[go: up one dir, main page]

WO2011142314A1 - Élément de conversion photoélectrique - Google Patents

Élément de conversion photoélectrique Download PDF

Info

Publication number
WO2011142314A1
WO2011142314A1 PCT/JP2011/060650 JP2011060650W WO2011142314A1 WO 2011142314 A1 WO2011142314 A1 WO 2011142314A1 JP 2011060650 W JP2011060650 W JP 2011060650W WO 2011142314 A1 WO2011142314 A1 WO 2011142314A1
Authority
WO
WIPO (PCT)
Prior art keywords
electron
compound
photoelectric conversion
conversion element
active layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/060650
Other languages
English (en)
Japanese (ja)
Inventor
邦仁 三宅
明子 岸田
伊藤　紳三郎
英生 大北
宏明 辨天
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Kyoto University NUC
Original Assignee
Sumitomo Chemical Co Ltd
Kyoto University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd, Kyoto University NUC filed Critical Sumitomo Chemical Co Ltd
Publication of WO2011142314A1 publication Critical patent/WO2011142314A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion element used for a photoelectric device such as a solar cell or an optical sensor.
  • the photoelectric conversion element is an element including a pair of electrodes including an anode and a cathode, and an organic active layer provided between the pair of electrodes.
  • one of the electrodes is made of a transparent or translucent material, and light is incident on the organic active layer from the transparent or translucent electrode side.
  • Charges (holes and electrons) are generated in the organic active layer by the energy (h ⁇ ) of light incident on the organic active layer, and the generated holes are directed to the anode and the electrons are directed to the cathode.
  • current (I) is supplied to the external circuit.
  • the organic active layer is composed of an electron-accepting compound (n-type semiconductor) and an electron-donating compound (p-type semiconductor).
  • An organic active layer in which an electron-accepting compound (n-type semiconductor) and an electron-donating compound (p-type semiconductor) are mixed and used is called a bulk hetero-type organic active layer.
  • the electron-accepting compound and the electron-donating compound constitute a phase of a fine and complex shape that continues from one electrode side to the other electrode side, and It forms a complex interface while separating.
  • An organic material used for the organic active layer of the photoelectric conversion element is an organic compound that absorbs light based on a ⁇ - ⁇ * transition.
  • a photoelectric conversion element including an organic active layer manufactured by applying a solution using an electron donating compound, an electron accepting compound, xylene and the like as a solvent on a substrate has been proposed (see Non-Patent Document 1).
  • the present invention provides the following [1] to [9].
  • the organic active layer includes an electron-donating compound and an electron-accepting compound.
  • the bond length between the electron-donating compound and the electron-accepting compound is about 1 ⁇ m 2 per area of the organic active layer image.
  • the photoelectric conversion element which is 100 micrometers or more.
  • At least one compound with the accepting compound is a polymer compound containing a repeating unit represented by the formula (I), and is represented by the formula (I) among all repeating units contained in the polymer compound.
  • a method for producing a photoelectric conversion element which is a polymer compound having the largest repeating unit ratio.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom or a substituent.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be linked to each other to form a cyclic structure
  • X 1 , X 2 and X 3 are each independently a sulfur atom, an oxygen atom, a selenium atom, —N ( R 7 ) — or —C (R 8 ) ⁇ C (R 9 ) — R 7, R 8 and R 9 each independently represents a hydrogen atom or a substituent
  • n and m each independently Represents an integer of 0 to 5.
  • a photoelectric conversion element obtainable by the production method according to [6].
  • a solar cell module including the photoelectric conversion element according to any one of [1] to [4] and [7].
  • An image sensor including the photoelectric conversion element according to any one of [1] to [4] and [7].
  • the photoelectric conversion element of the present invention has an anode, a cathode, and an organic active layer provided between the anode and the cathode, and has an electron donating compound and an electron accepting compound in the organic active layer,
  • the bond length between the electron-donating compound and the electron-accepting compound is It is 100 ⁇ m or more per 1 ⁇ m 2 area.
  • the photoelectric conversion element Concerning the photoelectric conversion element according to the present invention, the anode, the organic active layer, the electron donating compound and the electron accepting compound constituting the organic active layer, the cathode, and other components formed as necessary, This will be explained in detail.
  • a pair of electrodes As a basic form of the photoelectric conversion element of the present invention, a pair of electrodes, at least one of which is transparent or translucent, an electron donating compound (p-type organic semiconductor) and an electron-accepting compound (n-type organic semiconductor, etc.) And a bulk hetero-type organic active layer formed from an organic composition.
  • the photoelectric conversion element of the present invention is usually formed on a substrate.
  • the substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed.
  • Examples of the material for the substrate include glass, plastic, polymer film, and silicon.
  • the opposite electrode that is, the electrode far from the substrate
  • the transparent or translucent electrode material examples include a conductive metal oxide film, a translucent metal thin film, and the like. Specifically, it is formed using indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA that are composites thereof. And metal thin films formed using gold, platinum, silver, copper, etc., and films formed using ITO, IZO, tin oxide are preferred. Examples of the electrode forming method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.
  • the transparent or translucent electrode may be an anode or a cathode.
  • the other electrode may not be transparent, and as the electrode material of the electrode, a metal, a conductive polymer, or the like can be used.
  • the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like.
  • one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin.
  • Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof.
  • Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
  • an additional intermediate layer (such as a charge transport layer) other than the organic active layer may be provided.
  • the material used for the intermediate layer include alkali metal or alkaline earth metal halides or oxides such as lithium fluoride, and specifically lithium fluoride.
  • fine particles of inorganic semiconductor such as titanium oxide, a mixture of PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (4-styrenesulfonate)) (PEDOT: PSS) or the like may be used.
  • Organic active layer contained in the photoelectric conversion element of the present invention contains an electron donating compound and an electron accepting compound. Note that the electron-donating compound and the electron-accepting compound are relatively determined from the HOMO or LUMO energy level of the compound.
  • At least one of the electron donating compound and the electron accepting compound is preferably a polymer compound, and both the electron donating compound and the electron accepting compound are more preferably polymer compounds.
  • the electron-donating compound is not limited as long as it has absorption in the solar radiation wavelength region.
  • the electron donating compound is preferably a polymer compound having an energy level of the highest occupied molecular orbital of ⁇ 4.7 eV or lower and an energy level of the lowest unoccupied molecular orbital of ⁇ 4.0 eV or higher.
  • the electron donating compound may be a low molecular compound or a high molecular compound.
  • a polymer compound is preferable.
  • Examples of the electron donating compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic amines in side chains or main chains. And polysiloxane derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, among which polymer compounds are preferred.
  • Examples of the polymer compound which is a p-type semiconductor include polythiophene and derivatives thereof, a structure including dimers to pentamers in which thiophenes are bonded to each other, or a structure including dimers to pentamers in which thiophene derivatives are bonded to each other.
  • the polymer compound is preferably polythiophene and derivatives thereof.
  • the polythiophene derivative is a polymer compound having a thiophenediyl group having a substituent.
  • Polythiophene and its derivatives are preferably homopolymers.
  • a homopolymer is a polymer formed by bonding only a plurality of groups selected from the group consisting of a thiophenediyl group and a substituted thiophenediyl group.
  • the thiophene diyl group is preferably a thiophene-2,5-diyl group, and the thiophene diyl group having a substituent is preferably an alkylthiophene-2, 5-diyl group.
  • homopolymer polythiophene and derivatives thereof include poly (3-hexylthiophene-2,5-diyl) (P3HT), poly (3-octylthiophene-2,5-diyl), poly (3-dodecyl) Thiophene-2,5-diyl) and poly (3-octadecylthiophene-2,5-diyl).
  • P3HT poly (3-hexylthiophene-2,5-diyl)
  • poly3HT poly (3-octylthiophene-2,5-diyl)
  • poly (3-dodecyl) Thiophene-2,5-diyl) and poly (3-octadecylthiophene-2,5-diyl
  • polythiophenes and derivatives thereof which are homopolymers polythiophene homopolymers comprising thiophene diyl groups substituted with alkyl groups having 6
  • Examples of the polymer compound that is an electron donating compound include polymer compound A represented by the following structural formula (4).
  • Electrode-accepting compound As the electron-accepting compound, a polymer compound having an energy level of the highest occupied molecular orbital of ⁇ 5.0 eV or lower and an energy level of the lowest unoccupied molecular orbital of ⁇ 4.3 eV or higher is preferable.
  • Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C 60 fullerene, bathocuproine etc.
  • Phenanthrene derivatives metal oxides such as titanium oxide, and carbon nanotubes.
  • the electron accepting compound is preferably a compound containing a benzothiadiazole structure, a polymer compound containing a benzothiadiazole structure in a repeating unit, a compound containing a quinoxaline structure, a polymer compound containing a quinoxaline structure in a repeating unit, titanium oxide, carbon Nanotubes, fullerenes, fullerene derivatives, more preferably fullerenes, fullerene derivatives, compounds containing a benzothiadiazole structure, polymer compounds containing a benzothiadiazole structure in a repeating unit, compounds containing a quinoxaline structure, and a quinoxaline structure in a repeating unit More preferably, it is a compound containing a benzothiadiazole structure, a polymer compound containing a benzothiadiazole structure in a repeating unit, a compound containing a quinoxaline structure
  • Examples of the polymer compound containing a benzothiadiazole structure in the repeating unit include a polymer compound represented by the following structural formula (4).
  • fullerene, C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene include C 84 fullerene.
  • fullerene derivatives include C 60 fullerene derivatives, C 70 fullerene derivatives, C 76 fullerene derivatives, C 78 fullerene derivatives, and C 84 fullerene derivatives.
  • C 60 fullerene derivative examples include the following.
  • C70 fullerene derivatives include the following.
  • fullerene derivatives include [6,6] phenyl-C 61 butyric acid methyl ester (C 60 PCBM, [6,6] -Phenyl C 61 butyric acid methyl ester), and [6,6] phenyl-C 71.
  • Butyric acid methyl ester (C 70 PCBM, [6,6] -Phenyl C 71 butyric acid methyl ester), [6,6] Phenyl-C 85 butyric acid methyl ester (C 84 PCBM, [6,6] -Phenyl C 85 butyric acid methyl ester), [6,6] thienyl -C 61 butyric acid methyl ester ([6,6] -Thienyl C 61 butyric acid methyl ester) and the like.
  • the ratio of the electron accepting compound to the electron donating compound is preferably 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the electron donating compound, and 20 parts by weight to 500 parts by weight. It is more preferable that
  • the thickness of the organic active layer is usually preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.
  • the photoelectric conversion device of the present invention is a polymer compound in which at least one of an electron donating compound and an electron accepting compound includes a repeating unit represented by the following formula (I), Among all the repeating units contained, a polymer compound having the largest ratio of repeating units represented by the following formula (I) is preferable.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a substituent.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be connected to each other to form a cyclic structure.
  • X 1 , X 2 and X 3 each independently represents a sulfur atom, an oxygen atom, a selenium atom, —N (R 7 ) — or —C (R 8 ) ⁇ C (R 9 ) —.
  • R 7, R 8 and R 9 each independently represents a hydrogen atom or a substituent.
  • n and m each independently represents an integer of 0 to 5. When there are a plurality of R 1 , R 2 , R 5 , R 6 , X 1 , and X 3 , they may be the same or different.
  • n and m each independently represents an integer of 0 to 5. n and m are preferably an integer of 1 to 3, and more preferably 1.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a substituent. When R 1 to R 6 are substituents, groups having 1 to 30 carbon atoms are preferred.
  • substituents examples include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, and an octyloxy group.
  • an alkoxy group having 1 to 30 carbon atoms such as dodecyloxy group
  • an aryl group having 1 to 30 carbon atoms such as phenyl group and naphthyl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be connected to each other to form a cyclic structure.
  • Specific examples of the cyclic structure formed by connecting R 1 and R 2 and the cyclic structure formed by connecting R 5 and R 6 include the following cyclic structures.
  • cyclic structure formed by connecting R 3 and R 4 include the following cyclic structures.
  • R 12 and R 13 each independently represent a hydrogen atom or a substituent.
  • Examples of the substituent represented by R 12 and R 13 include the same groups as the substituents represented by R 1 to R 6 described above.
  • R 1 to R 6 are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • X 1 , X 2 and X 3 each independently represents a sulfur atom, an oxygen atom, a selenium atom, —N (R 7 ) — or —C (R 8 ) ⁇ C (R 9 ) —.
  • R 7, R 8 and R 9 each independently represents a hydrogen atom or a substituent.
  • substituents examples include alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl and dodecyl groups; Examples thereof include aryl groups having 1 to 30 carbon atoms such as a phenyl group and a naphthyl group.
  • X 1 , X 2 and X 3 are preferably sulfur atoms.
  • the repeating unit represented by the formula (I) is preferably a repeating unit represented by the following formula (I-1).
  • the polymer compound used in the present invention is a polymer compound containing a repeating unit represented by the formula (I), and among all the repeating units contained in the polymer compound, the compound represented by the formula (I) The content (number of moles) of the repeating unit represented is the largest.
  • the repeating unit represented by the formula (I) exceeds 50% with respect to the total of all repeating units in the polymer compound.
  • the repeating unit represented by the formula (I) is 52% or more based on the total of all repeating units in the polymer compound. More preferably, the repeating unit represented by the formula (I) is 55% or more with respect to the total of all repeating units in the polymer compound. Moreover, it is preferable that the repeating unit represented by a formula (I) is less than 100% with respect to the sum total of all the repeating units in a high molecular compound. More preferably, the repeating unit represented by the formula (I) is preferably 98% or less with respect to the total of all repeating units in the polymer compound. More preferably, the repeating unit represented by the formula (I) is 70% or less with respect to the total of all repeating units in the polymer compound.
  • the polymer compound used in the present invention preferably contains a repeating unit other than the repeating unit represented by the formula (I).
  • the polymer compound may further contain a repeating unit represented by the following formula (II).
  • ring A and ring B each independently represent an aromatic ring.
  • R 10 and R 11 each independently represents a hydrogen atom or a substituent.
  • R 10 and R 11 may be linked to form a cyclic structure.
  • R 10 and R 11 are substituents
  • substituents include methyl, ethyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Alkyl groups having 1 to 30 carbon atoms such as tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like, and aryl groups having 1 to 30 carbon atoms such as phenyl group and naphthyl group Etc.
  • R 10 and R 11 are preferably hydrocarbon groups such as alkyl groups and aryl groups, and more preferably alkyl groups. Moreover, when R ⁇ 10 >, R ⁇ 11 > is a substituent, it is preferable that a carbon atom number is 12 or more.
  • ring A and ring B examples include aromatic carbocycles such as benzene ring and naphthalene ring, and aromatic heterocycles such as thiophene.
  • Ring A and ring B are preferably 5- to 10-membered rings, and more preferably benzene rings or naphthalene rings.
  • the repeating unit represented by the formula (II) is preferably a repeating unit represented by the following formula (II-1).
  • R 10 and R 11 represent the same meaning as described above.
  • the polymer compound used in the present invention contains a repeating unit represented by the formula (II) in addition to the repeating unit represented by the formula (I), the compound of the formula (II) It is preferable that the ratio of the repeating unit represented by the formula (I) is next to the ratio of the repeating unit represented by the formula (I). The case where the repeating unit of the polymer compound is only the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) is more preferable.
  • the method for producing the polymer compound used in the present invention is not particularly limited. Since the synthesis of the polymer compound is easy, a method using a Suzuki coupling reaction is preferable. Moreover, the manufacturing method of the high molecular compound used for this invention can be implemented with reference to international publication 2010/016613.
  • the organic active layer may contain other components as necessary.
  • Other components include, for example, ultraviolet absorbers, antioxidants, sensitizers for sensitizing the function of generating charges by absorbed light, light stabilizers for increasing stability from ultraviolet rays, etc. Is mentioned.
  • Components other than the electron-donating compound and the electron-accepting compound constituting the organic active layer are 5 parts by weight or less, particularly 0.01 parts by weight with respect to 100 parts by weight of the total amount of the electron-donating compound and the electron-accepting compound. It is effective to add in a proportion of 3 parts by weight.
  • the organic active layer may contain a polymer compound other than the electron donating compound and the electron accepting compound as a polymer binder in order to improve mechanical properties.
  • the polymer binder those that do not inhibit the electron transport property or hole transport property are preferable, and those that do not strongly absorb visible light are preferably used.
  • Polymer binders include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, poly Examples include carbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • the organic active layer of the photoelectric conversion element of the present invention is an image of the organic active layer observed with a transmission electron microscope, and the image of the organic active layer in which light and dark are binarized. Is 100 ⁇ m or more per 1 ⁇ m 2 of the image area of the organic active layer.
  • Examples of the method for measuring the junction length between the electron donating compound and the electron accepting compound include a method of observing the active layer using a transmission electron microscope (TEM) and obtaining the length.
  • the electron-donating compound and the electron-accepting compound can be separated and observed from an image characteristic of the element contained in the electron-donating compound and the electron-accepting compound.
  • An image characteristic of the element includes an element mapping image by an energy filter TEM, an energy loss image using an energy value giving the same contrast as the element mapping image, and an energy dispersive X-ray analysis (STEM) using a scanning transmission electron microscope. Element mapping image by -EDX).
  • the bonding length between the electron donating compound and the electron accepting compound is preferably 100 ⁇ m or more and 300 ⁇ m or less, more preferably 115 ⁇ m or more and 250 ⁇ m or less, per 1 ⁇ m 2 of the image area of the organic active layer.
  • the phase separation structure of the electron donating compound material and the electron accepting compound material in the organic active layer is appropriately controlled, so that photocharge separation and charge transport are efficiently generated. And exhibit high photoelectric conversion efficiency.
  • Another aspect of the photoelectric conversion device of the present invention includes an anode, a cathode, and an organic active layer provided between the anode and the cathode, and an electron donating compound and an electron accepting property in the organic active layer.
  • examples of the method for binarizing the brightness of the organic active layer include the following methods.
  • An image showing phase separation between the electron-donating compound material and the electron-accepting compound material in the layer is obtained as a mapping image of sulfur atoms by a three-window method of electron energy loss spectroscopy (TEM-EELS) using a transmission electron microscope. .
  • TEM-EELS electron energy loss spectroscopy
  • the standard deviation calculated from the area fraction of the black part is preferably 0.03 to 0.09, and more preferably 0.04 to 0.08.
  • the phase separation structure of the electron donating compound material and the electron accepting compound material in the organic active layer is appropriately controlled, so that photocharge separation and charge transport are efficiently generated. And exhibit high photoelectric conversion efficiency.
  • the material of the electrode included in the photoelectric conversion element of this embodiment, the electron donating compound, the electron accepting compound, and the other constituent material formed as necessary include the material of the electrode included in the photoelectric conversion element of the above embodiment. , Electron-donating compound, electron-accepting compound, and the same materials as those of other components formed as necessary.
  • at least one of the electron donating compound and the electron accepting compound is a polymer compound containing a repeating unit represented by the formula (I), and the polymer compound Among all the repeating units contained therein, a polymer compound having the largest ratio of repeating units represented by formula (I) is preferable.
  • Another aspect of the photoelectric conversion device of the present invention includes an anode, a cathode, and an organic active layer provided between the anode and the cathode, and an electron donating compound and an electron accepting property in the organic active layer. And a lifetime of an excited state of at least one of an electron donating compound in the organic active layer and an electron accepting compound in the organic active layer is 1 ns or less.
  • the excited state means an excited singlet or an excited triplet generated as a result of absorbing light
  • the excited state lifetime is the number of excited states or the concentration of the first excited state generated.
  • the lifetime of the excited singlet or triplet of the compound is evaluated from the time when the initial absorption intensity of the excited state decreases to 1 / e by pump probe transient absorption spectroscopy using a femtosecond laser as the excitation light source. be able to.
  • E means the base of natural logarithm. A method for measuring transient absorption will be described using an organic thin film solar cell as an example.
  • a bulk hetero type organic active layer composed of an electron donating compound and an electron accepting compound is formed on a glass substrate by the same operation as in the production of the organic thin film solar cell.
  • A0 log (Ip / I0), where Ip is the intensity of the probe light incident on the active layer, and I0 is the intensity of the probe light transmitted through the active layer.
  • the absorbance of the active layer measured after the active layer is photoexcited with pump light and the time t has elapsed is defined as A (t).
  • ⁇ A absorption intensity of a chemical species newly generated (increased) or extinguished (decreased) in the active layer by photoexcitation
  • ⁇ A log (Ip / I)
  • log (Ip / I0) log (I0 / I).
  • ⁇ A absorption intensity at the wavelength of the probe light used.
  • an absorption spectrum of a chemical species newly generated (increased) or extinguished (decreased) in the active layer can be obtained at a certain delay time t as compared to before photoexcitation.
  • a time resolution of 100 fs can be achieved by using pulsed light with a femtosecond laser as a light source for both the probe light and the pump light.
  • the lifetime of the excited state is preferably 1 ns or less, more preferably 100 ps or less, and even more preferably 10 ps or less.
  • the charge separation efficiency is high in the organic active layer.
  • the photoelectric conversion efficiency of the photoelectric conversion element is increased.
  • the material of the electrode included in the photoelectric conversion element of this embodiment, the electron donating compound, the electron accepting compound, and the other constituent material formed as necessary include the material of the electrode included in the photoelectric conversion element of the above embodiment. , Electron-donating compound, electron-accepting compound, and the same materials as those of other components formed as necessary.
  • at least one of the electron-donating compound and the electron-accepting compound is a polymer compound containing a repeating unit represented by the formula (I), and is included in the polymer compound Among all the repeating units, a polymer compound having the largest ratio of the repeating units represented by the formula (I) is preferable.
  • Another aspect of the photoelectric conversion device of the present invention includes an anode, a cathode, and an organic active layer provided between the anode and the cathode, and an electron-donating compound and an electron-accepting compound are included in the organic active layer. And a fluorescence quenching rate of at least one of the electron donating compound in the organic active layer and the electron accepting compound in the organic active layer is 60% or more.
  • a method for measuring the fluorescence quenching rate will be described by taking an organic thin-film solar cell having a bulk hetero type organic active layer composed of an electron donating compound and an electron accepting compound as an example.
  • a bulk hetero-type organic active layer is formed on the glass substrate by the same operation as the production of the organic thin film solar cell.
  • a spectrofluorometer at least one of the electron-donating compound and the electron-accepting compound forming this active layer is photoexcited, and the observed fluorescence intensity from the electron-donating compound or the electron-accepting compound is ⁇ 1
  • the absorbance of the electron donating compound or electron accepting compound at this photoexcitation wavelength is A1.
  • the fluorescence intensity from the compound or electron accepting compound is ⁇ 2, and the absorbance of the electron donating compound or electron accepting compound at the photoexcitation wavelength is A2.
  • the fluorescence quenching rate ( ⁇ q) of the active layer of the photoelectric conversion element of the present invention is preferably 60% or more, and more preferably 70% or more. Since ⁇ q is 60% or more, the charge separation efficiency is high in the organic active layer, and the photoelectric conversion efficiency of the photoelectric conversion element is high.
  • the material of the electrode included in the photoelectric conversion element of this embodiment, the electron donating compound, the electron accepting compound, and the other constituent material formed as necessary include the material of the electrode included in the photoelectric conversion element of the above embodiment. , Electron-donating compound, electron-accepting compound, and the same materials as those of other components formed as necessary.
  • at least one of the electron donating compound and the electron accepting compound is a polymer compound containing a repeating unit represented by the formula (I), It is preferable that the polymer compound has the largest ratio of the repeating units represented by the formula (I) among all the repeating units contained in.
  • the organic active layer of the photoelectric conversion element of the present invention is a bulk hetero type, and is formed by coating using a solution containing the electron donating compound, the electron accepting compound, and other components blended as necessary. It can be formed by forming a film.
  • the solution can be applied on the anode or cathode to form an organic active layer.
  • another electrode can be formed on an organic active layer, and a photoelectric conversion element can be manufactured.
  • the solvent used for the coating film formation using a solution is a solvent having a boiling point of 100 ° C. or lower capable of dissolving the electron donating compound and the electron accepting compound used in the present invention. Moreover, as a solvent, you may mix a some solvent, The boiling point of at least 1 type of solvent is 100 degrees C or less. Examples of the solvent having a boiling point of 100 ° C.
  • the photoelectric conversion element or less used for controlling the junction length between the electron donating compound and the electron accepting compound to increase the photoelectric conversion efficiency of the photoelectric conversion element include carbon tetrachloride, chloroform, Examples thereof include halogenated saturated hydrocarbon solvents such as dichloromethane, dichloroethane, dichloropropane and chlorobutane, and ether solvents such as tetrahydrofuran and tetrahydropyran.
  • the organic material constituting the organic active layer can be usually dissolved in a solvent in an amount of 0.1% by weight or more. A more preferred solvent is chloroform.
  • spin coating method for film formation, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, gravure printing method, Application methods such as flexographic printing method, offset printing method, ink jet printing method, dispenser printing method, nozzle coating method, capillary coating method can be used, spin coating method, flexographic printing method, gravure printing method, ink jet printing method, dispenser A printing method is preferred.
  • a preferred embodiment of the method for producing a photoelectric conversion element is a step of producing an organic active layer by applying a solution containing an electron donating compound, an electron accepting compound, and a solvent having a boiling point of 100 ° C. or less on an anode or a cathode.
  • the electron-donating compound and the electron-accepting compound is a polymer compound containing a repeating unit represented by the formula (I), and is contained in all repeating units contained in the polymer compound.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a substituent.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be connected to each other to form a cyclic structure.
  • X 1 , X 2 and X 3 each independently represents a sulfur atom, an oxygen atom, a selenium atom, —N (R 7 ) — or —C (R 8 ) ⁇ C (R 9 ) —.
  • R 7, R 8 and R 9 each independently represents a hydrogen atom or a substituent.
  • n and m each independently represents an integer of 0 to 5.
  • R 1 , R 2 , R 5 , R 6 , X 1 , and X 3 may be the same or different.
  • a solution containing a polymer compound containing a repeating unit represented by the formula (I) and a solvent having a boiling point of 100 ° C. or less to form an organic active layer by a coating electron microscope.
  • the bonding length between the electron donating compound and the electron accepting compound is expressed as follows per 1 ⁇ m 2 of the area of the organic active layer image. It can be set to 100 ⁇ m or more, and further can be set to 100 ⁇ m or more and 300 ⁇ m or less.
  • a transmission electron is formed by coating and forming an organic active layer using a solution containing a polymer compound containing a repeating unit represented by formula (I) and a solvent having a boiling point of 100 ° C. or less. It is an image of an organic active layer in the range of 900 nm ⁇ 900 nm observed with a microscope, and the image obtained by binarizing the brightness and forming the white portion and the black portion is divided into nine sections having an equal area, The standard deviation calculated from the area fraction of the black portion of the compartment can be 0.09 or less, and can be 0.03 or more and 0.09 or less.
  • the photoelectric conversion element of the present invention can be operated as an organic thin film solar cell by generating a photovoltaic force between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
  • a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
  • the organic thin film solar cell can basically have the same module structure as a conventional solar cell module.
  • a solar cell module generally has a structure in which cells are formed on a support substrate made of metal, ceramic, etc., which is covered with a filling resin, protective glass, etc., and light is incident from the opposite side of the support substrate. Further, a transparent material such as tempered glass can be used for the support substrate, and a cell can be formed thereon so that light can enter from the transparent support substrate side.
  • a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. Even in an organic thin-film solar cell to which the organic photoelectric conversion element of the present invention is applied, these module structures can be appropriately selected depending on the purpose of use, the place of use and the environment.
  • a typical super straight type or substrate type module cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring. It is connected, and the collector electrode is arrange
  • plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency.
  • EVA ethylene vinyl acetate
  • the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin It is possible to eliminate the supporting substrate on one side.
  • the periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material.
  • a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.
  • a solar cell using a flexible support such as a polymer film
  • cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material.
  • the battery body can be produced.
  • it can also have a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391.
  • SCAF solar Energy Materials and Solar Cells, 48, p383-391.
  • a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.
  • a reaction vessel was charged with 0.945 g (1.60 mmol) of monomer (1), 0.918 g of monomer (2) (2.00 mmol) and 25 mg of tetrakis (triphenylphosphine) palladium (0), and the reaction was performed.
  • the inside of the container was sufficiently replaced with argon gas.
  • 50 g of toluene deaerated previously by bubbling with argon gas was added.
  • the resulting solution was stirred at 100 ° C. for about 10 minutes.
  • the reaction solution was cooled at room temperature (25 ° C.), and then the obtained reaction solution was allowed to stand and a separated toluene layer was recovered.
  • the obtained toluene layer was poured into methanol and re-precipitated, and the generated precipitate was collected.
  • This precipitate was dried under reduced pressure and then dissolved in chloroform.
  • the obtained chloroform solution was filtered to remove insoluble matters, and then passed through an alumina column for purification.
  • the obtained chloroform solution was concentrated under reduced pressure, poured into methanol, re-precipitated, and the generated precipitate was collected. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.93 g of a polymer.
  • polymer compound A this polymer is referred to as polymer compound A.
  • the polymer compound A had a polystyrene equivalent weight average molecular weight of 2.0 ⁇ 10 4 and a polystyrene equivalent number average molecular weight of 4.7 ⁇ 10 3 .
  • the ratio of the repeating unit represented by the formula (2 ′) calculated from the charging ratio among all the repeating units of the polymer compound A was 55.6%.
  • Example 1 (Production and evaluation of organic thin-film solar cells) A glass substrate on which an ITO film having a thickness of 300 nm was formed by vacuum evaporation was subjected to ultrasonic cleaning in this order for 15 minutes in toluene, acetone, and ethanol, respectively, followed by surface treatment by ozone UV treatment.
  • a chloroform solution containing a polymer compound A which is an electron-accepting compound and poly (3-hexylthiophene-2,5-diyl) (P3HT) (Resiregular, manufactured by Aldrich Co.) which is an electron-donating compound (high The weight ratio of molecular compound A / P3HT 1/1, and the total concentration of polymer compound A and P3HT was 1% by weight) was applied onto this PEDOT: PSS film by spin coating to produce an organic active layer. The thickness of the organic active layer was about 70 nm.
  • the organic thin film solar cell was heated at 140 ° C. for 10 minutes in the glove box.
  • the shape of the obtained organic thin film solar cell was a circle having a radius of 1.5 mm.
  • the obtained organic thin-film solar cell is irradiated with a constant light using a solar simulator (manufactured by Eagle Engineering, 500 W xenon light source device LHX-500E3: AM1.5G filter, irradiance 100 mW / cm 2 ), The voltage was measured to determine photoelectric conversion efficiency, short circuit current density, open circuit voltage, and fill factor. Jsc (short circuit current density) is 3.94 mA / cm 2 , Voc (open circuit voltage) is 1.19 V, ff (fill factor) is 0.42, and photoelectric conversion efficiency ( ⁇ ) is 1. 95%.
  • the energy level of HOMO was measured with a photoelectron spectrometer AC-2 (manufactured by Riken Keiki Co., Ltd.).
  • the LUMO energy level was calculated from the end of the absorption wavelength ( ⁇ th (nm)) using the following equation.
  • (LUMO energy level) (HOMO energy level) + 1240 / ⁇ th
  • the HOMO energy level of the polymer compound A was ⁇ 5.5 eV, and the LUMO energy level was ⁇ 3.6 eV.
  • the energy level of HOMO of P3HT was -4.9 eV, and the energy level of LUMO was -3.0 eV.
  • a histogram of the mapping image of the obtained sulfur atom is calculated, and the phase containing the polymer compound having a high sulfur atom (S) composition is white with the peak top of the obtained histogram as a threshold, and the polymer compound having a low S composition
  • Binarization was performed by setting the phase containing the black as black.
  • the binarized image obtained as described above was divided into nine sections having an equal area, and the area fraction of the black portion of each section was determined.
  • the above image analysis was performed using image analysis software image-J.
  • the average value and standard deviation of the area fractions of the nine black sections obtained were calculated. As a result, the average value of the area fraction of the black portion was 0.454, and the standard deviation of the area fraction of the black portion was 0.074.
  • Comparative Example 1 (Production and evaluation of organic thin-film solar cells) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that chlorobenzene was used instead of chloroform. As a result, Jsc was 0.91 mA / cm 2 , Voc was 1.06 V, ff was 0.48, and the photoelectric conversion efficiency ( ⁇ ) was 0.46%. Under this condition, the fluorescence quenching rate ( ⁇ q) of the polymer compound A was estimated. As a result, ⁇ q was 50%. Moreover, the average value of the area fraction of the black part observed by TEM was 0.581, and the standard deviation of the area fraction of the black part was 0.171.
  • Comparative Example 2 (Production and evaluation of organic thin-film solar cells) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that o-dichlorobenzene was used instead of chloroform. As a result, Jsc was 0.84 mA / cm 2 , Voc was 0.80 V, ff was 0.36, and the photoelectric conversion efficiency ( ⁇ ) was 0.24%. Moreover, the average value of the area fraction of the black part observed by TEM was 0.535, and the standard deviation of the area fraction of the black part was 0.221.
  • Comparative Example 3 (Production and evaluation of organic thin-film solar cells) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that xylene was used instead of chloroform. Consequently, Jsc is 1.37mA / cm 2, Voc is 0.91 V, ff is 0.54, the photoelectric conversion efficiency (eta) was 0.67%. Moreover, the average value of the area fraction of the black part observed by TEM was 0.476, and the standard deviation of the area fraction of the black part was 0.099.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)
  • Electroluminescent Light Sources (AREA)
  • Light Receiving Elements (AREA)

Abstract

La présente invention concerne un élément de conversion photoélectrique dont l'efficacité de conversion photoélectrique est élevée. L'élément de conversion photoélectrique comporte: une cathode, une anode, et une couche organique active disposée entre ladite anode et ladite cathode ; un composé donneur d'électrons et un composé accepteur d'électrons dans la couche organique active ; et dans une image qui est celle de la couche organique active observée avec un microscope électronique à transmission et qui réalise la binarisation en objets clairs et sombres, présente une longueur de jonction entre le composé donneur d'électrons et le composé accepteur d'électrons égale ou supérieure à 100 µm pour 1 µm2 de l'image de la couche active organique.
PCT/JP2011/060650 2010-05-10 2011-05-09 Élément de conversion photoélectrique Ceased WO2011142314A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-108574 2010-05-10
JP2010108574A JP5639783B2 (ja) 2010-05-10 2010-05-10 光電変換素子

Publications (1)

Publication Number Publication Date
WO2011142314A1 true WO2011142314A1 (fr) 2011-11-17

Family

ID=44914370

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/060650 Ceased WO2011142314A1 (fr) 2010-05-10 2011-05-09 Élément de conversion photoélectrique

Country Status (2)

Country Link
JP (1) JP5639783B2 (fr)
WO (1) WO2011142314A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11069869B2 (en) * 2017-10-23 2021-07-20 Sumitomo Chemical Company, Limited Photoelectric conversion element and method for producing the same
CN118978733A (zh) * 2024-07-31 2024-11-19 四川大学 一种光活性材料、光电神经电极及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013207252A (ja) * 2012-03-29 2013-10-07 Sumitomo Chemical Co Ltd 光電変換素子
CN105118921B (zh) * 2015-09-14 2017-08-04 中国科学院长春应用化学研究所 一种高外量子效率和宽光谱响应的有机光电探测器及其制备方法
WO2019082848A1 (fr) * 2017-10-23 2019-05-02 住友化学株式会社 Élément de conversion photoélectrique

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0974217A (ja) * 1995-09-07 1997-03-18 Nippon Shokubai Co Ltd 有機太陽電池
JP2004534863A (ja) * 2001-01-24 2004-11-18 ケンブリッジ ディスプレイ テクノロジー リミテッド 光学デバイスに使用すべきポリマーの調製に使用するモノマー
JP2006222429A (ja) * 2005-02-09 2006-08-24 Hewlett-Packard Development Co Lp 太陽電池用の高性能有機材料
WO2008044585A1 (fr) * 2006-10-11 2008-04-17 Toray Industries, Inc. matériau organique donneur d'électrons pour dispositifs photovoltaïques, matériau et dispositifs photovoltaïques
JP2008536317A (ja) * 2005-04-07 2008-09-04 ザ リージェンツ オブ ザ ユニバーシティー オブ カリフォルニア ポリマー自己組織化による高効率ポリマー太陽電池
JP2010041022A (ja) * 2008-07-08 2010-02-18 Sumitomo Chemical Co Ltd 光電変換素子
JP2010067642A (ja) * 2008-09-08 2010-03-25 Kyoto Univ 光電変換素子、その製造方法、及び太陽電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0974217A (ja) * 1995-09-07 1997-03-18 Nippon Shokubai Co Ltd 有機太陽電池
JP2004534863A (ja) * 2001-01-24 2004-11-18 ケンブリッジ ディスプレイ テクノロジー リミテッド 光学デバイスに使用すべきポリマーの調製に使用するモノマー
JP2006222429A (ja) * 2005-02-09 2006-08-24 Hewlett-Packard Development Co Lp 太陽電池用の高性能有機材料
JP2008536317A (ja) * 2005-04-07 2008-09-04 ザ リージェンツ オブ ザ ユニバーシティー オブ カリフォルニア ポリマー自己組織化による高効率ポリマー太陽電池
WO2008044585A1 (fr) * 2006-10-11 2008-04-17 Toray Industries, Inc. matériau organique donneur d'électrons pour dispositifs photovoltaïques, matériau et dispositifs photovoltaïques
JP2010041022A (ja) * 2008-07-08 2010-02-18 Sumitomo Chemical Co Ltd 光電変換素子
JP2010067642A (ja) * 2008-09-08 2010-03-25 Kyoto Univ 光電変換素子、その製造方法、及び太陽電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11069869B2 (en) * 2017-10-23 2021-07-20 Sumitomo Chemical Company, Limited Photoelectric conversion element and method for producing the same
CN118978733A (zh) * 2024-07-31 2024-11-19 四川大学 一种光活性材料、光电神经电极及其制备方法

Also Published As

Publication number Publication date
JP5639783B2 (ja) 2014-12-10
JP2011238762A (ja) 2011-11-24

Similar Documents

Publication Publication Date Title
Soci et al. Photoconductivity of a low‐bandgap conjugated polymer
US20120204960A1 (en) Organic photovoltaic cell and method for manufacturing the same
JP2013179181A (ja) 有機光電変換素子
CN102598337B (zh) 有机光电转换元件
US9362515B2 (en) Photoelectric conversion element
JP6674948B2 (ja) 光電変換素子
JP5639783B2 (ja) 光電変換素子
US20120211741A1 (en) Organic photovoltaic cell
KR101815755B1 (ko) 확장된 공액 구조의 페나진 유도체 및 이를 적용한 유기광전변환 고분자
JP5553728B2 (ja) 有機光電変換素子
EP2597695A1 (fr) Cellules solaires à hétérojonctions de grandeurs hybrides à agent tensioactif électro-actif amélioré
JP2015220331A (ja) 光電変換素子
WO2011052577A1 (fr) Élément de conversion photoélectrique organique et procédé de fabrication associé
JP2011246594A (ja) 高分子化合物及びそれを用いた光電変換素子
JP6032284B2 (ja) 有機光電変換素子の製造方法
JP2013084919A (ja) 光電変換素子
JP2017126677A (ja) 光電変換素子
JP2012021150A (ja) 高分子化合物の製造方法
JP2014197688A (ja) 光電変換素子
WO2011066954A1 (fr) Polymères π-conjugués contenant des unités fluoroarylvinylidène et procédé de préparation de ces derniers
JP6180099B2 (ja) 光電変換素子
KR101580385B1 (ko) 신규 억셉터를 함유한 중합체 제조방법 및 이를 이용한 유기 광전자 소자
Wienk et al. Low band gap polymer: fullerene solar cells
Carlé Development of polymers for large scale roll-to-roll processing of polymer solar cells
JP2017103268A (ja) 光電変換素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11780571

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11780571

Country of ref document: EP

Kind code of ref document: A1