WO2011138885A1 - Composé de polymère et élément de conversion photoélectrique organique utilisant celui-ci - Google Patents

Composé de polymère et élément de conversion photoélectrique organique utilisant celui-ci Download PDF

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WO2011138885A1
WO2011138885A1 PCT/JP2011/058478 JP2011058478W WO2011138885A1 WO 2011138885 A1 WO2011138885 A1 WO 2011138885A1 JP 2011058478 W JP2011058478 W JP 2011058478W WO 2011138885 A1 WO2011138885 A1 WO 2011138885A1
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polymer compound
fluorine atom
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上谷　保則
吉村　研
淳 藤原
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住友化学株式会社
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
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    • 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

Definitions

  • the present invention relates to a polymer compound and an organic photoelectric conversion element using the same.
  • Organic semiconductor materials are expected to be applied to organic photoelectric conversion elements such as organic solar cells and optical sensors.
  • the functional layer can be manufactured by an inexpensive coating method.
  • organic semiconductor materials that are various polymer compounds for the organic photoelectric conversion element has been studied.
  • WO2005 / 092947 includes 9,9-dioctylfluorene-2,7-diboronic acid ester and 5,5 ′′ ′′-dibromo-3 ′′, 4 ′′ -dihexyl- ⁇ -penta.
  • a polymer compound obtained by polymerizing thiophene has been proposed.
  • the present invention provides a polymer compound having a large absorbance of light having a long wavelength. That is, the present invention first provides a polymer compound containing a repeating unit represented by the formula (1).
  • T represents a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with a fluorine atom, an alkoxy group which may be substituted with a fluorine atom, or an aromatic carbocyclic group.
  • m represents an integer of 2 to 10.
  • a plurality of T may be the same or different.
  • R represents an alkyl group which may be substituted with a fluorine atom, an alkoxy group which may be substituted with a fluorine atom or an aromatic carbocyclic group.
  • Two Rs may be the same or different.
  • the present invention provides an organic photoelectric conversion device having a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron accepting compound and the polymer compound.
  • this invention provides the compound represented by Formula (2).
  • R represents the same meaning as described above.
  • Q represents a boric acid ester residue. Two Qs may be the same or different.
  • FIG. 1 is a graph showing an absorption spectrum of polymer compound A described later.
  • FIG. 2 is a graph showing an absorption spectrum of polymer compound B described later.
  • FIG. 3 is a graph showing an absorption spectrum of polymer compound C described later.
  • FIG. 4 is a figure which shows the absorption spectrum of the high molecular compound D mentioned later.
  • the polymer compound of the present invention contains a repeating unit represented by the above formula (1).
  • the carbon number of the alkyl group and alkoxy group represented by R is usually 1 to 20, preferably 2 to 18, and more preferably 3 to 12.
  • the alkyl group represented by R may be linear or cyclic.
  • a hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • alkyl group substituted with a fluorine atom examples include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
  • the alkoxy group represented by R may be linear or cyclic.
  • examples include a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group.
  • a hydrogen atom in the alkoxy group may be substituted with a fluorine atom.
  • alkoxy group substituted with a fluorine atom examples include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.
  • the aromatic carbocyclic group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon which may have a substituent, and the carbon number is usually 6 to 60, preferably 6-30.
  • the aromatic carbocyclic group include an optionally substituted phenyl group, 1-naphthyl group, and 2-naphthyl group.
  • substituents examples include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group, and an alkoxy group.
  • the carbon number and specific examples of the alkyl group and alkoxy group are the same as those described above for the alkyl group and alkoxy group represented by R.
  • the carbon number and specific examples of the alkyl group, alkoxy group, and aromatic carbocyclic group represented by T are the same as those described above for the alkyl group, alkoxy group, and aromatic carbocyclic group represented by R.
  • m represents an integer of 2 to 10.
  • m is preferably an integer of 3 to 8, and more preferably an integer of 4 to 6.
  • Examples of the repeating unit represented by the formula (1) include the following repeating units.
  • One preferable aspect of the repeating unit represented by Formula (1) is a repeating unit represented by Formula (1-1).
  • m1 and m2 independently represent an integer of 1 to 3.
  • T 1 Represents an alkyl group. 2
  • T 1 May be the same or different.
  • T 1 As the alkyl group represented by, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, isooctyl group Decyl group, dodecyl group, pentadecyl group and octadecyl group.
  • the carbon number of the alkyl group is usually 1-20, preferably 1-10.
  • the amount of the repeating unit represented by the formula (1) contained in the polymer compound of the present invention is the total amount in the polymer compound.
  • the content is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, based on the total number of repeating units.
  • the weight average molecular weight in terms of polystyrene of the polymer compound of the present invention is 10 3 ⁇ 10 8
  • the polymer compound of the present invention is preferably a conjugated polymer compound.
  • the conjugated polymer compound means a compound in which atoms constituting the main chain of the polymer compound are substantially conjugated.
  • the polymer compound of the present invention may have a repeating unit other than the repeating unit represented by the formula (1).
  • a divalent aromatic carbocyclic group such as a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, a fluorenediyl group, a frangiyl group,
  • divalent aromatic heterocyclic groups such as a pyrrole diyl group and a pyridinediyl group.
  • the polymer compound of the present invention may be produced by any method. For example, after synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, the monomer is dissolved in an organic solvent, if necessary, , And can be synthesized by polymerization using a known aryl coupling reaction using a catalyst, a ligand and the like.
  • the monomer can be synthesized with reference to, for example, a method disclosed in US2008 / 145571 and JP-A-2006-335933.
  • Polymerization by the aryl coupling reaction includes, for example, polymerization by Suzuki coupling reaction, polymerization by Yamamoto coupling reaction, polymerization by Kumada-Tamao coupling reaction, FeCl 3 Examples thereof include a polymerization reaction with an oxidant such as an oxidative polymerization by an electrochemical reaction.
  • Polymerization by Suzuki coupling reaction uses a palladium complex or nickel complex as a catalyst in the presence of an inorganic base or an organic base, and a ligand is added as necessary to have a boronic acid residue or a boric acid ester residue.
  • a monomer and a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a trifluoromethanesulfonate group (-OSO 2 CF 3 ), P-toluenesulfonate group (-OSO 2 C 6 H 4 CH 3 Polymerization in which a monomer having a sulfonate group such as -p) is reacted.
  • the inorganic base include sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, and potassium fluoride.
  • Examples of the organic base include tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetraethylammonium hydroxide.
  • Examples of the palladium complex include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, and bis (triphenylphosphine) palladium dichloride.
  • Examples of the nickel complex include bis (cyclooctadiene) nickel.
  • Examples of the ligand include triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, and tri (tert-butyl) phosphine. It is done. Details of the polymerization by the Suzuki coupling reaction are described in, for example, Journal of Polymer Science: Part A: Polymer Chemistry (Part A: Polymer Chemistry), 2001, Vol. 39, p. 1533-1556.
  • Polymerization by Yamamoto coupling reaction uses a catalyst and a reducing agent to react monomers having halogen atoms, monomers having sulfonate groups such as trifluoromethanesulfonate groups, or monomers having halogen atoms and monomers having sulfonate groups.
  • Catalysts include nickel zero-valent complexes such as bis (cyclooctadiene) nickel and ligands such as bipyridyl, [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel.
  • a catalyst comprising a nickel complex other than a nickel zero-valent complex such as dichloride and a ligand such as triphenylphosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine, if necessary.
  • the reducing agent include zinc and magnesium.
  • Polymerization by the Yamamoto coupling reaction may be performed using a dehydrated solvent in the reaction, may be performed in an inert atmosphere, or may be performed by adding a dehydrating agent to the reaction system. Details of the polymerization by Yamamoto coupling are described in, for example, Macromolecules, 1992, Vol. 25, p. 1214-1223.
  • Polymerization by Kumada-Tamao coupling reaction uses a nickel catalyst such as [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel dichloride, a compound having a magnesium halide group and a halogen atom.
  • a dehydrated solvent may be used for the reaction, the reaction may be performed in an inert atmosphere, or a dehydrating agent may be added to the reaction system.
  • a solvent is usually used.
  • the solvent may be selected in consideration of the type of polymerization reaction to be used, the raw material monomer, the solubility of the polymer to be formed, and the like. Specific examples include tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and organic solvents such as a mixed solvent obtained by mixing two or more of these solvents. It is done.
  • the polymerization reaction can also be carried out in a two-phase system of an organic solvent phase and an aqueous phase.
  • Solvents used for the Suzuki coupling reaction include tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and a mixed solvent in which two or more of these solvents are mixed. Organic solvents are preferred. A reaction in a two-phase system of an organic solvent phase and an aqueous phase is also preferable. The solvent used for the Suzuki coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions.
  • the solvent used for the Yamamoto coupling reaction is tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and a mixed solvent in which two or more of these solvents are mixed. Organic solvents are preferred.
  • the solvent used for the Yamamoto coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions.
  • the polymerization method by the Suzuki coupling reaction and the polymerization method by the Yamamoto coupling reaction are preferable, the polymerization method by the Suzuki coupling reaction and the zero-valent nickel complex.
  • the lower limit of the reaction temperature of the aryl coupling reaction is preferably ⁇ 100 ° C., more preferably ⁇ 20 ° C., and particularly preferably 0 ° C. from the viewpoint of reactivity.
  • the upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and particularly preferably 120 ° C. from the viewpoint of the stability of the monomer and the polymer compound.
  • a known method can be used as a method for removing the polymer compound of the present invention from the reaction solution after completion of the reaction.
  • the polymer compound of the present invention can be obtained by adding a reaction solution to lower alcohol such as methanol, filtering the deposited precipitate, and drying the filtered product.
  • a reaction solution such as methanol
  • the purity of the obtained polymer compound is low, it can be purified by recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, or the like.
  • the polymer compound of the present invention is used for the production of an organic photoelectric conversion device, if an active group remains in the polymerization reaction at the terminal of the polymer compound, characteristics such as durability of the organic photoelectric conversion device may deteriorate. For this reason, it is preferable to protect the terminal of the polymer compound with a stable group.
  • Examples of the stable group for protecting the terminal include an alkyl group optionally substituted with a fluorine atom, an alkoxy group optionally substituted with a fluorine atom, an aromatic carbocyclic group, and an amino substituted with an aromatic carbocyclic group.
  • Group, heterocyclic group and the like The number of carbon atoms and specific examples of the alkyl group which may be substituted with a fluorine atom, the alkoxy group which may be substituted with a fluorine atom and the aromatic carbocyclic group are the same as those described above with respect to those represented by R. is there.
  • Examples of the amino group substituted with an aromatic carbocyclic group include a phenylamino group and a diphenylamino group.
  • heterocyclic group examples include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group and the like.
  • a group active in the polymerization reaction remaining at the terminal of the polymer compound may be replaced with a hydrogen atom instead of a stable group. From the viewpoint of enhancing hole transportability, a group that imparts electron donating properties such as an amino group substituted with an aromatic carbocyclic group as a stable group for protecting the terminal is preferable.
  • the polymer compound is a conjugated polymer compound
  • the end of a group having a conjugated bond in which the conjugated structure of the main chain of the polymer compound and the conjugated structure of a stable group protecting the end are continuous is also protected.
  • a group for example, an aromatic carbocyclic group and an aromatic heterocyclic group can be mentioned.
  • the polymer compound of the present invention can be produced, for example, by polymerizing a compound represented by the formula (2) and a compound represented by the formula (3) when using the Suzuki coupling reaction. .
  • R and Q have the same meaning as described above.
  • T and m represent the same meaning as described above.
  • the boric acid ester residue represented by Q represents a group obtained by removing a hydroxyl group from boric acid diester, and specific examples thereof include groups represented by the following formula.
  • Me represents a methyl group
  • Et represents an ethyl group.
  • the compound represented by the formula (2) can be produced, for example, by dehydrating and condensing the compound represented by the formula (4) and an alcohol or diol in an organic solvent.
  • R represents the same meaning as described above. In the dehydration condensation, the slurry-like compound represented by formula (4) disappears and the reaction solution becomes a uniform solution, whereby the production of the compound represented by formula (2) can be confirmed.
  • the reaction solution is concentrated using an evaporator, the residue is washed with a hydrocarbon solvent having a relatively low boiling point such as hexane, and then filtered to obtain the compound represented by the formula (2).
  • a hydrocarbon solvent having a relatively low boiling point such as hexane
  • examples of the alcohol used for dehydration condensation include methanol, ethanol, propanol, 2-propanol, and butanol.
  • the diol that can be used for dehydration condensation include pinacol, catechol, ethylene glycol, and 1,3-propanediol.
  • a dehydrating agent such as anhydrous magnesium sulfate or anhydrous sodium sulfate may be added.
  • Formula (4) the following compounds are mentioned, for example.
  • the compound represented by the formula (4) is, for example, lithiated the compound represented by the formula (5) with an organic lithium compound such as butyllithium (n-BuLi), and then the lithiated compound and trimethoxyboric acid.
  • a compound represented by the formula (6) is produced by reacting with a boric acid ester such as, and the compound represented by the formula (6) can be produced by acid treatment with an acid such as dilute hydrochloric acid.
  • R represents the same meaning as described above.
  • the lithiation reaction is usually performed in an anhydrous ether solvent such as anhydrous tetrahydrofuran or anhydrous diethyl ether.
  • the reaction temperature is usually ⁇ 80 ° C.
  • the organic photoelectric conversion element of the present invention has a pair of electrodes and a functional layer provided between the electrodes, and the functional layer includes an electron-accepting compound and a repeating unit represented by the formula (1).
  • an electron-accepting compound As an electron-accepting compound, fullerene and a fullerene derivative are preferable.
  • the organic photoelectric conversion element 1. An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and a polymer compound containing a repeating unit represented by the formula (1); 2. An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and a polymer compound containing a repeating unit represented by formula (1); An organic photoelectric conversion element in which the electron-accepting compound is a fullerene derivative; Is mentioned.
  • the amount of the electron accepting compound in the functional layer containing the electron accepting compound and the polymer compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. It is preferably 20 to 500 parts by weight. In addition, 2.
  • the amount of the fullerene derivative in the functional layer containing the fullerene derivative and the polymer compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. More preferably, it is ⁇ 500 parts by weight.
  • the amount of the fullerene derivative in the functional layer is preferably 20 to 400 parts by weight, and preferably 40 to 250 parts by weight with respect to 100 parts by weight of the polymer compound. More preferred is 80 to 120 parts by weight. From the viewpoint of increasing the short-circuit current density, the amount of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight, and preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer compound. More preferred.
  • the polymer compound including the electron-accepting compound and the repeating unit represented by the formula (1) can efficiently absorb the spectrum of desired incident light.
  • the organic photoelectric conversion element of the present invention includes the above 1. , 2. From the standpoint of including a large number of heterojunction interfaces, the organic photoelectric conversion element is preferable. The organic photoelectric conversion element is more preferable. In the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the functional layer in the element.
  • the additional layer examples include a charge transport layer that transports holes or electrons, and a buffer layer.
  • the organic 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 an electrode is formed and an organic layer is formed.
  • the material for the substrate include glass, plastic, polymer film, and silicon.
  • the opposite electrode that is, the electrode far from the substrate is preferably transparent or translucent.
  • a material for the pair of electrodes a metal, a conductive polymer, or the like can be used.
  • the material of one of the pair of electrodes is preferably a material having a low work function.
  • Examples of the 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 alloys of two or more of them, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite Intercalation compounds are mentioned.
  • metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, And alloys of two or more of them, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt
  • the alloy examples 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.
  • the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Gold, platinum, silver, and copper are used, and ITO, indium / zinc / oxide, and tin oxide are preferable.
  • Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.
  • organic transparent conductive films such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.
  • a material used for the charge transport layer as the additional layer that is, the hole transport layer or the electron transport layer
  • an electron donating compound and an electron accepting compound described later can be used, respectively.
  • As a material used for the buffer layer as an additional layer halides or oxides of alkali metals or alkaline earth metals such as lithium fluoride can be used.
  • fine particles of an inorganic semiconductor such as titanium oxide can be used.
  • an organic thin film containing the polymer compound of the present invention can be used as the functional layer in the organic photoelectric conversion element of the present invention.
  • the organic thin film has a thickness of 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 organic thin film may contain the said high molecular compound individually by 1 type, or may contain it in combination of 2 or more types.
  • a low molecular compound and / or polymeric compounds other than the said high molecular compound can also be mixed and used as an electron-donating compound in an organic thin film.
  • Examples of the electron donating compound that the organic thin film may contain in addition to the polymer compound containing the repeating unit represented by the formula (1) include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligos. Thiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof Derivatives, polythienylene vinylene and its derivatives.
  • Examples of the electron accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone derivatives.
  • Diphenyldicyanoethylene and derivatives thereof diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, C 60 And phenanthroline derivatives such as carbon nanotubes and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
  • Fullerene and derivatives thereof are particularly preferable.
  • the electron-donating compound and the electron-accepting compound are relatively determined from the energy level of the energy level of these compounds.
  • Fullerene and its derivatives include C 60 , C 70 , C 84 And derivatives thereof.
  • a fullerene derivative represents a compound in which at least a part of fullerene is modified.
  • Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).
  • R a Is a group having an alkyl group, an aromatic carbocyclic group, an aromatic heterocyclic group or an ester structure. Multiple R a May be the same or different.
  • R b Represents an alkyl group or an aromatic carbocyclic group. Multiple R b May be the same or different.
  • R a And R b The carbon number and specific examples of the alkyl group and aromatic carbocyclic group represented by the above are the same as those described above with respect to the alkyl group and aromatic carbocyclic group represented by R.
  • R a In general, the aromatic heterocyclic group represented by the formula has 3 to 60 carbon atoms, and examples thereof include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group.
  • R a Examples of the group having an ester structure represented by the formula (V) include a group represented by the formula (V).
  • u1 represents an integer of 1 to 6
  • u2 represents an integer of 0 to 6
  • R c Represents an alkyl group, an aromatic carbocyclic group or an aromatic heterocyclic group.
  • R c The carbon number and specific examples of the alkyl group, aromatic carbocyclic group and aromatic heterocyclic group represented by a Are the same as those described above with respect to the alkyl group, aromatic carbocyclic group, and aromatic heterocyclic group.
  • C 60 Specific examples of the derivatives include the following.
  • C 70 Specific examples of the derivatives include the following.
  • the organic thin film may be produced by any method.
  • the organic thin film may be produced by a film formation method from a solution containing the polymer compound of the present invention, or an organic thin film may be formed by a vacuum deposition method. Good.
  • a method for producing an organic thin film by film formation from a solution include a method of producing an organic thin film by applying the solution on one electrode and then evaporating the solvent.
  • the solvent used for film formation from a solution is not particularly limited as long as it dissolves the polymer compound of the present invention.
  • the solvent examples include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, Examples thereof include halogenated hydrocarbon solvents such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran.
  • hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicycl
  • the polymer compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.
  • a coating method such as a printing method, an offset printing method, an inkjet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an inkjet printing method, and a dispenser printing method are preferable.
  • the organic photoelectric conversion element By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force 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. In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, 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 polystyrene equivalent weight average molecular weight of the polymer compound was determined by size exclusion chromatography (SEC). Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6 mm Id ⁇ 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF) Synthesis Example 1 (Synthesis of Compound (2)) In a 500 mL three-necked flask, 6.1 g (20.6 mmol) of compound (1) and 16.4 g (250 mmol) of powdered zinc were added, and then 200 ml of acetic acid was added.
  • SEC size exclusion chromatography
  • reaction solution was stirred for 15 minutes with a mechanical stirrer, heated and refluxed for 90 minutes, and then allowed to cool to room temperature (25 ° C.). Thereafter, the reaction solution was filtered through Celite, and the filtrate was concentrated with an evaporator. 150 ml of diethyl ether was added to the residue, and the obtained organic layer was washed with a 27 wt% aqueous sodium hydroxide solution, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated with an evaporator to obtain 4.8 g of a reaction intermediate having a diamine structure.
  • Example 1 (Synthesis of Compound (E)) A 300 ml three-necked flask was charged with 1.2 g (3.1 mmol) of compound (3), 0.75 g (6.35 mmol) of pinacol, and 50 ml of chloroform at room temperature (25 ° C.). The reaction solution was stirred until it became a homogeneous solution. Thereafter, 1.0 g of anhydrous magnesium sulfate was added to the reaction solution, and the mixture was further stirred for 4 hours. After stirring, the mixture was filtered, and the filtrate was concentrated with an evaporator.
  • the organic layer was washed twice with 20 ml of water, twice with 20 mL of a 3% by weight acetic acid aqueous solution and twice with 20 mL of water, and the resulting solution was poured into methanol to precipitate a polymer. I let you.
  • the polymer was filtered and dried to obtain 225 mg of polymer.
  • the obtained polymer was dissolved in 35 ml of trichlorobenzene and passed through a silica gel / alumina column. The obtained solution was added dropwise to methanol, and the precipitated polymer was filtered and dried to obtain 46 mg of polymer compound A.
  • the weight average molecular weight in terms of polystyrene of the polymer compound A was 1.7 ⁇ 10 5 .
  • the polymer compound A contains 50 mol% of the repeating units represented by the following formula in the total repeating units.
  • Example 3 (Synthesis of Compound (7)) A 100 ml three-necked flask was charged with 0.74 g (1.2 mmol) of compound (6), 0.29 g (2.5 mmol) of pinacol, and 30 ml of chloroform at room temperature (25 ° C.). The reaction solution was stirred while heating under reflux until a homogeneous solution was obtained. Thereafter, 1.0 g of anhydrous magnesium sulfate was added to the reaction solution, and the mixture was further stirred while heating under reflux for 4 hours. After stirring, the mixture was filtered, and the filtrate was concentrated with an evaporator.
  • the absorption spectrum of the organic thin film was measured with a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). The measured spectrum is shown in FIG.
  • the absorbance at 600 nm is shown in Table 1.
  • Example 5 Synthesis of polymer compound C
  • 150 mg (0.203 mmol) of compound (F) 150 mg (0.203 mmol) of compound (F)
  • 158 mg (0.200 mmol) of compound (7), methyl trioctyl ammonium chloride (trade name Aliquat 336 (registered trademark)) Sigma Aldrich Japan Co., Ltd.) was added in 77 mg, dissolved in 15 ml of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes.
  • the organic layer was washed twice with 30 ml of water, twice with 30 mL of a 3% by weight acetic acid aqueous solution and further twice with 30 mL of water, and the resulting solution was poured into methanol to precipitate a polymer.
  • the polymer was filtered and dried, and the resulting polymer was dissolved in 30 mL of o-dichlorobenzene, passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate the polymer.
  • the polymer was filtered and then dried to obtain 75 mg of a purified polymer.
  • polymer compound C The weight average molecular weight (Mw) in terms of polystyrene of the polymer compound C measured by GPC was 80000, and the number average molecular weight (Mn) in terms of polystyrene was 13000.
  • Synthesis Example 5 Synthesis of Compound (9) A compound synthesized by a method described in Advanced Functional Materials (Adv. Funct. Mater.), 2007, Vol. 17, pp. 3836-3842 in a 100 ml three-necked flask equipped with a Dimroth condenser in a nitrogen atmosphere.
  • Example 6 Synthesis of Compound (10)
  • 1.24 g (1.8 mmol) of compound (9), 0.44 g (3.7 mmol) of pinacol and 50 ml of chloroform are placed at room temperature, and the reaction solution is changed from a slurry to a homogeneous solution.
  • the mixture was stirred while being heated to reflux.
  • 1.0 g of anhydrous magnesium sulfate was added, and the mixture was further stirred with heating under reflux for 4 hours. After stirring, the mixture was filtered, and the resulting solution was concentrated with an evaporator.
  • the organic layer was washed twice with 20 ml of water, twice with 20 mL of a 3 wt% aqueous acetic acid solution and twice with 20 mL of water, and the resulting solution was poured into methanol to precipitate the polymer. It was.
  • the polymer was filtered and dried, and the resulting polymer was dissolved again in 20 mL of o-dichlorobenzene, passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate the polymer.
  • the polymer was filtered and then dried to obtain 63 mg of a purified polymer (polymer compound D).
  • Example 1 Comparative Example 1 (Measurement of absorbance of organic thin film) An organic thin film was prepared in the same manner as in Example 4 except that the high molecular compound B was used instead of the high molecular compound A, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. The absorbance at 600 nm is shown in Table 1.
  • Example 8 Measurement of absorbance of organic thin film An organic thin film was prepared in the same manner as in Example 4 except that the high molecular compound C was used instead of the high molecular compound A, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. The absorbance at 600 nm is shown in Table 1.
  • Example 9 Measurement of absorbance of organic thin film
  • An organic thin film was prepared in the same manner as in Example 4 except that the high molecular compound D was used instead of the high molecular compound A, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. The absorbance at 600 nm is shown in Table 1.
  • Example 10 Production and Evaluation of Organic Thin Film Solar Cell
  • a weight ratio of C60PCBM (phenyl C61-butyric acid methyl ester, product name: E100), which is an electron-accepting compound, and polymer compound A, which is an electron-donating compound, is 3: 1. And dissolved in o-dichlorobenzene so that the concentration of the mixture was 2% by weight.
  • the obtained solution was filtered through a Teflon (registered trademark) filter having a pore size of 1.0 ⁇ m to prepare a coating solution 1.
  • a glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment.
  • the coating solution 1 was applied onto the ITO film by spin coating to obtain a functional layer of an organic thin film solar cell.
  • the film thickness of the functional layer was 100 nm.
  • lithium fluoride was vapor-deposited with a film thickness of 4 nm by a vacuum vapor deposition machine, and then aluminum was vapor-deposited with a film thickness of 100 nm to produce an organic thin film solar cell.
  • the degree of vacuum at the time of vapor deposition was 1 to 9 ⁇ 10 ⁇ 3 Pa in all cases.
  • the shape of the organic thin film solar cell thus obtained was a square of 2 mm ⁇ 2 mm.
  • Jsc (short-circuit current density) of the obtained organic thin-film solar cell was irradiated with a constant light using a solar simulator (trade name OTENTO-SUN II: AM1.5G filter, irradiance 100 mW / cm 2 , manufactured by Spectrometer Co., Ltd.). Measured. Moreover, the electric current and voltage which generate
  • Example 11 (Production and Evaluation of Organic Thin Film Solar Cell) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 10 except that the polymer compound C was used instead of the polymer compound A. The obtained photoelectric conversion efficiency was 2.28%, and FF was 0.64.
  • Example 12 (Production and Evaluation of Organic Thin Film Solar Cell) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 10 except that the polymer compound D was used instead of the polymer compound A. The obtained photoelectric conversion efficiency was 1.05%, and FF was 0.62.
  • the polymer compound of the present invention has a large absorbance for light having a long wavelength and can be used for an organic photoelectric conversion device.

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Abstract

La présente invention concerne un composé polymère qui contient des motifs répétés représentés par la formule (1), a une absorbance élevée de lumière à des longueurs d'onde élevées, et peut être utilisé dans un élément de conversion photoélectrique organique. (Dans la formule, T représente un atome d'hydrogène, un atome de fluor, un groupe alkyle facultativement substitué par un atome de fluor, ou un groupe carbocyclique aromatique. m représente un entier de 2 à 10. La pluralité de T peuvent être identiques ou différents. R représente un groupe alkyle facultativement substitué par un atome de fluor, un groupe alcoxy facultativement substitué par un atome de fluor, ou un groupe carbocyclique aromatique. Les deux R peuvent être identiques ou différents.)
PCT/JP2011/058478 2010-05-06 2011-03-28 Composé de polymère et élément de conversion photoélectrique organique utilisant celui-ci WO2011138885A1 (fr)

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WO2015016626A1 (fr) * 2013-07-31 2015-02-05 주식회사 엘지화학 Copolymère et cellule solaire organique comprenant ledit copolymère

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