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WO2016181962A1 - Élément de conversion photoélectrique organique - Google Patents

Élément de conversion photoélectrique organique Download PDF

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Publication number
WO2016181962A1
WO2016181962A1 PCT/JP2016/063866 JP2016063866W WO2016181962A1 WO 2016181962 A1 WO2016181962 A1 WO 2016181962A1 JP 2016063866 W JP2016063866 W JP 2016063866W WO 2016181962 A1 WO2016181962 A1 WO 2016181962A1
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Prior art keywords
photoelectric conversion
conversion element
organic photoelectric
organic
derivatives
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Japanese (ja)
Inventor
ジョバンニ フェララ
崇広 清家
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to JP2017517950A priority Critical patent/JP6743812B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an organic photoelectric conversion element.
  • An organic photoelectric conversion element having an active layer containing an organic semiconductor has been attracting attention in recent years because the active layer can be produced by an inexpensive coating method.
  • an organic photoelectric conversion element is proposed in which an electron transport layer having a function of selectively extracting electrons and blocking holes is provided between the cathode and the active layer.
  • an electron transport layer for example, an electron transport layer using polyethyleneimine ethoxylate (PEIE) is known. (Non-Patent Document 1).
  • the present invention is as follows. [1] an active layer containing an organic semiconductor provided between a pair of electrodes consisting of an anode and a cathode; An organic photoelectric conversion element having an electron transport layer containing a polymer containing nitrogen provided between a cathode and an active layer, An organic photoelectric conversion element in which the number of nitrogen atoms (N) contained in the polymer and the number of nitrogen cations (N + ) satisfy a relationship of (N + ) / ⁇ (N + ) + (N) ⁇ ⁇ 0.2. [2] The organic photoelectric conversion device according to [1], wherein the polymer containing nitrogen is a polymer containing an amino group.
  • a step of forming a coating film by applying a solution containing a polymer containing nitrogen atoms on the cathode, a step of cleaning the surface of the coating film, and forming an active layer on the cleaned coating film The manufacturing method of the organic photoelectric conversion element including a process and the process of forming an anode.
  • a step of forming a hole transport layer on the active layer may be included after the step of forming the active layer and before the step of forming the anode.
  • the present invention is an organic photoelectric conversion element including an active layer including an organic semiconductor provided between a pair of electrodes, and an electron transporting layer including a polymer including a nitrogen atom provided between a cathode and an active layer.
  • the number of nitrogen atoms (ie, uncharged nitrogen atoms) present in the polymer (N) and the number of nitrogen cations (ie, cationic nitrogen atoms) (N + ) are (N + ) / ⁇ (N + )
  • the present invention relates to an organic photoelectric conversion element having a relationship of + (N) ⁇ ⁇ 0.2.
  • the organic photoelectric conversion element of this invention has an electron carrying layer containing the polymer containing nitrogen between a cathode and an active layer.
  • an electron carrying layer containing the polymer containing nitrogen between a cathode and an active layer.
  • a photoelectric conversion element in which a substrate, a cathode, an electron transport layer containing a polymer containing nitrogen, an active layer, and an anode are laminated in this order will be described.
  • the present invention is not limited to the photoelectric conversion elements stacked in the above order.
  • the organic photoelectric conversion element of the present invention may include a substrate.
  • the material of the substrate is not particularly limited as long as it can form an electrode on the substrate and does not change chemically when a layer containing an organic compound is formed.
  • a plate-shaped substrate containing glass, plastic, polymer film, silicon, aluminum foil, copper foil, stainless steel alloy and the like and having two main surfaces facing each other can be used.
  • a substrate in which a thin film of a conductive material that can be a cathode material such as indium / tin oxide is provided on one main surface of the substrate in advance may be used.
  • the organic photoelectric conversion element of the present invention includes a pair of electrodes composed of an anode and a cathode. At least one of the anode and the cathode is preferably a transparent or translucent electrode.
  • the light incident from the transparent or translucent electrode is absorbed in the active layer by one or more compounds selected from the group consisting of an electron accepting compound and an electron donating compound described later, whereby electrons and holes are generated. Combined excitons are generated.
  • the exciton moves in the active layer and reaches the heterojunction interface where the electron accepting compound and the electron donating compound are adjacent to each other, the difference between the HOMO energy and the LUMO energy at the interface causes the electrons and holes to be separated.
  • Charges (electrons and holes) are generated that can separate and move independently. The generated electric charges are taken out as electric energy (current) by moving to the electrodes.
  • the electrode provided on the substrate side may be a cathode or an anode.
  • metals, conductive polymers and the like can be used as the electrode material.
  • the electrode material metals, conductive polymers and the like can be used.
  • the metal or alloy is raised.
  • Specific examples of the alloy include magnesium-indium alloy, magnesium-aluminum alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
  • the electrode material is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, and ytterbium.
  • An alloy of one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin may be used. Specific examples of the alloy include magnesium-silver alloy and indium-silver alloy.
  • Electrode material graphite, graphite intercalation compound, polyaniline and derivatives thereof, polythiophene and derivatives thereof, and the like may be used.
  • Electrode material a dispersion of conductive material nanoparticles, nanowires, nanotubes, or the like may be used.
  • an electrode material having a functional group capable of forming a hydrogen bond with the functional group is prepared. It is preferable to use it. By using such an electrode material, the polymer having nitrogen tends to adhere firmly to the electrode surface and process resistance tends to be improved.
  • a conductive material that is an oxide (preferably a metal oxide) such as indium tin oxide (ITO), indium zinc oxide (IZO), and tin oxide is preferable.
  • the transparent or translucent electrode examples include a conductive metal oxide film and a translucent metal thin film.
  • a conductive metal oxide film and a translucent metal thin film examples include indium oxide, zinc oxide, tin oxide, titanium oxide, and composite films thereof made of conductive materials such as ITO, IZO, gold, platinum, silver, and copper are listed. .
  • Organic transparent conductive films such as polyaniline and derivatives thereof and polythiophene and derivatives thereof may be used.
  • nitrogen atoms in the polymer containing nitrogen react with hydroxyl groups on the electrode surface and are converted to nitrogen cations.
  • the cathode is preferably a metal oxide that easily reacts with moisture in the atmosphere to form a hydroxyl group, and specifically, an oxide containing tin oxide, zinc oxide, or titanium oxide is preferred.
  • the electrode is formed by forming a thin film of the conductive material on one main surface of the substrate by vacuum deposition, sputtering, ion plating, plating, or the like, and then patterning the thin film of the conductive material. can do.
  • the patterning can be performed by any suitable method, but can be performed, for example, by photolithography, etching, or the like.
  • the electron transport layer contained in the organic photoelectric conversion element of the present invention contains a polymer containing nitrogen.
  • the number of nitrogen atoms (N) and the number of nitrogen cations (N + ) in the nitrogen-containing polymer have a relationship of (N + ) / ⁇ (N + ) + (N) ⁇ ⁇ 0.2, and (N + ) / ⁇ (N + ) + (N) ⁇ ⁇ 0.5 is preferable.
  • the value of (N + ) / ⁇ (N + ) + (N) ⁇ can be obtained by subjecting an electron transport layer containing a polymer containing nitrogen to X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the number of nitrogen atoms (N) corresponds to the total number of primary amino group, secondary amino group and tertiary amino group contained in the polymer, and the number of nitrogen cations (N + ) is This corresponds to the number of substituted or unsubstituted ammonium cations contained in the polymer.
  • a part or all of the nitrogen-containing polymer may be neutralized with a Bronsted acid.
  • the Bronsted acid include inorganic acids such as hydrochloric acid and hydrobromic acid, and organic acids such as formic acid, acetic acid, oxalic acid and malonic acid.
  • the polymer containing nitrogen is preferably a polymer containing an amino group.
  • the nitrogen atom of the amino group in the polymer containing an amino group may have a hydroxyl group, a carboxyl group, a sulfonic acid group, or a phosphoric acid group substituent (for example, a hydroxyl group, a carboxyl group, a sulfonic acid group, or a phosphoric acid group).
  • the amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.
  • one or more repeating units having one or more amino groups selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group are random, block, An alternating or graft copolymerized polymer.
  • the polymer containing an amino group may have a repeating unit having no amino group.
  • the polymer containing an amino group may be partially or completely neutralized with a Bronsted acid.
  • Polymers containing amino groups include polyvinylamine, polyvinylalkylamine, polyalkyleneimine, polyaniline, polynucleotide, polyallylamine, polyalkyleneamine, polyvinylamine derivatives, polyvinylalkylamine derivatives, polyalkyleneimine derivatives, polyaniline derivatives. At least one selected from the group consisting of derivatives, derivatives of polynucleotides, derivatives of polyallylamine and derivatives of polyalkyleneamine is preferably used. A copolymer obtained by copolymerizing two or more repeating units constituting these polymers can also be suitably used.
  • At least one selected from the group consisting of polyvinylamine, polyallylamine, polyalkyleneamine, polyvinylamine derivatives, polyallylamine derivatives and polyalkyleneamine derivatives is more preferable.
  • a polyalkyleneimine derivative is preferred because of its high amino group density.
  • a derivative of polyvinylamine a part or all of hydrogen atoms (for example, hydrogen atoms bonded to nitrogen atoms) of polyvinylamine have a substituent (for example, hydroxyl group, carboxyl group, sulfonic acid group or phosphoric acid group).
  • a polymer substituted with an alkyl group which may be substituted (substituted polybilylamine), a polymer in which a part or all of nitrogen of polyvinylamine is a cationic nitrogen atom, a part or all of nitrogen of substituted polyvinylamine Are polymers in which is a cationic nitrogen atom.
  • the polyalkyleneimine is, for example, an alkyleneimine having 2 to 8 carbon atoms, particularly an alkylene having 2 to 4 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine. It is a polymer obtained by polymerizing one or more of imines by a conventional method. Polyalkyleneimines having various molecular weights can be synthesized by selecting the production method, and linear or branched ones can be synthesized. For example, linear polyethyleneimine has the formula:
  • n is in the range of 7 to 10000.
  • the branched polyethyleneimine is represented by the formula:
  • the polyalkyleneimine contains a primary amino group, a secondary amino group, and a tertiary amino group in the molecular skeleton.
  • a part or all of hydrogen atoms (for example, hydrogen atom bonded to nitrogen atom) of polyalkyleneimine are substituted (for example, hydroxyl group, carboxyl group, sulfonic acid group or phosphoric acid group).
  • the derivatives of polyalkyleneimine are, for example, polymers obtained by chemically modifying polyalkyleneimine by reacting with various compounds.
  • Polyalkyleneimine derivatives include, for example, polyalkyleneimine, aldehyde, ketone, alkyl halide, isocyanate, thioisocyanate, alkene, alkyne, vinyl compound (acrylonitrile, etc.), epoxy compound (epichlorohydrin, etc.), cyanamide, guanidine, urea, It can be produced by reacting with an organic acid (such as a fatty acid), an acid anhydride, or an acyl halide for modification.
  • an organic acid such as a fatty acid
  • anhydride such as a fatty acid
  • an acyl halide for modification.
  • Polyalkyleneimine derivatives are produced, for example, by reacting polyalkyleneimine or a polymer that has been chemically modified by reacting polyalkyleneimine with various compounds and reacting with Bronsted acid, metal oxide, etc. it can.
  • the polyalkyleneimine and the polyalkyleneimine derivative can have various structures depending on the production method, but the polyalkyleneimine and the polyalkyleneimine derivative in the present invention may be either linear or branched.
  • Polyalkyleneimines and polyalkyleneimine derivatives can have various molecular weights.
  • the weight average molecular weights of polyalkyleneimine and polyalkyleneimine derivatives used in the present invention are usually in the range of 300 to 400,000.
  • the weight average molecular weight is more preferably in the range of 10,000 to 400,000, especially 50,000 to 200,000.
  • a polymer having a linear or branched substituent in the polyalkyleneimine chain can be used.
  • polyethyleneimine derivatives are preferred.
  • the polyethyleneimine derivatives include polyethyleneimine derivatives obtained by introducing an alkyl group, alkylene oxide group, amino group or aryl group into polyethyleneimine, and polyethyleneimine derivatives obtained by introducing a crosslinkable group such as a hydroxyl group into polyethyleneimine. be able to. Of these, ethoxylated polyethyleneimine into which an ethylene oxide group has been introduced is preferred.
  • the thickness of the electron transport layer is usually preferably 5 nm or less and more preferably 2 nm or less.
  • the active layer is sandwiched between a pair of electrodes.
  • a mixture of an electron-accepting compound (n-type semiconductor) and an electron-donating compound (p-type semiconductor) can be used.
  • p-type semiconductor electron-donating compound
  • a bulk hetero type active layer may be mentioned.
  • the active layer plays a role of generating charges (holes and electrons) by using the energy of incident light, and thus has an essential function for the organic photoelectric conversion element.
  • the active layer contained in the photoelectric conversion element preferably contains an electron donating compound and an electron accepting compound.
  • one compound can be either an electron-donating compound or an electron-accepting compound.
  • 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, and the like.
  • 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 its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerenes such as C 60 and its derivatives, bathocuproine, etc.
  • Phenanthrene derivatives metal oxides such as titanium oxide, carbon nanotubes, and the like.
  • titanium oxide, carbon nanotube, fullerene, and fullerene derivatives are preferable, and fullerene and fullerene derivatives are more preferable.
  • fullerene examples include C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, such as C 84 fullerene, and the like.
  • fullerene derivative C 60 fullerene derivatives, C 70 fullerene derivatives, C 76 fullerene derivatives, C 78 fullerene derivatives, C 84 fullerene derivatives.
  • Specific examples of the fullerene derivative 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), [6,6] phenyl-C 71 butyric acid methyl ester Esters (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).
  • the ratio of the fullerene derivative is preferably 10 to 1000 parts by weight and preferably 20 to 500 parts by weight with respect to 100 parts by weight of the electron-donating compound. More preferred.
  • the thickness of the active layer is usually 1 nm to 100 ⁇ m, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.
  • the active layer may be a bulk hetero single layer in which an electron accepting compound and an electron donating compound are mixed as described above, or may be composed of a plurality of layers.
  • a heterojunction type in which an electron accepting layer containing an electron accepting compound and an electron supplying layer containing an electron donating compound are joined may be used.
  • a heterojunction type in which an electron-accepting layer containing a fullerene derivative and an electron-donating layer containing P3HT are joined can be given.
  • the ratio of the electron-accepting compound in the bulk hetero type active layer containing the electron-accepting compound and the electron-donating compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the electron-donating compound. More preferred is 500 parts by weight.
  • the organic photoelectric conversion device of the present invention may have an additional layer such as a hole transport layer.
  • the hole transport layer is provided between the anode and the active layer, and has a function of selectively extracting holes, an electronic block function, and the like. By providing the hole transport layer, a more efficient photoelectric conversion element can be obtained.
  • the compound used for the hole transport layer include polymer compounds such as PEDOT: PSS, polyaniline, and polythiophene, and oxides such as molybdenum oxide and tungsten oxide.
  • the above configuration may be either a form in which the anode is provided on the side closer to the substrate or a form in which the cathode is provided on the side closer to the substrate.
  • Each of the above layers may be configured as a single layer or a laminate of two or more layers.
  • the electron transport layer located between the active layer and the cathode is a layer containing a polymer containing nitrogen, and the number of nitrogen atoms (N) and the number of nitrogen cations (N + ).
  • N nitrogen atoms
  • N + the number of nitrogen cations
  • the organic photoelectric conversion element of the present invention includes a step of forming a coating film by applying a solution containing a polymer containing nitrogen on the cathode, a step of cleaning the surface of the coating film, and a step of cleaning the coating film. It can be manufactured by a manufacturing method including a step of forming an active layer and a step of forming an anode.
  • the organic photoelectric conversion device of the present invention typically has the above-described configurations a) to d). Since the organic photoelectric conversion element having the configuration b) is preferable, a method for producing the organic photoelectric conversion element having the configuration b) will be described below, but the present invention is not limited to the configuration.
  • a step of forming a coating film by applying a solution containing a polymer containing nitrogen on the cathode, a step of cleaning the surface of the coating film, a step of forming an active layer on the coating film, and the activity A method for producing an organic photoelectric conversion element including a step of forming a hole transport layer on a layer and a step of forming an anode on the hole transport layer will be described.
  • the electron transport layer can be obtained, for example, from a step of forming a coating film by applying a solution containing the above-mentioned nitrogen-containing polymer on the cathode and a step of cleaning the surface of the coating film.
  • Examples of the method for forming the coating film include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing.
  • Application methods such as gravure printing, flexographic printing method, offset printing method, ink jet printing method, dispenser printing method, nozzle coating method, slot die coating method, capillary coating method and the like.
  • the solvent used for the solution containing the polymer containing nitrogen water or an organic solvent can be used.
  • a solvent having high solubility and high storage stability for a long time can be selected.
  • the organic solvent include alcohol.
  • the alcohol include methoxyethanol and 2-propanol.
  • the coated film is preferably subjected to the next washing step in an undried state.
  • the polymer containing nitrogen is solidified by the washing step, and therefore, it tends to be difficult to expose a region having a high nitrogen cation concentration in the vicinity of the electrode by washing.
  • a method for maintaining the undried state it is preferable to use a sealed container during storage and transfer of the coating film.
  • the coating film surface can be subjected to a cleaning treatment to increase the content of nitrogen cations.
  • Nitrogen atoms in the polymer containing nitrogen are converted into nitrogen cations by hydrogen bonding with hydroxyl groups on the lower electrode surface, and there is a region with a higher nitrogen cation concentration in the vicinity of the electrode.
  • the cleaning treatment is effective as a step of exposing the region having a high nitrogen cation concentration.
  • the cleaning treatment includes a step of bringing the cleaning solution into contact with the coating film surface and a step of removing the cleaning solution remaining on the coating film surface thereafter.
  • a method for bringing the cleaning solution into contact with the coating film surface a method of immersing in the cleaning solution, a method of pouring the cleaning solution from a nozzle, a method of spraying the cleaning solution, or the like can be used.
  • a solvent that dissolves the polymer containing nitrogen can be used.
  • the cleaning solution for example, water or an acidic aqueous solution can be used.
  • an acidic aqueous solution it is preferably acidic enough not to dissolve the lower electrode and the like, and a solution containing an organic acid such as acetic acid, butyric acid, formic acid or citric acid is preferred.
  • an acetic acid aqueous solution having an acetic acid concentration of 5 to 90% by weight is preferred, an acetic acid aqueous solution having an acetic acid concentration of 25 to 80% by weight is more preferred, and an acetic acid aqueous solution having an acetic acid concentration of 50 to 70% by weight is preferred. Further preferred.
  • a drying method such as natural drying by air drying, drying under reduced pressure, or heat drying at a temperature below which the polymer containing nitrogen is not decomposed can be used.
  • the value of (N + ) / ⁇ (N + ) + (N) ⁇ can be obtained by subjecting the obtained electron transport layer containing a polymer containing nitrogen to X-ray photoelectron spectroscopy (XPS).
  • an active layer is formed on the electron transport layer according to a conventional method.
  • the step of forming the active layer is a coating liquid in which an electron accepting compound and an electron donating compound are mixed on the electron transport layer.
  • coating is a step of forming an electron-accepting layer by applying a coating liquid containing an electron-accepting compound on the electron-transporting layer; Forming an electron supply layer by applying a coating liquid containing an electron donating compound on the electron accepting layer.
  • the active layer can be formed by applying on the electron transporting layer a coating liquid obtained by mixing any of the aforementioned suitable active layer materials and a solvent.
  • the solvent include toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, unsaturated hydrocarbon solvents such as n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, and halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene , Ether solvents such as
  • the active layer can be formed by spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, gravure. Coating methods such as printing, flexographic printing, offset printing, inkjet printing, dispenser printing, nozzle coating, slot die coating, and capillary coating can be used.
  • a hole transport layer is formed on the active layer.
  • the hole transport layer can be formed by applying a coating liquid containing the polymer and a solvent.
  • a coating liquid for the hole transport layer a liquid dispersed in water or an organic solvent containing PEDOT: PSS, polyaniline, polythiophene, or the like can be used.
  • the coating method include the same methods as those used for the active layer.
  • a nanoparticle dispersion such as molybdenum oxide
  • Molybdenum oxide or the like can also be formed by a vacuum evaporation method.
  • an electrode to be an anode is formed on the hole transport layer.
  • a dispersion liquid of conductive material nanoparticles, nanowires, nanotubes, or the like is used for the anode, it can be formed by a coating method as in the active layer.
  • a metal film such as aluminum or silver is used as the anode, it can also be formed by a vacuum deposition method.
  • the operation mechanism of the organic photoelectric conversion element will be briefly described.
  • the incident light energy that has passed through the transparent or translucent electrode and entered the active layer is absorbed by one or more selected from the group consisting of an electron-accepting compound and an electron-donating compound, and electrons and holes are combined.
  • Excitons are generated.
  • the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are bonded, the difference between the HOMO energy and the LUMO energy at the interface causes the electrons and holes to be separated.
  • Charges (electrons and holes) are generated that can separate and move independently. The generated charges move to the electrodes (cathode and anode), respectively, and can be taken out as electric energy (current) outside the device.
  • the organic photoelectric conversion element manufactured by the manufacturing method of the present invention irradiates light such as sunlight from one or more selected from the group consisting of a transparent or translucent cathode and anode, so that a photovoltaic power is generated between the electrodes. And can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
  • the organic photoelectric conversion device manufactured by the manufacturing method of the present invention In the organic photoelectric conversion device manufactured by the manufacturing method of the present invention, light is transmitted through an electrode that is transparent or translucent in a state where a voltage is applied between the cathode and the anode, or in a state where no voltage is applied. The incident photocurrent flows. Therefore, the organic photoelectric conversion element manufactured by the manufacturing method of the present invention can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
  • Example 1 (Production and evaluation of organic thin-film solar cells) A glass substrate on which an ITO film with a thickness of 150 nm was formed by sputtering was washed with acetone and then subjected to ultraviolet ozone treatment to produce an ITO electrode having a clean surface.
  • a polymer containing nitrogen a solution obtained by diluting polyethyleneimine ethoxylate (PEIE) (manufactured by Aldrich, trade name polyethyleneimine, 80% ethoxylated solution, weight average molecular weight to 70,000) 1/50 times with deionized water, It apply
  • the thickness of the PEIE coating film was about 5 nm.
  • the ratio of the number of nitrogen cations to the total number of nitrogen atoms (that is, the total number of nitrogen atoms and nitrogen cations) in the obtained electron transport layer 1 was determined by the following method.
  • XPS X-ray photoelectron spectroscopy
  • Quantera SXM Quantera SXM
  • a polythiophene derivative manufactured by Solvay, product name: AQ1300 was applied on the active layer by spin coating, and then subjected to heat treatment on a hot plate at 70 ° C. for 5 minutes to form the hole transport layer 1. .
  • the thickness of the hole transport layer 1 was about 70 nm.
  • a silver nanowire dispersion liquid (manufactured by Cambrios, trade name Clear-Ohm ⁇ ⁇ ⁇ Ink-N) is applied onto the hole transport layer 1 by spin coating, and then treated on a hot plate at 70 ° C. for 5 minutes. Then, an anode was formed, and an organic thin film solar cell 1 was obtained.
  • the shape of the obtained organic thin film solar cell 1 was a square of 10 mm ⁇ 10 mm.
  • the obtained organic thin film solar cell is irradiated with constant light using a solar simulator (trade name CEP-2000: AM1.5G filter, irradiance 100 mW / cm 2 , manufactured by Spectrometer Co., Ltd.), and the generated current and voltage are measured.
  • the photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor (curve factor) were determined. The measurement results are shown in Table 2.
  • Example 2 An electron transport layer 2 was prepared in the same manner as in Example 1 except that an aqueous solution containing 5% by weight of acetic acid was used instead of deionized water in the cleaning treatment of the PEIE coating film in the preparation of the electron transport layer.
  • the XPS analysis results are listed in Table 1.
  • Example 3 Electron transport 3 was prepared in the same manner as in Example 1 except that an aqueous solution containing 25% by weight of acetic acid was used in the cleaning treatment of the PEIE coating film in the preparation of the electron transport layer. Furthermore, the organic thin film solar cell containing it was produced similarly to Example 1. The XPS analysis results of the electron transport layer 3 are shown in Table 1, and the photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Example 4 An electron transport layer 4 was prepared in the same manner as in Example 1 except that an aqueous solution containing 50% by weight of acetic acid was used in the cleaning treatment of the PEIE coating film in the preparation of the electron transport layer. Furthermore, the organic thin film solar cell containing it was produced similarly to Example 1. The XPS analysis results of the electron transport layer 4 are shown in Table 1, and the photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Example 5 In the active layer, PCE10 corresponding to p-type semiconductor material (trade name: OS010, manufactured by 1-Material Co.) and C 70 PCBM (product name ADS71BFA) corresponding to n-type semiconductor material, used are used. And the organic thin-film solar cell was produced by the same method as Example 1 except having used Ag (film thickness of 60 nm) by vacuum deposition in the anode. The photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Example 6 An organic thin-film solar cell was produced in the same manner as in Example 5 except that the electron transport 2 described in Example 2 was used. The photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Example 7 An organic thin film solar cell was produced in the same manner as in Example 5 except that Compound A was used as the polymer corresponding to the p-type semiconductor. Table 2 shows the photoelectric conversion characteristics of the obtained organic thin film solar cell.
  • Example 8 An organic thin film solar cell was produced in the same manner as in Example 6 except that Compound A was used as the polymer corresponding to the p-type semiconductor. Table 2 shows the photoelectric conversion characteristics of the obtained organic thin film solar cell.
  • Example 9 An organic thin-film solar cell was produced in the same manner as in Example 5 except that molybdenum trioxide (film thickness was about 15 nm) was used as the hole transport layer by vacuum deposition. The photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Example 10 An organic thin film solar cell was produced in the same manner as in Example 6 except that molybdenum trioxide (film thickness was about 15 nm) was used as the hole transport layer by vacuum deposition. The photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Example 1 After applying the PEIE layer, an organic thin film solar cell was produced in the same manner as in Example 1 except that the electron transport layer 5 that had not been subjected to the cleaning treatment was used.
  • the XPS analysis results of the electron transport layer 5 are shown in Table 1, and the photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Comparative Example 2 An electron transport layer 6 was produced in the same manner as in Comparative Example 1 except that the electron transport layer 6 obtained from a solution obtained by diluting the PEIE layer with deionized water 1/100 times was used. Furthermore, the organic thin film solar cell containing them was produced similarly to the comparative example 1. The photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • Comparative Example 3 An electron transport layer 7 was produced in the same manner as in Comparative Example 1 except that the electron transport layer 7 obtained from a solution obtained by diluting the PEIE layer with deionized water 1/300 times was used. Furthermore, the organic thin film solar cell containing it was produced similarly to the comparative example 1. The photoelectric conversion characteristics of the obtained organic thin film solar cell are shown in Table 2.
  • an organic photoelectric conversion element having excellent photoelectric conversion efficiency can be provided.

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  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un élément de conversion photoélectrique organique présentant une couche active comprenant un semi-conducteur organique disposé entre une paire d'électrodes comprenant une électrode positive et une électrode négative, et une couche de transport d'électrons contenant un polymère contenant de l'azote, la couche de transport d'électrons étant disposée entre l'électrode négative et la couche active, le nombre de cations d'azote (N+) et le nombre d'atomes d'azote (N) que contient le polymère sont tels que (N+)/{(N+)+(N)} ≥ 0,2.
PCT/JP2016/063866 2015-05-12 2016-05-10 Élément de conversion photoélectrique organique Ceased WO2016181962A1 (fr)

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