WO2012118156A1 - 酸化物焼結体およびスパッタリングターゲット - Google Patents
酸化物焼結体およびスパッタリングターゲット Download PDFInfo
- Publication number
- WO2012118156A1 WO2012118156A1 PCT/JP2012/055265 JP2012055265W WO2012118156A1 WO 2012118156 A1 WO2012118156 A1 WO 2012118156A1 JP 2012055265 W JP2012055265 W JP 2012055265W WO 2012118156 A1 WO2012118156 A1 WO 2012118156A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- oxide
- sputtering target
- sintered body
- ratio
- Prior art date
Links
- 238000005477 sputtering target Methods 0.000 title claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 claims abstract description 188
- 239000002184 metal Substances 0.000 claims abstract description 164
- 238000004544 sputter deposition Methods 0.000 claims abstract description 47
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 229910052738 indium Inorganic materials 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 17
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- 239000011135 tin Substances 0.000 claims description 129
- 239000011701 zinc Substances 0.000 claims description 128
- 238000009826 distribution Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 17
- 229910052718 tin Inorganic materials 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 21
- 239000010408 film Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- 230000002159 abnormal effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009694 cold isostatic pressing Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910007541 Zn O Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 229910007604 Zn—Sn—O Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
- C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
- H01L21/34—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 not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/963—Surface properties, e.g. surface roughness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
Definitions
- the present invention relates to an oxide sintered body and a sputtering target used when an oxide semiconductor thin film of a thin film transistor (TFT) used in a display device such as a liquid crystal display or an organic EL display is formed by a sputtering method.
- TFT thin film transistor
- Amorphous (amorphous) oxide semiconductors used for TFTs have higher carrier mobility than general-purpose amorphous silicon (a-Si), a large optical band gap, and can be deposited at low temperatures. It is expected to be applied to next-generation displays that require high resolution and high-speed driving, and resin substrates with low heat resistance.
- a sputtering method is preferably used in which a sputtering target made of the same material as the film is sputtered. In-plane uniformity of component composition and film thickness in the film surface direction (in the film surface) is smaller in the thin film formed by sputtering compared to thin films formed by ion plating, vacuum evaporation, and electron beam evaporation. This is because it has the advantage that a thin film having the same composition as the sputtering target can be formed.
- the sputtering target is usually formed by mixing and sintering oxide powder and machining.
- an In-containing amorphous oxide semiconductor [In—Ga—Zn—O, In—Zn—O, In—Sn—O (ITO), etc.] can be given. (For example, patent document 1 etc.).
- Patent Document 2 proposes a method of suppressing the occurrence of abnormal discharge and cracking during sputtering by performing long-time baking and controlling the structure so as not to contain a tin oxide phase.
- Patent Document 3 also suppresses abnormal discharge during sputtering by increasing the density of the ZTO-based sintered body by carrying out a two-step process of a low-temperature calcined powder manufacturing process of 900 to 1300 ° C. and a main baking process. A method has been proposed.
- a sputtering target used for manufacturing an oxide semiconductor film for a display device and an oxide sintered body that is a material thereof have excellent conductivity and a high relative density.
- An oxide semiconductor film obtained using the above sputtering target is desired to have high carrier mobility.
- a sputtering target that can be manufactured not by the high frequency (RF) sputtering method but by the direct current (DC) sputtering method that facilitates high-speed film formation.
- the film is usually formed by direct current plasma discharge in a mixed atmosphere of argon gas and oxygen gas.
- plasma discharge is continuously performed for a long time. Therefore, DC discharge is stably and continuously applied to the sputtering target over a long period from the start to the end of use of the sputtering target.
- black deposits called nodules may be formed on the erosion surface (discharge surface) of the sputtering target.
- This black deposit is considered to be mainly low-level (ie, many defects, for example, low density and many oxygen defects) In oxide or Sn oxide, and causes abnormal discharge during sputtering. .
- defects may occur in the film due to abnormal discharge, or particles may be generated starting from the nodules themselves, resulting in reduced display quality of the display device. It was the cause of the decrease in yield.
- Patent Document 2 described above was not examined from the viewpoint of increasing the density, and was insufficient to carry out DC discharge stably and continuously.
- Patent Document 3 was not examined from the viewpoint of improving the conductivity of the oxide sintered body, and was still insufficient to stably and continuously perform DC discharge.
- the present invention has been made in view of the above circumstances, and an object thereof is an oxide sintered body and a sputtering target that are suitably used for manufacturing an oxide semiconductor film for a display device, and have high conductivity and relative density.
- an oxide semiconductor film having high carrier mobility and in particular, no direct current is generated even when manufactured by a direct current sputtering method, and the direct current can be stably discharged for a long time.
- An object of the present invention is to provide an oxide sintered body and a sputtering target excellent in discharge stability.
- the oxide sintered body of the present invention that has solved the above problems is at least one selected from the group consisting of zinc oxide; tin oxide; Al, Hf, Ni, Si, Ga, In, and Ta.
- the dispersion coefficient ⁇ is 30 or less.
- the total amount of metal elements contained in the oxide sintered body is 1, and at least one selected from the group consisting of Al, Hf, Ni, Si, and Ta among the M metals.
- the seed metal is M1 metal and the contents (atomic%) of Zn, Sn, and M1 metal in all metal elements are [Zn], [Sn], and [M1 metal], respectively, [Zn]
- the ratio of [M1 metal] to + [Sn] + [M1 metal] the ratio of [Zn] to [Zn] + [Sn]
- the ratio of [Sn] to [Zn] + [Sn] are as follows: Satisfied.
- the total amount of metal elements contained in the oxide sintered body is 1, and among the M metals, a metal containing at least In or Ga is M2 metal, and occupies in all metal elements.
- contents (atomic%) of Zn, Sn, and M2 metal are [Zn], [Sn], and [M2 metal], respectively, [M2 metal] relative to [Zn] + [Sn] + [M2 metal]
- the ratio, the ratio of [Zn] to [Zn] + [Sn], and the ratio of [Sn] to [Zn] + [Sn] satisfy the following expressions, respectively.
- the oxide sintered body has a relative density of 90% or more and a specific resistance of 0.1 ⁇ ⁇ cm or less.
- the sputtering target of the present invention that has solved the above problems is a sputtering target obtained using the oxide sintered body according to any of the above, and the gist is that the Vickers hardness is 400 Hv or more. It is what you have.
- the dispersion coefficient ⁇ is 30 or less.
- the total amount of metal elements contained in the sputtering target is 1, and among the M metals, at least one metal selected from the group consisting of Al, Hf, Ni, Si, and Ta Is M1 metal, and Zn, Sn, and M1 metal content (atomic%) in all metal elements are [Zn], [Sn], and [M1 metal], respectively, [Zn] + [Sn ] + [M1 metal] to [M1 metal], [Zn] + [Sn] to [Zn], and [Zn] + [Sn] to [Sn]. It is.
- the total amount of metal elements contained in the sputtering target is 1, and among the M metals, a metal containing at least In or Ga is M2 metal, and Zn, Sn occupying in all metal elements.
- the content (atomic%) of the M2 metal is [Zn], [Sn], and [M2 metal], respectively, the ratio of [M2 metal] to [Zn] + [Sn] + [M2 metal], [ The ratio of [Zn] to [Zn] + [Sn] and the ratio of [Sn] to [Zn] + [Sn] satisfy the following expressions, respectively.
- the sputtering target has a relative density of 90% or more and a specific resistance of 0.1 ⁇ ⁇ cm or less.
- an oxide sintered body and a sputtering target having a low specific resistance and a high relative density can be obtained without adding a rare metal In and / or by reducing the amount of In. Can be greatly reduced.
- the sputtering target excellent in direct-current discharge stability is obtained continuously from the use start of a sputtering target to completion
- an oxide semiconductor film with high carrier mobility can be stably and inexpensively formed by a direct current sputtering method that facilitates high-speed film formation, so that productivity is improved.
- FIG. 3 shows the Vickers in the thickness direction for the sputtering target manufactured using the Al—ZTO sintered body of Experimental Example 1 (example of the present invention) and the sputtering target manufactured using the Ta—ZTO sintered body of Comparative Example 1. It is a graph which shows the result of the Gaussian distribution (normal distribution) curve of hardness.
- FIG. 4 shows the Vickers in the thickness direction for the sputtering target manufactured using the Ta—ZTO sintered body of Experimental Example 2 (example of the present invention) and the sputtering target manufactured using the Ta—ZTO sintered body of Comparative Example 1. It is a graph which shows the result of the Gaussian distribution (normal distribution) curve of hardness.
- FIG. 5 shows the Vickers in the thickness direction for the sputtering target manufactured using the In—ZTO sintered body of Example 3 (invention example) and the sputtering target manufactured using the Ta—ZTO sintered body of Comparative Example 1. It is a graph which shows the result of the Gaussian distribution (normal distribution) curve of hardness.
- FIG. 5 shows the Vickers in the thickness direction for the sputtering target manufactured using the In—ZTO sintered body of Example 3 (invention example) and the sputtering target manufactured using the Ta—ZTO sintered body of Comparative Example 1. It is a graph which shows the result of the Gaussian distribution (normal
- the present inventors suppress nodules even when the direct current sputtering method is applied.
- studies have been repeated.
- M metal metal selected from the group consisting of In and Ta
- the Vickers hardness is improved, and preferably, the variation in the thickness direction Vickers hardness is reduced, so that abnormal discharge during film formation is small, stable over time, and continuous DC discharge can be obtained. I found it.
- a TFT having an oxide semiconductor thin film formed using the above sputtering target has very high characteristics such as a carrier density of 15 cm 2 / Vs or more.
- the ratio of the total amount of M metal in all metal elements (Zn + Sn + M metal), Zn or Sn with respect to the total amount of Zn and Sn It has been found that it is sufficient to use a mixed powder in which the ratios of these are appropriately controlled and to carry out predetermined sintering conditions (preferably firing at a temperature of 1350 to 1650 ° C. for 5 hours or more in a non-reducing atmosphere).
- predetermined sintering conditions preferably firing at a temperature of 1350 to 1650 ° C. for 5 hours or more in a non-reducing atmosphere. The present invention has been completed.
- the present invention by controlling the hardness of the oxide sintered body (and also the sputtering target) (and controlling the hardness distribution in the thickness direction), generation of nodules during sputtering is suppressed, and a stable DC discharge is possible.
- the internal structure of the oxide sintered body such as the density of the oxide sintered body, internal defects, pore distribution, pore density, composition, and structure distribution, is probably It is considered that the hardness of the sintered product is affected, and the hardness (and hardness distribution) of the oxide sintered product has a good correlation with the quality of sputtering.
- the oxide sintered body of the present invention includes oxidation of at least one metal (M metal) selected from the group consisting of zinc oxide; tin oxide; Al, Hf, Ni, Si, Ga, In, and Ta. It is an oxide sintered body obtained by mixing and sintering a product, and is characterized in that the Vickers hardness is 400 Hv or more.
- M metal metal selected from the group consisting of zinc oxide; tin oxide; Al, Hf, Ni, Si, Ga, In, and Ta. It is an oxide sintered body obtained by mixing and sintering a product, and is characterized in that the Vickers hardness is 400 Hv or more.
- the Vickers hardness of the oxide sintered body according to the present invention is 400 Hv or more.
- the Vickers hardness of a sputtering target also becomes 400 Hv or more, and the DC discharge property at the time of sputtering improves.
- the upper limit is not particularly limited from the viewpoint of improving DC discharge performance, but is preferably controlled within an appropriate range as long as there is no defect such as cracking and a high-density sintered body can be obtained.
- the Vickers hardness is obtained by measuring the position of the surface of the cut surface obtained by cutting the oxide sintered body at the t / 2 (t: thickness) position.
- the dispersion coefficient ⁇ is preferably controlled to 30 or less.
- the dispersion coefficient is preferably as small as possible, and is preferably 25 or less.
- ten oxide sintered bodies are prepared and cut at a plurality of locations (t / 4 position, t / 2 position, 3 ⁇ t / 4 position) in the thickness direction (t) to obtain a surface. Expose and measure the Vickers hardness of the exposed part (surface position of the cut surface). The same operation is performed on 10 oxide sintered bodies, approximated by a Gaussian distribution represented by the following formula f (x), and a dispersion coefficient ⁇ of Vickers hardness in the thickness direction is calculated.
- ⁇ represents an average value of Vickers hardness.
- the M metal is at least one metal (M metal) selected from the group consisting of Al, Hf, Ni, Si, Ga, In, and Ta, and improves the Vickers hardness of the oxide sintered body and the sputtering target. As a result, direct current discharge is improved.
- M metal is also an element that greatly contributes to the improvement of the relative density and the reduction of the specific resistance of the Zn—Sn—O (ZTO) sintered body composed only of Zn and Sn. Improves.
- the M metal is an element useful for improving film characteristics formed by sputtering.
- the said M metal may be used independently and may use 2 or more types together.
- the preferable ratio of the metal elements constituting the oxide sintered body of the present invention varies depending on the type of M metal, as will be described in detail below.
- the M metal selected from the group consisting of Al, Hf, Ni, Si, Ga, In, and Ta includes at least In or Ga and includes or does not include M metal in all metal elements.
- the lower limit of the preferred ratio is different. In the former case, the lower limit of the preferred ratio is slightly increased.
- each case will be described in detail.
- M1 metal is at least one metal (M1 metal) selected from the group consisting of Al, Hf, Ni, Si, and Ta That is, when the M metal does not contain In and Ga There is such an M metal especially called “M1 metal”.
- M1 metal especially called “M1 metal”.
- the total amount of metal elements contained in the oxide sintered body is 1, and the contents (atomic%) of Zn, Sn, and M1 metals in the total metal elements are [Zn], [Sn], and [M1], respectively.
- Metal the ratio of [M1 metal] to [Zn] + [Sn] + [M1 metal]
- Ratios preferably satisfy the following formulas.
- M1 metal is a single amount when it contains M1 metal alone, and when it contains two or more types of M1 metal, it is a content of two or more types.
- [M1 metal] / ([Zn] + [Sn] + [M1 metal]) 0.01 to 0.30
- [Zn] / ([Zn] + [Sn]) 0.50-0.80
- [Sn] / ([Zn] + [Sn]) 0.20 to 0.50
- the ratio of [M1 metal] to [Zn] + [Sn] + [M1 metal] is preferably 0.01 to 0.30.
- M1 metal ratio is less than 0.01, the action due to the addition of M metal is not effectively exhibited, the DC discharge stability when used as a sputtering target is inferior, the mobility when a thin film is formed, and the reliability of the TFT sexuality etc. will decrease.
- M1 metal exceeds 0.30, the density of the sintered body cannot be increased to 90% or more, and the specific resistance increases, so that the DC plasma discharge is not stable and abnormal discharge is likely to occur. Become.
- a more preferable M1 metal ratio is 0.01 or more and 0.10 or less.
- the ratio of [Zn] to ([Zn] + [Sn]) (hereinafter sometimes simply referred to as Zn ratio) is preferably 0.50 to 0.80.
- Zn ratio is less than 0.50, the fine workability of the thin film formed by the sputtering method is lowered, and etching residues are likely to occur.
- the [Zn] ratio exceeds 0.80, the chemical resistance of the thin film after film formation becomes poor, and the elution rate by the acid becomes high at the time of fine processing, and high-precision processing cannot be performed.
- a more preferable [Zn] ratio is 0.55 or more and 0.70 or less.
- the ratio of [Sn] to ([Zn] + [Sn]) (hereinafter sometimes simply referred to as Sn ratio) is preferably 0.20 to 0.50.
- Sn ratio is less than 0.20, the chemical resistance of the thin film formed by the sputtering method is lowered, and during the fine processing, the elution rate due to the acid is increased, and high-precision processing cannot be performed.
- the [Sn] ratio exceeds 0.50, the fine workability of the thin film formed by the sputtering method is lowered, and etching residues are likely to occur.
- a more preferable [Sn] ratio is 0.25 or more and 0.40 or less.
- M metal contains at least In or Ga
- M2 metal The case where at least one of In and Ga is included among M metals is particularly called “M2 metal”.
- the total amount of metal elements contained in the oxide sintered body is 1, and the contents (atomic%) of Zn, Sn, and M2 metal in all metal elements are [Zn], [Sn], and [M2 metal], respectively. ],
- the ratio of [M2 metal] to [Zn] + [Sn] + [M2 metal] the ratio of [Zn] to [Zn] + [Sn] + [Sn] + [Sn].
- the ratios satisfy the following formulas.
- content of M2 metal is a single amount when it contains M2 metal alone, and when it contains two or more types of M2 metal, it is a content of two or more types.
- [M2 metal] / ([Zn] + [Sn] + [M2 metal]) 0.10 to 0.30
- [Zn] / ([Zn] + [Sn]) 0.50-0.80
- [Sn] / ([Zn] + [Sn]) 0.20 to 0.50
- the ratio of [M2 metal] to [Zn] + [Sn] + [M2 metal] (hereinafter sometimes simply referred to as M2 metal ratio) is preferably 0.10 to 0.30.
- M2 metal ratio is less than 0.10, the action due to the addition of the M2 metal is not effectively exhibited, the DC discharge stability when used as a sputtering target is inferior, the mobility when a thin film is formed, and the reliability of the TFT sexuality etc. will decrease.
- the M2 metal does not contain In and contains at least Ga
- the M2 metal ratio exceeds 0.30, the density of the sintered body cannot be increased to 90% or more, and the specific resistance is also low. Therefore, the DC plasma discharge is not stable and abnormal discharge is likely to occur. Further, the off-current of the TFT increases, and the characteristics as a semiconductor are impaired.
- a more preferable M2 metal ratio is 0.15 or more and 0.25 or less.
- the oxide sintered body of the present invention preferably satisfies a relative density of 90% or more and a specific resistance of 0.1 ⁇ ⁇ cm or less.
- the oxide sintered body of the present invention has a very high relative density, preferably 90% or more, and more preferably 95% or more.
- a high relative density not only can prevent the generation of cracks and nodules during sputtering, but also provides advantages such as maintaining a stable discharge continuously from the start to the end of use of the sputtering target.
- the oxide sintered body of the present invention has a small specific resistance, preferably 0.1 ⁇ ⁇ cm or less, more preferably 0.05 ⁇ ⁇ cm or less. Accordingly, film formation by a direct current sputtering method using plasma discharge using a direct current power source is possible, and physical vapor deposition (sputtering method) using a sputtering target can be efficiently performed on the production line of the display device.
- the oxide sintered body of the present invention includes oxidation of at least one metal (M metal) selected from the group consisting of zinc oxide; tin oxide; Al, Hf, Ni, Si, Ga, In, and Ta.
- M metal metal
- FIG. 1 and FIG. 2 show the basic steps from the raw material powder to the sputtering target.
- M metal 2 is that there is no heat treatment after atmospheric pressure sintering.
- an embodiment including two or more kinds of metal elements as the M metal is also included.
- the M metal may be manufactured based on the process of FIG. good.
- powdered oxides are mixed, pulverized, dried, granulated, molded, subjected to atmospheric pressure sintering, heat-treated, and then sintered to a sputtering target to obtain a sputtering target.
- the basic process is shown.
- the present invention is characterized in that the sintering conditions and the subsequent heat treatment conditions are appropriately controlled as described in detail below, and the other steps are not particularly limited, and the normally used steps are appropriately selected. You can choose.
- this invention is not the meaning limited to this, For example, it is preferable to control appropriately by the kind etc. of M metal.
- zinc oxide powder, tin oxide powder, and M oxide metal powder are mixed in a predetermined ratio, mixed and pulverized.
- the purity of each raw material powder used is preferably about 99.99% or more. This is because the presence of a trace amount of impurity elements may impair the semiconductor characteristics of the oxide semiconductor film.
- the blending ratio of each raw material powder is preferably controlled so that the ratio of Zn, Sn, and M metal falls within the above-described range.
- Mixing and pulverization are preferably performed by using a pot mill and adding the raw material powder together with water.
- the balls and beads used in these steps are preferably made of materials such as nylon, alumina, zirconia, and the like.
- the mixed powder obtained in the above step is dried and granulated, and then molded.
- the powder after drying and granulation is filled in a metal mold of a predetermined size, pre-molded by a mold press, and then molded by CIP (cold isostatic pressing) or the like.
- CIP cold isostatic pressing
- the molded body thus obtained is fired at normal pressure.
- sintering is preferably performed at a firing temperature of about 1350 ° C. to 1650 ° C. and a holding time of about 5 hours or more.
- a large amount of Zn 2 SnO 4 that contributes to the improvement of the relative density is formed in the sintered body.
- the relative density of the sputtering target is also increased, and the discharge stability is improved.
- the firing temperature is about 1450 ° C. to 1600 ° C.
- the holding time is about 8 hours or more.
- the firing atmosphere is preferably a non-reducing atmosphere.
- the sintered body thus obtained is subjected to heat treatment to obtain the oxide sintered body of the present invention.
- the heat treatment temperature about 1000 ° C. or more and the holding time: about 8 hours or more in order to enable plasma discharge with a DC power source.
- the specific resistance is reduced from, for example, about 100 ⁇ ⁇ cm (before heat treatment) to 0.1 ⁇ ⁇ cm (after heat treatment).
- the heat treatment temperature is about 1100 ° C. or more
- the holding time is about 10 hours or more.
- the heat treatment atmosphere is preferably a reducing atmosphere.
- the sputtering target of the present invention can be obtained by processing and bonding according to a conventional method.
- the Vickers hardness of the sputtering target thus obtained satisfies 400 Hv or more, as in the oxide sintered body described above, and the Vickers dispersion coefficient in the thickness direction preferably satisfies 30 or less.
- the Zn ratio, Sn ratio, M1 metal ratio, and M2 metal ratio of the sputtering target also satisfy the preferable ratios described in the oxide sintered body described above.
- the relative density and specific resistance of the sputtering target are also very good like the oxide sintered body, the preferable relative density is generally 90% or more, and the preferable specific resistance is approximately 0.1 ⁇ ⁇ cm. It is as follows.
- the molded body thus obtained was sintered at 1500 ° C. for 7 hours at normal pressure.
- Oxygen gas was introduced into the sintering furnace and sintered in an oxygen atmosphere.
- it was introduced into a heat treatment furnace and heat treated at 1200 ° C. for 10 hours.
- Nitrogen gas was introduced into the heat treatment furnace and heat treatment was performed in a reducing atmosphere.
- the relative density of the oxide sintered body of Experimental Example 1 obtained in this way was measured by Archimedes method and found to be 90% or more. Moreover, when the specific resistance of the oxide sintered body was measured by a four-terminal method, it was 0.1 ⁇ ⁇ cm or less, and a good result was obtained.
- the oxide sintered body was processed into a shape of 4 inches ⁇ and 5 mmt and bonded to a backing plate to obtain a sputtering target.
- the sputtering target thus obtained was attached to a sputtering apparatus, and an oxide semiconductor film was formed on a glass substrate (size: 100 mm ⁇ 100 mm ⁇ 0.50 mm) by a DC (direct current) magnetron sputtering method.
- the sputtering conditions were a DC sputtering power of 150 W, an Ar / 0.1 volume% O 2 atmosphere, and a pressure of 0.8 mTorr. As a result, no abnormal discharge (arcing) was observed from the start to the end of use of the sputtering target, and it was confirmed that the discharge was stably performed.
- the Vickers hardness on the sputtering surface of the sputtering target was measured, it was 438 Hv, which satisfied the range of the present invention (400 Hv or more). Furthermore, as a result of measuring the dispersion coefficient of the Vickers hardness in the depth direction from the sputtering surface of the sputtering target based on the above-described method, the preferable range (30 or less) of the present invention is satisfied, and the variation is very small. (See Table 1).
- the relative density and specific resistance of the oxide sintered body of Experimental Example 2 thus obtained were measured in the same manner as in Experimental Example 1 described above.
- the relative density was 90% or more, and the specific resistance was 0.1 ⁇ .
- -It was below cm, and the favorable result was obtained.
- the Vickers hardness of the above sputtering target was measured in the same manner as in Experimental Example 1, it was 441 Hv, which satisfied the range of the present invention (400 Hv or more). Furthermore, as a result of measuring the dispersion coefficient of the Vickers hardness in the depth direction from the discharge surface of the sputtering based on the above-described method, the dispersion satisfies the preferable range of the present invention (30 or less) and has very little variation. (See Table 1).
- the relative density and specific resistance of the oxide sintered body of Experimental Example 3 thus obtained were measured in the same manner as in Experimental Example 1 described above.
- the relative density was 90% or more, and the specific resistance was 0.1 ⁇ .
- -It was below cm, and the favorable result was obtained.
- the Vickers hardness of the above sputtering target was measured in the same manner as in Experimental Example 1, it was 441 Hv, which satisfied the range of the present invention (400 Hv or more). Furthermore, as a result of measuring the dispersion coefficient of the Vickers hardness in the depth direction from the discharge surface of the sputtering based on the above-described method, the dispersion satisfies the preferable range of the present invention (30 or less) and has very little variation. (See Table 1).
- the relative density and specific resistance of the oxide sintered body of Experimental Example 4 thus obtained were measured in the same manner as in Experimental Example 1 described above.
- the relative density was 90% or more, and the specific resistance was 0.1 ⁇ .
- -It was below cm, and the favorable result was obtained.
- the Vickers hardness of the sputtering target was measured in the same manner as in Experimental Example 1, it was 461 Hv, which satisfied the range of the present invention (400 Hv or more). Furthermore, as a result of measuring the dispersion coefficient of the Vickers hardness in the depth direction from the discharge surface of the sputtering based on the above-described method, the dispersion satisfies the preferable range of the present invention (30 or less) and has very little variation. (See Table 1).
- Comparative Example 1 The oxide of Comparative Example 1 was the same as Experimental Example 2 except that the molded body was sintered in a furnace at 1300 ° C. for 5 hours and heat-treated at 1200 ° C. for 10 hours. A sintered body was obtained.
- the carrier mobility was measured in the same manner as in Experimental Example 1 using the thin film formed under the above sputtering conditions, the carrier mobility was as low as 3.0 cm 2 / Vs.
- Figs. 3 to 6 show the results of Gaussian (normal distribution) curves of Vickers hardness for the sputtering targets of Experimental Examples 1 to 4.
- the result of the sputtering target of Comparative Example 1 is also shown for comparison. From these figures, it can be seen that according to the present invention, a sputtering target having a Vickers hardness higher than that of the comparative example and reduced variation is obtained.
- the M metal specified in the present invention is contained, the dispersion coefficient of specific resistance is suppressed to 0.02 or less, and the composition ratio of the metal constituting the oxide sintered body is also preferable of the present invention.
- Sputtering targets obtained using the oxide sintered bodies of Experimental Examples 1 to 5 that satisfy the requirements have a high relative density and a low specific resistance, and are stable for a long time even when manufactured by a direct current sputtering method. It turns out that it discharges.
- the thin film obtained using the said sputtering target has high carrier mobility, it turned out that it is very useful as an oxide semiconductor thin film.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
Description
[M1金属]/([Zn]+[Sn]+[M1金属])=0.01~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50
[M2金属]/([Zn]+[Sn]+[M2金属])=0.10~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50
[M1金属]/([Zn]+[Sn]+[M1金属])=0.01~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50
[M2金属]/([Zn]+[Sn]+[M2金属])=0.10~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50
すなわち、上記M金属がInおよびGaを含まない場合であり、このようなM金属を特に「M1金属」と呼ぶ。上記酸化物焼結体に含まれる金属元素の総量を1とし、全金属元素中に占める、Zn、Sn、M1金属の含有量(原子%)をそれぞれ、[Zn]、[Sn]、[M1金属]としたとき、[Zn]+[Sn]+[M1金属]に対する[M1金属]の比、[Zn]+[Sn]に対する[Zn]の比、[Zn]+[Sn]に対する[Sn]の比は、それぞれ下式を満足することが好ましい。なお、M1金属の含有量とは、M1金属を単独で含有するときは単独の量であり、M1金属を2種以上含有するときは2種以上の含有量である。
[M1金属]/([Zn]+[Sn]+[M1金属])=0.01~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50
M金属のうち、InおよびGaの少なくとも一種を含む場合を特に「M2金属」と呼ぶ。上記酸化物焼結体に含まれる金属元素の総量を1とし、全金属元素中に占めるZn、Sn、M2金属の含有量(原子%)をそれぞれ、[Zn]、[Sn]、[M2金属]としたとき、[Zn]+[Sn]+[M2金属]に対する[M2金属]の比、[Zn]+[Sn]に対する[Zn]の比、[Zn]+[Sn]に対する[Sn]の比は、それぞれ下式を満足するものである。なお、M2金属の含有量とは、M2金属を単独で含有するときは単独の量であり、M2金属を2種以上含有するときは2種以上の含有量である。
[M2金属]/([Zn]+[Sn]+[M2金属])=0.10~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50
本発明の酸化物焼結体は、相対密度が非常に高く、好ましくは90%以上であり、より好ましくは95%以上である。高い相対密度は、スパッタリング中での割れやノジュールの発生を防止し得るだけでなく、安定した放電を、スパッタリングターゲットの使用開始から終了に至るまで、常に連続して維持するなどの利点をもたらす。
本発明の酸化物焼結体は、比抵抗が小さく、0.1Ω・cm以下であることが好ましく、より好ましくは0.05Ω・cm以下である。これにより、直流電源を用いたプラズマ放電などによる直流スパッタリング法による成膜が可能となり、スパッタリングターゲットを用いた物理蒸着(スパッタリング法)を表示装置の生産ラインで効率よく行うことができる。
純度99.99%の酸化亜鉛粉末(JIS1種)、純度99.99%の酸化スズ粉末、および純度99.99%の酸化アルミニウム粉末を[Zn]:[Sn]:[Al]=73.9:24.6:1.5の比率で配合し、ナイロンボールミルで20時間混合した。参考のため、表1に、Zn比およびSn比を示している。Al比は0.015である。次に、上記工程で得られた混合粉末を乾燥、造粒し、金型プレスにて成形圧力0.5tonf/cm2で予備成形した後、CIPにて成形圧力3tonf/cm2で本成形を行った。
純度99.99%の酸化亜鉛粉末(JIS1種)、純度99.99%の酸化スズ粉末、および純度99.99%の酸化タンタル粉末を[Zn]:[Sn]:[Ta]=73.9:24.6:1.5の比率で配合し、1550℃で5時間焼結した後、1150℃で14時間熱処理したこと以外は、前述した実験例1と同様にして実験例2の酸化物焼結体を得た(Ta比=0.015)。
純度99.99%の酸化亜鉛粉末(JIS1種)、純度99.99%の酸化スズ粉末、および純度99.99%の酸化インジウム粉末を[Zn]:[Sn]:[In]=45.0:45.0:10.0の比率で配合し、1550℃で5時間焼結した(熱処理なし)こと以外は、前述した実験例1と同様にして実験例3の酸化物焼結体を得た(In比=0.10)。
純度99.99%の酸化亜鉛粉末(JIS1種)、純度99.99%の酸化スズ粉末、および純度99.99%の酸化ガリウム粉末を[Zn]:[Sn]:[Ga]=60.0:30.0:10.0の比率で配合し、1600℃で8時間焼結した後、1200℃で16時間熱処理したこと以外は、前述した実験例1と同様にして実験例4の酸化物焼結体を得た(Ga比=0.10)。
前述した実験例2において、炉内に成形体を1300℃で5時間保持して焼結し、1200℃で10時間熱処理したこと以外は、上記実験例2と同様にして比較例1の酸化物焼結体を得た。
Claims (10)
- 酸化亜鉛と;酸化スズと;Al、Hf、Ni、Si、Ga、In、およびTaよりなる群から選択される少なくとも1種の金属(M金属)の酸化物と、を混合および焼結して得られる酸化物焼結体であって、ビッカース硬度が400Hv以上であることを特徴とする酸化物焼結体。
- 厚み方向のビッカース硬度をガウス分布で近似したとき、その分散係数σが30以下である請求項1に記載の酸化物焼結体。
- 前記酸化物焼結体に含まれる金属元素の総量を1とし、
前記M金属のうち、Al、Hf、Ni、Si、およびTaよりなる群から選択される少なくとも1種の金属をM1金属とし、
全金属元素中に占める、Zn、Sn、M1金属の含有量(原子%)をそれぞれ、[Zn]、[Sn]、[M1金属]としたとき、[Zn]+[Sn]+[M1金属]に対する[M1金属]の比、[Zn]+[Sn]に対する[Zn]の比、[Zn]+[Sn]に対する[Sn]の比は、それぞれ下式を満足するものである請求項1または2に記載の酸化物焼結体。
[M1金属]/([Zn]+[Sn]+[M1金属])=0.01~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50 - 前記酸化物焼結体に含まれる金属元素の総量を1とし、
前記M金属のうち、少なくともInまたはGaを含む金属をM2金属とし、
全金属元素中に占める、Zn、Sn、M2金属の含有量(原子%)をそれぞれ、[Zn]、[Sn]、[M2金属]としたとき、[Zn]+[Sn]+[M2金属]に対する[M2金属]の比、[Zn]+[Sn]に対する[Zn]の比、[Zn]+[Sn]に対する[Sn]の比は、それぞれ下式を満足するものである請求項1または2に記載の酸化物焼結体。
[M2金属]/([Zn]+[Sn]+[M2金属])=0.10~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50 - 相対密度90%以上、比抵抗0.1Ω・cm以下である請求項1~4のいずれかに記載の酸化物焼結体。
- 請求項1~5のいずれかに記載の酸化物焼結体を用いて得られるスパッタリングターゲットであって、ビッカース硬度が400Hv以上であることを特徴とするスパッタリングターゲット。
- スパッタリング面から厚み方向のビッカース硬度をガウス分布で近似したとき、その分散係数σが30以下である請求項6に記載のスパッタリングターゲット。
- 前記スパッタリングターゲットに含まれる金属元素の総量を1とし、
前記M金属のうち、Al、Hf、Ni、Si、およびTaよりなる群から選択される少なくとも1種の金属をM1金属とし、
全金属元素中に占める、Zn、Sn、M1金属の含有量(原子%)をそれぞれ、[Zn]、[Sn]、[M1金属]としたとき、[Zn]+[Sn]+[M1金属]に対する[M1金属]の比、[Zn]+[Sn]に対する[Zn]の比、[Zn]+[Sn]に対する[Sn]の比は、それぞれ下式を満足するものである請求項6または7に記載のスパッタリングターゲット。
[M1金属]/([Zn]+[Sn]+[M1金属])=0.01~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50 - 前記スパッタリングターゲットに含まれる金属元素の総量を1とし、
前記M金属のうち、少なくともInまたはGaを含む金属をM2金属とし、
全金属元素中に占める、Zn、Sn、M2金属の含有量(原子%)をそれぞれ、[Zn]、[Sn]、[M2金属]としたとき、[Zn]+[Sn]+[M2金属]に対する[M2金属]の比、[Zn]+[Sn]に対する[Zn]の比、[Zn]+[Sn]に対する[Sn]の比は、それぞれ下式を満足するものである請求項6または7に記載のスパッタリングターゲット。
[M2金属]/([Zn]+[Sn]+[M2金属])=0.10~0.30
[Zn]/([Zn]+[Sn])=0.50~0.80
[Sn]/([Zn]+[Sn])=0.20~0.50 - 相対密度90%以上、比抵抗0.1Ω・cm以下である請求項6~9のいずれかに記載のスパッタリングターゲット。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/002,491 US20130334039A1 (en) | 2011-03-02 | 2012-03-01 | Oxide sintered body and sputtering target |
CN2012800113333A CN103429554A (zh) | 2011-03-02 | 2012-03-01 | 氧化物烧结体及溅射靶 |
KR1020137025605A KR20130133006A (ko) | 2011-03-02 | 2012-03-01 | 산화물 소결체 및 스퍼터링 타깃 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-045267 | 2011-03-02 | ||
JP2011045267A JP2012180247A (ja) | 2011-03-02 | 2011-03-02 | 酸化物焼結体およびスパッタリングターゲット |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012118156A1 true WO2012118156A1 (ja) | 2012-09-07 |
Family
ID=46758082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/055265 WO2012118156A1 (ja) | 2011-03-02 | 2012-03-01 | 酸化物焼結体およびスパッタリングターゲット |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130334039A1 (ja) |
JP (1) | JP2012180247A (ja) |
KR (1) | KR20130133006A (ja) |
CN (1) | CN103429554A (ja) |
TW (1) | TW201300344A (ja) |
WO (1) | WO2012118156A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107523794A (zh) * | 2017-09-07 | 2017-12-29 | 于盟盟 | 一种用于溅射透明导电薄膜的靶材 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104272463B (zh) | 2012-05-09 | 2017-08-15 | 株式会社神户制钢所 | 薄膜晶体管和显示装置 |
JP6068232B2 (ja) | 2012-05-30 | 2017-01-25 | 株式会社神戸製鋼所 | 薄膜トランジスタの半導体層用酸化物、薄膜トランジスタ、表示装置およびスパッタリングターゲット |
JP6002088B2 (ja) | 2012-06-06 | 2016-10-05 | 株式会社神戸製鋼所 | 薄膜トランジスタ |
TWI532187B (zh) | 2012-06-06 | 2016-05-01 | Kobe Steel Ltd | Thin film transistor |
JP6134230B2 (ja) | 2012-08-31 | 2017-05-24 | 株式会社神戸製鋼所 | 薄膜トランジスタおよび表示装置 |
JP2014225626A (ja) | 2012-08-31 | 2014-12-04 | 株式会社神戸製鋼所 | 薄膜トランジスタおよび表示装置 |
JP5722293B2 (ja) | 2012-10-19 | 2015-05-20 | 株式会社神戸製鋼所 | 薄膜トランジスタ |
KR102158075B1 (ko) * | 2013-04-12 | 2020-09-21 | 히타치 긴조쿠 가부시키가이샤 | 산화물 반도체 타깃, 산화물 반도체막 및 그 제조 방법, 및 박막 트랜지스터 |
JP6041219B2 (ja) | 2014-08-27 | 2016-12-07 | 日立金属株式会社 | スパッタリングターゲット |
JP6677095B2 (ja) * | 2015-11-20 | 2020-04-08 | 住友金属鉱山株式会社 | Sn−Zn−O系酸化物焼結体とその製造方法 |
JP6551683B2 (ja) * | 2016-03-11 | 2019-07-31 | 住友金属鉱山株式会社 | Sn−Zn−O系酸化物焼結体とその製造方法 |
WO2019026954A1 (ja) * | 2017-08-01 | 2019-02-07 | 出光興産株式会社 | スパッタリングターゲット、酸化物半導体薄膜、薄膜トランジスタおよび電子機器 |
JP2019131866A (ja) * | 2018-01-31 | 2019-08-08 | 住友金属鉱山株式会社 | 酸化物スパッタ膜、酸化物スパッタ膜の製造方法、酸化物焼結体及び透明樹脂基板 |
CN108546918B (zh) * | 2018-03-30 | 2020-01-07 | 湖北大学 | 一种超宽禁带氧化物合金半导体外延薄膜材料及其制备方法和应用 |
KR102192713B1 (ko) * | 2018-09-08 | 2020-12-17 | 바짐테크놀로지 주식회사 | 박막 증착용 스퍼터링 타겟 조성물 및 이의 제조방법 |
WO2020170949A1 (ja) | 2019-02-18 | 2020-08-27 | 出光興産株式会社 | 酸化物焼結体、スパッタリングターゲット及びスパッタリングターゲットの製造方法 |
TWI740216B (zh) * | 2019-09-24 | 2021-09-21 | 光洋應用材料科技股份有限公司 | 銦錫鎳氧化物靶材及其製造方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007277075A (ja) * | 2006-03-15 | 2007-10-25 | Sumitomo Metal Mining Co Ltd | 酸化物焼結体、その製造方法、それを用いた透明導電膜の製造方法、及び得られる透明導電膜 |
WO2010058533A1 (ja) * | 2008-11-20 | 2010-05-27 | 出光興産株式会社 | ZnO-SnO2-In2O3系酸化物焼結体及び非晶質透明導電膜 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW562870B (en) * | 2001-10-12 | 2003-11-21 | Tosoh Corp | Sputtering target |
KR101211747B1 (ko) * | 2005-09-22 | 2012-12-12 | 이데미쓰 고산 가부시키가이샤 | 산화물 재료 및 스퍼터링 타겟 |
KR101314946B1 (ko) * | 2005-09-27 | 2013-10-04 | 이데미쓰 고산 가부시키가이샤 | 스퍼터링 타겟, 투명 도전막 및 터치 패널용 투명 전극 |
US8753548B2 (en) * | 2008-12-12 | 2014-06-17 | Idemitsu Kosan Co., Ltd. | Composite oxide sintered body and sputtering target comprising same |
-
2011
- 2011-03-02 JP JP2011045267A patent/JP2012180247A/ja active Pending
-
2012
- 2012-03-01 US US14/002,491 patent/US20130334039A1/en not_active Abandoned
- 2012-03-01 WO PCT/JP2012/055265 patent/WO2012118156A1/ja active Application Filing
- 2012-03-01 CN CN2012800113333A patent/CN103429554A/zh active Pending
- 2012-03-01 KR KR1020137025605A patent/KR20130133006A/ko not_active Application Discontinuation
- 2012-03-02 TW TW101106961A patent/TW201300344A/zh unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007277075A (ja) * | 2006-03-15 | 2007-10-25 | Sumitomo Metal Mining Co Ltd | 酸化物焼結体、その製造方法、それを用いた透明導電膜の製造方法、及び得られる透明導電膜 |
WO2010058533A1 (ja) * | 2008-11-20 | 2010-05-27 | 出光興産株式会社 | ZnO-SnO2-In2O3系酸化物焼結体及び非晶質透明導電膜 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107523794A (zh) * | 2017-09-07 | 2017-12-29 | 于盟盟 | 一种用于溅射透明导电薄膜的靶材 |
Also Published As
Publication number | Publication date |
---|---|
KR20130133006A (ko) | 2013-12-05 |
TW201300344A (zh) | 2013-01-01 |
JP2012180247A (ja) | 2012-09-20 |
CN103429554A (zh) | 2013-12-04 |
US20130334039A1 (en) | 2013-12-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012118156A1 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
WO2012118150A1 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
JP5651095B2 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
JP5796812B2 (ja) | 酸化物焼結体およびスパッタリングターゲット、並びにその製造方法 | |
JP5750065B2 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
JP5750063B2 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
WO2012039351A1 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
JP5883368B2 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
JP2014058415A (ja) | 酸化物焼結体およびスパッタリングターゲット、並びにその製造方法 | |
WO2012096267A1 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
JP5952891B2 (ja) | 酸化物焼結体、およびスパッタリングターゲットの製造方法 | |
JPWO2016084636A1 (ja) | 酸化物焼結体、スパッタリング用ターゲット、及びそれを用いて得られる酸化物半導体薄膜 | |
JP2019038735A (ja) | 酸化物焼結体、酸化物焼結体の製造方法、スパッタリング用ターゲット、及び非晶質の酸化物半導体薄膜 | |
JP2017154910A (ja) | 酸化物焼結体及びスパッタリング用ターゲット | |
JP5750064B2 (ja) | 酸化物焼結体およびスパッタリングターゲット | |
JP2017019668A (ja) | 酸化物焼結体およびスパッタリングターゲット、並びにそれらの製造方法 | |
JP2017168572A (ja) | 酸化物半導体薄膜、酸化物焼結体、薄膜トランジスタ及び表示装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12751806 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14002491 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137025605 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12751806 Country of ref document: EP Kind code of ref document: A1 |