TW202313520A - Molybdenum oxide based sintered body, sputtering target, oxide thin film using the sintered body, and thin film transistors and display devices including the thin films - Google Patents
Molybdenum oxide based sintered body, sputtering target, oxide thin film using the sintered body, and thin film transistors and display devices including the thin films Download PDFInfo
- Publication number
- TW202313520A TW202313520A TW111134818A TW111134818A TW202313520A TW 202313520 A TW202313520 A TW 202313520A TW 111134818 A TW111134818 A TW 111134818A TW 111134818 A TW111134818 A TW 111134818A TW 202313520 A TW202313520 A TW 202313520A
- Authority
- TW
- Taiwan
- Prior art keywords
- sintered body
- oxide
- thin film
- moo
- weight
- Prior art date
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 54
- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 39
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000005477 sputtering target Methods 0.000 title claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 43
- 150000004706 metal oxides Chemical class 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000010408 film Substances 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- -1 MoO 2 and MoO 3 Chemical compound 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 16
- 239000000843 powder Substances 0.000 description 20
- 239000010949 copper Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000013077 target material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 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
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
Classifications
-
- 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
- C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
- H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
-
- 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
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
- H10K59/1213—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
-
- 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
-
- 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
- C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
-
- 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/404—Refractory metals
-
- 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/407—Copper
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Structural Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Geometry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thin Film Transistor (AREA)
Abstract
Description
本發明關於低反射、耐化學性及耐熱性優秀的氧化鉬基燒結體、使用該燒結體的薄膜、包含該薄膜的薄膜電晶體及顯示裝置。The present invention relates to a molybdenum oxide-based sintered body excellent in low reflection, chemical resistance, and heat resistance, a thin film using the sintered body, a thin film transistor including the thin film, and a display device.
通常，平板顯示器（FPD，flat panel display）、觸控螢幕面板、太陽能電池、發光二極體（LED，light emitting diode）、有機發光二極體（OLED，organic light emitting diode）使用低反射率的導電薄膜。Generally, flat panel displays (FPD, flat panel display), touch screen panels, solar cells, light emitting diodes (LED, light emitting diode), organic light emitting diodes (OLED, organic light emitting diode) use low reflectivity conductive film.
作為代表性的材料有氧化銦錫（ITO，In 2O 3-SnO 2），氧化銦錫組合物用於形成可視光線透射度及導電率較高的導電薄膜。雖然，這種氧化銦錫組合物具備優秀的低反射性能，但是，存在其經濟性低下的問題，因此，正持續研究代替所有氧化銦或部分氧化銦的材料。 A representative material is indium tin oxide (ITO, In 2 O 3 -SnO 2 ), and the indium tin oxide composition is used to form a conductive film with high visible light transmittance and high conductivity. Although such an indium tin oxide composition has excellent low-reflection performance, it has a problem of low economical efficiency. Therefore, research is continuing on materials that can replace all or part of indium oxide.
然而，在這種研究中，所關注的部分主要關於由靶材形成的薄膜的低反射率，因此，當長時間使用時，實際上需要考慮耐化學性、耐熱性等特性，以便增加薄膜的可靠性。However, in this kind of research, the part of concern is mainly about the low reflectance of the film formed from the target material, so when it is used for a long time, it is actually necessary to consider characteristics such as chemical resistance and heat resistance in order to increase the film's reliability.
現有技術文獻 專利文獻 專利文獻0001：韓國公開專利第10-2008-0058390號 prior art literature patent documents Patent Document 0001: Korean Laid-Open Patent No. 10-2008-0058390
技術問題technical problem
另一方面，本發明人注意到，現有的氧化鉬靶材表現出低反射特性，但耐熱性及耐化學性相對較差。On the other hand, the present inventors noticed that the existing molybdenum oxide target exhibits low reflection characteristics, but relatively poor heat resistance and chemical resistance.
為此，本發明的技術目的在於，提供藉由向作為主要材料的氧化鉬混合添加規定範圍的特定金屬氧化物和金屬形成的低反射特性、耐熱性、耐化學性均優秀的濺鍍靶材用燒結體、由此形成的金屬氧化物薄膜及形成有上述金屬氧化物薄膜的薄膜電晶體和顯示裝置。Therefore, the technical purpose of the present invention is to provide a sputtering target material excellent in low reflection characteristics, heat resistance, and chemical resistance, which is formed by mixing and adding a specific metal oxide and metal in a predetermined range to molybdenum oxide as the main material. A sintered body, a metal oxide thin film formed therefrom, a thin film transistor and a display device formed with the above metal oxide thin film are used.
本發明的其他目的及優點可藉由以下詳細說明及發明要求保護範圍變得更加明確。Other purposes and advantages of the present invention can become more clear from the following detailed description and the protection scope of the invention.
技術方案Technical solutions
為了實現上述技術目的，本發明提供的氧化物燒結體包含：氧化鉬，包含MoO 2和MoO 3，在上述MoO 2及MoO 3中，MoO 2的含量為50重量百分比至90重量百分比；金屬氧化物M1，選自由Nb 2O 5、Ta 2O 5、ZrO 2、TiO 2、SnO 2及WO 3組成的群組中的一種以上；以及金屬M2，選自由Mo、Ti、Cr、W及Cu組成的群組中的一種以上，相對於相應燒結體的總重量，至少包含70重量百分比以上的氧化鉬。 In order to achieve the above-mentioned technical purpose, the oxide sintered body provided by the present invention includes: molybdenum oxide, including MoO 2 and MoO 3 , in the above-mentioned MoO 2 and MoO 3 , the content of MoO 2 is 50% by weight to 90% by weight; metal oxide M1, one or more selected from the group consisting of Nb 2 O 5 , Ta 2 O 5 , ZrO 2 , TiO 2 , SnO 2 and WO 3 ; and metal M2 selected from Mo, Ti, Cr, W and Cu One or more of the group of components contains at least 70% by weight or more of molybdenum oxide relative to the total weight of the corresponding sintered body.
根據本發明一實施例，相對於100重量百分比的相應氧化物燒結體，可包含1.0重量百分比至5.0重量百分比的上述金屬M2。According to an embodiment of the present invention, relative to 100 weight percent of the corresponding oxide sintered body, the above-mentioned metal M2 may comprise 1.0 weight percent to 5.0 weight percent.
根據本發明一實施例，相對於100重量百分比的相應氧化物燒結體，包含95.0重量百分比至99.0重量百分比的上述氧化鉬和金屬氧化物M1，上述氧化鉬與上述金屬氧化物M1的含量比例可以為75：25至90：10的重量比。According to an embodiment of the present invention, relative to 100% by weight of the corresponding oxide sintered body, 95.0% to 99.0% by weight of the above-mentioned molybdenum oxide and metal oxide M1 are included, and the content ratio of the above-mentioned molybdenum oxide and the above-mentioned metal oxide M1 can be A weight ratio of 75:25 to 90:10.
根據本發明一實施例，上述氧化物燒結體的電阻率為1×10 -2Ωcm以下，相對密度可以為95％以上。 According to an embodiment of the present invention, the above-mentioned oxide sintered body has a resistivity of 1×10 −2 Ωcm or less, and a relative density of 95% or more.
並且，本發明提供包括上述燒結體的濺鍍靶材。Furthermore, the present invention provides a sputtering target including the above-mentioned sintered body.
並且，本發明提供由上述濺鍍靶材製成的氧化物薄膜。Furthermore, the present invention provides an oxide thin film made of the above-mentioned sputtering target.
根據本發明一實施例，上述氧化物薄膜可用於閘極層、源極層及汲極層中的一個。According to an embodiment of the present invention, the above oxide thin film may be used for one of the gate layer, the source layer and the drain layer.
並且，本發明提供包括上述氧化物薄膜的顯示裝置。Furthermore, the present invention provides a display device including the above oxide thin film.
發明的效果The effect of the invention
根據本發明實施例，可藉由將氧化鉬作為主要成分向其混合添加規定範圍的特定金屬氧化物M1和金屬M2，改善氧化鉬基燒結體的燒結性並確保高密度。According to an embodiment of the present invention, the sinterability of the molybdenum oxide-based sintered body can be improved and high density can be ensured by adding molybdenum oxide as a main component to the specific metal oxide M1 and metal M2 in a specified range.
並且，由上述燒結體製成的薄膜具有低反射特性，而且，具有優秀的耐熱性及耐化學性。由此，可確保由上述薄膜製成的薄膜電晶體或顯示裝置的工作可靠性。Furthermore, the thin film made of the above-mentioned sintered body has low reflection characteristics, and also has excellent heat resistance and chemical resistance. Thereby, the operational reliability of a thin film transistor or a display device made of the above thin film can be ensured.
除此之外，本發明所屬技術領域具有通常知識者可藉由以下記載的具體內容或在實施本發明的過程中明確理解本發明的其他效果。In addition, those with ordinary knowledge in the technical field of the present invention can clearly understand other effects of the present invention from the specific content described below or during the process of implementing the present invention.
以下，詳細說明本發明。Hereinafter, the present invention will be described in detail.
在本說明書中使用的所有術語（包括技術術語及科學術語）的含義與本發明所屬技術領域具有通常知識者通常理解的含義相同。並且，通常使用的詞典中定義的術語應解釋成含義與相關技術在文脈上所具有的含義相同，除非在本說明書中明確定義，否則不應以理想化或過於形式化的含義加以解釋。The meanings of all terms (including technical terms and scientific terms) used in this specification are the same as those commonly understood by those with ordinary knowledge in the technical field to which the present invention belongs. Also, terms defined in commonly used dictionaries should be construed to have the same meanings as contextualized meanings of related technologies, and should not be interpreted in idealized or overly formalized meanings unless clearly defined in this specification.
並且，在說明書的全文內容中，當表示某部分「包括」其他結構要素時，除非存在特別相反的記載，否則意味著還包括其他結構要素，並不排除其他結構要素。並且，在整個說明書中，「上方」或「上」等不僅意味著位元於物件部分的上方或下方的情況，而且，還包括在其中間存在其他部分的情況，這並不意味著位於以重力方向為基準的上方。而且，在本說明書中，「第一」、「第二」等術語僅用於區分結構要素，並不表示任意順序或重要程度。In addition, in the entire content of the specification, when it is indicated that a certain part "includes" other structural elements, unless there is a particularly contrary description, it means that other structural elements are also included, and other structural elements are not excluded. And, throughout the specification, "above" or "upper" and the like not only mean the case where the bit is above or below the part of the object, but also include the case where there are other parts in between, which does not mean that it is located above or below the part of the object. The direction of gravity is above the datum. Moreover, in this specification, terms such as "first" and "second" are only used to distinguish structural elements, and do not indicate any order or degree of importance.
燒結體及濺鍍靶材Sintered body and sputtering target
在本發明的一例中，金屬氧化物燒結體用於製備將氧化鉬作為主要成分的濺鍍靶材。In one example of the present invention, the metal oxide sintered body is used to prepare a sputtering target mainly composed of molybdenum oxide.
根據一具體例，上述燒結體包含：氧化鉬，包含MoO 2和MoO 3，在上述MoO 2及MoO 3中，MoO 2的含量為50重量百分比至90重量百分比；金屬氧化物M1，選自由Nb 2O 5、Ta 2O 5、ZrO 2、TiO 2、SnO 2及WO 3組成的群組中的一種以上；以及金屬M2，選自由Mo、Ti、Cr、W及Cu組成的群組中的一種以上，相對於相應燒結體的總重量，至少包含70重量百分比以上的氧化鉬作為主要成分。 According to a specific example, the above-mentioned sintered body includes: molybdenum oxide, including MoO 2 and MoO 3 , in the above-mentioned MoO 2 and MoO 3 , the content of MoO 2 is 50% by weight to 90% by weight; metal oxide M1, selected from Nb One or more of the group consisting of 2 O 5 , Ta 2 O 5 , ZrO 2 , TiO 2 , SnO 2 and WO 3 ; and metal M2 selected from the group consisting of Mo, Ti, Cr, W and Cu One or more kinds, containing at least 70% by weight or more of molybdenum oxide as a main component relative to the total weight of the corresponding sintered body.
在將上述金屬氧化物燒結體用作靶材形成薄膜的情況下，所形成的薄膜具有低反射特性，同時，藉由最佳化氧化鉬的比例及組成成分來提高耐熱性及耐化學性。In the case of forming a thin film using the metal oxide sintered body as a target, the formed thin film has low reflection characteristics, and at the same time, heat resistance and chemical resistance are improved by optimizing the ratio and composition of molybdenum oxide.
以下，詳細說明各個組成成分。Hereinafter, each component will be described in detail.
氧化鉬作為鉬與氧相結合的成分，例如有MoO 2、MoO 3、MoO 4等。本發明中的氧化鉬包含MoO 2、MoO 3。 Molybdenum oxide is a component in which molybdenum and oxygen are combined, for example, there are MoO 2 , MoO 3 , MoO 4 and the like. Molybdenum oxide in the present invention includes MoO 2 and MoO 3 .
對於構成上述氧化鉬的MoO 2和MoO 3的含量，MoO 2為50重量百分比至90重量百分比，MoO 3為10重量百分比至50重量百分比。在MoO 2含量小於50重量百分比的情況下，因MoO 3含量的增加而導致燒結密度的降低，因此，當蒸鍍薄膜時，化學穩定性並不理想。另一方面，在MoO 2含量大於90重量百分比的情況下，燒結密度可因MoO 2含量的增加而增加，但是，隨著靶材強度的降低，可導致靶材內產生龜裂。另一方面，若按照MoO 2/MoO 3重量百分比顯示，則其比例為1～16。 Regarding the contents of MoO 2 and MoO 3 constituting the above molybdenum oxide, MoO 2 is 50 wt % to 90 wt %, and MoO 3 is 10 wt % to 50 wt %. In the case where the MoO 2 content is less than 50% by weight, the sintered density decreases due to an increase in the MoO 3 content, and therefore, the chemical stability is not ideal when a thin film is evaporated. On the other hand, when the content of MoO 2 is greater than 90% by weight, the sintered density can be increased due to the increase of the content of MoO 2 , however, as the strength of the target material decreases, cracks can be generated in the target material. On the other hand, if displayed in terms of MoO 2 /MoO 3 weight percent, the ratio is 1-16.
在本發明的氧化物燒結體所包含的添加成分中的一個為金屬氧化物M1，上述金屬氧化物M1為Nb 2O 5、Ta 2O 5、ZrO 2、TiO 2、SnO 2及WO 3組成的群組中的一種以上。 One of the additive components contained in the oxide sintered body of the present invention is metal oxide M1, and the metal oxide M1 is composed of Nb 2 O 5 , Ta 2 O 5 , ZrO 2 , TiO 2 , SnO 2 and WO 3 More than one of the groups of .
上述金屬氧化物M1作為氧化摻雜物，用於改善耐化學性及耐熱性等特性，可藉由添加上述金屬氧化物來提高氧化鉬的耐化學性及耐熱性。在以下說明中，將以元件符號M1表示Nb 2O 5、Ta 2O 5、ZrO 2、TiO 2、SnO 2及WO 3中的一種以上成分。 The above-mentioned metal oxide M1 is used as an oxidation dopant to improve properties such as chemical resistance and heat resistance, and the chemical resistance and heat resistance of molybdenum oxide can be improved by adding the above-mentioned metal oxide. In the following description, one or more components among Nb 2 O 5 , Ta 2 O 5 , ZrO 2 , TiO 2 , SnO 2 , and WO 3 will be represented by the symbol M1.
在本發明的氧化物燒結體所包含的添加成分中的另一個為選自由Mo、Ti、Cr、W、及Cu組成的群組中的一種以上的金屬M2。Another of the additive components contained in the oxide sintered body of the present invention is one or more metals M2 selected from the group consisting of Mo, Ti, Cr, W, and Cu.
上述金屬M2作為金屬摻雜物，具有輔助氧化鉬的燒結性並提高密度的效果，可藉由添加上述金屬來提高氧化鉬的耐化學性及耐熱性等特性。在以下說明中，將以元件符號M2表示Mo、Ti、Cr、W及Cu中的一種以上成分。The above-mentioned metal M2, as a metal dopant, has the effect of assisting the sinterability of molybdenum oxide and increasing the density, and the chemical resistance and heat resistance of molybdenum oxide can be improved by adding the above-mentioned metal. In the following description, one or more components among Mo, Ti, Cr, W, and Cu will be represented by element symbol M2.
在包含上述氧化鉬、金屬氧化物M1及金屬M2的金屬氧化物燒結體中，相對於100重量百分比的相應燒結體，包含95.0重量百分比至99.0重量百分比的氧化鉬和金屬氧化物；包含1.0重量百分比至5.0重量百分比的金屬M2。其中，氧化鉬和金屬氧化物M1的含量比例可以為75：25至90：10重量比。相對於相應金屬氧化物燒結體的總重量，當氧化鉬的比例佔據75重量百分比以上時，在蒸鍍薄膜的情況下，可獲得低反射特性。In the metal oxide sintered body comprising the above-mentioned molybdenum oxide, metal oxide M1 and metal M2, relative to 100 weight percent of the corresponding sintered body, 95.0 weight percent to 99.0 weight percent of molybdenum oxide and metal oxide are included; 1.0 weight percent percent to 5.0 weight percent metal M2. Wherein, the content ratio of molybdenum oxide and metal oxide M1 may be 75:25 to 90:10 by weight. When the proportion of molybdenum oxide occupies 75% by weight or more with respect to the total weight of the corresponding metal oxide sintered body, low reflection characteristics can be obtained in the case of vapor-deposited thin films.
以上述方式形成的本發明氧化物燒結體的相對密度為95％以上，其上限值並沒有限制。並且，氧化物燒結體的電阻率為1×10 -2Ωcm以下，其下限值並沒有限制。而且，對於氧化物燒結體所包含的晶粒尺寸並沒有限制，作為一例，可以為1μm至20μm，具體地，可以為1μm至10μm。 The relative density of the oxide sintered body of the present invention formed in the above manner is 95% or more, and the upper limit is not limited. In addition, the resistivity of the oxide sintered body is 1×10 -2 Ωcm or less, and the lower limit thereof is not limited. Furthermore, there is no limitation on the size of crystal grains contained in the oxide sintered body, and as an example, it may be 1 μm to 20 μm, specifically, it may be 1 μm to 10 μm.
並且，本發明再一實施例的濺鍍靶材包括：氧化物燒結體，作為主要成分包含上述氧化鉬；以及墊板，與上述燒結體的一面相接合，用於支撐上述燒結體。Furthermore, a sputtering target according to still another embodiment of the present invention includes: an oxide sintered body containing the molybdenum oxide as a main component; and a backing plate bonded to one surface of the sintered body to support the sintered body.
其中，墊板作為支撐濺鍍靶材用燒結體的基板，可無限制地使用在本領域中通常使用的墊板。在此情況下，對於構成墊板的材料及其形狀並沒有特別限制。In addition, as a backing board, the backing board normally used in this field can be used without limitation as a board|substrate which supports the sintered compact for sputtering targets. In this case, there are no particular limitations on the material constituting the backing plate and its shape.
氧化物燒結體及濺鍍靶材的製備方法Preparation method of oxide sintered body and sputtering target
以下，說明本發明一實施方式的氧化物燒結體及濺鍍靶材的製備方法。但是，並不限定於下述製備方法，也可根據需求改變各個製程的步驟或選擇性地混合執行。Hereinafter, a method for producing an oxide sintered body and a sputtering target according to an embodiment of the present invention will be described. However, it is not limited to the preparation method described below, and the steps of each process may be changed or selectively mixed according to needs.
作為較佳一實施例，上述製備方法可包括：第一步驟（i），混合氧化鉬、至少一種金屬氧化物M1及至少一種金屬M2；第二步驟（ii），對混合而成的原料粉末進行燒結；第三步驟（iii），對由材料粉末燒結而成的燒結體進行加工；以及第四步驟（iv），向墊板焊接燒結體來完成靶材。As a preferred embodiment, the above preparation method may include: the first step (i), mixing molybdenum oxide, at least one metal oxide M1 and at least one metal M2; the second step (ii), mixing the raw material powder performing sintering; the third step (iii), processing the sintered body obtained by sintering the material powder; and the fourth step (iv), welding the sintered body to the backing plate to complete the target.
以下，按照各個製程說明上述製備方法。Hereinafter, the above-mentioned production method will be described according to each production process.
首先，在第一步驟中，按照所期望的化學成分對由MoO 2和MoO 3組成的氧化鉬粉末；Nb 2O 5、Ta 2O 5、ZrO 2、TiO 2、SnO 2及WO 3粉末中的一種以上的金屬氧化物M1；以及Mo、Ti、Cr、W及Cu中的一種以上的金屬M2進行稱量並混合。 First, in the first step, the molybdenum oxide powder composed of MoO 2 and MoO 3 ; Nb 2 O 5 , Ta 2 O 5 , ZrO 2 , TiO 2 , SnO 2 and WO 3 powders are More than one metal oxide M1; and more than one metal M2 among Mo, Ti, Cr, W and Cu are weighed and mixed.
具體地，上述原料粉末包含95.0重量百分比至99.0重量百分比的氧化鉬和金屬氧化物M1；1.0重量百分比至5.0重量百分比的金屬M2，上述氧化鉬和上述金屬氧化物M1的混合比例可以為75：25至90：10重量比。在此情況下，在氧化鉬粉末中，MoO 2的比例可以為50重量百分比～90重量百分比。 Specifically, the above-mentioned raw material powder contains 95.0% by weight to 99.0% by weight of molybdenum oxide and metal oxide M1; 1.0% by weight to 5.0% by weight of metal M2, and the mixing ratio of the above-mentioned molybdenum oxide and the above-mentioned metal oxide M1 can be 75: 25 to 90:10 weight ratio. In this case, in the molybdenum oxide powder, the ratio of MoO 2 may be 50% by weight to 90% by weight.
根據一具體例，在上述第一步驟中，稱量氧化鉬和金屬氧化物M1，以使得（MoO 2＋MoO 3＋M1）/（MoO 2＋MoO 3）重量百分比的比例變為1.03％至1.30％。 According to a specific example, in the above-mentioned first step, the molybdenum oxide and the metal oxide M1 are weighed so that the weight percent ratio of (MoO 2 +MoO 3 +M1 )/(MoO 2 +MoO 3 ) becomes 1.03% to 1.30%.
接著，向混合的原料粉末添加金屬粉末M2，稱量上述金屬粉末M2，以使得上述金屬粉末M2的（MoO 2＋MoO 3＋M1＋M2）/（MoO 2＋MoO 3＋M1）重量百分比的比例變為1.03％至1.3％。其中，MoO 2的含量和MoO 3的含量在分子和分母中分別相同。對於混合的粉末可利用氧化鋯球執行乾式球磨製程。 Next, metal powder M2 is added to the mixed raw material powder, and the metal powder M2 is weighed so that the ratio of (MoO 2 +MoO 3 +M1+M2)/(MoO 2 +MoO 3 +M1) weight percentage of the above metal powder M2 becomes 1.03% to 1.3%. Wherein, the content of MoO 2 and the content of MoO 3 are the same in the numerator and denominator respectively. For mixed powders a dry ball milling process can be performed using zirconia balls.
氧化鋯球可被稱量為粉末量的1倍～3倍，球磨能夠以100rpm～300rpm的速度執行7小時～9小時。完成乾式球磨後，可藉由過篩完成粉末混合。Zirconia balls can be weighed as 1 to 3 times the amount of powder, and ball milling can be performed at a speed of 100rpm to 300rpm for 7 hours to 9 hours. After dry ball milling, powder mixing can be done by sieving.
隨後，在第二步驟中，為了燒結混合粉末，可向碳模具內部和下部沖床纏繞0.1mm～0.5mm的碳片並裝入100g～300g的混合粉末。裝入粉末後，覆蓋碳片並設置上部沖床。Then, in the second step, in order to sinter the mixed powder, a carbon sheet of 0.1mm˜0.5mm may be wound inside the carbon mold and the lower punch and charged with 100g˜300g of the mixed powder. After loading the powder, cover the carbon sheet and set up the upper punch.
若藉由如上所述的過程完成燒結模具的準備，則可向熱壓機裝入燒結模具來執行燒結過程。燒結時，升溫速度為2℃～10℃/分鐘，最高熱處理溫度為700℃至900℃，可維持1小時至3小時。在升溫及維持溫度的過程中，壓力可維持在20Mpa～50Mpa。If the preparation of the sintering mold is completed through the process as described above, the sintering mold can be loaded into the hot press to perform the sintering process. During sintering, the heating rate is 2°C to 10°C/min, the maximum heat treatment temperature is 700°C to 900°C, and can be maintained for 1 hour to 3 hours. In the process of heating up and maintaining the temperature, the pressure can be maintained at 20Mpa~50Mpa.
然後，在第三步驟中，取出完成燒結的燒結體進行加工。具體地，取出燒結體後，取出靶材上下部的碳片後，對靶材的表面進行研磨加工。為了去除碳片，可分別在上下部加工1mm以上。Then, in the third step, the sintered body that has been sintered is taken out for processing. Specifically, after taking out the sintered body and taking out the carbon pieces at the upper and lower parts of the target, the surface of the target is ground. In order to remove carbon flakes, it is possible to process more than 1mm on the upper and lower parts respectively.
接著，在第四步驟中，向墊板焊接經加工的燒結體。Next, in the fourth step, the processed sintered body is welded to a backing plate.
較佳地，可使用銦作為黏結劑，使得焊接率達到95％以上。Preferably, indium can be used as a binder, so that the welding rate can reach more than 95%.
可藉由上述過程製造金屬氧化物靶材。較佳地，所製造的靶材的目標密度為95％以上，具體為97.5％以上。A metal oxide target can be manufactured through the above process. Preferably, the target density of the manufactured target is above 95%, specifically above 97.5%.
氧化物薄膜oxide film
在本發明的另一例中，金屬氧化物薄膜由上述氧化鉬基靶材蒸鍍而成。可將上述燒結體用作靶材執行濺鍍來形成上述金屬氧化物薄膜。In another example of the present invention, the metal oxide thin film is vapor-deposited from the above-mentioned molybdenum oxide-based target. The above-mentioned metal oxide thin film may be formed by performing sputtering using the above-mentioned sintered body as a target.
上述氧化物薄膜的成分可隨著蒸鍍氣體產生細微變化，上述氧化物靶材藉由濺鍍製造而成，因此，實際組成成分與上述靶材相同。由此，可形成相對密度大於95％且具備高密度特性及1×10 -2Ωcm以下的優秀電阻特性的氧化物薄膜。並且，可藉由向作為主要材料的氧化鉬添加規定範圍的特定金屬氧化物和金屬，實現氧化鉬比例及成分最佳化來提高耐化學性及耐熱性。 The composition of the above-mentioned oxide thin film can change slightly with the evaporation gas, and the above-mentioned oxide target is manufactured by sputtering, so the actual composition is the same as that of the above-mentioned target. As a result, an oxide thin film having a relative density greater than 95% and having high density characteristics and excellent resistance characteristics of 1×10 -2 Ωcm or less can be formed. In addition, chemical resistance and heat resistance can be improved by adding specific metal oxides and metals within a specified range to molybdenum oxide as the main material to optimize the ratio and composition of molybdenum oxide.
根據一具體例，在以350℃的溫度條件熱處理30分鐘以上後，上述氧化物薄膜的光反射率變化率△R可以為30％以下，具體為20％以下，更具體地，可以為15％以下，藉由以下式1計算： 式1： 光反射率變化率（△R，％）＝（R 2－R 1）/R 1×100 在上述式1中， R 1為熱處理前的薄膜在550nm波長處的光反射率， R 2為熱處理後的薄膜在550nm波長處的光反射率。 According to a specific example, after heat treatment at 350°C for more than 30 minutes, the light reflectance change rate ΔR of the above-mentioned oxide film may be 30% or less, specifically 20% or less, more specifically, 15% Below, it is calculated by the following formula 1: Formula 1: Light reflectance change rate (△R, %)=(R 2 -R 1 )/R 1 ×100 In the above formula 1, R 1 is the temperature of the film before heat treatment The light reflectance at the wavelength of 550nm, R2 is the light reflectance of the heat-treated film at the wavelength of 550nm.
具體地，在熱處理前，上述氧化物薄膜在550nm波長處的光反射率R 1為10.5％以下，更具體地，可以為10.4％以下。並且，在以350℃的溫度條件熱處理30分鐘以上後，在550nm波長處的光反射率R 2可以為12.5％以下，更具體地，可以為12％以下。在此情況下，光反射率R 1、R 2及光反射率變化率△R的下限值並沒有特別限制。 Specifically, before heat treatment, the light reflectance R 1 of the oxide thin film at a wavelength of 550 nm is 10.5% or less, more specifically, may be 10.4% or less. And, after the heat treatment at 350° C. for 30 minutes or more, the light reflectance R 2 at a wavelength of 550 nm may be 12.5% or less, more specifically, 12% or less. In this case, the lower limit values of the light reflectances R 1 and R 2 and the light reflectance change rate ΔR are not particularly limited.
另一方面，上述光反射率是指以360nm～740nm的平均波長和/或550nm波長為基準測定的，但並不限定於此。On the other hand, the above-mentioned light reflectance is measured based on an average wavelength of 360 nm to 740 nm and/or a wavelength of 550 nm, but is not limited thereto.
本發明的金屬氧化物薄膜可藉由所屬領域中通常使用的濺鍍法蒸鍍而成。在此情況下，可利用直流式濺鍍機（DC Sputter）執行濺鍍。The metal oxide thin film of the present invention can be evaporated by the sputtering method commonly used in the field. In this case, sputtering may be performed using a direct current sputtering machine (DC Sputter).
上述金屬氧化物薄膜可用於薄膜電晶體（TFT）的閘極層、源極層及汲極層中的至少一個。並且，上述薄膜電晶體可用於有機發光二極體電視（OLED TV）、便攜式手機、平板電腦等顯示裝置。The above metal oxide film can be used for at least one of the gate layer, the source layer and the drain layer of the thin film transistor (TFT). Moreover, the above-mentioned thin film transistor can be used in display devices such as organic light-emitting diode televisions (OLED TVs), portable mobile phones, and tablet computers.
作為具體例，本發明實施例的金屬氧化物薄膜可用於閘極層下部的低反射層。具有上述用途的薄膜不僅降低基板的反射率，而且提高閘電極的黏結性。As a specific example, the metal oxide thin film of the embodiment of the present invention can be used for the low reflection layer under the gate layer. The thin film with the above purpose not only reduces the reflectivity of the substrate, but also improves the adhesion of the gate electrode.
其中，基板可以為通常用於顯示裝置製程中的多種基板的一個，例如，玻璃板、金屬板、塑膠板、塑膠膜等。具體地，基板可以為用於有機發光二極體電視、便攜式手機或平板電腦的透明前面板。另一方面，閘電極可由銅、銀等普通電極物質製成。Wherein, the substrate may be one of various substrates commonly used in display device manufacturing processes, such as glass plates, metal plates, plastic plates, plastic films, and the like. Specifically, the substrate may be a transparent front panel for an organic light emitting diode television, a portable mobile phone or a tablet computer. On the other hand, the gate electrode can be made of common electrode materials such as copper and silver.
薄膜蒸鍍可藉由將直流式濺鍍機的功率密度（Power density）設為1.0w/cm 2～2.0w/cm 2並在氬氣（Ar Gas）氣體中的常溫條件下執行。此時，金屬氧化物薄膜的厚度可以為300Å至500Å，但並不限定於此。並且，可在金屬氧化物薄膜上方蒸鍍銅（Cu）薄膜。在此情況下，銅薄膜可被蒸鍍為3000Å至6000Å的厚度。 Thin film evaporation can be carried out by setting the power density (Power density) of the DC sputtering machine to 1.0w/cm 2 -2.0w/cm 2 and performing it under normal temperature conditions in argon (Ar Gas) gas. At this time, the thickness of the metal oxide thin film may be 300Å to 500Å, but is not limited thereto. Also, a copper (Cu) thin film may be vapor-deposited over the metal oxide thin film. In this case, the copper thin film can be evaporated to a thickness of 3000Å to 6000Å.
另一方面，反射率的測定可藉由所屬領域的已知方法執行。作為一例，可在形成金屬氧化物薄膜的基板面進行測定，測定在360nm～740nm的平均波長和/或550nm波長處的光反射率。在此情況下，光反射率為10.5％以下。On the other hand, the measurement of reflectance can be performed by known methods in the art. As an example, the measurement may be performed on the substrate surface on which the metal oxide thin film is formed, and the light reflectance at an average wavelength of 360 nm to 740 nm and/or at a wavelength of 550 nm may be measured. In this case, the light reflectance is 10.5% or less.
本發明實施例的金屬氧化物薄膜具有優秀的耐熱性、耐化學性。雖然，耐熱性、耐化學性評估可藉由如下方式執行，但並不限定於此。The metal oxide thin film of the embodiment of the present invention has excellent heat resistance and chemical resistance. Although the evaluation of heat resistance and chemical resistance can be performed in the following manner, it is not limited thereto.
為了評估耐熱性，可使用將以上述方式蒸鍍的薄膜在200℃～400℃的環境中熱處理30分鐘以上的方法。通常，熱處理可在真空熱處理爐和/或氫氣熱處理爐中執行。熱處理後，可藉由觀察薄膜的特性變化來評估耐熱性。作為耐熱性指標的一例，熱處理後的反射率R 2與熱處理前的反射率R 1之差（R 2－R 1）大致為1.5％以下，具體地，可以為1.2％以下。並且，也可基於藉由上述式1計算的反射率變化率△R進行評估。 In order to evaluate the heat resistance, a method of heat-treating the thin film deposited as described above in an environment of 200° C. to 400° C. for 30 minutes or more can be used. Typically, heat treatment can be performed in a vacuum heat treatment furnace and/or a hydrogen heat treatment furnace. After heat treatment, heat resistance can be evaluated by observing the change in properties of the film. As an example of the heat resistance index, the difference (R 2 −R 1 ) between the reflectance R 2 after the heat treatment and the reflectance R 1 before the heat treatment is approximately 1.5% or less, specifically, 1.2% or less. In addition, the evaluation may be performed based on the reflectance change rate ΔR calculated by the above-mentioned Equation 1.
並且，為了評估耐化學性，可使用光微影法在所形成的薄膜上形成微圖案並觀察形成的微圖案的截面。具體地，在上述本發明的由金屬氧化物和銅兩層形成的薄膜上塗敷1μm～2μm厚度的光阻（Positive PR Strip）後，在60℃～80℃溫度條件下烘烤（Backing）0.5小時～2小時來固化光阻。隨後，對準遮罩（PRMask）進行曝光來形成具有規定線寬的圖案。可對這種圖案進行蝕刻（etching）來形成由金屬氧化物和銅組成的兩層微圖案。在以上述方式形成有微圖案的基板去除光阻後，可用FIB-SEM觀察微圖案中的金屬氧化物的截面。由此，即使在蝕刻後，本發明的薄膜也不會產生殘渣，因此，可評估耐化學性。Also, in order to evaluate chemical resistance, a micropattern may be formed on the formed thin film using photolithography and a cross section of the formed micropattern may be observed. Specifically, after coating a photoresist (Positive PR Strip) with a thickness of 1 μm to 2 μm on the above-mentioned thin film formed of two layers of metal oxide and copper of the present invention, bake (Backing) at a temperature of 60°C to 80°C for 0.5 hours ~2 hours to cure the photoresist. Subsequently, an alignment mask (PRMask) is exposed to form a pattern with a predetermined line width. This pattern can be etched to form a two-layer micropattern composed of metal oxide and copper. After the photoresist is removed from the substrate formed with the micropattern in the above manner, the cross section of the metal oxide in the micropattern can be observed with FIB-SEM. Thereby, even after etching, the thin film of the present invention does not generate residue, and therefore, chemical resistance can be evaluated.
以下，藉由實施例詳細說明本發明。但是，以下實施例僅為本發明的示例，本發明並不限定於以下實施例。Hereinafter, the present invention will be described in detail by means of examples. However, the following examples are merely examples of the present invention, and the present invention is not limited to the following examples.
實施例1Example 1
稱量粉末，使得MoO 2/MoO 3重量百分比的比例變為6.8、（MoO 2＋MoO 3＋Nb 2O 5＋Mo）/（MoO 2＋MoO 3＋Nb 2O 5）重量百分比的比例變為1.05。將稱量的粉末放入1L的塑膠筒，以上述粉末量的三倍投入氧化鋁球。使用3mm～10mm的氧化鋁球。若投入完所稱量的粉末和球，則利用球磨機器以170rpm～230rpm的速度實施8小時的乾式混合。隨後，利用熱壓機（Hot Press）對所獲得的乾式粉末進行加壓燒結。在此情況下，熱壓機的內部真空條件為10 -1torr，升溫速度為3℃～7℃，最高溫度為750℃～800℃，維持時間為1小時～3小時，待進行燒結後，執行爐內冷卻。 The powder was weighed so that the ratio of MoO 2 /MoO 3 by weight became 6.8, and the ratio of (MoO 2 +MoO 3 +Nb 2 O 5 +Mo)/(MoO 2 +MoO 3 +Nb 2 O 5 ) by weight became 1.05. Put the weighed powder into a 1L plastic cylinder, and put three times the amount of powder into the alumina ball. Alumina balls of 3 mm to 10 mm are used. After the weighed powder and balls were thrown in, dry mixing was performed for 8 hours at a speed of 170 rpm to 230 rpm using a ball mill. Subsequently, the obtained dry powder was subjected to pressure sintering using a hot press (Hot Press). In this case, the internal vacuum condition of the hot press is 10 -1 torr, the heating rate is 3°C-7°C, the maximum temperature is 750°C-800°C, and the maintenance time is 1 hour to 3 hours. After sintering, Perform furnace cool down.
測定得出：以上述方式獲得的實施例1的金屬氧化物燒結體的燒結密度為97.6％，電阻率為1.15×10 -3Ωcm。 It was measured that the sintered density of the metal oxide sintered body of Example 1 obtained in the above manner was 97.6%, and the resistivity was 1.15×10 -3 Ωcm.
實施例2Example 2
除使用MoO 2/MoO 3重量百分比的比例變為6.6、（MoO 2＋MoO 3＋Nb 2O 5＋Mo）/（MoO 2＋MoO 3＋Nb 2O 5）重量百分比的比例從1.05變為1.08的稱量粉末外，藉由與上述實施例1相同的方式製備實施例2的燒結體。 Weighing powders except that the weight percent ratio of MoO 2 /MoO 3 is changed to 6.6, and the ratio of (MoO 2 + MoO 3 + Nb 2 O 5 + Mo)/(MoO 2 + MoO 3 + Nb 2 O 5 ) weight percent is changed from 1.05 to 1.08 Also, the sintered body of Example 2 was prepared in the same manner as in Example 1 above.
測定得出：以上述方式獲得的實施例2的燒結體的燒結密度為97.8％，電阻率為1.2×10 -3Ωcm。 It was measured that the sintered body of Example 2 obtained in the above manner had a sintered density of 97.8%, and a resistivity of 1.2×10 -3 Ωcm.
實施例3Example 3
除使用MoO 2/MoO 3重量百分比的比例變為6.5、（MoO 2＋MoO 3＋Nb 2O 5＋Mo）/（MoO 2＋MoO 3＋Nb 2O 5）重量百分比的比例從1.05變為1.18的稱量粉末外，藉由與上述實施例1相同的方式製備實施例3的燒結體。 Weighing powder except that the weight percent ratio of MoO 2 /MoO 3 is changed to 6.5, and the ratio of (MoO 2 +MoO 3 +Nb 2 O 5 +Mo)/(MoO 2 +MoO 3 +Nb 2 O 5 ) weight percent is changed from 1.05 to 1.18 Also, the sintered body of Example 3 was prepared in the same manner as in Example 1 above.
測定得出：以上述方式獲得的實施例3的燒結體的燒結密度為99.9％，電阻率為1.07×10 -3Ωcm。 It was measured that the sintered body of Example 3 obtained in the above manner had a sintered density of 99.9%, and a resistivity of 1.07×10 -3 Ωcm.
比較例1Comparative example 1
除未使用Mo金屬而使用（MoO 2＋MoO 3＋Nb 2O 5）/（MoO 2＋MoO 3＋Nb 2O 5）重量百分比的比例為1的稱量粉末外，藉由與上述實施例1相同的方式製備比較例1的燒結體。 In the same manner as in Example 1 above, except that Mo metal was not used and a weight percentage ratio of (MoO 2 +MoO 3 +Nb 2 O 5 )/(MoO 2 +MoO 3 +Nb 2 O 5 ) was 1 was used. A sintered body of Comparative Example 1 was prepared.
測定得出：以上述方式獲得的比較例1的燒結體的燒結密度為96.1％，電阻率為1.27×10 -3Ωcm。 It was measured that the sintered body of Comparative Example 1 obtained in the above manner had a sintered density of 96.1%, and a resistivity of 1.27×10 -3 Ωcm.
實驗例1：燒結體的物性評估Experimental example 1: Physical property evaluation of sintered body
以下，表1示出實施例1至實施例3及比較例1所製備的各個燒結體相關物性結果。Table 1 below shows the physical property results of each sintered body prepared in Example 1 to Example 3 and Comparative Example 1.
表1
如以上表1所示，在實施例和比較例中，電阻率均為基準值1×10 -2Ωcm以下，而目標密度均為95％以上。然而，在目標密度的層面上，可確認到實施例1至實施例3優於比較例1，電阻率也低於比較例1。由此可知，當蒸鍍薄膜時，目標密度相對較高的實施例1至實施例3在電漿形成方面更加穩定。 As shown in Table 1 above, in both Examples and Comparative Examples, the resistivity was below the reference value of 1×10 -2 Ωcm, and the target density was above 95%. However, it was confirmed that Examples 1 to 3 are superior to Comparative Example 1 in terms of the target density, and the resistivity is also lower than that of Comparative Example 1. It can be seen from this that, when evaporating thin films, Examples 1 to 3 with relatively higher target densities are more stable in terms of plasma formation.
實驗例2：薄膜的物性評估Experimental example 2: Physical property evaluation of thin film
將實施例1至實施例3及比較例1所製備的燒結體用作靶材形成薄膜後，可藉由以下方式評估薄膜的耐熱性。After using the sintered bodies prepared in Examples 1 to 3 and Comparative Example 1 as targets to form films, the heat resistance of the films can be evaluated in the following manner.
具體地，利用各個燒結體製備用作閘極層下部的低反射層的薄膜。這種薄膜用於提高低反射及閘電極在基板（玻璃）上的黏結性。Specifically, each sintered body was used to prepare a thin film used as a low reflection layer under the gate layer. This film is used to improve the low reflection and adhesion of the gate electrode on the substrate (glass).
低反射薄膜藉由利用直流式濺鍍機以0.5w/cm 2～3.6w/cm 2的功率密度（Power density）在氬氣氣體下向透明玻璃基板蒸鍍包含實施例1至實施例3及比較例1的燒結體的靶材來形成薄膜，蒸鍍的薄膜厚度為350Å。 The low-reflection film is vapor-deposited on the transparent glass substrate under argon gas with a DC sputtering machine at a power density of 0.5w/cm 2 to 3.6w/cm 2 , including Examples 1 to 3 and The target material of the sintered body of Comparative Example 1 was used to form a thin film, and the thickness of the evaporated film was 350Å.
隨後，在上述薄膜上形成電極。電極藉由銅靶材利用直流式濺鍍機以0.5w/cm 2～3.6w/cm 2的功率密度（Power density）在氬氣氣體下形成，薄膜厚度為6000Å。 Subsequently, electrodes were formed on the above thin film. The electrode is formed under argon gas with a DC sputtering machine using a copper target at a power density of 0.5w/cm 2 to 3.6w/cm 2 , and the film thickness is 6000Å.
在這種狀態下，在玻璃基板面測定薄膜的初始反射率後，在真空熱處理爐以350℃的溫度熱處理30分鐘以上後，再次測定反射率來比較兩個反射率。在此情況下，基於在360nm～740nm的平均波長和/或550nm波長處的反射率數值計算反射率，其結果如以下表2所示。In this state, after measuring the initial reflectance of the film on the surface of the glass substrate, heat treatment in a vacuum heat treatment furnace at 350° C. for 30 minutes or more, and then measuring the reflectance again to compare the two reflectances. In this case, the reflectance was calculated based on the average wavelength of 360 nm to 740 nm and/or the reflectance value at a wavelength of 550 nm, the results of which are shown in Table 2 below.
表2
如以上表2所示，雖然比較例1的初始反射率相對優秀，但是，經熱處理後，其反射率會大幅增加。As shown in Table 2 above, although the initial reflectance of Comparative Example 1 is relatively excellent, its reflectance will increase significantly after heat treatment.
與此相比，實施例1～實施例3的初始反射率均優秀，熱處理後的反射率變化也不大。尤其，在實施例的情況下，在氫熱處理爐中以350℃的溫度熱處理30分鐘以上後，反射率與初始反射率之間的變化在10％以內，由此可知，相比於比較例，具有更加優秀的薄膜特性。In contrast, Examples 1 to 3 have excellent initial reflectance, and the change in reflectance after heat treatment is not large. In particular, in the case of the examples, after heat treatment at a temperature of 350° C. for more than 30 minutes in a hydrogen heat treatment furnace, the change between the reflectance and the initial reflectance is within 10%, which shows that compared with the comparative examples, Has more excellent film properties.
M1:金屬氧化物 M2:金屬 M1: metal oxide M2: metal
圖1為示出氫熱處理後的反射率基於是否包含金屬M2而變化的曲線圖。FIG. 1 is a graph showing changes in reflectance after hydrogen heat treatment depending on whether or not metal M2 is contained.
M2:金屬 M2: metal
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0124217 | 2021-09-16 | ||
| KR1020210124217A KR102646917B1 (en) | 2021-09-16 | 2021-09-16 | Molybdenum oxide based sintered body, metal oxide thin film using the sintered body, and thin film transistors and displa devices comprising the thin films |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW202313520A true TW202313520A (en) | 2023-04-01 |
Family
ID=85523673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW111134818A TW202313520A (en) | 2021-09-16 | 2022-09-15 | Molybdenum oxide based sintered body, sputtering target, oxide thin film using the sintered body, and thin film transistors and display devices including the thin films |
Country Status (3)
| Country | Link |
|---|---|
| KR (2) | KR102646917B1 (en) |
| CN (1) | CN115819083B (en) |
| TW (1) | TW202313520A (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121799A (en) * | 2004-03-09 | 2013-05-29 | 出光兴产株式会社 | Sputtering target, transparent conductive film, thin film transistor substrate, method for manufacturing thin film transistor substrate, and liquid crystal display device |
| JP4670097B2 (en) | 2005-04-27 | 2011-04-13 | Ａｇｃセラミックス株式会社 | Target and method for producing high refractive index film using the target |
| US20070071985A1 (en) | 2005-09-29 | 2007-03-29 | Prabhat Kumar | Sputtering target, low resistivity, transparent conductive film, method for producing such film and composition for use therein |
| KR101255707B1 (en) * | 2006-08-29 | 2013-04-17 | 엘지디스플레이 주식회사 | Thin Film Transistor device and method for fabricating thereof |
| JP5214194B2 (en) * | 2007-08-10 | 2013-06-19 | 住友化学株式会社 | Organic electroluminescence device including metal-doped molybdenum oxide layer and manufacturing method |
| KR20140023491A (en) * | 2012-08-16 | 2014-02-27 | 삼성코닝정밀소재 주식회사 | Sputtering target and organic light emitting diode display device including black matrix deposited by the same |
| CN104649664A (en) * | 2013-11-21 | 2015-05-27 | 青岛润鑫伟业科贸有限公司 | Molybdenum dioxide conductive ceramic material |
| EP3467140A1 (en) * | 2017-10-06 | 2019-04-10 | Plansee SE | Target material for deposition of molybdenum oxide layers |
| KR102315765B1 (en) * | 2018-03-13 | 2021-10-22 | 제이엑스금속주식회사 | Oxide thin film, and oxide sintered body for sputtering target for producing oxide thin film |
| JP6766276B2 (en) * | 2018-08-09 | 2020-10-07 | Ｊｘ金属株式会社 | Oxide sputtering target and its manufacturing method, and oxide thin film formed by using the oxide sputtering target. |
| EP3715496B1 (en) * | 2019-03-29 | 2024-07-17 | Plansee SE | Sputtering target for producing layers containing molybdenum oxide |
-
2021
- 2021-09-16 KR KR1020210124217A patent/KR102646917B1/en active IP Right Grant
-
2022
- 2022-09-15 TW TW111134818A patent/TW202313520A/en unknown
- 2022-09-16 CN CN202211128996.5A patent/CN115819083B/en active Active
-
2024
- 2024-03-07 KR KR1020240032499A patent/KR20240038936A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20240038936A (en) | 2024-03-26 |
| KR20230041149A (en) | 2023-03-24 |
| KR102646917B1 (en) | 2024-03-13 |
| CN115819083A (en) | 2023-03-21 |
| CN115819083B (en) | 2024-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4552950B2 (en) | Oxide sintered body for target, manufacturing method thereof, manufacturing method of transparent conductive film using the same, and transparent conductive film obtained | |
| JP5306308B2 (en) | Sputtering target, transparent conductive oxide, and method for producing sputtering target | |
| JP4730204B2 (en) | Oxide sintered compact target and method for producing oxide transparent conductive film using the same | |
| JP5561358B2 (en) | Transparent conductive film | |
| KR101184353B1 (en) | Transparent conductive film, sintered body target for transparent conductive film fabrication, and transparent conductive base material and display device using the same | |
| KR20070088246A (en) | Sintered body target for transparent conductive film fabrication, transparent conductive film fabricated by using the same, and transparent conductive base material comprising this conductive film formed thereon | |
| US20040222089A1 (en) | Sputtering target and transparent electroconductive film | |
| KR20090063946A (en) | Indium tin oxide target and manufacturing method of transparent conductive film using the same | |
| TW201938823A (en) | Oxide thin film, and oxide sintered body for sputtering target for producing oxide thin film | |
| JP4770310B2 (en) | Transparent conductive film, transparent conductive substrate and oxide sintered body | |
| JP2015030896A (en) | Sputtering target and oxide transparent conductive film | |
| JP2000072537A (en) | Target for transparent conducting layer, transparent conducting glass and transparent conducting film | |
| WO2019208240A1 (en) | Shield layer, method for producing shield layer, and oxide sputtering target | |
| JP2019194352A (en) | Shield layer and manufacturing method of shield layer and oxide sputtering target | |
| TW202313520A (en) | Molybdenum oxide based sintered body, sputtering target, oxide thin film using the sintered body, and thin film transistors and display devices including the thin films | |
| JP2007113026A (en) | Transparent electrically conductive film and transparent electrically conductive base material comprising the same | |
| JP5907086B2 (en) | Indium oxide-based oxide sintered body and method for producing the same | |
| TW202315852A (en) | Molybdenum oxide based sintered body, sputtering target, oxide thin film using the sintered body, and thin film transistors and display devices including the thin films | |
| KR102315283B1 (en) | Metal oxide thin film containing molybdenum oxide as the main component, and thin film transistors and display devices in which such thin films are formed | |
| KR102315308B1 (en) | Metal oxide sintered body containing molybdenum oxide as the main component and sputtering target comprising the same | |
| CN114916228B (en) | Metal oxide sintered body containing molybdenum oxide as main component and sputtering target material containing same | |
| KR20220082407A (en) | Metal oxide sintered body forming a thin film with low reflectivity and sputtering target comprising the same | |
| JP5290350B2 (en) | Transparent electrode film | |
| TWI424076B (en) | A transparent conductive film and a transparent conductive substrate using the same | |
| WO2013042747A1 (en) | Oxide sintered body, method for producing same, and oxide transparent conductive film |