JP2006236747A - Transparent electrode and manufacturing method of transparent electrode - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent electrode, and a manufacturing method of the transparent electrode, excellent in etching properties, and enjoying a low resistance value, high transmittance, and excellent surface smoothness. <P>SOLUTION: The transparent electrode has transparent high-refractive-index layers and metal particles alternately laminated on a transparent base material with a total film thickness of 30 nm or more and 100 nm or less, a surface resistance value of 1Ω/sq. or more and 13Ω/sq. or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transparent electrode having a transparent conductive film having improved etching properties, low resistance, high transmittance, and good surface smoothness, and a method for producing the same.

The transparent conductive film is an article having high conductivity despite being transparent. Examples of the transparent conductive film include metal films such as Pt, Au, Ag, and Cu, SnO ₂ , In ₂ O ₃ , CdO, ZnO, There are oxides such as Sb-doped SnO ₂ , F-doped SnO ₂ , Al-doped ZnO, Sn-doped In ₂ O ₃ or complex oxide films with dopants, non-oxides such as chalcogenide, LaB ₆ , TiN, and TiC. Among them, an indium oxide film (hereinafter sometimes referred to as ITO) doped with tin is most widely used because of its excellent electrical characteristics and ease of processing by etching.

  An article having such a low electrical resistance (low specific resistance) and a transparent conductive film having a high visible light transmittance, such as a transparent conductive film, is a liquid crystal image display device, organic electroluminescence (hereinafter also referred to as organic EL). ) Image display device, plasma display panel (PDP), flat display transparent electrode such as field emission display (FED), solar cell transparent electrode, electronic paper, touch panel, electromagnetic shielding material, infrared reflection film, etc. It's being used. Among them, recently, there has been a great increase in the need for a large-size display panel and a small portable display panel, and organic EL image display devices and FEDs have attracted attention as one of next-generation displays.

  For these applications, it is necessary to reduce the power consumption of the display element, and it is effective to develop a transparent electrode exhibiting a low resistance value while maintaining a high visible light transmittance. In particular, the organic EL element that is being developed recently is a self-luminous type and has been developed mainly for small portable terminals, so there is a great expectation for reducing the resistance of the transparent electrode. In addition, regarding PDP and FED, since they have a structure with high power consumption, there is a great expectation for the development of a low-resistance transparent electrode.

  Conventionally, as a method for producing a transparent conductive film, it is mainly formed by a vacuum deposition method, a sputtering method, an ion plating method, a vacuum plasma CVD method, a spray pyrolysis method, a thermal CVD method, a sol-gel method, or the like.

  In particular, in liquid crystal display elements, elements and devices having high electric field responsiveness are required, and for that purpose, transparent conductive films having high electron mobility are required. Moreover, in an organic EL element, since a current drive system is adopted, a transparent conductive film having a lower resistance is required.

  Usually, in vacuum deposition or sputtering, the oxygen partial pressure is adjusted to control oxygen vacancies in the film, or the crystallinity is increased by adjusting the energy of the deposited particles, the substrate temperature, etc. to improve the doping efficiency, Both low resistance and high transparency are achieved.

  Furthermore, there is a method of heat-treating the transparent electrode produced by the above method in order to realize a reduction in resistance. However, it is very difficult to make a good time smoothness, a low resistance value, and a high permeability with only a thin film such as ITO. Further, since the treatment temperature reaches several hundred degrees, a low heat resistant polymer base material cannot be used.

  Use of a transparent conductive film laminate is effective as a means for realizing a low-resistance transparent electrode without performing heat treatment. The transparent conductive film laminate is obtained by sandwiching a metal thin film having excellent conductivity between transparent high refractive index thin films. The conductivity of the transparent conductive film laminate depends mainly on the conductivity of the metal thin film layer, and high conductivity that cannot be achieved with a conventional transparent conductive film can be obtained. This transparent conductive film laminate is very useful because it can be designed to have optimum optical and electrical characteristics depending on the application by selecting the material and film thickness of each thin film layer. Have been proposed. For example, a laminate in which a transparent high refractive index layer and a transparent metal layer are laminated (for example, see Patent Document 1), and a laminate in which a transparent high refractive index layer and a transparent metal layer are laminated on a substrate having a gas barrier layer. Body (for example, refer to Patent Document 2), article (for example, refer to Patent Document 3) in which a tin oxide film is formed on the surface of a laminate of a transparent high refractive index layer and a transparent metal layer, a metal oxide film and a metal layer 6 to 20 alternately stacked layers (see, for example, Patent Document 4), and organic EL manufacturing methods using a transparent conductive film and metal layer stack as an anode (for example, see Patent Document 5). Etc. are disclosed.

However, in the case of the transparent conductive film laminate disclosed in each of the above-mentioned patent documents, since a layer containing a metal is formed, the etching properties of each layer are different, so that patterning in the same process is very difficult. . In addition, when various etching processes are present, there is a problem that productivity is inferior compared with a case where the other etching processes are not performed.
JP 2002-15623 A JP 2001-297630 A JP 2003-168571 A JP 2004-42412 A JP 2003-115393 A

  The present invention has been made in view of the above problems, and its object is to provide a transparent electrode having excellent etching properties, low resistance, high transmittance, and good surface smoothness, and a method for producing the transparent electrode. It is.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
Transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less. Transparent electrode characterized by

(Claim 2)
The metal particles are at least one selected from Au, Ag, Al, Cu, Pt and alloys thereof, and the average particle diameter of the metal particles is 1 nm or more and 10 nm or less. Item 2. The transparent electrode according to Item 1.

(Claim 3)
The transparent electrode according to claim 1, wherein the transparent high refractive index layer is a transparent conductive film.

(Claim 4)
The transparent conductive film is doped with In ₂ O ₃ , Sn-doped indium oxide (ITO), ZnO, In ₂ O ₃ —ZnO amorphous oxide (IZO), Al-doped ZnO (AZO), and Ga. ZnO (GZO), any of the preceding claims, characterized in that a main component a transparent conductive film formed of at least one material selected from SnO ₂ (FTO) and TiO ₂ doped with SnO _2, F-containing 2. The transparent electrode according to item 1.

(Claim 5)
The average ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the total thickness of the laminated film is 1.0 atm% or more and 10 atm% or less. The transparent electrode according to claim 1, wherein the transparent electrode is a transparent electrode.

(Claim 6)
The ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the thickness direction is 1.0 atm% or more and 50 atm% or less. The transparent electrode according to any one of claims 1 to 5, characterized in that:

(Claim 7)
Transparent transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less A method for producing a transparent electrode for producing an electrode, comprising:
The transparent high-refractive index layer excites the gas 1 by supplying a gas 1 containing a thin film forming gas to the discharge space and applying a high-frequency electric field to the discharge space at or near atmospheric pressure. Step 1 of forming a thin film on a substrate by exposing the material to excited gas 1, and supplying gas 2 containing an oxidizing gas to the discharge space under atmospheric pressure or a pressure in the vicinity thereof after Step 1 Formed by performing step 2 of exciting the gas 2 by applying a high-frequency electric field to the discharge space and exposing the substrate having a thin film formed of the gas 1 to the excited gas 2;
The method for producing a transparent electrode is characterized in that the metal particles are applied onto the transparent high refractive index layer by a coating method.

(Claim 8)
Transparent transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less A method for producing a transparent electrode for producing an electrode, comprising:
The transparent high refractive index layer has at least a discharge gas of a transparent conductive film forming gas having a discharge gas and a thin film forming gas as main components, with the space between the counter electrodes (discharge space) being at or near atmospheric pressure. Introduced between the counter electrodes, a high-frequency voltage is applied between the counter electrodes to bring the discharge gas into a plasma state, and then the substrate is exposed to the transparent conductive film forming gas in the plasma state to form a thin film on the substrate. After forming, the thin film on the base material is exposed to an oxidizing gas, and further, the thin film on the base material is alternately exposed to the transparent conductive film forming gas in the plasma state and the oxidizing gas,
The method for producing a transparent electrode is characterized in that the metal particles are applied onto the transparent high refractive index layer by a coating method.

(Claim 9)
Transparent transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less A method for producing a transparent electrode for producing an electrode, comprising:
The transparent high-refractive index layer is formed in a plasma state by introducing a reactive gas containing a reducing gas and a transparent conductive film forming gas into a discharge space at atmospheric pressure or near atmospheric pressure, and the substrate is in the plasma state. Formed on the substrate by exposure to reactive gases of
The method for producing a transparent electrode is characterized in that the metal particles are applied onto the transparent high refractive index layer by a coating method.

(Claim 10)
The metal particles are at least one selected from Au, Ag, Al, Cu, Pt and alloys thereof, and the average particle diameter of the metal particles is 1 nm or more and 10 nm or less. Item 10. The method for producing a transparent electrode according to any one of Items 7 to 9.

(Claim 11)
The method for producing a transparent electrode according to claim 7, wherein the transparent high refractive index layer is a transparent conductive film.

(Claim 12)
The transparent conductive film is doped with In ₂ O ₃ , Sn-doped indium oxide (ITO), ZnO, In ₂ O ₃ —ZnO amorphous oxide (IZO), Al-doped ZnO (AZO), and Ga. ZnO (GZO), any claim 7-11, characterized in that a main component a transparent conductive film formed of at least one material selected from SnO ₂ (FTO) and TiO ₂ doped with SnO _2, F-containing A method for producing the transparent electrode according to claim 1.

(Claim 13)
The average ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the total film thickness of the laminated film is 10 atm% or less. The manufacturing method of the transparent electrode of any one of Claims 7-12 to do.

(Claim 14)
The ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the thickness direction is 1.0 atm% or more and 50 atm% or less. The method for producing a transparent electrode according to claim 7, wherein the method is a transparent electrode.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the transparent electrode which is excellent in etching property, has a low resistance value, a high transmittance | permeability, and favorable surface smoothness, and a transparent electrode can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor has alternately laminated transparent high refractive index layers and metal particles on a transparent substrate, and has a total film thickness of 30 nm or more and 100 nm or less, and the surface. It has been found that a transparent electrode having a resistance value of 1Ω / □ or more and 13Ω / □ or less can realize a transparent electrode having excellent etching properties, low resistance, high transmittance, and good surface smoothness. It is up to the present invention.

  That is, in the transparent electrode of the present invention, it is possible to perform etching with a simultaneous solvent by making it exist as a metal particle between transparent high refractive index layers without forming a metal layer as described in each of the aforementioned patent documents. Etching characteristics are good. Moreover, the transmittance | permeability in low resistance (13 ohms / square or less) and visible light 400nm -800nm is 90% or more, The transparent electrode which has favorable surface smoothness was able to be obtained.

  Details of the present invention will be described below.

  The transparent electrode of the present invention is characterized in that transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate.

  First, the transparent high refractive index layer according to the present invention will be described.

  The transparent high refractive index layer according to the present invention is a transparent conductive film mainly composed of a metal oxide. The transparent conductive film is generally well known as an industrial material, and is a transparent film that hardly absorbs visible light (400 to 700 nm) and is transparent. It is used as a transparent electrode or an antistatic film because the transmission characteristics of a free charged substance carrying electricity is high in the visible light range, is transparent, and has high electrical conductivity.

  In the present invention, it is referred to as a “layer”, but it may be formed on the object to be processed to such an extent that it has a function depending on the application, and it is not necessarily required to be a continuous film covering all or part of the object to be processed. There is no.

In the present invention, the transparent conductive film according to the present invention includes In ₂ O ₃ , Sn-doped indium oxide (ITO), ZnO, In ₂ O ₃ —ZnO amorphous oxide (IZO), and Al-doped ZnO. It is excellent that the main component is at least one transparent conductive film forming material selected from (AZO), Ga-doped ZnO (GZO), SnO ₂ , F-doped SnO ₂ (FTO), and TiO _2. It is most widely used because it has excellent electrical characteristics and is easily processed by etching. ITO and AZO films have an amorphous structure or a crystalline structure. On the other hand, the IZO film has an amorphous structure.

  In the present invention, the transparent conductive film according to the present invention is characterized by being formed by an atmospheric pressure plasma CVD method in which a thin film is formed under the atmospheric pressure described below or a pressure in the vicinity thereof. As the reactive gas used for forming a certain metal oxide layer, an organometallic compound having an oxygen atom in the molecule is preferable. For example, indium hexafluoropentanedionate, indiummethyl (trimethyl) acetylacetate, indium acetylacetonate, indium isoporopoxide, indium trifluoropentanedionate, tris (2,2,6,6-tetramethyl 3,5 -Heptanedionate) indium, di-n-butylbis (2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, Examples thereof include zinc acetylacetonate. Of these, indium acetylacetonate, tris (2,2,6,6-tetramethyl 3,5-heptanedionate) indium, zinc acetylacetonate and di-n-butyldiacetoxytin are particularly preferable. .

  Examples of the reactive gas used for doping include aluminum isopropoxide, nickel acetylacetonate, manganese acetylacetonate, boron isopropoxide, n-butoxyantimony, tri-n-butylantimony, di-n-butylbis ( 2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, tetrabutyltin, zinc acetylacetonate, propylene hexafluoride, A cyclobutane octafluoride, methane tetrafluoride, etc. can be mentioned.

  Examples of the reactive gas used for adjusting the resistance value of the transparent conductive film include titanium triisopropoxide, tetramethoxysilane, tetraethoxysilane, and hexamethyldisiloxane.

In the transparent conductive film according to the present invention, the metal oxide preferably contains at least one element selected from In, Zn, Sn, Ti, Ga, and Al. As the metal oxide, In ₂ O ₃ , preferably at least one selected from ZnO and SnO ₂ . At this time, a carbon atom or a nitrogen atom may be contained as a subcomponent, but from the viewpoint of obtaining a transparent conductive film that satisfies the object of the present invention, the content of carbon atom or nitrogen atom is preferably 20 atm% or less.

  The amount ratio of the reactive gas used as the main component of the transparent conductive film and the reactive gas used in a small amount for the purpose of doping differs depending on the type of the transparent conductive film to be formed. For example, the reactive gas amount is adjusted so that the Sn / (In + Sn) atomic ratio of the ITO film obtained by doping tin into indium oxide is in the range of 0.1 to 30 atm%. Preferably, it adjusts so that it may become the range of 0.1-20 atm%. The atomic ratio of In and Sn can be obtained by XPS measurement.

  In the transparent conductive film (FTO) obtained by doping fluorine with tin oxide, the reactive gas is used so that the F / (Sn + F) atomic ratio of the obtained FTO film is in the range of 0.01 to 30 atm%. Adjust the quantity ratio. The atomic ratio of Sn and F can be determined by XPS measurement.

  In a transparent conductive film (AZO) obtained by doping aluminum into ZnO, the amount of reactive gas is adjusted so that the Al / (Zn + Al) atomic ratio of the obtained AZO film is in the range of 0.1 to 30 atm%. Adjust the ratio. The atomic ratio of Al and F can be determined by XPS measurement.

In the In ₂ O ₃ —ZnO amorphous transparent conductive film (IZO), the amount ratio of the reactive gas is adjusted so that the atomic ratio of In / (Zn + In) is in the range of 10 to 90 atm%. The number of atoms such as In and Zn can be obtained by XPS measurement.

  In the present invention, as an XPS surface analyzer used for XPS measurement, ESCALAB-200R manufactured by VG Scientific, Inc. can be used. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  As a measurement, first, the range of the binding energy of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

  Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

  The obtained spectrum is COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, the processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as the atomic concentration (at%).

  Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

  Subsequently, the metal particle which comprises the transparent electrode of this invention is demonstrated.

  Conventionally, as a method for realizing a low-resistance transparent electrode, a laminated body in which a metal layer is provided between the transparent high refractive index layers described above is described in Patent Documents 1 to 5 described above. For example, a vacuum deposition method, an ion plating method, a sputtering method, or the like is applied to the formation of the metal thin film layer, and an ion plating method or a sputtering method is particularly preferable. In the ion plating method, a desired metal or sintered body is resistance-heated in a reactive gas plasma, or heated by an electron beam to perform vacuum deposition to form a metal thin film. In the sputtering method, a desired metal material is used as a target, an inert gas such as argon or neon is used as a sputtering gas, and a metal thin film is formed using a direct current sputtering method or a high frequency sputtering method. However, the metal thin films formed by these vacuum deposition methods, ion plating methods, sputtering methods, etc. have different etching characteristics between the metal thin film and the transparent high refractive index layer, so that patterning as a transparent electrode is performed in the same process. It was difficult.

  In the transparent electrode of the present invention, instead of a metal layer between transparent high refractive index layers, metal particles having a specific average particle size are applied without forming a thin film, and transparent high refractive index layers and metal particles are alternately provided. As a result, the etching characteristics are improved and, for example, other performance as a transparent electrode necessary for the organic EL element can be achieved.

  The metal particles according to the present invention include Au, Ag, Al, Cu, Pt and alloys thereof having an average particle diameter of 1 nm or more and 10 nm or less from the viewpoint that the object and effects of the present invention can be exhibited. It is preferable that at least one selected.

  In the method for producing a transparent electrode of the present invention, as a method for forming the metal particles according to the present invention on the transparent high refractive index layer, the metal particles dispersed in an appropriate dispersion medium are applied by a coating method. For example, as a coating method, a spin coating method, a blade coating method, a dip coating method, a die coating method, a bar coating method, a casting method, a spray coating method, or the like can be appropriately selected and applied.

  The transparent electrode of the present invention is formed by alternately laminating transparent high refractive index layers and metal particles. The number of laminated layers is not particularly limited and may be two or more, preferably 2 It is the range of -50 layers, Preferably it is about 2-30 layers.

  In the transparent electrode of the present invention, the total film thickness in the state where the transparent high refractive index layers and the metal particles are alternately laminated is 30 nm or more and 100 nm or less, and the total film thickness is less than 30 nm. If the surface resistance value becomes too high, and the total film thickness exceeds 100 nm, the transparency (transmittance) is lowered, the surface irregularities are increased, the flatness is impaired, and the etching property is reduced, which is preferable. Absent.

  In addition, the transparent electrode of the present invention is characterized in that the surface resistance value in a state where transparent high refractive index layers and metal particles are alternately laminated is 1Ω / □ or more and 13Ω / □ or less. That is, by allowing the metal particles to be present in the state of particles between the transparent high refractive index layers, it is possible to realize the surface resistance value defined above, and as a result, it is possible to realize a transparent electrode having a low resistance value.

  In the transparent electrode of the present invention, in a laminate in which transparent high refractive index layers and metal particles are alternately laminated, the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the entire film thickness of the laminated film The average ratio of the number of metal atoms contained in the metal particles is preferably 1.0 atm% or more and 10 atm% or less, and the transparent conductive film-forming material contained in the transparent high refractive index layer in the thickness direction The ratio of the number of metal atoms contained in the metal particles to the number of material atoms is preferably 1.0 atm% or more and 50 atm% or less from the viewpoint that the objective effect of the present invention can be exhibited.

  The base material atom of the transparent conductive film forming material referred to in the present invention refers to an element such as In, Zn, Sn, or Ti, and the metal contained in the metal particles refers to Au, Ag, Al, Cu, Pt. Etc.

  The number of atoms defined in the present invention can be determined using a known analysis means, for example, using a high resolution transmission electron microscope and an energy dispersive X-ray analyzer (EDS) “Voager”. can do.

  A laminate obtained by alternately laminating transparent high refractive index layers and metal particles is embedded in a room temperature curable epoxy resin, and then cured for 2 days in an ambient temperature of 40 ° C., and the resulting cured product is obtained. The surface is smoothed using an ultramicrotome equipped with a diamond knife.

  An observation sample is prepared by placing a section cut out with an ultramicrotome on a grid mesh with a microgrid. Thereafter, the structure and each atomic distribution are measured with a 200 kV field emission TEM “JEM-2010F” (manufactured by JEOL Ltd.) and an energy dispersive X-ray analyzer (EDS) “Voager” (manufactured by ThermoNORAN). The conditions are set as follows.

Acceleration voltage: 200 kV
TEM image observation magnification: 50000 to 500000 times EDS measurement time (Live time): 50 seconds Measurement energy range: 0 to 2000 eV
It is preferable that the transparent conductive film of this invention is provided on the transparent base material, and if it is a film | membrane formed with the material which can hold | maintain a metal oxide layer, it will not specifically limit.

  Specifically, a homopolymer such as ethylene, polypropylene, butene or a polyolefin (PO) resin such as a copolymer or a copolymer, an amorphous polyolefin resin (APO) such as a cyclic polyolefin, polyethylene terephthalate (PET), Polyester resins such as polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) Polyvinyl alcohol resins such as polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin , Polyvini Butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP) Fluorine-based resins such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), and perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA) can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a base film.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film pure ace (manufactured by Teijin Ltd.), and cellulose triacetate film Konicakat Commercial products such as KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.

  In the transparent conductive film of the present invention, since the base material is transparent and the metal oxide layer formed on the base material is also transparent, it can be used as a transparent substrate such as an organic EL element. .

  In addition, the base material according to the present invention using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material according to the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Moreover, in the base material which concerns on this invention, you may perform surface treatments, such as a corona treatment, a flame treatment, a plasma treatment, a glow discharge process, a roughening process, a chemical treatment, before forming a vapor deposition film.

Furthermore, you may form an anchor coating agent layer in the base-material surface concerning this invention for the purpose of the adhesive improvement with a vapor deposition film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

  The base material is conveniently a long product wound up in a roll shape. The base material used in the present invention is preferably 10 to 200 μm, more preferably 50 to 100 μm, as the film thickness.

  Subsequently, the manufacturing method of the transparent electrode of this invention is demonstrated.

  In the method for producing a transparent electrode of the present invention, as a method for forming a transparent high refractive index layer, a raw material is sputtered, coated, ion-assisted, plasma CVD, or an atmospheric pressure or a pressure near atmospheric pressure described later. The method of forming a transparent high refractive index layer according to the present invention is characterized in that it is formed by using a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure.

  Below, as a manufacturing method of the transparent electrode of this invention, the atmospheric pressure plasma CVD method which can be used suitably for formation of the transparent high refractive index layer which concerns on this invention is demonstrated in detail.

  The plasma CVD method is also called a plasma-assisted chemical vapor deposition method or PECVD method, and various inorganic substances can be applied in a three-dimensional form with good coverage and adhesion, and without increasing the substrate temperature too much. This is a technique capable of forming a film.

  In ordinary CVD (chemical vapor deposition), volatile and sublimated organometallic compounds adhere to the surface of a high-temperature substrate, causing a decomposition reaction due to heat, producing a thermally stable inorganic thin film. That's it. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and cannot be used for forming a film on a plastic substrate.

  On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) where a gas in a plasma state exists, and a volatilized / sublimated organometallic compound is introduced into the plasma space. The inorganic thin film is formed by spraying on the base material after the decomposition reaction occurs. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions and radicals, so that the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of a substrate on which an inorganic material is formed and can sufficiently form a film on a plastic substrate.

  However, in the plasma CVD method, it is necessary to ionize the gas by applying an electric field to the gas, and since the film is usually formed in a reduced pressure space of about 0.101 kPa to 10.1 kPa, a large area is required. When forming the film, the equipment is large and the operation is complicated, and this method has a problem of productivity.

  On the other hand, the plasma CVD method near atmospheric pressure does not need to be reduced in pressure and has higher productivity than the plasma CVD method under vacuum, and has a high film density because the plasma density is high. Faster, and even under high pressure conditions under atmospheric pressure, compared to the normal conditions of CVD, the mean free path of gas is very short, so that a very flat film is obtained. The optical properties are good. From the above, in the present invention, it is more preferable to apply the atmospheric pressure plasma CVD method than the plasma CVD method under vacuum.

  As one method for forming the transparent high refractive index layer according to the present invention, the transparent high refractive index layer is transparent and has a low refractive index in the first discharge space in which a high-frequency electric field is generated under atmospheric pressure or in the vicinity thereof. A gas 1 containing a layer forming gas is supplied and excited, and the substrate is exposed to the excited gas 1 to perform a first step of forming a transparent low refractive index layer on the substrate. A gas 2 containing an oxidizing gas is supplied to the discharge space in which a high-frequency electric field has been generated for excitation, and the transparent low refractive index layer formed in the first step is exposed to the excited gas 2. It is one of the features that it is formed by performing the above process.

  In the present invention, the excited gas means that at least part of the molecules in the gas move from the existing state to a higher state by obtaining energy, and the excited gas molecules and radicalized gas molecules. A gas containing ionized gas molecules corresponds to this.

  That is, the space between the counter electrodes (discharge space) is at or near atmospheric pressure, a metal oxide forming gas including a discharge gas, a reducing gas and a metal oxide gas is introduced between the counter electrodes, and the high frequency voltage is opposed. A metal oxide forming gas is applied between the electrodes to form a plasma state, and then the transparent substrate is exposed to the metal oxide forming gas in the plasma state to form a thin film on the transparent substrate. A transparent high refractive index layer is formed by exposing the thin film formed on the material to a gas in which a discharge gas and an oxidizing gas are excited to a plasma state.

  Next, the gas forming the transparent high refractive index layer according to the present invention will be described. The gas used is basically a gas containing a discharge gas and a transparent high refractive index film forming gas as constituent components.

  The discharge gas is an excited state or a plasma state in the discharge space and serves to give an energy to the thin film transparent high refractive index film forming gas to an excited or plasma state, and is a rare gas or a nitrogen gas. Examples of the noble gas include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc., and the dense and low specific resistance values described in the present invention. In order to obtain the effect of forming a thin film having helium, helium and argon are preferably used. The discharge gas is preferably contained in an amount of 90.0 to 99.9% by volume with respect to 100% by volume of the total gas.

  In the formation of the transparent high refractive index layer according to the present invention, the transparent conductive film forming gas is a gas that receives energy from the discharge gas in the discharge space and enters an excited state or a plasma state to form a transparent conductive thin film, or reacts. It is also a gas that controls and accelerates the reaction. The transparent conductive film forming gas is preferably contained in an amount of 0.01 to 10% by volume, more preferably 0.1 to 3% by volume in the total gas.

  In the present invention, in forming the transparent conductive film, the transparent conductive thin film is more uniformly and densely formed by containing a reducing gas selected from hydrogen, hydrocarbons such as methane, and water in the transparent conductive film forming gas. It is possible to improve electrical conductivity, adhesion, and crack resistance. The reducing gas is preferably 0.0001 to 10% by volume, more preferably 0.001 to 5% by volume with respect to 100% by volume of the total gas.

The transparent high refractive index layer according to the present invention is formed by exposing a discharge gas and an oxidizing gas to a gas excited to a plasma state. The oxidizing gas used in the present invention includes oxygen, ozone, peroxidation. Examples thereof include hydrogen and carbon dioxide. Examples of the discharge gas at this time include a gas selected from nitrogen, helium, and argon. The concentration of the oxidizing gas component in the mixed gas composed of the oxidizing gas and the discharge gas is preferably 0.0001 to 30% by volume, more preferably 0.001 to 15% by volume, particularly 0.01 to 10% by volume. It is preferable to make it. The optimum value of the concentration of each of the oxidizing gas species and the discharge gas selected from nitrogen, helium, and argon can be appropriately selected depending on the substrate temperature, the number of oxidation treatments, and the treatment time. As the oxidizing gas, oxygen and carbon dioxide are preferable, and a mixed gas of oxygen and argon is more preferable.
The present invention supplies the gas 1 containing a thin film forming gas to the discharge space at or near atmospheric pressure, and excites the gas 1 by applying a high frequency electric field to the discharge space, thereby exciting the substrate. In the thin film manufacturing method in which at least step 1 of forming a thin film on a substrate by exposure to gas 1 is performed, after step 1, gas 2 containing an oxidizing gas in the discharge space under atmospheric pressure or a pressure in the vicinity thereof. Supplying and exciting the gas 2 by applying a high-frequency electric field to the discharge space, and exposing the base material having the thin film to the excited gas 2 makes it possible to obtain a good quality thin film even if the production speed is increased. Can be formed.

  In step 1 of the method for producing a transparent conductive film of the present invention, the gas 1 supplied to the space between the opposing electrodes (discharge space) is at least a discharge gas excited by an electric field and its energy and is in a plasma state or an excited state. A thin film forming gas for forming a thin film is included.

  In the present invention, following step 1, the gas 2 containing an oxidizing gas is supplied to the discharge space under atmospheric pressure or a pressure in the vicinity thereof, and the high-frequency electric field is applied to the discharge space to It is preferable to perform step 2 of exciting and exposing the substrate having a thin film to the excited gas 2.

  The gas 2 preferably contains a discharge gas, and preferably contains 50% by volume or more of nitrogen as the discharge gas from the viewpoint of cost.

  It is preferable to perform the process by alternately repeating the process 1 and the process 2, and even if the substrate is reciprocated between the process 1 and the process 2, the process 1 and the process 2 are installed alternately and continuously. It is also possible that the substrate passes through them and is continuously processed.

  Hereinafter, the present invention will be described in more detail.

  First, step 1 will be described.

  The high-frequency electric field in step 1 is preferably a superposition of the first high-frequency electric field and the second high-frequency electric field, and the discharge space is constituted by the first and second electrodes facing each other, and the first high-frequency electric field is formed. A method of applying an electric field to the first electrode and applying the second high-frequency electric field to the second electrode is preferable.

The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the strength of the discharge start electric field. It is preferable that the relationship with IV1 satisfies V1 ≧ IV1> V2 or V1> IV1 ≧ V2, and the output density of the second high-frequency electric field is 1 W / cm ² or more.

  When the superimposed high-frequency electric field is both a sine wave, the frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field higher than the frequency ω1 are superimposed, and the waveform has the frequency ω1. The sine wave has a sawtooth waveform in which a sine wave having a higher frequency ω2 is overlapped.

  In the present invention, the strength of the discharge starting electric field refers to the strength of the lowest electric field at which discharge can be started in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual thin film formation method. Refers to that. The strength of the discharge start electric field varies somewhat depending on the gas type supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but in the same discharge space, it is governed by the strength of the discharge start electric field of the discharge gas. Is done.

  By applying a high frequency electric field to the discharge space, it is presumed that a discharge capable of forming a thin film is caused and high density plasma necessary for forming the thin film can be generated.

  Although the superposition of the continuous wave of the sine wave has been described above, the present invention is not limited to this, and both pulse waves may be used, one may be a continuous wave and the other may be a pulse wave. Further, it may have a third electric field.

  Here, the strength of the high-frequency electric field (applied electric field strength) and the strength of the discharge starting electric field referred to in the present invention are those measured by the following method.

Measuring method of strength V1 and V2 (unit: kV / mm) of high frequency electric field:
A high-frequency voltage probe (P6015A) is installed in each electrode portion, and an output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength is measured.

Measuring method of intensity IV (unit: kV / mm) of electric field for starting discharge:
A discharge gas is supplied between the electrodes to increase the strength of the electric field between the electrodes, and the strength of the electric field at which discharge starts is defined as the strength IV of the discharge start electric field. The measuring instrument is the same as the measurement of the strength of the high-frequency electric field.

  By adopting such a discharge condition, even a discharge gas having a high discharge start electric field strength, such as nitrogen gas, can start discharge, maintain a high density and stable plasma state, and form a thin film at high speed. It can be done.

  When the discharge gas is nitrogen gas according to the above measurement, the intensity IV (1/2 Vp-p) of the discharge start electric field is about 3.7 kV / mm. Therefore, in the above relationship, the first high frequency electric field is Is applied as V1 ≧ 3.7 kV / mm, whereby the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary for initiating discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, It is an important point of the present invention to form a dense and high-quality thin film by increasing the plasma density by high frequency and high power density.

  Also, by increasing the output density of the first high-frequency electric field, the output density of the second high-frequency electric field can be improved while maintaining the uniformity of discharge. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film formation speed and an improvement in film quality can be achieved.

  As described above, a gas 1 containing a thin film forming gas introduced between the counter electrodes is discharged into a plasma state, and the substrate which is left stationary between the counter electrodes or transferred between the electrodes A thin film is first formed on the substrate by exposure to the excited gas 1.

  Next, step 2 will be described.

  In the present invention, following the step 1 of forming a thin film on a substrate, a step 2 of exciting the gas 2 containing an oxidizing gas by atmospheric pressure plasma and exposing the thin film to the excited gas 2 is performed. It is necessary to do. Thereby, a high-performance thin film can be formed even if the production rate is increased.

  The high-frequency electric field in step 2 is also preferably a superposition of the third high-frequency electric field and the fourth high-frequency electric field, and the discharge space is constituted by the third and fourth electrodes facing each other, and the third high-frequency electric field is formed. A method of applying an electric field to the third electrode and applying the fourth high-frequency electric field to the fourth electrode is preferable. Thereby, a dense and high-quality thin film can be obtained.

The frequency ω4 of the fourth high-frequency electric field is higher than the frequency ω3 of the third high-frequency electric field, the third high-frequency electric field strength V3, the fourth high-frequency electric field strength V4, and the discharge start electric field strength. The relationship with IV2 satisfies V3 ≧ IV2> V4 or V3> IV2 ≧ V4, and the output density of the second high-frequency electric field is preferably 1 W / cm ² or more from the viewpoint of obtaining a high-quality thin film.

  The third power supply for supplying the third high-frequency electric field and the fourth high-frequency electric field, the fourth power supply and the third electrode, the fourth electrode, and other application methods are the same as the first high-frequency electric field and the second high-frequency electric field in step 1 above. A method similar to that used in the electric field can be applied.

<Gap between electrodes>
The distance between the first electrode, the second electrode, and the third electrode and the fourth electrode facing each other is such that when a dielectric is provided on one of the electrodes, the conductive metal matrix of the dielectric surface and the other electrode is provided. It means the shortest distance from the surface of the material, and when a dielectric is provided for both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the strength of the applied electric field, the purpose of using the plasma, etc. From the viewpoint of performing, 0.1 to 5 mm is preferable, and 0.5 to 2 mm is particularly preferable.

<container>
In order to avoid the influence of outside air, it is preferable that the whole atmospheric pressure plasma processing apparatus used in the present invention is stored in one container, or the process 1 and the process 2 are stored in separate containers. As the container, a processing container made of Pyrex (registered trademark) glass or the like is preferably used, but it is also possible to use a metal as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.

<Power supply>
As the first power source (high frequency power source) and the third power source (high frequency power source) installed in the atmospheric pressure plasma processing apparatus used in the present invention,
Manufacturer Frequency Product name Shinko Electric 3kHz SPG3-4500
Shinko Electric 5kHz SPG5-4500
Kasuga Electric 15kHz AGI-023
Shinko Electric 50kHz SPG50-4500
HEIDEN Laboratory 100kHz * PHF-6k
Pearl industry 200kHz CF-2000-200k
Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source) and the fourth power source (high frequency power source),
Manufacturer Frequency Product name Pearl Industry 800kHz CF-2000-800k
Pearl industry 2MHz CF-2000-2M
Pearl Industry 13.56MHz CF-5000-13M
Pearl industry 27MHz CF-2000-27M
Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

<Power>
In the present invention, the output density of the second electrode (second high-frequency electric field) and the fourth electrode (fourth high-frequency electric field) of the electric field applied between the opposing electrodes is 1 W / cm ² or more, and plasma is applied. And energy is given to gas 1 or gas 2. The upper limit value of the power supplied to the second electrode is preferably 20 W / cm ² , more preferably 10 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by applying an electric field having an output density of 1 W / cm ² or more to the first electrode (first high-frequency electric field) and the third electrode (third high-frequency electric field), the uniformity of the second high-frequency electric field is achieved. The output density can be improved while maintaining the above. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power density applied to the first electrode and the third electrode is preferably 50 W / cm ² .

<Current value>
At this time, the relationship between the current I1 of the first high-frequency electric field and the current I2 of the second high-frequency electric field is preferably I1 <I2. I1 is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} , I2 is preferably ^{10mA / cm 2 ~1000mA / cm 2} , more preferably is ^{20mA / cm 2 ~500mA / cm 2} .

The relationship between the current I3 of the third high-frequency electric field and the current I4 of the fourth high-frequency electric field is preferably I3 <I4. I3 is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . The current I4 of the fourth high frequency electric field is preferably ^{10mA / cm 2 ~1000mA / cm 2} , more preferably ^{20mA / cm 2 ~500mA / cm 2} .

<Waveform>
Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

<electrode>
An electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic spray coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic sprayed coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are preferable, and 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or titanium alloy as the metal base material and using the dielectric as above, there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and long-term use under harsh conditions Can withstand.

  The metallic base material of the electrode useful in the present invention is a titanium alloy or titanium metal containing 70% by mass or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium metal is 70% by mass or more, it can be used without any problem, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very little iron atom, carbon atom, nitrogen atom, oxygen atom, hydrogen atom, etc. As content, it has 99 mass% or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin in addition to the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more. These titanium alloys or titanium metals have a thermal expansion coefficient that is about 1/2 smaller than that of stainless steel, such as AISI 316, and are combined with a dielectric described later applied on the titanium alloy or titanium metal as a metallic base material. It can withstand the use at high temperature for a long time.

  On the other hand, as a required characteristic of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable, and examples of such a dielectric include ceramics such as alumina and silicon nitride, Alternatively, there are glass lining materials such as silicate glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, a dielectric provided by spraying alumina is preferable.

  Alternatively, as one of the specifications that can withstand high power as described above, the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is. The porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved because the dielectric has a low porosity. Examples of the dielectric having such a void and a low void ratio include a high-density, high-adhesion ceramic spray coating by an atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform sealing treatment.

  The above-mentioned atmospheric plasma spraying method is a technique in which fine powder such as ceramics, wire, or the like is put into a plasma heat source and sprayed onto a metallic base material to be coated as fine particles in a molten or semi-molten state to form a film. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons. The plasma gas injection speed is high, and since the sprayed material collides with the metallic base material at a higher speed than conventional arc spraying or flame spraying, high adhesion strength and high density coating can be obtained. Specifically, reference can be made to a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A No. 2000-301655. By this method, the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.

  Another preferable specification that can withstand high power is that the dielectric thickness is 0.5 to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

In order to further reduce the porosity of the dielectric, it is preferable to further perform a sealing treatment with an inorganic compound on the sprayed film such as ceramics as described above. As the inorganic compound, a metal oxide is preferable, and among these, a compound containing silicon oxide (SiO _x ) as a main component is particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment for promoting the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are sequentially repeated several times, mineralization is further improved and a dense electrode without deterioration can be obtained.

In the case of performing a sealing treatment that cures by a sol-gel reaction after coating a ceramic sprayed film using the metal alkoxide or the like of the dielectric-coated electrode according to the present invention as a sealing liquid, the content of the metal oxide after curing is 60 It is preferably at least mol%. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the content of SiO _x (x is 2 or less) after curing is preferably 60 mol% or more. The cured SiO _x content is measured by analyzing a tomographic layer of the dielectric layer by XPS (X-ray photoelectron spectroscopy).

  In the electrode used for forming the transparent conductive film of the present invention, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with at least the base material of the electrode is adjusted to be 10 μm or less. However, from the viewpoint of obtaining the effects described in the present invention, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less. In this way, the dielectric surface of the dielectric-coated electrode can be polished and the dielectric thickness and the gap between the electrodes can be kept constant, the discharge state can be stabilized, the heat shrinkage difference and Distortion and cracking due to residual stress can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish of the dielectric surface is preferably performed at least on the dielectric in contact with the substrate. Furthermore, the centerline average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

  In the dielectric-coated electrode used in the present invention, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C. The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without causing dielectric breakdown at the voltage used in the atmospheric pressure plasma treatment. Such heat-resistant temperature can be applied within the range of the difference between the linear thermal expansion coefficient of the metallic base material and the dielectric material by applying the dielectric material provided by the above-mentioned ceramic spraying or layered glass lining with different bubble mixing amounts. This can be achieved by appropriately combining means for appropriately selecting the materials.

  Hereinafter, an apparatus for forming a transparent low refractive index layer and a transparent high refractive index layer using a plasma CVD method at or near atmospheric pressure will be described in detail.

  In the present invention, the plasma discharge treatment is performed at atmospheric pressure or a pressure in the vicinity thereof. Here, the atmospheric pressure vicinity represents a pressure of 20 kPa to 110 kPa, but in order to obtain a good effect described in the present invention. 93 kPa to 104 kPa is preferable.

  FIG. 1 is a schematic configuration diagram showing an example of a plate electrode type atmospheric pressure plasma processing apparatus preferably used in the present invention. In step 1 (in the figure, a region surrounded by a one-dot chain line, the same applies hereinafter), a counter electrode (discharge space) is formed by the movable gantry electrode (first electrode) 8 and the square electrode (second electrode) 7, A high frequency electric field is applied between the electrodes, a gas 1 containing a discharge gas 11 and a thin film forming gas 12 is supplied through a gas supply pipe 15, flows out into a discharge space through a slit 5 formed in the rectangular electrode 7, and gas 1 is excited by the discharge plasma, and the surface of the substrate 4 placed on the movable gantry electrode 8 is exposed to the excited gas 1 (37 in the figure), whereby a thin film is formed on the substrate surface.

  Next, the base material 4 gradually moves together with the movable gantry electrode 8 to the step 2 (in the figure, a region surrounded by a two-dot chain line, the same applies hereinafter). In FIG. 1, the first electrode in step 1 and the third electrode in step 2 are common electrodes, and the first power source in step 1 and the third power source in step 2 are common power sources.

  In step 2, a counter electrode (discharge space) is formed by the movable gantry electrode (third electrode) 8 and the square electrode (fourth electrode) 3, and a high frequency electric field is applied between the counter electrodes, and the discharge gas 13 and the oxidation gas are oxidized. A gas 2 containing a reactive gas 14 is supplied through a gas supply pipe 16, passes through a slit 6 formed in the rectangular electrode 3, flows into a discharge space, is excited by discharge plasma, and is placed on a movable gantry electrode 8. By exposing the surface of the material 4 to the excited gas 2 (38 in the figure), the thin film on the substrate surface is oxidized. The moving gantry electrode 8 has moving means (not shown) capable of moving and stopping on the support table 9 at a constant speed.

  In order to adjust the temperature of the gas 2, it is preferable to have a temperature adjusting means 17 in the middle of the supply pipe 16.

  By reciprocating between the thin film formation in step 1 and the oxidation treatment step in step 2, a thin film having a desired film thickness can be formed.

  A first power source 31 is connected to the first electrode (moving gantry electrode) 8, a second power source 33 is connected to the second electrode 7, and a first filter 32 and a second filter are connected between these electrodes and the power source, respectively. A filter 34 is connected. The first filter 32 makes it difficult to pass a current having a frequency from the first power supply 31 and makes it easy to pass a current having a frequency from the second power supply 33, and the second filter 34 is vice versa. Filters having respective functions of making it difficult to pass a current having a frequency from the first power source 31 and making it easy to pass a current having a frequency from the first power source 31 are used.

  In step 1 of the atmospheric pressure plasma processing apparatus in FIG. 1, the first electrode 8 and the second electrode 7 are formed between the counter electrodes, and the first electrode 8 has a frequency ω1 from the first power source 31 and an electric field strength V1. The first high-frequency electric field of current I1 is applied, and the second high-frequency electric field of frequency ω2, electric field strength V2, and current I2 from the second power source 33 is applied to the second electrode 7. ing. The first power supply 31 can apply a higher frequency electric field strength (V1> V2) than the second power supply 33, and the first frequency ω1 of the first power supply 8 is lower than the second frequency ω2 of the second power supply 33. Can be applied.

  Similarly, in step 2, the frequency ω1 from the first power source 31 and the strength of the electric field are increased from the first electrode 8 between the counter electrode composed of the third electrode 8 (common to the first electrode) and the fourth electrode 3. The first high-frequency electric field having the current V1 and the current I1 is applied, and the fourth electrode 3 is applied with the frequency ω4 from the fourth power source 35, the electric field strength V4, and the fourth high-frequency electric field having the current I4. It has become.

  The first power supply 31 can apply a higher frequency electric field strength (V1> V4) than the fourth power supply 35, and the first frequency ω1 of the first power supply 8 is lower than the second frequency ω4 of the fourth power supply 35. Can be applied.

  FIG. 1 shows a measuring instrument used for measuring the strength of the high-frequency electric field (applied electric field strength) and the strength of the discharge starting electric field. Reference numerals 25 and 26 are high-frequency voltage probes, and reference numerals 27 and 28 are oscilloscopes.

  As described above, by applying two types of high-frequency voltages having different frequencies to the rectangular electrode 7 and the movable gantry electrode 8 forming the counter electrode, a good plasma discharge can be achieved even if an inexpensive gas such as nitrogen gas is used. It is possible to form a thin film having excellent performance by performing treatment in an oxidizing atmosphere immediately thereafter. This apparatus is suitable for forming a thin film of a single wafer using a flat substrate such as glass, and is particularly suitable for forming a transparent conductive film having high conductivity and easy etching.

  In the present invention, when forming the transparent conductive film, it is more preferable to use a thin film forming apparatus having shielding blades as shown in FIG. 2A is a plan view of the thin film forming apparatus, and FIG. 2B is a front view thereof. In step 1, a counter electrode is composed of a square electrode (second electrode) 41 and a movable gantry electrode (first electrode) 42 in which a slit 55 through which gas passes through the center by two electrode plates and two space members 44 is formed. Is configured. The gas 1 supplied from the supply pipe is blown into the discharge space from the outlet of the slit 55, and plasma is generated in the discharge space formed by the gap between the bottom surface of the square electrode (second electrode) 41 and the movable frame electrode (first electrode) 42. Excited by. The substrate 4 on the movable gantry electrode 42 is exposed to the excited gas 1 (37 'in the figure) to form a thin film. The movable gantry electrode 42 gradually moves while the base material 4 is placed, and moves the thin film formed on the base material 4 to the step 2. The gas 2 supplied from the oxidizing gas supply pipe is similarly excited in the discharge space, exposing the thin film formed in step 1 to the excited gas 2 (38 'in the figure). In the above apparatus, the shielding blades 48 and 49 are provided on both sides of the square electrodes 41 and 43, and in the formation of the transparent conductive film, the oxidizing atmosphere in step 2 requires a very small amount of oxygen. Oxygen in the atmosphere contains an excessive amount and is suitable for suppressing the influence of the atmosphere and supplying a controlled oxygen concentration to the substrate surface.

  The deposited film thickness of the thin film formed in Step 1 is preferably 10 nm or less, and it is preferable to repeat Step 1 and Step 2 a plurality of times, and the formed thin film has a film thickness of 50 nm to 1 μm. Preferably there is.

  When the thin film formed on the substrate is used as a transparent conductive film and as an electrode for various display elements, a patterning process for drawing a circuit on the substrate is indispensable, and whether patterning can be easily performed or not. This is an important issue for process suitability. In general, patterning is often performed by a photolithographic method, and portions that do not require conduction are dissolved and removed by etching. Therefore, it is important that there is no residue and the speed of dissolution of the unnecessary portions by the etching solution. The transparent conductive film obtained by the thin film manufacturing method of the present invention has very good etching properties.

  FIG. 3 is a schematic view showing an example of a roll rotating electrode type atmospheric pressure plasma processing apparatus useful for the present invention.

  In the atmospheric pressure plasma processing apparatus shown in FIG. 3, the plasma generation site for forming the thin film in step 1 and the site for plasma excitation of the oxidizing gas in step 2 are in series with the rotation direction of the roll rotating electrode (first electrode) 70. The apparatus has a structure in which the first electrode in step 1 and the third electrode in step 2 serve as a common roll electrode.

  A gas 1 is supplied by a gas supply pipe 60 between the counter electrodes (discharge space) between the roll rotating electrode (first electrode) 70 and the square electrode (second electrode) 50 in Step 1, and the gas 1 is plasma-discharged. The roll rotating electrode (the third electrode and the first electrode are common) 70 and the rectangular electrode (in common with the second electrode) formed in Step 2 are formed on the base material F and are adjacently disposed on the roll rotating electrode. The oxidizing gas 2 is supplied by a gas supply pipe 61 between the counter electrodes (discharge space) with the fourth electrode 51, and the gas 2 is excited by plasma discharge, and the surface of the thin film formed in the step 1 is applied. It has a structure for oxidation treatment.

  In Step 1, the roll rotating electrode (first electrode) 70 is supplied with the first high frequency electric field having the frequency ω1, the electric field strength V1 and the current I1 from the first power source 71, and the square electrode (second electrode) 50. The second power source 73 applies a second high frequency electric field having a frequency ω2, an electric field strength V2, and a current I2.

  A first filter 72 is installed between the roll rotation electrode (first electrode) 70 and the first power supply 71, and the first filter 72 passes a current from the first power supply 71 to the first electrode 70. It is designed so that the current from the second power source 73 is grounded and the current from the second power source 73 to the first power source 71 is not easily passed. Further, a second filter 74 is installed between the square electrode (second electrode) 50 and the second power source 73, and the second filter 74 has a current flowing from the second power source 73 to the second electrode 50. Is designed so that the current from the first power supply 71 is grounded and the current from the first power supply 71 to the second power supply 73 is difficult to pass.

  Further, in step 2, in the discharge space (between the counter electrodes) between the roll rotating electrode (the third electrode is shared with the first electrode) 70 and the square electrode (fourth electrode) 51, the roll rotating electrode 70 Is a third high-frequency electric field of frequency ω3, electric field strength V3, and current I3 from a third power source (common to the first power source) 71, and a square electrode (fourth electrode) 51 has a frequency from a fourth power source 75. A fourth high-frequency electric field of ω4, electric field strength V4, and current I4 is applied.

  The base material F is unwound from the original winding (not shown) and is transported or is transported from the previous process, and air or the like that is entrained by the base material by the nip roll 65 via the guide roll 64. It is cut off and transferred to the square electrode 50 while being wound while being in contact with the roll rotating electrode 70, and between the opposing electrodes of the roll rotating electrode (first electrode) 70 and the square electrode (second electrode) 50 ( Plasma is generated in the discharge space. The substrate F is wound while being in contact with the roll rotating electrode 70, the gas 1 is excited by plasma, and a thin film is formed on the substrate F by the excited gas 1 (57 in the figure). Subsequently, the base material F moves to step 2, the gas 2 containing the oxidizing gas is excited, and the surface of the thin film is exposed to the excited gas 2 (58 in the figure), whereby the oxidation treatment is performed. Further, it is discharged through a guide roll 67.

  During the thin film formation, the temperature is adjusted by an electrode temperature adjusting means (not shown) in order to heat or cool the roll rotating electrode (first electrode) 70 and the square electrode (second electrode) 50, (fourth electrode) 51. It is preferable that the medium is sent to both electrodes by a liquid feed pump and the temperature is adjusted from the inside of the electrode.

  The discharged substrate F is wound up or transferred to the next process. The wound base material F may be repeatedly subjected to the same treatment as described above.

  FIG. 4 shows an atmospheric pressure plasma processing apparatus in which two roll rotating electrode type processing apparatuses shown in FIG. 3 are arranged in series. Thereby, the base material F can be processed in two stages, and further, the number of stages can be increased to perform multi-stage processing. In addition, a laminated thin film may be formed by changing processing conditions for each processing apparatus.

  As a thin film formed by such a roll rotating electrode type plasma processing apparatus, it is suitable for forming a thin film using a film substrate, and the above-mentioned various thin films can be formed. In particular, it is suitable for forming an antireflection film, an antiglare film, an insulating film, and the like using a transparent conductive film or an organic metal compound that can be formed relatively thick.

  FIG. 5 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 3 and the dielectric material coated thereon.

  In FIG. 5, a roll electrode 35a is formed by covering a conductive metallic base material 35A and a dielectric 35B thereon. In order to control the electrode surface temperature during the plasma discharge treatment, a temperature adjusting medium (water, silicon oil or the like) can be circulated.

  FIG. 6 is a perspective view showing an example of the structure of the conductive metal base material of the movable gantry electrode and the square electrode of FIGS. 1 to 3 and the dielectric material coated thereon.

  In FIG. 6, a square electrode 36 has a coating of a dielectric 36B similar to FIG. 5 on a conductive metallic base material 36A, and the structure of the electrode is a metallic square pipe. It becomes a jacket that allows temperature adjustment during discharge.

  5 and 6, a roll electrode 35a and a square electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then using an inorganic compound sealing material. And sealed. The ceramic dielectric may be a single-walled coating with a thickness of about 1 mm. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  The atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2004-68143, 2003-49272, International Patent No. 02/48428, etc. in addition to the above description. And an atmospheric pressure plasma discharge treatment apparatus.

  Further, as another method for producing the transparent electrode of the present invention, the formation of the transparent high refractive index layer is performed by setting the space between the counter electrodes (discharge space) to atmospheric pressure or a pressure in the vicinity thereof, and using the discharge gas and the thin film forming gas. At least the discharge gas of the transparent conductive film forming gas as the main constituent component was introduced between the counter electrodes, and a high frequency voltage was applied between the counter electrodes to bring the discharge gas into a plasma state, and subsequently into a plasma state. After forming the thin film on the base material by exposing the base material to the transparent conductive film forming gas, the thin film on the base material is exposed to the oxidizing gas, and the thin film on the base material is further exposed to the plasma-state transparent conductive film forming gas And being exposed to the oxidizing gas alternately.

  That is, in the present invention, the plasma discharge treatment is performed at or near atmospheric pressure, and the atmospheric pressure plasma discharge treatment apparatus according to the present invention has two electrodes facing each other, for example, one electrode being a ground electrode. The other electrode arranged at a position has a counter electrode constituted by an applied electrode, and a mixed gas containing at least a discharge gas and a thin film forming gas is introduced between these counter electrodes (sometimes referred to as a discharge space), A high-frequency voltage from a high-frequency power source is applied between the opposing electrodes to discharge the mixture gas, thereby bringing the mixed gas into an excited or plasma state, and the excited or plasma mixed gas (specifically, the discharge gas in the mixed gas is first excited or plasmad. In addition, upon receiving energy from the excited or plasma state discharge gas, the thin film forming gas becomes excited or plasma state. By exposing the substrate to a stationary or transferring the discharge space into a thin film forming gas) in a plasma state, a method for forming a thin film of transparent high refractive index layer on a substrate. In another type of atmospheric pressure plasma discharge treatment apparatus, a mixed gas is excited or in a plasma state between the counter electrodes (discharge space) in the same manner as described above, and the mixed gas in the plasma state is blown out in a jet form outside the counter electrode. The base material (which may be stationary or moved) is exposed to the plasma mixed gas in a space (called processing space) between the lower surface of the counter electrode and the base material. This is a jet type apparatus for forming a thin film of a transparent high refractive index layer on the surface. Also, the discharge gas and the thin film forming gas are not mixed and used, but the discharge gas is introduced into the discharge space to be excited or plasma state, jetted into the processing space and jetted into the processing space, and the thin film forming gas introduced into the processing space separately. Some devices expose the substrate in an excited or plasma state.

  As the plasma discharge treatment, electrode configuration, and manufacturing conditions applicable to the above manufacturing method, those shown in FIGS. 1 to 6 can be appropriately adjusted and used.

  Further, as a method of manufacturing a transparent electrode according to the present invention, a transparent high refractive index layer is formed under a pressure at or near atmospheric pressure, and a reactive gas containing a reducing gas and a transparent conductive film forming gas is used as a discharge space. It is characterized by being formed on a substrate by introducing it into a plasma state and exposing the substrate to a reactive gas in the plasma state.

  That is, under a pressure at or near atmospheric pressure, a reactive gas is introduced into the discharge space to form a plasma state, and the substrate is exposed to the plasma-state reactive gas to thereby form a transparent conductive film on the substrate. In the method for forming a transparent conductive film, the reactive gas contains a reducing gas.

In the atmospheric pressure plasma CVD according to the present invention, a high-frequency voltage exceeding 0.5 kHz and power (power density) of 100 W / cm ² or less are supplied between opposing electrodes to excite a reactive gas. Then plasma is generated.

  In the present invention, the upper limit of the frequency of the high-frequency voltage applied between the electrodes is preferably 150 MHz or less. More preferably, it is 15 MHz or less.

  Moreover, as a lower limit of the frequency of a high frequency voltage, Preferably it is 0.5 kHz or more, More preferably, it is 10 kHz or more. More preferably, the frequency exceeds 100 KHz.

Further, the lower limit value of the power supplied between the electrodes is preferably 0.1 W / cm ² or more, more preferably 1 W / cm ² or more. As an upper limit, Preferably it is 100 W / cm < ² > or less, More preferably, it is 60 W / cm < ² > or less. The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

  As the plasma discharge treatment, electrode configuration, and manufacturing conditions applicable to the above manufacturing method, those shown in FIGS. 1 to 6 can be appropriately adjusted and used.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of transparent electrode >>
[Preparation of transparent electrode 1]
(Formation of transparent conductive film)
As a base material, it formed on the roll-shaped polyethylene terephthalate film of thickness 100 micrometers using the following atmospheric pressure plasma discharge processing apparatus so that the film thickness of a transparent conductive film might be set to 10 nm on the following discharge conditions. This is called a transparent conductive film forming method 1.

  The atmospheric pressure plasma discharge processing apparatus having the roll rotating electrode shown in FIG. 3 was used. Here, the roll electrode was manufactured by performing ceramic spraying on the dielectric and covering it with 1 mm in thickness. The square electrode was also processed in the same manner for the square hollow titanium pipe, and the gap between the electrodes was set to 1 mm on the roll electrode, and two electrodes were installed for forming the thin film in step 1 and for oxidizing the step 2. Furthermore, a stainless steel jacket roll base material having a cooling function with cooling water was used on the roll electrode side. During plasma discharge, the first electrode (roll rotating electrode) and the second electrode (square tube fixed electrode group) were adjusted and kept at 80 ° C., and the roll rotating electrode was rotated by a drive to form a thin film.

(Process 1: Film formation process)
<Power supply conditions>
The first power source was not used and only the second power source was used.

Second power supply (Pearl Industries high frequency power supply): ω2 = 13.56 MHz, V2 = 750 V, I2 = 150 mA, output density = 7 W / cm ²
Gap between electrodes: 1.0mm
<Gas 1 condition>
In acetylacetonate gas for vaporization: 10 L / min, 150 ° C.
Dibutyltin diacetate vaporizing Ar gas: 0.5 L / min, 100 ° C.
Discharge gas: Ar gas 20L / min
Reducing gas: H ₂ gas 0.5 L / min
(Process 2: Oxidation process)
<Power supply conditions>
The third power source is not used and only the fourth power source is used. Fourth power source (Pearl Industries high frequency power source): ω4 = 13.56 MHz, V4 = 750 V, I4 = 150 mA / cm ² , output density = 7 W / cm ²
Gap between electrodes: 1.0mm
<Gas 2 conditions>
Discharge gas: Ar gas 20L / min
Oxidizing gas: O ₂ gas 0.005 L / min
(Give metal particles)
Silver with respect to the number of In atoms contained in the transparent high-refractive-index layer in the total film thickness is spin-coated with silver nanoink (manufactured by Vacuum Metallurgical Co., Ltd.) containing silver particles having an average particle diameter of 4 nm on the formed transparent conductive film. The coating was performed under the condition that the average ratio of the number of atomic atoms of the particles was 7 atm%, followed by firing for 30 minutes in a 200 ° C. blowing-type drying furnace.

(Formation of transparent conductive film)
Next, a transparent conductive film having a thickness of 10 nm was formed on the surface provided with silver particles in the same manner as described above, and a transparent electrode 1 having a total film thickness of 20 nm was produced.

[Production of transparent electrodes 2 to 6]
In preparation of the said transparent electrode 1, formation of a transparent conductive film and provision of a metal particle were repeated, and the transparent electrodes 2-6 which consist of the total film thickness of Table 1 were produced.

  In addition, each of the produced transparent electrodes has a ratio of the number of silver atoms to the number of In atoms contained in the transparent high refractive index layer in the thickness direction, and the above-described high-resolution transmission electron microscope and energy dispersive X-ray analyzer ( As a result of measurement using EDS) “Voager”, all were in the range of 4.0 atm% or more and 35 atm% or less.

<< Evaluation of transparent electrode >>
(Measurement of transmittance)
According to JIS-R-1635, the transmittance at 550 nm is measured using a Hitachi spectrophotometer U-4000 type. If the transmittance is 95% or more, A, 90% or more, less than 95% B If less than 90%, C was determined.

  If it was A or B in the evaluation rank, it was determined that there was no practical problem.

[Measurement of surface resistance]
According to JIS-R-1637, it calculated | required by the four terminal method. For the measurement, Lorester GP, MCP-T600 manufactured by Mitsubishi Chemical Corporation is used. If the surface resistance is in the range of 1Ω / □ or more and less than 7Ω / □, A, 7Ω / □ or more, and less than 13Ω / □, B, If it was 13Ω / □ or more, it was determined as C.

  If it was A or B in the evaluation rank, it was determined that there was no practical problem.

[Evaluation of surface roughness]
Using DEKTAK3030 manufactured by Sloane, sweep it over 1 mm under a load of 20 mg at an arbitrary position on the transparent electrode, measure the distance between the largest concave portion and the largest convex portion, and perform this five times. The average value was calculated | required and the surface unevenness | corrugation was determined according to the following reference | standard.

  If it was A or B in the following evaluation rank, it was determined that there was no practical problem.

A: The average distance between the largest concave portion and the largest convex portion is less than 5 nm. B: The average distance between the largest concave portion and the largest convex portion is 6 nm or more and less than 10 nm. C: The average distance between the largest concave portion and the largest convex portion. 11 nm or more [Evaluation of etching properties]
A photolithographic photosensitive solution was applied onto the transparent conductive film of each sample, dried, subjected to pattern exposure, developed, and then immersed in an etching solution (30 ° C.) having the following composition for etching treatment. The etching time was sampled at 30 seconds, 45 seconds, 60 seconds, 120 seconds, and 180 seconds. Subsequently, washing and drying were performed, and the cross section of the boundary portion between the etched portion and the non-etched portion was observed with an electron microscope for the dried sample, and the degree of film removal was visually evaluated.

<Etching solution composition>
An etching solution was prepared by mixing water, concentrated hydrochloric acid and a 40 mass% ferric chloride solution at a mass ratio of 85: 8: 7.

<Evaluation level of etching pattern>
A: The transparent conductive film can be removed in 30 seconds and the boundary portion of the etching pattern can be removed. B: The transparent conductive film can be removed in 45 seconds and the boundary portion of the etching pattern can be removed. C: Transparent in 60 seconds. The conductive film can be removed and the boundary portion of the etching pattern is good. D: The transparent conductive film can be removed in 120 seconds, but the boundary portion of the etching pattern is not very good. E: Transparent conductivity even if it exceeds 180 seconds. There was a portion where the film remained slightly, and the boundary portion of the etching pattern was jagged (uneven). F: The transparent conductive film remained in an island shape even after 180 seconds.

  If it was the range of AC in the said evaluation rank, it determined with there being no problem practically.

  Table 1 shows the evaluation results obtained as described above.

  As is clear from the results shown in Table 1, transparent high refractive index layers and silver particles are alternately laminated on a transparent substrate, and the transparent electrode of the present invention having a total film thickness of 30 nm or more and 100 nm or less is As compared with the comparative example, it can be seen that it has good etching properties and has excellent transparency, conductivity and surface smoothness.

Example 2
<< Preparation of transparent electrode >>
In the transparent electrode 4 (total film thickness of 80 nm) described in Example 1, the ratio of the number of silver atoms to the number of In atoms contained in the transparent high refractive index layer in the thickness direction is appropriately changed by changing the silver particle application conditions. Transparent electrodes 11 to 15 were produced in the same manner except that (minimum value & maximum value) was changed as shown in Table 2.

<< Evaluation of transparent electrode >>
About each produced said transparent electrode, it carried out similarly to the method of Example 1, and measured the transmittance | permeability, the measurement of surface resistance value, the evaluation of surface unevenness, and the evaluation of etching property, and showed the obtained result. It is shown in 2.

  As is clear from the results shown in Table 2, in the transparent electrode in which transparent high refractive index layers and silver particles are alternately laminated on a transparent substrate, the number of In atoms contained in the transparent high refractive index layer in the thickness direction It can be seen that the transparent electrode having a ratio range (minimum value & maximum value) of the number of silver atoms with respect to 10 to 1.0 atm% is 10 atm% or less exhibits more excellent effects.

Example 3
<< Preparation of transparent electrode >>
In the transparent electrode 4 (total film thickness of 80 nm) described in Example 1, the conditions for applying silver particles are changed as appropriate, and the number of silver particles relative to the number of In atoms contained in the transparent high refractive index layer in the total film thickness. Transparent electrodes 21 to 26 were produced in the same manner except that the average ratio was changed as shown in Table 3.

<< Evaluation of transparent electrode >>
About each produced said transparent electrode, it carried out similarly to the method of Example 1, and measured the transmittance | permeability, the measurement of surface resistance value, the evaluation of surface unevenness, and the evaluation of etching property, and showed the obtained result. 3 shows.

  As is clear from the results shown in Table 3, in the transparent electrode in which transparent high refractive index layers and silver particles are alternately laminated on a transparent substrate, the number of In atoms contained in the transparent high refractive index layer in the total film thickness It can be seen that the transparent electrode having an average ratio of the number of atoms of silver particles to 1.0 atm% or more and 10 atm% or less exhibits a more excellent effect.

Example 4
<< Preparation of transparent electrode >>
Transparent electrodes 31 to 37 were produced in the same manner except that the average particle diameter of the silver particles used in the transparent electrode 4 (total film thickness 80 nm) described in Example 1 was changed as shown in Table 4.

<< Evaluation of transparent electrode >>
About each produced said transparent electrode, it carried out similarly to the method of Example 1, and measured the transmittance | permeability, the measurement of surface resistance value, the evaluation of surface unevenness, and the evaluation of etching property, and showed the obtained result. 4 shows.

  As is clear from the results shown in Table 4, in the transparent electrode in which transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the average particle diameter is 1 nm or more and 10 nm or less as the metal particles to be used. It turns out that the more excellent effect is exhibited by using a certain silver particle.

Example 5
<< Preparation of transparent electrode >>
[Preparation of transparent electrode 41]
In the transparent electrode 4 (total film thickness of 80 nm) described in Example 1, instead of providing metal particles,
According to the method described in Example 1 of Japanese Patent Laid-Open No. 2002-15623, a transparent electrode 41 was produced in the same manner except that an alloy metal layer made of silver, palladium, and copper was provided using a direct current magnetron sputtering method. .

[Preparation of transparent electrode 42]
In the transparent electrode 4 (total film thickness of 80 nm) described in Example 1, the gold nano ink containing gold particles having an average particle diameter of 4 nm was used instead of the silver nano ink containing silver particles having an average particle diameter of 4 nm for the application of the metal particles. A transparent electrode 42 was produced in the same manner except that (Vacuum Metallurgy) was used.

[Preparation of transparent electrode 43]
In the transparent electrode 4 (total film thickness of 80 nm) described in Example 1, the addition of metal particles was replaced with silver nanoink containing silver particles having an average particle diameter of 4 nm, and copper nanoink containing copper particles having an average particle diameter of 4 nm A transparent electrode 43 was produced in the same manner except that (vacuum metallurgy) was used.

[Preparation of transparent electrode 44]
In the transparent electrode 4 (total film thickness of 80 nm) described in Example 1, the transparent conductive film was reduced according to the method described in the example of JP-A-2003-234028 under atmospheric pressure or pressure near atmospheric pressure. A transparent electrode 44 was produced in the same manner except that a reactive gas containing a gas and a transparent conductive film forming gas was introduced into the discharge space to obtain a plasma state and formed according to a method of exposing to a reactive gas in a plasma state. This is called a transparent conductive film forming method 2.

[Preparation of transparent electrode 45]
In the transparent electrode 4 (total film thickness 80 nm) described in Example 1, according to the method described in the example of Japanese Patent Application Laid-Open No. 2004-63195, the transparent conductive film is set to atmospheric pressure or a pressure in the vicinity thereof. , Introducing at least a discharge gas of the transparent conductive film forming gas mainly composed of a discharge gas and a thin film forming gas between the counter electrodes, applying a high frequency voltage between the counter electrodes to bring the discharge gas into a plasma state, Subsequently, after forming the thin film on the base material by exposing the base material to the transparent conductive film forming gas in a plasma state, the thin film on the base material is exposed to an oxidizing gas, and the thin film on the base material is further in a plasma state A transparent electrode 45 was produced in the same manner except that it was formed by alternately exposing to a transparent conductive film forming gas and an oxidizing gas. This is referred to as a transparent conductive film forming method 3.

  As is clear from the results shown in Table 5, it can be seen that the transparent electrode 41 formed by applying metal atoms to the sputtering method to form a metal layer has extremely poor etching properties.

  In addition, excellent results could be obtained even when gold particles or copper particles were used as metal particles instead of silver particles. In addition, it was confirmed that excellent results were similarly obtained by forming the transparent conductive film by the forming method 2 or the forming method 3 instead of the forming method 1.

It is a schematic block diagram which shows an example of the flat electrode type atmospheric pressure plasma processing apparatus used for this invention. It is a schematic block diagram of the thin film forming apparatus which has the shielding blade | wing preferably used for this invention. It is a schematic block diagram which shows an example of the roll rotating electrode type atmospheric pressure plasma processing apparatus used for this invention. It is a figure which shows the atmospheric pressure plasma processing apparatus which has arrange | positioned two roll rotating electrode type atmospheric pressure plasma processing apparatuses in series. It is a perspective view which shows an example of the structure of the electroconductive metal base material of a roll rotating electrode, and the dielectric material coat | covered on it. It is a perspective view which shows an example of the structure of the electroconductive metal preform | base_material of a square electrode, and the dielectric material coat | covered on it.

Explanation of symbols

3, 43 4th electrode 4, F base material 5, 6, 55, 56 Slit 7, 41, 50 Second electrode 8, 42, 70 First electrode 9 Support base 11, 13 Discharge gas 12 Thin film forming gas 14 Oxidizing property Gas 15, 16, 60, 61 Gas supply pipe 17 Temperature adjusting means 31, 71 First power source 32, 72 First filter 33, 73 Second power source 34, 74 Second filter 35, 75 Fourth power source 36, 76 Fourth Filter 37, 57 Excited gas 1
38, 58 Excited gas 2
44 Spacer 46, 47 Square electrode width 48, 49 Shielding blade 64, 67 Guide roll 65 Nip roll G1 Interelectrode gap G2, G3 Electrode slit gap

Claims (14)

Transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less. Transparent electrode characterized by The metal particles are at least one selected from Au, Ag, Al, Cu, Pt and alloys thereof, and the average particle diameter of the metal particles is 1 nm or more and 10 nm or less. Item 2. The transparent electrode according to Item 1. The transparent electrode according to claim 1, wherein the transparent high refractive index layer is a transparent conductive film. The transparent conductive film is doped with In ₂ O ₃ , Sn-doped indium oxide (ITO), ZnO, In ₂ O ₃ —ZnO amorphous oxide (IZO), Al-doped ZnO (AZO), and Ga. ZnO (GZO), any of the preceding claims, characterized in that a main component a transparent conductive film formed of at least one material selected from SnO ₂ (FTO) and TiO ₂ doped with SnO _2, F-containing 2. The transparent electrode according to item 1. The average ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the total thickness of the laminated film is 1.0 atm% or more and 10 atm% or less. The transparent electrode according to claim 1, wherein the transparent electrode is a transparent electrode. The ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the thickness direction is 1.0 atm% or more and 50 atm% or less. The transparent electrode according to any one of claims 1 to 5, characterized in that: Transparent transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less A method for producing a transparent electrode for producing an electrode, comprising:
The transparent high-refractive index layer excites the gas 1 by supplying a gas 1 containing a thin film forming gas to the discharge space and applying a high-frequency electric field to the discharge space at or near atmospheric pressure. Step 1 of forming a thin film on a substrate by exposing the material to excited gas 1, and supplying gas 2 containing an oxidizing gas to the discharge space under atmospheric pressure or a pressure in the vicinity thereof after Step 1 Formed by performing step 2 of exciting the gas 2 by applying a high-frequency electric field to the discharge space and exposing the substrate having a thin film formed of the gas 1 to the excited gas 2;
The method for producing a transparent electrode is characterized in that the metal particles are applied onto the transparent high refractive index layer by a coating method. Transparent transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less A method for producing a transparent electrode for producing an electrode, comprising:
The transparent high refractive index layer has at least a discharge gas of a transparent conductive film forming gas having a discharge gas and a thin film forming gas as main components, with the space between the counter electrodes (discharge space) being at or near atmospheric pressure. Introduced between the counter electrodes, a high-frequency voltage is applied between the counter electrodes to bring the discharge gas into a plasma state, and then the substrate is exposed to the transparent conductive film forming gas in the plasma state to form a thin film on the substrate. After forming, the thin film on the base material is exposed to an oxidizing gas, and further, the thin film on the base material is alternately exposed to the transparent conductive film forming gas in the plasma state and the oxidizing gas,
The method for producing a transparent electrode is characterized in that the metal particles are applied onto the transparent high refractive index layer by a coating method. Transparent transparent high refractive index layers and metal particles are alternately laminated on a transparent substrate, the total film thickness is 30 nm or more and 100 nm or less, and the surface resistance value is 1Ω / □ or more and 13Ω / □ or less A method for producing a transparent electrode for producing an electrode, comprising:
The transparent high-refractive index layer is formed in a plasma state by introducing a reactive gas containing a reducing gas and a transparent conductive film forming gas into a discharge space at atmospheric pressure or near atmospheric pressure, and the substrate is in the plasma state. Formed on the substrate by exposure to reactive gases of
The method for producing a transparent electrode is characterized in that the metal particles are applied onto the transparent high refractive index layer by a coating method. The metal particles are at least one selected from Au, Ag, Al, Cu, Pt and alloys thereof, and the average particle diameter of the metal particles is 1 nm or more and 10 nm or less. Item 10. The method for producing a transparent electrode according to any one of Items 7 to 9. The method for producing a transparent electrode according to claim 7, wherein the transparent high refractive index layer is a transparent conductive film. The transparent conductive film is doped with In ₂ O ₃ , Sn-doped indium oxide (ITO), ZnO, In ₂ O ₃ —ZnO amorphous oxide (IZO), Al-doped ZnO (AZO), and Ga. ZnO (GZO), any claim 7-11, characterized in that a main component a transparent conductive film formed of at least one material selected from SnO ₂ (FTO) and TiO ₂ doped with SnO _2, F-containing A method for producing the transparent electrode according to claim 1. The average ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the total film thickness of the laminated film is 10 atm% or less. The manufacturing method of the transparent electrode of any one of Claims 7-12 to do. The ratio of the number of metal atoms contained in the metal particles to the number of base material atoms of the transparent conductive film forming material contained in the transparent high refractive index layer in the thickness direction is 1.0 atm% or more and 50 atm% or less. The method for producing a transparent electrode according to claim 7, wherein the method is a transparent electrode.

Images