WO2024075810A1 - Film de conversion photoélectrique organique ainsi que procédé de fabrication de celui-ci, élément de conversion photoélectrique organique, et composition d'encre semi-conductrice organique - Google Patents

Film de conversion photoélectrique organique ainsi que procédé de fabrication de celui-ci, élément de conversion photoélectrique organique, et composition d'encre semi-conductrice organique Download PDF

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WO2024075810A1
WO2024075810A1 PCT/JP2023/036345 JP2023036345W WO2024075810A1 WO 2024075810 A1 WO2024075810 A1 WO 2024075810A1 JP 2023036345 W JP2023036345 W JP 2023036345W WO 2024075810 A1 WO2024075810 A1 WO 2024075810A1
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photoelectric conversion
organic semiconductor
type organic
organic photoelectric
ink composition
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千浩 中林
茂 中根
英典 中山
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三菱ケミカル株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—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
    • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
    • 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

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  • the present invention relates to an organic photoelectric conversion film, an organic photoelectric conversion element, a method for producing an organic photoelectric conversion film, and an organic semiconductor ink composition.
  • organic photoelectric conversion elements such as organic solar cells and photosensors (photodiodes) using the coating method as a method for fabricating photoelectric conversion elements with low energy costs and features not found in conventional silicon photoelectric conversion elements, such as flexibility and near-infrared detection.
  • One form of these organic photoelectric conversion elements is known to have a structure in which a hole transport layer, active layer (organic photoelectric conversion layer), electron transport layer, and upper electrode are arranged in that order on top of a lower electrode.
  • Such organic photoelectric conversion elements are required to have heat resistance capable of withstanding a heating environment such as a reflow process during element manufacturing.
  • a heating environment such as a reflow process during element manufacturing.
  • elements subjected to a heat resistance test simulating a heating environment during element manufacturing may show a decrease in characteristics due to insufficient heat resistance of the organic photoelectric conversion layer.
  • One of the causes of this is deterioration of the film quality of the organic photoelectric conversion layer.
  • the p-type organic semiconductor and the n-type organic semiconductor each form a nanometer-order cocontinuous domain (bulk heterojunction structure: BHJ structure).
  • the heat resistance of this cocontinuous domain is low, and heating can increase the growth of each domain and the crystallization of each material, which can impair the smoothness of the surface of the organic photoelectric conversion layer.
  • Such deterioration of the film quality of the organic photoelectric conversion layer causes practical problems such as characteristic variations between pixels of an image sensor and poor image output. Under such circumstances, various studies have been conducted to improve the heat resistance of the organic photoelectric conversion film and suppress the surface unevenness of the organic photoelectric conversion layer.
  • Non-Patent Document 1 reports that by using a block copolymer in which PCBM is introduced into the poly(3-alkylthiophene) side chain, it is possible to suppress the surface unevenness of the organic photoelectric conversion layer caused by the crystallization of PCBM, compared to an organic photoelectric conversion film made of a poly(3-alkylthiophene)/PCBM mixture.
  • Non-Patent Document 1 is a technique for a specific material.
  • the present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide an organic photoelectric conversion film that can improve the heat resistance of an organic photoelectric conversion element without using a specific material such as that disclosed in Non-Patent Document 1 or without developing a new organic semiconductor, a method for producing the same, and an organic photoelectric conversion element having such an organic photoelectric conversion film.
  • An organic photoelectric conversion film containing a p-type organic semiconductor and an n-type organic semiconductor The molecular weight of the n-type organic semiconductor is 500 to 5000;
  • the n-type organic semiconductor has a content ratio of an n-type organic semiconductor having a fullerene skeleton of 0 to 10 parts by mass per 100 parts by mass of an n-type organic semiconductor not having a fullerene skeleton,
  • the organic photoelectric conversion film has a surface roughness Ra of 0.1 to 10 nm after a heat resistance test in which the film is held at a temperature of 200° C. for 50 minutes.
  • [5] A method for producing an organic photoelectric conversion film according to any one of [1] to [3], forming a coating film by applying an organic semiconductor ink composition containing the p-type organic semiconductor, the n-type organic semiconductor, and a solvent; and forming an organic photoelectric conversion film by solidifying the coating film.
  • [6] The method for producing an organic photoelectric conversion film according to [5], wherein the solvent contains an aromatic hydrocarbon solvent.
  • [7] The method for producing an organic photoelectric conversion film according to [5] or [6], wherein the organic semiconductor ink composition is substantially free of high-boiling point additives.
  • the molecular weight of the n-type organic semiconductor is 500 to 5000;
  • the n-type organic semiconductor is an organic semiconductor ink composition in which a content ratio of an n-type organic semiconductor having a fullerene skeleton is 0 to 10 parts by mass per 100 parts by mass of an n-type organic semiconductor not having a fullerene skeleton, and the organic semiconductor ink composition is substantially free of a high-boiling point additive.
  • an organic photoelectric conversion film capable of improving the heat resistance of an organic photoelectric conversion element, and a method for producing the same. According to the present invention, it is possible to provide an organic photoelectric conversion element having high heat resistance. According to the present invention, it is possible to provide an organic semiconductor ink composition which can obtain an organic photoelectric conversion film capable of improving the heat resistance of an organic photoelectric conversion element.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of an embodiment of an organic photoelectric conversion element of the present invention.
  • 1 is a microscopic image of the film surface of the organic photoelectric conversion film obtained in Example 1 after a heat resistance test.
  • 1 is a microscopic image of the film surface of the organic photoelectric conversion film obtained in Example 2 after a heat resistance test.
  • 1 is a microscopic image of the film surface of the organic photoelectric conversion film obtained in Example 3 after a heat resistance test.
  • 1 is a microscopic image of the film surface of the organic photoelectric conversion film obtained in Example 4 after a heat resistance test.
  • 1 is a microscopic image of the film surface of the organic photoelectric conversion film obtained in Comparative Example 1 after a heat resistance test.
  • the "total solid content of the organic semiconductor ink composition” refers to all components in the organic semiconductor ink composition other than the solvent. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solid content.
  • the numerical range expressed using "to” means a range including the numerical values before and after "to" as the lower and upper limits.
  • the organic photoelectric conversion film of this embodiment contains a p-type organic semiconductor and an n-type organic semiconductor.
  • the p-type organic semiconductor is not particularly limited and any known compound can be used, preferably a donor organic semiconductor (compound).
  • the p-type organic semiconductor is preferably a polymer compound.
  • a hole-transporting organic compound that is a p-type conjugated polymer compound can be mentioned, and a polymer compound that has the property of easily donating electrons can be used.
  • the polymer compound means a polymer having a molecular weight distribution and a weight average molecular weight of 10,000 or more in terms of standard polystyrene, determined by size exclusion chromatography.
  • the p-type organic semiconductor is preferably a compound having a skeleton with excellent hole transport properties.
  • skeletons having excellent hole transport properties include a carbazole structure, a thiophene structure, a benzodithiophene structure, a thienothiophene structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure, and a pyrene structure.
  • Compounds that can form a film by mixing with an n-type organic semiconductor to be described later and applying the mixture are preferred.
  • the p-type organic semiconductor is preferably a polymer compound containing a repeating structure represented by the following formula (II):
  • n is a positive integer.
  • the polymer compound containing the repeating unit represented by formula (II) may be a compound described in Japanese Patent No. 5898782, or may be a compound commercially available from 1-material or Sigma-Aldrich.
  • the weight average molecular weight of the p-type organic semiconductor used in this embodiment is preferably 10,000 or more, more preferably 50,000 or more, since the characteristics as a p-type semiconductor are easily expressed.
  • the upper limit is preferably 150,000, more preferably 100,000, from the viewpoint of solubility in a solvent.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 10,000 to 150,000, or 50,000 to 100,000.
  • the weight average molecular weight of the p-type organic semiconductor is a value determined by size exclusion chromatography.
  • the n-type organic semiconductor is an acceptor semiconductor, and is mainly represented by an electron transporting compound, which is a compound that has a tendency to accept electrons. More specifically, it refers to the compound that has a larger electron affinity when two compounds are used in contact with each other. Therefore, any compound that has electron accepting properties can be used as the acceptor compound.
  • the n-type organic semiconductor is an organic compound with a molecular weight of 500 to 5000.
  • the molecular weight is more preferably 800 to 4000, and even more preferably 1000 to 3000. If the molecular weight is equal to or greater than the lower limit, the compound has excellent ability to form a BHJ structure with the p-type organic semiconductor, and if the molecular weight is equal to or less than the upper limit, the compound has excellent solubility in a solvent.
  • n-type organic semiconductors include condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives, etc.), 5- to 7-membered heterocyclic compounds containing a nitrogen atom, an oxygen atom, or a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazoline, tetrazole, pyrazole ...
  • condensed aromatic carbocyclic compounds naphthalene derivatives, anthracene derivatives, phen
  • the metal complexes include those having a ligand such as an aryl azole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyrazine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), a polyarylene compound, a fluorene compound, a cyclopentadiene compound, a silyl compound, or a nitrogen-containing heterocyclic compound.
  • a ligand such as an aryl azole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, pur
  • the content ratio of the n-type organic semiconductor having a fullerene skeleton is 0 to 10 parts by mass, preferably 0 to 5 parts by mass, and more preferably 0 to 2 parts by mass, per 100 parts by mass of the n-type organic semiconductor not having a fullerene skeleton.
  • the n-type organic semiconductor is preferably a fullerene skeleton-free semiconductor that does not substantially contain an n-type organic semiconductor having a fullerene skeleton.
  • substantially not containing an n-type organic semiconductor having a fullerene skeleton means that the n-type organic semiconductor having a fullerene skeleton is not responsible for transporting electrons of the charges generated in the photoelectric conversion layer, and it is permissible to contain a small amount of an n-type organic semiconductor having a fullerene skeleton in order to improve the morphology of the photoelectric conversion layer.
  • the content ratio of the n-type organic semiconductor having a fullerene skeleton may be 5 parts by mass or less, or 2 parts by mass or less, relative to 100 parts by mass of the content of the n-type organic semiconductor not having a fullerene skeleton.
  • the n-type organic semiconductor used in this embodiment preferably contains a compound represented by the following formula (I), particularly from the viewpoint of compatibility with p-type organic semiconductors and ability to form a BHJ-type photoelectric conversion layer.
  • A represents an atom selected from Group 14 of the periodic table
  • X 1 to X 4 each independently represent a hydrogen atom or a halogen atom
  • R 1a and R 1b each independently represent a linear or branched alkyl group
  • R 2 to R 5 each independently represent a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched thioalkyl group, or a hydrogen atom.
  • A is preferably a carbon atom or a silicon atom.
  • X 1 to X 4 each independently represent a hydrogen atom or a halogen atom, and the halogen atom is preferably a fluorine atom or a chlorine atom.
  • R 1a and R 1b each independently represent a linear or branched alkyl group, and the alkyl group preferably has 4 to 24 carbon atoms, more preferably 6 to 16 carbon atoms, and even more preferably 8 to 12 carbon atoms.
  • linear or branched alkyl groups having 8 to 24 carbon atoms include linear alkyl groups such as n-octyl, n-decyl, lauryl, myristyl, palmityl, and stearyl; primary alkyl groups having branches such as 2-ethylhexyl and 2-butyloctyl; and secondary alkyl groups such as 2-octyl, 2-nonyl, and 2-decyl.
  • Linear alkyl groups and primary alkyl groups having branches are preferred, with 2-ethylhexyl and 2-butyloctyl being more preferred.
  • R 2 to R 5 are each independently a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched thioalkyl group, or a hydrogen atom, and the alkyl group, alkoxy group, and thioalkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 16 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • Each of R2 and R3 is preferably an alkyl group or alkoxy group having 6 to 12 carbon atoms, and each of R4 and R5 is preferably a hydrogen atom.
  • R 1a and R 1b are the same group, it is preferable that R 2 and R 3 are different groups selected from an alkyl group and an alkoxy group, and it is desirable that R 4 and R 5 are each a hydrogen atom.
  • ⁇ Content ratio of p-type organic semiconductor and n-type organic semiconductor> The present inventors have found that one of the parameters related to the thermal stability of an organic photoelectric conversion film is the ratio of a p-type organic semiconductor to an n-type organic semiconductor in the organic photoelectric conversion film.
  • the ratio of the p-type organic semiconductor to the n-type organic semiconductor in the organic photoelectric conversion film of this embodiment may be 0.2 to 2.0, may be 0.2 to 1.8, may be 0.2 to 1.6, may be 0.25 to 1.5, may be 0.25 to 1.4, or may be 0.3 to 1.2.
  • the thermal stability of the organic photoelectric conversion film is likely to be improved, and an organic photoelectric conversion film having a small surface roughness Ra after a heat resistance test is likely to be obtained.
  • the n-type organic semiconductor is relatively more, the organic photoelectric conversion element characteristics tend to be improved.
  • the organic photoelectric conversion film of the present embodiment may contain other components as necessary in addition to the above-mentioned p-type organic semiconductor and n-type organic semiconductor.
  • the organic photoelectric conversion film when the organic photoelectric conversion film is a film obtained by solidifying a coating of an organic semiconductor ink composition (hereinafter also simply referred to as "ink composition") described below, the organic photoelectric conversion film may contain components derived from the ink composition. Examples of other components include stabilizers, viscosity modifiers, curing agents, and high-boiling point additives described below.
  • the total content of other components contained in the organic photoelectric conversion film of this embodiment is preferably 10 mass% or less, more preferably 5 mass% or less, even more preferably 2 mass% or less, and particularly preferably 1 mass% or less, based on 100 mass% of the mass of the organic photoelectric conversion film. That is, the total content of the p-type organic semiconductor and the n-type organic semiconductor in the organic photoelectric conversion film of this embodiment is preferably 90 to 100 mass%, more preferably 95 to 100 mass%, still more preferably 98 to 100 mass%, and particularly preferably 99 to 100 mass%, based on 100 mass% of the mass of the organic photoelectric conversion film.
  • the organic photoelectric conversion film of this embodiment has a surface roughness Ra after a heat resistance test of 0.1 to 10 nm, preferably 0.1 to 5 nm, and more preferably 0.1 to 2 nm.
  • the heat resistance test is performed using a sample having a film thickness of 50 to 500 nm, by holding the sample for 50 minutes at a temperature of 200° C. in a nitrogen atmosphere (an atmosphere in which the water vapor and oxygen concentrations are controlled to 10 ppm or less) in a dark place without actively irradiating the sample with ultraviolet light, visible light, infrared light, etc.
  • the organic photoelectric conversion film of this embodiment has a surface roughness Ra of 0.1 to 10 nm, preferably 0.1 to 5 nm, and more preferably 0.1 to 2 nm after the heat resistance test.
  • the temperature condition of the heat resistance test being T°C means that the temperature of the organic photoelectric conversion film is T°C.
  • the surface roughness Ra after the heat resistance test can be used as an index of the thermal stability of the organic photoelectric conversion film.
  • the heat resistance test when the domains of the p-type organic semiconductor and the n-type organic semiconductor constituting the organic photoelectric conversion film are enlarged or crystallized, the smoothness of the surface of the organic photoelectric conversion film is impaired, and the surface roughness Ra increases.
  • the smaller the difference in surface roughness Ra before and after the heat resistance test the more the film quality deterioration due to heating is suppressed.
  • it is important that the surface roughness Ra after the heat resistance test is generally small.
  • the thermal stability of the organic photoelectric conversion film it is possible to increase the heat resistance of an organic photoelectric conversion element including the organic photoelectric conversion film.
  • an organic photoelectric conversion element in which the film quality of the organic photoelectric conversion layer is not easily deteriorated even after a reflow process during element production.
  • the ratio of the p-type organic semiconductor to the n-type organic semiconductor contained in the organic photoelectric conversion film, i.e., in the ink composition, the selection of the type of solvent in the ink composition, and the type and amount of additives contained in the ink composition can be factors that determine the surface roughness Ra of the organic photoelectric conversion film after a heat resistance test.
  • the method for producing an organic photoelectric conversion film of this embodiment includes a step of forming a coating film by applying an ink composition containing a p-type organic semiconductor, an n-type organic semiconductor, and a solvent, and a step of obtaining an organic photoelectric conversion film by solidifying the coating film. That is, the method for producing an organic photoelectric conversion film of this embodiment includes forming a coating film by applying an ink composition containing a p-type organic semiconductor, an n-type organic semiconductor, and a solvent, and forming an organic photoelectric conversion film by solidifying the formed coating film. Specifically, the ink composition is applied to a coating target to form a coating film (unsolidified film), and then the solvent in the coating film is removed to form a solidified film of the ink composition (organic photoelectric conversion film).
  • the method for forming a coating of the ink composition may be a known wet film-forming method such as spin coating.
  • the conditions for spin coating may be appropriately set according to a standard method, taking into account the viscosity of the ink composition, etc.
  • the solvent in the coating film can be removed by a known method such as heat drying or reduced pressure drying.
  • the solvent contained in the ink composition of this embodiment may be any solvent that can dissolve the p-type organic semiconductor and the n-type organic semiconductor.
  • aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and cyclohexylbenzene
  • Aromatic solvents such as aromatic halogen-containing solvents such as chlorobenzene and o-dichlorobenzene
  • Aliphatic halogen-containing solvents such as 1,2-dichloroethane
  • Aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA)
  • Ether solvents such as aromatic ethers such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,
  • aromatic hydrocarbon solvents are preferred from the viewpoint of the solubility of p-type organic semiconductors and n-type organic semiconductors.
  • Examples of the p-type organic semiconductor and n-type organic semiconductor used in the ink composition of this embodiment include the compounds described above as the p-type organic semiconductor and n-type organic semiconductor used in the organic photoelectric conversion film.
  • the n/p ratio in the ink composition of this embodiment can be considered to be the same as the n/p ratio in the organic photoelectric conversion film.
  • examples of the other components used in the ink composition include the components described above as the other components used in the organic photoelectric conversion film.
  • the total content of other components in the total solid content of the ink composition of this embodiment, and the total content of the p-type organic semiconductor and the n-type organic semiconductor can be considered to be the same as the content in the organic photoelectric conversion film.
  • the solids concentration of the ink composition of this embodiment i.e., the total solids content excluding the solvent from the ink composition, is preferably 10 to 40 mg/mL, and more preferably 15 to 30 mg/mL. If it is equal to or higher than the lower limit, the film-forming properties of the photoelectric conversion layer are excellent, and if it is equal to or lower than the upper limit, the ink composition can be easily prepared and is easy to handle.
  • the high-boiling point additive partially dissolves either or both of the p-type organic semiconductor and the n-type organic semiconductor when the ink composition is applied and dried, thereby maintaining the fluidity of these, and assisting in the formation of a bulk heterojunction that is expected to exhibit high performance as an organic photoelectric conversion film.
  • the boiling point of the high-boiling additive is 200° C. or higher, and although there is no particular upper limit, it is usually 350° C. or lower.
  • the molecular weight of the high boiling point additive is less than 500, preferably 50 to 400, and more preferably 100 to 300. Examples of the high boiling point additive include naphthalene-based compounds.
  • the naphthalene-based compounds are not particularly limited, and examples thereof include 1-phenylnaphthalene (boiling point: 320° C.), 1-methylnaphthalene (boiling point: 241° C.), 1-ethylnaphthalene (boiling point: 260° C.), 1-chloronaphthalene (boiling point: 263° C.), 1-bromonaphthalene (boiling point: 282° C.), and 1-fluoronaphthalene (boiling point: 212° C.).
  • Organic photoelectric conversion element of the present embodiment has a photoelectric conversion layer which is the organic photoelectric conversion film of the present embodiment described above.
  • the structure of the organic photoelectric conversion element of this embodiment can be, for example, as described in JP 2007-324587 A, and is not particularly limited.
  • the organic photoelectric conversion element may have a structure in which a transparent electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a metal electrode are laminated in this order on a transparent substrate, or a structure in which a transparent electrode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a metal electrode are laminated in this order on a transparent substrate.
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic photoelectric conversion element of this embodiment.
  • this organic photoelectric conversion element 10 a first electrode 11, a hole transport layer 12, a photoelectric conversion layer 13, an electron transport layer 14, and a second electrode 15 as a lower electrode are laminated in this order.
  • the hole transport layer 12, the photoelectric conversion layer 13, and the electron transport layer 14 form an organic photoelectric film 20.
  • a substrate is provided on the side of the first electrode 11 opposite the hole transport layer 12.
  • the organic photoelectric conversion element may include a substrate to support the first electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, the second electrode, etc.
  • the substrate may be provided on either the first electrode side or the second electrode side, or on both sides, but is preferably provided at least on the first electrode side.
  • the substrate can be made of any material, but if light is incident from the substrate side, it must be made of a highly transparent material.
  • materials constituting the substrate include inorganic materials such as glass, sapphire, and titania; organic materials such as polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, fluororesin, vinyl chloride, polyethylene, cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, and polynorbornene; paper materials such as paper and synthetic paper; and composite materials such as metals such as stainless steel, titanium, and aluminum whose surfaces are coated or laminated to impart insulating properties.
  • the constituent materials of the substrate may be used alone or in combination of two or more.
  • the substrate may have another layer laminated thereon in order to impart gas barrier properties or control the surface condition.
  • the thickness of the substrate can be freely designed depending on the application and constituent materials of the organic photoelectric conversion element, but a thicker substrate is preferable in terms of strength as a support member, while a thinner substrate is preferable in terms of cost. Therefore, a film- or plate-shaped substrate with a thickness of about 10 ⁇ m to 50 mm is usually used.
  • the electrodes (first electrode, second electrode) can be made of any material having electrical conductivity.
  • Examples of materials constituting the electrodes include metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, and sodium, or alloys thereof; metal oxides such as indium oxide and tin oxide, or composite oxides thereof (e.g., ITO and IZO); conductive polymers such as polyaniline, polypyrrole, polythiophene, and polyacetylene; conductive polymers to which dopants such as acids such as hydrochloric acid, sulfuric acid, and sulfonic acid, Lewis acids such as FeCl3 , halogen atoms such as iodine, and metal atoms such as sodium and potassium have been added; and conductive composite materials in which conductive particles such as metal particles, carbon black, fullerene, and carbon nanotubes are dispersed in a matrix such as a polymer binder.
  • the electrode may be made of one material alone or two or more materials in combination.
  • an organic photoelectric conversion element at least one pair (two electrodes) is provided, and a photoelectric conversion layer is provided between the pair of electrodes.
  • at least one of the pair of electrodes is transparent (i.e., transmits light absorbed by the photoelectric conversion layer for power generation).
  • transparent electrodes include complex oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO); and thin metal films.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • thin metal films There is no specific limit to the range of light transmittance, but considering the photoelectric conversion efficiency of the organic photoelectric conversion element, 80% or more is preferable. Light transmittance can be measured with a normal spectrophotometer.
  • the electrode has a function of collecting holes and electrons generated in the photoelectric conversion layer, and therefore, as a material for the electrode, it is preferable to use a material suitable for collecting holes and electrons from among the above-mentioned materials.
  • electrode materials suitable for collecting holes include materials having a high work function, such as Au and ITO.
  • Electrode materials suitable for collecting electrons include materials with low work functions, such as aluminum (Al).
  • the thickness of the electrodes there are no particular limitations on the thickness of the electrodes, and it is determined appropriately taking into consideration the material used and the required conductivity, transparency, etc., but it is usually around 10 nm to 100 ⁇ m.
  • the method for forming the electrodes is not limited, but they can be formed by a dry process such as vacuum deposition or sputtering. They can also be formed by a wet process using a conductive ink composition. Any conductive ink composition can be used, such as a conductive polymer or a metal particle dispersion.
  • the electrodes can be laminated in two or more layers, and can be surface-treated to improve their properties (e.g., electrical properties, wettability).
  • the hole transport layer may be made of a known hole transport material, including, but not limited to, a hole transport polymer such as a polytriarylamine compound represented by the following chemical formula:
  • a hole transport polymer such as a polytriarylamine compound represented by the following chemical formula:
  • 2,7-bis (4-bromophenyl) -9,9-dihexylfluorene described in JP 2019-173032 A 2-amino-9,9-dihexylfluorene
  • 4- 4- (1,1-bis (4'-bromo- [1,1'-biphenyl] -4-yl) ethyl) phenyl) -1,2-dihydrocyclobuta [a] naphthalene synthesized polytolyl arylamine compound
  • 4,4'-dibromobiphenyl 2-amino-9,9-dihexylfluorene
  • the method for forming the hole transport layer is not particularly limited, but it is preferably formed by a wet film formation method using a hole transporting polymer.
  • a composition for forming the hole transport layer containing a hole transporting polymer and a solvent is used.
  • the solvent in the composition for forming the hole transport layer is sufficient if it dissolves the hole transport polymer, and is a solvent that dissolves the hole transport polymer at room temperature in an amount of 0.05% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, and amide-based solvents are preferred.
  • ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); and aromatic ethers such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole.
  • aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA)
  • aromatic ethers such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-meth
  • ester solvent examples include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
  • aromatic hydrocarbon solvents include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, and methylnaphthalene.
  • amide solvent examples include N,N-dimethylformamide and N,N-dimethylacetamide, and dimethylsulfoxide can also be used.
  • the concentration of the hole transport polymer in the composition for forming the hole transport layer can be any concentration as long as it does not significantly impair the effect of this embodiment.
  • a lower concentration is preferable in terms of uniformity of the film thickness, while a higher concentration is preferable in terms of preventing defects from occurring in the hole transport layer.
  • the concentration is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the concentration of the solvent in the composition for forming the hole transport layer is usually 10% by mass or more, preferably 30% by mass or more, and more preferably 50% by mass or more.
  • the composition for forming a hole transport layer is usually heated after coating.
  • the heating method is not particularly limited, but in the case of drying by heating, the layer formed using the composition for forming a hole transport layer is usually heated to 100° C. or higher, preferably 120° C. or higher, more preferably 150° C. or higher, and usually 400° C. or lower, preferably 350° C. or lower, more preferably 300° C. or lower.
  • the heating time is usually 1 minute or more, preferably 24 hours or less.
  • the heating means is not particularly limited, but the laminate having the formed layer may be placed on a hot plate or heated in an oven. For example, the heating condition may be 120° C. or more on a hot plate for 1 minute or more.
  • the thickness of the hole transport layer is 50 nm or more and 100 nm or less, and in another embodiment, it is more than 100 nm and 400 nm or less, preferably 350 nm or less, i.e., 50 nm or more and 400 nm or less, preferably 50 nm or more and 350 nm or less.
  • the thickness of the hole transport layer is preferably thick in that the effect of reducing dark current due to the provision of the hole transport layer as a blocking layer is easily achieved, and is preferably thin in that the angle of incidence of light can be made wide in a CMOS image sensor using an organic photoelectric conversion element and the organic photoelectric conversion element can be made thin.
  • the hole transport layer preferably has a LUMO (lowest unoccupied molecular orbital) that is shallower by 0.3 eV or more than the n-type organic semiconductor of the photoelectric conversion layer, more preferably has a LUMO that is shallower by 0.5 eV or more, and even more preferably has a LUMO that is shallower by 1.0 eV or more.
  • the difference in HOMO (highest occupied molecular orbital) between the hole transport layer and the p-type organic semiconductor of the photoelectric conversion layer is preferably within 0.5 eV, and more preferably within 0.3 eV.
  • the photoelectric conversion layer is a layer that absorbs light and separates electric charges.
  • the thickness of the photoelectric conversion layer can be arbitrarily designed depending on the configuration of the photoelectric conversion layer and the use of the organic photoelectric conversion element, but is preferably 10 nm to 1 ⁇ m. If it is equal to or more than the lower limit, light absorption is sufficient and efficiency is likely to be high, and if it is equal to or less than the upper limit, internal resistance is reduced and loss is likely to be small.
  • the photoelectric conversion layer of the organic photoelectric conversion element of the present embodiment can usually be formed by a method in which the above-described ink composition is applied onto a carrier transport layer (a hole transport layer or an electron transport layer) to form a coating film, and then the coating film is solidified.
  • a carrier transport layer a hole transport layer or an electron transport layer
  • an electron transport layer may be provided between the photoelectric conversion layer and the second electrode in order to increase the photoelectric conversion efficiency and easily reduce dark current.
  • the electron transport layer is formed from a compound capable of efficiently transporting electrons generated in the photoelectric conversion layer to the second electrode.
  • the electron transporting compound used in the electron transport layer is required to have a high efficiency of electron injection from the photoelectric conversion layer and a high electron mobility so as to efficiently transport the injected electrons.
  • the difference in LUMO between the electron transport layer and the n-type organic semiconductor of the photoelectric conversion layer is preferably 1.5 eV or less, and more preferably 1.0 eV or less.
  • the electron transport layer when dark current is reduced by the electron transport layer, preferably has a HOMO that is 0.3 eV or more deeper than the p-type semiconductor of the photoelectric conversion layer, more preferably has a HOMO that is 0.5 eV or more deeper, and even more preferably has a HOMO that is 1.0 eV or more deeper.
  • electron transport compounds used in the electron transport layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP Patent Publication 59-194393), metal complexes of 10-hydroxybenzo[h]quinoline, oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Patent Publication 5,645,948), quinoxaline compounds (JP Patent Publication 6-207169), phenanthroline derivatives (JP Patent Publication 5-331459), 2-t-butyl-9,10-N,N'-dicyanoanthraquinone diimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, and n-type zinc selenide.
  • metal complexes such as aluminum complexe
  • Metal oxides such as titanium oxide, zinc oxide, tin oxide, and cerium oxide can also be used as materials for forming the electron transport layer.
  • the method for forming the electron transport layer can be a method of wet-forming nanoparticles of the metal oxide and drying them to form a metal oxide layer, or a method of wet-forming a precursor and converting it by heating.
  • the thickness of the electron transport layer is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.
  • the above upper and lower limits can be combined in any way. For example, it may be 1 to 300 nm, or 5 to 100 nm.
  • the electron transport layer can be formed by a wet deposition method or a vacuum deposition method, but the vacuum deposition method is usually used.
  • the organic photoelectric conversion element may include constituent layers other than the above-described substrate, first and second electrodes, hole transport layer, photoelectric conversion layer, and electron transport layer, as long as the effects of this embodiment are not significantly impaired.
  • the organic photoelectric conversion element may be provided with a protective film to cover the photoelectric conversion layer portion and further the electrode portion in order to minimize the influence of the outside air.
  • the protective layer may be composed of, for example, a polymer film such as a styrene resin, an epoxy resin, an acrylic resin, a polyurethane, a polyimide, a polyvinyl alcohol, a polyvinylidene fluoride, a polyethylene-polyvinyl alcohol copolymer, or the like; an inorganic oxide film or a nitride film such as silicon oxide, silicon nitride, or aluminum oxide; or a laminated film thereof.
  • a polymer film such as a styrene resin, an epoxy resin, an acrylic resin, a polyurethane, a polyimide, a polyvinyl alcohol, a polyvinylidene fluoride, a polyethylene-polyvinyl alcohol copolymer, or the like
  • an inorganic oxide film or a nitride film such as silicon oxide, silicon nitride, or aluminum oxide
  • the method for forming the protective film there are no limitations on the method for forming the protective film.
  • the protective film when the protective film is a polymer film, examples of the method include a method of coating and drying a polymer solution, and a method of coating or evaporating a monomer and polymerizing it.
  • a polymer film it is also possible to carry out a crosslinking process or form a multi-layer film.
  • the protective film is an inorganic film such as an inorganic oxide film or a nitride film, for example, a vacuum process such as a sputtering method or a vapor deposition method, or a solution process such as the sol-gel method can be used.
  • a charge injection layer may be provided between the first electrode and the hole transport layer, or between the electron transport layer and the second electrode.
  • the organic photoelectric conversion element may be provided with an optical filter that does not transmit ultraviolet light on the light incident side, for example. Since ultraviolet light generally accelerates the deterioration of organic photoelectric conversion elements, blocking this ultraviolet light can extend the life of the organic photoelectric conversion element.
  • a manufacturing method of an organic photoelectric conversion element having a first electrode, a hole transport layer, a photoelectric conversion layer, and a second electrode on a substrate in this order will be described as an example.
  • the organic photoelectric conversion element is usually manufactured by laminating the first electrode, the hole transport layer, the photoelectric conversion layer, and the second electrode on a substrate in this order by the above-mentioned method.
  • a forming process of an electron transport layer, etc., which is provided as necessary, is provided between these layers.
  • the photoelectric conversion layer of the organic photoelectric conversion element may be subjected to a pretreatment such as a thermal annealing treatment or a solvent annealing treatment before the organic photoelectric conversion element is completed.
  • the solvent annealing treatment is a treatment in which the photoelectric conversion layer is exposed to a specific solvent atmosphere, and can be carried out by a known method. It is preferable to subject the coating film to a thermal annealing treatment, which also serves as a drying treatment for removing the solvent in the coating film. The drying treatment and the thermal annealing treatment may be performed separately.
  • the thermal annealing method include a method of directly heating using a hot plate, a hot air heating method, an infrared heating method, and a light heating method using a flash lamp.
  • the outer surface of the carrier transport layer side (the surface opposite to the photoelectric conversion layer) of a laminate in which a photoelectric conversion layer is formed on a carrier transport layer can be heated by contacting it with a hot plate.
  • the heating temperature in the thermal annealing treatment is preferably, for example, 80 to 300° C.
  • the heating time in the thermal annealing treatment is preferably, for example, 1 second to 30 minutes.
  • the heating temperature of the drying treatment or thermal annealing treatment of the photoelectric conversion layer being t°C means that the temperature of the photoelectric conversion layer is t°C.
  • a preferred embodiment of the method for subjecting the organic photoelectric conversion film to a thermal annealing treatment is as follows.
  • a thermal annealing treatment is carried out, which also serves as a drying treatment, immediately after the formation of a coating film of the ink composition.
  • a coating film of the ink composition is formed, dried by a reduced pressure drying method to solidify the coating film, and then subjected to a thermal annealing treatment.
  • a step of laminating a carrier transport layer (a hole transport layer or an electron transport layer) that is not deteriorated by the heat of the thermal annealing treatment on the solidified organic photoelectric conversion film can be provided.
  • the photoelectric conversion element of this embodiment is used, for example, in an optical sensor or an image sensor.
  • the optical sensor or image sensor may have a known configuration.
  • the heat resistance test was a heating test simulating a heating environment such as that during a reflow process in element production, and was carried out under conditions in which the organic photoelectric conversion element was held at a temperature of 200° C. for 50 minutes.
  • Example 1 [Formation of Hole Transport Layer] A surface of an ITO substrate having a pattern of a transparent conductive film of indium tin oxide (ITO) formed as an electrode on a glass substrate was treated with an ultraviolet ozone cleaner (NL-UV253, manufactured by Japan Laser Electronics Co., Ltd.) for 10 minutes, and then a hole transport layer was formed as follows.
  • ITO indium tin oxide
  • a polytriarylamine compound (hole transport polymer) shown in the following formula (1) was dissolved in 1 mL of anisole to prepare a composition for forming a hole transport layer.
  • This composition was spin-coated on the electrode surface of the ITO substrate at a rotation speed of 1000 rpm for 60 seconds, and then heated and dried at 240°C for 30 minutes to form a hole transport layer with a thickness of 300 nm.
  • the p-type organic semiconductor used was the compound represented by the above formula (II) (weight average molecular weight: 80,000).
  • the n-type organic semiconductor used was a compound (molecular weight 1339) of the above formula (I) in which A is a carbon atom, X 1 to X 4 are each a chlorine atom, R 1a and R 1b are each a 2-ethylhexyl group, R 2 is a 2-ethylhexyl group, R 3 is a 2-ethylhexyloxy group, and R 4 and R 5 are each a hydrogen atom.
  • An organic semiconductor ink composition was prepared by dissolving 0.11 g of a p-type organic semiconductor and 0.03 g of an n-type organic semiconductor in 9.68 mL of o-xylene.
  • the n/p ratio was 0.3
  • the solid concentration of the organic semiconductor ink composition was 14 mg/mL.
  • the obtained organic semiconductor ink composition was spin-coated onto the hole transport layer at 1000 revolutions per minute, and then heat-treated (thermal annealing treatment) at 120° C. for 10 minutes to form a photoelectric conversion layer.
  • FIG. 2 shows a micrograph of the surface of the photoelectric conversion layer (organic photoelectric conversion film) after the heat resistance test observed with a scanning probe microscope (hereinafter simply referred to as "micrograph of the surface of the organic photoelectric conversion film").
  • Example 2 An organic photoelectric conversion element was produced in the same manner as in Example 1, except that the amount of the n-type organic semiconductor used was changed to 0.07 g.
  • the n/p ratio of the photoelectric conversion layer and the surface roughness Ra of the photoelectric conversion layer are shown in Table 1, and a microscope image of the surface of the organic photoelectric conversion film is shown in FIG.
  • Example 3 An organic photoelectric conversion element was produced in the same manner as in Example 1, except that the amount of the n-type organic semiconductor used was changed to 0.10 g.
  • the n/p ratio of the photoelectric conversion layer and the surface roughness Ra of the photoelectric conversion layer are shown in Table 1, and a microscope image of the surface of the organic photoelectric conversion film is shown in FIG.
  • Example 4 An organic photoelectric conversion element was produced in the same manner as in Example 1, except that the amount of the n-type organic semiconductor used was changed to 0.13 g.
  • the n/p ratio of the photoelectric conversion layer and the surface roughness Ra of the photoelectric conversion layer are shown in Table 1, and a microscope image of the surface of the organic photoelectric conversion film is shown in FIG.
  • the surface roughness Ra of the organic photoelectric conversion layer after the heat resistance test was 0.8 to 1.2 nm in Examples 1 to 4.
  • the surface roughness Ra of the organic photoelectric conversion layer after the heat resistance test in Comparative Example 1 was 25.1 nm. Since the organic photoelectric conversion films of Examples 1 to 4 have a small surface roughness Ra after the heat resistance test, it is expected that practical problems such as characteristic variations between pixels of an image sensor and poor image output are unlikely to occur.
  • Comparative Example 1 since the n-type organic semiconductor was in excess relative to the p-type organic semiconductor, the compatibility between the two was insufficient, and it is believed that the excess n-type organic semiconductors aggregated and crystallized during the heat resistance test process, resulting in the large surface roughness Ra.
  • Example 4 it is believed that the excess amount of the n-type organic semiconductor was appropriately suppressed, thereby suppressing aggregation and crystallization of the n-type organic semiconductor, thereby improving the surface roughness.
  • the surface roughness Ra was small and high smoothness was obtained. This is believed to be because the p-type organic semiconductor, which is a polymer compound, is less likely to crystallize than the n-type organic semiconductor.

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Abstract

L'invention fournit un film de conversion photoélectrique organique qui permet d'augmenter la résistance à la chaleur d'un élément de conversion photoélectrique organique. Le film de conversion photoélectrique organique de l'invention comprend un semi-conducteur organique de type p et un semi-conducteur organique de type n. La masse moléculaire dudit semi-conducteur organique de type n est comprise entre ５００ et ５０００. Ledit semi-conducteur organique de type n est tel que la proportion de teneur en semi-conducteur organique de type n ayant un squelette fullerène est de 0 à 10 parties en masse pour 100 parties en masse de teneur en semi-conducteur organique de type n exempt de squelette fullerène, et présente une rugosité superficielle (Ra) comprise entre ０,１ et １０ｎｍ après un essai de résistance à la chaleur au cours duquel un maintien de cinquante minutes sous des conditions de température à 200°C est effectué.
PCT/JP2023/036345 2022-10-05 2023-10-05 Film de conversion photoélectrique organique ainsi que procédé de fabrication de celui-ci, élément de conversion photoélectrique organique, et composition d'encre semi-conductrice organique WO2024075810A1 (fr)

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Citations (6)

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KR20100062855A (ko) * 2008-12-01 2010-06-10 광주과학기술원 플러렌 유도체, 이를 포함하는 유기태양전지, 및 이를 포함하는 유기박막트랜지스터
JP2012142407A (ja) * 2010-12-28 2012-07-26 Mitsubishi Chemicals Corp 光電変換素子及びその製造方法、並びにインク
WO2013176180A1 (fr) * 2012-05-23 2013-11-28 東レ株式会社 Élément de puissance photovoltaïque et procédé de fabrication d'un élément de puissance photovoltaïque
WO2019098003A1 (fr) * 2017-11-17 2019-05-23 ソニーセミコンダクタソリューションズ株式会社 Élément de conversion photoélectrique et dispositif d'imagerie à semi-conducteurs
WO2020130133A1 (fr) * 2018-12-20 2020-06-25 三菱ケミカル株式会社 Photodiode organique et capteur cmos infrarouge
JP2021057579A (ja) * 2019-09-30 2021-04-08 東レ株式会社 有機半導体組成物、光起電力素子、光電変換デバイスおよび光起電力素子の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100062855A (ko) * 2008-12-01 2010-06-10 광주과학기술원 플러렌 유도체, 이를 포함하는 유기태양전지, 및 이를 포함하는 유기박막트랜지스터
JP2012142407A (ja) * 2010-12-28 2012-07-26 Mitsubishi Chemicals Corp 光電変換素子及びその製造方法、並びにインク
WO2013176180A1 (fr) * 2012-05-23 2013-11-28 東レ株式会社 Élément de puissance photovoltaïque et procédé de fabrication d'un élément de puissance photovoltaïque
WO2019098003A1 (fr) * 2017-11-17 2019-05-23 ソニーセミコンダクタソリューションズ株式会社 Élément de conversion photoélectrique et dispositif d'imagerie à semi-conducteurs
WO2020130133A1 (fr) * 2018-12-20 2020-06-25 三菱ケミカル株式会社 Photodiode organique et capteur cmos infrarouge
JP2021057579A (ja) * 2019-09-30 2021-04-08 東レ株式会社 有機半導体組成物、光起電力素子、光電変換デバイスおよび光起電力素子の製造方法

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