WO2009145152A1 - Film conducteur transparent et son procédé de fabrication - Google Patents

Film conducteur transparent et son procédé de fabrication Download PDF

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Publication number
WO2009145152A1
WO2009145152A1 PCT/JP2009/059542 JP2009059542W WO2009145152A1 WO 2009145152 A1 WO2009145152 A1 WO 2009145152A1 JP 2009059542 W JP2009059542 W JP 2009059542W WO 2009145152 A1 WO2009145152 A1 WO 2009145152A1
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Prior art keywords
transparent conductive
zinc oxide
oxide
conductive film
zinc
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PCT/JP2009/059542
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English (en)
Japanese (ja)
Inventor
崇 口山
憲治 山本
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株式会社カネカ
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Publication of WO2009145152A1 publication Critical patent/WO2009145152A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering

Definitions

  • the present invention mainly includes touch panels, PDPs, LCDs, electroluminescence (EL) display materials, transparent electrodes and back electrodes of solar cells, transparent intermediate layers of hybrid solar cells, low dielectric constant films used in compound semiconductor high-speed devices, and surface elasticity.
  • the present invention relates to a transparent conductive film capable of achieving high environmental variability and a method for producing the same in a heater material.
  • ITO indium tin oxide
  • tin oxide zinc oxide
  • a transparent conductive layer is formed by a physical vapor deposition method (PVD method) such as magnetron sputtering method or molecular beam epitaxy method or a chemical vapor deposition method (CVD method) such as thermal CVD or plasma CVD
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • thermal CVD or plasma CVD vapor deposition method
  • electroless method A method formed by an electroless method is known.
  • ITO is a very excellent material as a transparent conductive material, and is currently widely used for a transparent conductive layer.
  • indium as a raw material may be depleted, and there is an urgent need to search for a material that can replace ITO in terms of resources and cost.
  • Non-patent document 1 describes that ZnO is excellent in transparency as compared with ITO, but is inferior in stability to moisture and heat.
  • Patent Documents 1 to 3 describe techniques for improving the chemical stability of ZnO by adding chromium, cobalt, silicon, or the like to ZnO.
  • Patent Documents 1 and 2 are limited to qualitative evaluation of etching characteristics, and quantitative properties are not clear regarding chemical stability, and durability in a high-temperature and high-humidity environment is not satisfactory.
  • Patent Document 3 states that the chemical stability is effective in durability in a high-temperature and high-humidity environment.
  • silicon is contained in an amount of about 5 atom%, the conductivity is lowered.
  • the present inventors have conducted intensive studies, and as a result, by adding silicon atoms to the zinc oxide structure in the zinc oxide transparent conductive layer, amorphous zinc oxide transparent conductive oxide can be obtained. It has been found that a physical layer can be formed, and that by adding a conductive dopant, the zinc oxide transparent conductive layer can exhibit high conductivity and can improve environmental variability.
  • the present invention has the following configuration.
  • the ratio of the surface resistance immediately after the formation of the transparent conductive film and the surface resistance after standing for 10 days in an environment of 85 ° C./85% RH is 0.5 to 2.0.
  • a transparent conductive film exhibiting good characteristics in “conductivity” and “environmental variability” which are particularly important elements in a touch panel, an electroluminescence electrode substrate, a solar cell, and the like.
  • the present invention provides a transparent conductive film having a transparent conductive oxide layer composed mainly of at least one zinc oxide on a base material, wherein the zinc oxide has an amorphous structure, and aluminum or gallium is changed to zinc.
  • the transparent conductive film is characterized by containing 0.1 to 3.0 atom% and further containing 3.0 to 18.0 atom% of silicon atoms with respect to zinc.
  • Zinc oxide is a compound with strong ion binding properties, and thin film materials are weak against water and chemicals. In order to reinforce this weak point, a method of blocking moisture by first providing a clothing layer on the surface of the zinc oxide transparent thin film is considered.
  • a moisture barrier material is generally a material such as a metal material or polyolefin, and is often not suitable for a transparent conductive film material such as an opaque material or an insulator.
  • Japanese Patent Application Laid-Open No. 10-237630 describes a method of forming a transparent conductive layer by a reactive sputtering method using a reactive gas such as carbon dioxide as a carrier gas on a metal target.
  • FIG. 1 is a cross-sectional view of a transparent conductive film according to the present invention.
  • a zinc oxide transparent conductive oxide layer 2 is formed on the substrate 1 (FIG. 1).
  • the base material 1 may be selected depending on the application, but when used as a transparent electrode, the hard or soft material is not particularly limited as long as it is a substrate that is transparent at least in the visible light region. As long as it is a hard material, a glass substrate such as alkali glass, borosilicate glass, or non-alkali glass is a typical example, but a sapphire substrate or the like can also be used.
  • a glass substrate such as alkali glass, borosilicate glass, or non-alkali glass is a typical example, but a sapphire substrate or the like can also be used.
  • the thickness of the glass substrate can be arbitrarily selected depending on the purpose of use, but 0.5 to 4.5 mm can be exemplified as a preferable range in consideration of the balance between handling and weight.
  • a glass substrate that is too thin is not easily strong enough to be broken by impact.
  • a glass substrate that is too thick becomes heavy and affects the thickness of the device, making it difficult to use it for portable devices.
  • a thick substrate is not preferable in terms of transparency and cost.
  • soft materials include thermoplastic resins such as acrylic resins, polyesters, and polycarbonate resins, and films made of thermosetting resins such as polyurethane, but particularly excellent optical isotropy and water vapor barrier properties.
  • a film mainly composed of a cycloolefin polymer (COP) which is excellent in the above can be used effectively.
  • the COP film examples include a norbornene polymer, a copolymer of norbornene and an olefin, and an unsaturated alicyclic hydrocarbon polymer such as cyclopentadiene. From the viewpoint of water vapor barrier properties, it is preferable that the main chain and side chain of the film constituting molecule do not contain a functional group having a large polarity, such as a carbonyl group or a hydroxyl group.
  • the thickness of these substrates can be arbitrarily selected according to the purpose of use, but handling is easy if it is about 0.03 mm to 3.0 mm.
  • Thin films are difficult to handle and lack strength. Also, thick films have problems with transparency and cost, and increase the thickness of the device, making it difficult to use for portable devices.
  • PEN polyethylene naphthalate
  • PES polyethersulfone
  • the substrate film can be stretched to give a phase difference.
  • a phase difference it is possible to produce a low reflection panel by combining with a polarizing plate, and it is expected that the visibility of an image is greatly improved.
  • phase difference can be imparted by using a known method. For example, it is possible by stretching or orientation treatment such as uniaxial stretching or biaxial stretching. At this time, the orientation of the polymer skeleton can be promoted by applying a temperature close to the glass transition temperature to the film.
  • the preferred range of the retardation value varies depending on the intended function, but in the case of providing an antireflection function, it is preferable to select the retardation value within the range of 50 to 300 nm. Thus, the vicinity of 137 nm, which is 1/4, is more preferable.
  • the zinc oxide transparent conductive oxide of the present invention can be formed thereon using a photoelectric conversion layer or a light emitting layer as a base material.
  • the photoelectric conversion layer may be a layer made of amorphous or crystalline silicon or a multi-component compound semiconductor.
  • an organic metal complex having aluminum or rare earth atom as a metal center can be used.
  • the zinc oxide transparent conductive oxide layer 2 in the present invention is amorphous.
  • the zinc oxide transparent conductive oxide layer 2 in the present invention is amorphous.
  • the doping amount is preferably 3.0 to 18.0 atom% of silicon atoms with respect to zinc atoms.
  • 4.0 to 16.0 atom% is preferable, and 5.0 to 15.0 atom% is more preferable. In terms of reliability testing, 9.0 to 16.0 atom% is preferable.
  • Silicon dioxide necessary for making the zinc oxide transparent conductive oxide into an amorphous structure is, for example, Wakabayashi, J. et al. Soc. Mat. Sci. , Japan, 49, 6, 617 (2000), requires 7 to 10 atom% or more. Further, the obtained oxide has very low conductivity and does not function as a transparent conductive oxide. However, in the present invention, by using a conductive dopant simultaneously with silicon dioxide, it becomes a transparent conductive oxide having an amorphous structure even at a lower doping amount, and can be used as a transparent conductive film.
  • a doping agent is added to the zinc oxide transparent conductive oxide layer 2 for the purpose of imparting conductivity.
  • the doping agent aluminum or gallium is suitable.
  • the doping amount is 0.1 to 3.0 atom% with respect to zinc, it is possible to obtain the conductivity of the transparent conductive oxide necessary for the present invention, and 0.3 to 0.3 to exhibit higher conductivity. It is preferably 2.8 atom%, more preferably 0.4 to 2.6 atom%, and particularly preferably 0.5 to 2.5 atom%.
  • the doping amount is small, the conductivity is not improved due to insufficient doping.
  • the doping amount is large, the excess dopant is segregated near the crystal grain boundary of zinc oxide or enters between the lattices and hinders the movement of carriers, so that the conductivity is lowered.
  • the transparent conductive oxide layer can be deposited on the substrate by irradiation with any of plasma particles, electron beams, molecular beams, and lasers. . Further, the irradiation can be performed by irradiating the sintered body of zinc oxide.
  • the sintered body of zinc oxide preferably has the same composition as the transparent conductive oxide layer.
  • plasma particle, electron beam, molecular beam, and laser irradiation means include magnetron sputtering, electron beam (EB) vapor deposition, molecular beam epitaxy (MBE), and pulsed laser deposition (PLD).
  • EB electron beam
  • MBE molecular beam epitaxy
  • PLD pulsed laser deposition
  • a transparent conductive film can be suitably produced by any of the above methods.
  • a large area such as a roll-to-roll film substrate
  • the magnetron sputtering method is suitable among the above methods.
  • the target material used for magnetron sputtering is a mixture of oxide containing zinc oxide as the main component, conductive oxide aluminum oxide or gallium oxide, and silicon dioxide for amorphous structuring. It can be produced by adhering to a backing plate.
  • the conductivity of the transparent conductive oxide necessary for the present invention can be obtained when zinc oxide is doped with aluminum oxide or gallium oxide in an amount of 0.1 to 3.0 atom% of aluminum or gallium with respect to zinc. In order to exhibit higher conductivity, 0.3 to 2.8 atom% is preferable, 0.4 to 2.6 atom% is more preferable, and 0.5 to 2.5 atom% is particularly preferable.
  • the transparent conductive film necessary for the present invention can be produced by doping the thin film to be formed in a necessary amount. If the doping amount is 3.0 to 18.0 atom% of silicon with respect to zinc, the zinc oxide transparent conductive oxide has an amorphous structure, and the characteristics necessary for the present invention can be achieved. Further, from the viewpoint of conductivity and the like, 4.0 to 16.0 atom% is preferable, and 5.0 to 15.0 atom% is more preferable. In terms of reliability testing, 9.0 to 16.0 atom% is preferable.
  • the plasma power is not particularly limited, but is preferably 10 W to 600 W from the viewpoint of productivity and crystallinity. If it is too low, the film may not be formed. If it is too high, there is a concern about damage to the substrate and damage to the device.
  • the film thickness of the transparent conductive oxide layer 2 is preferably 150 to 1000 mm. By using a transparent conductive oxide layer having a thickness in this range, a transparent conductive film having both high transparency and conductivity can be produced.
  • a method for detecting the doping amount contained in the transparent conductive oxide layer 2 will be described.
  • the detection of the doping amount can be accurately detected by any method as long as it is a method usually used for elemental analysis.
  • elemental analysis means such as atomic absorption analysis and fluorescent X-ray analysis
  • spectroscopic techniques such as X-ray photoelectron spectroscopy, Auger electron spectroscopy, electron beam microanalyzer, and secondary ion mass spectrometry.
  • energy dispersive X-ray analysis is a relatively simple technique that can perform elemental analysis with high accuracy simultaneously with shape observation using a scanning electron microscope (SEM) or transmission electron microscope (TEM).
  • the doping amount can be easily calculated by the following equation by relative comparison with zinc.
  • the surface resistance of the transparent conductive film to be produced varies depending on the intended use. For example, in the case of a solar cell or an EL element, about 10 to 20 ⁇ / ⁇ is preferable, and in the case of a touch panel or the like, about 200 to 1000 ⁇ / ⁇ . preferable.
  • a scanning electron microscope JSM-6390-LA manufactured by JEOL Ltd.
  • the crystallinity was evaluated by an X-ray diffraction method.
  • a resistivity meter Loresta GP MCT-610 manufactured by Mitsubishi Chemical Corporation was used. The ratio between the surface resistance immediately after the formation of the transparent conductive film and the surface resistance after being left in an environment of 85 ° C./85% RH for 10 days was defined as a reliability test result.
  • the reliability test was evaluated as follows. After measuring the surface resistance of the transparent conductive film immediately after film formation, put it into a constant temperature and humidity tester set at 85 ° C / 85% RH, leave it for 10 days, take out the transparent conductive film, and cool it down to room temperature. Was measured. The evaluation was performed using the following formula.
  • the value of the reliability test result indicates the quality stability of the transparent conductive film, and this value is preferably 0.5 to 2.0. 0.8 to 2.0 is more preferable, 1.0 to 2.0 is more preferable, and 1.0 to 1.6 is particularly preferable. Most preferred is 1.0 to 1.3.
  • the resistance is unstable, which leads to deterioration of the image for display materials, deterioration of conversion efficiency for materials such as solar cells, and deterioration of accuracy for materials such as touch panels. It is not preferable for the above reason that the value of the surface resistance increases or decreases after the reliability test.
  • Examples 1 to 10, Comparative Examples 1 to 3 A transparent conductive oxide layer was magnetron-sputtered on alkali-free glass (trade name OA-10, film thickness 0.7 mm, manufactured by Nippon Electric Glass Co., Ltd.).
  • alkali-free glass trade name OA-10, film thickness 0.7 mm, manufactured by Nippon Electric Glass Co., Ltd.
  • sintered bodies having respective compositions were used as the target.
  • the film forming conditions were as follows: substrate temperature was 200 ° C., argon gas was used at 10.0 sccm as a carrier gas, DC power of 200 W was applied at a pressure of 1.5 Pa, and a film was formed for 5 minutes to form a 500-inch zinc oxide transparent conductive film. An oxide layer was produced.
  • Table 1 shows the examination results of the above examples and comparative examples.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Laminated Bodies (AREA)

Abstract

Selon l’invention, lorsqu'un oxyde conducteur transparent à base d'oxyde de zinc est mis sous forme d'un film mince, la résistivité de celui-ci est facilement accrue à cause de l'air ou de l'humidité, et ainsi l'oxyde conducteur transparent à base d'oxyde de zinc ne peut pas être utilisé comme film conducteur transparent. Bien que l'oxyde conducteur transparent à base d'oxyde de zinc soit conçu pour avoir une structure amorphe afin de supprimer l'augmentation de résistivité due à la diffusion aux joints de grain, l'oxyde de zinc a une bonne cristallinité et donc il a été difficile de former une couche d'oxyde conducteur transparent à base d'oxyde de zinc amorphe conducteur. Par l'ajout de dioxyde de silicium comme additif pour l'amorphisation et l'ajout d'aluminium ou de gallium comme agent dopant conducteur, une couche d'oxyde conducteur transparent à base d'oxyde de zinc amorphe conducteur peut être formée. En conséquence, un film conducteur transparent pratique peut être fabriqué.
PCT/JP2009/059542 2008-05-27 2009-05-25 Film conducteur transparent et son procédé de fabrication WO2009145152A1 (fr)

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JP2008137400 2008-05-27

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010090101A1 (fr) * 2009-02-06 2010-08-12 株式会社カネカ Dispositif de conversion photoélectrique en film mince et procédé de fabrication apparenté
CN102560391A (zh) * 2010-12-24 2012-07-11 海洋王照明科技股份有限公司 一种导电膜制备方法、导电膜及应用
JP2013069420A (ja) * 2011-09-20 2013-04-18 Kaneka Corp 透明電極付き基板
CN103380229A (zh) * 2011-02-25 2013-10-30 三菱综合材料株式会社 透明氧化物膜及其制造方法
JP2013237188A (ja) * 2012-05-15 2013-11-28 Toray Ind Inc ガスバリア性フィルム
JP2014055348A (ja) * 2012-08-10 2014-03-27 Mitsubishi Materials Corp 透明酸化物膜形成用スパッタリングターゲット及びその製造方法
WO2014069367A1 (fr) * 2012-10-30 2014-05-08 Jx日鉱日石金属株式会社 Corps fritté en oxyde électroconducteur et film à faible indice de réfraction produit au moyen dudit oxyde électroconducteur
JP2014514442A (ja) * 2011-03-25 2014-06-19 ▲海▼洋王照明科技股▲ふん▼有限公司 多元素ドープ酸化亜鉛薄膜、その製作方法及び応用
JP5550768B1 (ja) * 2012-07-03 2014-07-16 Ｊｘ日鉱日石金属株式会社 焼結体及びアモルファス膜
TWI631579B (zh) * 2012-07-03 2018-08-01 Ｊｘ日鑛日石金屬股份有限公司 Sintered body and amorphous film

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Publication number Priority date Publication date Assignee Title
JPS6433811A (en) * 1987-04-04 1989-02-03 Gunze Kk Transparent conductive film and its manufacture
JPH0845352A (ja) * 1994-08-02 1996-02-16 Sekisui Chem Co Ltd 透明導電体
JPH08111123A (ja) * 1994-08-17 1996-04-30 Asahi Glass Co Ltd 透明導電膜とその製造方法およびスパッタリングターゲット
JPH11322413A (ja) * 1998-02-16 1999-11-24 Japan Energy Corp 光透過膜、高抵抗透明導電膜、光透過膜形成用スパッタリングタ―ゲット及び高抵抗透明導電膜の製造方法
JP2000040429A (ja) * 1998-07-24 2000-02-08 Sumitomo Metal Mining Co Ltd 酸化亜鉛系透明導電膜の製造方法
JP2002217429A (ja) * 2001-01-22 2002-08-02 Sanyo Electric Co Ltd 光電変換素子
JP2004292873A (ja) * 2003-03-26 2004-10-21 Sumitomo Heavy Ind Ltd 酸化亜鉛膜の製造方法
WO2006129410A1 (fr) * 2005-05-30 2006-12-07 Nippon Mining & Metals Co., Ltd. Cible de pulvérisation cathodique et procédé de fabrication idoine

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6433811A (en) * 1987-04-04 1989-02-03 Gunze Kk Transparent conductive film and its manufacture
JPH0845352A (ja) * 1994-08-02 1996-02-16 Sekisui Chem Co Ltd 透明導電体
JPH08111123A (ja) * 1994-08-17 1996-04-30 Asahi Glass Co Ltd 透明導電膜とその製造方法およびスパッタリングターゲット
JPH11322413A (ja) * 1998-02-16 1999-11-24 Japan Energy Corp 光透過膜、高抵抗透明導電膜、光透過膜形成用スパッタリングタ―ゲット及び高抵抗透明導電膜の製造方法
JP2000040429A (ja) * 1998-07-24 2000-02-08 Sumitomo Metal Mining Co Ltd 酸化亜鉛系透明導電膜の製造方法
JP2002217429A (ja) * 2001-01-22 2002-08-02 Sanyo Electric Co Ltd 光電変換素子
JP2004292873A (ja) * 2003-03-26 2004-10-21 Sumitomo Heavy Ind Ltd 酸化亜鉛膜の製造方法
WO2006129410A1 (fr) * 2005-05-30 2006-12-07 Nippon Mining & Metals Co., Ltd. Cible de pulvérisation cathodique et procédé de fabrication idoine

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2010090101A1 (ja) * 2009-02-06 2012-08-09 株式会社カネカ 薄膜光電変換装置およびその製造方法
WO2010090101A1 (fr) * 2009-02-06 2010-08-12 株式会社カネカ Dispositif de conversion photoélectrique en film mince et procédé de fabrication apparenté
CN102560391A (zh) * 2010-12-24 2012-07-11 海洋王照明科技股份有限公司 一种导电膜制备方法、导电膜及应用
CN103380229A (zh) * 2011-02-25 2013-10-30 三菱综合材料株式会社 透明氧化物膜及其制造方法
JP2014514442A (ja) * 2011-03-25 2014-06-19 ▲海▼洋王照明科技股▲ふん▼有限公司 多元素ドープ酸化亜鉛薄膜、その製作方法及び応用
JP2013069420A (ja) * 2011-09-20 2013-04-18 Kaneka Corp 透明電極付き基板
JP2013237188A (ja) * 2012-05-15 2013-11-28 Toray Ind Inc ガスバリア性フィルム
JP5550768B1 (ja) * 2012-07-03 2014-07-16 Ｊｘ日鉱日石金属株式会社 焼結体及びアモルファス膜
JP2014141386A (ja) * 2012-07-03 2014-08-07 Jx Nippon Mining & Metals Corp 焼結体及びアモルファス膜
JP2014141392A (ja) * 2012-07-03 2014-08-07 Jx Nippon Mining & Metals Corp 焼結体及びアモルファス膜
JP2014159634A (ja) * 2012-07-03 2014-09-04 Jx Nippon Mining & Metals Corp 焼結体及びアモルファス膜
JP2014166950A (ja) * 2012-07-03 2014-09-11 Jx Nippon Mining & Metals Corp 焼結体及びアモルファス膜
TWI631579B (zh) * 2012-07-03 2018-08-01 Ｊｘ日鑛日石金屬股份有限公司 Sintered body and amorphous film
JP2014055348A (ja) * 2012-08-10 2014-03-27 Mitsubishi Materials Corp 透明酸化物膜形成用スパッタリングターゲット及びその製造方法
WO2014069367A1 (fr) * 2012-10-30 2014-05-08 Jx日鉱日石金属株式会社 Corps fritté en oxyde électroconducteur et film à faible indice de réfraction produit au moyen dudit oxyde électroconducteur

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