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WO2011070951A1 - Panneau d'électronique organique et procédé de fabrication associé - Google Patents

Panneau d'électronique organique et procédé de fabrication associé Download PDF

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Publication number
WO2011070951A1
WO2011070951A1 PCT/JP2010/071452 JP2010071452W WO2011070951A1 WO 2011070951 A1 WO2011070951 A1 WO 2011070951A1 JP 2010071452 W JP2010071452 W JP 2010071452W WO 2011070951 A1 WO2011070951 A1 WO 2011070951A1
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WO
WIPO (PCT)
Prior art keywords
organic
organic electronics
layer
electrode
electronics panel
Prior art date
Application number
PCT/JP2010/071452
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English (en)
Japanese (ja)
Inventor
小島　茂
源田　和男
Original Assignee
コニカミノルタホールディングス株式会社
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Application filed by コニカミノルタホールディングス株式会社 filed Critical コニカミノルタホールディングス株式会社
Priority to JP2011545180A priority Critical patent/JPWO2011070951A1/ja
Publication of WO2011070951A1 publication Critical patent/WO2011070951A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • 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
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80516—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
    • H10K59/80522—Cathodes combined with auxiliary electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
    • 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 relates to an organic electronics panel and a method for manufacturing the same, and more particularly, to a method for wiring an organic electronics element used in an organic electronics panel, and more particularly to an organic electroluminescence element and an electrode wiring of an organic photoelectric conversion element. It is.
  • Organic electronics elements are elements that perform electrical operations using organic substances.
  • organic electronics elements are expected to exhibit features such as energy saving, low cost, and flexibility, and technologies that replace conventional inorganic semiconductors based on silicone. It is attracting attention as.
  • organic electronics elements emit light, control current and voltage, or generate electricity by charging light or charge by passing an electric current through an electrode through a very thin film of organic matter. It is an element to do.
  • organic electroluminescence (hereinafter, also referred to as organic EL) panels are attracting attention for applications such as display applications and illumination applications, in particular, because thin surface light sources can be obtained.
  • an organic EL panel When an organic EL panel is used for illumination, if the light emitting area is increased, the influence of the resistance of the transparent electrode is increased, and the luminance uniformity in the surface is reduced.
  • An organic EL panel with poor luminance uniformity not only looks bad, but also causes problems such as a decrease in light emission efficiency due to current loss and the accompanying heat generation. In addition, problems such as a reduction in device life occur due to the influence of heat generation.
  • development of a panel with good luminance uniformity and no current loss is demanded.
  • the organic EL element since the organic EL element generally has low resistance to moisture and oxygen, it is necessary to prevent the organic EL element from the influence of moisture and oxygen by using a sealing member such as a sealing can and a sealing plate.
  • the organic photoelectric conversion element is an organic electronic element having a structure similar to that of the organic electroluminescence element, but the light emitting layer of the organic electroluminescence element is a photoelectric conversion layer made of a thin film of an organic compound, and this is sandwiched between electrodes.
  • This is an element that has such a configuration and generates electricity when irradiated with light. Therefore, when a thin-film organic photoelectric conversion element is used as a solar cell, it can be easily reduced in size and weight, and has a relatively stable output even in a low illuminance environment or a high temperature environment as compared with an existing inorganic semiconductor solar cell. The solar cell can be obtained.
  • the organic photoelectric conversion element similarly to the organic EL element, carrier traps are formed in the photoelectric conversion layer due to the influence of moisture, oxygen, and the like, thereby preventing the collection of carriers generated by charge separation. . As a result, this not only causes a decrease in power generation efficiency, but also affects the lifetime of the organic photoelectric conversion element. Therefore, in the organic photoelectric conversion element as well, it has been studied to secure the performance by using a sealing material having a barrier performance against gas components such as moisture and oxygen.
  • Patent Document 1 describes a method of routing wiring outside the sealing structure, but there is a problem that efficient power supply is not always possible due to the space of the sealing member or the like. It was.
  • An electronic panel and a method for manufacturing the same are provided.
  • An organic electronics element having a structure in which an organic compound layer including at least a functional layer made of an organic compound is sandwiched between a first electrode and a second electrode arranged at opposing positions on a support substrate;
  • An organic electronics panel having a configuration in which a sealing member covering an element and the support substrate are closely sealed, and a wiring member is disposed in the tightly sealed interior, when viewed from a light emitting surface or a light receiving surface
  • the organic electronics panel is characterized in that the functional layer made of the organic compound and the wiring member are arranged so that at least a part thereof overlaps.
  • organic electronics panel according to 1, wherein the organic electronics element is an organic electroluminescence element in which the functional layer is a light emitting layer.
  • organic electronics panel according to 1 wherein the organic electronics element is an organic photoelectric conversion element in which the functional layer is a photoelectric conversion layer.
  • the distance (sealing margin) between the light emitting unit or the power generation unit and the end of the substrate is 2 mm or more and 10 mm or less.
  • the present invention it is possible to obtain a large-area organic electronics panel that is excellent in driving life and durability, can efficiently perform power feeding or power generation, and a method for manufacturing the same while maintaining space.
  • production area It is sectional drawing which shows an example of a structure of the organic electronics panel of this invention. It is sectional drawing which shows an example of a structure of the organic electronics panel of a comparative example. It is a cross-sectional structure schematic diagram which shows an example of the manufacturing method of the organic electronics panel of this invention. It is sectional drawing which shows the structure of the organic electroluminescent panel 101 produced in the Example. It is sectional drawing which shows the structure of the organic electroluminescent panel 102 produced in the Example. It is sectional drawing which shows the structure of the organic electroluminescent panel 103 produced in the Example. It is sectional drawing which shows the structure of the organic electroluminescent panel 104 produced in the Example.
  • the inventor has intensively studied a method for performing highly efficient wiring while maintaining space saving. As a result, it is possible to manufacture a thin and flexible organic electronics panel by using a close sealing (solid sealing) type sealing method, but this close sealing type sealing method is In the case of using it, a sealing margin (sealing portion, sealing region) is required around the functional layer region for light emission or power generation. If a wiring member is further arranged around the sealing margin, both the sealing margin and the installation space for the wiring member are required, resulting in an increase in the size of the organic electronics panel.
  • a close sealing (solid sealing) type sealing method In the case of using it, a sealing margin (sealing portion, sealing region) is required around the functional layer region for light emission or power generation. If a wiring member is further arranged around the sealing margin, both the sealing margin and the installation space for the wiring member are required, resulting in an increase in the size of the organic electronics panel.
  • an organic compound layer including at least a functional layer made of an organic compound is sandwiched between a first electrode and a second electrode arranged at opposing positions on the support substrate.
  • An organic electronics panel having a configuration in which the organic electronics element having the configuration described above is provided, and having a configuration in which the sealing member that covers the organic electronics element and the support substrate are tightly sealed, and the wiring member is disposed in the tightly sealed interior
  • the functional layer made of the organic compound and the wiring member are arranged so that at least a part thereof overlaps, and the wiring is formed inside the adhesive seal.
  • the driving life of the organic electronics panel is increased by adopting such a configuration.
  • the reason for this is not clear, but it is presumed that the wiring member disposed on the electrode also serves as a heat sink, preventing the organic compound layer from being heated and extending its driving life.
  • the distance from the light emitting end or the power generation end to the sealing end is preferably 2 mm or more and 10 mm or less.
  • the sealing margin is narrow. However, if it is too narrow, water or oxygen may enter from the surroundings, causing damage to the organic layer. Therefore, 2 mm or more and 10 mm or less are preferable, 2 mm or more and 7 mm or less are more preferable, and 2 mm or more and 5 mm or less are the most preferable.
  • the inventor has verified the characteristics of an organic electronics panel produced by changing the sealing margin distance when stored in a high-humidity environment, as shown in FIG.
  • FIG. 1 is a graph showing the relationship between the length of the sealing margin and the dark spot generation area.
  • the organic EL panel produced by changing the width of the sealing margin was stored at 60 ° C. in an environment of 90% RH for 250 hours, and then a luminescence image was taken, and a constant non-luminous portion (dark spot ( DS)).
  • DS dark spot
  • FIG. 2 is a cross-sectional view showing an example of the configuration of the organic electronics panel of the present invention.
  • FIG. 2 shows an organic compound layer including a pair of electrode groups formed by the first electrode 3 and the second electrode 4 formed on the support substrate 2 and at least a light emitting layer or a photoelectric conversion layer (power generation layer) therebetween.
  • 5 is a schematic cross-sectional view showing an organic electronic device 1 having a configuration in which 5 is sandwiched, and an organic electronic panel 1 that is tightly (solidly) sealed by a sealing member 9 and a sealing adhesive 11 covering the organic electronic device.
  • an organic compound layer 5 including, for example, an anode made of ITO and a light emitting layer or a photoelectric conversion layer is further formed thereon as a first electrode 3 on a flexible substrate that is a support substrate 2.
  • a cathode that is the second electrode 4 made of aluminum or the like is laminated to form an organic electronics element.
  • the support substrate 2 on which the organic electronics element is formed is tightly sealed by a sealing member 9. That is, the sealing member 9 is in close contact with the organic electronics element and the support substrate 2 that is a resin substrate by the sealing adhesive 11 and covers the entire surface, thereby sealing and isolating the organic electronics element from the external space.
  • the organic electronics panel 1 is configured.
  • the first electrode 3 and the second electrode 4 are adhered and joined (connected) by the wiring member 8 via the conductive adhesive 7. Further, the wiring member 8 is disposed so as to overlap the light emitting region or the power generation region.
  • the close sealing is also referred to as solid sealing, and all the gaps are made of resin (sealing adhesive) so as not to leave a space between the support substrate 2 on which the organic electronics element is formed and the sealing member 9.
  • the organic electronic element that is, the organic compound layer 5 is sealed by covering with 11).
  • the wiring member 8 is usually provided so as to cover the transparent first electrode 3 having a high resistance, and power can be supplied efficiently. Further, the wiring member 8 is also provided so as to overlap with the light emitting region or the power generation region, so that it is possible to reduce the thickness and the resistance.
  • the electrode lead is not only the joint with the electrode lead-out portion, but also the sealing adhesive 11. Can be firmly fixed without peeling or loosening.
  • the electrode lead-out portion does not have to be formed outside the sealing member, and the electrode area can be designed in a compact manner. In particular, there is an advantage in the case of an electrode using a transparent conductive film such as ITO. .
  • the wiring member is provided in the region tightly sealed by the sealing member, and the electrode lead is taken out from the close (solid) sealing portion, so that the performance of the organic electronics element is reduced in a space-saving manner.
  • the sealing member when a flexible resin substrate is used for the sealing member, it is an excellent sealing method that is strong against bending and displacement.
  • FIG. 3 is a cross-sectional view showing an example of the structure of a comparative organic electronics panel.
  • the first electrode 3 provided on the flexible substrate that is the support substrate 2, the organic compound layer 5 including the light emitting layer or the photoelectric conversion layer, the second electrode 4, and the like.
  • the structure in which the organic electronics elements formed by being laminated are not sealed with a sealing member or the like is shown.
  • FIG. 4 is a cross-sectional schematic diagram showing an example of a method for manufacturing an organic electronics panel according to the present invention, focusing on a connection portion between an electrode lead and an electrode lead portion of an organic electronics element.
  • an organic electronic device is formed by sequentially laminating an organic compound layer 5 constituting an organic electronic device composed of a hole transporting layer, a light emitting layer, an electron transporting layer (not shown above) and the like, and a second electrode 4 (cathode).
  • the 2nd electrode 4 is formed so that the extraction electrode 6 comprised from ITO for a drive may be connected.
  • ITO can be formed by forming ITO on the entire surface of the flexible support substrate 2 by sputtering, vapor deposition, or the like, and then etching into a desired pattern to form the first electrode 3 and the extraction electrode 6. .
  • it may be formed by a method in which a desired resist pattern is formed in advance and ITO is evaporated and the resist pattern is lifted off.
  • ITO can be directly formed by sputtering, vapor deposition or the like using a metal mask or the like in which a desired pattern is opened.
  • the organic compound layer 5 and the second electrode 4 may be patterned so as to form pixels in a matrix, or may be uniformly formed on the entire surface for uses such as illumination. good.
  • an anisotropic conductive film is used as the conductive adhesive 7 and temporarily adhered to the second electrode 4 on the ITO electrode lead-out portion which is the lead-out electrode 6 on the support substrate (resin substrate) 2.
  • the wiring member 8 (copper foil) and its junction are aligned and bonded together.
  • This adhesion is preferably performed under the pressure bonding conditions of the anisotropic conductive film.
  • the anisotropic conductive film can be connected by thermocompression bonding at a pressure of 0.1 to 10 MPa and a temperature of about 80 to 180 ° C. for several seconds to several minutes.
  • the temperature at the time of adhesion of the conductive adhesive 7 is preferably 140 ° C.
  • the lead electrode 6 and the wiring member 8 are bonded using the conductive adhesive 7, it is preferable that heating from both sides of the support substrate 2 and the sealing member 9 is uniformly cured.
  • the heating means is not particularly limited, and may be a heat plate, an oven, a laminator using a pressure roll, etc., as long as it can apply temperature and pressure. Generally, an ACF crimping machine or a bonder is used.
  • both the electrode lead and the resin substrate side it is preferable to be at the same temperature, it is preferable to be within the above temperature range. Heating from both sides is preferable from the viewpoint of uniform curing of the conductive adhesive, stronger bonding, and less peeling.
  • the anisotropic conductive film used as the conductive adhesive 7 has conductive particles, for example, metal nuclei themselves (for example, gold, nickel, or silver) or resin nuclei (for example, gold-plated ones) dispersed in a binder.
  • a binder a thermoplastic resin or a thermosetting resin is used, and among them, a thermosetting resin, particularly an epoxy resin is preferable.
  • a conductive paste having a similar structure may be used.
  • An anisotropic conductive film in which nickel fibers (fibrous) are oriented can be used as a filler.
  • the anisotropic conductive film When the anisotropic conductive film is thermocompression bonded to the support substrate, electrical connection in the thickness direction is made by the conductive particles, and at the same time, mechanical bonding is made by the binder resin.
  • the binder resin include thermosetting resins such as epoxy resins and phenol resins, and thermoplastic resins such as polyamideimide. From the viewpoint of resin fluidity, connection reliability, cost, pot life, and the like, a film-like resin is used. Epoxy resins are preferred.
  • the conductive particles include metal particles such as nickel, copper and silver, and composite particles in which the surface of plastic particles such as acrylic resin and styrene resin is coated with a metal plating film such as nickel and gold.
  • composite particles in which the particles themselves are flexible and have a restorable plastic particle coated with a metal plating film such as nickel or gold are suitable.
  • the conductive particle diameter is usually 3.0 to 5.0 ⁇ m as an average particle diameter.
  • a fluid material such as a conductive paste, for example, a silver paste or the like may be used. It can also be formed by printing or the like using a conductive paste on the electrode lead portion.
  • the sealing region or close-contact sealing refers to a space sandwiched between the support substrate 2 and the sealing member 9.
  • the sealing region or the inside of the tight seal is filled with an adhesive or the like.
  • the wiring member 8 is formed of a conductor.
  • the electrode lead that can be used in the present invention is not particularly limited as long as it is a member that has a low resistance value and can be made into a thin film, but the wiring member is preferably formed of a metal foil and is applicable to the present invention.
  • the metal foil include aluminum foil, rolled copper foil, silver foil, and gold foil. Among these, aluminum foil and copper foil, which have a low resistance value, are easy to form a thin film, and are suitable for cost, can be used.
  • the stress relaxation layer 10 is not particularly limited as long as it can deform itself and prevent damage to the organic compound layer 5.
  • a resin or the like can be used. Specifically, polyethylene, polypropylene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, polyimide, polyurethane, polystyrene, ABS resin, acrylic resin, polyacetal resin, etc. These resins can be used.
  • the inorganic film 12 between the second electrode 4 and the wiring member 8.
  • an insulating film is preferable.
  • silicon oxide, silicon nitride, aluminum oxide, or the like can be used.
  • the water content of the conductive adhesive 7 or the wiring member 8 is preferably 100 ppm or less. It is preferable from the viewpoint that the water permeability of the cured film can be kept low by suppressing the mixing of water below this level, thereby strengthening the adhesion and at the same time curing it at a low water content.
  • the moisture content may be measured by any method.
  • a volumetric moisture meter Karl Fischer
  • an infrared moisture meter a microwave transmission moisture meter
  • a heat-dry weight method e.g., a GC / MS, IR, DSC (Differential scanning calorimeter) and TDS (temperature programmed desorption analysis).
  • a precision moisture meter AVM-3000 Omnitech or the like, moisture can be measured from a pressure increase caused by evaporation of moisture, and moisture content of a film or a solid film can be measured.
  • sealing member 9 for example, a 50 ⁇ m thick PET (polyethylene terephthalate) laminated with an aluminum foil (30 ⁇ m thick) can be used.
  • a sealing adhesive 11 for example, a thermosetting adhesive (epoxy adhesive)
  • epoxy adhesive epoxy adhesive
  • an ultraviolet curable resin can also be used.
  • an ultraviolet curable resin active energy ray irradiation is required.
  • the organic electronics element is damaged when irradiated with ultraviolet rays, it is necessary to reduce the amount of ultraviolet irradiation as much as possible when using an ultraviolet curable resin.
  • a thermosetting resin Various known materials such as epoxy resins, acrylic resins, and silicone resins can be used.
  • an epoxy thermosetting adhesive resin that is excellent in moisture resistance and water resistance and has little shrinkage upon curing.
  • thermosetting resin adheresive
  • the thermosetting resin is applied uniformly along the aluminum surface of the sealing member 9 (PET laminated with an aluminum foil) using a dispenser, for example, and then the sealing member 9 is electrically connected.
  • press-bonding for example, pressure 0.5 MPa
  • it is temporarily bonded so that air (cavity) does not remain.
  • a pressure roll or a press may be used.
  • the temporarily bonded organic electronics panel is placed on, for example, a hot plate and heated (for example, at a temperature of 120 ° C. for 30 minutes) to thermally cure the thermosetting adhesive, thereby tightly sealing the organic electronics element (solid
  • solid The organic electronics panel 1 is manufactured by sealing.
  • the lead electrode 6 and the wiring member 8 connected to the lead electrode 6 are fixed between the sealing member 9 and the support substrate 2 by the cured sealing adhesive 11, so that the electrode lead portion or the flexible member is sufficiently strong.
  • the circuit board can be fixed.
  • the heating or pressure bonding time is appropriately selected depending on the type, amount, and area of the adhesive, but is temporarily bonded at a pressure of about 0.1 to 3 MPa, and the temperature is 80 to 180 ° C. and the heat curing time is 5 seconds to 10 minutes. Select within the range.
  • a heated crimping roll it is preferable to use because it can simultaneously perform crimping (temporary bonding) and heating, and can eliminate internal voids at the same time.
  • a dispenser can be used, or a coating method such as roll coating, spin coating, screen printing, spray coating, or the like can be used depending on the material.
  • Solid sealing is a form in which there is no space between the sealing substrate and the organic electronics element substrate, as described above, and is covered with a cured resin, and has a sealing material-filled close-contact structure, and the electrode leads are also fixed in the sealing resin. Then, the electrode lead is taken out from the tightly sealed (solid) sealed portion.
  • An organic electronics panel that has a solid sealing structure that can maintain sufficient adhesion (bonding) strength in the connection between the electrode lead and the electrode, and that can take out the electrode lead without degrading the performance of the organic electronics element. It is a manufacturing method.
  • the material of each component is not particularly limited. That is, the first electrode (anode), organic compound layer, second electrode (cathode), conductive adhesive (anisotropic conductive film), adhesive, etc. constituting the support substrate, the sealing member, and the organic electronics element are Various known materials can be used.
  • a substrate made of a resin (plastic) in the form of a sheet or film can be used as the support substrate 2.
  • transparent plastics such as polyester, polymethacrylate, and polycarbonate having high transparency to light emission are suitable.
  • a gas barrier film in which a gas barrier layer of aluminum oxide, silicon oxide, silicon nitride or the like is laminated on the resin substrate in a thickness range of 1 nm to several hundred nm.
  • the gas barrier layer can also be formed on one surface or both surfaces of the resin substrate using thin film forming means such as plasma CVD, sputtering, or vapor deposition.
  • the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and it conforms to JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by the method is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the sealing member 9 examples include metals such as stainless steel, aluminum, and magnesium alloys, polyethylene terephthalate, polycarbonate, polystyrene, nylon, plastics such as polyvinyl chloride, and composites thereof, glass, and the like.
  • a layer in which a gas barrier layer such as aluminum, aluminum oxide, silicon oxide, or silicon nitride is laminated can be used in the same manner as the resin substrate.
  • the gas barrier layer can be formed by sputtering, vapor deposition or the like on both surfaces or one surface of the sealing member before molding the sealing member, or may be formed on both surfaces or one surface of the sealing member after sealing by a similar method. .
  • the oxygen permeability is 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is 1 ⁇ It is preferably 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the sealing member may be a film laminated with a metal foil such as aluminum.
  • a method for laminating the polymer film on one side of the metal foil a generally used laminating machine can be used.
  • the adhesive polyurethane-based, polyester-based, epoxy-based, acrylic-based adhesives and the like can be used. You may use a hardening
  • a hot melt lamination method, an extrusion lamination method and a coextrusion lamination method can also be used, but a dry lamination method is preferred.
  • a metal foil when forming a metal foil by sputtering or vapor deposition, or when forming from a fluid electrode material such as a conductive paste, it is created by using a polymer film as a base material and forming a metal foil on this. May be.
  • Organic EL element has a structure in which one or a plurality of organic compound layers are laminated between electrodes.
  • various organic compounds such as an anode layer / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode layer, etc.
  • a functional layer made of a compound has a structure in which it is laminated as necessary. The simplest structure is an anode layer / light emitting layer / cathode layer.
  • Examples of organic compound materials used for the hole injection / transport layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), and the like.
  • a polymer material such as a representative conductive polymer is used.
  • Examples of the organic compound material used for the light emitting layer include carbazole-based light emitting materials such as 4,4′-dicarbazolylbiphenyl and 1,3-dicarbazolylbenzene, (di) azacarbazoles, 1,3 , 5-tripyrenylbenzene and the like, low molecular light emitting materials typified by pyrene light emitting materials, polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles and the like polymer light emitting materials. Of these, a low molecular weight light emitting material having a molecular weight of 10,000 or less is preferably used as the light emitting material.
  • the light emitting material applied to the light emitting layer may preferably contain about 0.1 to 20% by mass of a dopant.
  • the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, and phosphorescent dyes.
  • fluorescent dyes such as perylene derivatives and pyrene derivatives
  • phosphorescent dyes for example, ortho represented by tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonato) iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, etc.
  • complex compounds such as metalated iridium complexes.
  • Electrode injection / transport layer Examples of the constituent material of the electron injection / transport layer include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinate) zinc, and the following nitrogen-containing five-membered ring derivatives. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred.
  • each functional layer As the organic compound material used for these light emitting layers and each functional layer, a material having a polymerization reactive group such as a vinyl group in the molecule is used, and a cross-linked / polymerized film is formed after film formation to form each functional layer. May be.
  • anode layer As the conductive material used for the anode layer, a material having a work function larger than 4 eV is suitable, and silver, gold, platinum, palladium and the like and alloys thereof, metal oxides such as tin oxide, indium oxide and ITO, Furthermore, organic conductive resins such as polythiophene and polypyrrole are used.
  • Cathode layer As the conductive material used for the cathode layer, those having a work function smaller than 4 eV are suitable, such as magnesium and aluminum. Typical examples of the alloy include magnesium / silver and lithium / aluminum.
  • Each functional layer described above is formed on a support substrate and sealed with a sealing member to constitute an organic EL panel.
  • Organic photoelectric conversion element Although an organic photoelectric conversion element is demonstrated, it is not limited to the following forms.
  • organic photoelectric conversion element which can be used by this invention, If it is an element which has an anode and a cathode and at least 1 or more photoelectric conversion layer pinched
  • the configuration of the photoelectric conversion layer is not particularly limited as long as it is a configuration in which an organic semiconductor material is stacked.
  • a heterojunction type in which a p-type semiconductor material and an n-type semiconductor material are stacked, or both a p-type and an n-type semiconductor.
  • a so-called bulk heterojunction type in which materials are mixed and have a microphase separation structure can be given. From the viewpoint of improving internal quantum efficiency, a configuration excellent in charge separation efficiency is preferable, and a bulk heterojunction structure is more preferable in the present application.
  • the organic photoelectric conversion element which concerns on this invention when using the organic photoelectric conversion element which concerns on this invention as a solar cell, it is preferable to use the organic-semiconductor material which has the absorption characteristic optimal for a sunlight spectrum, and it is a blacker external appearance from a viewpoint of efficiency and design property.
  • An organic photoelectric conversion element is preferable.
  • a transparent electrode, a photoelectric conversion layer, and a counter electrode are sequentially laminated on one surface of a support.
  • An organic photoelectric conversion element may be configured with other layers. Further, it may be an electron transport layer having a hole blocking ability or a hole transport layer having an electron blocking ability.
  • a hole transport layer or an electron block layer is provided between the photoelectric conversion layer and the anode (usually the transparent electrode side), and the photoelectric conversion layer.
  • anode / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / cathode (ii) Anode / hole transport layer having electron blocking ability / photoelectric conversion layer / hole block Electron transport layer / cathode buffer layer / cathode (iii) anode / anode buffer layer / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / cathode (iv) anode / anode Buffer layer / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / cathode buffer layer / cathode As described above, the organic photoelectric conversion element is laminated by stacking the layers. .
  • the thin film forming method can be applied to form each of the above-described structures, but can be preferably applied particularly to the formation of each layer excluding the anode and the cathode.
  • each functional layer may be formed by a vacuum method, a dry method such as a sputtering method, or may be formed by a wet method such as coating or printing.
  • Example 1 Production of Organic EL Panel: Present Invention >> [Production of Organic EL Panel 101] (Production of gas barrier flexible film (support substrate)) As a flexible film, a 100 ⁇ m thick polyethylene naphthalate film (a film made by Teijin DuPont, hereinafter abbreviated as PEN) is formed on the entire surface by an atmospheric pressure plasma discharge treatment having the structure described in JP-A-2004-68143.
  • PEN polyethylene naphthalate film
  • a gas barrier film (thickness 500 nm) composed of SiO 2 is continuously formed on a flexible film, and has an oxygen permeability of 0.001 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less, water vapor A gas barrier flexible film having a permeability of 0.001 g / (m 2 ⁇ 24 h) or less was produced.
  • ITO film indium tin oxide having a thickness of 120 nm is formed by sputtering on the gas barrier flexible film prepared above, and patterned by photolithography, and the first electrode 3 as shown in FIG. And the extraction electrode 6 was formed.
  • the pattern was such that the light emission area was 50 mm square.
  • the following hole transport layer forming coating solution was applied by an extrusion coater and then dried to form a hole transport layer as an organic compound layer. Formed. The hole transport layer forming coating solution was applied so that the thickness after drying was 50 nm.
  • a low pressure mercury lamp with a wavelength of 184.9 nm is used as a cleaning surface modification treatment for the gas barrier flexible film, the irradiation intensity is 15 mW / cm 2 , The distance was 10 mm.
  • the charge removal treatment was performed using a static eliminator with weak X-rays.
  • ⁇ Drying and heat treatment conditions After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment.
  • the back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.
  • the white light emitting layer forming coating liquid shown below is applied on the hole transporting layer of the gas barrier flexible film having the hole transporting layer formed thereon by an extrusion coating machine, and then dried to form a light emitting layer. did.
  • the white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.
  • an electron injection layer was formed on the formed electron transport layer.
  • the substrate was put into a vacuum chamber and the pressure was reduced to 5 ⁇ 10 ⁇ 4 Pa.
  • cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
  • Second electrode Next, a second electrode was formed on the formed electron injection layer and extraction electrode. Subsequently, aluminum prepared in a tungsten vapor deposition boat was heated under a vacuum of 5 ⁇ 10 ⁇ 4 Pa. A mask pattern was formed so that the emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.
  • a gas barrier flexible film was cut into a prescribed size to produce an organic EL device.
  • a wiring member was connected to the produced organic EL element using an anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Corporation.
  • As the wiring member a 30 ⁇ m thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) was used.
  • pressure bonding is performed using a commercially available ACF pressure bonding apparatus so as to have the shape shown in FIG. 5: temperature 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), pressure 2 MPa, and 10 seconds. went.
  • a sealing member was bonded to the organic EL element to which the wiring member (aluminum foil) was connected using a commercially available roll laminating apparatus, and the organic EL panel 101 was manufactured.
  • sealing member a 30 ⁇ m thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), a polyethylene terephthalate (PET) film (12 ⁇ m thick) with an adhesive for dry lamination (two-component reaction type urethane adhesive).
  • PET polyethylene terephthalate
  • the laminate used adheresive layer thickness 1.5 ⁇ m was used.
  • thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 ⁇ m along the adhesive surface (glossy surface) of the aluminum foil using a dispenser.
  • thermosetting adhesive bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY), and an epoxy adduct curing accelerator were used as an epoxy adhesive.
  • the sealing substrate is closely attached and arranged so as to cover the wiring member, and is tightly sealed using a pressure-bonding roll under a thickening condition, a pressure-rolling temperature of 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min.
  • a pressure-bonding roll under a thickening condition, a pressure-rolling temperature of 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min.
  • FIG. 5 shows a cross-sectional view of the organic EL panel 101 produced as described above.
  • E represents a light emitting area
  • L represents a sealing margin
  • L is 4 mm.
  • a polyethylene resin was disposed as the stress relaxation layer 10 so as to have the shape shown in FIG.
  • PRIMACOR 3460 manufactured by Dow Chemical Japan Co., Ltd. was used.
  • PRIMACOR 3460 was used as a 50 ⁇ m sheet by the inflation method.
  • a wiring member was arranged in the same manner as the production of the organic EL panel 101, and the organic EL panel 102 was produced by tightly sealing.
  • FIG. 6 shows a cross-sectional view of the organic EL panel 102 produced as described above.
  • a flexible printed circuit board formed by bonding polyimide resin on both sides of the rolled copper foil and using it was used.
  • the FPC polyimide resin acts as the stress relaxation layer 10B.
  • the FPC was pressure-bonded with ACF in the same manner as the production of the organic EL panel 102.
  • FIG. 7 shows a cross-sectional view of the organic EL panel 103.
  • the cut substrate was transferred to a commercially available sputtering apparatus on which a SiO 2 target was placed, and the inside of the apparatus was evacuated.
  • a 50 nm SiO 2 film was provided as the inorganic film 12 on the second electrode using a sputtering apparatus.
  • FIG. 8 shows a cross-sectional view of the organic EL panel 104.
  • Comparative Example >> A comparative organic EL panel 105 having the configuration shown in FIG. 3 was produced according to the following method.
  • the second electrode was formed and was cut.
  • the cut substrate was transferred to a commercially available sputtering apparatus in which a SiN target was placed, and the inside of the apparatus was evacuated.
  • a 200 nm SiN film was provided on the second electrode using a sputtering apparatus.
  • the substrate provided with the SiN film was taken out into the atmosphere, the wiring member 8 was installed, and the organic EL panel 105 was produced.
  • ⁇ Voltage change before and after storage is less than 0.5V ⁇ : Voltage change before and after storage is 0.5V or more and less than 1.0V ⁇ : Voltage change before and after storage is 1.0V [Evaluation of drive life] Using the drive life evaluation device prepared for each organic EL panel manufactured in combination with a commercially available constant current power supply and a spectral radiance meter (CS-2000 manufactured by Konica Minolta), the drive life was evaluated according to the following method. It was.
  • a current of 10 mA / cm 2 was applied to each organic EL element, and the change in luminance over time was measured with a spectral radiance meter.
  • the relative lifetime of each organic EL panel when the luminance of each organic EL panel is half the lifetime immediately after driving is defined as the half-life and the half-life of the organic EL panel 101 is defined as 100. This was taken as a measure of the driving life.
  • Example 2 Production of Organic Photoelectric Conversion Panel (Organic Thin Film Solar Cell) 201 >> In the production of the organic EL panel 104 described in Example 1, an organic photoelectric conversion panel 201 was produced in the same manner except that the formation of the organic compound layer was changed as described below.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention a trait à un panneau d'électronique organique à grande surface, ledit panneau étant doté d'une excellente durée de vie de commande ainsi que d'une excellente durabilité et permettant d'obtenir une alimentation en énergie ou une production d'énergie efficace tout en gagnant de l'espace. La présente invention a également trait à son procédé de fabrication. Ce panneau d'électronique organique est équipé d'un élément d'électronique organique configuré de manière à ce qu'une couche de composé chimique organique, qui inclut au moins une couche fonctionnelle constituée d'un composé chimique organique, soit prise en sandwich entre une première électrode et une seconde électrode qui sont disposées sur un substrat de support à des emplacements situés à l'opposé l'un de l'autre, et le panneau d'électronique organique est configuré de manière à être étroitement et hermétiquement fermé au moyen du substrat de support et un élément d'étanchéité qui recouvre l'élément d'électronique organique. Un élément de câblage est disposé dans l'intérieur étroitement et hermétiquement fermé et l'élément de câblage et la couche fonctionnelle constituée du composé chimique organique sont agencés de manière à ce qu'au moins certaines parties de ceux-ci se chevauchent, lorsqu'ils sont vus depuis la face électroluminescente ou la face de réception de lumière.
PCT/JP2010/071452 2009-12-11 2010-12-01 Panneau d'électronique organique et procédé de fabrication associé WO2011070951A1 (fr)

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JP2016154270A (ja) * 2016-05-30 2016-08-25 ローム株式会社 有機薄膜太陽電池
JP2017188354A (ja) * 2016-04-07 2017-10-12 株式会社小糸製作所 車両用灯具、及び有機ｅｌ素子の検査方法
JP2018097943A (ja) * 2016-12-08 2018-06-21 コニカミノルタ株式会社 有機エレクトロルミネッセンス発光装置
WO2020071017A1 (fr) * 2018-10-01 2020-04-09 コニカミノルタ株式会社 Composition mixte d'élément électroluminescent organique
JP2021174884A (ja) * 2020-04-24 2021-11-01 フジプレアム株式会社 ペロブスカイト型太陽電池
CN116528603A (zh) * 2023-05-31 2023-08-01 广州追光科技有限公司 一种有机太阳能电池及其制备方法

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KR20140044848A (ko) * 2011-07-04 2014-04-15 꼼미사리아 아 레네르지 아또미끄 에 오 에네르지 알떼르나띠브스 암전류 또는 누설전류를 제어하는 커패시터를 구비하는 포토다이오드 장치
WO2013004746A1 (fr) * 2011-07-04 2013-01-10 Commissariat à l'énergie atomique et aux énergies alternatives Dispositif de type photodiode contenant une capacite pour la régulation du courant d'obscurite ou de fuite
EP2849535A4 (fr) * 2012-05-09 2015-10-07 Mitsubishi Chem Corp Dispositif électroluminescent organique
JP2014044972A (ja) * 2012-08-24 2014-03-13 Konica Minolta Inc 有機エレクトロルミネッセンス素子、表示装置、照明装置及び有機エレクトロルミネッセンス素子の製造方法
WO2014057678A1 (fr) * 2012-10-11 2014-04-17 パナソニック株式会社 Élément électroluminescent organique et appareil d'éclairage
WO2014073284A1 (fr) * 2012-11-06 2014-05-15 日東電工株式会社 Élément el organique
WO2014076912A1 (fr) * 2012-11-13 2014-05-22 パナソニック株式会社 Élément électroluminescent organique et dispositif d'éclairage
JP2017188354A (ja) * 2016-04-07 2017-10-12 株式会社小糸製作所 車両用灯具、及び有機ｅｌ素子の検査方法
JP2016154270A (ja) * 2016-05-30 2016-08-25 ローム株式会社 有機薄膜太陽電池
JP2018097943A (ja) * 2016-12-08 2018-06-21 コニカミノルタ株式会社 有機エレクトロルミネッセンス発光装置
WO2020071017A1 (fr) * 2018-10-01 2020-04-09 コニカミノルタ株式会社 Composition mixte d'élément électroluminescent organique
JPWO2020071017A1 (ja) * 2018-10-01 2021-09-02 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子用の混合組成物
JP7196926B2 (ja) 2018-10-01 2022-12-27 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子用の混合組成物
JP2021174884A (ja) * 2020-04-24 2021-11-01 フジプレアム株式会社 ペロブスカイト型太陽電池
CN116528603A (zh) * 2023-05-31 2023-08-01 广州追光科技有限公司 一种有机太阳能电池及其制备方法
CN116528603B (zh) * 2023-05-31 2024-06-11 广州追光科技有限公司 一种有机太阳能电池及其制备方法

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