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WO2018168225A1 - Composition pour la production de dispositif électronique, procédé de production de composition pour la production de dispositif électronique, film mince organique et procédé de production de film mince organique - Google Patents

Composition pour la production de dispositif électronique, procédé de production de composition pour la production de dispositif électronique, film mince organique et procédé de production de film mince organique Download PDF

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Publication number
WO2018168225A1
WO2018168225A1 PCT/JP2018/002707 JP2018002707W WO2018168225A1 WO 2018168225 A1 WO2018168225 A1 WO 2018168225A1 JP 2018002707 W JP2018002707 W JP 2018002707W WO 2018168225 A1 WO2018168225 A1 WO 2018168225A1
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organic
layer
electronic device
composition
thin film
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PCT/JP2018/002707
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English (en)
Japanese (ja)
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北　弘志
田中　達夫
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コニカミノルタ株式会社
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Priority to JP2019505749A priority Critical patent/JP6984649B2/ja
Publication of WO2018168225A1 publication Critical patent/WO2018168225A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • 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

Definitions

  • the present invention relates to a composition for producing an electronic device, a method for producing a composition for producing an electronic device, an organic thin film, and a method for producing an organic thin film, and in particular, a selection range of a solvent that can be used when producing an electronic device such as an organic electronic element.
  • the present invention relates to a composition for producing an electronic device that can produce an electronic device having a laminated thin film without being limited, excellent in solvent resistance, and without affecting element performance.
  • an organic electroluminescence element typified by an organic electroluminescence element (hereinafter also referred to as an organic EL element)
  • a thin film forming method by a vacuum deposition method is widely used.
  • the thin film forming method by the vacuum deposition method requires high vacuum and high temperature for vapor deposition, and problems such as a limited molecular weight of usable compounds and an increase in the size of a manufacturing apparatus have become obvious.
  • a method for producing an organic EL element by a coating method using a solution containing an organic compound instead of the vacuum vapor deposition method has been actively developed.
  • Patent Document 1 discloses a method for manufacturing an organic EL element by a spin coating method, which is one of coating methods, for an efficient method of forming an organic thin film in which organic EL elements are stacked.
  • a spin coating method which is one of coating methods, for an efficient method of forming an organic thin film in which organic EL elements are stacked.
  • all organic layers that have been conventionally considered difficult are applied and formed by selecting an organic compound or a coating solvent constituting the organic EL element. That is, it may be considered that one method for imparting resistance to the solution used in the next step to the previously applied organic thin film has been proposed.
  • Patent Document 1 makes it possible to manufacture an organic EL element by a coating method, but there are many restrictions such as the organic compound constituting each layer, the coating solvent, and the order of lamination, and further improvement has been desired. .
  • Patent Document 2 discloses a laminating technique using a polymer material. This is a method utilizing the solvent resistance of the polymer thin film.
  • a thin film layer made of a polymer material is known to cause deterioration of device performance because it is difficult to remove impurities derived from the polymer material, and it is difficult to pursue emission luminance and the like.
  • the solvent that can dissolve the organic compound contained in each organic thin film is limited, and when a polymer material is used, the performance of the device may be deteriorated. There are challenges.
  • the present invention has been made in view of the above problems and circumstances, and the solution to the problem is that the selection range of the solvent that can be used at the time of manufacturing an electronic device is not limited, it has excellent solvent resistance and also affects element performance.
  • a composition for producing an electronic device and a method for producing the same and an organic thin film containing the composition for producing an electronic device and a method for producing the same It is to be.
  • the present inventor in the process of examining the cause of the above-mentioned problems, when forming a plurality of stacked organic thin films, the organic thin films previously formed are applied to the top thereof. It was thought that one of the solutions was to provide solvent resistance to the solution. Therefore, attention was focused on cellulose nanofiber (CNF) that can effectively change the properties of the solution (composition) with a small amount of addition.
  • CNF cellulose nanofiber
  • the thixotropy that is one of the characteristics of CNF makes it possible to impart solvent resistance.
  • CNF is used to form an organic EL element, it imparts solvent resistance to an organic thin film that does not inherently have solvent resistance. It has become possible to form a laminated organic thin film easily.
  • An electronic device manufacturing composition containing an organic material for an electronic device,
  • the composition for electronic device preparation containing a cellulose nanofiber.
  • composition for producing an electronic device according to item 1 wherein the cellulose nanofiber is contained in a range of 0.001 to 20000 ppm by mass.
  • Item 3 The composition for producing an electronic device according to Item 1 or 2, which is an inkjet ink.
  • composition for producing an electronic device according to any one of Items 1 to 3, wherein a content of the cellulose nanofiber is 5% by mass or less based on a mass of the organic material for an electronic device.
  • composition for producing an electronic device according to any one of Items 1 to 4, wherein the organic material for an electronic device is a material for an organic electroluminescence element.
  • a method for producing a composition for producing an electronic device according to any one of items 1 to 5, The manufacturing method of the composition for electronic device manufacture which has the process of mixing the said organic material for electronic devices, and the said cellulose nanofiber.
  • the solvent resistance is improved by forming a cluster of cellulose nanofibers by partial bonding via hydrogen bonding between nanofibers.
  • the organic thin film can be stacked without narrowing the selection range of the solvent, and it is not necessary to use a polymer material or the like as the solvent, so that the device performance is not affected.
  • cellulose nanofibers are electrically inactive, the influence on device performance is small.
  • Cellulose nanofibers are presumed to have an effect of amorphizing the state of the organic thin film by suppressing the crystallization of the film components and expressing the effect of separating the layers (foreign matter mixing effect).
  • Schematic diagram showing an example of a display device composed of organic EL elements Schematic diagram of display part A Schematic showing the pixel circuit Schematic diagram of passive matrix type full color display device Sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element of a bulk heterojunction type Sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem type bulk heterojunction layer
  • the composition for electronic device manufacture of this invention is a composition for electronic device preparation containing the organic material for electronic devices, Comprising: A cellulose nanofiber is contained.
  • This feature is a technical feature common to or corresponding to the invention according to the present embodiment.
  • the cellulose nanofiber is contained within a range of 0.001 to 20000 mass ppm so that the viscosity can be easily adjusted and an electronic device having good performance is produced. It is preferable in that it can be performed.
  • composition for producing an electronic device of the present invention is preferably an inkjet ink from the viewpoint of producing various electronic devices.
  • Viscosity adjustment can be easily performed so that the content of the cellulose nanofiber is 5% by mass or less based on the mass of the organic material for an electronic device, and an electronic device with good performance is manufactured. It is preferable at the point which can do.
  • the organic material for an electronic device is a material for an organic electroluminescence element in that the lifetime of the light emitting element and high luminous efficiency can be effectively obtained.
  • a method for producing a composition for producing an electronic device of the present invention comprising: It has the process of mixing the said organic material for electronic devices, and the said cellulose nanofiber.
  • composition for producing an electronic device of the present invention is suitably used for an organic thin film.
  • the manufacturing method of the organic thin film of this invention has the process of apply
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the ratios such as “%” and “ppm” are based on mass.
  • the composition for electronic device manufacture of this invention is a composition for electronic device preparation containing the organic material for electronic devices, Comprising: A cellulose nanofiber is contained.
  • the composition for producing an electronic device of the present invention is preferably an inkjet ink that is applied using an inkjet method.
  • the composition for producing an electronic device is used for coating, it is also referred to as a coating composition.
  • the organic material for electronic devices is an organic material used for electronic devices.
  • the electronic device include color filters such as an organic EL element, a light emitting diode (LED), a liquid crystal element, a solar cell (photoelectric conversion element), a touch panel, and a liquid crystal display device.
  • the electronic device is preferably an organic EL element, and the organic material for an electronic device is preferably an organic material for an organic EL element.
  • the organic material for electronic devices means the solid component of the said organic material, and shall not contain an organic solvent.
  • the content of cellulose nanofibers is preferably in the range of 0.001 to 20000 mass ppm with respect to the total mass of the composition for producing an electronic device. If 0.001 mass ppm or more is contained, viscosity adjustment is easy and a sufficient solvent resistance effect can be obtained. If it is 20000 mass ppm or less, clogging by an inkjet coating method without gelation, etc. Does not occur. As a result, an electronic device with good performance can be manufactured. Furthermore, it is preferable that content of a cellulose nanofiber is 5 mass% or less with respect to the mass of the organic material for electronic devices, More preferably, it is 2 mass% or less.
  • the cellulose nanofiber according to the present invention refers to a cellulose microfibril or an aggregate of cellulose microfibrils, and refers to a cellulose fiber having a width on the order of 2 to several hundred nm.
  • Cellulose nanofibers can be produced from cellulosic materials.
  • the cellulose material is not particularly limited, and natural celluloses such as various kinds of wood, non-wood pulp, microbial-produced cellulose, valonia cellulose, and squirt cellulose can be used, and pulping methods, purification methods, bleaching methods, etc. Is not particularly limited.
  • a highly purified cellulose material such as bleached pulp or dissolved pulp.
  • Cellulose nanofibers chemically modified cellulose nanofibers obtained by subjecting the cellulose material to chemical treatment according to the purpose and then performing defibrating treatment can be used.
  • serisch KY100G manufactured by Daicel Finechem Co., Ltd.
  • the composition for producing an electronic device of the present invention preferably contains an organic solvent in addition to the organic material for an electronic device and cellulose nanofiber.
  • the organic solvent contained in the composition for electronic device preparation means the liquid medium which consists of an organic compound which can melt
  • Liquid media for dissolving or dispersing the organic material for electronic devices according to the present invention include ketones such as methylene chloride, methyl ethyl ketone, tetrahydrofuran (THF), cyclohexanone, ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate.
  • Fatty acid esters such as chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as 2,2,3,3-tetrafluoro-1-propanol (TFPO), and aromatic hydrocarbons such as toluene, xylene, mesitylene and cyclohexylbenzene , Aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, n-butanol, s-butanol, t-butanol alcohols, DMF (N, N-dimethyl formamide), DMSO (Dimethyl sulfoxide), ethers, etc.
  • Organic solvents, elements From the viewpoint of suppressing the amount of the solvent contained therein, a solvent having a boiling point in the range of 50 to 180 ° C. is preferable.
  • the manufacturing method of the composition for electronic device manufacture of this invention has the process of mixing the organic material for electronic devices, and a cellulose nanofiber. Specifically, after dissolving or dispersing the organic material for an electronic device in an organic solvent that can dissolve or disperse the organic material for the electronic device, for example, by filtering with a filter or the like, a solution is prepared, The composition for producing an electronic device of the present invention can be produced by adding and mixing cellulose nanofibers.
  • the organic thin film of this invention contains the said composition for electronic device preparation.
  • the organic thin film of the present invention is preferably applied to, for example, at least one organic functional layer of the organic EL element.
  • examples of the organic functional layer include a plurality of organic functional layers such as an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, a hole transport layer, and a hole injection layer.
  • the organic thin film of the present invention may be used for at least one of these organic functional layers, and is not particularly limited.
  • an electron transport layer a hole blocking layer, a light emitting layer, an electron blocking layer It is preferably either a layer or a hole transport layer, and more preferably one or more of a hole blocking layer, a light emitting layer, and an electron blocking layer.
  • the light emitting layer is preferable from the viewpoints of light emission efficiency and durability.
  • the organic EL device includes an anode, a cathode, and one or more organic functional layers (also referred to as “organic EL layer” or “organic compound layer”) sandwiched between these electrodes on a substrate.
  • organic EL layer also referred to as “organic compound layer” or “organic compound layer”
  • the substrate that can be used in the organic EL device according to the present invention (hereinafter also referred to as a base, a support substrate, a base material, a support, etc.) is not particularly limited, and a glass substrate, a plastic substrate, or the like can be used. Further, 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 plastic substrate.
  • the substrate has a thickness of 1 ⁇ m or more and a water vapor transmission rate of 1 g / (m 2 ⁇ 24 h ⁇ atm in a test based on JIS Z-0208. ) (25 ° C.) or less is preferred.
  • the glass substrate include alkali-free glass, low alkali glass, and soda lime glass.
  • Alkali-free glass is preferable from the viewpoint of low moisture adsorption, but any of these may be used as long as it is sufficiently dried.
  • the resin film used as the base material of the plastic substrate is not particularly limited.
  • polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC) ), Cellulose acetates such as cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate, cellulose nitrate, or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate , Norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone PES), polyphenylene sulfide, polysulfones, polyetherimides, poly
  • organic / inorganic hybrid resin examples include those obtained by combining an organic resin and an inorganic polymer (for example, silica, alumina, titania, zirconia, etc.) obtained by a sol-gel reaction.
  • an inorganic polymer for example, silica, alumina, titania, zirconia, etc.
  • norbornene (or cycloolefin-based) resins such as Arton (manufactured by JSR) or Apel (manufactured by Mitsui Chemicals) are particularly preferable.
  • the plastic substrate that is normally produced has a relatively high moisture permeability and may contain moisture inside the substrate. Therefore, when using such a plastic substrate, it is preferable to provide a film (hereinafter referred to as “barrier film” or “water vapor sealing film”) that suppresses intrusion of water vapor, oxygen, or the like on the resin film.
  • a film hereinafter referred to as “barrier film” or “water vapor sealing film” that suppresses intrusion of water vapor, oxygen, or the like on the resin film.
  • the material constituting the barrier film is not particularly limited, and an inorganic film, an organic film, a hybrid of both, or the like is used.
  • a film may be formed, and the water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method according to JIS K 7129-1992 is 0.01 g / ( m 2 ⁇ 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is preferably 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
  • the material constituting the barrier film is not particularly limited as long as it has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen, and examples thereof include metal oxides, metal oxynitrides, and metal nitrides.
  • An inorganic material, an organic material, a hybrid material of both, or the like can be used.
  • Metal oxide, metal oxynitride or metal nitride includes silicon oxide, titanium oxide, indium oxide, tin oxide, metal oxide such as indium tin oxide (ITO), aluminum oxide, metal nitride such as silicon nitride And metal oxynitrides such as silicon oxynitride and titanium oxynitride.
  • the barrier film has a water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) of 0.01 g / (m 2 ⁇ 24 h) measured by a method according to JIS K 7129-1992.
  • the following barrier films are preferable, and further, the oxygen permeability measured by a method according to JIS K 7126-1987 is 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less, and the water vapor permeability.
  • the method of providing the barrier film on the resin film is not particularly limited, and any method may be used.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating Method plasma polymerization method, atmospheric pressure plasma polymerization method, CVD method (chemical vapor deposition: for example, plasma CVD method, laser CVD method, thermal CVD method, etc.), coating method, sol-gel method, etc. can be used.
  • CVD method chemical vapor deposition: for example, plasma CVD method, laser CVD method, thermal CVD method, etc.
  • coating method sol-gel method, etc.
  • sol-gel method sol-gel method, etc.
  • the opaque substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • anode As the anode of the organic EL element, a material having a work function (4 eV or more) metal, alloy, metal electrically conductive compound, or a mixture thereof is preferably used.
  • the “metal conductive compound” refers to a compound of a metal and another substance having electrical conductivity, and specifically, for example, a metal oxide, a halide or the like. That has electrical conductivity.
  • Electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • the anode can be produced by forming a thin film made of these electrode materials on the substrate by a known method such as vapor deposition or sputtering.
  • a pattern having a desired shape may be formed on the thin film by a photolithography method, and when a pattern accuracy is not required (about 100 ⁇ m or more), a desired shape can be formed at the time of vapor deposition or sputtering of the electrode material.
  • a pattern may be formed through a mask. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%.
  • the sheet resistance as the anode is several hundred ⁇ / sq. The following is preferred. Further, although the film thickness of the anode depends on the material constituting it, it is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • the organic functional layer (also referred to as “organic EL layer” or “organic compound layer”) includes at least a light-emitting layer.
  • the light-emitting layer is a current flowing through an electrode composed of a cathode and an anode. Specifically, it refers to a layer containing an organic compound that emits light when an electric current is passed through an electrode composed of a cathode and an anode.
  • the organic EL device used in the present invention may have a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer in addition to the light emitting layer as necessary, and these layers are cathodes. And the anode.
  • Anode / light emitting layer / cathode ii) Anode / hole injection layer / light emitting layer / cathode
  • Anode / light emitting layer / electron injection layer / cathode iv) Anode / hole injection layer / light emitting layer / electron Injection layer / cathode
  • anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode etc.
  • a cathode buffer layer (for example, lithium fluoride) may be inserted between the electron injection layer and the cathode, and an anode buffer layer (for example, copper phthalocyanine) may be inserted between the anode and the hole injection layer. ) May be inserted.
  • anode buffer layer for example, copper phthalocyanine
  • the light emitting layer according to the present invention 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, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
  • the light emitting layer may be a layer having a single composition, or may be a laminated structure including a plurality of layers having the same or different compositions.
  • the light emitting layer itself may be provided with functions such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer.
  • an injection function capable of injecting holes from an anode or a hole injection layer and applying electrons from a cathode or an electron injection layer when an electric field is applied to the light emitting layer
  • a light-emitting function that provides a recombination field of electrons and holes inside the light-emitting layer and connects it to light emission.
  • a function may be added.
  • the light emitting layer may have a difference in the ease of hole injection and the ease of electron injection, and the transport function represented by the mobility of holes and electrons may be large or small. The one having a function of moving at least one of the charges is preferable.
  • the type of the light emitting material used for the light emitting layer is not particularly limited, and conventionally known light emitting materials for organic EL elements can be used.
  • a light-emitting material is mainly an organic compound, and has a desired color tone, for example, Macromol. Symp. 125, pages 17 to 26, and the like.
  • the light emitting material may be a polymer material such as p-polyphenylene vinylene or polyfluorene, and a polymer material in which the light emitting material is introduced into a side chain or a polymer material having the light emitting material as a main chain of the polymer. May be used. Note that, as described above, since the light emitting material may have a hole injection function and an electron injection function in addition to the light emission performance, most of the hole injection material and the electron injection material described later may be used as the light emitting material. Can be used.
  • the main component when the layer is composed of two or more organic compounds, the main component is called a host, the other components are called dopants, and the host and dopant are used in combination in the light emitting layer of the present invention.
  • the mixing ratio of the light-emitting layer dopant (hereinafter also referred to as light-emitting dopant) to the host compound as the main component is preferably 0.1 to less than 30% by mass.
  • the dopant used in the light emitting layer is roughly classified into two types, that is, a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.
  • fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes.
  • a phosphorescent compound is a compound in which light emission from an excited triplet is observed, and is a compound having a phosphorescence quantum yield of 0.001 or more at 25 ° C.
  • the phosphorescence quantum yield is preferably 0.01 or more, more preferably 0.1 or more.
  • the phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the above phosphorescence quantum yield in any solvent.
  • the phosphorescent dopant is a phosphorescent compound, and a typical example thereof is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound or an osmium compound. , Rhodium compounds, palladium compounds, or platinum compounds (platinum complex compounds). Among them, iridium compounds, rhodium compounds, and platinum compounds are preferable, and iridium compounds are most preferable.
  • dopants are compounds described in the following documents or patent publications. J. et al. Am. Chem. Soc. 123, 4304-4312, International Publication Nos. 2000/70655, 2001/93642, 2002/02714, 2002/15645, 2002/44189, 2002/081488, JP 2002-280178.
  • Gazette 2001-181616, 2002-280179, 2002-181617, 2002-280180, 2001-247859, 2002-299060, 2001-313178 Gazette, 2002-302671, 2001-345183, 2002-324679, 2002-332291, 2002-50484, 2002-332292, 2002-83684 Publication, JP 2002-540572, JP 2002-117978, 2002-338588, 2002-170684, 2002-352960, 2002-50483, 2002-1000047 Gazette, 2002-173684 gazette, 2002-359082 gazette, 2002-17584 gazette, 2002-363552 gazette, 2002-184582 gazette, 2003-7469 gazette, special table 2002-525808.
  • Only one type of light emitting dopant may be used, or a plurality of types of light emitting dopants may be used. By simultaneously extracting light emitted from these dopants, a light emitting element having a plurality of light emission maximum wavelengths can be configured. For example, both a phosphorescent dopant and a fluorescent dopant may be added.
  • the light emitting dopants contained in each layer may be the same or different, may be a single type, or may be a plurality of types.
  • a polymer material in which the luminescent dopant is introduced into a polymer chain or the luminescent dopant is used as a polymer main chain may be used.
  • the host compound examples include those having a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, and an oligoarylene compound. Transport materials and hole transport materials are also suitable examples.
  • the host compound When applied to a blue or white light emitting element, a display device, and a lighting device, the host compound preferably has a maximum fluorescence wavelength of 415 nm or less. When a phosphorescent dopant is used, the phosphorescence of the host compound is 0- More preferably, the 0 band is 450 nm or less.
  • a compound having a hole transporting ability and an electron transporting ability, preventing emission light from being increased in wavelength, and having a high Tg (glass transition temperature) is preferable.
  • the luminescent dopant may be dispersed throughout the layer containing the host compound or may be partially dispersed. A compound having another function may be added to the light emitting layer.
  • a light emitting layer can be formed by using the above-mentioned materials to form a thin film by a known method such as vapor deposition, spin coating, casting, LB, ink jet transfer, or printing.
  • the light emitting layer formed is particularly preferably a molecular deposited film.
  • the molecular deposition film refers to a thin film formed by deposition from the gas phase state of the compound or a film formed by solidification from the molten state or liquid phase state of the compound.
  • this molecular deposited film and a thin film (molecular accumulation film) formed by the LB method can be distinguished from each other by a difference in aggregated structure and higher order structure and a functional difference resulting therefrom.
  • the phosphorescent dopant and host compound which are said luminescent materials as an organic material for electronic devices which concerns on this invention. That is, a light emitting layer, a phosphorescent dopant and a host compound, an organic solvent, and a solution containing cellulose nanofiber (composition for producing an electronic device), spin coating method, casting method, ink jet method, spray method, printing It is preferable to form by a coating method such as a coating method or a slot type coater because a light emitting layer made of a molecular deposited film can be formed. Among these, the inkjet method is preferable from the viewpoints that a homogeneous film is easily obtained and pinholes are hardly generated.
  • the dissolved carbon dioxide concentration with respect to the organic solvent under an atmospheric pressure condition of 50 ° C. or less is 1 ppm to saturation with respect to the organic solvent.
  • the concentration is preferably used.
  • a method of bubbling carbon dioxide gas in a solution containing a phosphorescent dopant and a host compound and an organic solvent, or a supercritical fluid containing an organic solvent and carbon dioxide is used. The supercritical chromatography method used is mentioned.
  • the hole injection material used for the hole injection layer has either a hole injection property or an electron barrier property.
  • the hole transport material used for the hole transport layer has an electron barrier property and a function of transporting holes to the light emitting layer. Therefore, in the present invention, the hole transport layer is included in the hole injection layer.
  • hole injection material and hole transport material may be either organic or inorganic.
  • triazole derivatives for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives , Hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, thiophene oligomers and other conductive polymer oligomers.
  • arylamine derivatives and porphyrin compounds are preferred.
  • aromatic tertiary amine compounds and styrylamine compounds are preferable, and aromatic tertiary amine compounds are more preferable.
  • aromatic tertiary amine compound and styrylamine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N ′.
  • the hole transport material of the hole transport layer preferably has a fluorescence maximum wavelength at 415 nm or less. That is, the hole transport material is preferably a compound that has a hole transport ability, prevents the emission of light from becoming longer, and has a high Tg.
  • the above-described hole injection material and hole transport material are known from, for example, a vacuum deposition method, a spin coating method, a casting method, an LB method, an ink jet method, a transfer method, and a printing method. This method can be formed by thinning the film.
  • the hole injection material and the hole transport material are preferably used as the organic material for electronic devices according to the present invention.
  • the said hole injection material and hole transport material, the organic solvent, and the solution (composition for electronic device preparation) containing a cellulose nanofiber are spin-coated, the cast method, the inkjet method, the spray method, the printing method, It is preferably formed by coating such as a slot type coater method.
  • the inkjet method is preferable from the viewpoints that a homogeneous film is easily obtained and pinholes are hardly generated.
  • the thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m.
  • the hole injection layer and the hole transport layer may each have a single-layer structure composed of one or more of the above materials, or a laminated structure composed of a plurality of layers having the same composition or different compositions. Also good.
  • a positive hole injection layer and a positive hole transport layer although a different material is normally used among said materials, you may use the same material.
  • the electron injecting layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material can be selected from conventionally known compounds.
  • Examples of materials used for this electron injection layer include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, and carbodiimides. , Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.
  • a series of electron transfer compounds described in Japanese Patent Application Laid-Open No. 59-194393 is disclosed as a material for forming a light emitting layer in the publication, but as a result of investigations by the present inventors, electron injection is performed. It was found that it can be used as a material.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron injection material.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviated as Alq 3 ), 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), etc.
  • Alq 3 8-quinolinol aluminum
  • metal-free or metal phthalocyanine or those whose terminal is substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron injection material.
  • an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron injection material.
  • the preferable compound used for an electron carrying layer has a fluorescence maximum wavelength in 415 nm or less. That is, the compound used for the electron transport layer is preferably a compound that has an electron transport ability, prevents emission of longer wavelengths, and has a high Tg.
  • the electron injection layer is formed by thinning the electron injection material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, an ink jet method, a transfer method, or a printing method. Can do. In this invention, it is preferable to use the said electron injection material as an organic material for electronic devices which concerns on this invention.
  • a solution containing the above electron injection material, an organic solvent, and cellulose nanofiber (composition for producing an electronic device) is applied to a spin coat method, a cast method, an ink jet method, a spray method, a printing method, a slot type coater method, etc. It is preferable to form by coating. Among these, the inkjet method is preferable from the viewpoints that a homogeneous film is easily obtained and pinholes are hardly generated.
  • the thickness of the electron injection layer is not particularly limited, but is usually selected in the range of 5 nm to 5 ⁇ m.
  • the electron injection layer may have a single layer structure composed of one or more of these electron injection materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
  • an electron carrying layer is contained in an electron injection layer.
  • the electron transport layer is also referred to as a hole blocking layer (hole blocking layer). Examples thereof include, for example, International Publication No. 2000/70655, JP 2001-313178 A, JP 11-204258 A, and the like. No. 11-204359, and “Organic EL devices and their industrialization front line (issued by NTT, Inc., November 30, 1998)”, page 237, and the like.
  • a buffer layer may be present between the anode and the light emitting layer or the hole injection layer, and between the cathode and the light emitting layer or the electron injection layer.
  • the buffer layer is a layer that is provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission efficiency. “The organic EL element and the forefront of its industrialization (issued on November 30, 1998 by NTS Corporation) ) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123 to 166), which includes an anode buffer layer and a cathode buffer layer.
  • anode buffer layer Details of the anode buffer layer are also described in JP-A-9-45479, 9-260062, 8-28869, etc., and specific examples thereof include a phthalocyanine buffer layer represented by copper phthalocyanine, vanadium oxide. And an oxide buffer layer, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • a metal buffer layer typified by strontium or aluminum examples thereof include an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, and an oxide buffer layer typified by aluminum oxide.
  • the buffer layer is desirably a very thin film, and depending on the material, the thickness is preferably in the range of 0.1 to 100 nm. Furthermore, in addition to the basic constituent layers, layers having other functions may be appropriately laminated as necessary.
  • the cathode of the organic EL element generally uses a metal having a low work function (less than 4 eV) (hereinafter referred to as an electron injecting metal), an alloy, a metal electroconductive compound, or a mixture thereof as an electrode material. Things are used. Specific examples of such electrode materials include sodium, magnesium, lithium, aluminum, indium, rare earth metals, sodium-potassium alloys, magnesium / copper mixtures, magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / Aluminum oxide (Al 2 O 3 ) mixture, lithium / aluminum mixture, and the like.
  • the cathode may contain a Group 13 metal element. preferable. That is, in the present invention, as described later, the surface of the cathode is oxidized with oxygen gas in a plasma state to form an oxide film on the cathode surface, thereby preventing further oxidation of the cathode and improving the durability of the cathode. Can be made. Therefore, the electrode material of the cathode is preferably a metal having a preferable electron injection property required for the cathode and capable of forming a dense oxide film.
  • the cathode electrode material containing the Group 13 metal element examples include aluminum, indium, a magnesium / aluminum mixture, a magnesium / indium mixture, and an aluminum / aluminum oxide (Al 2 O 3 ) mixture. And lithium / aluminum mixtures.
  • the mixing ratio of each component of the said mixture can employ
  • the cathode can be produced by forming a thin film on the organic compound layer (organic EL layer) using the electrode material described above by a method such as vapor deposition or sputtering.
  • the sheet resistance as a cathode is several hundred ⁇ / sq.
  • the film thickness is usually selected from the range of 10 nm to 1 ⁇ m, preferably 50 to 200 nm.
  • the manufacturing method of the organic thin film of this invention has the process of apply
  • a method for producing an organic EL element comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
  • a thin film made of a desired electrode material for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm, thereby producing an anode. To do.
  • an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are element materials, is formed thereon.
  • these organic thin films can be thinned by spin coating, casting, ink jet, spraying, vapor deposition, printing, slot coating, etc., but a homogeneous film can be obtained.
  • the ink jet method is preferable because it is easy and pinholes are hardly generated, and in the present invention, the composition for producing an electronic device according to the present invention can be used. Different film formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 It is desirable to select appropriately within the range of ⁇ 50 nm / second, the substrate temperature of ⁇ 50 to 300 ° C., and the thickness of 0.1 nm to 5 ⁇ m.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a cathode is provided.
  • a desired organic EL element can be obtained.
  • the organic EL element is preferably manufactured from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
  • the organic EL element sealing means is not particularly limited. For example, after sealing the outer periphery of the organic EL element with a sealing adhesive, a sealing member is provided so as to cover the light emitting region of the organic EL element. The method of arranging is mentioned.
  • sealing adhesive examples include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. Can be mentioned. Moreover, heat
  • a polymer film and a metal film can be preferably used from the viewpoint of reducing the thickness of the organic EL element.
  • inert gases such as nitrogen and argon, fluorinated hydrocarbons, and silicon oil are used. Inert liquids can also be injected. Further, the gap between the sealing member and the display area of the organic EL element can be evacuated, or a hygroscopic compound can be sealed in the gap.
  • the multi-color display device using the above organic EL element is provided with a shadow mask only at the time of forming a light emitting layer, and other layers are common, so there is no need for patterning such as a shadow mask.
  • a film can be formed by a method, an inkjet method, a printing method, or the like.
  • the method is not limited, but a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.
  • the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.
  • a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, and various light emission sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • the display device and the display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in a car.
  • the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc.
  • the organic EL element according to the present invention may be used as an organic EL element having a resonator structure.
  • Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.
  • the organic EL device according to the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display that directly recognizes a still image or a moving image. It may be used as a device (display).
  • the driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, it is possible to produce a full-color display device by using two or more organic EL elements of the present invention having different emission colors.
  • FIG. 1 is a schematic diagram illustrating an example of a display device including organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
  • the display 41 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
  • the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside.
  • the pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display image information on the display unit A.
  • FIG. 2 is a schematic diagram of the display unit A.
  • the display unit A includes a wiring unit including a plurality of scanning lines 55 and data lines 56, a plurality of pixels 53, and the like on a substrate.
  • the main members of the display unit A will be described below.
  • FIG. 2 shows a case where the light emitted from the pixel 53 is extracted in the direction of the white arrow (downward).
  • the scanning lines 55 and the plurality of data lines 56 in the wiring portion are each made of a conductive material, and the scanning lines 55 and the data lines 56 are orthogonal to each other in a lattice shape and are connected to the pixels 53 at the orthogonal positions (details are shown in the figure). Not shown).
  • the pixel 53 When a scanning signal is applied from the scanning line 55, the pixel 53 receives an image data signal from the data line 56, and emits light according to the received image data.
  • Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region that emit light on the same substrate.
  • FIG. 3 is a schematic diagram illustrating a pixel circuit.
  • the pixel includes an organic EL element 60, a switching transistor 61, a driving transistor 62, a capacitor 63, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 60 for a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied to the drain of the switching transistor 61 from the control unit B (not shown in FIG. 3, but shown in FIG. 1) via the data line 56.
  • the switching transistor 61 When a scanning signal is applied from the control unit B to the gate of the switching transistor 61 via the scanning line 55, the switching transistor 61 is turned on, and the image data signal applied to the drain is supplied to the capacitor 63 and the driving transistor 62. Is transmitted to the gate. By transmitting the image data signal, the condenser 63 is charged according to the potential of the image data signal, and the drive of the drive transistor 62 is turned on.
  • the drive transistor 62 has a drain connected to the power supply line 67 and a source connected to the electrode of the organic EL element 60, and the power supply line 67 changes to the organic EL element 60 according to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 61 is turned off. However, even if the driving of the switching transistor 61 is turned off, the capacitor 63 holds the potential of the charged image data signal, so that the driving of the driving transistor 62 is kept on and the next scanning signal is applied. Until then, the organic EL element 60 continues to emit light.
  • the driving transistor 62 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 60 emits light.
  • the organic EL element 60 emits light by providing a switching transistor 61 and a drive transistor 62, which are active elements, for each of the organic EL elements 60 of a plurality of pixels, and a plurality of pixels 53 (not shown in FIG. 3). 2) Each organic EL element 60 emits light. Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 60 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But you can.
  • the potential of the capacitor 63 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • FIG. 4 is a schematic view of a passive matrix display device.
  • a plurality of scanning lines 55 and a plurality of image data lines 56 are provided in a lattice shape so as to face each other with the pixel 53 interposed therebetween.
  • the scanning signal of the scanning line 55 is applied by sequential scanning, the pixel 53 connected to the applied scanning line 55 emits light according to the image data signal.
  • the passive matrix method there is no active element in the pixel 53, and the manufacturing cost can be reduced.
  • FIG. 5 is a cross-sectional view showing an example of a solar cell having a single configuration (a configuration having one bulk heterojunction layer) composed of a bulk heterojunction type organic photoelectric conversion element.
  • a bulk heterojunction type organic photoelectric conversion element 200 has a transparent electrode (anode) 202, a hole transport layer 207, a bulk heterojunction layer photoelectric conversion unit 204, and an electron transport layer (or an electron transport layer) on one surface of a substrate 201.
  • 208 and a counter electrode (cathode) 203 are sequentially stacked.
  • the substrate 201 is a member that holds the transparent electrode 202, the photoelectric conversion unit 204, and the counter electrode 203 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 201 side, the substrate 201 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. A transparent member is preferred.
  • the substrate 201 for example, a glass substrate or a resin substrate is used.
  • the substrate 201 is not essential.
  • the bulk heterojunction organic photoelectric conversion element 200 may be configured by forming the transparent electrode 202 and the counter electrode 203 on both surfaces of the photoelectric conversion unit 204.
  • the photoelectric conversion unit 204 is a layer that converts light energy into electrical energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which don't just donate or accept electrons like an electrode, but donates or accepts electrons by photoreaction.
  • the transport direction of electrons and holes can be controlled.
  • FIG. 6 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element having a tandem bulk heterojunction layer.
  • the transparent electrode 202 and the first photoelectric conversion unit 209 are sequentially stacked on the substrate 201, and then the charge recombination layer (intermediate electrode) 205 is stacked, and then the second light conversion unit 206, Next, by stacking the counter electrode 203, a tandem structure can be obtained.
  • Examples of materials that can be used for the layer as described above include n-type semiconductor materials and p-type semiconductor materials described in paragraphs 0045 to 0113 of JP-A-2015-149483.
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency.
  • the coating method is also excellent in production speed.
  • the n-type semiconductor material and p-type semiconductor material which comprise said bulk heterojunction layer can be used as an organic material for electronic devices which concerns on this invention.
  • a bulk heterojunction layer by coating a solution containing the n-type semiconductor material and the p-type semiconductor material, an organic solvent, and cellulose nanofibers.
  • the n-type semiconductor material and the p-type semiconductor material In a coating solution containing an organic solvent and cellulose nanofibers, the dissolved carbon dioxide concentration in the organic solvent under an atmospheric pressure condition of 50 ° C. or less is preferably 1 ppm to a saturated concentration in the organic solvent.
  • a method of bubbling carbon dioxide in a solution containing an n-type semiconductor material and a p-type semiconductor material, an organic solvent, and cellulose nanofibers, or organic Examples include supercritical chromatography using a supercritical fluid containing a solvent and carbon dioxide.
  • the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.
  • the photoelectric conversion portion (bulk heterojunction layer) 204 may be configured as a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of the mixture ratios of the electron acceptor and the electron donor are changed. It may consist of layers. Next, the electrode which comprises an organic photoelectric conversion element is demonstrated.
  • the organic photoelectric conversion element positive and negative charges generated in the bulk heterojunction layer are taken out from the transparent electrode and the counter electrode via the p-type organic semiconductor material and the n-type organic semiconductor material, respectively, and function as a battery. To do.
  • Each electrode is required to have characteristics suitable for carriers passing through the electrode.
  • the counter electrode is preferably an electrode for taking out electrons.
  • the conductive material may be a single layer, or in addition to a conductive material, a resin that holds these may be used in combination.
  • the counter electrode material is required to have sufficient conductivity, a work function close to the extent that no Schottky barrier is formed when bonded to the n-type semiconductor material, and no deterioration. That is, the metal preferably has a work function 0 to 0 or 3 eV larger than the LUMO of the n-type semiconductor material used for the bulk heterojunction layer, and preferably has a work function of 4.0 to 5.1 eV. On the other hand, it is not preferable that the work function is deeper than that of the transparent electrode (anode) for extracting holes, and a metal having a work function shallower than that of the n-type semiconductor material may cause interlayer resistance. A metal having a work function of 4.8 eV is preferred. Therefore, aluminum, gold, silver, copper, indium, or an oxide-based material such as zinc oxide, ITO, or titanium oxide is also preferable. More preferably, they are aluminum, silver, and copper, More preferably, it is silver.
  • the work function of these metals can be similarly measured using ultraviolet photoelectron spectroscopy (UPS).
  • An alloy may be used if necessary.
  • a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum, etc. are suitable. It is.
  • the counter electrode can be produced by forming a thin film of these electrode materials by a 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 counter electrode side is made light transmissive
  • a conductive material suitable for the counter electrode 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 conductive light
  • a film of a transmissive material By providing a film of a transmissive material, a light transmissive counter electrode can be obtained.
  • the transparent electrode is preferably an electrode for extracting holes.
  • the transparent electrode when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm.
  • transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.
  • Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.
  • the intermediate electrode material required in the case of the tandem structure is preferably a layer using a compound having both transparency and conductivity, and the materials (ITO, AZO, FTO, etc.) used in the transparent electrode , Transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al and Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS, polyaniline, etc.) Can do.
  • Transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al and Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS, polyaniline, etc.
  • a hole transport layer and an electron block layer are provided between the bulk heterojunction layer and the transparent electrode. It is preferable.
  • the hole transport layer PEDOT such as Clevius manufactured by Heraeus Co., polyaniline and a doped material thereof, cyan compounds described in WO2006 / 019270, and the like can be used.
  • the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer has a rectifying effect that prevents electrons generated in the bulk heterojunction layer from flowing to the transparent electrode side.
  • the electronic block function is provided.
  • Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function.
  • triarylamine compounds described in JP-A-5-271166 metal oxides such as molybdenum oxide, nickel oxide, and tungsten oxide can be used.
  • a layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used.
  • the means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.
  • the organic photoelectric conversion device of the present invention more efficiently extracts charges generated in the bulk heterojunction layer by forming an electron transport layer, a hole blocking layer, and a buffer layer in the middle of the bulk heterojunction layer and the counter electrode. Therefore, it is preferable to have these layers.
  • the electron transport layer octaazaporphyrin, a p-type semiconductor perfluoro product (perfluoropentacene, perfluorophthalocyanine, etc.) can be used.
  • the p-type semiconductor material used for the bulk heterojunction layer is used.
  • the electron transport layer having a HOMO level deeper than the HOMO level is provided with a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the counter electrode side.
  • Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.
  • n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide.
  • n-type inorganic oxide such as zinc oxide or gallium oxide, a layer made of a single n-type semiconductor material used for the bulk heterojunction layer, or the like can also be used.
  • alkali metal compounds such as lithium fluoride, sodium fluoride, cesium fluoride, and the like can be used.
  • an alkali metal compound that has a function of further doping an organic semiconductor molecule and improving electrical junction with the metal electrode (cathode).
  • an alkali metal compound layer it may be particularly referred to as a buffer layer.
  • a structure having various intermediate layers in the element may be employed.
  • 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 substrate When light that is photoelectrically converted enters from the substrate side, the substrate is preferably a member that can transmit this photoelectrically converted light, that is, a member that is transparent to the wavelength of the light to be photoelectrically converted.
  • the substrate for example, a glass substrate, a resin substrate and the like are preferably mentioned, but it is desirable to use a transparent resin film from the viewpoint of light weight and flexibility.
  • a transparent resin film There is no restriction
  • polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc.
  • Resin films vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like.
  • the resin film transmittance of 80% or more at 0 ⁇ 800 nm can be preferably applied to a transparent resin film according to the present invention.
  • a transparent resin film according to the present invention is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.
  • the transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • 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.
  • Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.
  • a barrier coat layer may be formed in advance on the transparent substrate.
  • the organic photoelectric conversion element according to the present invention may have various optical function layers for the purpose of more efficient light reception of sunlight.
  • the optical functional layer for example, a light condensing layer such as an antireflection film or a microlens array, or a light diffusing layer that can scatter the light reflected by the counter electrode and enter the bulk heterojunction layer again can be provided. Good.
  • the antireflection layer can be provided as the antireflection layer.
  • the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ⁇ 1.63 because the transmittance can be improved by reducing the interface reflection between the film substrate and the easy adhesion layer.
  • the method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • the condensing layer for example, it is processed to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably within a range of 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction is generated and colored, and if it is too large, the thickness becomes thick, which is not preferable.
  • the light scattering layer examples include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.
  • the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.
  • the electrode can be subjected to mask vapor deposition during vacuum deposition or patterned by a known method such as etching or lift-off.
  • the pattern may be formed by transferring a pattern formed on another substrate.
  • a method of sealing a cap made of aluminum or glass by bonding with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element with an adhesive Method of pasting, spin coating of organic polymer materials with high gas barrier properties (polyvinyl alcohol, etc.), inorganic thin films with high gas barrier properties (silicon oxide, aluminum oxide, etc.) or organic films (parylene etc.) under vacuum And a method of laminating them in a composite manner.
  • Example 1 ⁇ Preparation of Coating Compositions 1-1 to 1-7, 1-11 to 1-20 >> The solid components (organic materials for electronic devices) shown in Table I below were dissolved in the solvent shown in Table I, and then filtered through a hydrophobic PVDF (polyvinylidene fluoride) 0.45 ⁇ m filter (manufactured by Whatman) at room temperature. Then, coating compositions 1-1 to 1-7 were prepared in an air atmosphere. Next, 2 mg of cellulose nanofiber (Serish KY100G, manufactured by Daicel Finechem Co., Ltd.) was added to each of the coating compositions 1-1 to 1-7 to obtain coating compositions 1-11 to 1-17, respectively.
  • PVDF polyvinylidene fluoride
  • compositions for producing electronic devices 1-18 to 1-20, respectively.
  • content (mass ppm) with respect to the whole coating composition of a cellulose nanofiber has shown the numerical value of the result of rounding off the numerical value below a ppm order.
  • a substrate (NH Techno Glass Co., Ltd .: NA-45) having a 150 nm film of indium tin oxide (ITO) formed on a 50 mm ⁇ 50 mm glass was ultrasonically cleaned with iso-propyl alcohol and dried with dry nitrogen gas. UV ozone cleaning was performed for 5 minutes to obtain a transparent support substrate.
  • the coating compositions 1-1 to 1-7 and 1-11 to 1-20 were formed by an ink jet method using an ink jet drawing apparatus equipped with an ink jet head (“KM512L” manufactured by Konica Minolta). Films were heated in vacuum at 150 ° C. for 3 hours to obtain thin film pre-rinse samples 1-1 to 1-7 and 1-11 to 1-19.
  • the coating composition 1-20 was used Was clogged with the head and could not be formed, so the film was formed by extrusion coating.
  • the thin film pre-rinse evaluation sample 1-1 was set on a spin coater, rinsed with the above-mentioned solvent by spin coating under a condition of 1000 rpm for 300 seconds using 6 ml of the solvent described in Table I, and vacuum After heating at 150 ° C. for 3 hours, a post-rinse evaluation sample 1-1 after rinsing was obtained. The same treatment was performed on the pre-rinse evaluation samples 1-2 to 1-7 and 1-11 to 1-20, and post-rinse evaluation samples 1-2 to 1-7 and 1-11 to 1-20 were obtained.
  • the absorbance at 360 nm before and after the rinsing treatment was measured with a spectrophotometer (Hitachi UV-3300), and the residual rate of the thin film after the rinsing treatment of each sample was obtained by the following formula to determine the durability (solvent resistance) of the thin film. It was used as an indicator.
  • the rinse treatment refers to a treatment in which a solvent is applied on a thin film set for solvent resistance evaluation, and a compound constituting the thin film is dissolved and washed off.
  • Residual rate (absorbance after rinsing) / (absorbance before rinsing) ⁇ 100 Those with a residual rate of less than 10% were indicated as “X”, those with a residual ratio of 10% to less than 60% as “ ⁇ ”, and those with a residual ratio of 60% or more as “ ⁇ ”.
  • the thin film (organic thin film) produced from the coating composition of the present invention is excellent in solvent resistance.
  • a gas barrier flexible film having an oxygen permeability of 0.001 mL / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 0.001 g / (m 2 ⁇ 24 h) or less was produced.
  • a 120 nm thick indium tin oxide (ITO) film is formed on the prepared gas barrier flexible film by sputtering, and patterned by photolithography.
  • a first electrode layer (anode) was formed. The pattern was such that the light emission area was 50 mm square.
  • ITO indium tin oxide
  • PSS polystyrene sulfonate
  • Clevious P VP AI 4083 manufactured by Heraeus
  • Example 1 Formation of Light-Emitting Layer
  • the coating composition 1-4 produced in Example 1 was formed by the inkjet method, and then held at 120 ° C. for 30 minutes to form a light-emitting layer having a thickness of 40 nm. .
  • Example 1 Formation of Electron Transport Layer Subsequently, the coating composition 1-6 prepared in Example 1 was formed by an ink jet method, and then held at 120 ° C. for 30 minutes to form an electron having a thickness of 30 nm. It was set as the transport layer.
  • an organic EL element (2-1).
  • a sealing member a flexible aluminum foil (made by Toyo Aluminum Co., Ltd.) having a thickness of 30 ⁇ m, a polyethylene terephthalate (PET) film (12 ⁇ m thickness) and an adhesive for dry lamination (two-component reaction type urethane) (Adhesive layer thickness of 1.5 ⁇ m) was used.
  • a thermosetting adhesive as a sealing adhesive was uniformly applied to the aluminum surface at a thickness of 20 ⁇ m along the adhesive surface (shiny surface) of the aluminum foil using a dispenser. This was dried under a vacuum of 100 Pa or less for 12 hours.
  • thermosetting adhesive an epoxy adhesive mixed with the following (A) to (C) was used.
  • DGEBA Bisphenol A diglycidyl ether
  • DIY Dicyandiamide
  • C Epoxy adduct-based curing accelerator
  • the sealing substrate is closely attached and arranged so as to cover the joint between the take-out electrode and the electrode lead, and the thickening conditions and the pressure roll temperature using the pressure roll are used.
  • the organic EL element 2-1 was produced by tightly sealing at 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min.
  • Each organic EL element produced above was subjected to the following evaluations.
  • (1) Measurement of emission luminance Each organic EL element is lit at room temperature (about 23 to 25 ° C.) under a constant luminance condition of 1000 cd / m 2 , and a spectral radiance meter CS-2000 (manufactured by Konica Minolta) ) was used to measure the light emission luminance of each organic EL element, and the light emission luminance (current is constant) at the light emission luminance of 1000 cd / m 2 was determined.
  • Table II the light emission luminance of the organic EL elements 2-1 is 100, and the light emission luminances of the organic EL elements 2-1 to 2-11 are shown as relative values.
  • a transparent electrode was formed by patterning an indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a width of 2 mm using a normal photolithography technique and hydrochloric acid etching. The patterned transparent electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.
  • ITO indium tin oxide
  • a conductive polymer Clevious P VP AI 4083 (manufactured by Heraeus), was spin-coated at a thickness of 60 nm, and then dried by heating at 140 ° C. in the atmosphere for 10 minutes. After this, the substrate was brought into the glove box and operated under a nitrogen atmosphere. First, the substrate was heat-treated at 140 ° C. for 10 minutes in a nitrogen atmosphere.
  • a p-type semiconductor material 1.0 mass% of PCPDTBT (Natural Mat.
  • the element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁇ 3 Pa or less, and then 0.5 nm of lithium fluoride and 80 nm of Al were evaporated. Finally, heating was performed at 120 ° C. for 30 minutes to obtain an organic photoelectric conversion element. The vapor deposition rate was 2 nm / second for all, and the size was 2 mm square.
  • the obtained organic photoelectric conversion device was sealed using an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere. This was designated as organic photoelectric conversion element 3-1.
  • the present invention provides an electronic device having a laminated thin film without limiting the selection range of solvents that can be used in the production of electronic devices such as organic electronics elements, excellent solvent resistance, and without affecting element performance. It can utilize for the composition for electronic device manufacture which made it possible to manufacture a device.

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Abstract

L'invention concerne une composition pour la production de dispositifs électroniques qui contient des nanofibres de cellulose, tout en contenant un matériau organique pour dispositifs électroniques.
PCT/JP2018/002707 2017-03-17 2018-01-29 Composition pour la production de dispositif électronique, procédé de production de composition pour la production de dispositif électronique, film mince organique et procédé de production de film mince organique WO2018168225A1 (fr)

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JP2019102564A (ja) * 2017-11-30 2019-06-24 コニカミノルタ株式会社 有機機能性薄膜、有機機能性積層膜、有機エレクトロルミネッセンス素子、光電変換素子及び有機機能性薄膜形成用塗布液
CN113097410A (zh) * 2021-03-19 2021-07-09 深圳市华星光电半导体显示技术有限公司 显示面板及其制作方法、显示装置
WO2023100614A1 (fr) * 2021-12-02 2023-06-08 株式会社ダイセル Pâte pour couche de conversion photoélectrique et son application
US20230354487A1 (en) * 2020-03-24 2023-11-02 Sharp Kabushiki Kaisha Method for producing functional element, and functional element
WO2025088993A1 (fr) * 2023-10-27 2025-05-01 富士フイルム株式会社 Procédé de fabrication de cellule solaire et cellule solaire

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JP2010198957A (ja) * 2009-02-26 2010-09-09 Konica Minolta Opto Inc 樹脂基板、それを用いた有機エレクトロルミネッセンス素子、表示装置、及び照明装置
JP2012028307A (ja) * 2010-06-23 2012-02-09 Oji Paper Co Ltd 有機ｅｌ素子の製造方法及び有機ｅｌ素子。
WO2013031687A1 (fr) * 2011-08-31 2013-03-07 コニカミノルタホールディングス株式会社 Film d'arrêt de gaz, son procédé de production et substrat d'élément électronique utilisant celui-ci

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JP2010198957A (ja) * 2009-02-26 2010-09-09 Konica Minolta Opto Inc 樹脂基板、それを用いた有機エレクトロルミネッセンス素子、表示装置、及び照明装置
JP2012028307A (ja) * 2010-06-23 2012-02-09 Oji Paper Co Ltd 有機ｅｌ素子の製造方法及び有機ｅｌ素子。
WO2013031687A1 (fr) * 2011-08-31 2013-03-07 コニカミノルタホールディングス株式会社 Film d'arrêt de gaz, son procédé de production et substrat d'élément électronique utilisant celui-ci

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019102564A (ja) * 2017-11-30 2019-06-24 コニカミノルタ株式会社 有機機能性薄膜、有機機能性積層膜、有機エレクトロルミネッセンス素子、光電変換素子及び有機機能性薄膜形成用塗布液
JP6996260B2 (ja) 2017-11-30 2022-01-17 コニカミノルタ株式会社 有機機能性薄膜、有機機能性積層膜、有機エレクトロルミネッセンス素子、光電変換素子及び有機機能性薄膜形成用塗布液
US20230354487A1 (en) * 2020-03-24 2023-11-02 Sharp Kabushiki Kaisha Method for producing functional element, and functional element
US12150220B2 (en) * 2020-03-24 2024-11-19 Sharp Kabushiki Kaisha Method for manufacturing light-emitting element inlcuding quantum dots
CN113097410A (zh) * 2021-03-19 2021-07-09 深圳市华星光电半导体显示技术有限公司 显示面板及其制作方法、显示装置
WO2023100614A1 (fr) * 2021-12-02 2023-06-08 株式会社ダイセル Pâte pour couche de conversion photoélectrique et son application
WO2025088993A1 (fr) * 2023-10-27 2025-05-01 富士フイルム株式会社 Procédé de fabrication de cellule solaire et cellule solaire

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