  • the film forming apparatus used in the present embodiment will be described with reference to FIG.
  • the film forming apparatus 30 of FIG. 21 has a susceptor 21 for mounting the substrate 20, carrier gas supply means 22a for supplying a carrier gas, and flow rate adjustment for adjusting the flow rate of the carrier gas delivered from the carrier gas supply means 22a.
  • Valve 23a carrier gas (dilution) supply means 22b for supplying carrier gas (dilution), flow control valve 23b for adjusting the flow rate of carrier gas delivered from carrier gas (dilution) supply means 22b, and raw material solution 24a, a container 25 for containing water 25a, an ultrasonic transducer 26 mounted on the bottom of the container 25, a supply tube 27 comprising a quartz tube having an inner diameter of 40 mm, a supply tube 27
  • the supply pipe 27 is constituted by two zones of a supply pipe (raw material side) 27a in which a heater (raw material side) 28a is installed and a supply pipe (substrate side) 27b in which a heater (substrate side) 28b is installed.
  • the susceptor 21 is made of quartz, and the surface on which the substrate 20 is placed is inclined from the horizontal surface. By supplying both the supply pipe 27 and the susceptor 21 to be the film forming chamber with quartz, it is possible to suppress the mixing of impurities derived from the device into the film formed on the substrate 20.
  • the ultrasonic transducer was vibrated, and the vibration was propagated to the raw material solution 24 a through the water 25 to atomize the raw material solution 24 a to generate mist.
  • the mist was conveyed by the carrier gas to the supply pipe 27a, and the mist was evaporated and oxidized to generate gaseous iridium oxide.
  • the generated metal oxide gas gaseous iridium oxide
  • the carrier gas is supplied to the substrate 20 in the supply pipe 27b by the carrier gas, and then the metal oxide gas is at atmospheric pressure at 350 ° C. By reacting in the vicinity, a film was formed on the substrate.
  • the film forming time was 60 minutes.
  • the film obtained by the above was subjected to film identification using an X-ray diffractometer, and the obtained film was an ⁇ -Ir 2 O 3 film.
  • the result of XRD is shown in FIG.
  • Hall effect measurement was performed on the obtained ⁇ -Ir 2 O 3 film, it was found that the F value is 1.000, the carrier gas is “p”, and it is a p-type semiconductor.
  • the carrier concentration was 1.12 ⁇ 10 22 (/ cm 3 ), and the mobility was 1.60 (cm 2 / V ⁇ s).
  • the film surface is observed using an atomic force microscope (AFM), it can be seen that the surface roughness (Ra) is 9.443 nm and the surface smoothness is excellent.
  • the surface roughness (Ra) was calculated based on JIS B0601 using a surface shape measurement result for an area of 90 ⁇ m square by an atomic force microscope (AFM).
  • the p-type oxide semiconductor film obtained by the formation method of the present invention can be used in all fields such as semiconductors (for example, compound semiconductor electronic devices etc.), electronic parts / electrical equipment parts, optical / electrophotographic related devices, industrial members, etc. Although they can be used, they are particularly useful for semiconductor devices and the like because they are excellent in p-type semiconductor characteristics.

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  • Crystallography & Structural Chemistry (AREA)
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  • Metallurgy (AREA)
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  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
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Abstract

L'invention concerne un procédé de formation qui permet de former industriellement et avantageusement un film semi-conducteur d'oxyde de type p qui présente d'excellentes caractéristiques de semi-conducteur. Selon la présente invention, un gaz d'oxyde métallique qui a été obtenu par chauffage et sublimation d'un corps solide d'un oxyde métallique (tel que de l'oxyde d'iridium) est utilisé en tant que matière première pour faire croître des cristaux sur une base (telle qu'un substrat de saphir) et former un film semi-conducteur d'oxyde de type p qui a une structure de corindon, une épaisseur de film d'au moins 50 nm, et une rugosité de surface inférieure ou égale à 10 nm.
PCT/JP2018/042345 2017-11-15 2018-11-15 Procédé de formation de film semi-conducteur d'oxyde de type p Ceased WO2019098294A1 (fr)

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Cited By (1)

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JP2023044693A (ja) * 2021-09-18 2023-03-31 国立大学法人大阪大学 金属酸化物結晶の製造方法、金属酸化物エピタキシャル結晶積層基板の製造方法、半導体装置の製造方法、金属酸化物結晶、金属酸化物エピタキシャル結晶積層基板、半導体装置、及び金属酸化物結晶製造装置

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JP2011516388A (ja) * 2008-04-10 2011-05-26 コミッサリア ア ロンネルジー アトミック エ オ ゾンネルジー ザルテルナティーフ 高温で化学的に活性化された昇華によりシード上に酸化亜鉛（ＺｎＯ）の多結晶および単結晶を調製する方法およびこの方法を行うためのデバイス
WO2016035696A1 (fr) * 2014-09-02 2016-03-10 株式会社Flosfia Structure stratifiée, procédé de fabrication de celle-ci, dispositif à semi-conducteur, et film cristallin

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JP2011516388A (ja) * 2008-04-10 2011-05-26 コミッサリア ア ロンネルジー アトミック エ オ ゾンネルジー ザルテルナティーフ 高温で化学的に活性化された昇華によりシード上に酸化亜鉛（ＺｎＯ）の多結晶および単結晶を調製する方法およびこの方法を行うためのデバイス
WO2016035696A1 (fr) * 2014-09-02 2016-03-10 株式会社Flosfia Structure stratifiée, procédé de fabrication de celle-ci, dispositif à semi-conducteur, et film cristallin

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2023044693A (ja) * 2021-09-18 2023-03-31 国立大学法人大阪大学 金属酸化物結晶の製造方法、金属酸化物エピタキシャル結晶積層基板の製造方法、半導体装置の製造方法、金属酸化物結晶、金属酸化物エピタキシャル結晶積層基板、半導体装置、及び金属酸化物結晶製造装置
JP7763408B2 (ja) 2021-09-18 2025-11-04 国立大学法人大阪大学 金属酸化物結晶の製造方法、金属酸化物エピタキシャル結晶積層基板の製造方法、半導体装置の製造方法、金属酸化物結晶、金属酸化物エピタキシャル結晶積層基板、半導体装置、及び金属酸化物結晶製造装置

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