WO2012161095A1 - 導電膜用素材、導電膜積層体、電子機器、及びそれらの製造方法 - Google Patents
導電膜用素材、導電膜積層体、電子機器、及びそれらの製造方法 Download PDFInfo
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- WO2012161095A1 WO2012161095A1 PCT/JP2012/062696 JP2012062696W WO2012161095A1 WO 2012161095 A1 WO2012161095 A1 WO 2012161095A1 JP 2012062696 W JP2012062696 W JP 2012062696W WO 2012161095 A1 WO2012161095 A1 WO 2012161095A1
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- Prior art keywords
- conductive film
- oxide
- tin
- amorphous layer
- mass
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 87
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005477 sputtering target Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- 238000004544 sputter deposition Methods 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 20
- 229910001887 tin oxide Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 10
- -1 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 229910001882 dioxygen Inorganic materials 0.000 description 9
- 238000005530 etching Methods 0.000 description 8
- 230000002349 favourable effect Effects 0.000 description 8
- 229910003437 indium oxide Inorganic materials 0.000 description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 8
- 238000001755 magnetron sputter deposition Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 229910006404 SnO 2 Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- 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
- C23C14/3492—Variation of parameters during sputtering
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a conductive film material, a conductive film stack, an electronic device, and a method for manufacturing a conductive film material or a conductive film stack.
- the transparent conductive film Since the transparent conductive film has conductivity and optical transparency, it is used as a transparent electrode, an electromagnetic wave shielding film, a planar heating film, an antireflection film, and the like, and has recently attracted attention as a touch panel electrode.
- touch panels There are various types of touch panels such as a resistive film type, a capacitive coupling type, and an optical type.
- the transparent conductive film is used in, for example, a resistance film type that specifies a touch position by contacting upper and lower electrodes, a capacitive coupling method that senses a change in capacitance, and the like.
- the transparent conductive film used for the resistance film type is required to have high durability because the transparent conductive films are in mechanical contact with each other on the principle of operation.
- the transparent conductive film used in the capacitive coupling method and some resistive film types has good etching properties because a large number of transparent electrodes are formed by etching so as to have a specific pattern. Desired.
- a transparent conductive film is arrange
- a first indium tin oxide layer that is an amorphous film and a second indium that is a crystallized film are formed on one surface of a transparent substrate.
- the thing in which the tin oxide layer was formed in order is known.
- the tin content in the first indium tin oxide layer is 5 to 20 wt% in terms of oxide
- the tin content in the second indium tin oxide layer is 1 to 4 in terms of oxide. It is known that it is weight% (for example, refer patent document 1).
- the durability is required for the transparent conductive film, and the durability can be improved by making it crystalline.
- many transparent electrodes may be formed on the transparent conductive film by etching, and if it is crystalline, it becomes difficult to form the transparent electrode by etching. For example, when the transparent conductive film is crystalline, the etching rate decreases, so it takes time to form the transparent electrode, and the shape of the transparent electrode may not be a desired shape.
- an amorphous film that is easy to etch is formed, and after this amorphous film is etched to form a transparent electrode, it is crystallized by heat treatment.
- the amorphous film is required to be easily crystallized by heat treatment.
- An amorphous film is also required to have a low specific resistance when crystallized. When the specific resistance is low, the sheet resistance can be in a favorable range even if the film thickness is thin.
- the transparent conductive film is required to have high transmittance, and high transmittance can be obtained by reducing the film thickness.
- the specific resistance when crystallized is significantly smaller than that containing 3% by mass, and the sheet resistance is in a good range.
- the sheet resistance can be reduced by increasing the film thickness, but the transmittance decreases as the film thickness increases. Even if the film thickness is in a preferable range, if the film thickness is different, the optical characteristics change, and it is necessary to readjust optical components and equipment using the optical characteristics.
- the present invention has been made to solve the above problems, and provides a conductive film material from which a transparent conductive film having crystallinity and having a good thickness and sheet resistance can be obtained; It aims at providing the electrically conductive film laminated body which has a transparent conductive film which has the property and thickness and sheet resistance are favorable, and an electronic device which has this electrically conductive film laminated body. Furthermore, this invention aims at providing the manufacturing method of the above-mentioned raw material for electrically conductive films, and an electrically conductive film laminated body.
- the conductive film material of the present invention has a transparent substrate, a first amorphous layer, and a second amorphous layer.
- the first amorphous layer is made of indium tin oxide that is laminated on a transparent substrate and contains 2% by mass to 15% by mass of tin in terms of oxide.
- the second amorphous layer is laminated on the first amorphous layer, and is composed of indium tin oxide containing 2% by mass to 15% by mass of tin in terms of oxide, and in terms of tin oxide Is different from the content of tin oxide in the first amorphous layer.
- the conductive film laminate of the present invention has a transparent substrate, a first crystalline layer, and a second crystalline layer.
- a 1st crystalline layer is laminated
- the second crystalline layer is laminated on the first crystalline layer, is composed of indium tin oxide containing 2% by mass or more and 15% by mass or less of tin in terms of oxide, and in terms of tin oxide The content is different from the content in terms of oxide of tin in the first crystalline layer.
- the electronic device of the present invention has the above-described conductive film laminate of the present invention.
- the method for producing a conductive film material of the present invention includes a first film formation step and a second film formation step.
- the first sputtering target is formed by sputtering using a first sputtering target made of indium tin oxide containing 5% by mass to 15% by mass in terms of oxide on a transparent substrate.
- An amorphous layer is formed.
- the second film forming step uses a second sputtering target made of indium tin oxide containing tin in an amount of 2% by mass or more and less than 7% by mass in terms of oxide directly on the surface of the first amorphous layer.
- a second amorphous layer is formed by a sputtering method.
- the tin content (content in terms of oxide) in the second sputtering target is different from the tin content (content in terms of oxide) in the first sputtering target.
- the method for producing a conductive film laminate of the present invention includes a material production process and a heat treatment process.
- the conductive film material is manufactured by the above-described method for manufacturing a conductive film material of the present invention.
- the heat treatment step the conductive film material is heat treated to crystallize the first amorphous layer and the second amorphous layer.
- the conductive film material of the present invention when the first amorphous layer and the second amorphous layer having a predetermined composition are stacked to form a conductive film precursor, A crystalline transparent conductive film in which the sheath resistance is in a favorable range can be obtained. If one amorphous layer does not crystallize by itself, but the other amorphous layer crystallizes, both layers can be crystallized by combining them to a certain thickness. it can.
- the first crystalline layer and the second crystalline layer having a predetermined composition are laminated to form a transparent conductive film having a good thickness and sheet resistance. , Durability and reliability can be good.
- the above-described conductive film material of the present invention can be easily manufactured by having a predetermined step.
- an above-described electrically conductive film laminated body of this invention can be easily manufactured by having a predetermined
- FIG. 1 is a cross-sectional view showing an example of a conductive film material of the present invention.
- the conductive film material 1 includes, for example, a transparent substrate 2, a base layer 3, a first amorphous layer 4, and a second amorphous layer 5 in this order.
- the conductive film material 1 of the present invention is used for the production of a conductive film laminate having a crystalline transparent conductive film on a transparent substrate 2, and the first amorphous layer 4 and the second layer are formed by heat treatment.
- the amorphous layer 5 is crystallized to become a crystalline transparent conductive film.
- the amorphous and crystallinity in the present invention means a resistance value change rate (%) (%) obtained by measuring a resistance value before and after being immersed in an HCl aqueous solution (concentration: 1.5 mol / L) for 5 minutes. Resistance value after immersion / resistance value before immersion) ⁇ 100), and when the resistance value change rate exceeds 200%, it is assumed to be amorphous, and the resistance value change rate is 200% or less. The case is assumed to be crystalline.
- the transparent substrate 2 includes, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamides such as nylon 6 and nylon 66, polyimide, polyarylate, polycarbonate, polyacrylate, and polyether. Sulphone, polysulfone, unstretched or stretched plastic films of these copolymers, and the like are preferable.
- the transparent base material 2 can also use another plastic film with high transparency. Among these, a plastic film made of polyethylene terephthalate is particularly preferable.
- a primer layer such as a hard coat may be formed on one or both surfaces of the transparent substrate 2.
- the transparent substrate 2 may be subjected to surface treatment such as easy adhesion treatment, plasma treatment, corona treatment and the like.
- the thickness of the transparent substrate 2 is preferably 10 to 200 ⁇ m, more preferably 50 to 180 ⁇ m, from the viewpoint of flexibility and durability.
- the underlayer 3 is not necessarily essential, but is preferably provided in order to promote crystallization of the first amorphous layer 4 and the second amorphous layer 5.
- the underlayer 3 may be any layer as long as it can promote crystallization of the first amorphous layer 4 and the second amorphous layer 5, for example, an inorganic material such as a metal or its oxide, sulfide, fluoride, etc. What consists of a compound is preferable, and what consists of silicon oxide or aluminum oxide is preferable normally. More preferred is silicon oxide, especially SiO x (x is 1.5 to 2).
- the thickness of the underlayer 3 may be any thickness that can promote crystallization of the first amorphous layer 4 and the second amorphous layer 5, preferably 1 nm or more, and more preferably 3 nm or more. By setting the thickness of the underlayer 3 to 1 nm or more, crystallization of the first amorphous layer 4 and the second amorphous layer 5 can be effectively promoted. If the thickness of the underlayer 3 is about 5 nm, the crystallization of the first amorphous layer 4 and the second amorphous layer 5 can be sufficiently promoted. Can be improved.
- the first amorphous layer 4 and the second amorphous layer 5 constitute a conductive film precursor that is crystallized by heat treatment to become a crystalline transparent conductive film.
- Each of the first amorphous layer 4 and the second amorphous layer 5 is made of indium tin oxide, which is an oxide of indium and tin.
- indium tin oxide tin is converted into an oxide (SnO 2 and so on) and 2 to 15% by mass.
- oxide constituting the indium tin oxide include indium oxide, tin oxide, and a composite oxide of indium oxide and tin oxide.
- the first amorphous layer 4 and the second amorphous layer 5 are both amorphous. Further, the first amorphous layer 4 and the second amorphous layer 5 are different in content in terms of oxide of tin in indium tin oxide.
- the first amorphous layer 4 and the second amorphous layer 5 which are conductive film precursors are made amorphous so that the etching property can be improved.
- the first amorphous layer 4 and the second amorphous layer 5 that are conductive film precursors both contain indium tin oxide in an amount of 2% by mass to 15% by mass in terms of oxide. By comprising, it can crystallize by heat processing and it can be set as a crystalline transparent conductive film, The thickness and sheet resistance can also be made into a favorable range.
- the first amorphous layer 4 and the second amorphous layer 5 are different in content in terms of oxide of tin in indium tin oxide, thereby facilitating crystallization.
- the thickness and the sheet resistance of the crystalline transparent conductive film can be within a favorable range, and the sheet resistance can be easily adjusted.
- the first amorphous layer 4 and the second amorphous layer 5 are preferably both made of indium tin oxide, but indium as necessary and within the scope of the present invention.
- Components other than tin oxide can be contained. Examples of components other than indium tin oxide include oxides such as aluminum, zirconium, gallium, silicon, tungsten, zinc, titanium, magnesium, cerium, and germanium.
- the content of components other than indium tin oxide in the first amorphous layer 4 is 10% by mass or less, preferably 5% by mass or less, and preferably 3% by mass in the entire first amorphous layer 4. The following is more preferable, and 1% by mass or less is particularly preferable.
- the content of components other than indium tin oxide in the second amorphous layer 5 is 10% by mass or less in the entire second amorphous layer 5, and preferably 5% by mass or less. 3 mass% or less is more preferable, and 1 mass% or less is especially preferable.
- tin content Content in terms of oxide of tin in indium tin oxide in first amorphous layer 4 and content in terms of oxide of tin in indium tin oxide in second amorphous layer 5 Any of them may be many.
- the content of tin in the indium tin oxide in terms of oxide is simply referred to as tin content.
- the tin content in the first amorphous layer 4 is larger than the tin content in the second amorphous layer 5, the tin content in the first amorphous layer 4 is 5 mass%.
- the content of tin is preferably 15% by mass or less, and the content of tin in the second amorphous layer 5 is preferably 2% by mass or more and less than 7% by mass. By allocating such content, crystallization can be further promoted, and the thickness and sheet resistance can be in a favorable range.
- the tin content in the first amorphous layer 4 is more preferably 7% by mass or more and 13% by mass or less, and the tin content in the second amorphous layer 5 is more preferably 2% by mass or more and 5% by mass or less. preferable.
- the tin content in the second amorphous layer 5 is larger than the tin content in the first amorphous layer 4, the tin content in the first amorphous layer 4 is 2
- the content of tin in the second amorphous layer 5 is preferably 5% by mass or more and 15% by mass or less. By setting it as such content, crystallization can be accelerated
- the content of tin in the first amorphous layer 4 is more preferably 2% by mass or more and 5% by mass or less, and the content of tin in the second amorphous layer 5 is more preferably 7% by mass or more and 13% by mass or less. preferable.
- the tin content in the first amorphous layer 4 and the tin content in the second amorphous layer 5 may be large, but the first amorphous layer 4 and the second amorphous layer 4 Since the degree of freedom in thickness when crystallizing the amorphous layer 5 is large, that is, it can be crystallized in a wider range of thickness, and the adjustment of the sheet resistance of the crystalline transparent conductive film is easy, the former, That is, it is preferable that the tin content in the first amorphous layer 4 is larger than the tin content in the second amorphous layer 5.
- the thickness of the layer with the larger content in terms of tin oxide is a [nm]
- the thickness in terms of tin oxide When the thickness of the layer with the smaller content is b [nm], the total thickness a + b is preferably 15 ⁇ a + b ⁇ 50, and more preferably 18 ⁇ a + b ⁇ 30.
- the thickness a + b By setting the thickness a + b within the above range, the first amorphous layer 4 and the second amorphous layer 5 can be easily crystallized, and the relationship between the thickness of the crystalline transparent conductive film and the sheet resistance can be obtained. Can be good.
- the thickness a of the first amorphous layer 4 is preferably 6 nm or more, and more preferably 8 nm or more.
- the thicknesses a and b preferably satisfy b ⁇ 12 ⁇ a / 2.
- the first amorphous layer 4 and the second amorphous layer 5 are more easily crystallized, and the relationship between the thickness of the crystalline transparent conductive film and the sheet resistance can be improved.
- the conductive film material 1 can be a conductive film stack having a crystalline transparent conductive film by crystallizing the first amorphous layer 4 and the second amorphous layer 5 by heat treatment.
- the heat treatment is preferably performed, for example, in the atmosphere at 100 to 170 ° C., preferably 125 to 150 ° C. for 5 to 180 minutes, preferably 10 to 60 minutes.
- the heat treatment temperature is 170 ° C. and the heat treatment time is 180 minutes, so that the crystallization can be sufficiently achieved.
- transparent other than the first amorphous layer 4 and the second amorphous layer 5 Damage to the substrate 2 and the like can be suppressed, and productivity can be improved.
- FIG. 2 is a cross-sectional view showing an example of a conductive film laminate 11 obtained by heat-treating the conductive film material 1.
- the conductive film laminate 11 includes, for example, a transparent substrate 2, a base layer 3, a first crystalline layer 12, and a second crystalline layer 13 in this order.
- the first crystalline layer 12 is obtained by crystallizing the first amorphous layer 4, and the second crystalline layer 13 is obtained by crystallizing the second amorphous layer 5. is there.
- the crystalline transparent conductive film is composed of the first crystalline layer 12 and the second crystalline layer 13.
- the crystalline transparent conductive film is not necessarily limited to the one composed of only the first crystalline layer 12 and the second crystalline layer 13, for example, the first crystalline layer.
- a crystalline layer having an intermediate composition may be provided between the first crystalline layer 12 and the second crystalline layer 13.
- a large number of transparent electrodes or the like may be formed by etching in the first crystalline layer 12 and the second crystalline layer 13 constituting the crystalline transparent conductive film.
- Each of the first crystalline layer 12 and the second crystalline layer 13 is made of indium tin oxide which is an oxide of indium and tin, and in the indium tin oxide, tin is 2% by mass in terms of oxide. More than 15 mass% is contained. Further, both the first crystalline layer 12 and the second crystalline layer 13 are crystalline. Further, the first crystalline layer 12 and the second crystalline layer 13 are different in content in terms of oxide of tin in indium tin oxide. Note that indium tin oxide preferably has a crystal structure of indium oxide (In 2 O 3 ), and tin is preferably substituted at the site of indium.
- first crystalline layer 12 and the second crystalline layer 13 are made of indium tin oxide containing 2% by mass or more and 15% by mass or less of tin in terms of oxide, and each other is tin.
- the thickness and sheet resistance can be in a favorable range.
- the relationship between the content and thickness of tin in the first crystalline layer 12 and the second crystalline layer 13 is, for example, the tin in the first amorphous layer 4 and the second amorphous layer 5. It can be set to be the same as the relationship between the content and the thickness.
- the specific resistance of the crystalline transparent conductive film having the first crystalline layer 12 and the second crystalline layer 13 is preferably 4.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, and preferably 3.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. cm or less is more preferable, and 3.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less is particularly preferable.
- the sheet resistance value of the crystalline transparent conductive film is preferably 50 to 500 ⁇ / ⁇ , and more preferably 70 to 200 ⁇ / ⁇ .
- the conductive film laminate 11 is suitably used for an electronic device, and particularly suitably for an electronic device having a display unit and a touch panel disposed on the front surface of the display unit.
- the conductive film laminate 11 is used as a substrate having a transparent electrode in a touch panel.
- Examples of the touch panel to which the conductive film stack 11 is applied include a resistance film type that identifies a touch position by contacting upper and lower electrodes, and a capacitive coupling method that senses a change in capacitance.
- the conductive film material 1 is formed by forming a first amorphous layer 4 and a second amorphous layer 5 in this order after forming a base layer 3 on a transparent substrate 2 as necessary. Can be manufactured.
- the film forming method is not necessarily limited, and a sputtering method, an ion plating method, and a vacuum evaporation method can be applied, and the sputtering method is particularly preferable.
- the first amorphous layer 4 is formed by sputtering using a first sputtering target made of indium tin oxide, for example.
- the first sputtering target preferably contains 2% by mass to 15% by mass of tin in terms of oxide in indium tin oxide.
- Indium tin oxide in the first sputtering target is preferably formed of a sintered body which is sintered by mixing a tin oxide (SnO 2) and indium oxide (In 2 O 3).
- the second amorphous layer 5 is formed by a sputtering method using, for example, a second sputtering target made of indium tin oxide. It is preferable that 2nd sputtering target contains 2 mass% or more and 15 mass% or less of tin in oxide conversion in indium tin oxide.
- the indium tin oxide in the second sputtering target is preferably composed of a sintered body obtained by mixing and sintering tin oxide (SnO 2 ) and indium oxide (In 2 O 3 ).
- the tin content (content in terms of oxide) in the second sparing target is different from the tin content (content in terms of oxide) in the first sputtering target.
- the tin content in the first sputtering target and the second sputtering target can be appropriately selected according to the desired first amorphous layer 4 and second amorphous layer 5.
- the tin content in the first sputtering target is preferably 5% by mass or more and 15% by mass or less, and the tin content in the second sputtering target is 2% by mass. % Or more and less than 7% by mass.
- the content of tin in oxide conversion in the first sputtering target is more preferably 7% by mass or more and 13% by mass or less, and the content in tin conversion of tin in the second sputtering target is 2% by mass or more and 5% by mass. % Or less is more preferable.
- the content of tin in oxide conversion in the first sputtering target is preferably 2% by mass or more and less than 7% by mass
- the content of tin in terms of oxide in the sputtering target 2 is preferably 5% by mass or more and 15% by mass or less.
- the content of tin in oxide conversion in the first sputtering target is more preferably 2% by mass or more and 5% by mass or less
- the content in tin conversion of tin in the second sputtering target is 7% by mass or more and 13% by mass. % Or less is more preferable.
- the first amorphous layer 4 and the second amorphous layer 5 are formed by mixing, for example, argon gas with 0.5 to 10% by volume, preferably 0.8 to 6% by volume of oxygen gas. Sputtering is preferably performed while introducing the mixed gas. By performing sputtering while introducing such a mixed gas, it is possible to form an amorphous material that is easy to crystallize when heat-treated and has a sheet resistance within a good range when crystallized. I can make a film.
- the conductive film laminate 11 can be manufactured by heat-treating the conductive film material 1 to crystallize the first amorphous layer 4 and the second amorphous layer 5.
- the heat treatment is preferably performed, for example, in the atmosphere in the above temperature and time range.
- Examples 1 to 5 are examples, and examples 6 and 7 are comparative examples.
- the thicknesses in Examples 1 to 7 are values obtained from the optical characteristics or the sputtering film formation rate and the sputtering time, and are not actually measured thicknesses.
- Example 1 A SiO 2 film having a thickness of 32 ⁇ was formed as a base layer on a PET (polyethylene terephthalate) film having a thickness of 100 ⁇ m, which was a transparent substrate.
- the SiO 2 film was formed by performing AC magnetron sputtering at a pressure of 0.2 Pa while introducing a mixed gas in which 28% by volume of oxygen gas was mixed with argon gas using a boron-doped polysilicon target. The thickness of the SiO 2 film was adjusted by adjusting the power density and the sputtering time.
- the SiO 2 film on the PET film which the SiO 2 film is formed the target A (hereinafter, referred to as ITO target A) made of indium tin oxide using a mixture of 1.4% by volume of oxygen gas to argon gas While introducing the mixed gas, DC magnetron sputtering was performed at a pressure of 0.25 Pa to form a first amorphous layer having a thickness of 151 ⁇ (first film forming step).
- the ITO target A is made of a sintered body obtained by mixing and sintering 10% by mass of tin oxide (SnO 2 ) and 90% by mass of indium oxide (In 2 O 3 ).
- the thickness of the first amorphous layer was adjusted by adjusting the power density and the sputtering time.
- the tin content (content in terms of oxide) in the first amorphous layer is estimated to be approximately 10% by mass.
- a target gas made of indium tin oxide (hereinafter referred to as ITO target B) is used on the first amorphous layer, and a mixed gas in which 1.4 vol% oxygen gas is mixed with argon gas is introduced.
- ITO target B a target gas made of indium tin oxide
- DC magnetron sputtering was performed at a pressure of 0.25 Pa to form a second amorphous layer having a thickness of 47 ⁇ (second film forming step), and a conductive film material was manufactured (material manufacturing). Process).
- the ITO target B is made of a sintered body obtained by mixing and sintering 3 % by mass of tin oxide (SnO 2 ) and 97% by mass of indium oxide (In 2 O 3 ). The thickness of the second amorphous layer was adjusted by adjusting the power density and the sputtering time.
- the obtained conductive film material was heat-treated at 150 ° C. for 100 minutes in the atmosphere to produce a conductive film laminate (heat treatment step).
- Example 2 Example 1 except that the thickness of the SiO 2 film was changed to 53 ⁇ , the thickness of the first amorphous layer was changed to 96 ⁇ , and the thickness of the second amorphous layer was changed to 99 ⁇ .
- a conductive film material was manufactured, and heat treatment was performed to manufacture a conductive film stack.
- Example 3 Example 1 except that the thickness of the SiO 2 film was changed to 71 ⁇ , the thickness of the first amorphous layer was changed to 131 ⁇ , and the thickness of the second amorphous layer was changed to 134 ⁇ .
- a conductive film material was manufactured, and heat treatment was performed to manufacture a conductive film stack.
- Example 4 A PET film on which a SiO 2 film was formed was produced in the same manner as in Example 1 except that the thickness of the SiO 2 film was changed to 70 ⁇ .
- This SiO 2 film is a SiO 2 film on the PET film which is formed, using an ITO target B, while introducing a mixed gas of 1.4% by volume of oxygen gas to argon gas, at a pressure of 0.25Pa DC magnetron sputtering was performed to form a first amorphous layer having a thickness of 134 ⁇ (first film formation step). Note that the thickness of the first amorphous layer was adjusted by adjusting the power density and the sputtering time.
- first amorphous layer DC magnetron sputtering was performed at a pressure of 0.25 Pa using a target A and introducing a mixed gas obtained by mixing 1.4 vol% oxygen gas into argon gas. Then, a second amorphous layer having a thickness of 131 angstroms was formed (second film formation step), and a conductive film material was produced (material production step). Note that the thickness of the second amorphous layer was adjusted by adjusting the power density and the sputtering time. The obtained conductive film material was subjected to heat treatment at 150 ° C. for 100 minutes in the atmosphere to produce a conductive film laminate (heat treatment step).
- Example 5 A PET film on which a SiO 2 film was formed was produced in the same manner as in Example 1 except that the thickness of the SiO 2 film was changed to 31 ⁇ .
- This SiO 2 film is a SiO 2 film on the PET film which is formed, using an ITO target A, while introducing a mixed gas of 1.4% by volume of oxygen gas to argon gas, at a pressure of 0.25Pa DC magnetron sputtering was performed to form a first amorphous layer having a thickness of 86 ⁇ (first film formation step). Note that the thickness of the first amorphous layer was adjusted by adjusting the power density and the sputtering time.
- the ITO target C is made of a sintered body obtained by mixing and sintering 5% by mass of tin oxide (SnO 2 ) and 95% by mass of indium oxide (In 2 O 3 ).
- the thickness of the second amorphous layer was adjusted by adjusting the power density and the sputtering time.
- the obtained conductive film material was heat treated in the same manner as in Example 1 to produce a conductive film laminate.
- Example 6 A PET film on which a SiO 2 film was formed was produced in the same manner as in Example 1 except that the thickness of the SiO 2 film was changed to 52 ⁇ .
- This SiO 2 film is a SiO 2 film on the PET film which is formed, using an ITO target A, while introducing a mixed gas of 1.4% by volume of oxygen gas to argon gas, at a pressure of 0.25Pa DC magnetron sputtering was performed to form an amorphous film having a thickness of 195 angstrom, which was used as a comparative material.
- the thickness of the amorphous film was adjusted by adjusting the power density and the sputtering time. Thereafter, heat treatment was performed at 150 ° C. for 100 minutes in the air to produce a comparative laminate.
- Example 7 A comparative material and a comparative laminate were manufactured in the same manner as in Example 6 except that the thickness of the SiO 2 film was 51 angstroms, ITO target B was used, and the amorphous film thickness was changed to 186 angstroms. did.
- Example 1 the materials and laminates of Examples 1 to 7 were evaluated as follows. The results are shown in Table 1.
- 10ITO contains 10% by mass of tin in terms of oxide
- 3ITO contains 3% by mass of tin in terms of oxide
- 5ITO has 5% in terms of oxide of tin. This indicates the content by mass.
- the resistance value was measured before and after immersing the laminate in an aqueous HCl solution (concentration 1.5 mol / L) for 5 minutes, and the resistance value change rate (%) ((resistance value after immersion / resistance value before immersion) ⁇ 100) Asked.
- the resistance value change rate is an index of crystallinity, and a resistance value change rate of 200% or less has crystallinity.
- the specific resistance of the transparent conductive film was determined by the following formula (1).
- the thickness of the transparent conductive film in the formula (1) is the sum of the first amorphous layer and the second amorphous layer in the materials and laminates of Examples 1 to 5, and Example 6 In the materials and laminates 7 and 7, the thickness of the amorphous film was used.
- Specific resistance [ ⁇ ⁇ cm] sheet resistance value [ ⁇ / ⁇ ] ⁇ thickness [ ⁇ ] ⁇ 10 8 (1)
- a conductive film laminate comprising a transparent conductive film having crystallinity and good thickness and sheet resistance obtained by heat-treating the conductive film material of the present invention is industrially applied to electronic devices such as touch panels. It is possible to use.
- the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2011-113480 filed on May 20, 2011 are cited herein as disclosure of the specification of the present invention. Incorporated.
- SYMBOLS 1 Material for electrically conductive films, 2 ... Transparent base material, 3 ... Underlayer, 4 ... 1st amorphous layer, 5 ... 2nd amorphous layer, 11 ... Conductive film laminated body, 12 ... 1st Crystalline layer, 13 ... second crystalline layer
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Abstract
Description
また、透明導電膜は、表示部の前面に配置されることから、高い光透過率が求められる。
さらに、本発明は、上記した導電膜用素材及び導電膜積層体の製造方法を提供することを目的とする。
導電膜用素材1は、例えば、透明基材2、下地層3、第1の非晶質層4、及び第2の非晶質層5をこの順に有する。本発明の導電膜用素材1は、透明基材2上に結晶性透明導電膜を有する導電膜積層体の製造に用いられるものであり、熱処理によって第1の非晶質層4と第2の非晶質層5とが結晶化されて結晶性透明導電膜となる。
導電膜用素材1は、透明基材2上に、必要に応じて下地層3を形成した後、第1の非晶質層4、及び第2の非晶質層5をこの順に形成することにより製造できる。成膜方法は、必ずしも限定されず、スパッタリング法、イオンプレーティング法、真空蒸着法を適用でき、特にスパッタリング法が好ましい。
例1~5が実施例であり、例6、7が比較例である。また、例1~7における厚さは、光学特性あるいはスパッタ成膜レートとスパッタ時間から求めた値であり、実際に測定した厚さではない。
透明基材である厚さ100μmのPET(ポリエチレンテレフタレート)フィルム上に、下地層として厚さ32オングストロームのSiO2膜を形成した。SiO2膜は、ボロンドープポリシリコンターゲットを用い、アルゴンガスに28体積%の酸素ガスを混合した混合ガスを導入しつつ、0.2Paの圧力でACマグネトロンスパッタを行って形成した。なお、SiO2膜の厚さの調整は、電力密度とスパッタ時間とを調整して行った。
なお、ITOターゲットAは、10質量%の酸化スズ(SnO2)と90質量%の酸化インジウム(In2O3)とを混合し焼結させた焼結体からなる。また、第1の非晶質層の厚さの調整は、電力密度とスパッタ時間とを調整して行った。なお、第1の非晶質層におけるスズの含有量(酸化物換算での含有量)は、およそ10質量%と推定される。
なお、ITOターゲットBは、3質量%の酸化スズ(SnO2)と97質量%の酸化インジウム(In2O3)とを混合し焼結させた焼結体からなる。また、第2の非晶質層の厚さの調整は、電力密度とスパッタ時間とを調整して行った。
SiO2膜の厚さを53オングストローム、第1の非晶質層の厚さを96オングストローム、第2の非晶質層の厚さを99オングストロームにそれぞれ変更した以外は、例1と同様にして導電膜用素材を製造し、熱処理を行って導電膜積層体を製造した。
(例3)
SiO2膜の厚さを71オングストローム、第1の非晶質層の厚さを131オングストローム、第2の非晶質層の厚さを134オングストロームにそれぞれ変更した以外は、例1と同様にして導電膜用素材を製造し、熱処理を行って導電膜積層体を製造した。
SiO2膜の厚さを70オングストロームに変更した以外は、実施例1と同様にしてSiO2膜が形成されたPETフィルムを製造した。このSiO2膜が形成されたPETフィルムのSiO2膜上に、ITOターゲットBを用い、アルゴンガスに1.4体積%の酸素ガスを混合した混合ガスを導入しつつ、0.25Paの圧力でDCマグネトロンスパッタを行って、厚さ134オングストロームの第1の非晶質層を形成した(第1の成膜工程)。なお、第1の非晶質層の厚さの調整は、電力密度とスパッタ時間とを調整して行った。
得られた導電膜用素材に対して、大気中で150℃、100分間の熱処理を行って導電膜積層体を製造した(熱処理工程)。
SiO2膜の厚さを31オングストロームに変更した以外は、実施例1と同様にしてSiO2膜が形成されたPETフィルムを製造した。このSiO2膜が形成されたPETフィルムのSiO2膜上に、ITOターゲットAを用い、アルゴンガスに1.4体積%の酸素ガスを混合した混合ガスを導入しつつ、0.25Paの圧力でDCマグネトロンスパッタを行って、厚さ86オングストロームの第1の非晶質層を形成した(第1の成膜工程)。なお、第1の非晶質層の厚さの調整は、電力密度とスパッタ時間とを調整して行った。
得られた導電膜用素材に対しては、例1と同様にして熱処理を行って導電膜積層体を製造した。
SiO2膜の厚さを52オングストロームに変更した以外は、実施例1と同様にしてSiO2膜が形成されたPETフィルムを製造した。このSiO2膜が形成されたPETフィルムのSiO2膜上に、ITOターゲットAを用い、アルゴンガスに1.4体積%の酸素ガスを混合した混合ガスを導入しつつ、0.25Paの圧力でDCマグネトロンスパッタを行って、厚さ195オングストロームの非晶質膜を形成して比較用素材とした。また、非晶質膜の厚さの調整は、電力密度とスパッタ時間とを調整して行った。その後、大気中で150℃、100分間の熱処理を行って比較用の積層体を製造した。
SiO2膜の厚さを51オングストロームとし、ITOターゲットBを用い、非晶質膜の厚さを186オングストロームに変更した以外は、例6と同様にして比較用素材、比較用の積層体を製造した。
なお、表中、「10ITO」はスズを酸化物換算で10質量%含有するもの、「3ITO」はスズを酸化物換算で3質量%含有するもの、「5ITO」はスズを酸化物換算で5質量%含有するものを示す。
積層体をHCl水溶液(濃度1.5mol/L)に5分間浸漬する前後で抵抗値を測定し、抵抗値変化率(%)((浸漬後の抵抗値/浸漬前の抵抗値)×100)を求めた。なお、既に説明したように、抵抗値変化率は、結晶性の指標となるものであり、抵抗値変化率が200%以下のものが結晶性を有する。
素材、積層体のそれぞれについて、100mm×100mmのサイズに切断し、Lorester(三菱化学社製、商品名)を用いて四探針法により透明導電膜のシート抵抗値を測定した。このシート抵抗値を用いて、下記式(1)により透明導電膜の比抵抗を求めた。ここで、式(1)における透明導電膜の厚さは、例1~5の素材及び積層体では、第1の非晶質層及び第2の非晶質層を合計した厚さとし、例6、7の素材及び積層体では、非晶質膜の厚さとした。
比抵抗[Ω・cm]=シート抵抗値[Ω/□]×厚さ[Å]÷108 ……(1)
なお、2011年5月20日に出願された日本特許出願2011-113480号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (13)
- 透明基材と、
前記透明基材上に積層され、スズを酸化物換算で2質量%以上15質量%以下含有するインジウムスズ酸化物からなる第1の非晶質層と、
前記第1の非晶質層上に積層され、スズを酸化物換算で2質量%以上15質量%以下含有するインジウムスズ酸化物からなり、かつスズの酸化物換算での含有量が前記第1の非晶質層におけるスズの酸化物換算での含有量と異なる第2の非晶質層と、
を有することを特徴とする導電膜用素材。 - 前記第1の非晶質層及び前記第2の非晶質層のうち、スズの酸化物換算での含有量が多い方の層におけるスズの酸化物換算での含有量が5質量%以上15質量%以下であり、スズの酸化物換算での含有量が少ない方の層におけるスズの酸化物換算での含有量が2質量%以上7質量%未満であることを特徴とする請求項1に記載の導電膜用素材。
- 前記第1の非晶質層及び前記第2の非晶質層のうち、スズの酸化物換算での含有量が多い方の層の厚さをa[nm]、スズの酸化物換算での含有量が少ない方の層の厚さをb[nm]としたとき、これらの合計した厚さa+bは、15≦a+b≦50を満たすことを特徴とする請求項1又は2に記載の導電膜用素材。
- 前記第1の非晶質層及び前記第2の非晶質層のうち、スズの酸化物換算での含有量が多い方の層の厚さをa[nm]、スズの酸化物換算での含有量が少ない方の層の厚さをb[nm]としたとき、b≧12-a/2を満たすことを特徴とする請求項1乃至3のいずれか1項に記載の導電膜用素材。
- 前記第1の非晶質層におけるスズの酸化物換算での含有量は、前記第2の非晶質層におけるスズの酸化物換算での含有量よりも多いことを特徴とする請求項1乃至4のいずれか1項に記載の導電膜用素材。
- 前記透明基材と前記第1の非晶質層との間にケイ素酸化物層を有することを特徴とする請求項1乃至5のいずれか1項に記載の導電膜用素材。
- 前記第1の非晶質層及び前記第2の非晶質層は、熱処理により結晶化されていることを特徴とする請求項1乃至6のいずれか1項に記載の導電膜用素材。
- 前記透明基材が、ポリエチレンテレフタレートであることを特徴とする請求項1乃至7のいずれか1項に記載の導電膜用素材。
- 透明基材と、
前記透明基材上に積層され、スズを酸化物換算で2質量%以上15質量%以下含有するインジウムスズ酸化物からなる第1の結晶性層と、
前記第1の結晶性層上に積層され、スズを酸化物換算で2質量%以上15質量%以下含有するインジウムスズ酸化物からなり、かつスズの酸化物換算での含有量が前記第1の結晶性層におけるスズの酸化物換算での含有量と異なる第2の結晶性層と、
を有することを特徴とする導電膜積層体。 - 請求項9に記載の導電膜積層体を有することを特徴とする電子機器。
- 透明基材上に、スズを酸化物換算で5質量%以上15質量%以下含有するインジウムスズ酸化物からなる第1のスパッタリングターゲットを用いてスパッタリング法により第1の非晶質層を成膜する第1の成膜工程と、
前記第1の非晶質層の表面に直接、スズを酸化物換算で2質量%以上7質量%未満含有するインジウムスズ酸化物からなる第2のスパッタリングターゲットを用いてスパッタリング法により第2の非晶質層を成膜する第2の成膜工程と、
を有することを特徴とする導電膜用素材の製造方法。
但し、第2のスパッタリングターゲットにおけるスズの含有量(酸化物換算での含有量)は、第1のスパッタリングターゲットにおけるスズの含有量(酸化物換算での含有量)とは異なる。 - 請求項11に記載の製造方法によって導電膜用素材を製造する素材製造工程と、
前記導電膜用素材を熱処理して前記第1の非晶質層及び前記第2の非晶質層を結晶化させる熱処理工程と、
を有することを特徴とする導電膜積層体の製造方法。 - 前記熱処理工程が、温度100~170℃で30~180分間で行なうことを特徴とする、請求項12に記載の導電膜積層体の製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2013084376A (ja) * | 2011-10-06 | 2013-05-09 | Nitto Denko Corp | 透明導電性フィルム |
WO2014157312A1 (ja) * | 2013-03-29 | 2014-10-02 | 株式会社カネカ | 透明導電積層フィルムおよびその製造方法 |
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JP2017057505A (ja) * | 2014-04-30 | 2017-03-23 | 日東電工株式会社 | 透明導電性フィルム及びその製造方法 |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0843841A (ja) * | 1994-07-27 | 1996-02-16 | Toppan Printing Co Ltd | 透明導電膜の形成方法 |
JP2006244771A (ja) * | 2005-03-01 | 2006-09-14 | Nitto Denko Corp | 透明導電性フィルムおよびタッチパネル |
JP2010061942A (ja) * | 2008-09-03 | 2010-03-18 | Toppan Printing Co Ltd | 透明導電性フィルムおよびタッチパネル |
JP2011003446A (ja) * | 2009-06-19 | 2011-01-06 | Bridgestone Corp | 透明導電膜、透明導電性フィルムおよび透明導電膜の製造方法、並びに透明導電膜を用いたフレキシブルディスプレイ装置 |
JP2012114070A (ja) * | 2010-11-05 | 2012-06-14 | Nitto Denko Corp | 透明導電性フィルム、その製造方法及びそれを備えたタッチパネル |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN2539375Y (zh) * | 2002-04-15 | 2003-03-05 | 湖南三才光电信息材料有限公司 | 一种高稳定的柔性透明导电复合膜 |
JP2007329468A (ja) * | 2006-05-10 | 2007-12-20 | Kumamoto Univ | 発光素子およびその製造方法 |
-
2012
- 2012-05-17 JP JP2013516330A patent/JPWO2012161095A1/ja active Pending
- 2012-05-17 KR KR20137029436A patent/KR20140027230A/ko not_active Application Discontinuation
- 2012-05-17 WO PCT/JP2012/062696 patent/WO2012161095A1/ja active Application Filing
- 2012-05-17 CN CN201280023895.XA patent/CN103548097A/zh active Pending
- 2012-05-18 TW TW101117764A patent/TW201301310A/zh unknown
-
2013
- 2013-11-20 US US14/085,001 patent/US20140079927A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0843841A (ja) * | 1994-07-27 | 1996-02-16 | Toppan Printing Co Ltd | 透明導電膜の形成方法 |
JP2006244771A (ja) * | 2005-03-01 | 2006-09-14 | Nitto Denko Corp | 透明導電性フィルムおよびタッチパネル |
JP2010061942A (ja) * | 2008-09-03 | 2010-03-18 | Toppan Printing Co Ltd | 透明導電性フィルムおよびタッチパネル |
JP2011003446A (ja) * | 2009-06-19 | 2011-01-06 | Bridgestone Corp | 透明導電膜、透明導電性フィルムおよび透明導電膜の製造方法、並びに透明導電膜を用いたフレキシブルディスプレイ装置 |
JP2012114070A (ja) * | 2010-11-05 | 2012-06-14 | Nitto Denko Corp | 透明導電性フィルム、その製造方法及びそれを備えたタッチパネル |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9332633B2 (en) | 2011-10-06 | 2016-05-03 | Nitto Denko Corporation | Transparent conductive film |
US8669476B2 (en) | 2011-10-06 | 2014-03-11 | Nitto Denko Corporation | Transparent conductive film |
JP2013084376A (ja) * | 2011-10-06 | 2013-05-09 | Nitto Denko Corp | 透明導電性フィルム |
WO2014157312A1 (ja) * | 2013-03-29 | 2014-10-02 | 株式会社カネカ | 透明導電積層フィルムおよびその製造方法 |
JPWO2014157312A1 (ja) * | 2013-03-29 | 2017-02-16 | 株式会社カネカ | 透明導電積層フィルムおよびその製造方法 |
WO2015102099A1 (ja) * | 2013-12-30 | 2015-07-09 | 日本写真印刷株式会社 | 透明導電性シート、および透明導電性シートを用いたタッチパネル |
WO2015159805A1 (ja) * | 2014-04-15 | 2015-10-22 | 旭硝子株式会社 | 積層体、導電性積層体、および電子機器 |
JPWO2015159805A1 (ja) * | 2014-04-15 | 2017-04-13 | 旭硝子株式会社 | 積層体、導電性積層体、および電子機器 |
WO2015166963A1 (ja) * | 2014-04-30 | 2015-11-05 | 日東電工株式会社 | 透明導電性フィルム及びその製造方法 |
JP2015221939A (ja) * | 2014-04-30 | 2015-12-10 | 日東電工株式会社 | 透明導電性フィルム及びその製造方法 |
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JP2016074221A (ja) * | 2015-11-27 | 2016-05-12 | 日東電工株式会社 | 導電性積層体、パターン配線付き透明導電性積層体、および光学デバイス |
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