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WO2011046011A1 - Film conducteur transparent à propriétés barrières, son procédé de fabrication, et élément électroluminescent organique et photopile organique utilisant le film conducteur transparent à propriétés barrières - Google Patents

Film conducteur transparent à propriétés barrières, son procédé de fabrication, et élément électroluminescent organique et photopile organique utilisant le film conducteur transparent à propriétés barrières Download PDF

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Publication number
WO2011046011A1
WO2011046011A1 PCT/JP2010/066664 JP2010066664W WO2011046011A1 WO 2011046011 A1 WO2011046011 A1 WO 2011046011A1 JP 2010066664 W JP2010066664 W JP 2010066664W WO 2011046011 A1 WO2011046011 A1 WO 2011046011A1
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Prior art keywords
layer
transparent conductive
transparent
group
barrier
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Japanese (ja)
Inventor
宏 高田
昌紀 後藤
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2011536086A priority Critical patent/JP5673547B2/ja
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention can be suitably used as a barrier transparent electrode for photoelectric conversion elements such as organic EL elements and organic solar cells, has excellent barrier properties, conductivity, chemical resistance, and in addition, suitable for dehydration treatment and smoothness.
  • the present invention relates to an organic EL device and an organic solar cell, which are excellent in barrier properties, a method for producing the same, and a performance deterioration with time.
  • the organic EL element is a self-luminous material, it has many excellent features such as low driving voltage and low power consumption, high brightness, quick response, wide viewing angle, and thinning of the element. It has attracted attention as a lighting device that replaces incandescent bulbs and fluorescent lamps, or as a flat display device that replaces liquid crystal displays and plasma displays.
  • the organic solar cell uses conventional silicon-based and inorganic compound-based materials because it has excellent features such as a simple manufacturing method, low production cost, light weight, thinness, and flexibility and design. It is expected as a power generation device to replace solar cells.
  • an organic EL element or an organic solar cell is formed by laminating a transparent base material / transparent electrode / organic functional layer / counter electrode / sealing layer.
  • the organic functional layer has a light emitting capability. The light emission generated in the organic light emitting layer by applying a voltage between both electrodes is extracted to the outside through the transparent electrode.
  • the thickness of the organic functional layer is extremely thin (100 nm or less), and if the irregularities on the surface of the transparent electrode are large, current leakage and electric field concentration occur between the two electrodes, leading to deterioration of device performance (photoelectric characteristics, lifetime, etc.). . Therefore, high smoothness is required for the transparent electrode surface.
  • the organic functional layer is likely to be deteriorated or altered by water vapor or oxygen, the transparent substrate is required to have high gas barrier properties.
  • the film base material has a greatly inferior gas barrier function for blocking water vapor, oxygen and the like compared to the glass base material, the use of the film base material causes the performance of the organic photoelectric conversion element to deteriorate. Therefore, in order to prevent the performance deterioration of the organic photoelectric conversion element, it is essential to improve the gas barrier function of the film base material.
  • a barrier transparent conductive film in which a gas barrier layer such as a metal oxide layer is formed on a film substrate and then a transparent conductive layer such as ITO is laminated has been proposed.
  • a gas barrier layer such as a metal oxide layer
  • a transparent conductive layer such as ITO
  • a transparent gas barrier thin film mainly composed of a metal oxide and a protective film mainly composed of an organic crosslinked body are sequentially formed on the transparent film by a vacuum film forming method.
  • a technique for improving the gas barrier property, chemical resistance, and surface smoothness of a transparent transparent conductive film by laminating a transparent conductive thin film made of a metal oxide has been proposed (see, for example, Patent Document 1).
  • the method of forming all of the gas barrier thin film, organic protective film, and transparent conductive thin film by the vacuum film formation method is inferior in productivity, and if the film formation rate is increased to improve productivity, the film surface becomes rough. Since the formation of spike-like projections occurs, there is a problem that the productivity and the smoothness of the film surface cannot be compatible.
  • an object of the present invention is to provide a low-cost barrier transparent conductive film having excellent barrier properties, electrical conductivity and chemical resistance, and having excellent dehydration suitability (hereinafter referred to as dehydration) and smoothness, and its production. It is to provide a method. Another object of the present invention is to provide an organic EL element and an organic solar cell with improved performance stability over time by using the barrier transparent conductive film of the present invention as a transparent electrode.
  • a transparent transparent conductive film in which at least a transparent barrier layer and a transparent conductive layer are laminated on a transparent film substrate, and having at least one transparent resin layer between the transparent barrier layer and the transparent conductive layer, And the said transparent conductive layer contains the network structure of a metal fine wire at least,
  • the barriering transparent conductive film characterized by the above-mentioned.
  • An organic EL device in which at least one of the opposing electrodes is composed of a transparent conductive film, wherein the transparent conductive film is the barrier transparent conductive film according to any one of 1 to 4 above.
  • Organic EL element is composed of a transparent conductive film, wherein the transparent conductive film is the barrier transparent conductive film according to any one of 1 to 4 above.
  • An organic solar battery in which at least one of the opposing electrodes is formed of a transparent conductive film, wherein the transparent conductive film is the barrier transparent conductive film according to any one of 1 to 4 above.
  • Organic solar cell in which at least one of the opposing electrodes is formed of a transparent conductive film, wherein the transparent conductive film is the barrier transparent conductive film according to any one of 1 to 4 above.
  • a barrier transparent conductive film having excellent barrier properties, electrical conductivity and chemical resistance, and also excellent in dewaterability and smoothness. Therefore, it can be preferably used as a barrier transparent electrode of a photoelectric conversion element such as an organic EL element or an organic solar cell, which requires high barrier properties, conductivity, smoothness, and further low water content.
  • the performance stability of the device can be greatly improved.
  • the wet process can be applied to the manufacturing method of the barrier transparent conductive film of the present invention, it is effective in improving productivity and reducing energy as compared with the manufacturing method using the conventional vacuum process, and reducing the cost. And improved environmental aptitude.
  • the barrier transparent conductive film having the above configuration when the present inventors applied the barrier transparent conductive film having the above configuration to an organic EL element or an organic solar battery, the barrier transparent conductive film having a protective film mainly composed of an organic crosslinked body was used. It was found that the obtained device was inferior in stability over time, such as device life, as compared with a device using a barrier transparent conductive film having no protective film. When the present inventors diligently analyzed about this cause, it became clear that in the barrier-type transparent conductive film having a protective film, the element performance deteriorates by the following mechanism.
  • Moisture diffused in the protective film is easily covered in the dehydration process such as heat treatment and vacuum treatment before manufacturing the organic photoelectric conversion element because both sides of the protective film are covered with the gas barrier film and the metal oxide transparent conductive film. Can not be removed.
  • the inventors of the present application have conducted extensive studies to overcome the above-described problems in the conventional barrier transparent conductive film, and as a result, a transparent barrier layer, a transparent resin layer, and a fine metal wire network structure are formed on the transparent film substrate. It is possible to realize a barrier transparent conductive film having excellent barrier properties and conductivity, suitability for patterning treatment (chemical resistance), and excellent dehydrating properties by a transparent transparent conductive film having a structure in which transparent conductive layers are sequentially laminated. I found it.
  • the transparent conductive layer is a transparent film base having a transparent barrier layer with a transparent resin as an adhesive.
  • a barrier transparent conductive film excellent in smoothness of the conductive layer could be obtained by transferring it onto a material to produce a barrier transparent conductive film having the above structure.
  • the dewaterability of the barrier transparent conductive film which was a problem of the prior art, has been improved because the transparent conductive layer according to the present invention including the network structure of fine metal wires has a sufficient aperture ratio (transparent It is thought that the water accumulated in the transparent resin layer or the like can be easily removed by dehydration because the projected area of the conductive layer has the ratio of the area where there is no fine metal wire to the total area) .
  • the said aperture ratio and electroconductivity of a transparent conductive layer were able to be aimed at by using the network structure of a metal fine wire for a transparent conductive layer.
  • the organic EL element or the organic solar cell is transparent. It is difficult to obtain sufficient conductivity required for use as an electrode.
  • a smooth surface cannot be obtained with a conductive layer in which a fine metal wire network structure is formed on a substrate.
  • a conductive material that is inferior in surface smoothness such as a thin metal wire, it is possible to achieve a high level of smoothness required for organic EL elements and organic solar cells.
  • a vacuum process is not required for film forming of a transparent resin layer and a transparent conductive layer at least, it is possible to reduce manufacturing cost significantly.
  • the device performance stability over time can be significantly improved by applying the barrier transparent conductive film having the above characteristics to the transparent electrode of an organic EL device or an organic solar cell.
  • the barrier transparent conductive film of the present invention is a barrier transparent conductive film in which at least a transparent barrier layer and a transparent conductive layer are laminated on a transparent film substrate, and at least between the transparent barrier layer and the transparent conductive layer.
  • This is a technical feature common to the inventions according to claims 1 to 4, characterized in that it has one transparent resin layer and the transparent conductive layer includes at least a metal thin wire network structure.
  • “transparent” means a visible light wavelength measured by a method according to “Testing method of total light transmittance of plastic-transparent material” of JIS K 7361-1 (corresponding to ISO 13468-1). It means that the total light transmittance in the region is 60% or more.
  • the surface roughness (Ry_f) of the transparent conductive layer may be 1 nm ⁇ Ry_f ⁇ 50 nm.
  • a network structure of fine metal wires is formed on a release surface of a release substrate having a release surface roughness (Ry_d) of 1 nm ⁇ Ry_d ⁇ 50 nm.
  • barrier transparent conductive film of the present invention include an organic EL device in which at least one of opposing electrodes is formed of a transparent conductive film and a transparent conductive film of an organic solar cell.
  • the transparent film base material used for the barrier transparent conductive film of the present invention is not particularly limited as long as it has high light transmissivity, and its material, shape, structure, thickness, etc. are known ones. It can be suitably selected from the inside.
  • Examples thereof include vinyl resin films, polyether ether ketone resin films, polysulfone resin films, polyether sulfone resin films, polycarbonate resin films, polyamide resin films, polyimide resin films, acrylic resin films, and triacetyl cellulose resin films. If the resin film has a transmittance of 80% or more in the visible wavelength (380 to 780 nm), the transmission according to the present invention is used. It can be preferably applied to the resin film.
  • biaxially stretched polyethylene terephthalate (PET) film in terms of transparency, heat resistance, ease of handling, strength and cost, biaxially stretched polyethylene terephthalate (PET) film, biaxially stretched polyethylene naphthalate (PEN) film, polyethersulfone (PES) film, polycarbonate ( PC) film, and more preferably a biaxially stretched polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film.
  • PET polyethylene terephthalate
  • PEN biaxially stretched polyethylene naphthalate
  • PES polyethersulfone
  • PC polycarbonate
  • the transparent film substrate used in the present invention can be subjected to a surface treatment or an easy-adhesion layer in order to improve the film forming property and adhesion of the transparent barrier layer.
  • a conventionally well-known technique can be used about a surface treatment or an easily bonding layer.
  • the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • the material for the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, epoxy copolymer, and the like. it can.
  • the refractive index of the easy adhesion layer adjacent to the film is set to 1.57 to 1.63, so that the interface reflection between the film substrate and the easy adhesion layer is achieved. This is more preferable because the transmittance can be improved.
  • a method for adjusting the refractive index it can be carried out by mixing an oxide sol having a relatively high refractive index such as a tin oxide sol or a cerium oxide sol with the material of the easy-adhesion layer, and adjusting the ratio as appropriate.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • the hard-coat layer may be formed previously.
  • the transparent barrier layer related to the transparent conductive film with a barrier property of the present invention has a dense structure capable of suppressing the permeation of gas molecules, and has a function of preventing deterioration or alteration of the organic photoelectric conversion element due to intrusion of water vapor or oxygen. Have.
  • the gas barrier function of the transparent barrier layer according to the present invention is such that the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method according to JIS K 7129-1992 is 1 ⁇ . It is preferably 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less, more preferably 10 ⁇ 4 g / (m 2 ⁇ 24 h) or less, and particularly preferably 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ atm) (1 atm is 1.01325 ⁇ 10 5 Pa. .) Is preferably 1 ⁇ 10 ⁇ 4 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less, more preferably 1 ⁇ 10 ⁇ 5 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less. .
  • the transparent barrier layer according to the present invention is preferably composed of a silicon compound such as silicon oxide or silicon nitride, a metal compound such as metal oxide or metal nitride, or a mixture thereof.
  • a method for forming the transparent barrier layer any method can be used as long as it can form a target thin film.
  • a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, or the like is suitable for forming a silicon compound or metal compound layer.
  • Japanese Patent Registration No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, The forming methods described in JP-A-2002-361774 can be applied.
  • the component contained in the transparent barrier layer is not particularly limited as long as it satisfies the above performance, but for example, one type selected from the group consisting of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like.
  • Oxides, nitrides, or oxynitrides containing silicon or metal are preferable.
  • an oxide, nitride, or oxynitride containing at least one silicon or metal selected from the group consisting of Si, Al, In, Sn, and Zn is more preferable.
  • each may have the same composition or a different composition.
  • the thickness of the transparent barrier layer is not particularly limited, but if it is too thick, cracks may occur due to bending stress and the barrier property may be impaired.If it is too thin, the film is distributed in islands and the barrier property is sufficiently obtained. There may not be. Therefore, the thickness of the barrier layer is preferably in the range of 5 nm to 1000 nm, more preferably 10 nm to 1000 nm, and most preferably 10 nm to 200 nm.
  • silicon oxide, silicon nitride or silicon oxynitride as the barrier layer in order to achieve both barrier properties and high transparency.
  • SiOx which is a silicon oxide
  • SiNy which is silicon nitride
  • 1.2 ⁇ y ⁇ 1.3 when y ⁇ 1.2, coloring may increase.
  • SiOxNy which is silicon oxynitride
  • an oxygen-rich film in order to improve the substrate adhesion, and specifically, 1 ⁇ x ⁇ 2 and 0 ⁇ y. It is preferable to satisfy ⁇ 1.
  • a nitrogen-rich film is preferable, and specifically, it is preferable to satisfy 0 ⁇ x ⁇ 0.8 and 0.8 ⁇ y ⁇ 1.3. .
  • the transparent resin layer related to the transparent conductive film of the present invention functions as an adhesive between the transparent barrier layer and the transparent conductive layer according to the present invention and also functions as a protective layer for the transparent barrier layer, and is transparent in the visible region.
  • the resin material is not particularly limited as long as it is a certain resin material, but is preferably a water-insoluble water-soluble resin, for example, a curable resin or a thermoplastic resin, in order to perform a cleaning process or a patterning process on the transparent conductive layer. Resin or the like can be used.
  • curable resins include thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among these curable resins, facilities for resin curing are simple and excellent in workability.
  • the ultraviolet curable resin is a resin that is cured through a crosslinking reaction or the like by ultraviolet irradiation, and a component containing a monomer having an ethylenically unsaturated double bond is preferably used.
  • a resin that is cured through a crosslinking reaction or the like by ultraviolet irradiation and a component containing a monomer having an ethylenically unsaturated double bond is preferably used.
  • an acrylic urethane resin, a polyester acrylate resin, an epoxy acrylate resin, a polyol acrylate resin, or the like can be suitably used.
  • Acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates including methacrylates) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Corporation) is preferably used.
  • UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, generally as disclosed in JP-A-59-151112. Can be used.
  • ultraviolet curable epoxy acrylate resin examples include those produced by reacting an epoxy acrylate with an oligomer, a reactive diluent and a photoreaction initiator added thereto. Those described in JP-A No. 1-105738 can be used.
  • UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.
  • the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond.
  • Monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.
  • 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethane (meth) acrylate are the main components of the binder.
  • the photoinitiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.
  • the photoinitiator can also be used as a photosensitizer.
  • a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.
  • the photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.
  • the transparent conductive layer relating to the barrier transparent conductive film of the present invention includes at least a network structure of fine metal wires.
  • the light transmittance of the transparent conductive layer according to the present invention is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more as the total light transmittance.
  • the total light transmittance can be measured according to a known method using a spectrophotometer or the like.
  • the electrical resistance of the transparent conductive layer according to the present invention is preferably 1000 ⁇ / ⁇ or less, more preferably 100 ⁇ / ⁇ or less, as the surface resistivity. If it exceeds 1000 ⁇ / ⁇ , it may not function sufficiently as a general transparent electrode.
  • an organic photoelectric conversion element it is preferably 50 ⁇ / ⁇ or less, more preferably 10 ⁇ / ⁇ or less, and particularly preferably 1 ⁇ / ⁇ or less.
  • the surface resistivity can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity test method using a conductive plastic four-probe method), or a commercially available surface resistivity meter can be used. And can be measured easily.
  • the thickness of the transparent conductive layer according to the present invention is not particularly limited. For example, by changing the width and thickness of the thin metal wire, the diameter and the weight per unit area are changed when the thin metal wire is a metal nanowire. It can be selected as appropriate according to the conditions.
  • the transparent conductive layer of the present invention can contain a transparent binder resin or the like in order to maintain a network structure of fine metal wires.
  • the transparent binder resin is not particularly limited as long as it is a transparent resin capable of forming a coating liquid.
  • a polyester resin, a polystyrene resin, an acrylic resin, a polyurethane resin, an acrylic urethane resin, a polycarbonate resin, Cellulose resins, butyral resins, etc. can be used alone or in combination.
  • the metal wire network structure according to the present invention is a thin wire made of a metal material such as a single metal or alloy, arranged in a uniform mesh, straight or curved stripe or comb shape, Triangles such as regular triangles, isosceles triangles, right triangles, squares such as squares, rectangles, rhombuses, parallelograms, trapezoids, (positive) hexagons, (positive) n-gons such as (positive) octagons, circles, ellipses Arrangement of geometric pattern line patterns with regular combinations of star shapes, arrangement of irregular figure line patterns, arrangement of straight or curved metal thin lines in a mesh shape Etc. can be configured.
  • the metal wire network structure according to the present invention can function as a conductive network structure.
  • the composition of the fine metal wire is not particularly limited, and may be composed of one or more metals such as a noble metal element and a base metal element, but noble metals (for example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium, Osmium and the like) and at least one metal belonging to the group consisting of iron, cobalt, copper, tin and nickel, and more preferably at least silver from the viewpoint of conductivity. Furthermore, in order to achieve both conductivity and stability, it is also preferable that silver and at least one metal other than silver be included.
  • noble metals for example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium, Osmium and the like
  • at least one metal belonging to the group consisting of iron, cobalt, copper, tin and nickel and more preferably at least silver from the viewpoint of conductivity.
  • silver and at least one metal other than silver be included.
  • the cross-sectional area of the fine metal wires is 1 ⁇ 10 ⁇ 4 ⁇ m 2 to 1 ⁇ 10 It is preferably 4 ⁇ m 2 .
  • the cross-sectional areas of the fine metal wires are equal, it is preferable to increase the thickness of the fine metal wires because the transparency can be improved. From the viewpoint of transparency, increasing the aperture ratio (ratio of the area where the thin metal wire is not present in the projected area of the transparent conductive layer to the total area), that is, reducing the width of the fine metal wire and widening the interval. It is preferable to do.
  • the width and thickness of the fine metal wires are preferably 1 ⁇ 10 ⁇ 2 ⁇ m to 1 ⁇ 10 2 ⁇ m, and the line spacing is 1 ⁇ 10 ⁇ 1 ⁇ m to 1 ⁇ 10 3 ⁇ m. Is preferred.
  • the surface resistivity of the transparent conductive layer including the metal wire network structure according to the present invention is preferably 50 ⁇ / ⁇ or less, more preferably 10 ⁇ / ⁇ or less, and particularly preferably 1 ⁇ / ⁇ or less. Further, from the viewpoints of transmittance and dehydrability, the aperture ratio is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.
  • a known method can be used as a method for forming a network structure of fine metal wires according to the present invention.
  • a method of forming a fine metal wire pattern using a photolithography method a method of directly forming a pattern using a printing method or an inkjet method, or a method of forming a pattern by exposing and developing using a silver salt photosensitive material Good.
  • electroless plating or electrolytic plating may be used in combination with the above method.
  • the printing method, the ink jet method (particularly the electrostatic ink jet method), the method using a silver salt photosensitive material, or the method using these in combination with electroless plating or electrolytic plating has a continuous and accurate network structure of fine metal wires. In addition, it is preferable because it can be formed at low cost.
  • a metal nanowire mesh can be formed by a printing method or a coating method using a dispersion liquid containing metal nanowires, and the metal nanowire mesh structure according to the present invention can be applied.
  • Forming the network structure of fine metal wires according to the present invention with metal nanowires is particularly preferable because the smoothness and dehydrating property of the transparent conductive layer according to the present invention can be improved.
  • the metal nanowire refers to a linear structure having a metal element as a main component.
  • the metal nanowire in the present invention means a linear structure having a diameter from the atomic scale to the nm size.
  • the metal nanowire according to the present invention preferably has an average length of 3 ⁇ m or more, more preferably 3 to 500 ⁇ m, particularly 3 to 300 ⁇ m in order to form a long conductive path with one metal nanowire. It is preferable.
  • the relative standard deviation of the length is preferably 40% or less.
  • an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint.
  • the average diameter of the metal nanowire is preferably 10 to 300 nm, more preferably 30 to 200 nm.
  • the relative standard deviation of the diameter is preferably 20% or less.
  • the surface resistivity of the transparent conductive layer containing the metal nanowire according to the present invention is preferably 100 ⁇ / ⁇ or less, more preferably 50 ⁇ / ⁇ or less, and particularly preferably 10 ⁇ / ⁇ or less. Further, from the viewpoints of transmittance and dewaterability, the aperture ratio is preferably 80% or more, and particularly preferably 90% or more.
  • a metal composition of the metal nanowire which concerns on this invention, although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. Further, in order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires, and resistance to magnesium), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.
  • the means for producing the metal nanowire according to the present invention there are no particular limitations on the means for producing the metal nanowire according to the present invention, and known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction
  • the method for producing silver nanowires can easily produce silver nanowires in an aqueous system, and the conductivity of silver is the highest among metals. It can be preferably applied as a method for producing a metal nanowire according to the present invention.
  • Ry representing the surface roughness of the transparent conductive layer means the maximum height, and is a value obtained by extending the definition of the two-dimensional maximum height defined in JIS B601 (1994) to three dimensions. Instead of the length l, it is defined as the maximum height in the region where the reference area S is extracted from the sample surface. That is, the surface roughness (Ry) in the present invention is a value representing the distance between the highest peak surface and the lowest valley surface in the reference area. In the present invention, the reference area is set to 80 ⁇ m ⁇ 80 ⁇ m or more.
  • a commercially available atomic force microscope can be used for the measurement of Ry.
  • it can be measured by the following method.
  • a sample cut to a size of about 1 cm square is set on a horizontal sample stage on a piezo scanner, and a cantilever Is approached to the sample surface, and when the atomic force is reached, scanning is performed in the XY directions, and the unevenness of the sample at that time is detected by piezo displacement in the Z direction.
  • a piezo scanner that can scan 120 ⁇ m in the XY direction and 2 ⁇ m in the Z direction is used.
  • the cantilever is a silicon cantilever SI-DF40 (resonance frequency 250 to 390 kHz, spring constant 42 N / m) manufactured by Seiko Instruments Inc., and a scanning frequency of 80 ⁇ 80 ⁇ m or more is measured in a DFM mode (Dynamic Force Mode). Ry is obtained by measuring at 0.5 Hz or less. Usually, Ry can be calculated automatically using measurement data analysis software.
  • a transparent resin is overcoated so as to completely cover the network structure of fine metal wires, and the conductive fiber layer appears on the surface and the transparent conductive film A method of uniformly cutting or polishing the surface so that the surface roughness of the layer is 1 nm ⁇ Ry_f ⁇ 50 nm.
  • D A transparent film substrate having a transparent barrier layer using a transparent resin as an adhesive after forming a transparent conductive layer including a network structure of fine metal wires on the release surface of the releasable substrate. A method of transferring to the top can be used.
  • the method (d) is preferably used for the method for producing the barrier transparent conductive film of the present invention, it will be described with reference to the drawings.
  • the surface of the transparent conductive layer of the barrier transparent conductive film can be easily and stably highly smoothed.
  • FIG. 1 is a cross-sectional view of a film A having a transparent conductive layer 13 including a network structure of metal nanowires 12 on a releasable substrate 11, and the transparent conductive layer 13 includes a binder resin in addition to the metal nanowires 12. May be included.
  • a resin substrate, a resin film, or the like can be suitably used as the releasable substrate used in the method for producing a barrier transparent conductive film of the present invention.
  • combination such as a polyethylene terephthalate resin, a vinyl chloride resin, an acrylic resin, a polycarbonate resin, a polyimide resin, a polyethylene resin, a polypropylene resin
  • a substrate or film composed of a single layer or multiple layers of resin is preferably used.
  • a glass substrate or a metal substrate can also be used.
  • a surface treatment may be applied to the surface (release surface) of the releasable base material by applying a release agent such as silicon resin, fluororesin, or wax as necessary.
  • the surface of the releasable substrate is preferably highly smooth because it affects the surface smoothness of the transparent conductive layer of the barrier transparent conductive film obtained after the transfer of the transparent conductive layer.
  • the maximum height ( Ry_d) is preferably Ry_d ⁇ 50 nm, and more preferably 1 nm ⁇ Ry_d ⁇ 50 nm.
  • Ry_d is larger than 50 nm, current leakage or electric field concentration occurs between both electrodes of the element, and there is a high possibility that the element performance (photoelectric characteristics, lifetime, etc.) is deteriorated.
  • Ry_d is smaller than 1 nm, the peelability during transfer may be poor.
  • the method for forming the metal wire network structure on the release surface of the releasable substrate is not particular limitation on the method for forming the metal wire network structure on the release surface of the releasable substrate, but it is applied to the formation of the transparent conductive layer from the viewpoint of improving productivity and quality and reducing environmental impact. It is preferable to use a printing method or a printing method. As coating methods, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method Etc. can be used.
  • a letterpress (letter) printing method a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used.
  • physical surface treatment such as corona discharge treatment or plasma discharge treatment can be applied to the surface of the releasable substrate as a preliminary treatment for improving the adhesion and coating properties.
  • a metal nanowire dispersion liquid is applied (or printed) on a release surface of a releasable substrate 11 and dried to form a transparent conductive layer having a network structure of metal nanowires 12 on the surface of the releasable substrate. 13 is formed to produce film A.
  • a transparent resin layer 16 is applied or printed on a transparent film substrate 15 having a transparent barrier layer 14 to produce a film B.
  • the obtained transparent conductive layer of film A and metal nanowire layer of film B are bonded as shown in FIG.
  • the transparent conductive layer is transferred to the transparent film substrate side by peeling the releasable substrate 11 to produce a barrier transparent conductive film.
  • the metal nanowires can be present exclusively on the surface of the transparent conductive layer after transfer, a barrier transparent conductive film having excellent surface conductivity can be formed. Moreover, since the surface of the transparent conductive layer after the transfer reflects the smoothness of the surface of the releasable substrate, the transparency in the barrier transparent conductive film can be obtained by using a releasable substrate having excellent smoothness. The smoothness of the conductive layer can be improved.
  • a part of the transparent resin layer may enter the transparent conductive layer as shown in FIG. 4 or may constitute a part of the surface of the transparent conductive layer.
  • the transparent resin layer can also be composed of a plurality of layers having different resins.
  • the metal nanowire dispersion liquid may contain additives such as a binder and a surfactant in addition to the metal nanowires. Moreover, those additives may be contained in the transparent conductive layer.
  • the transparent conductive layer is calendered or heat treated to increase the adhesion between the metal nanowires, or plasma treatment to reduce the contact resistance between the metal nanowires is a network of metal nanowires. It is effective as a method for improving the conductivity of the structure.
  • the mold release surface of the mold release base material may carry out the hydrophilic treatment by corona discharge (plasma) etc. previously.
  • the transparent resin layer can be applied (or printed) to the transparent conductive layer and bonded to a transparent film substrate having a transparent barrier layer.
  • the bonding method can carry out by a sheet press, a roll press, etc.
  • the roll press is a method in which a film to be bonded is sandwiched between the rolls, and the rolls are rotated.
  • a roll press can be suitably used because it applies uniform pressure and is more productive than a sheet press.
  • the film thickness Dr of the transparent resin layer after curing is preferably thicker than the film thickness Dc of the transparent conductive layer formed on the surface of the releasable substrate, but if Dr is too thick, it is transparent. In some cases, it takes time to dehydrate the resin layer. On the other hand, when Dr is thinner than Dc, the adhesion between the transparent conductive layer and the transparent barrier layer becomes insufficient, and the transparent conductive layer may not be successfully transferred to the barrier layer side. Or the unevenness
  • Dc ⁇ Dr ⁇ Dc ⁇ 10 is preferable, Dc ⁇ Dr ⁇ Dc ⁇ 5 is more preferable, and Dc ⁇ Dr ⁇ 3Dc is more preferable.
  • the film thickness Dr of the transparent resin layer after curing is preferably larger than the value of the surface roughness Ry (b) of the transparent barrier layer, but if Dr is too thick, the transparent resin layer The dehydration process may take time.
  • Dr is smaller than Ry (b) , the adhesion between the transparent conductive layer and the transparent barrier layer becomes insufficient, and the transparent conductive layer may not be successfully transferred to the barrier layer side. Or the unevenness
  • Dc ⁇ Dr ⁇ Dc ⁇ 10 is preferable, Dc ⁇ Dr ⁇ Dc ⁇ 5 is more preferable, and Dc ⁇ Dr ⁇ 3Dc is more preferable.
  • the transparent conductive layer of the barrier transparent conductive film of the present invention can be patterned as necessary. There is no particular limitation on the patterning process. For example, in the manufacturing method of the present invention, a patterned transparent conductive layer can be formed on the surface of the releasable substrate and then transferred. Patterning can also be performed after the barriering transparent conductive film of the present invention is produced.
  • the following method can be used.
  • the following method can be used as a specific method for patterning the barrier transparent conductive film after production.
  • a method of patterning a liquid that can etch a network structure of fine metal wires in a negative pattern using a printing method after forming the barrier transparent conductive film of the present invention 5.
  • the light-emitting layer is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer. May be an interface between the light emitting layer and the adjacent layer, but is preferably within the layer of the light emitting layer because of deactivation of excitons between layers.
  • the film thickness of the light emitting layer is not particularly limited, but it is 2 from the viewpoint of the uniformity of the film to be formed, the application of unnecessary high voltage during light emission, and the improvement of the stability of the emission color with respect to the drive current. It is preferable to adjust to a range of ⁇ 200 nm, and more preferably to a range of 5 to 100 nm.
  • the host-guest type light emitting layer is formed by a wet process
  • the boiling point of the solvent, the vapor pressure at 20 ° C., the functional group of the solvent, and the molecular weight of the light emitting host are selected.
  • the voltage rise during continuous driving is suppressed.
  • a host compound also referred to as a light emitting host
  • a light emitting dopant contained in the light emitting layer will be described.
  • the host compound in the present invention is a phosphorescent quantum yield of phosphorescence emission at a room temperature (25 ° C.) having a mass ratio of 20% or more in the compound contained in the light emitting layer. Is a compound of less than 0.1.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • known host compounds may be used alone or in combination of two or more.
  • the organic EL element can be made highly efficient.
  • the host compound is preferably a compound represented by the following general formula (a).
  • X represents NR ′, O, S, CR′R ′′ or SiR′R ′′.
  • R ′ and R ′′ each represent a hydrogen atom or a substituent.
  • Ar represents an atomic group necessary for forming an aromatic ring.
  • N represents an integer of 0 to 8.
  • Examples of the substituent represented by R ′ and R ′′ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group).
  • alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group.
  • Aromatic hydrocarbon ring group also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, Fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic A cyclic group (for example, pyridyl group, pyr
  • X is preferably NR ′ or O
  • R ′ is an aromatic hydrocarbon group (also referred to as an aromatic carbocyclic group or an aryl group, such as a phenyl group, p-chlorophenyl group, mesityl group, tolyl group).
  • xylyl group xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group), or an aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group) , Pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, phthalazinyl group and the like are particularly preferable.
  • aromatic hydrocarbon group and aromatic heterocyclic group may each have a substituent represented by R ′ or R ′′ in X of the general formula (a).
  • examples of the aromatic ring represented by Ar include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • the aromatic ring may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent represented by R ′ or R ′′ in X of the general formula (a).
  • examples of the aromatic hydrocarbon ring represented by Ar include a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, Examples include a pyranthrene ring and anthraanthrene ring. These rings may further have substituents each represented by R ′ and R ′′ in X of the partial structure represented by
  • examples of the aromatic heterocycle represented by Ar include a furan ring, a dibenzofuran ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring.
  • These rings may further have substituents represented by R ′ and R ′′ in the general formula (a).
  • the aromatic ring represented by Ar is preferably a carbazole ring, a carboline ring, a dibenzofuran ring, or a benzene ring, and more preferably a carbazole ring, A carboline ring and a benzene ring, more preferably a benzene ring having a substituent, and particularly preferably a benzene ring having a carbazolyl group.
  • the aromatic ring represented by Ar is preferably a condensed ring having 3 or more rings, and the aromatic hydrocarbon condensed ring in which 3 or more rings are condensed is a specific example.
  • aromatic heterocycle condensed with three or more rings include an acridine ring, a benzoquinoline ring, a carbazole ring, a carboline ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, a cyclazine ring, Quindrine ring, tepenidine ring, quinindrin ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (any one of the carbon atoms constituting the carboline ring is a nitrogen atom) Phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzodif
  • n represents an integer of 0 to 8, preferably 0 to 2, particularly preferably 1 to 2 when X is O or S.
  • the light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (polymerizable light emission).
  • a high molecular weight material when used, a phenomenon in which the compound is likely to be difficult to escape, such as swelling or gelation, due to the compound taking in the solvent is likely to occur.
  • it is preferable to use a material having a molecular weight of 1,500 or less at the time of coating and it is more preferable to use a material having a molecular weight of 1,000 or less at the time of coating.
  • a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.
  • Specific examples of known host compounds include compounds described in the following documents.
  • a fluorescent dopant or a phosphorescent dopant can be used. From the viewpoint of obtaining an organic EL element with higher luminous efficiency, light emission used in the light-emitting layer or light-emitting unit of the organic EL element.
  • a dopant it is preferable to contain a phosphorescence dopant simultaneously with containing said host compound.
  • the phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL element.
  • the phosphorescent dopant according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound). Rare earth complexes, most preferably iridium compounds.
  • Injection layer electron injection layer, hole injection layer >> The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.
  • An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.
  • Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
  • anode buffer layer hole injection layer
  • copper phthalocyanine is used.
  • examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • it may be a polyanion having fluorine (F) in the compound.
  • F fluorine
  • Nafion manufactured by Dupont
  • Flemion manufactured by Asahi Glass Co., Ltd.
  • cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
  • Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc.
  • the buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m, although it depends on the material.
  • ⁇ Blocking layer hole blocking layer, electron blocking layer>
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and their forefront of industrialization” (published by NTT Corporation on November 30, 1998). There is a hole blocking (hole blocking) layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
  • the hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
  • the hole blocking layer preferably contains the azacarbazole derivative mentioned as the host compound described above.
  • the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers.
  • 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
  • the ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by, for example, the following method.
  • Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA, is used as a keyword.
  • the ionization potential can be obtained as a value obtained by rounding off the second decimal place of a value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
  • the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
  • a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
  • the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.
  • the film thickness of the hole blocking layer and the electron transporting layer according to the present invention is preferably 3 to 100 nm, more preferably 5 to 30 nm.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
  • Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • the above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
  • No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.
  • NPD 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • JP-A-4-308 4,4 ′, 4 ′′ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
  • JP-A-11-251067 J. Org. Huang et. al.
  • a so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.
  • these materials are preferably used because a light-emitting element with higher efficiency can be obtained.
  • the hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • a hole transport layer having a high p property doped with impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
  • a hole transport layer having such a high p property because a device with lower power consumption can be produced.
  • the electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
  • the electron transport layer can be provided as a single layer or a plurality of layers.
  • an electron transport material also serving as a hole blocking material used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode.
  • any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
  • the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • n-type electron transport layer doped with impurities examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • an electron transport layer having such a high n property because an element with lower power consumption can be produced.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 ⁇ m or more)
  • a pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light emission luminance is improved, which is convenient.
  • a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a film thickness of 1 to 20 nm. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
  • substrate As a substrate (hereinafter also referred to as a support substrate) that can be used in the organic EL element of the present invention, there is no particular limitation on the type of glass, plastic and the like, and it may be transparent or opaque. When extracting light from the substrate side, the substrate is preferably transparent. Examples of the transparent substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable substrate is a resin film capable of giving flexibility to the organic EL element.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfone , Polyetherimide, polyether ketone imide, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (manufactured by J
  • An inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film, and a barrier film having a water vapor permeability of 0.01 g / m 2 / day ⁇ atm or less is preferable. Further, a high barrier film having an oxygen permeability of 10 ⁇ 3 g / m 2 / day or less and a water vapor permeability of 10 ⁇ 5 g / m 2 / day or less is preferable.
  • the material for forming the barrier film may be any material that has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the method for forming the barrier film is not particularly limited.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.
  • external extraction quantum efficiency (%) (number of photons emitted to the outside of the organic EL element) / (number of electrons sent to the organic EL element) ⁇ 100.
  • a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination.
  • the ⁇ max of light emission of the organic EL element is preferably 480 nm or less.
  • the sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.
  • Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a polymer film and a metal film can be preferably used because the organic EL element can be thinned.
  • the polymer film measured oxygen permeability by the method based on JIS K 7126-1987 is 1 ⁇ 10 -3 ml / m 2 / 24h or less, as measured by the method based on JIS K 7129-1992 water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is preferably that of 1 ⁇ 10 -3 g / (m 2 / 24h) or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
  • an sealing layer by forming an inorganic or organic layer in contact with the substrate by covering the electrode and the organic layer on the outer side of the electrode facing the substrate with the organic layer interposed therebetween.
  • the material for forming the film may be a material having a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase.
  • a vacuum can also be used.
  • a hygroscopic compound can also be enclosed inside.
  • hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate.
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • an organic solar cell has the following configuration.
  • the organic EL device Similarly, by sandwiching the power generation layer between the hole transport layer and the electron transport layer, the efficiency of taking out holes
  • the power generation layer itself also increases the rectification of holes and electrons (selectivity for carrier extraction), so that the power generation layer is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as in (IV). It may be a configuration (also referred to as a pin configuration).
  • the tandem configuration (V described above) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.
  • the positive electrodes are respectively formed on the pair of comb-like electrodes.
  • a back-contact type organic photoelectric conversion element in which a hole transport layer and an electron transport layer are formed and a power generation layer is disposed thereon can also be configured.
  • the organic solar cell of the present invention is characterized in that the transparent transparent conductive film of the present invention is used in the “transparent substrate / anode” portion of the above-described constituent elements.
  • the organic solar cell of the present invention has a hole transporting layer between the anode and the bulk heterojunction layer because it is possible to more efficiently take out the charges generated in the bulk heterojunction layer (power generation layer). It is preferable.
  • the hole transport layer for example, PEDOT (polyethylenedioxythiophene), polyaniline and its doped material, cyan compounds described in WO2006019270 and the like can be used.
  • PEDOT polyethylenedioxythiophene
  • polyaniline and its doped material cyan compounds described in WO2006019270 and the like.
  • cyan compounds described in WO2006019270 and the like can be used.
  • a material having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer is used for the hole transport layer, electrons generated in the bulk heterojunction layer do not flow to the anode side.
  • Such a rectification effect electrolectronic block function
  • Such a hole transport layer may be called an electron block layer.
  • the organic solar cell of the present invention preferably uses a hole transport layer having such an electron blocking function.
  • a hole transport layer can also be comprised with the p-type semiconductor material single-piece
  • the hole transport layer As a means for forming the hole transport layer, either a vacuum deposition method or a solution coating method can be used, but a solution coating method is preferably used. If the hole transport layer is formed by a solution coating method before forming the bulk heterojunction layer, the surface of the hole transport layer is smoothed by the leveling action of the coating liquid, and the influence of leakage or the like inside the device can be reduced.
  • the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons, and these may form a heterojunction in substantially two layers, A bulk heterojunction that is in a mixed state inside one layer may be formed, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency.
  • p-type semiconductor material examples include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.
  • condensed polycyclic aromatic low molecular weight compound examples include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthanthene, bisanthene, zeslene.
  • Examples of the derivative having a condensed polycycle include International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216.
  • conjugated polymer for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and its oligomer, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer described in WO2008000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO2008000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160, Nature Mat. vol.
  • P3HT poly-3-hexylthiophene
  • polypyrrole and its oligomer polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as ⁇ -conjugated polymers such as polysilane and polygermane.
  • oligomeric materials not polymer materials, include thiophene hexamer ⁇ -seccithiophene ⁇ , ⁇ -dihexyl- ⁇ -sexualthiophene, ⁇ , ⁇ -dihexyl- ⁇ -kinkethiophene, ⁇ , ⁇ -bis (3 Oligomers such as -butoxypropyl) - ⁇ -sexithiophene can be preferably used.
  • the electron transport layer is formed on the power generation layer by coating, there is a problem that the electron transport layer solution dissolves the power generation layer. Therefore, a material that can be insolubilized after coating by a solution process may be used. .
  • Such materials include materials that can be insolubilized by polymerizing and crosslinking the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or a material in which soluble substituents react and become insoluble (pigmented) by applying energy such as heat, as described in US Patent Application Publication No. 2003/136964, and Japanese Patent Application Laid-Open No. 2008-16834 And so on.
  • n-type semiconductor material used for the power generation layer is not particularly limited.
  • Aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, and perylenetetracarboxylic acid diimide, and polymer compounds containing imidized compounds thereof can be used. .
  • Fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed and efficiently are preferable.
  • Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc.
  • PCBM [6,6] -phenyl C61-butyric acid methyl ester
  • PCBnB [6,6] -phenyl C61-butyric acid-n-butyl ester
  • PCBiB [6,6] -phenyl C61-buty Rick acid-isobutyl ester
  • PCBH [6,6] -phenyl C61-butyric acid-n-hexyl ester
  • fullerene derivative having a substituent and having improved solubility such as fullerene having an ether group.
  • the organic solar cell of the present invention has an electron transporting layer between the bulk heterojunction layer and the cathode because it is possible to more efficiently extract charges generated in the bulk heterojunction layer (power generation layer). It is preferable.
  • octaazaporphyrin, p-type semiconductor perfluoro products perfluoropentacene, perfluorophthalocyanine, etc.
  • a material having a HOMO level deeper than the HOMO level of the p-type semiconductor material used for the bulk heterojunction layer is used for the electron transport layer, holes generated in the bulk heterojunction layer are allowed to flow to the cathode side. Such a rectifying effect (hole blocking function) is provided.
  • Such an electron transport layer is sometimes called a hole blocking layer.
  • the organic solar cell of the present invention preferably uses an electron transport layer having such a hole blocking function.
  • n-type semiconductor materials such as phenanthrene compounds such as bathocuproine, naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and N-type inorganic oxides such as titanium oxide, zinc oxide, and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.
  • an electron transport layer can also be comprised with the n-type semiconductor material single-piece
  • a vacuum vapor deposition method or a solution coating method can be used, but a solution coating method is preferably used.
  • the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.
  • the cathode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination.
  • a conductive material for the cathode a metal, an alloy, an electrically conductive compound, or a mixture thereof having a low work function (4 eV or less) can be used.
  • Specific examples of such cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of these metals and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, magnesium / silver
  • An aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum, or the like can be preferably used.
  • the cathode can be produced by forming a thin film of these materials using a film forming method such as vapor deposition or sputtering.
  • the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light coming to the cathode side can be reflected to the anode side and reused in the power generation layer, and the photoelectric conversion efficiency can be further improved.
  • the cathode may be a nanoparticle, nanowire, or nanostructure made of metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.) or carbon, or a nanowire dispersion. If so, a transparent and highly conductive cathode can be easily formed by a coating method.
  • a conductive material suitable for the cathode such as aluminum and aluminum alloy, silver and silver compound is made thin with a film thickness of about 1 to 20 nm, and then the transparent electrode A light-transmitting cathode can be obtained by providing the conductive light-transmitting material film mentioned in the description.
  • ⁇ Middle layer ⁇ As a material for the intermediate electrode required in the case of the tandem structure as in (V), it is preferable to use a compound having both transparency and conductivity, and transparent metal oxides such as ITO, AZO, FTO, and titanium oxide. In addition, a very thin metal layer such as Ag, Al, Au or the like, or a nanoparticle / nanowire, a conductive polymer material such as PEDOT, polyaniline, or a doped material thereof can be preferably used.
  • the hole transport layer and the electron transport layer described above include a combination that works as an intermediate electrode (charge recombination layer) by appropriately combining and stacking, and such a configuration simplifies the manufacturing process. be able to.
  • the organic solar cell of the present invention is preferably sealed using a known method in order to prevent deterioration due to oxygen and moisture in the environment.
  • a specific sealing means the sealing method described in the description of the organic EL element can be used.
  • the barrier transparent conductive film of the present invention has excellent barrier properties, electrical conductivity and chemical resistance, and is also excellent in dehydration and smoothness, and can be preferably used for various organic photoelectric conversion elements. Among them, it can be particularly preferably used as a transparent electrode of an organic EL device or an organic thin film solar cell in which barrier properties, low water content and smoothness of a transparent electrode are strictly required in addition to conductivity and transparency.
  • total light transmittance, surface resistivity, surface roughness (Ry), and water vapor transmission rate (gas barrier property) were measured by the following methods.
  • Total light transmittance Based on JIS K 7361-1: 1997, measurement was performed using a haze meter HGM-2B manufactured by Suga Test Instruments Co., Ltd.
  • Example 1 [Production and Performance Evaluation of Barrier Transparent Conductive Film Using Silver Nanowires] (Production of silver nanowires)
  • silver nanowires were used as metal nanowires.
  • Silver nanowires are described in Adv. Mater. , 2002, 14, 833-837 and WO2008 / 073143A2, with reference to the production of silver nanowires having an average diameter of 60 nm and an average length of 30 ⁇ m, and using ultrafiltration, the silver nanowires are filtered and washed with water After that, a dispersant and a surfactant were added and redispersed in pure water to prepare a silver nanowire dispersion (silver nanowire content: 5 mass%).
  • coating was performed using a spin coater.
  • a silver nanowire network is prepared by applying the silver nanowire dispersion liquid to a releasable base material that has been subjected to corona discharge treatment so that the basis weight of the silver nanowires is 60 mg / m 2 , followed by drying at 120 ° C. for 30 minutes.
  • a transparent conductive layer including the structure was formed.
  • the transparent conductive layer obtained had a surface resistivity of 15 ⁇ / ⁇ and a surface roughness: Ry of 250 nm.
  • an ultraviolet curable transparent resin manufactured by JSR, NN803 was applied as a transparent resin layer (corresponding to a dry film thickness of 0.2 ⁇ m) to evaporate the solvent component. Then, it bonded with the transparent conductive layer side of the releasable base material which has the said transparent conductive layer, and roll-pressed. Subsequently, after the transparent resin layer is sufficiently cured by irradiating ultraviolet rays, the transparent conductive layer is transferred to the transparent film substrate side by peeling off the release substrate, thereby producing a barrier transparent conductive film BCM1. did.
  • the ultraviolet curable transparent resin is applied as a transparent resin layer (corresponding to a dry film thickness of 0.2 ⁇ m), the solvent component is vaporized, and then irradiated with ultraviolet rays.
  • the transparent resin layer was fully cured.
  • an ITO transparent conductive layer having a film thickness of about 100 nm was formed by an argon sputtering method using an ITO target to produce a barrier transparent conductive film BCO1.
  • a barrier transparent conductive film BCO6 was prepared in the same manner as in BCO1, except that in the method for producing the transparent conductive film BCO1, the formation of the transparent resin layer was excluded and the ITO transparent conductive layer was formed directly on the barrier layer.
  • each sample after patterning was cut into the same size, subjected to dehydration treatment at 90 ° C. for 1 hour and 12 hours in a dry nitrogen gas atmosphere, and the water content [g / m 2 ] after each treatment time was measured.
  • the obtained measurement results are shown in Table 1.
  • the barrier property the case where almost no change was observed in the water vapor transmission rate after patterning with respect to before the patterning, and the case where the water vapor transmission rate after patterning increased and the barrier property was deteriorated were indicated by x.
  • Dehydration is when the decrease in water content after 12 hours treatment is 10 ⁇ 4 g / m 2 or less with respect to the water content after 1 hour dehydration treatment, and when it is 10 ⁇ 4 to 10 ⁇ 3 g / m 2 . Is larger than ⁇ , 10 ⁇ 2 g / m 2 , and x is shown.
  • BCM6 and BCO6 show deterioration in barrier properties because the barrier layer was attacked by an alkaline aqueous solution used as a resist developer or removal solution in the patterning process, whereas in BCM1-5, BCM7 and BCO1-5 Since the transparent resin layer functions as a protective layer for the barrier layer, it is considered that the deterioration of the barrier property associated with the patterning process is prevented.
  • the inventive examples BCM1 to BCM5 and BCM7 are all compatible with chemical resistance, surface roughness and dewaterability.
  • the reason why the surface roughness of BCM1 is slightly inferior to that of BCM2 to 5 is considered to be the effect that the thickness of the transparent resin layer is slightly insufficient with respect to the surface roughness: Ry of the transparent conductive layer.
  • the thickness of the transparent resin layer is preferably thin as long as the surface roughness of the transparent conductive layer formed on the transparent barrier layer or the releasable substrate can be absorbed. It was.
  • Example 2 [Production and Performance Evaluation of Barrier Transparent Conductive Film Using Silver Fine Particles] (Preparation of self-assembled silver fine particle layer forming solution)
  • a self-assembled silver fine particle layer forming solution was prepared according to the following formulation. (The number is% by mass.) BYK-410 (manufactured by BYK Chemie) 0.11 SPAN-80 (manufactured by Tokyo Chemical Industry) 0.11 Dichloroethane 75.63 Cyclohexanone 0.42 Silver powder (average particle size 70 nm) 3.59 BYK-348 (0.02% aqueous solution; manufactured by BYK Chemie) 19.98 ZonylFSH (DuPont) 0.08 Butver B-76 (Solutia) 0.08 (Formation of transparent conductive layer on releasable substrate)
  • CHC clear hard coat layer
  • the above-mentioned self-assembled silver fine particle layer forming solution is applied to a releasable base material that has been subjected to corona discharge treatment, and left at 25 ° C. for 1 minute to cause the silver fine particles to self-assemble into a net shape to form a random network shape.
  • After forming a silver fine particle layer it processed at 150 degreeC for 1 minute.
  • a transparent conductive layer including a structure in which fine metal wires made of silver fine particles were networked was formed.
  • the transparent conductive layer obtained had a surface resistivity of 20 ⁇ / ⁇ and a surface roughness: Ry of 1.7 ⁇ m.
  • a film thickness capable of absorbing the surface roughness of the transparent conductive layer by using an ultraviolet curable transparent resin (manufactured by JSR, NN803) as a transparent resin layer on the barrier layer of the transparent film substrate having the transparent barrier layer described in Example 1.
  • a dry film thickness (corresponding to 2.0 ⁇ m) and vaporizing the solvent component, it was bonded to the transparent conductive layer side of the releasable substrate having the transparent conductive layer and roll-pressed.
  • the transparent resin layer is sufficiently cured by irradiating ultraviolet rays, the transparent conductive layer is transferred to the transparent film substrate side by peeling off the release substrate, thereby producing a barrier transparent conductive film SAM1. did.
  • the barrier transparent conductive films SAM1 and 2 produced as described above were evaluated in the same manner as in Example 1. The obtained measurement results are shown in Table 2.
  • SAM1-2 was found to be excellent in barrier properties and dewaterability, similar to BCM1-5 in Example 1.
  • the transparent conductive layer including the network structure of silver nanowires was superior in surface roughness.
  • the transparent conductive layer including the network structure of silver nanowires is superior in dewaterability because the thickness of the transparent resin layer can be designed to be thin.
  • Example 3 [Production and Performance Evaluation of Organic EL Element] (Synthesis of hole injection material) 142.68 g (16.03 mmol of Nafion monomer unit SE-10072: manufactured by Dupont) and 173.45 g of deionized water were poured into a 500 ml flask. A ferric sulfate solution was made by dissolving 0.0667 g ferric sulfate hydrate with deionized water to a total mass of 12.2775 g. Next, 1.40 g ferric sulfate solution and 1.72 g (7.224 mmol) sodium persulfate were added to the flask and stirred well.
  • the flask contents were poured into a 500 ml 3-neck flask. The mixture was then stirred in the reaction vessel for 30 minutes. 0.63 ml (5.911 mmol) of 3,4-ethylenedioxythiophene was added to the reaction mixture with stirring. The polymerization was allowed to proceed with stirring at about 23 ° C. After 1 hour and 7 minutes, the polymerization liquid turned very dark blue.
  • FIG. 5 is an exploded perspective view of the organic EL element.
  • FIG. 5C is a perspective view in which the anode 22 is formed on the base material 21 in a tile shape.
  • a hole injection layer 23 is formed on the anode 22 as shown in FIG. 5B, and a hole blocking layer, an electron transport layer, and a cathode 24 are further formed on the hole injection layer 23 as shown in FIG. ).
  • an ITO transparent conductive layer having a film thickness of about 100 nm was formed by an argon sputtering method using an ITO target to produce a transparent conductive glass BCG1.
  • the barrier transparent conductive films BCM1 to 6, BCO1 to 6, and the transparent conductive glass BCG1 prepared in Example 1 were cut into 9.6 ⁇ 11.2 cm ⁇ , and a known photolithography method as shown in FIG. 5C.
  • humidity was adjusted for 48 hours in an environment of 25 ° C.-30% RH, followed by drying / dehydration treatment at 90 ° C.-1 h in a dry nitrogen gas atmosphere.
  • an organic EL device was produced by the following procedure.
  • each layer of the organic EL element was formed by the following procedure.
  • Each of the vapor deposition crucibles in a commercially available vacuum vapor deposition apparatus was filled with the optimum amount of the constituent material of each layer for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • vapor deposition is performed in a pattern as shown in FIG. 5B using a vapor deposition mask so as to overlap the hole injection layer after wiping. It was.
  • the hole blocking layer, the electron transport layer, and the cathode were formed in a pattern as shown in FIG. 5A using a vapor deposition mask.
  • Ir-1 and Ir-14 and compound a-7 were co-evaporated at a deposition rate of 0.1 nm / second so that the concentration of Ir-1 was 13% by mass and Ir-14 was 3.7% by mass.
  • a green-red phosphorescent light emitting layer having a maximum wavelength of 622 nm and a thickness of 10 nm was formed.
  • E-1 and Compound a-7 were co-evaporated at a deposition rate of 0.1 nm / second so that E-1 was 10% by mass, and a blue phosphorescent light emitting layer having a maximum emission wavelength of 471 nm and a thickness of 15 nm was formed. Formed.
  • a flexible sealing member On the produced organic EL element, a flexible sealing member was used in which polyethylene terephthalate was used as a base material and Al 2 O 3 was deposited in a thickness of 300 nm. Adhesive is applied to the periphery of the cathode electrode except for the ends so that an external lead terminal of the anode electrode and the cathode electrode can be formed. In addition, an external extraction terminal for the cathode electrode was formed.
  • Rectification ratio current value when +3 V is applied / current value when ⁇ 3 V is applied ⁇ : Rectification ratio of 10 3 or more ⁇ : Rectification ratio of 10 2 or more and less than 10 3 ⁇ : Rectification ratio of less than 10 2 [Evaluation of element life]
  • the initial luminance 5000 cd / m was continuously emit light at a constant voltage so as to be 2, obtains the time until the luminance is reduced by half, and 100 the half-life of ELG1, was evaluated by the following criteria.
  • the rectification ratio and the light emission are improved as the surface roughness of the transparent conductive layer is improved (that is, the film thickness of the transparent conductive layer is increased).
  • the lifetime of the element deteriorates due to the influence of the water content of the transparent conductive layer.
  • the organic EL elements ELM1 to ELM5 of the present invention good results were obtained in any of the rectification ratio, the light emitting property, and the element lifetime, similar to the ELG1 using the transparent conductive glass as the anode electrode.
  • the organic EL device of the present invention using this barrier transparent conductive film the effect of improving the device performance can be clearly confirmed.
  • Example 4 [Production and Performance Evaluation of Organic Solar Cell] Using the barrier transparent conductive films BCM1-6, BCO1-6, and transparent conductive glass BCG1 prepared in Example 1 that were subjected to patterning by the photolithography method as an anode (anode electrode), the following procedure was used. An organic solar cell was produced.
  • P3HT manufactured by Prectronics: regioregular poly-3-hexylthiophene
  • PCBM manufactured by Frontier Carbon: 6,6-phenyl-C61-butyric acid methyl ester
  • the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 ⁇ 10 ⁇ 4 Pa or less, and then fluorinated at a deposition rate of 0.01 nm / second.
  • vaporization is performed so that the light receiving part is 2 ⁇ 2 mm.
  • cathode electrode cathode electrode
  • the obtained element was moved to a nitrogen chamber and sealed with a sealing cap and a UV curable resin to produce an organic solar cell PVM1 having a light receiving portion of 2 ⁇ 2 mm size.
  • PCE (%) [Jsc (mA / cm 2 ) ⁇ Voc (V) ⁇ FF (%)] / 100 mW / cm 2
  • Evaluation of heat resistance [Jsc (mA / cm 2 ) ⁇ Voc (V) ⁇ FF (%)] / 100 mW / cm 2
  • Retention ratio 90 or more Retention ratio 50 or more, less than 90 ⁇ : Retention ratio less than 50
  • Retention rate (%) (Jsc after temperature / humidity cycle) / (Jsc before temperature / humidity cycle) ⁇ 100 The obtained measurement results are shown in Table 4.

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Abstract

L'invention concerne un film conducteur transparent à propriétés barrières, son procédé de fabrication, un élément électroluminescent (EL) organique et une photopile organique, caractérisés en ce que le film conducteur transparent à propriétés barrières a au moins une couche barrière transparente et une couche conductrice transparente stratifiée sur un matériau de base de type anticollant, et de plus a au moins une couche de résine transparente entre la couche barrière transparente et la couche conductrice transparente, et en ce que la couche conductrice transparente susmentionnée contient au moins une structure de réseau de fils de métal fins.
PCT/JP2010/066664 2009-10-14 2010-09-27 Film conducteur transparent à propriétés barrières, son procédé de fabrication, et élément électroluminescent organique et photopile organique utilisant le film conducteur transparent à propriétés barrières Ceased WO2011046011A1 (fr)

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JP2011536086A JP5673547B2 (ja) 2009-10-14 2010-09-27 バリア性透明導電フィルムの製造方法、及び該バリア性透明導電フィルムを用いた有機ｅｌ素子及び有機太陽電池

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JP2009-237176 2009-10-14

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PCT/JP2010/066664 Ceased WO2011046011A1 (fr) 2009-10-14 2010-09-27 Film conducteur transparent à propriétés barrières, son procédé de fabrication, et élément électroluminescent organique et photopile organique utilisant le film conducteur transparent à propriétés barrières

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JP2013164941A (ja) * 2012-02-10 2013-08-22 Konica Minolta Inc 透明電極の製造方法、透明電極及びそれを用いた有機電子素子
JP2013179173A (ja) * 2012-02-28 2013-09-09 Sumitomo Chemical Co Ltd 光電変換素子
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CN103383869A (zh) * 2012-06-01 2013-11-06 苏州诺菲纳米科技有限公司 低雾度透明导电电极
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WO2015045965A1 (fr) * 2013-09-30 2015-04-02 富士フイルム株式会社 Stratifié pour panneaux tactiles, et panneau tactile
KR20150068293A (ko) * 2013-12-10 2015-06-19 한양대학교 산학협력단 미세 구조체를 갖는 기판, 및 그 제조 방법
JP2016058395A (ja) * 2015-12-01 2016-04-21 コニカミノルタ株式会社 透明電極及び有機電子素子
KR20160059531A (ko) * 2014-11-18 2016-05-27 영남대학교 산학협력단 은나노와이어 투명전극 제조방법
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JP2016196179A (ja) * 2015-04-06 2016-11-24 大日本印刷株式会社 導電性フィルムの製造方法及び導電性フィルム
KR101685069B1 (ko) * 2016-04-01 2016-12-09 금오공과대학교 산학협력단 패턴이 형성된 플렉서블 투명전극의 제조방법
KR20170131440A (ko) 2015-03-27 2017-11-29 린텍 가부시키가이샤 투명 도전층 적층용 필름, 그의 제조 방법 및 투명 도전성 필름
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JP2013073746A (ja) * 2011-09-27 2013-04-22 Toshiba Corp 透明電極積層体
JP2013164941A (ja) * 2012-02-10 2013-08-22 Konica Minolta Inc 透明電極の製造方法、透明電極及びそれを用いた有機電子素子
JP2013179173A (ja) * 2012-02-28 2013-09-09 Sumitomo Chemical Co Ltd 光電変換素子
WO2013141275A1 (fr) * 2012-03-23 2013-09-26 富士フイルム株式会社 Stratifié conducteur transparent et panneau tactile
JP2013198990A (ja) * 2012-03-23 2013-10-03 Fujifilm Corp 透明導電膜積層体及びタッチパネル
CN103383869A (zh) * 2012-06-01 2013-11-06 苏州诺菲纳米科技有限公司 低雾度透明导电电极
CN103383869B (zh) * 2012-06-01 2016-11-23 苏州诺菲纳米科技有限公司 低雾度透明导电电极
KR101381240B1 (ko) * 2013-04-05 2014-04-04 와이엠티 주식회사 터치 스크린 패널의 제조 방법 및 이에 의하여 제조된 터치 스크린 패널
WO2015045965A1 (fr) * 2013-09-30 2015-04-02 富士フイルム株式会社 Stratifié pour panneaux tactiles, et panneau tactile
KR20150068293A (ko) * 2013-12-10 2015-06-19 한양대학교 산학협력단 미세 구조체를 갖는 기판, 및 그 제조 방법
KR101627050B1 (ko) * 2013-12-10 2016-06-03 엘지디스플레이 주식회사 미세 구조체를 갖는 기판, 및 그 제조 방법
KR20160059531A (ko) * 2014-11-18 2016-05-27 영남대학교 산학협력단 은나노와이어 투명전극 제조방법
KR101677339B1 (ko) 2014-11-18 2016-11-18 영남대학교 산학협력단 은나노와이어 투명전극 제조방법
KR20170131440A (ko) 2015-03-27 2017-11-29 린텍 가부시키가이샤 투명 도전층 적층용 필름, 그의 제조 방법 및 투명 도전성 필름
WO2016163364A1 (fr) * 2015-04-06 2016-10-13 大日本印刷株式会社 Produit stratifié électroconducteur, panneau tactile, et procédé de production d'un produit stratifié électroconducteur
JP2016196179A (ja) * 2015-04-06 2016-11-24 大日本印刷株式会社 導電性フィルムの製造方法及び導電性フィルム
KR20170134531A (ko) * 2015-04-06 2017-12-06 다이니폰 인사츠 가부시키가이샤 도전성 적층체, 터치 패널 및 도전성 적층체의 제조 방법
US11247444B2 (en) 2015-04-06 2022-02-15 Dai Nippon Printing Co., Ltd. Electroconductive layered product, touch panel, and process for producing electroconductive layered product
US11760070B2 (en) 2015-04-06 2023-09-19 Dai Nippon Printing Co., Ltd. Electroconductive layered product, touch panel, and process for producing electroconductive layered product
KR102681839B1 (ko) * 2015-04-06 2024-07-04 다이니폰 인사츠 가부시키가이샤 도전성 적층체, 터치 패널 및 도전성 적층체의 제조 방법
JP2016058395A (ja) * 2015-12-01 2016-04-21 コニカミノルタ株式会社 透明電極及び有機電子素子
KR101685069B1 (ko) * 2016-04-01 2016-12-09 금오공과대학교 산학협력단 패턴이 형성된 플렉서블 투명전극의 제조방법
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KR102005262B1 (ko) 2017-08-21 2019-07-31 금오공과대학교 산학협력단 패턴이 형성된 플렉서블 투명전극의 제조방법
CN110416341A (zh) * 2018-04-27 2019-11-05 北京铂阳顶荣光伏科技有限公司 导电电极膜层和光伏元件

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