JP7295540B2 - 成膜方法、及び、半導体装置の製造方法 - Google Patents
成膜方法、及び、半導体装置の製造方法 Download PDFInfo
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- JP7295540B2 JP7295540B2 JP2021543936A JP2021543936A JP7295540B2 JP 7295540 B2 JP7295540 B2 JP 7295540B2 JP 2021543936 A JP2021543936 A JP 2021543936A JP 2021543936 A JP2021543936 A JP 2021543936A JP 7295540 B2 JP7295540 B2 JP 7295540B2
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- bismuth
- oxide film
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- gallium
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- 238000000034 method Methods 0.000 title claims description 71
- 239000004065 semiconductor Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 239000000758 substrate Substances 0.000 claims description 98
- 239000003595 mist Substances 0.000 claims description 83
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 57
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 57
- 150000001622 bismuth compounds Chemical class 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 45
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 44
- 229910052797 bismuth Inorganic materials 0.000 claims description 39
- 150000002259 gallium compounds Chemical class 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 14
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 12
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 10
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003437 indium oxide Inorganic materials 0.000 claims description 7
- ZREIPSZUJIFJNP-UHFFFAOYSA-K bismuth subsalicylate Chemical compound C1=CC=C2O[Bi](O)OC(=O)C2=C1 ZREIPSZUJIFJNP-UHFFFAOYSA-K 0.000 claims description 6
- 229960000782 bismuth subsalicylate Drugs 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229940036348 bismuth carbonate Drugs 0.000 claims description 5
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 4
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002472 indium compounds Chemical class 0.000 claims description 4
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- NLDDQRVTQQXDTH-UHFFFAOYSA-K Cl[Bi](Cl)(Cl)=O Chemical compound Cl[Bi](Cl)(Cl)=O NLDDQRVTQQXDTH-UHFFFAOYSA-K 0.000 claims description 3
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 claims description 3
- 229940068603 bismuth chloride oxide Drugs 0.000 claims description 3
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 3
- JAONZGLTYYUPCT-UHFFFAOYSA-K bismuth subgallate Chemical compound OC(=O)C1=CC(O)=C2O[Bi](O)OC2=C1 JAONZGLTYYUPCT-UHFFFAOYSA-K 0.000 claims description 3
- 229960000199 bismuth subgallate Drugs 0.000 claims description 3
- ZZUFUNZTPNRBID-UHFFFAOYSA-K bismuth;octanoate Chemical compound [Bi+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O ZZUFUNZTPNRBID-UHFFFAOYSA-K 0.000 claims description 3
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 3
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- MYXUYXMJVQWRPU-UHFFFAOYSA-N triethoxybismuthane Chemical compound [Bi+3].CC[O-].CC[O-].CC[O-] MYXUYXMJVQWRPU-UHFFFAOYSA-N 0.000 claims description 3
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- VDQDGCAHVVNVDM-UHFFFAOYSA-K bismuth;triperchlorate Chemical compound [Bi+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O VDQDGCAHVVNVDM-UHFFFAOYSA-K 0.000 claims 1
- 239000000243 solution Substances 0.000 description 81
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 29
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000370 acceptor Substances 0.000 description 17
- 239000012159 carrier gas Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- SPZQBIKOLJJINP-UHFFFAOYSA-K [Bi+3].CC([O-])=[O+][O-].CC([O-])=[O+][O-].CC([O-])=[O+][O-] Chemical compound [Bi+3].CC([O-])=[O+][O-].CC([O-])=[O+][O-].CC([O-])=[O+][O-] SPZQBIKOLJJINP-UHFFFAOYSA-K 0.000 description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 2
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- DWRNSCDYNYYYHT-UHFFFAOYSA-K gallium(iii) iodide Chemical compound I[Ga](I)I DWRNSCDYNYYYHT-UHFFFAOYSA-K 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- H01L21/02104—Forming layers
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/0242—Crystalline insulating materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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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
- 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
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
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- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Description
図1に示す成膜装置10は、基板70上に酸化物膜を形成する装置である。成膜装置10は、基板70が配置される炉12と、炉12を加熱するヒータ14と、炉12に接続されたミスト供給装置20と、炉12に接続された排出管80を備えている。
次に、成膜装置10を用いた成膜方法について説明する。実施例1では、基板70として、表面に(010)結晶面が露出しているβ型酸化ガリウム(β‐Ga2O3)の単結晶によって構成された基板を用いる。また、実施例1では、基板70の表面に、β型酸化ガリウム膜を形成する。また、実施例1では、溶液60として、塩化ガリウム(GaCl3またはGa2Cl6)と塩基性硝酸ビスマス(4BiNO3(OH)2・BiO(OH))が溶解した水溶液を用いる。塩化ガリウムは、酸化ガリウム膜の原料である。塩基性硝酸ビスマスは、酸化ガリウム膜にドープするためのビスマスを供給する。すなわち、実施例1では、酸化物膜がβ型酸化ガリウム膜であり、酸化物膜材料が塩化ガリウムであり、ビスマス化合物が塩基性硝酸ビスマスである。溶液60には、0.5mol/Lの濃度で塩化ガリウムが溶解しており、0.01mol/Lの濃度で塩基性硝酸ビスマスが溶解している。また、実施例1では、搬送ガス64として窒素ガスを用い、希釈ガス66として窒素ガスを用いる。
次に、実施例2の成膜方法について説明する。実施例2では、基板70としてサファイア(Al2O3)によって構成された基板を用いる。また、実施例2では、基板70の表面に、α型酸化ガリウム膜を形成する。また、実施例2では、溶液60として、臭化ガリウム(GaBr3、Ga2Br6)と塩基性硝酸ビスマスが溶解した水溶液を用いる。臭化ガリウムは、酸化ガリウム膜の原料である。塩基性硝酸ビスマスは、酸化ガリウム膜にドープするためのビスマスを供給する。すなわち、実施例2では、酸化物膜がα型酸化ガリウム膜、酸化物膜材料が臭化ガリウム、ビスマス化合物が塩基性硝酸ビスマスである。溶液60には、0.1mol/Lの濃度で臭化ガリウムが溶解しており、0.001mol/Lの濃度で塩基性硝酸ビスマスが溶解している。また、実施例2では、搬送ガス64として窒素ガスを用い、希釈ガス66として窒素ガスを用いる。
次に、実施例3の成膜方法について説明する。実施例3では、基板70として、ガラスによって構成された基板を用いる。また、実施例3では、基板70の表面に、酸化亜鉛膜(ZnO)を形成する。また、実施例3では、溶液60として、酢酸亜鉛(ZnAc2:但し、Acはアセチル基を表す)と塩基性硝酸ビスマスが溶解した水溶液を用いる。酢酸亜鉛は、酸化亜鉛膜の原料である。塩基性硝酸ビスマスは、酸化亜鉛膜にドープするためのビスマスを供給する。すなわち、実施例3では、酸化物膜が酸化亜鉛膜、酸化物膜材料が酢酸亜鉛、ビスマス化合物が塩基性硝酸ビスマスである。溶液60には、0.05mol/Lの濃度で酢酸亜鉛が溶解しており、0.001mol/Lの濃度で塩基性硝酸ビスマスが溶解している。また、実施例3では、搬送ガス64として窒素ガスを用い、希釈ガス66として窒素ガスを用いる。
Claims (20)
- ビスマスがドープされており、半導体または導体の特性を有し、酸化インジウム、酸化ガリウム、酸化ガリウムを含む酸化物、または、これらを組み合わせた酸化物により構成された酸化物膜を基体上に形成する成膜方法であって、
前記基体を加熱しながら、前記酸化物膜の構成元素を含む酸化物膜材料とビスマス化合物が溶解した溶液のミストを前記基体の表面に供給する工程、
を有し、
前記ビスマス化合物が、ビスマスエトキシド、酢酸ビスマス、2-エチルヘキサン酸ビスマス、オクタン酸ビスマス、ナフテン酸ビスマス、次没食子酸ビスマス、次サリチル酸ビスマス、塩化酸化ビスマス、クエン酸ビスマス、オキシ酢酸ビスマス、オキシ過塩素酸ビスマス、オキシサリチル酸ビスマス、ヨウ化ビスマス、水酸化ビスマス、オキシ炭酸二ビスマス、硫化ビスマス、硫酸ビスマス、及び、炭酸ビスマスからなるグループから選択される物質である、成膜方法。 - 前記酸化物膜材料と前記ビスマス化合物が溶解した溶液のミストを前記基体の前記表面に供給する前記工程が、
前記酸化物膜材料と前記ビスマス化合物の両方が溶解した溶液からミストを生成する工程と、
前記酸化物膜材料と前記ビスマス化合物の両方が溶解した前記溶液の前記ミストを前記基体の前記表面に供給する工程、
を有する請求項1の成膜方法。 - 前記酸化物膜材料と前記ビスマス化合物が溶解した溶液のミストを前記基体の前記表面に供給する前記工程が、
前記酸化物膜材料が溶解した溶液からミストを生成する工程と、
前記ビスマス化合物が溶解した溶液からミストを生成する工程と、
前記酸化物膜材料が溶解した前記溶液の前記ミストと前記ビスマス化合物が溶解した前記溶液の前記ミストを前記基体の前記表面に供給する工程、
を有する請求項1の成膜方法。 - 前記酸化物膜が、単結晶膜である請求項1~3のいずれか一項の成膜方法。
- 前記酸化物膜が、酸化インジウム、酸化ガリウム、または、これらを組み合わせた酸化物により構成されており、
前記酸化物膜材料が、インジウム化合物、及び、ガリウム化合物の少なくとも1つを含む、
請求項1~4のいずれか一項の成膜方法。 - 前記酸化物膜が、酸化ガリウム、または、酸化ガリウムを含む酸化物により構成されており、
前記酸化物膜材料が、ガリウム化合物である、
請求項1~4のいずれか一項の成膜方法。 - 前記ガリウム化合物が、有機物である請求項6の成膜方法。
- 前記ガリウム化合物が、金属錯体である請求項6または7の成膜方法。
- 前記ガリウム化合物が、ガリウムアセチルアセトナートである請求項6~8のいずれか一項の成膜方法。
- 前記ガリウム化合物が、ハロゲン化物である請求項6の成膜方法。
- 前記ガリウム化合物が、塩化ガリウムである請求項6または10の成膜方法。
- 前記酸化物膜材料と前記ビスマス化合物が溶解した前記溶液の前記ミストに含まれるビスマス原子の数が、前記酸化物膜材料と前記ビスマス化合物が溶解した前記溶液の前記ミストに含まれるインジウム原子、アルミニウム原子、及び、ガリウム原子の総数の1000倍以下である、請求項1~11のいずれか一項の成膜方法。
- 前記基体が、酸化ガリウムにより構成されている請求項1~12のいずれか一項の成膜方法。
- 前記基体が、β‐Ga2O3により構成されている請求項13の成膜方法。
- 前記基体が、α‐Ga2O3により構成されている請求項13の成膜方法。
- 前記基体が、α‐Al2O3により構成されている請求項1~12のいずれか一項の成膜方法。
- 前記酸化物膜が、β‐Ga2O3により構成されている請求項1~16のいずれか一項の成膜方法。
- 前記酸化物膜が半導体膜であり、
前記酸化物膜にアクセプタをドープする工程を有する、
請求項1~17のいずれか一項の成膜方法。 - 前記酸化物膜を形成するときに、前記基体を400~1000℃に加熱する請求項1~18のいずれか一項の成膜方法。
- 半導体装置の製造方法であって、請求項1~19のいずれか一項の成膜方法によって前記酸化物膜を形成する工程を備える、製造方法。
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