WO2014115770A1 - Substrat électroconducteur transparent et son procédé de production - Google Patents

Substrat électroconducteur transparent et son procédé de production Download PDF

Info

Publication number
WO2014115770A1
WO2014115770A1 PCT/JP2014/051268 JP2014051268W WO2014115770A1 WO 2014115770 A1 WO2014115770 A1 WO 2014115770A1 JP 2014051268 W JP2014051268 W JP 2014051268W WO 2014115770 A1 WO2014115770 A1 WO 2014115770A1
Authority
WO
WIPO (PCT)
Prior art keywords
transparent conductive
conductive film
film
partial pressure
oxide
Prior art date
Application number
PCT/JP2014/051268
Other languages
English (en)
Japanese (ja)
Inventor
中山　徳行
勝史 小野
和彦 大久保
Original Assignee
住友金属鉱山株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to JP2014558595A priority Critical patent/JPWO2014115770A1/ja
Publication of WO2014115770A1 publication Critical patent/WO2014115770A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
    • 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
    • G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/702—Amorphous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • 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

Definitions

  • the present invention relates to a transparent conductive base material having a transparent conductive film that is crystalline and has a low resistance, and a manufacturing method for forming the transparent conductive film by a sputtering method.
  • the transparent conductive film Since the transparent conductive film has high conductivity and high transmittance in the visible light region, it is used for flat panel displays and solar cell electrodes. In particular, in recent years, capacitive touch panels have become widespread for smartphones and tablet PCs, and the usage is increasing in those applications.
  • Capacitive touch panels can be broadly classified into those using glass substrates and those using film substrates, depending on the substrate.
  • the film capacitive touch panel using a film base material is not only excellent in flexibility and workability, but also light in weight when enlarged, and excellent in impact resistance. Demand growth is remarkable. Under such circumstances, development of transparent conductive films suitable for film capacitive touch panels has been actively promoted.
  • the transparent conductive films used in the capacitive touch panel are not limited to film base materials, but are ITO (Indium-Tin-Oxide) films in which tin is added to indium oxide. Since a capacitive touch panel is required to have high visibility, it is necessary to make the ITO film, which is a transparent electrode, an extremely thin film. At the same time, the ITO film is required to exhibit a low electrical resistance while being an extremely thin film.
  • the film thickness of the ITO film is set to 20-30 nm, and it is required to achieve a lower surface resistance value at that film thickness, and it is proposed to provide a refractive index buffer on the surface. (See Patent Document 3).
  • the ITO film is required to be a crystalline film.
  • the ITO film is advantageously a crystalline film with less change in surface resistance over time.
  • a PET film having low heat resistance is used as the film substrate. Since the PET film has a glass transition temperature of about 80 ° C., generally, a hard coat layer made of an acrylic organic material or the like is formed on both surfaces thereof, and the heat resistance temperature is increased to about 150 ° C. for use. Therefore, in the method for producing an ITO crystal film, an amorphous film formed by sputtering is generally crystallized by heat treatment, but it is necessary to keep the heating temperature at 150 ° C. or less in the film formation and heat treatment.
  • an ITO crystal film generally exhibits the lowest resistance when tin oxide is 10% by weight.
  • an ITO crystal film containing 10% by weight of tin oxide is not used. The reason is that the crystallization start temperature of the ITO film becomes higher as the amount of tin oxide increases.
  • the PET film should be crystallized at a heat resistant temperature of 150 ° C. I can't. At the same time, crystallization becomes difficult as the film thickness decreases.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-244771 discloses a thin film made of an indium-tin composite oxide having a small ratio of tin oxide from the film substrate side, and an indium-tin composite oxide having a large ratio of tin oxide on the thin film. It has been proposed to provide a thin film of material.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2012-1114070 discloses a transparent film for the purpose of providing a transparent conductive film having a transparent conductive thin film capable of shortening the crystallization time by the heat treatment described above.
  • the transparent conductive film which has the transparent conductive thin film laminated body which consists of a specific transparent conductive thin film of at least 2 layers is described in the at least one surface of a base material.
  • Each of the transparent conductive thin films is a crystalline film of an indium composite oxide containing indium oxide or an oxide of a tetravalent metal element, and on the surface side of the transparent conductive thin film laminate,
  • the first transparent conductive thin film has a first transparent conductive thin film having an indium oxide or tetravalent metal element oxide ratio of more than 0 and not more than 6% by weight, from the surface side of the transparent conductive thin film laminate.
  • the total thickness of the transparent conductive laminated film is limited to 20 to 30 nm.
  • a thin film made of an indium-tin composite oxide having a relatively small surface resistance and a small proportion of indium / tin composite oxide, or a thin film having a small proportion of indium oxide or an oxide of a tetravalent metal element has been used.
  • the interface of the laminated film composed of at least two layers becomes a factor of high resistance.
  • a thin film made of an amorphous indium composite oxide is formed by sputtering using an oxide sintered body (see Patent Document 4), but the interface of the transparent conductive laminated film can be eliminated. A method has not yet been found.
  • the present invention aims to provide a transparent conductive base material having a transparent conductive film that is crystalline and has a low resistance used for a capacitive touch panel, and a manufacturing method for forming the transparent conductive film by a sputtering method.
  • Patent Documents 1 and 2 an indium-tin composite with a small proportion of tin oxide that is easy to crystallize but does not have a sufficiently low surface resistance value.
  • a thin film made of an oxide or a thin film with a small proportion of oxide of indium oxide or tetravalent metal element (hereinafter referred to as thin film A) and an indium-tin composite with a large proportion of tin oxide that is difficult to crystallize but has a sufficiently low surface resistance
  • a sufficiently low resistance cannot be obtained as a whole due to the influence of the interface between the thin film A and the thin film B.
  • a transparent conductive substrate on which a crystalline transparent conductive film is formed The transparent conductive film is sequentially formed as two layers of a first amorphous transparent conductive film and a second amorphous transparent conductive film, and then the obtained transparent conductive film laminate is heat-treated.
  • the first amorphous transparent conductive film is different from the second amorphous transparent conductive film in that the total weight ratio of oxides of divalent to hexavalent metal elements represented by the following formula (A) is different from that of the second amorphous transparent conductive film:
  • a transparent conductive substrate characterized in that the total weight ratio of oxides of divalent to hexavalent metal elements in the crystalline transparent conductive film is 16% by weight or less. ⁇ Total weight of oxide of divalent to hexavalent metal element / (weight of indium oxide + total weight of oxide of divalent to hexavalent metal element) ⁇ ⁇ 100 (%)
  • the oxide of the divalent to hexavalent metal element is any one of zinc oxide, gallium oxide, tin oxide, titanium oxide, or tungsten oxide.
  • a transparent conductive substrate is provided.
  • the first amorphous transparent conductive film is indium oxide represented by the following formula (B), or at least one or more types Consisting of indium oxide containing a tetravalent metal element oxide in a total weight ratio of 10% by weight or less
  • the second amorphous transparent conductive film contains an oxide of a tetravalent metal element in a total weight ratio that is greater than the total weight ratio of the first transparent conductive film and is 25% by weight or less.
  • the transparent conductive substrate which is a single layer and crystalline, contains at least one or more tetravalent metal element oxides in a total weight ratio of 5 to 16% by weight. Provided. ⁇ Total weight of oxide of tetravalent metal element / (weight of indium oxide + total weight of oxide of at least one tetravalent metal element) ⁇ ⁇ 100 (%)
  • the first amorphous transparent conductive film is indium oxide represented by the following formula (B), or at least one or more types Comprising indium oxide containing a tetravalent metal element oxide in a total weight ratio of 25% by weight or less
  • the second amorphous transparent conductive film contains an oxide of a tetravalent metal element in a total weight ratio that is less than the total weight ratio of the first transparent conductive film and is 10% by weight or less.
  • the transparent conductive substrate which is a single layer and crystalline, contains at least one or more tetravalent metal element oxides in a total weight ratio of 5 to 16% by weight. Provided. ⁇ Total weight of oxide of tetravalent metal element / (weight of indium oxide + total weight of oxide of at least one tetravalent metal element) ⁇ ⁇ 100 (%)
  • the transparent conductive substrate according to the third or fourth aspect wherein the tetravalent metal element oxide is tin oxide or titanium oxide. Provided.
  • the transparent conductive film according to any one of the first to fifth aspects wherein the total film thickness of the single-layer and crystalline transparent conductive film is 35 nm or less.
  • a functional substrate is provided.
  • the total film thickness of the single-layered crystalline transparent conductive film is 35 nm or less, and the first or second non-conductive film
  • a transparent conductive substrate characterized in that the film thickness of at least one of the crystalline transparent conductive films is 10 nm or more.
  • the transparent substrate is a resin film.
  • a transparent conductive substrate is provided.
  • the first and second amorphous transparent conductive films are both tetravalent metal element oxides. 6.
  • the tin oxide containing 3% by weight or more, the total film thickness of the single-layer and crystalline transparent conductive film is 25 nm or less, and the surface resistance value is 125 ⁇ / ⁇ or less.
  • a transparent conductive substrate according to any one of the above is provided.
  • any one of the first to ninth inventions two layers of the first and second amorphous transparent conductive films are formed on one or both surfaces of the transparent substrate.
  • a method for producing a transparent conductive substrate comprising: In the first step, the oxygen partial pressure of the first amorphous transparent conductive film with respect to the optimum oxygen partial pressure of the first amorphous transparent conductive film, and the second amorphous transparent conductive film The average ratio of the oxygen partial pressure of the second amorphous transparent conductive film to the optimum oxygen partial pressure of the first and second amorphous transparent conductive films is 18% or more, and oxygen in the sputtering film formation of the first and second amorphous transparent conductive films At least one of the partial
  • the oxygen partial pressure in the sputtering film formation of the first and second amorphous transparent conductive films is in either case, the oxygen partial pressure is lower than the optimum oxygen partial pressure, and the oxygen partial pressure in the sputtering film formation of the first amorphous transparent conductive film is higher than the oxygen partial pressure in the film formation of the second amorphous transparent conductive film.
  • a method for producing the characteristic transparent conductive substrate is provided.
  • the first amorphous structure with respect to the optimum oxygen partial pressure of the first amorphous transparent conductive film is 18 to 91%.
  • the volume ratio of oxygen in the heat treatment atmosphere is 20 to 100%.
  • a method of manufacturing a substrate is provided.
  • a thin film made of a tin composite oxide or a thin film with a high proportion of oxide of a tetravalent metal element is formed under specific conditions, formed into a two-layer laminate, and then heat-treated to form a single layer. It becomes possible to eliminate the adverse effect of the interface, and as a result, a crystalline transparent conductive film exhibiting a sufficiently low resistance can be obtained.
  • the transparent conductive film manufacturing method of the present invention is a capacitive touch panel using a resin film as a base material.
  • the present invention can be preferably applied to the production of
  • FIG. 1 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 5 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 6 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing
  • FIG. 7 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 8 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 9 is a schematic cross-sectional view showing a transparent conductive substrate according to an embodiment of the present invention.
  • FIG. 10 is a graph showing the relationship between oxygen partial pressure and specific resistance in the sputtering film formation of a transparent conductive film made of indium oxide (containing 7.5% by weight of tin oxide).
  • FIG. 11 is a photograph showing a cross-sectional TEM image of the transparent conductive film of Example 2.
  • FIG. 12 is a photograph of electron diffraction of the transparent conductive film of Example 2.
  • FIG. 13 is a graph showing the relationship between the film thickness direction of the transparent conductive film of Example 2 and the tin oxide content.
  • FIG. 14 is a photograph showing a cross-sectional TEM image of the transparent conductive film of Comparative Example 5.
  • FIG. 15 is a photograph of electron diffraction near the surface of the transparent conductive film of Comparative Example 5.
  • FIG. 16 is a photograph of electron diffraction near the interface with the undercoat of the transparent conductive film of Comparative Example 5.
  • FIG. 17 is a photograph of a cross-sectional TEM image of the transparent conductive film of Example 19.
  • FIG. 18 is a photograph of electron diffraction of the transparent conductive film of Example 19.
  • FIG. 19 is a graph showing the relationship between the film thickness direction of the transparent conductive film of Example 19 and the tin oxide content.
  • the transparent conductive substrate of the present invention comprises indium oxide or indium oxide containing at least one oxide of a divalent to hexavalent metal element on one or both sides of a transparent substrate.
  • the first amorphous transparent conductive film is different from the second amorphous transparent conductive film in that the total weight ratio of oxides of divalent to hexavalent metal elements represented by the following formula (A) is different from that of the second amorphous transparent conductive film:
  • the total weight ratio of oxides of divalent to hexavalent metal elements in the crystalline transparent conductive film is 16% by weight or less. ⁇ Total weight of oxide of divalent to hexavalent metal element / (weight of indium oxide + total weight of oxide of divalent to hexavalent metal element) ⁇ ⁇ 100 (%)
  • High-quality thin films or amorphous thin films (thin film B) with a large proportion of oxides of tetravalent metal elements are combined.
  • the present invention by forming a two-layer amorphous transparent conductive film laminate on a substrate under specific conditions, long-distance diffusion of constituent element ions at the laminate interface is likely to occur,
  • the two-layer structure is made into a single layer by heat treatment, and thereby, even if the film thickness is thin, it is sufficiently crystallized at a heating temperature of 150 ° C. or less, and a low resistance transparent conductive laminated film is obtained.
  • a first amorphous transparent conductive film (21) and a second amorphous transparent film are sequentially formed on one or both surfaces of a transparent substrate (1).
  • the amorphous transparent conductive film laminate (2) is composed of two layers of a first amorphous transparent conductive film (21) and a second amorphous transparent conductive film (22). All are made of indium oxide or indium oxide containing at least one oxide of a divalent to hexavalent metal element.
  • the oxide of the divalent to hexavalent metal element is preferably at least one selected from the group consisting of zinc oxide, gallium oxide, tin oxide, titanium oxide, niobium oxide and tungsten oxide.
  • the first amorphous transparent conductive film (21) and the second amorphous transparent conductive film (22) are represented by the formula (A) of an oxide of at least one or more divalent to hexavalent metal elements. It is preferable that the total weight ratios indicated by
  • the single-layer and crystalline transparent conductive film (3) comprises at least one oxide of a 2-6 hexavalent metal element in a weight ratio represented by the formula (A) exceeding 0% by weight and 16% by weight or less. It is more preferable to contain 5 to 12% by weight.
  • the total weight ratio of the oxides of at least one or more divalent to hexavalent metal elements contained in the single-layer and crystalline transparent conductive film (3) is the same as that of the first amorphous transparent conductive film (21) and the first transparent conductive film (21). It is determined by the value based on the film thickness and the total weight ratio (formula (A)) of each of the two amorphous transparent conductive films (22).
  • the total weight ratio of the oxides of at least one or more divalent to hexavalent metal elements (formula (A)) contained in the single layer and crystalline transparent conductive film (3) is a viewpoint that a low surface resistance value can be obtained. From 0 to 16% by weight, preferably 5 to 12% by weight.
  • the film thickness of the single-layer and crystalline transparent conductive film (3) is preferably 35 nm or less, and more preferably 25 nm or less, considering the improvement in the visibility of the film capacitive touch panel.
  • the amorphous transparent conductive film laminate composed of two layers is transformed into a single layer and a crystalline transparent conductive film by heat treatment.
  • the thin film structure is observed with a cross-sectional TEM image, and lattice fringes continue from the surface of the transparent conductive film to the interface with the underlying layer (such as an undercoat layer described later), and the transparent conductive film laminate 2 is formed. This is determined by not confirming the interface between the layers.
  • the transparent conductive film after the heat treatment of the present invention is a polycrystal, if the two-layer state is maintained even after the heat treatment, the lattice stripes in the cross-sectional TEM image are not continuous, and the transparent conductive film laminate described above This is confirmed because the two-layer amorphous transparent conductive film interface constituting the film remains.
  • the composition of the oxide of the 2-6 hexavalent metal element of the single-layer and crystalline transparent conductive film is discontinuous at the interface between the two amorphous transparent conductive films constituting the transparent conductive film laminate. There may be.
  • the total weight ratio of oxides of at least one or more divalent to hexavalent metal elements contained in the first amorphous transparent conductive film and the second amorphous transparent conductive film (formula (A))
  • the difference in the amount exceeds 6% by weight, discontinuity tends to occur, but the reduction of the surface resistance value, which is an object of the present invention, is achieved.
  • the total weight ratio of at least one or more divalent to hexavalent metal element oxides contained in either the first or second amorphous transparent conductive film is 2% by weight or less, It is more preferable that the composition of the oxide is continuously changed, and it is more preferable that the oxide is in a state close to homogenization.
  • a non-alkali glass substrate, a synthetic quartz substrate, a resin substrate, a resin film substrate, etc. are mentioned.
  • various opaque substrates such as a silicon substrate, a metal plate such as stainless steel, a foil, or a polyimide film can be used.
  • a transparent film substrate (4) is preferable, and various resin films having transparency can be used.
  • polyester resin for example, polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, polyvinyl chloride resin, poly Examples thereof include vinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and the like.
  • polyester resins, polycarbonate resins, and polyolefin resins are particularly preferable.
  • An acrylic hard coat layer may be appropriately formed on the surface of these resin films.
  • oxides of divalent to hexavalent metal elements contained in the transparent conductive film are preferable.
  • the single-layered and crystalline transparent conductive film (6) formed on one or both sides of the transparent film base (4) is at least one tetravalent metal element.
  • the single-layer and crystalline transparent conductive film (6) once forms the amorphous transparent conductive film laminate (5) composed of two layers in FIG. 3 and heat-treats it under predetermined conditions. Can be obtained.
  • the first amorphous transparent conductive film (51) constituting the two-layer amorphous transparent conductive film laminate (5) is composed of indium oxide or at least one or more kinds.
  • the tetravalent metal element oxide is preferably 10% by weight or less in terms of the total weight ratio represented by the formula (B), and is preferably made of indium oxide containing 1 to 6% by weight of the tetravalent metal element oxide.
  • the second amorphous transparent conductive film (52) comprises at least one or more tetravalent metal element oxides in a total weight ratio (formula (B)) in the first amorphous transparent conductive film. It is preferably made of indium oxide containing more than 25% by weight exceeding the total weight ratio of the conductive film.
  • the oxide of the tetravalent metal element is preferably either tin oxide or titanium oxide.
  • the single-layer and crystalline transparent conductive film (6) preferably contains at least one oxide of a tetravalent metal element in an amount of 16% by weight or less in terms of the total weight ratio represented by (Formula (B)).
  • the total weight ratio of the oxides of at least one tetravalent metal element contained in the single-layer crystalline transparent conductive film (6) (formula (B)) is the first amorphous transparent conductive film ( 51) and the thickness of each of the second amorphous transparent conductive films (52) and a value based on the total weight ratio (formula (B)).
  • the total weight ratio of the oxides of at least one tetravalent metal element (formula (B)) contained in the single-layer and crystalline transparent conductive film (6) is from the viewpoint that a low surface resistance value can be obtained. It is preferably 16% by weight or less, more preferably 5 to 12% by weight. Further, the film thickness of the single-layered and crystalline transparent conductive film (6) is preferably 35 nm or less, more preferably 25 nm or less, considering the improvement in the visibility of the film capacitive touch panel. Furthermore, from the viewpoint of ease of crystallization, the film thickness of the first amorphous transparent conductive film (51) is more preferably 10 nm or more.
  • the single-layered and crystalline transparent conductive film (8) formed on one side or both sides of the transparent film base (4) is at least one tetravalent metal element.
  • This is a transparent conductive film (13) containing 16% by weight or less of the above oxide in terms of the total weight ratio represented by (formula (B)).
  • the single layer and crystalline transparent conductive film (8) once forms the amorphous transparent conductive film laminate (7) having two layers in FIG. 5 and heat-treats it under predetermined conditions. Can be obtained.
  • the first amorphous transparent conductive film (71) constituting the two-layer amorphous transparent conductive film laminate (7) has at least one tetravalent metal element.
  • the total weight ratio (formula (B)) of the oxide is preferably indium oxide containing 25% by weight or less exceeding the total weight ratio of the second amorphous transparent conductive film (72) described below.
  • the second amorphous transparent conductive film (72) is made of indium oxide or an oxide of at least one tetravalent metal element in a total weight ratio represented by (formula (B)) of 10%. Indium oxide containing 1% to 6% by weight or less is preferable.
  • the oxide of the tetravalent metal element is preferably selected from tin oxide or titanium oxide.
  • the single-layer and crystalline transparent conductive film (8) preferably contains 16% by weight or less of the oxide of at least one tetravalent metal element in the total weight ratio represented by the formula (B).
  • the total weight ratio of the oxides of at least one tetravalent metal element contained in the single-layer and crystalline transparent conductive film (8) (formula (B)) is the first amorphous transparent conductive film ( 71) and a value based on the respective film thicknesses and the total weight ratio of the second amorphous transparent conductive film (72).
  • the total weight ratio of the oxides of at least one tetravalent metal element (formula (B)) contained in the single layer and crystalline transparent conductive film (8) is that a low surface resistance value can be obtained.
  • the content is preferably 25% by weight or less, more preferably 5 to 12% by weight.
  • the film thickness of the single-layer and crystalline transparent conductive film (8) is preferably 35 nm or less, more preferably 25 nm or less, considering the improvement in the visibility of the film capacitive touch panel.
  • the thickness of the second amorphous transparent conductive film (72) is preferably 10 nm or more.
  • the single-layer and crystalline transparent conductive film may be formed on one or both sides of the transparent film substrate of FIGS. 1 to 6 via an undercoat layer.
  • FIG. 7 shows a case where an amorphous transparent conductive film laminate (2) comprising two layers is formed on one side of a transparent film substrate (1) through an undercoat layer (9) as in FIG. ing. When this is heat-treated under predetermined conditions, as shown in FIG. 8, a single layer and crystalline transparent conductive film (6) is formed on one side of the transparent film substrate (1) as in FIG. 9).
  • the thickness of the transparent film substrate (4) is preferably in the range of 2 to 200 ⁇ m, more preferably in the range of 2 to 120 ⁇ m, and more preferably 2 in the application of the capacitive touch panel. It is preferable that the thickness is ⁇ 100 ⁇ m.
  • the thickness of the transparent film substrate (4) is less than 2 ⁇ m, the mechanical strength as a film is insufficient, and the transparent film substrate (4) is rolled to form a transparent conductive film laminate (2, 5 or 7)
  • the operation of continuously forming the undercoat layer (9) and the pressure-sensitive adhesive layer (10 in FIG. 9) may be difficult.
  • the transparent substrate (1) or transparent film substrate (4) is subjected to an etching treatment or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. on the surface in advance.
  • a transparent substrate (1) or a transparent film substrate (4) of an amorphous transparent conductive film laminate (2, 5 or 7) or an undercoat layer (9) comprising two layers provided thereon ) May be improved.
  • dust removal and cleaning can be performed by solvent cleaning or ultrasonic cleaning. May be.
  • the arithmetic average roughness Ra of the transparent substrate (1) or the transparent film substrate (4) is 1.0 nm or less on the surface on which the transparent conductive film laminate (2, 5, or 7) is formed. Preferably, it is 0.7 nm or less, more preferably 0.6 nm or less, and particularly preferably 0.5 nm or less.
  • the transparent conductive film laminate (2, 5 or 7) can be crystallized by heating for a relatively short time, and the crystallized single-layer and crystalline transparent conductive film (3, 6 or 8) can be low resistance.
  • the lower limit of the arithmetic average roughness Ra of the transparent substrate surface is not particularly limited, but is preferably 0.1 nm or more from the viewpoint of imparting winding property when the substrate is wound into a roll. More preferably, it is 2 nm or more.
  • the amorphous transparent conductive thin film laminate (2, 5 or 7) of the transparent film substrate (4) is used. It is preferable that an undercoat layer (9) is formed on the surface on the side on which is formed. Thereby, the surface unevenness
  • the transparent film substrate (4) having a predetermined surface roughness In the case of using, crystallization can be performed at a relatively low temperature or a short-time heat treatment.
  • the undercoat layer (9) shown in FIGS. 7 and 8 can be formed of an inorganic material, an organic material, or a mixture of an inorganic material and an organic material.
  • the inorganic substance for example, silicon oxide, magnesium fluoride, aluminum oxide and the like are preferably used.
  • organic substances include organic substances such as acrylic resins, urethane resins, melamine resins, alkyd resins, and siloxane polymers.
  • a thermosetting resin made of a mixture of a melamine resin, an alkyd resin, and an organosilane condensate as the organic substance.
  • the undercoat layer (9) can be formed using the above materials by a dry process such as a vacuum deposition method, a sputtering method, or an ion plating method, or a wet process (coating method).
  • the undercoat layer (9) may be a single layer or a plurality of layers of two or more layers.
  • the thickness of the undercoat layer (9) (in the case of a plurality of layers, the thickness of each layer) is preferably 300 nm or less.
  • An adhesive layer can be provided on the other surface of the transparent substrate (1) or the transparent film substrate (4).
  • FIG. 9 an example which provided the transparent adhesive layer (10) and the transparent adhesive layer (10) in the surface of the one side of the transparent film base material (4) of FIG. 4 is shown.
  • the transparent pressure-sensitive adhesive layer (10) can be used without particular limitation as long as it has transparency.
  • an acrylic pressure-sensitive adhesive is preferably used from the viewpoint that it is excellent in optical transparency, exhibits adhesive properties such as appropriate wettability, cohesiveness and adhesiveness, and is excellent in weather resistance and heat resistance.
  • the transparent pressure-sensitive adhesive layer (10) is scratch resistant to the transparent conductive film laminate (6) provided on one surface of the transparent substrate (1) or the transparent film substrate (4) due to its cushioning effect. And a touch point characteristic for touch panels, so-called pen input durability and surface pressure durability. From the viewpoint of better performing this function, it is desirable to set the elastic coefficient of the transparent pressure-sensitive adhesive layer (10) in the range of 1 to 100 N / cm 2 and the thickness in the range of 1 ⁇ m or more, usually 5 to 100 ⁇ m. When the thickness of the transparent pressure-sensitive adhesive layer (10) is less than 1 ⁇ m, the cushioning effect cannot be expected.
  • the manufacturing method of a transparent conductive base material is transparent which consists of two layers of the 1st and 2nd amorphous transparent conductive film on the single side
  • the first step is a step of once forming a two-layer amorphous transparent conductive film laminate by sputtering on one or both sides of a transparent substrate.
  • a DC magnetron sputtering method As a sputtering method to be applied, a DC magnetron sputtering method is preferable. From the viewpoint of realizing high-speed stable film formation, a dual magnetron sputtering method is also preferable. In addition, various magnetron sputtering methods such as a pulse magnetron sputtering method, an RF + DC magnetron sputtering method, and an RF magnetron sputtering method may be employed.
  • the target used for sputtering film formation is preferably an oxide sintered body target as exemplified in Patent Document 4.
  • Metal or alloy targets are possible, but productivity and controllability are poor.
  • the oxide sintered compact target is oxidized according to the composition of the single layer and crystalline transparent conductive film obtained after the heat treatment, that is, the composition of the two layers of amorphous transparent conductive film constituting the transparent conductive film laminate. Indium oxide or indium oxide containing at least one oxide of a divalent to hexavalent metal element is selected.
  • each oxide sintered compact target contains an oxide of a 2-6 hexavalent metal element, the content is appropriately controlled according to each composition of the target two-layer amorphous transparent conductive film. Is done.
  • Sputtering film formation using a sintered oxide target must be performed in a sputtering apparatus chamber that has been evacuated until a high vacuum level is reached.
  • a film is formed in a low vacuum chamber, the remaining water molecules have an adverse effect.
  • Water molecules in the atmosphere at the time of sputtering film formation act to terminate dangling bonds in an amorphous film containing indium oxide as a main component, and thus prevent crystal growth of the indium oxide phase. For this reason, it is preferable that the partial pressure of water in the film forming atmosphere is small.
  • the partial pressure of water in the sputtering film formation is preferably 0.1% or less, more preferably 0.07% or less with respect to the partial pressure of the argon gas.
  • the specific value of the partial pressure of water is preferably 2 ⁇ 10 ⁇ 4 Pa or less, more preferably 1.5 ⁇ 10 ⁇ 4 Pa or less, and 1 ⁇ 10 ⁇ 4 Pa or less. Is preferred.
  • the inside of the sputtering apparatus chamber is set to 2 ⁇ 10 ⁇ 4 Pa or less, preferably 1.5 ⁇ so that the partial pressure of water is in the above range before starting the film formation. It is preferable to evacuate to 10 ⁇ 4 Pa or less, more preferably 1 ⁇ 10 ⁇ 4 Pa or less, to create an atmosphere in which impurities such as moisture in the apparatus and organic gas generated from the substrate are removed.
  • the substrate temperature in the sputtering film formation preferably exceeds 100 ° C.
  • an amorphous film made of indium oxide having a large oxide content of a bivalent to hexavalent metal is crystallized into an indium oxide phase in a heat treatment step described later. Is easily promoted, and a single-layer and crystalline transparent conductive film is obtained.
  • the substrate temperature is 120 More preferably, it is 130 degreeC or more, It is more preferable that it is 130 degreeC or more, It is especially preferable that it is 140 degreeC or more.
  • the substrate temperature is preferably 250 ° C. or lower, but from the viewpoint of suppressing thermal damage to the transparent film substrate, 200 ° C. or lower is preferable, 180 ° C. or lower is more preferable, and 170 ° C. or lower is more preferable. A temperature of not higher than ° C is particularly preferred.
  • Sputtering film formation using an oxide sintered compact target is performed by reactive sputtering in which a rare gas and an oxygen gas, which are inert gases, and preferably a sputtering gas composed of an argon gas and an oxygen gas is introduced.
  • a rare gas and an oxygen gas which are inert gases
  • a sputtering gas composed of an argon gas and an oxygen gas is introduced.
  • sputtering film formation in which only argon gas is introduced may be performed.
  • FIG. 10 shows a change in specific resistance with respect to oxygen partial pressure of a transparent conductive film (hereinafter referred to as ITO 7.5) made of indium oxide containing 7.5% by weight of tin oxide having a thickness of 30 nm.
  • ITO 7.5 transparent conductive film
  • the ratio of the DC output to the sputtering target area, that is, the DC power density is about 1.1 W / cm 2 .
  • the specific resistance of ITO 7.5 shows a minimum value at an oxygen partial pressure of 6.9 ⁇ 10 ⁇ 3 Pa.
  • the oxygen partial pressure at which the specific resistance of the amorphous transparent conductive film shows a minimum value is defined as “optimal oxygen partial pressure”.
  • the specific resistance increases as the oxygen partial pressure decreases. This region is defined as an “oxygen partial pressure insufficient region”.
  • this region is defined as an “oxygen partial pressure excess region”.
  • the film is mostly formed in an optimum oxygen partial pressure or a slightly oxygen partial pressure excess region. The reason is to achieve both low specific resistance and high transmittance.
  • the “optimal oxygen partial pressure” tends to shift to a higher oxygen partial pressure side as the amount of tin oxide in ITO increases.
  • the shift is performed under a film forming condition of about 1.1 W / cm 2 with a low DC power density. Is not so noticeable.
  • the DC power density exceeds that, the shift becomes clear when the DC power density is about 3.4 W / cm 2 , for example.
  • At least one of the oxygen partial pressures in the sputtering film formation of the first and second amorphous transparent conductive films is lower than the optimum oxygen partial pressure, and the first It is preferable that the oxygen partial pressure in the sputtering film formation of the amorphous transparent conductive film is equal to or higher than the oxygen partial pressure in the sputtering film formation of the second amorphous transparent conductive film.
  • the oxygen partial pressure in the sputtering film formation of the first and second amorphous transparent conductive films is lower than the optimum oxygen partial pressure, and the first amorphous transparent conductive film
  • the oxygen partial pressure in the sputtering film formation is larger than the oxygen partial pressure in the sputtering film formation of the second amorphous transparent conductive film.
  • the average ratio of the oxygen partial pressure to the optimum oxygen partial pressure of the first amorphous transparent conductive film and the oxygen partial pressure to the optimum oxygen partial pressure of the second amorphous transparent conductive film is 18 to 91%. It is preferable that the film is formed by sputtering so as to be, more preferably 18 to 72%, and even more preferably 18 to 56%.
  • the average ratio of the oxygen partial pressure is the ratio of the oxygen partial pressure to the optimum oxygen partial pressure of the first amorphous transparent conductive film, and the optimum oxygen partial pressure of the second amorphous transparent conductive film. Means the arithmetic mean of the oxygen partial pressure ratios.
  • At least one of the oxygen partial pressures in the sputtering film formation of the first and second amorphous transparent conductive films is lower than the optimum oxygen partial pressure, and
  • the oxygen partial pressure when the first amorphous transparent conductive film is formed by sputtering is equal to or higher than the oxygen partial pressure when the second amorphous transparent conductive film is formed by sputtering.
  • the oxygen partial pressure for forming the first amorphous transparent conductive film is 6.3 ⁇ 10 ⁇ 3 Pa (about 91% of the optimum oxygen partial pressure).
  • the oxygen partial pressure when forming the second amorphous transparent conductive film is set to be lower than 6.3 ⁇ 10 ⁇ 3 Pa and lower than the optimum oxygen partial pressure.
  • the ratio of the oxygen partial pressure of the second amorphous transparent conductive film to the oxygen partial pressure of the first amorphous transparent conductive film is more preferably 85% or less.
  • the state in which the oxygen content of the transparent conductive film laminate is significantly reduced is unbalanced. Obtainable.
  • the transparent conductive film stack is heat-treated in an oxidizing atmosphere, for example, an atmosphere having an oxygen volume ratio of 20 to 100% in a second manufacturing process described later, the oxygen partial pressure inside and outside the transparent conductive film stack is determined.
  • the oxygen difference is increased, and oxygen diffusion is activated even at a low heat treatment temperature of 200 ° C. or less particularly in a transparent film substrate.
  • the diffusion of divalent to hexavalent metal elements constituting the oxide, particularly tetravalent tin and titanium is activated.
  • the first and second amorphous transparent conductive films constituting the transparent conductive film laminate are optimally used for the first and second amorphous transparent conductive films.
  • Sputtering is preferably carried out by setting the average ratio to 18 to 91% with respect to the oxygen partial pressure, more preferably 18 to 72%, and particularly preferably 18 to 56%. This makes it possible to crystallize the single-layer and crystalline transparent conductive film formed on the transparent substrate of the present invention at a lower temperature or in a shorter time, or to lower the surface resistance.
  • the first amorphous transparent conductive film constituting the transparent conductive film laminated body is set to an optimum oxygen partial pressure of the first amorphous transparent conductive film.
  • the second amorphous transparent conductive film layer is formed with respect to the optimum oxygen partial pressure of the second amorphous transparent conductive film. It is preferable to perform sputtering film formation at an oxygen partial pressure of 22 to 65%.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 60 to 122% with respect to the optimum oxygen partial pressure.
  • the ratio of 100% or more is preferably when the ratio of the DC power to the target area in sputtering film formation, that is, the DC power density is 1.4 W / cm 2 or less.
  • the ratio of the first amorphous transparent conductive film to the optimum oxygen partial pressure and the second amorphous transparent conductive film are promoted for promoting the formation of a single layer of the transparent conductive film laminate. It is preferable that the film is formed by sputtering so that the difference from the ratio to the optimum oxygen partial pressure is 3% or more, more preferably 5% or more, and further more preferably 10% or more. Preferably, it is 30% or more.
  • the present invention in order to crystallize a single-layer and crystalline transparent conductive film formed on a transparent substrate at a low temperature or in a short time, or to further reduce the surface resistance, It is effective to form the second amorphous transparent conductive film located on the surface side in the oxygen partial pressure insufficient region.
  • the oxygen diffusion is activated and the divalent to hexavalent valences constituting the oxide together therewith.
  • diffusion of metal elements, particularly tin and titanium is activated, in the present invention, the oxygen content of only the second amorphous transparent conductive film located on the surface side of the transparent conductive film laminate is reduced. In some cases, a more remarkable effect can be obtained.
  • the transparent conductive film laminated body in the present invention is heat-treated in an oxidizing atmosphere, particularly an atmosphere containing oxygen, in the second step.
  • the volume ratio of oxygen contained in the heat treatment atmosphere is preferably set to 20 to 100%.
  • the volume ratio of oxygen is more preferably set to 20 to 80%. This lower limit of 20% refers to the atmospheric atmosphere. That is, an atmosphere having a higher oxygen volume ratio than the air atmosphere is preferable. Therefore, in the second step, the two-layer amorphous transparent conductive film stack formed in the predetermined oxygen partial pressure deficient region in the first step is heat-treated in an atmosphere having a relatively high oxygen ratio. Thus, a single-layer and crystalline transparent conductive film can be obtained.
  • the temperature of the heat treatment is preferably in the range of heat resistance of the transparent substrate. From the viewpoint of reducing the thermal load in the production process, 250 ° C. or lower is preferable. Further, from the viewpoint of suppressing thermal damage to the transparent film substrate, 100 to 200 ° C. is preferable, 120 to 150 ° C. is more preferable, and 130 to 150 ° C. is further preferable. Depending on the type of substrate, the time is 30 to 120 minutes for resin films.
  • the amorphous transparent conductive film is formed using a general batch-type sputtering apparatus or a winding-type sputtering apparatus with a DC power of sputtering per target area, that is, a DC power density of 1.1 W / cm 2 ( It was carried out as Examples 1 to 12 and 21 to 25, Comparative Examples 1 to 7) or 3.4 w / cm 2 (Examples 13 to 20).
  • ⁇ Heat treatment> The heat treatment is performed in an atmosphere of air (oxygen volume ratio 20%), oxygen (oxygen volume ratio 100%) or nitrogen (oxygen volume ratio 0%) using a heat circulation oven or a heat treatment furnace capable of controlling the atmosphere, and the temperature is The test was carried out at 150 ° C. with the time controlled to 30 to 120 minutes. Table 1 summarizes the details of the sample preparation conditions.
  • ⁇ Film thickness> The film thickness of the undercoat layer and the transparent conductive film was measured by a stylus method using a surface shape measuring device Alpha-Step IQ manufactured by Tencor.
  • ⁇ Surface resistance value and specific resistance value> The surface resistance value and specific resistance value of the transparent conductive film were measured by a 4-terminal 4-probe method using a resistivity meter Loresta EP MCP-T360 manufactured by Mitsubishi Analytech.
  • ⁇ Single layer> Regarding the formation of a single layer of the transparent conductive film, the cross-sectional structure of the transparent conductive film after heat treatment was observed with a transmission electron microscope apparatus HF-2200 (TEM) manufactured by Hitachi High-Tech. It confirmed with the presence or absence of the interface originating in the electrically conductive film laminated body. At the same time, the composition distribution in the thickness direction of the transparent conductive film crystallized by heat treatment was examined using a NORAN EDS apparatus VANTAGE.
  • TEM transmission electron microscope apparatus
  • Example 1 As a transparent film substrate, a polyethylene terephthalate film (trade name: 50KBCHABB, hereinafter referred to as PET film) having a thickness of 50 ⁇ m and having hard coat (hereinafter referred to as HC) layers formed on both surfaces made by Kimoto was used. A silicon oxide film was formed as an undercoat layer on one surface of the film base so as to have a thickness of 30 nm.
  • PET film polyethylene terephthalate film having a thickness of 50 ⁇ m and having hard coat (hereinafter referred to as HC) layers formed on both surfaces made by Kimoto was used.
  • a silicon oxide film was formed as an undercoat layer on one surface of the film base so as to have a thickness of 30 nm.
  • a thin film (ITO 7.5) made of indium oxide containing 0.5 wt% was formed by sputtering to form a two-layer amorphous transparent conductive film laminate.
  • the optimum oxygen partial pressures of the first and second amorphous transparent conductive films were examined. At 1 W / cm 2 , all were 6.9 ⁇ 10 ⁇ 3 Pa.
  • the total gas pressure of the sputtering gas composed of a mixed gas of argon and oxygen was 0.3 Pa.
  • the oxygen partial pressure for forming the first and second amorphous transparent conductive films was made the same, and 2.1 ⁇ 10 ⁇ 3 Pa in the oxygen partial pressure insufficient region. These oxygen partial pressures are 30% in average ratio with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the temperature of the film substrate is stably maintained at 150 ° C., and the ultimate vacuum in the sputtering apparatus chamber is at least 1.0 to 2.0 ⁇ 10 ⁇ 4 Pa or less.
  • a film was formed by introducing a sputtering gas composed of argon and oxygen so as to achieve one of the above oxygen partial pressures.
  • the first and second amorphous transparent conductive films are adjusted to have a film thickness of 10 nm and 12 nm, respectively, and the total film thickness of the two-layer amorphous transparent conductive film stack is 22 nm. It was.
  • a transparent film substrate in which an amorphous transparent conductive film laminate composed of two layers is formed on the undercoat layer, that is, the transparent conductive substrate is taken out from the sputtering apparatus chamber, and then heated in a hot air circulation oven. An atmospheric heat treatment at 150 ° C. was performed for 60 minutes. The oxygen volume ratio in the atmosphere is 20%. The film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • Example 1 the oxygen partial pressures for forming the first and second amorphous transparent conductive films were the same, and 2.1 ⁇ 10 ⁇ 3 Pa in the oxygen partial pressure deficient region. The pressures were set to 3.0 ⁇ 10 ⁇ 3 Pa (Example 2), 4.5 ⁇ 10 ⁇ 3 Pa (Example 3), and 6.3 ⁇ 10 ⁇ 3 Pa (Example 4).
  • a transparent conductive substrate was produced in the same manner as in Example 1. These oxygen partial pressures are 43%, 65%, and 91% in average ratios when the first and second amorphous transparent conductive films are both at the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the oxygen partial pressure is an optimum oxygen partial pressure of 6.9 ⁇ 10 ⁇ 3 Pa (Examples 5 and 6), and the second amorphous transparent conductive film Example 1 except that the oxygen partial pressure was changed to 1.5 ⁇ 10 ⁇ 3 Pa (Example 5) and 3.0 ⁇ 10 ⁇ 3 Pa (Example 6) in the oxygen partial pressure deficient region.
  • a transparent conductive substrate was prepared.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 100% (Examples 5 and 6) with respect to the optimum oxygen partial pressure.
  • the oxygen partial pressure is 22% (Example 5) and 43% (Example 6) with respect to the optimum oxygen partial pressure, and both the first and second amorphous transparent conductive films are at the optimum oxygen partial pressure.
  • the average ratio is 61% and 72%.
  • Example 7 The first amorphous transparent conductive film is formed into a thin film made of indium oxide containing 7.5% by weight of tin oxide having a thickness of 12 nm, and the second amorphous transparent conductive film is oxidized to a thickness of 10 nm.
  • a thin film made of indium oxide containing 2% by weight of tin was used, and a transparent conductive substrate was produced in the same manner as in Example 1.
  • the first amorphous transparent conductive film and the second amorphous transparent conductive film were made upside down with respect to Examples 1 to 4, and the oxygen in the first amorphous transparent conductive film
  • the optimum partial pressure of oxygen is 6.9 ⁇ 10 ⁇ 3 Pa (Examples 7 and 8), and the oxygen partial pressure excess region is 8.4 ⁇ 10 ⁇ 3 Pa (Example 9).
  • the oxygen partial pressure of the transparent conductive film was 1.5 ⁇ 10 ⁇ 3 Pa (Example 7) and 3.0 ⁇ 10 ⁇ 3 Pa (Examples 8 and 9) in the oxygen partial pressure deficient region
  • a transparent conductive substrate was produced in the same manner as in Example 1.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 100% (Examples 7 and 8) and 122% (Example 9) with respect to the optimum oxygen partial pressure.
  • the oxygen partial pressure of the amorphous transparent conductive film is 22% (Example 7) and 43% (Examples 8 and 9) with respect to the optimum oxygen partial pressure.
  • the average ratio is 61%, 72%, and 83% with respect to the case where the transparent conductive film has an optimal oxygen partial pressure.
  • Tables 1 and 2 The film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is formed into a thin film made of indium oxide containing 3.3% by weight of tin oxide with a thickness of 15 nm, and the second amorphous transparent conductive film is oxidized with a thickness of 10 nm.
  • the thin film was made of indium oxide containing 10% by weight of tin.
  • the optimum oxygen partial pressure of the second amorphous transparent conductive film was examined, it was 6.9 ⁇ 10 ⁇ 3 Pa at a DC power density of 1.1 W / cm 2 .
  • the oxygen partial pressure of the first amorphous transparent conductive film is 3.0 ⁇ 10 ⁇ 3 Pa (Example 10) in the region where oxygen partial pressure is insufficient and the optimum oxygen partial pressure is 6.9 ⁇ 10 ⁇ 3 Pa (implemented).
  • Example 11 except that the oxygen partial pressure of the second amorphous transparent conductive film was changed to 3.0 ⁇ 10 ⁇ 3 Pa (Examples 10 and 11) in the oxygen partial pressure insufficient region.
  • a transparent conductive substrate was prepared in the same manner as in 1.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 43% (Example 10) and 100% (Example 11) with respect to the optimum oxygen partial pressure.
  • the oxygen partial pressure of the transparent conductive film is 43% (Examples 10 and 11) with respect to the optimum oxygen partial pressure, and both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the average ratio is 43% and 72%.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is a thin film made of indium oxide containing 10% by weight of tin oxide having a thickness of 10 nm.
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 15 nm.
  • the oxygen partial pressure of the first amorphous transparent conductive film was changed to a thin film made of indium oxide containing 3.3% by weight, and the oxygen partial pressure was 6.9 ⁇ 10 ⁇ 3 Pa, the second A transparent conductive substrate was produced in the same manner as in Examples 1 to 4, except that the oxygen partial pressure of the amorphous transparent conductive film was changed to 3.0 ⁇ 10 ⁇ 3 Pa in the oxygen partial pressure deficient region. .
  • the oxygen partial pressure of the first amorphous transparent conductive film is 100% of the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure.
  • the average ratio is 72% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the first amorphous transparent conductive film is made of indium oxide containing 21% by weight of tin oxide having a thickness of 20 nm
  • the second amorphous transparent conductive film is made of indium oxide having a thickness of 15 nm.
  • a transparent conductive substrate was produced in the same manner as in Examples 1 to 4, except that the thin film was changed to a thin film and the DC power density was changed to 3.4 W / cm 2 .
  • the optimum oxygen partial pressures of the first and second amorphous transparent conductive films were examined, they were 1.5 ⁇ 10 ⁇ 2 Pa and 9.0 ⁇ 10 ⁇ 3 Pa, respectively.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 60% with respect to the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is with respect to the optimum oxygen partial pressure. 30%, and the average ratio is 45% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is made of indium oxide containing 25% by weight of tin oxide having a thickness of 20 nm
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 15 nm.
  • a transparent conductive substrate was produced in the same manner as in Examples 1 to 4, except that the thin film was made of indium oxide containing 3.3 wt%, and the DC power density was changed to 3.4 W / cm 2 .
  • the optimum oxygen partial pressures of the first and second amorphous transparent conductive films were examined, they were 1.5 ⁇ 10 ⁇ 2 Pa and 9.0 ⁇ 10 ⁇ 3 Pa, respectively.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 60% with respect to the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is with respect to the optimum oxygen partial pressure. 30%, and the average ratio is 45% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is a thin film made of indium oxide containing 10% by weight of tin oxide having a thickness of 10 nm.
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 20 nm.
  • Transparent conductive substrates were prepared in the same manner as in Examples 1 to 4, except that the thin film was made of indium oxide containing 7.5% by weight, and the DC power density was changed to 3.4 W / cm 2 . When the optimum oxygen partial pressures of the first and second amorphous transparent conductive films were examined, both were 1.5 ⁇ 10 ⁇ 2 Pa.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 60% of the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 50% with respect to the partial pressure, and the average ratio is 55% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is formed into a thin film made of indium oxide containing 7.5% by weight of tin oxide having a thickness of 10 nm, and the second amorphous transparent conductive film is oxidized to a thickness of 20 nm.
  • a thin film composed of indium oxide containing 7.5% by weight of tin that is, a film configuration having the same composition as that of Example 15 and that the DC power density was changed to 3.4 W / cm 2.
  • Transparent conductive substrates were prepared in the same manner as in Examples 1 to 4.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 60% of the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 50% with respect to the partial pressure, and the average ratio is 55% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is a thin film made of indium oxide containing 10% by weight of tin oxide having a thickness of 10 nm.
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 25 nm.
  • a transparent conductive substrate was prepared in the same manner as in Examples 1 to 4, except that the DC power density was changed to 3.4 W / cm 2 on a thin film made of indium oxide containing 10% by weight.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 60% of the optimum oxygen partial pressure, and the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure.
  • the first amorphous transparent conductive film is a thin film made of indium oxide containing 10% by weight of tin oxide having a thickness of 10 nm.
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 15 nm.
  • a transparent conductive substrate was produced in the same manner as in Examples 1 to 4, except that the thin film was made of indium oxide containing 3.3 wt%, and the DC power density was changed to 3.4 W / cm 2 .
  • the optimum oxygen partial pressures of the first and second amorphous transparent conductive films were 1.5 ⁇ 10 ⁇ 2 Pa and 9.0 ⁇ 10 ⁇ 3 Pa, respectively, as described in Examples 14 and 15. It was.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 40% of the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 33% with respect to the partial pressure, and the average ratio is 37% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is made of indium oxide containing 10% by weight of tin oxide having a thickness of 15 nm
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 10 nm.
  • a transparent conductive substrate was produced in the same manner as in Examples 1 to 4, except that the thin film was made of indium oxide containing 3.3 wt%, and the DC power density was changed to 3.4 W / cm 2 . Since only the film thickness configuration of Example 18 was changed, the optimum oxygen partial pressures of the first and second amorphous transparent conductive films were 1.5 ⁇ 10 ⁇ 2 Pa and 9.0 ⁇ 10 respectively. -3 Pa.
  • the oxygen partial pressure of the first amorphous transparent conductive film was 40% of the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film was Is 33% with respect to the optimum oxygen partial pressure, and 37% in average ratio with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is a thin film made of indium oxide containing 10% by weight of tin oxide having a thickness of 10 nm.
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 15 nm.
  • a transparent conductive substrate was produced in the same manner as in Examples 1 to 4, except that the thin film was made of indium oxide containing 3.3 wt%, and the DC power density was changed to 3.4 W / cm 2 .
  • the optimum oxygen partial pressures of the first and second amorphous transparent conductive films are 1.5 ⁇ 10 ⁇ 2 Pa and 9.0 ⁇ 10 ⁇ 3 Pa, respectively, as in Example 18.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 20% with respect to the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure.
  • the average ratio is 17% with respect to the case where the first and second amorphous transparent conductive films are both at the optimum oxygen partial pressure.
  • the first amorphous transparent conductive film is a thin film made of indium oxide containing 12% by weight of tin oxide having a thickness of 10 nm.
  • the second amorphous transparent conductive film is made of titanium oxide having a thickness of 15 nm.
  • a transparent conductive substrate was prepared in the same manner as in Examples 1 to 4 except that the thin film was made of indium oxide containing 1% by weight.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 70% with respect to the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 41% with respect to the partial pressure, and the average ratio is 56% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is made of indium oxide containing 12% by weight of tin oxide having a thickness of 10 nm
  • the second amorphous transparent conductive film is made of gallium oxide having a thickness of 15 nm.
  • a transparent conductive substrate was prepared in the same manner as in Examples 1 to 4 except that the thin film was made of indium oxide containing 1.5% by weight.
  • the optimal oxygen partial pressure of the first amorphous transparent conductive film at a DC power density of 1.1 W / cm 2 is 8.1 ⁇ 10 ⁇ 3 Pa, which is the same as in Example 21, and the second amorphous transparent conductive film
  • the optimum oxygen partial pressure of the conductive film was examined and found to be 7.5 ⁇ 10 ⁇ 3 Pa.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 70% with respect to the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 40% with respect to the partial pressure, and the average ratio is 55% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is a thin film made of indium oxide containing 12% by weight of tin oxide having a thickness of 10 nm
  • the second amorphous transparent conductive film is made of tungsten oxide having a thickness of 15 nm.
  • a transparent conductive substrate was prepared in the same manner as in Examples 1 to 4 except that the thin film was made of indium oxide containing 1% by weight.
  • the optimal oxygen partial pressure of the first amorphous transparent conductive film at a DC power density of 1.1 W / cm 2 is 8.1 ⁇ 10 ⁇ 3 Pa, which is the same as in Example 21, and the second amorphous transparent conductive film
  • the optimum oxygen partial pressure of the conductive film was examined and found to be 6.0 ⁇ 10 ⁇ 3 Pa.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 70% with respect to the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 35% with respect to the partial pressure, and the average ratio is 53% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • Tables 1 and 2 The film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is made of a thin film made of indium oxide containing 12% by weight of tin oxide having a thickness of 10 nm
  • the second amorphous transparent conductive film is made of zinc oxide having a thickness of 15 nm.
  • a transparent conductive substrate was prepared in the same manner as in Examples 1 to 4 except that the thin film was made of indium oxide containing 1% by weight.
  • the optimal oxygen partial pressure of the first amorphous transparent conductive film at a DC power density of 1.1 W / cm 2 is 8.1 ⁇ 10 ⁇ 3 Pa, which is the same as in Example 21, and the second amorphous transparent conductive film
  • the optimum oxygen partial pressure of the conductive film was examined and found to be 7.5 ⁇ 10 ⁇ 3 Pa.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 70% with respect to the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 40% with respect to the partial pressure, and the average ratio is 55% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • Tables 1 and 2 The film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • Example 25 A transparent conductive substrate was produced in exactly the same manner as in Example 8, except that the atmosphere and time for heat treatment of the obtained amorphous transparent conductive film laminate were changed to oxygen and 30 minutes. In this case, the oxygen volume ratio of the heat treatment atmosphere is 100%. The film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the oxygen partial pressure of the first amorphous transparent conductive film is set to 6.0 ⁇ 10 ⁇ 4 Pa (Comparative Example 1) in the region where oxygen partial pressure is insufficient, and the optimal oxygen partial pressure is 6.9 ⁇ 10 ⁇ 3 Pa (Comparative Example). 2) 8.4 ⁇ 10 ⁇ 3 Pa (Comparative Example 3) and 9.0 ⁇ 10 ⁇ 3 Pa (Comparative Example 4) in the oxygen partial pressure excess region, the oxygen content of the second amorphous transparent conductive film
  • the pressure was 6.0 ⁇ 10 ⁇ 4 Pa (Comparative Example 1) in the oxygen partial pressure insufficient region, the optimum oxygen partial pressure 6.9 ⁇ 10 ⁇ 3 Pa (Comparative Example 2), and the oxygen partial pressure excessive region 8.4 ⁇ .
  • Transparent conductive substrates were produced in the same production steps as in Examples 1 to 4 except that the pressure was changed to 10 ⁇ 3 Pa (Comparative Examples 3 and 4). In this case, the DC power density was 1.1 W / cm 2 under the same conditions as in Examples 1 to 4.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 9% (Comparative Example 1), 100% (Comparative Example 2), 122% (Comparative Example 3) with respect to the optimum oxygen partial pressure.
  • the oxygen partial pressure of the second amorphous transparent conductive film is 9% (Comparative Example 1), 100% (Comparative Example 2), 122% (Comparative Examples 3 and 4), and 9%, 100%, 122%, and 126 in average ratios when the first and second amorphous transparent conductive films are both at the optimum oxygen partial pressure. %.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • the first amorphous transparent conductive film is made of indium oxide containing 2% by weight of tin oxide having a thickness of 15 nm
  • the second amorphous transparent conductive film is made of tin oxide having a thickness of 10 nm.
  • a transparent conductive substrate was prepared by changing to a thin film made of indium oxide containing 40% by weight. In this case, the DC power density was 1.1 W / cm 2 under the same conditions as in Examples 1 to 4.
  • the optimum oxygen partial pressure of the second amorphous transparent conductive film was examined prior to forming the above-mentioned two-layer amorphous transparent conductive film laminate. As a result, 1.2 ⁇ 10 ⁇ 2 Pa Met.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 6.9 ⁇ 10 ⁇ 3 Pa, which is the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is oxygen It was set to 9.0 ⁇ 10 ⁇ 3 Pa in the partial pressure insufficient region.
  • a transparent conductive substrate was produced in the same manner as in Example 1 except for the conditions described above.
  • the oxygen partial pressure of the first amorphous transparent conductive film is 100% of the optimum oxygen partial pressure
  • the oxygen partial pressure of the second amorphous transparent conductive film is the optimum oxygen partial pressure. It is 75% with respect to the partial pressure, and the average ratio is 88% with respect to the case where both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • Example 6 A transparent conductive substrate was produced in the same manner as in Example 1 except that the atmosphere for heat treatment of the obtained amorphous transparent conductive film laminate was changed to nitrogen. In this case, the oxygen volume ratio in the heat treatment atmosphere is 0%. The film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • Example 7 A transparent conductive substrate was produced in exactly the same manner as in Example 1, except that the oxygen partial pressure of the second amorphous transparent conductive film was changed to 3.0 ⁇ 10 ⁇ 3 Pa.
  • the oxygen partial pressure of the second amorphous transparent conductive film is 43% of the optimum oxygen partial pressure, and both the first and second amorphous transparent conductive films have the optimum oxygen partial pressure.
  • the average ratio is 37%.
  • the film thickness, surface resistance value and specific resistance value, and presence / absence of crystallization of the transparent conductive substrate thus obtained were examined, and the results are shown in Tables 1 and 2.
  • At least one of the two amorphous transparent conductive films constituting the transparent conductive film laminate contains tetravalent tin oxide.
  • Sputtering film formation under the conditions of indium oxide to be used tin oxide content of the two-layer amorphous transparent conductive film is in the range of 0 to 10% by weight, and DC power density is 1.1 W / cm 2 It is common to implement.
  • the difference between Examples 1 to 12 and Comparative Examples 1 to 4 is that the oxygen partial pressure is different when two amorphous transparent conductive films are formed by sputtering.
  • the oxygen partial pressure of the first amorphous transparent conductive film with respect to the optimum oxygen partial pressure of the first amorphous transparent conductive film and the second amorphous transparent conductive film is in the range of 30 to 91%. For this reason, in Examples 1 to 12, crystallization was performed even by heat treatment in air at 150 ° C. for 60 minutes, and a low surface resistance value suitable for capacitive touch panel applications and the like was obtained.
  • Comparative Example 1 the average ratio was not in the range of 30 to 91% but was as low as 9%. For this reason, it is not crystallized even by atmospheric heat treatment at 150 ° C. for 60 minutes, and the surface resistance value is high.
  • Comparative Examples 2 to 4 unlike Examples 1 to 12, the average ratio is a high condition of 100% or more, which exceeds the above range. For this reason, it is not crystallized even by atmospheric heat treatment at 150 ° C. for 60 minutes, and the surface resistance value is high.
  • the content of one tetravalent tin oxide of the two amorphous transparent conductive films constituting the transparent conductive film laminate is 21 wt% or 25 wt%. Sputtered film was formed under the condition of DC power density of 3.4 W / cm 2 and crystallized sufficiently after atmospheric heat treatment at 150 ° C. for 60 minutes, resulting in a low surface resistance value suitable for capacitive touch panel applications. It has been.
  • the content of one tetravalent tin oxide of the two amorphous transparent conductive films constituting the transparent conductive film laminate is 40% by weight, and 25% by weight. Over. For this reason, it is not crystallized even by atmospheric heat treatment at 150 ° C. for 60 minutes, and the surface resistance value is high.
  • the tin oxide content of the two amorphous transparent conductive films constituting the transparent conductive film laminate was 3.3 to 10% by weight, and the DC power density was 3.4 W / cm.
  • Sputtering film formation is performed under the conditions of 2 .
  • the ratio of the oxygen partial pressure of the first amorphous transparent conductive film to the optimum oxygen partial pressure of the first amorphous transparent conductive film is 60 to 122.
  • one of the two amorphous transparent conductive films constituting the transparent conductive film laminate was not tetravalent tin oxide, but tetravalent titanium oxide, trivalent gallium oxide, Hexavalent tungsten oxide or divalent zinc oxide is used. Sputtered films were formed under the same conditions as in Examples 1 to 12, and then crystallized sufficiently by atmospheric heat treatment at 150 ° C. for 60 minutes, resulting in a low surface resistance value suitable for capacitive touch panel applications. ing.
  • Example 25 after sputtering film formation under the same conditions as in Example 8, heat treatment was performed at 150 ° C. in an oxygen atmosphere. As a result, it has been sufficiently crystallized in an atmospheric heat treatment time of 30 minutes, and a low surface resistance value suitable for capacitive touch panel applications and the like has been obtained.
  • Comparative Example 6 as in Example 25, after sputtering film formation under the same conditions as in Example 8, heat treatment was performed at 150 ° C. in a nitrogen atmosphere. Since the volume ratio of oxygen contained in the heat treatment atmosphere is 0%, it is not crystallized and has a high surface resistance.
  • Comparative Example 7 when the oxygen partial pressure of the second amorphous transparent conductive film is higher than the oxygen partial pressure of the first amorphous transparent conductive film, it is not crystallized and the surface resistance The value is high.
  • Example 1 to 25 the cross-sectional structure of the transparent conductive film after the heat treatment was observed by TEM. As a result, in all of Examples 1 to 25, the layered body interface did not exist and was formed into a single layer. In the cross-sectional TEM image of the transparent conductive film after the heat treatment of Example 2 shown in FIG. 11, it is confirmed that the lattice stripes have reached the interface with the undercoat layer from the transparent conductive film surface, so that the single layer is formed. Is done. Further, as a result of examining the composition distribution in the film thickness direction of the cross section of the transparent conductive film after the heat treatment of Example 2 by EDS analysis shown in FIG. Since the composition in the vicinity of the average content is taken, it is considered that the composition is close to monolayering.
  • Comparative Examples 1 to 7 were subjected to the same TEM observation, but were not crystallized or remained in two layers.
  • the thin film made of indium oxide containing 2% by weight of tin oxide formed as the first amorphous transparent conductive film is crystallized.
  • the transparent conductive base material of the present invention has a single layer and a crystalline structure formed by the heat treatment under the predetermined conditions by the production method of the present invention. It is clear that a transparent conductive film is formed.
  • the transparent conductive substrate of the present invention can be used for a capacitive touch panel for smartphones and tablet PCs because a high-quality transparent conductive film having a low crystallinity is formed on the substrate.
  • SYMBOLS 1 Amorphous transparent electrically conductive film laminated body 3, 6, 8 which consists of 2 layers of transparent base materials 2, 5, 7 Single layer and crystalline transparent conductive film 4 Transparent film base material 9 Undercoat layer 10 Adhesive Layers 11 to 14 Transparent conductive films 21, 51, 71 First amorphous transparent conductive film 22, 52, 72 Second amorphous transparent conductive film

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
  • Physical Vapour Deposition (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

La présente invention a pour objet de réaliser un film électroconducteur transparent, dans lequel un film électroconducteur transparent obtenu en amenant une structure à deux couches en une couche simple est formé sur un substrat en film transparent, et de réaliser un procédé de production pour amener un stratifié de film électroconducteur transparent à deux couches en une seule couche. L'invention réalise à cet effet un substrat électroconducteur transparent dans lequel un film électroconducteur transparent cristallin monocouche comprenant de l'oxyde d'indium et contenant un oxyde d'au moins un type d'élément métallique bivalent à hexavalent est formé sur une surface ou sur les deux surfaces d'un substrat transparent, le substrat électroconducteur transparent étant caractérisé en ce que : le film électroconducteur transparent est réalisé en formant un premier film électroconducteur transparent amorphe et un deuxième film électroconducteur transparent amorphe dans cet ordre sous la forme de deux couches, et en soumettant ensuite le stratifié de film électroconducteur transparent obtenu à un traitement thermique; le pourcentage massique total du ou des oxydes du ou des éléments métalliques bivalents à hexavalents dans le premier film électroconducteur transparent amorphe est différent de celui du deuxième film électroconducteur transparent amorphe; et le pourcentage massique total du ou des oxydes du ou des éléments métalliques bivalents à hexavalents dans le film électroconducteur transparent cristallin est inférieur ou égal à 16 % massiques.
PCT/JP2014/051268 2013-01-24 2014-01-22 Substrat électroconducteur transparent et son procédé de production WO2014115770A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014558595A JPWO2014115770A1 (ja) 2013-01-24 2014-01-22 透明導電性基材ならびにその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013010695 2013-01-24
JP2013-010695 2013-01-24

Publications (1)

Publication Number Publication Date
WO2014115770A1 true WO2014115770A1 (fr) 2014-07-31

Family

ID=51227561

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/051268 WO2014115770A1 (fr) 2013-01-24 2014-01-22 Substrat électroconducteur transparent et son procédé de production

Country Status (3)

Country Link
JP (1) JPWO2014115770A1 (fr)
TW (1) TW201438921A (fr)
WO (1) WO2014115770A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015166963A1 (fr) * 2014-04-30 2015-11-05 日東電工株式会社 Film conducteur transparent, et procédé de fabrication de celui-ci
WO2016031746A1 (fr) * 2014-08-25 2016-03-03 東洋紡株式会社 Film polymère revêtu par une couche d'agent de couplage au silane
WO2016088807A1 (fr) * 2014-12-05 2016-06-09 日東電工株式会社 Film électroconducteur transparent et capteur tactile dans lequel celui-ci est utilisé
WO2016092902A1 (fr) * 2014-12-09 2016-06-16 リンテック株式会社 Film conducteur transparent et procédé de production d'un film conducteur transparent
WO2017010419A1 (fr) * 2015-07-10 2017-01-19 東洋紡株式会社 Corps stratifié et son procédé de fabrication
JP2019016446A (ja) * 2017-07-04 2019-01-31 日東電工株式会社 透明導電性フィルム及びタッチパネル
US10303284B2 (en) 2014-04-30 2019-05-28 Nitto Denko Corporation Transparent conductive film and method for producing the same
CN113366354A (zh) * 2019-01-31 2021-09-07 日东电工株式会社 聚酯薄膜、及包含该聚酯薄膜的偏光板
CN114007856A (zh) * 2019-06-27 2022-02-01 日东电工株式会社 透明导电性薄膜
JP7505865B2 (ja) 2019-07-23 2024-06-25 Tdk株式会社 透明導電体及び有機デバイス
JP7509690B2 (ja) 2019-06-27 2024-07-02 日東電工株式会社 結晶化インジウムスズ複合酸化物膜、透明導電性フィルムおよびその製造方法

Citations (9)

* Cited by examiner, † Cited by third party
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
JPH09226046A (ja) * 1996-02-22 1997-09-02 Mitsui Toatsu Chem Inc 透明導電性積層体及びその製造方法
JP2008071531A (ja) * 2006-09-12 2008-03-27 Nitto Denko Corp 透明導電性積層体及びそれを備えたタッチパネル
JP2008210613A (ja) * 2007-02-26 2008-09-11 Toppan Printing Co Ltd 透明導電性積層体及びそれを用いた表示装置
WO2008123420A1 (fr) * 2007-03-30 2008-10-16 Mitsui Mining & Smelting Co., Ltd. Procédé de fabrication d'un film électroconducteur transparent de type à oxyde d'indium
JP2009224152A (ja) * 2008-03-14 2009-10-01 Sumitomo Metal Mining Co Ltd 透明電極、透明導電性基板および透明タッチパネル
JP2012112031A (ja) * 2010-11-05 2012-06-14 Nitto Denko Corp 透明導電性フィルムの製造方法
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
JP2012134085A (ja) * 2010-12-24 2012-07-12 Nitto Denko Corp 透明導電性フィルムおよびその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
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
JPH09226046A (ja) * 1996-02-22 1997-09-02 Mitsui Toatsu Chem Inc 透明導電性積層体及びその製造方法
JP2008071531A (ja) * 2006-09-12 2008-03-27 Nitto Denko Corp 透明導電性積層体及びそれを備えたタッチパネル
JP2008210613A (ja) * 2007-02-26 2008-09-11 Toppan Printing Co Ltd 透明導電性積層体及びそれを用いた表示装置
WO2008123420A1 (fr) * 2007-03-30 2008-10-16 Mitsui Mining & Smelting Co., Ltd. Procédé de fabrication d'un film électroconducteur transparent de type à oxyde d'indium
JP2009224152A (ja) * 2008-03-14 2009-10-01 Sumitomo Metal Mining Co Ltd 透明電極、透明導電性基板および透明タッチパネル
JP2012112031A (ja) * 2010-11-05 2012-06-14 Nitto Denko Corp 透明導電性フィルムの製造方法
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
JP2012134085A (ja) * 2010-12-24 2012-07-12 Nitto Denko Corp 透明導電性フィルムおよびその製造方法

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US10303284B2 (en) 2014-04-30 2019-05-28 Nitto Denko Corporation Transparent conductive film and method for producing the same
WO2015166963A1 (fr) * 2014-04-30 2015-11-05 日東電工株式会社 Film conducteur transparent, et procédé de fabrication de celui-ci
WO2016031746A1 (fr) * 2014-08-25 2016-03-03 東洋紡株式会社 Film polymère revêtu par une couche d'agent de couplage au silane
US10857762B2 (en) 2014-08-25 2020-12-08 Toyobo Co., Ltd. Polymer film coated with a layer of silane coupling agent
JPWO2016031746A1 (ja) * 2014-08-25 2017-06-15 東洋紡株式会社 シランカップリング剤層積層高分子フィルム
US10217543B2 (en) 2014-12-05 2019-02-26 Nitto Denko Corporation Transparent electroconductive film and touch sensor in which same is used
WO2016088807A1 (fr) * 2014-12-05 2016-06-09 日東電工株式会社 Film électroconducteur transparent et capteur tactile dans lequel celui-ci est utilisé
JP2016110831A (ja) * 2014-12-05 2016-06-20 日東電工株式会社 透明導電性フィルムおよびそれを用いたタッチセンサ
WO2016092902A1 (fr) * 2014-12-09 2016-06-16 リンテック株式会社 Film conducteur transparent et procédé de production d'un film conducteur transparent
JPWO2016092902A1 (ja) * 2014-12-09 2017-09-21 リンテック株式会社 透明導電膜及び透明導電膜の製造方法
WO2017010419A1 (fr) * 2015-07-10 2017-01-19 東洋紡株式会社 Corps stratifié et son procédé de fabrication
JPWO2017010419A1 (ja) * 2015-07-10 2018-06-14 東洋紡株式会社 積層体およびその製造方法
TWI717369B (zh) * 2015-07-10 2021-02-01 日商東洋紡股份有限公司 疊層體及其製造方法
JP2019016446A (ja) * 2017-07-04 2019-01-31 日東電工株式会社 透明導電性フィルム及びタッチパネル
CN113366354A (zh) * 2019-01-31 2021-09-07 日东电工株式会社 聚酯薄膜、及包含该聚酯薄膜的偏光板
CN113474689A (zh) * 2019-01-31 2021-10-01 日东电工株式会社 聚酯薄膜、及包含该聚酯薄膜的偏光板
CN114007856A (zh) * 2019-06-27 2022-02-01 日东电工株式会社 透明导电性薄膜
JP7492916B2 (ja) 2019-06-27 2024-05-30 日東電工株式会社 透明導電性フィルム
JP7509690B2 (ja) 2019-06-27 2024-07-02 日東電工株式会社 結晶化インジウムスズ複合酸化物膜、透明導電性フィルムおよびその製造方法
JP7505865B2 (ja) 2019-07-23 2024-06-25 Tdk株式会社 透明導電体及び有機デバイス

Also Published As

Publication number Publication date
JPWO2014115770A1 (ja) 2017-01-26
TW201438921A (zh) 2014-10-16

Similar Documents

Publication Publication Date Title
WO2014115770A1 (fr) Substrat électroconducteur transparent et son procédé de production
TWI381401B (zh) Transparent conductive film and manufacturing method thereof
TW201233827A (en) Transparent electroconductive film and manufacturing method therefor
Ren et al. Highly transparent conductive ITO/Ag/ITO trilayer films deposited by RF sputtering at room temperature
JP2011134464A (ja) 透明導電性積層体およびその製造方法ならびにタッチパネル
TW201301310A (zh) 導電膜用素材、導電膜積層體、電子機器及其等之製造方法
JP6524068B2 (ja) 透明導電フィルムおよびその製造方法
TW201539276A (zh) 透明導電體及觸控面板
KR101959712B1 (ko) 적외선 흡수층을 포함하는 광학 필름
CN109778129B (zh) 一种基于超薄金属的透明导电薄膜
CN105845752B (zh) 一种应用于柔性光电器件的透明导电薄膜及其制备方法
JP2001121641A (ja) 透明導電積層体
KR20150075173A (ko) 투명 전도성 산화물과 은 나노 와이어를 포함하는 투명 전극 및 그 제조방법
JP2005071901A (ja) 透明導電性積層フィルム
WO2015159805A1 (fr) Stratifié, stratifié conducteur, et dispositif électronique
WO2011093274A1 (fr) Substrat présentant une structure multicouche conductrice transparente et son procédé de fabrication
JPH06251632A (ja) 屈曲性に優れた透明導電性フィルムおよびその製造法
JP6356520B2 (ja) 透明電極付き基板及びその製造方法
JP6404064B2 (ja) 透明導電性フィルム及びその製造方法
WO2020189229A1 (fr) Procédé de fabrication d'un substrat sur lequel sont fixées des électrodes transparentes
WO2015186507A1 (fr) Film conducteur transparent
TWI824213B (zh) 可撓式透明導電複合膜及其製造方法
JP2010168647A (ja) 導電性薄膜の前駆薄膜及び該薄膜から得られる透明導電性薄膜
JPH06251631A (ja) 平坦性に優れた透明導電性フィルムおよびその製造法
KR20170021619A (ko) AZO/Ag/AZO 다층박막 구조를 갖는 플렉시블 투명 전극 및 그 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14742771

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014558595

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14742771

Country of ref document: EP

Kind code of ref document: A1