WO2015005202A1 - 半導体装置及びその製造方法、並びに結晶及びその製造方法 - Google Patents
半導体装置及びその製造方法、並びに結晶及びその製造方法 Download PDFInfo
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- WO2015005202A1 WO2015005202A1 PCT/JP2014/067715 JP2014067715W WO2015005202A1 WO 2015005202 A1 WO2015005202 A1 WO 2015005202A1 JP 2014067715 W JP2014067715 W JP 2014067715W WO 2015005202 A1 WO2015005202 A1 WO 2015005202A1
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- aluminum
- oxide
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- 239000013078 crystal Substances 0.000 title claims abstract description 391
- 239000004065 semiconductor Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000010431 corundum Substances 0.000 claims abstract description 77
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 77
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 57
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 55
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims description 108
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 94
- 239000002994 raw material Substances 0.000 claims description 94
- 230000015572 biosynthetic process Effects 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 69
- 150000004767 nitrides Chemical class 0.000 claims description 61
- -1 aluminum compound Chemical class 0.000 claims description 53
- 239000010419 fine particle Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 150000002259 gallium compounds Chemical class 0.000 claims description 17
- 150000002472 indium compounds Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000005121 nitriding Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 abstract description 41
- 239000010408 film Substances 0.000 description 122
- 239000000243 solution Substances 0.000 description 61
- 239000010409 thin film Substances 0.000 description 56
- 239000000758 substrate Substances 0.000 description 34
- 229910001195 gallium oxide Inorganic materials 0.000 description 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 26
- 239000012159 carrier gas Substances 0.000 description 22
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 21
- 229910052733 gallium Inorganic materials 0.000 description 21
- 239000003595 mist Substances 0.000 description 18
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000000137 annealing Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 7
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- 229910002601 GaN Inorganic materials 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 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 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005468 ion implantation Methods 0.000 description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DEVXQDKRGJCZMV-UHFFFAOYSA-K Aluminum acetoacetate Chemical compound [Al+3].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O DEVXQDKRGJCZMV-UHFFFAOYSA-K 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- DWRNSCDYNYYYHT-UHFFFAOYSA-K gallium(iii) iodide Chemical compound I[Ga](I)I DWRNSCDYNYYYHT-UHFFFAOYSA-K 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- SKWCWFYBFZIXHE-UHFFFAOYSA-K indium acetylacetonate Chemical compound CC(=O)C=C(C)O[In](OC(C)=CC(C)=O)OC(C)=CC(C)=O SKWCWFYBFZIXHE-UHFFFAOYSA-K 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
-
- 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
-
- 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
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- 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
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/04—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their crystalline structure, e.g. polycrystalline, cubic or particular orientation of crystalline planes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/122—Single quantum well structures
Definitions
- the present invention relates to a semiconductor device including a corundum structure oxide crystal, a manufacturing method thereof, and a crystal and a manufacturing method thereof.
- a mist CVD method is known as a method for forming an ⁇ -phase single phase of a highly crystalline gallium oxide thin film on a film formation sample (Patent Document 1).
- a raw material solution is prepared by dissolving a gallium compound such as gallium acetylacetonate in an acid such as hydrochloric acid, and a raw material mist is generated by misting the raw material solution.
- the raw material mist is covered with a carrier gas.
- a high-crystalline gallium oxide thin film is formed on the film formation sample by supplying the film formation surface of the film formation sample and reacting the raw material mist at about 400 ° C. to form a thin film on the film formation surface. Yes.
- Gallium oxide has an extremely large band gap of 5 eV or more and is expected to be applied to power devices.
- corundum-structured gallium oxide ( ⁇ phase) is disclosed in Non-Patent Document 1 as a mixed crystallization technique with indium, aluminum, iron, chromium, and the like. Functional addition and device application are expected.
- the most stable phase of gallium oxide is said to be a beta-gallia structure ( ⁇ phase), and the corundum structure is a metastable phase.
- a beta-gallia structural phase appears in post-treatment at high temperature and film formation at high temperature, and it is difficult to create and maintain a single phase.
- it is considered that the use of a single-phase crystal phase is suitable for semiconductor device applications, and it is considered to be the greatest problem in device application of corundum gallium oxide materials.
- the problems will be summarized below during film formation and after film formation.
- Patent Document 1 During the film formation of gallium oxide, the most stable phase is easily formed as the reaction temperature increases. Also in Patent Document 1, as shown in FIG. 2, it is a pure ⁇ phase up to 400 ° C., but the ⁇ phase begins to mix at 450 ° C., and at 500 ° C., the ⁇ phase becomes more dominant than the ⁇ phase. Under such circumstances, in Patent Document 1, the raw material mist is reacted at 400 ° C. in order to form an ⁇ -phase thin film.
- the reaction temperature affects the deposition rate and dopant concentration, and when forming a mixed crystal film, it affects the atomic ratio of the constituent metal elements, so optimize these parameters. Therefore, we want to change the reaction temperature appropriately. In particular, it is considered that it is desirable to make the film forming temperature as high as possible in order to reduce impurities in the semiconductor crystal, and therefore, establishment of a high temperature film forming method is a problem.
- the semiconductor device process includes a process that requires heating. Even if the ⁇ phase can be formed, part or all of the phase transitions to the ⁇ phase by this heating step.
- Specific heating processes include impurity thermal diffusion processes, surface / interface modification processes, hot implantation, and post-ion implantation crystallinity improvement annealing, and all these heating processes must be avoided to realize devices. Is impractical and improving heat resistance is essential for industrial applications.
- Non-Patent Document 1 discloses that annealing treatment is effective for activating tin dopant in the ⁇ phase of gallium oxide, in the prior art, when ⁇ -type Ga 2 O 3 is annealed, one crystal is obtained. This is not possible because part or all of the phase transitions to the ⁇ phase.
- the present invention has been made in view of such circumstances, and provides a semiconductor device or crystal in which phase transition of a corundum structure oxide crystal at high temperature is suppressed.
- a corundum structure oxide crystal containing one or both of indium atoms and gallium atoms The oxide crystal is a semiconductor device or a crystal structure containing an aluminum atom in at least a gap between lattice points of a crystal lattice.
- a corundum structure oxide crystal containing one or both of indium atoms and gallium atoms The oxide crystal contains an aluminum atom, A semiconductor device or a crystal structure, wherein a c-axis length when the oxide crystal contains an aluminum atom is larger than a c-axis length when the oxide crystal does not contain an aluminum atom.
- the present inventors used aluminum halide as an aluminum source, and formed a film by supplying fine particles obtained by atomizing a raw material solution dissolved in water together with a gallium source to a film forming chamber.
- aluminum halide is not suitable as an aluminum source.
- the present inventors reviewed the X-ray diffraction graph again to find out the origin of this mysterious phenomenon. Then, when the position of the peak was observed in detail, it was found that the position of the peak of X-ray diffraction was slightly shifted to the low angle side in the thin film formed using the raw material solution containing the aluminum halide and the gallium source. .
- the fact that the position of the X-ray diffraction peak shifts to the lower angle side means that the c-axis length of the crystal has increased.
- aluminum has a smaller atomic radius than gallium, if gallium is replaced with aluminum, the c-axis length will be small, and the X-ray diffraction peak position should shift to the high angle side.
- the phenomenon that the peak position of the X-ray diffraction was shifted to the low angle side was not observed.
- the c-axis length should be small. Then, it is derived from the phenomenon that the c-axis length is increased by the addition of aluminum.
- Aluminum added as aluminum halide does not replace gallium, but enters the gaps between the lattice points of the crystal lattice, thereby It means that the crystal lattice expands. And since the aluminum which exists in the clearance gap between this lattice point inhibits a phase transition, it is thought that the phase transition temperature to (beta) phase when heat-processing was performed became high remarkably. Further, such a phenomenon is not limited to corundum structure gallium oxide, and is considered to be similarly applied to a corundum structure oxide crystal containing one or both of indium atoms and gallium atoms.
- a corundum structure oxide crystal containing one or both of indium atoms and gallium atoms contains aluminum atoms on one or both of the lattice points of the crystal lattice and the gaps between the lattice points,
- the atomic ratio of aluminum atoms present on lattice points of the crystal lattice of the oxide crystal is greater than 0 and less than or equal to 2.9% with respect to the total of indium atoms and gallium atoms in the oxide crystal Device or crystal structure.
- the present inventors added a small amount of conventional aluminum acetylacetonate to create a thin film made of oxide crystals in which aluminum atoms are present on lattice points.
- the present inventors have found that the atomic ratio of aluminum atoms on lattice points is greater than 0 and 2.9% or less with respect to the sum of indium atoms and gallium atoms. This means that even if the amount is very small, aluminum atoms have an effect of suppressing the phase transition from the ⁇ phase to the ⁇ phase. It has not been conventionally known that such a small amount of aluminum atoms exhibits a phase transition suppressing effect.
- the present inventors have shown that the aluminum atom exhibits an extremely excellent phase transition suppressing effect when present in the gaps between the lattice points, but exhibits a certain degree of phase transition suppressing effect even when present on the lattice points. It was revealed.
- corundum structure oxidation containing one or both of indium atoms and gallium atoms is performed. An oxide crystal that hardly undergoes phase transition can be obtained while substantially maintaining the original crystal properties of the physical crystal.
- the structural example of the semiconductor device or crystal structure which can be manufactured with the manufacturing method of the oxide crystal thin film of one Embodiment of this invention is shown. It is a block diagram of the mist CVD apparatus used in the Example of this invention. It is an XRD pattern which shows that an alpha phase peak moves to the low angle side with the increase in the addition amount of aluminum bromide in a raw material solution. (A) is an XRD pattern showing that the ⁇ -phase peak moves to the lower angle side as the amount of aluminum bromide added in the raw material solution increases, and (b) shows aluminum acetylacetate in the raw material solution. It is an XRD pattern which shows that an alpha phase peak moves to a high angle side with the increase in the addition amount of a nate.
- (A) is an XRD pattern before and after annealing of an oxide crystal prepared under condition 1 where no aluminum is added
- (b) is an oxide crystal prepared under condition 2 where aluminum bromide is added to the raw material solution. It is an XRD pattern before and after annealing. It is an XRD pattern before and behind annealing of the oxide crystal created on the conditions which added aluminum acetylacetonate in the raw material solution.
- (A) is an XRD pattern showing the effect of providing an iron oxide buffer between the GaN substrate and the oxide crystal.
- (B) is an XRD pattern showing that an ⁇ -phase oxide crystal is formed even when an iron oxide buffer is provided between the SiC substrate and the oxide crystal.
- the semiconductor device or crystal structure of one embodiment of the first aspect of the present invention is a corundum structure oxide crystal containing one or both of indium atoms and gallium atoms.
- the oxide crystal contains an aluminum atom in at least a gap between lattice points of the crystal lattice.
- the “crystal structure” is a structure including one or more crystal layers, and may include a layer other than the crystal layer (eg, an amorphous layer).
- the crystal layer is preferably a single crystal layer, but may be a polycrystalline layer.
- the corundum structure oxide crystal targeted by this embodiment includes one or both of indium atoms and gallium atoms. It is essential that aluminum atoms exist in the gaps between the lattice points of the crystal lattice, and may exist only in the gaps between the lattice points, and exist both in the gaps between the lattice points and on the lattice points. You may do it.
- the “lattice point” means a point where a metal atom (eg, indium atom, gallium atom) constituting a corundum structure exists.
- the c-axis length of the crystal lattice is larger than when the aluminum atom is not in the gap between the lattice points. Also grows. Further, since the aluminum atoms inhibit the phase transition, the effect of suppressing the phase transition can be obtained by the presence of the aluminum atoms in the gaps between the lattice points.
- the extent to which the c-axis length increases is determined by the amount of aluminum on the lattice points and the amount of aluminum in the gaps between the lattice points, but the oxidation relative to the c-axis length when the oxide crystal does not contain aluminum atoms.
- the value of the ratio of c-axis length when the physical crystal contains an aluminum atom is, for example, 1.0001 or more. Specifically, for example, 1.0001, 1.0002, 1.0003, 1.0004, 1.0005, 1.0006, 1.0007, 1.0008, 1.0009, 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.01, 1.02, 1.03, 1.04, 1.05, 1. 06, 1.07, 1.08, 1.09, 1.1, and may be within a range between any two of the numerical values exemplified here. Note that the value of this ratio is influenced by the composition of the oxide crystal, the film formation method, the proportion of aluminum atoms, and the like.
- the oxide crystal containing an aluminum atom does not contain an aluminum atom. It is preferable to form oxide crystals by the same film formation method (eg, mist CVD method) and measure the c-axis length of the obtained oxide crystals using the same apparatus. In addition, since the lattice constant and c-axis length of the film formation sample are also affected by the film formation sample, the same film formation sample should be used when comparing the c-axis length.
- composition of atoms on lattice points forming a corundum structure of a corundum structure oxide crystal containing one or both of an indium atom and a gallium atom is represented by the general formula (1).
- General formula (1): In X Al Y Ga Z O 3 ( a 0 ⁇ X ⁇ 2,0 ⁇ Y ⁇ 2,0 ⁇ Z ⁇ 2, X + Y + Z 1.5 ⁇ 2.5, a 0 ⁇ X or 0 ⁇ Z.)
- Al in the general formula (1) represents an aluminum atom existing on a lattice point
- Y indicating the amount of Al may be 0 or may be larger than 0 (that is, Y> 0). ).
- X and Y when X and Y are 0, it becomes ⁇ -type Ga 2 O 3
- X and Z when X and Z are 0, ⁇ -type In 2 O 3
- Z It may be a Ga-rich composition with ⁇ 0.5 and X ⁇ 0.5, or an In-rich composition with X ⁇ 0.5 and Z ⁇ 0.5.
- X, Y, and Z are specifically, for example, 0, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 and 2 and may be in a range between any two of the numerical values exemplified here.
- X + Y or X + Y + Z is, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2 .5, and may be within a range between any two of the numerical values exemplified here.
- the corundum structure oxide crystal targeted by this embodiment has a metal or oxygen atom in the gaps between the lattice points. Also included are metal-excess oxides and oxygen-excess oxides in which atoms are present.
- the composition containing both the atom which exists on a lattice point, and the atom which exists in the clearance gap between lattice points is also a composition represented by the said general formula.
- the composition of the corundum structure oxide crystal targeted by this embodiment is not limited to the above, and even a crystal in which a metal element that becomes a trivalent ion such as Ti or Ni exists on a lattice point. Good. Further, an impurity (eg, Sn) that imparts electrical conductivity to the corundum structure oxide crystal may be added.
- the atomic ratio of aluminum atoms present on the lattice points is not particularly limited, but is preferably greater than 0 and 2.9% or less with respect to the sum of indium atoms and gallium atoms. Since such a small amount of aluminum atoms does not have a great influence on the crystal properties such as the band gap width, according to this embodiment, the corundum structure oxide crystal containing one or both of indium atoms and gallium atoms is essential. Thus, it is possible to obtain an oxide crystal that hardly undergoes phase transition while substantially maintaining the crystal physical properties.
- the atomic ratio of aluminum atoms is, for example, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0 .8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9%, and within the range between any two of the numerical values exemplified here It may be. Strictly speaking, the atomic ratio of aluminum atoms can be determined by SIMS measurement, but it can also be calculated approximately from the peak of X-ray diffraction.
- the point of the present invention is that crystal growth is performed so that aluminum atoms enter gaps between lattice points of the corundum structure oxide crystal.
- the inventors of the present invention have used aluminum acetylacetonate that has been conventionally used as an aluminum source in a film formation method (eg, mist CVD or a similar method) in which film formation is performed using a finely divided raw material solution. Instead, by using aluminum halide (fluoride, chloride, bromide, aluminum iodide), it has succeeded in including aluminum atoms in the gaps between lattice points, and has excellent characteristics that it is difficult to undergo phase transition. Corundum structure oxide crystals were obtained.
- a method for forming a semiconductor device or a method for manufacturing a crystal structure comprising a crystal forming step of forming fine corundum structure oxide crystals by supplying fine particles to a film formation chamber, wherein the aluminum compound contains an aluminum halide.
- the present inventors made it possible to introduce aluminum atoms into gaps between lattice points by using aluminum halide, which is a film forming method in which film formation is performed using a finely divided raw material solution. Another method may be adopted as long as it can be introduced into the gap between the points.
- the temperature of the film formation chamber can be made relatively high, or the temperature of the heating process after the crystal formation process can be made high. Benefits are gained. Specifically, after the crystal formation step, a film formation sample on which a thin film of oxide crystals is formed is taken out of the film formation chamber, and a semiconductor device is manufactured by performing device processes such as ion implantation, etching, and photolithography. However, in these device processes, the formed corundum structure oxide crystals are exposed to high temperatures in impurity thermal diffusion processes, surface / interface modification processes, hot implantation, post-implantation crystallinity improvement annealing, etc.
- the phase transition from the ⁇ phase to the ⁇ phase is likely to occur.
- the temperature of these high-temperature processes can be made relatively high, process efficiency and semiconductor manufactured The quality of the equipment can be stabilized.
- the temperature at which the oxide crystal is heated in the process after the crystal formation step is, for example, 400 ° C. or higher, preferably 400 to 1000 ° C. Specifically, this temperature is, for example, 400, 500, 600, 700, 800, 900, 1000 ° C., and may be within a range between any two of the numerical values exemplified here.
- the raw material solution can be prepared by dissolving one or both of an indium compound and a gallium compound and an aluminum compound in a solvent.
- indium compounds include indium organometallic complexes (eg, indium acetylacetonate) and indium halides (fluorination, chloride, bromide, indium iodide).
- gallium compound include gallium organometallic complexes (eg, gallium acetylacetonate) and gallium halides (fluorination, chloride, bromide, gallium iodide).
- the aluminum compound contains at least aluminum halide.
- the aluminum halide include fluorination, chloride, bromide, or aluminum iodide.
- the indium compound and the gallium compound a halide is preferable from the viewpoint that the amount of carbon impurities mixed in the crystal is small, the film formation rate is high, and a corundum structure is likely to be formed even at high temperature, Bromide or iodide is more preferred, and bromide is particularly preferred.
- the aluminum halide aluminum bromide is preferable. This is because in this case, aluminum atoms easily enter the gaps between the lattice points.
- the indium compound, the aluminum compound, and the gallium compound may be dissolved in the same raw material solution, and the raw material fine particles generated by preparing separate raw material solutions and separately forming fine particles are formed before the film formation chamber or in the film formation chamber. You may mix.
- the indium compound and the gallium compound may be made fine from one raw material solution, and the aluminum compound may be made fine from another raw material solution.
- the organometallic complex is preferably used as a raw material solution different from the halide.
- the anion exchange reaction proceeds, and gallium acetylacetonate and aluminum bromide are generated. This is because there may be a problem that the ratio of aluminum atoms decreases.
- the concentration of the indium compound, gallium compound, aluminum halide, and aluminum organometallic complex in the raw material solution is not particularly limited, but is, for example, 0.001 to 10 mol / L, preferably 0.005 to 2 mol / L, respectively.
- L. This concentration is 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.0. It is 1, 0.2, 0.5, 1, 2, 5, 10 mol / L, and may be within a range between any two of the numerical values exemplified here.
- the solvent of the raw material solution water (preferably ultrapure water), an organic solvent (eg, methanol), or various solvents that can be microparticulated such as a mixture of water and an organic solvent can be used and formed.
- the solvent is preferably water, and preferably does not contain an organic solvent.
- a dopant compound can be added to the raw material solution, whereby conductivity can be imparted to the thin film to be formed, and it can be used as a semiconductor layer.
- the reaction solution may contain a compound other than the compounds described here, but preferably does not contain an organic compound.
- a small amount of an organic acid eg, acetic acid
- the method for producing raw material fine particles by making the raw material solution fine particles is not particularly limited, but a general method is to apply ultrasonic vibration to the raw material solution to form fine particles. Also, in other methods, for example, the raw material fine particles can be generated by atomizing the raw material solution by spraying the raw material solution.
- Carrier gas The carrier gas is, for example, nitrogen, but a gas such as argon, oxygen, ozone, or air may be used.
- the flow rate of the carrier gas is not particularly limited, but is, for example, 0.1 to 50 L / min, preferably 0.5 to 10 L / min. Specifically, this flow rate is, for example, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 L / min, and may be in a range between any two of the numerical values exemplified here.
- Film formation chamber, film formation sample, film formation Raw material fine particles are supplied to the film formation chamber by the carrier gas, and a reaction takes place in the film formation chamber to form a thin film on the film formation sample placed in the film formation chamber. Is done.
- the thin film formed on the deposition target sample is a thin film of a corundum structure oxide crystal (preferably an oxide single crystal).
- the film formation chamber is a space in which a thin film is formed, and its configuration and material are not particularly limited.
- the film forming chamber is configured to supply a carrier gas containing raw material fine particles from one end of a quartz tube and to discharge exhaust gas from the other end of the quartz tube as in the embodiment.
- the film formation sample may be arranged so that the film formation surface is horizontal, or may be arranged so as to be inclined at, for example, 45 degrees toward the carrier gas supply side.
- a fine channel method using a channel of several mm or less as a reaction region, or a linear nozzle is provided on the substrate, from which raw material fine particles (and carrier gas) are sprayed in a direction perpendicular to the substrate, and the nozzle is linear
- a linear source method of moving in the vertical direction or a film formation chamber by a method in which a plurality of methods are mixed or derived may be used.
- the film forming chamber is configured such that the inner space can be heated to a desired temperature by, for example, surrounding the film forming chamber with a heater. Further, the film formation chamber may be pressurized or depressurized instead of atmospheric pressure.
- the heating temperature of the film formation chamber during film formation is not particularly limited as long as it is a temperature at which a raw material solute (gallium compound, indium compound, aluminum halide, aluminum organometallic complex, etc.) contained in the raw material solution can be chemically reacted.
- a raw material solute gallium compound, indium compound, aluminum halide, aluminum organometallic complex, etc.
- the heating temperature is preferably 500 ° C. or higher, and more preferably 550 ° C. or higher.
- the phase transition to the ⁇ phase was easy, but in the method of this embodiment, the aluminum halide functions as a phase transition inhibitor and the phase transition to the ⁇ phase is suppressed. .
- the heating temperature is, for example, 300, 400, 450, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 700, 800, 900, 1000, 1500 ° C. It may be within a range between any two of the numerical values exemplified here.
- the film formation sample is not particularly limited as long as a thin film can be formed, but a substrate or a thin film having a corundum structure is preferable.
- the substrate having a corundum structure include a sapphire substrate and an ⁇ -type gallium oxide substrate.
- the thin film having a corundum structure include a thin film having a corundum structure formed on a base substrate having a corundum structure or another structure. This is preferable because a thin film having a corundum structure such as ⁇ -type gallium oxide can be easily formed on a substrate or thin film having a corundum structure.
- the film formation sample may not have a corundum structure.
- the film formation sample having no corundum structure include a substrate or a thin film (eg, GaN crystal) having a hexagonal crystal structure.
- a corundum structure oxide crystal can be formed directly or through a buffer layer on a substrate or thin film having a hexagonal crystal structure.
- As the buffer layer according to the experiments by the present inventors, an iron oxide (Fe 2 O 3 ) layer of an amorphal phase formed at a relatively low temperature of 200 to 500 ° C. was particularly effective.
- the “amorphous phase” in this specification includes those in which microcrystals are dispersed in an amorphal phase.
- the film formation temperature of the iron oxide layer is, for example, 200, 250, 300, 350, 400, 450, 500 ° C., and is within a range between any two of the numerical values exemplified here. May be.
- FIG. 1 shows an example of a semiconductor device or crystal body that can be manufactured by the method of this embodiment.
- the crystalline stress relaxation layer 2, the semiconductor layer 3, the cap layer 4, and the insulating film 5 are formed in this order on the base substrate 1. You may laminate on the base substrate 1 in order from an insulating film.
- the crystalline stress relaxation layer 2 and the cap layer 4 may be omitted if not necessary.
- the base substrate 1 and the semiconductor layer 3 or the semiconductor layer 3 and the insulating film 5 are formed of different materials having a corundum structure, the semiconductor layer 3 and the insulating film 5, the base substrate 1 and the semiconductor layer 3, and the crystallinity
- a structural phase transition prevention layer having a corundum structure may be formed in at least one of the stress relaxation layer 2 and the semiconductor layer 3 and between the cap layer 4 and the insulating film 5.
- the crystal growth temperature for forming the crystalline stress relaxation layer 2, the semiconductor layer 3, the cap layer 4, and the insulating film 5 is higher than the crystal structure transition temperature below the formation layer, a structural phase transition prevention layer is formed.
- the corundum structure from changing to a different crystal structure.
- the formation temperature of the crystalline stress relaxation layer 2 the semiconductor layer 3, the cap layer 4 and the insulating film 5 is lowered in order to prevent the phase transition of the crystal structure, the crystallinity is lowered. Therefore, it is difficult to suppress the change of the crystal structure by lowering the film formation temperature, and the formation of the structural phase transition prevention layer is effective.
- a group III nitride crystal layer may be formed on the oxide crystal directly or via a buffer layer.
- the group III nitride crystal layer is preferably uniaxially oriented, but may not be uniaxially oriented.
- the group III nitride crystal layer is usually formed by a film formation method (MOCVD method, HVPE method, etc.) having a film formation temperature of 570 ° C. or higher when mass-producing products. Since a corundum structure oxide crystal containing one or both is likely to undergo a phase transition when exposed to such a high temperature, conventionally, such an oxide crystal is used as a base sample (substrate or substrate) of a group III nitride crystal layer.
- the oxide crystal As a thin film), it was difficult to use.
- the oxide crystal since the phase transition of the oxide crystal is suppressed by containing aluminum atoms in the gaps between the lattice points, the oxide crystal is converted into a group III nitride crystal layer. It can be used as a base sample for formation.
- the film forming temperature is 570 ° C. or higher, for example, 570 to 1300 ° C., specifically, for example, 570, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, and 1300 ° C., and may be within a range between any two of the numerical values exemplified here.
- a semiconductor device or crystal structure of an embodiment of the second aspect of the present invention is a corundum structure oxide crystal containing one or both of indium atoms and gallium atoms.
- the oxide crystal contains aluminum atoms on one or both of the lattice points of the crystal lattice and the gaps between the lattice points, and the atomic ratio of the aluminum atoms present on the lattice points of the crystal lattice of the oxide crystal Is greater than 0 and 2.9% or less with respect to the sum of indium atoms and gallium atoms in the oxide crystal.
- the description of “crystal structure” is the same as in the first aspect.
- the semiconductor device or structure crystal according to the first aspect is required to have aluminum atoms in the gaps between the lattice points of the crystal lattice.
- the corundum The position where the aluminum atom exists in the structure oxide crystal is not limited, and the aluminum atom may be present on one or both of the lattice points of the crystal lattice and the gap between the lattice points. That is, aluminum atoms may exist only on the lattice points of the crystal lattice, or may exist only in the gaps between the lattice points, or both.
- the inventors show that the aluminum atom exhibits an extremely excellent phase transition suppression effect when present in the gaps between the lattice points, but exhibits a certain degree of phase transition suppression effect even when present on the lattice points.
- the effect of suppressing the phase transition is compared with the atomic ratio of aluminum atoms in which the atomic ratio of aluminum atoms on the lattice points is greater than 0 and 2.9% or less with respect to the sum of indium atoms and gallium atoms. It was discovered that even if it is small, it can be demonstrated. Since such a small amount of aluminum atoms does not have much influence on crystal properties such as the band gap width, conventionally, such a small amount of aluminum atoms has not been added.
- the invention of the second aspect is not intended to affect the crystal physical properties such as the band gap width, but is not conventionally attempted to obtain the effect of suppressing the phase transition of the aluminum atom, 2.9. % Of aluminum atoms are added.
- the atomic ratio of aluminum atoms is, for example, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0 .8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9%, and within the range between any two of the numerical values exemplified here It may be.
- the atomic ratio of aluminum atoms can be determined by SIMS measurement, but it can also be calculated approximately from the peak of X-ray diffraction.
- the c-axis length of the oxide crystal containing aluminum atoms is determined by the amount of aluminum on the lattice points and the amount of aluminum in the gaps between the lattice points, and is relative to the c-axis length when the oxide crystals do not contain aluminum atoms.
- the value of the ratio of c-axis length is, for example, 0.9991 or more. Specifically, the value of this ratio is, for example, 0.9991, 0.9992, 0.9993, 0.9994, 0.9995, 0.9996, 0.9997, 0.9998, 0.9999, 1, 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.01, 1.02, 1.03, 1.
- the value of this ratio is influenced by the composition of the oxide crystal, the film formation method, the proportion of aluminum atoms, and the like. It is not limited by the value of the ratio.
- the oxide crystal containing an aluminum atom does not contain an aluminum atom. It is preferable to form oxide crystals by the same film formation method (eg, mist CVD method) and measure the c-axis length of the obtained oxide crystals using the same apparatus.
- the same film formation sample should be used when comparing the c-axis length.
- corundum structure oxide crystal containing one or both of indium atoms and gallium atoms is the same as in the first aspect.
- the group III nitride crystal layer may be formed on such an oxide crystal directly or via a buffer layer, as in the first aspect.
- the semiconductor device manufacturing method or crystal structure manufacturing method according to the second aspect is basically the same as the method according to the first aspect. Therefore, the following explanation will be focused on the differences.
- the aluminum compound in order to introduce aluminum atoms into the gaps between lattice points, it is an essential requirement to use aluminum halide as the aluminum compound.
- aluminum halide only the abundance of aluminum atoms is defined.
- the type of the aluminum compound is not particularly limited, and for example, one or both of an aluminum organometallic complex and an aluminum halide can be used.
- the c-axis length when the oxide crystal contains an aluminum atom is 0.9991 times or more than the c-axis length when the oxide crystal does not contain an aluminum atom.
- the atomic ratio of aluminum atoms existing on the lattice points of the crystal lattice of the oxide crystal to the sum of indium atoms and gallium atoms in the oxide crystal hereinafter referred to as “in the oxide crystal”.
- one or both of the indium compound and the gallium compound and the raw material fine particles produced by finely pulverizing the same or different raw material solutions in which the aluminum compound is dissolved in a solvent together or separately are formed.
- Supplying the film chamber to form a corundum structure oxide crystal, wherein the aluminum compound has a c-axis length when the oxide crystal contains an aluminum atom, and the oxide crystal does not contain an aluminum atom A method for manufacturing a semiconductor device or a method for manufacturing a crystal structure, which is mixed to be 0.9991 times or more than the c-axis length in the case, is provided.
- the atomic ratio of aluminum atoms to the total of indium atoms and gallium atoms in the raw material does not necessarily match the aluminum atomic ratio in the oxide crystal.
- the aluminum atomic ratio in the raw material for making the aluminum atomic ratio in the crystal larger than 0 and 2.9% or less varies depending on the compound used. For example, when an aluminum organometallic complex (eg, aluminum acetylacetonate) is used as the aluminum compound, the aluminum atomic ratio in the oxide crystal tends to increase, so the aluminum atomic ratio in the oxide crystal is 2.9% or less. In order to do this, it is necessary to sufficiently reduce the aluminum organometallic complex added to the raw material.
- aluminum organometallic complex eg, aluminum acetylacetonate
- the aluminum ratio in the oxide crystal is difficult to increase. Therefore, even if the aluminum atomic ratio in the raw material is about four times, the atomic ratio of aluminum atoms in the oxide crystal Can be significantly smaller than 2.9% or less.
- the aluminum atomic ratio in the raw material is, for example, 0.1 to 20, specifically, for example, 0.1, 0.5, 1 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9 .5, 10, 15, 20, and may be within a range between any two of the numerical values exemplified here.
- a corundum structure oxide crystal containing one or both of an indium atom and a gallium atom, and a group III nitride provided on the oxide crystal directly or via a buffer layer A semiconductor device or crystal structure including a physical crystal layer (thin film) is provided.
- Corundum structure oxide crystal by supplying raw material fine particles produced by atomizing the same or different raw material solutions in which one or both of an indium compound and a gallium compound are dissolved in a solvent together or separately into a film forming chamber A method of forming a semiconductor device, and a nitride crystal layer forming step of forming a group III nitride crystal layer directly or via a buffer layer on the oxide crystal, or a crystal structure A method of manufacturing a body is provided.
- the raw material fine particles include an aluminum compound.
- the group III nitride layer is formed by a film forming method having a film forming temperature of 570 ° C. or higher (eg, MOCVD method, HVPE, etc.) from the viewpoint of realizing high mass productivity and obtaining [0] good crystallinity. Method).
- the oxide crystal contains an aluminum atom.
- this viewpoint is characterized in that a group III nitride crystal layer is provided on the oxide crystal.
- the oxide crystal is not necessarily required to contain aluminum atoms.
- the oxide crystal preferably contains an aluminum atom.
- X, Y, and Z are, for example, 0, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0, respectively. .7, 0.8, 0.9, 1 and may be within a range between any two of the numerical values exemplified here.
- X + Y + Z is, for example, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, and any of the numerical values exemplified here Or within a range between the two.
- a step of nitriding the oxide crystal layer may be provided before the nitride crystal layer forming step.
- the nitriding treatment can be performed by, for example, a method of performing plasma treatment on the oxide crystal layer in an atmosphere containing nitrogen gas.
- the corundum structure oxide crystal has a crystal structure similar to a hexagonal crystal, and the group III nitride crystal is also a hexagonal crystal. Therefore, the nitriding treatment of the corundum structure oxide crystal is compared with the nitriding treatment of ⁇ -gallium oxide. And easy.
- an oxynitride layer including one or both of indium atoms and gallium atoms is formed between the oxide crystal layer and the nitride crystal layer.
- an oxide crystal layer containing one or both of indium atoms and gallium atoms may be further provided on the nitride crystal layer directly or via a buffer layer.
- a sandwich structure in which the nitride crystal layer is sandwiched between the oxide crystal layers is formed.
- a nitride crystal layer and an oxide crystal layer may be further repeatedly formed.
- a quantum well can be formed by such a sandwich structure.
- the oxide crystal layer on the nitride crystal layer may have an ⁇ -type crystal structure (corundum structure) or a ⁇ -type crystal structure.
- a semiconductor device comprising a group III nitride crystal layer and an oxide crystal layer provided thereon and containing one or both of indium atoms and gallium atoms, or A crystalline structure.
- a method or a method of manufacturing a crystal structure is provided.
- an oxide crystal layer is formed on the group III nitride crystal layer.
- This oxide crystal may have an ⁇ -type crystal structure (corundum structure) or a ⁇ -type crystal structure.
- the contents described in the first to third viewpoints regarding the group III nitride crystal layer are also applicable to this viewpoint unless contrary to the purpose.
- the oxide crystal has a corundum structure
- the contents described in the first to third viewpoints of the corundum structure oxide crystal also apply to this viewpoint unless it is contrary to the purpose.
- a step of oxidizing the nitride crystal layer may be provided before the oxide crystal layer forming step.
- the surface of the nitride crystal layer is partially or completely oxidized, and the affinity between the nitride crystal layer and the oxide crystal layer is improved.
- the oxidation treatment can be performed by a method such as performing plasma treatment on the nitride crystal layer in an atmosphere containing oxygen, for example.
- an oxynitride layer containing one or both of indium atoms and gallium atoms is formed between the nitride crystal layer and the oxide crystal layer.
- a group III nitride crystal layer containing one or both of indium atoms and gallium atoms may be further provided directly on the oxide crystal layer or via a buffer layer.
- a sandwich structure in which the oxide crystal layer is sandwiched between the nitride crystal layers is formed.
- the oxide crystal layer and the nitride crystal layer may be further repeatedly formed.
- a quantum well can be formed by such a sandwich structure.
- a transparent conductive electrode such as indium oxide and gallium oxide
- an insulating film such as aluminum oxide and gallium oxide as an oxide crystal
- the oxide crystal layer and the nitride crystal layer may be doped.
- indium oxide can be doped with tin to form a high-quality transparent conductive film
- gallium oxide can be doped with iron. Can be improved.
- the base substrate, the oxide crystal layer, and the nitride crystal layer are formed from the base substrate, the oxide crystal layer, and the nitride crystal layer, respectively.
- the difference in lattice constant between the materials forming the surface is small, and a material having a relatively close crystal structure such as a trigonal crystal or a hexagonal crystal such as a corundum structure Preferably there is.
- a nitride crystal layer or an InAlGaO-based material, particularly InAlGaO having a corundum structure is preferably formed on a 4H or 6H silicon carbide substrate, and indium oxide is preferable on a gallium nitride substrate.
- the CVD apparatus 19 adjusts the flow rate of the carrier gas sent from the sample stage 21 on which the film-forming sample 20 such as the base substrate is placed, the carrier gas source 22 that supplies the carrier gas, and the carrier gas source 22.
- a film forming chamber 27 and a heater 28 installed around the film forming chamber 27 are provided.
- the sample stage 21 is made of quartz, and the surface on which the deposition target sample 20 is placed is inclined from the horizontal plane. Both the film formation chamber 27 and the sample stage 21 are made of quartz, so that impurities derived from the apparatus are prevented from being mixed into the thin film formed on the film formation target sample 20.
- a c-plane ⁇ -type sapphire substrate with a side of 10 mm and a thickness of 600 ⁇ m is placed on the sample stage 21, and the heater 28 is operated to form the inside of the film formation chamber 27.
- the temperature of was raised to the temperature shown in Table 1.
- the flow rate adjusting valve 23 is opened to supply the carrier gas from the carrier gas source 22 into the film forming chamber 27, and the atmosphere in the film forming chamber 27 is sufficiently replaced with the carrier gas. Adjusted to min. Nitrogen gas was used as the carrier gas.
- the ultrasonic vibrator 26 was vibrated at 2.4 MHz, and the vibration was propagated to the raw material solution 24a through the water 25a, whereby the raw material solution 24a was atomized to generate raw material fine particles.
- the raw material fine particles are introduced into the film forming chamber 27 by the carrier gas, react in the film forming chamber 27, and form a thin film on the film forming sample 20 by the CVD reaction on the film forming surface of the film forming sample 20. Formed.
- Table 1 shows the results of identifying the composition ratio of the raw material solution, the concentration, the reaction temperature, and the crystal phase of the formed thin film.
- the crystal phase was identified by scanning 2 ⁇ / ⁇ at an angle of 15 to 95 degrees using an XRD diffractometer for thin films. The measurement was performed using CuK ⁇ rays.
- ⁇ is a condition under which only a peak derived from an ⁇ -phase oxide crystal mainly composed of ⁇ -Ga 2 O 3 was observed, and “ ⁇ ” represents ⁇ -Ga 2 O 3 .
- ⁇ -mix is the condition where both the ⁇ -phase and ⁇ -phase peaks are observed and no single phase is obtained
- “None” is It means that no peak was observed.
- FIG. 3 a part of the XRD pattern used for identification is shown in FIG.
- the XRD pattern is shown so that the aluminum ion ratio in the raw material solution increases from the top to the bottom (from the top 1: 0, 1: 0.2, 1: 1, 1: 2, 1: 4).
- the gallium concentration in the raw material solution was fixed at 0.1 mol / L.
- the peak near 41.7 degrees is derived from sapphire (Al 2 O 3 ) as the base substrate, and the peak near 40.3 degrees (hereinafter referred to as “ ⁇ -phase peak”) is ⁇ It is a peak derived from an ⁇ -phase oxide crystal containing Ga 2 O 3 as a main component.
- the top one of the five patterns in FIG. 3 was obtained for pure ⁇ -Ga 2 O 3 prepared using a raw material solution containing no aluminum, and the four patterns below it were This is obtained for an oxide crystal manufactured using a raw material solution containing aluminum.
- the oxide crystal produced using the raw material solution containing aluminum is considered to contain aluminum, but if aluminum is present on the lattice points of the crystal lattice by replacing gallium, Since the atomic radius of aluminum is smaller than that of gallium, the c-axis length of the crystal lattice becomes shorter. As a result, the position of the ⁇ -phase peak should shift to the higher angle side (right side in FIG. 3) as the amount of aluminum increases. It is. However, according to actual experimental results, the position of the ⁇ -phase peak shifts to the low angle side (left side in FIG. 3) as the amount of aluminum increases. This result means that the c-axis length is increased by the addition of aluminum, and at the same time, aluminum is present in the gaps between lattice points in the crystal.
- FIG. 4A shows the result when aluminum bromide is used as the aluminum compound
- FIG. 4B shows the result when aluminum acetylacetonate is used as the aluminum compound.
- the ⁇ phase peak shifts to the low angle side (left side in FIG. 3) as the amount of aluminum increases
- FIG. 4B using aluminum acetylacetonate the ⁇ -phase peak is shifted to the low angle side (right side in FIG. 3) as the amount of aluminum increases.
- the film formation conditions were a film formation temperature of 500 ° C., a film formation time of 10 minutes, a carrier gas of nitrogen, and a flow rate of 5 L / min.
- “Condition 1” forms a film using only an aqueous solution of gallium bromide 0.1 mol / L
- “Condition 2” forms a film using an aqueous solution adjusted to a concentration of 0.1 mol / L for both gallium bromide and aluminum bromide. It was. Thereafter, annealing was performed at 800 ° C. for 30 minutes in a nitrogen atmosphere.
- FIGS. 5A to 5B show XRD patterns before and after annealing for the oxide crystals formed under conditions 1 and 2.
- FIG. 5 (a) in “Condition 1” in which the raw material solution does not contain an aluminum compound, a ⁇ -phase-derived peak is clearly observed at around 38 degrees, and conversely, the ⁇ -phase-derived peak intensity is significantly reduced. It was seen. This means that a phase transition from ⁇ phase to ⁇ phase was caused.
- FIG. 5B in “Condition 2” in which the raw material solution contains an aluminum compound, only an ⁇ -phase peak near 40 degrees is observed, and there is a large difference in peak intensity before and after annealing. There was no.
- the ⁇ -type oxide crystal thin film obtained according to the present invention maintains the ⁇ -type structure even when annealed at 800 ° C., that is, impurity thermal diffusion process, surface / interface modification process, hot implantation, ion implantation. This suggests the availability of many existing mass-production processes such as post-crystallinity improvement annealing, and demonstrates the usefulness of the present invention.
- Condition 1 of the above “5-3” without an iron oxide buffer layer (however, the film forming temperature is 600 ° C.)
- Condition 2 (however, the film forming temperature is 600 ° C., the same applies hereinafter)
- Condition 2 (however, the film forming temperature is 600 ° C., the same applies hereinafter)
- Condition 2 (however, the film forming temperature is 600 ° C., the same applies hereinafter)
- Condition 2 of “5-3” above with an iron oxide buffer layer was measured. The result is shown in FIG. As shown in FIG. 7A, when the film was formed under the condition 2 of the above “5-3” with an iron oxide buffer layer, an ⁇ -phase single-phase oxide crystal was formed.
- Condition 1 where no aluminum is present, only the ⁇ phase can be observed, whereas in Condition 2 where aluminum is present in a very small amount in the crystal film, the ⁇ phase appears, and the effect of the present invention is remarkably exhibited.
- Similar results were obtained even when the film formation temperature of the iron oxide buffer layer was 350 ° C. Further, an iron oxide buffer layer is formed on a commercially available SiC substrate by the same method as described above, and then oxidized on condition 2 of the above “5-3” (however, the film forming temperature is 600 ° C., the same applies hereinafter). A product crystal was formed, and the XRD pattern of the oxide crystal was measured. The result is shown in FIG. As shown in FIG. 7B, an ⁇ -phase single-phase oxide crystal was also formed on the SiC substrate via the iron oxide buffer layer.
- GaN thin film formation experiment on ⁇ -gallium oxide thin film An ⁇ -gallium oxide thin film was formed on a (0001) sapphire substrate by mist CVD.
- As the raw material solution a solution in which gallium acetylacetonate was dissolved in ultrapure water to a concentration of 0.1 mol / L was used.
- the film formation conditions were a film formation temperature of 500 ° C., a film formation time of 10 minutes, the carrier gas was oxygen, and the flow rate was 5 L / min.
- the ⁇ -gallium oxide thin film was transferred into the MBE apparatus, the ⁇ -gallium oxide thin film temperature was set to 570 ° C., and the ⁇ -gallium oxide thin film was irradiated with nitrogen plasma to perform nitriding treatment on the surface. It was confirmed by high-speed electron diffraction and X-ray photoelectron spectroscopy that a gallium nitride layer was formed on the surface of the ⁇ -gallium oxide thin film by nitriding.
- the GaN thin film was formed by irradiating the ⁇ -gallium oxide thin film having the gallium nitride layer formed on the surface in this manner with gallium and nitrogen plasma in an MBE apparatus.
- GaN substrate was used as a growth substrate. After organic cleaning of the substrate, a gallium oxide thin film was grown using a mist CVD method.
- As the raw material solution a solution in which gallium acetylacetonate was dissolved in ultrapure water to a concentration of 0.1 mol / L was used.
- the film formation conditions were film formation temperatures of 430 ° C., 450 ° C. and 470 ° C., a film formation time of 60 minutes, the carrier gas was oxygen, and the flow rate was 5 L / min.
- the XRD pattern was measured about the formed gallium oxide thin film. As a result, a ⁇ phase peak was observed and no ⁇ phase peak was observed regardless of the film formation temperature. Moreover, when the electrical characteristics of this gallium oxide thin film were evaluated, it showed a high value of 0.8 M ⁇ cm.
- Base substrate 2 Crystalline stress relaxation layer 3: Semiconductor layer 4: Cap layer 5: Insulating film 19: Mist CVD apparatus 20: Film formation sample 21: Sample stage 22: Carrier gas source 23: Flow control valve 24: Mist generation source 24a: raw material solution 25: mist generation source 25a: water 26: ultrasonic vibrator 27: film formation chamber 28: heater
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Abstract
Description
(1)インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、少なくとも、結晶格子の格子点間の隙間にアルミニウム原子を含有する、半導体装置、又は結晶構造体。
(2)インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、アルミニウム原子を含有し、
前記酸化物結晶がアルミニウム原子を含有する場合のc軸長が、前記酸化物結晶がアルミニウム原子を含有しない場合のc軸長よりも大きい、半導体装置、又は結晶構造体。
(1)インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、結晶格子の格子点上と格子点間の隙間の一方又は両方にアルミニウム原子を含有し、
前記酸化物結晶の結晶格子の格子点上に存在するアルミニウム原子の原子比は、前記酸化物結晶中のインジウム原子とガリウム原子の合計に対して0より大きく且つ2.9%以下である、半導体装置、又は結晶構造体。
(2)インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、アルミニウム原子を含有し、
前記酸化物結晶がアルミニウム原子を含有する場合のc軸長が、前記酸化物結晶がアルミニウム原子を含有しない場合のc軸長に対して0.9991倍以上である、半導体装置、又は結晶構造体。
1-1.第1観点の半導体装置、又は結晶構造体の構造
本発明の第1観点の一実施形態の半導体装置、又は結晶構造体は、インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、前記酸化物結晶は、少なくとも、結晶格子の格子点間の隙間にアルミニウム原子を含有する。「結晶構造体」とは、一層以上の結晶層を含む構造体であり、結晶層以外の層(例:アモルファス層)を含んでいてもよい。また、結晶層は、単結晶層であることが好ましいが、多結晶層であってもよい。
一般式(1):
InXAlYGaZO3(0≦X≦2、0≦Y≦2、0≦Z≦2、X+Y+Z=1.5~2.5であり、0<X又は0<Zである。)
一般式(2):
α型InXGaYFeZO3(0≦X≦2、0≦Y≦2、0<Z≦2、X+Y+Z=1.5~2.5であり、X≧0.5又はY≧0.5)
本発明のポイントは、コランダム構造酸化物結晶の格子点間の隙間にアルミニウム原子が入り込むように結晶成長を行ったことである。
そして、本発明者らは、微粒子化した原料溶液を用いて成膜を行う成膜方法(例:ミストCVD又はこれに類似した方法)において、アルミニウム源として従来使用されてきたアルミニウムアセチルアセトナートの代わりに、ハロゲン化アルミニウム(フッ化、塩化、臭化、ヨウ化アルミニウム)を用いることによって、格子点間の隙間にアルミニウム原子を含ませることに成功し、相転移しにくいという優れた特性を有するコランダム構造酸化物結晶を得た。
原料溶液は、インジウム化合物とガリウム化合物の一方又は両方と、アルミニウム化合物をそれぞれ溶媒に溶解させることによって作製することができる。インジウム化合物としては、インジウム有機金属錯体(例:インジウムアセチルアセトナート)や、ハロゲン化インジウム(フッ化、塩化、臭化、ヨウ化インジウム)が挙げられる。ガリウム化合物としては、ガリウム有機金属錯体(例:ガリウムアセチルアセトナート)や、ハロゲン化ガリウム(フッ化、塩化、臭化、ヨウ化ガリウム)が挙げられる。アルミニウム化合物は、少なくともハロゲン化アルミニウムを含む。ハロゲン化アルミニウムとしては、フッ化、塩化、臭化、又はヨウ化アルミニウムが挙げられる。
原料溶液を微粒子化して原料微粒子を生成する方法は、特に限定されないが、原料溶液に超音波振動を印加して微粒子化する方法が一般的である。また、これ以外の方法でも、例えば、原料溶液を噴霧することによって原料溶液を微粒子化することによっても原料微粒子を生成することができる。
キャリアガスは、例えば窒素であるが、アルゴン、酸素、オゾン、空気などのガスを用いてもよい。また、キャリアガスの流量は、特に限定されないが、例えば、0.1~50L/minであり、好ましくは0.5~10L/minである。この流量は、具体的には例えば、0.5、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10L/minであり、ここで例示した数値の何れか2つの間の範囲内であってもよい。
原料微粒子は、キャリアガスによって成膜室に供給され、成膜室において反応が起こって成膜室内に載置された被成膜試料上に薄膜が形成される。被成膜試料上に形成される薄膜は、コランダム構造酸化物結晶(好ましくは酸化物単結晶)の薄膜である。
成膜室は、薄膜形成が行われる空間であり、その構成や材料は特に限定されない。成膜室は、一例では、実施例のように石英管の一端から原料微粒子を含むキャリアガスを供給し、石英管の他端から排ガスを排出する構成である。この構成の場合、被成膜試料は、成膜面が水平になるように配置してもよく、キャリアガスの供給側に向けて例えば45度に傾斜するように配置してもよい。また、数mm以下のチャネルを反応領域として利用するファインチャネル法や、基板上に直線状のノズルを設け、ここから基板に垂直方向に原料微粒子(およびキャリアガス)を吹き付け、さらにノズルを直線状の出口とは垂直方向に移動させるというリニアソース法や、複数の方式を混合した、あるいは派生させた方式による成膜室を利用してもよい。ファインチャネル法では、均質な薄膜作製と原料の利用効率の向上が可能であるし、リニアソース法では、将来の大面積基板およびロールツーロールでの連続成膜が可能である。成膜室は、例えば成膜室の周囲をヒータで取り囲む等によって内部空間を所望温度に加熱できる構成になっている。また、成膜室は、大気圧ではなく加圧や減圧をしてもよい。
2-1.第2観点の半導体装置、又は結晶構造体の構造
本発明の第2観点の一実施形態の半導体装置、又は結晶構造体は、インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、前記酸化物結晶は、結晶格子の格子点上と格子点間の隙間の一方又は両方にアルミニウム原子を含有し、前記酸化物結晶の結晶格子の格子点上に存在するアルミニウム原子の原子比は、前記酸化物結晶中のインジウム原子とガリウム原子の合計に対して0より大きく且つ2.9%以下である。「結晶構造体」の説明は、第1観点と同様である。
第2観点の半導体装置の製造方法、又は結晶構造体の製造方法は、基本的には、第1観点の方法と同じであるので、以下、差異点を中心に説明を進める。
従って、本実施形態によれば、インジウム化合物及びガリウム化合物の一方又は両方と、アルミニウム化合物をそれぞれ溶媒に溶解した同一又は別々の原料溶液を一緒に又は別々に微粒子化して生成される原料微粒子を成膜室に供給してコランダム構造酸化物結晶を形成する工程を備え、前記アルミニウム化合物は、前記酸化物結晶がアルミニウム原子を含有する場合のc軸長が、前記酸化物結晶がアルミニウム原子を含有しない場合のc軸長に対して0.9991倍以上になるように混合される、半導体装置の製造方法、又は結晶構造体の製造方法が提供される。
本発明の第3観点によれば、インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶と、前記酸化物結晶上に直接または緩衝層を介して設けられたIII族窒化物結晶層(薄膜)とを備える、半導体装置、又は結晶構造体が提供される。また、インジウム化合物及びガリウム化合物の一方又は両方をそれぞれ溶媒に溶解した同一又は別々の原料溶液を一緒に又は別々に微粒子化して生成される原料微粒子を成膜室に供給してコランダム構造酸化物結晶を形成する結晶形成工程と、前記酸化物結晶上に、直接または緩衝層を介してIII族窒化物結晶層を形成する窒化物結晶層形成工程とを備える、半導体装置の製造方法、又は結晶構造体の製造方法が提供される。好ましくは、前記原料微粒子は、アルミニウム化合物を含む。好ましくは、前記III族窒化物層は、高い量産性の実現、および[0]良好な結晶性を得るという観点から、成膜温度が570℃以上である成膜法(例:MOCVD法、HVPE法)で形成される。
本発明の第4観点によれば、III族窒化物結晶層と、その上に設けられ且つインジウム原子及びガリウム原子の一方又は両方を含む酸化物結晶層とを備える、半導体装置、又は結晶構造体が提供される。また、III族窒化物結晶層上に直接または緩衝層を介して酸化物結晶層を形成する酸化物結晶層形成工程を備え、前記酸化物結晶層形成工程は、インジウム化合物及びガリウム化合物の一方又は両方をそれぞれ溶媒に溶解した同一又は別々の原料溶液を一緒に又は別々に微粒子化して生成される原料微粒子を成膜室に供給して酸化物結晶層を形成する工程を備える、半導体装置の製造方法、又は結晶構造体の製造方法が提供される。
まず、図2を用いて、本実施例で用いたCVD装置19を説明する。CVD装置19は、下地基板等の被成膜試料20を載置する試料台21と、キャリアガスを供給するキャリアガス源22と、キャリアガス源22から送り出されるキャリアガスの流量を調節するための流量調節弁23と、原料溶液24aが収容されるミスト発生源24と、水25aが入れられる容器25と、容器25の底面に取り付けられた超音波振動子26と、内径40mmの石英管からなる成膜室27と、成膜室27の周辺部に設置されたヒータ28を備えている。試料台21は、石英からなり、被成膜試料20を載置する面が水平面から傾斜している。成膜室27と試料台21をどちらも石英で作製することにより、被成膜試料20上に形成される薄膜内に装置由来の不純物が混入することを抑制している。
表1に示す原料濃度になるよう金属臭化物を超純水に溶解させたアルミニウム・ガリウムの混合水溶液を調整した。比較例の条件は、非特許文献1を参照した。ただし、非特許文献1には濃度を変化させた実験がなかったので、材料、溶解方法などは全て文献と同様とし、濃度のみを変化させた溶液を調整した。この原料溶液24aをミスト発生源24内に収容した。
次に、被成膜試料20として、1辺が10mmの正方形で厚さ600μmのc面α型サファイア基板を試料台21上に設置させ、ヒータ28を作動させて成膜室27内の温度を表1に示す温度にまで昇温させた。次に、流量調節弁23を開いてキャリアガス源22からキャリアガスを成膜室27内に供給し、成膜室27の雰囲気をキャリアガスで十分に置換した後、キャリアガスの流量を5L/minに調節した。キャリアガスとしては、窒素ガスを用いた。
次に、超音波振動子26を2.4MHzで振動させ、その振動を水25aを通じて原料溶液24aに伝播させることによって原料溶液24aを微粒子化させて原料微粒子を生成した。
この原料微粒子が、キャリアガスによって成膜室27内に導入され、成膜室27内で反応して、被成膜試料20の成膜面でのCVD反応によって被成膜試料20上に薄膜を形成した。
5-1.成膜時の相転移抑制効果の実証
原料溶液の組成比、濃度、反応温度、および形成された薄膜の結晶相を同定した結果を表1に示す。
結晶相の同定は、薄膜用XRD回折装置を用いて、15度から95度の角度で2θ/ωスキャンを行うことによって行った。測定は、CuKα線を用いて行った。全ての実験で下地基板であるサファイア由来のピークと、酸化ガリウムを主成分とする酸化物結晶由来のピークのみが検出された。表中の表記内容について、「α」は、α-Ga2O3を主成分とするα相の酸化物結晶由来のピークのみが観測された条件、「β」はβ-Ga2O3を主成分とするβ相の酸化物結晶のピークが観測された条件、「β混」は、α相とβ相の両方のピークが観測され、単相が得られていない条件、「無」はピークが観測されなかったことを意味する。
次に、同定に使用したXRDパターンの一部を図3に示す。図3では、上から順に下にいくにつれて、原料溶液中のアルミニウムイオン比率が増加するようにXRDパターンを示した(上から1:0、1:0.2、1:1、1:2、1:4)。原料溶液中のガリウム濃度は0.1mol/Lに固定した。
図4(a)では、表2に示すように、Ga:Al=1:1の場合に、α相ピークの位置が2θ=40.27度から40.14度に変化している。ブラッグの式(2dsinθ=λ)でλが一定なので、Al添加による格子定数の変化は、d2/d1=sinθ1/sinθ2でα相ピーク位置の変化前後のθをラジアンに変換して代入すると、d2/d1≒1.0031となり、c軸長が約0.3%長くなったことが分かる。同様の計算によって、Ga:Al=1:0.2の場合に、d2/d1≒1.0007となった。
さらに、α型酸化物についてアニール処理の際の熱耐性評価の実験を行った。成膜条件は成膜温度500℃、成膜時間10分、キャリアガスには窒素、流量5L/minとした。
「条件1」は臭化ガリウム0.1mol/Lの水溶液のみを、「条件2」は臭化ガリウム、臭化物アルミニウムともに0.1mol/Lの濃度になるよう調整した水溶液を用いて成膜を行った。その後、窒素雰囲気で800℃30分のアニール処理を行った。条件1及び2で形成した酸化物結晶について、アニール処理前後のXRDパターンを図5(a)~(b)に示す。図5(a)に示すように、原料溶液にアルミニウム化合物を含有しない「条件1」では38度付近にβ相由来のピークがはっきりと観測され、逆にα相由来のピーク強度に著しい減少が見られた。これはα相からβ相への相転移が引き起こされたことを意味する。一方、図5(b)に示すように、原料溶液にアルミニウム化合物を含有させた「条件2」は40度付近のα相由来のピークのみが観測され、アニール前後でピーク強度にも大きな差が無かった。このことから、相転移が生じず、結晶膜がコランダム構造を維持していることが分かる。また、図4~図5の結果を合わせると、原料溶液に臭化アルミニウムを含ませることによって、格子点間の隙間にアルミニウム原子が導入され、このアルミニウム原子によって相転移が抑制されたことを示している。このように、本発明により得られたα型酸化物結晶薄膜が800℃のアニール処理でもα型構造を維持することは、不純物熱拡散プロセス、表面・界面改質プロセス、ホットインプランテーション、イオン注入後結晶性改善アニールなど、多くの既存量産プロセスの利用可能性を示唆するものであると言え、本発明の有用性を示すものである。
上記の「5-3」の条件2で形成した酸化物結晶上に成膜温度が800℃以上であるMOCVD法によってIII族窒化物層を形成した。酸化物結晶のXRDパターンを測定したところ、図5(b)と同様に、III族窒化物層の成膜前後でα相ピークの強度がほとんど変化しなかった。
市販のGaN基板上にミストCVD法によって酸化鉄バッファ層を形成した。酸化鉄バッファ層は、上記のCVD装置19を用いて形成し、成膜温度は300℃とした。キャリアガス及び微粒子化の条件は上記と同様にした。成膜は30秒間行った。次に、(1)酸化鉄バッファ層なしで上記の「5-3」の条件1(但し成膜温度は600℃、)、(2)酸化鉄バッファ層なしで上記の「5-3」の条件2(但し成膜温度は600℃、以下同じ)、(3)酸化鉄バッファ層ありで上記の「5-3」の条件2という3つの条件で酸化物結晶を形成し、この酸化物結晶のXRDパターンを測定した。その結果を図7(a)に示す。図7(a)に示すように、酸化鉄バッファ層ありで上記の「5-3」の条件2で成膜した場合、α相単相の酸化物結晶が形成された。アルミニウムが存在しなかった条件1の場合にはβ相しか観測できないのに対して、アルミニウムが結晶膜中に微量に存在する条件2では、α相が現れており、本発明の効果を顕著に表している。なお、酸化鉄バッファ層の成膜温度を350℃にしても同様の結果が得られた。
また、市販のSiC基板上に上記と同様の方法で酸化鉄バッファ層を形成し、その上に、上記の「5-3」の条件2(但し成膜温度は600℃、以下同じ)で酸化物結晶を形成し、この酸化物結晶のXRDパターンを測定した。その結果を図7(b)に示す。図7(b)に示すように、SiC基板上にも酸化鉄バッファ層を介してα相単相の酸化物結晶が形成された。
(0001)サファイア基板上にミストCVD法によってα-酸化ガリウム薄膜を形成した。原料溶液には、ガリウムアセチルアセトナートを超純水に濃度が0.1mol/Lとなるように溶解させたものを用いた。成膜条件は成膜温度500℃、成膜時間10分、キャリアガスは、酸素で、流量を5L/minとした。
次に、α-酸化ガリウム薄膜をMBE装置内に搬送し、α-酸化ガリウム薄膜温度を570度に設定し、α-酸化ガリウム薄膜に窒素プラズマを照射することにより表面の窒化処理を行った。窒化処理によりα-酸化ガリウム薄膜表面に窒化ガリウム層が形成されたことが、高速電子線回折測定およびX線 光電子分光測定により確認された。このように表面に窒化ガリウム層が形成されたα-酸化ガリウム薄膜の上にMBE装置内にてガリウムおよび窒素プラズマを照射することにより、GaN薄膜の成膜を行った。
成長用基板として(0001)GaN基板を用いた。この基板に有機洗浄を施した後、ミストCVD法を用いて酸化ガリウム薄膜を成長させた。原料溶液には、ガリウムアセチルアセトナートを超純水に濃度が0.1mol/Lとなるように溶解させたものを用いた。成膜条件は、成膜温度430℃,450℃470℃、成膜時間60分、キャリアガスは、酸素で、流量を5L/minとした。
形成した酸化ガリウム薄膜について、XRDパターンを測定した。その結果、成膜温度に関わらず、β相ピークが観察され、α相ピークが観察されなかった。また、この酸化ガリウム薄膜の電気特性評価を行ったところ、0.8MΩcmという高い値を示した。
2:結晶性応力緩和層
3:半導体層
4:キャップ層
5:絶縁膜
19:ミストCVD装置
20:被成膜試料
21:試料台
22:キャリアガス源
23:流量調節弁
24:ミスト発生源
24a:原料溶液
25:ミスト発生源
25a :水
26:超音波振動子
27:成膜室
28:ヒータ
Claims (35)
- インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、少なくとも、結晶格子の格子点間の隙間にアルミニウム原子を含有する、半導体装置、又は結晶構造体。 - 前記酸化物結晶の結晶格子の格子点上に存在するアルミニウム原子の原子比は、前記酸化物結晶中のインジウム原子とガリウム原子の合計に対して0より大きく且つ2.9%以下である請求項1に記載の半導体装置、又は結晶構造体。
- インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、アルミニウム原子を含有し、
前記酸化物結晶がアルミニウム原子を含有する場合のc軸長が、前記酸化物結晶がアルミニウム原子を含有しない場合のc軸長よりも大きい、半導体装置、又は結晶構造体。 - インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、結晶格子の格子点上と格子点間の隙間の一方又は両方にアルミニウム原子を含有し、
前記酸化物結晶の結晶格子の格子点上に存在するアルミニウム原子の原子比は、前記酸化物結晶中のインジウム原子とガリウム原子の合計に対して0より大きく且つ2.9%以下である、半導体装置、又は結晶構造体。 - インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶を備え、
前記酸化物結晶は、アルミニウム原子を含有し、
前記酸化物結晶がアルミニウム原子を含有する場合のc軸長が、前記酸化物結晶がアルミニウム原子を含有しない場合のc軸長に対して0.9991倍以上である、半導体装置、又は結晶構造体。 - 前記酸化物結晶のコランダム構造を形成する格子点上の原子の組成は、InXAlYGaZO3(0≦X≦2、0≦Y≦2、0≦Z≦2、X+Y+Z=1.5~2.5であり、0<X又は0<Zである。)からなる、請求項1~請求項5の何れか1つに記載の半導体装置、又は結晶構造体。
- 0<Yである、請求項6に記載の半導体装置、又は結晶構造体。
- 前記酸化物結晶上に、直接または緩衝層を介してIII族窒化物結晶層を備える、請求項1~請求項7の何れか1つに記載の半導体装置、又は結晶構造体。
- インジウム化合物及びガリウム化合物の一方又は両方と、アルミニウム化合物をそれぞれ溶媒に溶解した同一又は別々の原料溶液を一緒に又は別々に微粒子化して生成される原料微粒子を成膜室に供給してコランダム構造酸化物結晶を形成する結晶形成工程を備え、前記アルミニウム化合物は、ハロゲン化アルミニウムを含む、半導体装置の製造方法、又は結晶構造体の製造方法。
- 前記アルミニウム化合物は、アルミニウム有機金属錯体とハロゲン化アルミニウムの両方を含む、請求項9に記載の方法。
- インジウム化合物及びガリウム化合物の一方又は両方と、アルミニウム化合物をそれぞれ溶媒に溶解した同一又は別々の原料溶液を一緒に又は別々に微粒子化して生成される原料微粒子を成膜室に供給してコランダム構造酸化物結晶を形成する工程を備え、
前記アルミニウム化合物は、前記酸化物結晶がアルミニウム原子を含有する場合のc軸長が、前記酸化物結晶がアルミニウム原子を含有しない場合のc軸長に対して0.9991倍以上になるように混合される、半導体装置の製造方法、又は結晶構造体の製造方法。 - 前記アルミニウム化合物は、アルミニウム有機金属錯体とハロゲン化アルミニウムの一方又は両方である、請求項11に記載の方法。
- 前記結晶形成工程において前記成膜室内の温度が300~1500℃である、請求項9~請求項12の何れか1つに記載の方法。
- 前記結晶形成工程において前記成膜室内の温度が450℃以上である、請求項13に記載の方法。
- 前記結晶形成工程後に、前記酸化物結晶を400℃以上に加熱する加熱工程をさらに備える、請求項9~請求項14の何れか1つに記載の方法。
- 前記酸化物結晶上に、直接または緩衝層を介してIII族窒化物結晶層を形成する窒化物結晶層形成工程をさらに備える、請求項9~請求項15の何れか1つに記載の方法。
- 前記III族窒化物結晶層は、成膜温度が570℃以上である、請求項16に記載の方法。
- インジウム原子及びガリウム原子の一方又は両方を含むコランダム構造酸化物結晶層と、前記酸化物結晶層上に直接または緩衝層を介して設けられたIII族窒化物結晶層とを備える、半導体装置、又は結晶構造体。
- 前記酸化物結晶は、アルミニウム原子を含有する、請求項18に記載の半導体装置、又は結晶構造体。
- 前記酸化物結晶層の組成は、InXAlYGaZO3(0≦X≦2、0≦Y≦2、0≦Z≦2、X+Y+Z=1.5~2.5であり、0<X又は0<Zである。)からなる、請求項18又は請求項19に記載の半導体装置、又は結晶構造体。
- 前記窒化物結晶層の組成は、InX1AlY1GaZ1N(0≦X1≦1、0≦Y1≦1、0≦Z1≦1、X1+Y1+Z1=0.8~1.2である。)からなる、請求項18~請求項20の何れか1つに記載の半導体装置、又は結晶構造体。
- 前記酸化物結晶層と前記窒化物結晶層の間に、インジウム原子及びガリウム原子の一方又は両方を含む酸窒化物層をさらに備える、請求項18~請求項21の何れか1つに記載の半導体装置、又は結晶構造体。
- 前記窒化物結晶層上に直接または緩衝層を介して、インジウム原子及びガリウム原子の一方又は両方を含む酸化物結晶層をさらに備える、請求項18~請求項22の何れか1つに記載の半導体装置、又は結晶構造体。
- インジウム化合物及びガリウム化合物の一方又は両方をそれぞれ溶媒に溶解した同一又は別々の原料溶液を一緒に又は別々に微粒子化して生成される原料微粒子を成膜室に供給してコランダム構造酸化物結晶層を形成する結晶形成工程と、前記酸化物結晶層上に、直接または緩衝層を介してIII族窒化物結晶層を形成する窒化物結晶層形成工程とを備える、半導体装置の製造方法、又は結晶構造体の製造方法。
- 前記原料微粒子は、アルミニウム化合物を含む、請求項24に記載の方法。
- 前記III族窒化物結晶層は、成膜温度が570℃以上である、請求項24又は請求項25に記載の方法。
- 前記窒化物結晶層形成工程の前に、前記酸化物結晶層に対して窒化処理を行う工程をさらに備える、請求項24~請求項26の何れか1つに記載の方法。
- III族窒化物結晶層と、その上に設けられ且つインジウム原子及びガリウム原子の一方又は両方を含む酸化物結晶層とを備える、半導体装置、又は結晶構造体。
- 前記酸化物結晶層は、アルミニウム原子を含有する、請求項28に記載の半導体装置、又は結晶構造体。
- 前記窒化物結晶層の組成は、InX1AlY1GaZ1N(0≦X1≦1、0≦Y1≦1、0≦Z1≦1、X1+Y1+Z1=0.8~1.2である。)からなる、請求項28又は請求項29に記載の半導体装置、又は結晶構造体。
- 前記酸化物結晶層の組成は、InXAlYGaZO3(0≦X≦2、0≦Y≦2、0≦Z≦2、X+Y+Z=1.5~2.5であり、0<X又は0<Zである。)からなる、請求項28~請求項30の何れか1つに記載の半導体装置、又は結晶構造体。
- 前記窒化物結晶層と前記酸化物結晶層の間に、インジウム原子及びガリウム原子の一方又は両方を含む酸窒化物層をさらに備える、請求項28~請求項31の何れか1つに記載の半導体装置、又は結晶構造体。
- 前記酸化物結晶層上に直接または緩衝層を介してIII族窒化物層をさらに備える、請求項28~請求項32の何れか1つに記載の半導体装置、又は結晶構造体。
- III族窒化物結晶層上に直接または緩衝層を介して酸化物結晶層を形成する酸化物結晶層形成工程を備え、前記酸化物結晶層形成工程は、インジウム化合物及びガリウム化合物の一方又は両方をそれぞれ溶媒に溶解した同一又は別々の原料溶液を一緒に又は別々に微粒子化して生成される原料微粒子を成膜室に供給して酸化物結晶層を形成する工程を備える、半導体装置の製造方法、又は結晶構造体の製造方法。
- 前記酸化物結晶層形成工程の前に、前記窒化物結晶層に対して酸化処理を行う工程をさらに備える、請求項34に記載の方法。
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JP2016155962A (ja) * | 2015-02-25 | 2016-09-01 | 株式会社Flosfia | 蛍光体組成物の製造方法および発光装置 |
WO2020027244A1 (ja) * | 2018-08-01 | 2020-02-06 | 出光興産株式会社 | 化合物 |
WO2020066575A1 (ja) * | 2018-09-27 | 2020-04-02 | 信越化学工業株式会社 | 積層体、半導体装置及び積層体の製造方法 |
WO2023176591A1 (ja) * | 2022-03-16 | 2023-09-21 | 出光興産株式会社 | 焼結体、スパッタリングターゲット、酸化物薄膜、薄膜トランジスタ、電子機器、及び焼結体の製造方法 |
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EP2754738B1 (en) * | 2011-09-08 | 2021-07-07 | Tamura Corporation | Schottky-barrier diode |
US10087547B2 (en) * | 2015-12-21 | 2018-10-02 | The Regents Of The University Of California | Growth of single crystal III-V semiconductors on amorphous substrates |
US11515172B2 (en) * | 2019-06-28 | 2022-11-29 | Flosfia Inc. | Method of etching object |
US11462402B2 (en) * | 2020-10-21 | 2022-10-04 | Cornell University | Suboxide molecular-beam epitaxy and related structures |
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JP2016155962A (ja) * | 2015-02-25 | 2016-09-01 | 株式会社Flosfia | 蛍光体組成物の製造方法および発光装置 |
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JP2021168406A (ja) * | 2018-09-27 | 2021-10-21 | 信越化学工業株式会社 | 積層体、半導体装置及びミストcvd装置 |
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WO2020066575A1 (ja) * | 2018-09-27 | 2020-04-02 | 信越化学工業株式会社 | 積層体、半導体装置及び積層体の製造方法 |
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US11990521B2 (en) | 2018-09-27 | 2024-05-21 | Shin-Etsu Chemical Co., Ltd. | Laminate, semiconductor device, and method for manufacturing laminate |
WO2023176591A1 (ja) * | 2022-03-16 | 2023-09-21 | 出光興産株式会社 | 焼結体、スパッタリングターゲット、酸化物薄膜、薄膜トランジスタ、電子機器、及び焼結体の製造方法 |
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US9966439B2 (en) | 2018-05-08 |
JP6459001B2 (ja) | 2019-01-30 |
US20180226472A1 (en) | 2018-08-09 |
US20160149005A1 (en) | 2016-05-26 |
JPWO2015005202A1 (ja) | 2017-03-02 |
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