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WO2012111782A1 - Procédé de fabrication d'un élément de conversion photoélectrique organique - Google Patents

Procédé de fabrication d'un élément de conversion photoélectrique organique Download PDF

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WO2012111782A1
WO2012111782A1 PCT/JP2012/053733 JP2012053733W WO2012111782A1 WO 2012111782 A1 WO2012111782 A1 WO 2012111782A1 JP 2012053733 W JP2012053733 W JP 2012053733W WO 2012111782 A1 WO2012111782 A1 WO 2012111782A1
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atom
polymer compound
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photoelectric conversion
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岳仁 加藤
吉村　研
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing an organic photoelectric conversion element.
  • the organic photoelectric conversion element has advantages such as that the number of organic layers in the element can be reduced and the organic layer can be manufactured by a printing method, and can be manufactured easily and inexpensively compared to an inorganic photoelectric conversion element. it can.
  • inferior photoelectric conversion efficiency of the organic photoelectric conversion element has hindered practical use.
  • JP 2009-158734 A describes that an organic photoelectric conversion element is manufactured by forming an active layer using a liquid containing a polymer compound P3HT and o-dichlorobenzene.
  • the organic photoelectric conversion element obtained by this method does not have sufficient photoelectric conversion efficiency.
  • the present invention provides an organic photoelectric conversion element having high photoelectric conversion efficiency. That is, the present invention relates to a method for producing an organic photoelectric conversion device comprising a pair of electrodes and an active layer containing a polymer compound between the pair of electrodes, the active layer comprising a polymer compound and a fluorine-containing solvent. The manufacturing method of the organic photoelectric conversion element formed from the liquid containing this is provided.
  • FIG. 1 is a diagram showing an example of a layer configuration of an organic photoelectric conversion element in the production method of the present invention.
  • FIG. 2 is a diagram showing another example of the layer configuration of the organic photoelectric conversion element in the production method of the present invention.
  • FIG. 3 is a diagram showing another example of the layer configuration of the organic photoelectric conversion element in the production method of the present invention.
  • 10 represents an organic photoelectric conversion element
  • 20 represents a substrate
  • 32 represents a first electrode
  • 34 represents a second electrode.
  • Reference numeral 40 denotes an active layer
  • 42 denotes a first active layer
  • 44 denotes a second active layer
  • 52 denotes a first intermediate layer
  • 54 denotes a second intermediate layer.
  • each member in the drawings shown in the following description may be different from the actual scale.
  • members, such as an electrode lead wire, also exist in an organic photoelectric conversion element description and illustration are abbreviate
  • one of the substrate thickness directions may be referred to as “upper” or “upper”, and the other of the substrate thickness directions may be referred to as “lower” or “lower”.
  • This vertical relation is set for convenience of explanation, and is not necessarily applied to the process and the situation where the organic photoelectric conversion element is actually manufactured.
  • the basic structure of the organic photoelectric conversion element according to the present invention is a structure having a pair of electrodes and an active layer.
  • At least one of the pair of electrodes is usually transparent or translucent.
  • the anode is usually a transparent or translucent electrode.
  • the organic photoelectric conversion element may have an opaque electrode.
  • the opaque electrode is usually a cathode.
  • the position of the active layer in the organic photoelectric conversion element is between the pair of electrodes.
  • the active layer may be a single layer or a plurality of layers. A layer other than the active layer may be provided between the pair of electrodes, and this layer may be referred to as an intermediate layer in this specification.
  • the active layer contains one or more organic compounds. At least one organic compound is a polymer compound.
  • the organic compound examples include an electron donating compound (p-type semiconductor) and an electron accepting compound (n-type semiconductor).
  • the active layer may be a single layer or a laminate in which a plurality of layers are stacked.
  • the active layer is of a so-called pn heterojunction type in which a layer formed of an electron donating compound (electron donating layer) and a layer formed of an electron accepting compound (electron accepting layer) are superimposed.
  • Examples include a bulk heterojunction type in which a bulk heterojunction structure is formed by mixing a form, an electron donating compound and an electron accepting compound.
  • the active layer in the present invention may be in any form.
  • the active layer is formed from a liquid containing a polymer compound and a fluorine-containing solvent.
  • the active layer is preferably formed by applying a liquid containing a polymer compound and a fluorine-containing solvent on one electrode.
  • a stacked body in which an active layer 40 is sandwiched between a first electrode 32 and a second electrode 34 is mounted on the substrate 20 to constitute the organic photoelectric conversion element 10.
  • the substrate 20 is transparent or translucent.
  • At least one of the first electrode 32 and the second electrode 34 is transparent or translucent.
  • the first electrode 32 is transparent or translucent.
  • Which of the first electrode 32 and the second electrode 34 is an anode and which is a cathode is not particularly limited.
  • the organic photoelectric conversion element 10 when the organic photoelectric conversion element 10 is manufactured by sequentially laminating from the substrate 20 side, it is preferable that the vapor deposition is performed in a later process when the vapor deposition method is used for film formation of the cathode (for example, aluminum).
  • the cathode for example, aluminum
  • the first electrode 32 is an anode and the second electrode 34 is a cathode.
  • the substrate 20 and the first electrode 32 are formed to be transparent or translucent so that the light can be taken from the substrate 20 side. In the example of FIG.
  • the active layer 40 is composed of two layers, a first active layer 42 and a second active layer 44, and is a pn heterojunction type active layer.
  • One of the first active layer 42 and the second active layer 44 is an electron accepting layer, and the other layer is an electron donating layer.
  • a first intermediate layer 52 and a second intermediate layer 54 are provided.
  • the first intermediate layer 52 is located between the active layer 40 and the first electrode 32
  • the second intermediate layer 54 is located between the active layer 40 and the second electrode 34. Only one of the first intermediate layer 52 and the second intermediate layer 54 may be provided.
  • each intermediate layer is depicted as a single layer, but each intermediate layer may be composed of a plurality of layers.
  • the intermediate layer may have various functions.
  • the first intermediate layer 52 may be, for example, a hole transport layer, an electron blocking layer, a hole injection layer, and a layer having other functions.
  • the second electrode 34 is a cathode
  • the second intermediate layer 54 can be, for example, an electron transport layer, an electron block layer, and a layer having other functions.
  • the positions of the intermediate layers are also changed accordingly.
  • the polymer compound which is an electron donating compound or an electron accepting compound contained in the active layer is not particularly limited, and is determined relatively from the energy level of the energy level of these compounds.
  • polymer compound examples include the cyclic structures shown below. And polymer compounds containing structures such as methylcyclobutane, 4-ethylcyclohexane, xylene, styrene, ethylbenzene, thiophene, imidazole, thiazole, pyrrole, and oxazole.
  • ethyleneimine ethylene oxide, ethylene sulfide, acetylene oxide, acetylene sulfide, azacyclobutane 1,3-propylene oxide, trimethylene sulfide, oxetium ion, thietium ion, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyrrole, furan, thiophene, piperidine , Tetrahydropyran, tetrahydrothiopyran, thiapyran, hexamethyleneimine, hexamethylene oxide, hexamethylene sulfide, azatropyridene, oxycycloheptatriene, thiotropyridene, and the like.
  • Examples of the polymer compound contained in the active layer include a polymer compound having a structural unit represented by the formula (1).
  • Ar 1 And Ar 2 are the same or different and each represents a trivalent aromatic group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 And R 8 are the same or different, hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, Amide group, imide group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, aryl An alkenyl group, an arylalkynyl group, a carboxyl group or a cyano group is represented.
  • n 1 or 2. When n is 2, two Z may be the same or different.
  • the polymer compound having the structural unit represented by the formula (1) may be a polymer compound further including any one of the structural units of the following formulas (2-1) to (2-10).
  • R 21 ⁇ R 42 Each independently represents a hydrogen atom or a substituent.
  • X 21 ⁇ X 30 Each independently represents a sulfur atom, an oxygen atom or a selenium atom.
  • R 21 ⁇ R 42 As the substituent represented by, for example, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, Aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, acyl group, acyloxy group, Examples thereof include an amide group, a heterocyclic group, a carboxy group optionally having a substituent, a nitro group, and a cyano group.
  • R 21 , R 22 And R 35 Is preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent and an alkylthio group which may have a substituent, and an alkyl which may have a substituent.
  • An alkoxy group which may have a group and a substituent is more preferable, and an alkyl group which may have a substituent is more preferable.
  • R 21 , R 22 , R 35 , R 39 And R 42 Is preferably a branched alkyl group.
  • R 23 , R 24 , R 27 , R 28 , R 31 , R 32 , R 33 , R 34 , R 37 , R 38 , R 40 And R 41 Is preferably a halogen atom or a hydrogen atom, more preferably a fluorine atom or a hydrogen atom, and even more preferably a hydrogen atom.
  • R 25 , R 26 , R 29 And R 30 Is preferably a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group or an arylalkyl group, more preferably a hydrogen atom or an arylalkyl group.
  • R 36 Is preferably a hydrogen atom, a halogen atom, an acyl group or an acyloxy group, more preferably an acyl group or an acyloxy group.
  • X 21 ⁇ X 30 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, but from the viewpoint of increasing the short circuit continuous density of the photoelectric conversion element in the present invention, a sulfur atom and an oxygen atom are preferable, and a sulfur atom is more preferable.
  • the polymer compound is represented by formula (2-1), formula (2-2), formula (2-3), or formula (2-10).
  • the polymer compound having the structural unit represented by the formula (1) may be a polymer compound further including a structural unit represented by the formula (2).
  • R 43 , R 44 And R 45 Are the same or different and each represents a hydrogen atom or a substituent.
  • W 1 And W 2 Are the same or different and each represents a cyano group, a monovalent organic group having a fluorine atom, a halogen atom or a hydrogen atom.
  • Examples of the monovalent organic group having a fluorine atom represented by the formula include a fluorinated aryl group, a fluorinated alkyl group, a fluorinated alkylthio group, a fluorinated sulfonyl group, and a fluorinated acetyl group.
  • Examples of the fluorinated alkyl group include a fluoromethyl group.
  • Examples of the fluorinated aryl group include a fluorophenyl group.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • W 1 And W 2 Is preferably a fluorine atom.
  • Y 1 Is preferably a sulfur atom or an oxygen atom.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • the alkyl group may be linear, branched or cyclic. The alkyl group usually has 1 to 30 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, n-pentyl group, isopentyl group, 2- Methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3, 7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, eicosyl group and other chain alkyl groups
  • the alkoxy group may be linear, branched or cyclic.
  • the carbon number of the alkoxy group is usually 1-20.
  • Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group Group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, and lauryloxy group.
  • substituted alkoxy group examples include trifluoromethoxy group and pentafluoroethoxy group.
  • Fluorinated alkoxy groups having 1 to 20 carbon atoms such as perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group and 2-methoxyethyloxy group.
  • the alkylthio group may be linear or branched, and may be a cycloalkylthio group.
  • Carbon number of the alkylthio group is usually 1 to 20, and specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, Examples include a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.
  • the aryl group usually has 6 to 60 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a C1 to C12 alkoxyphenyl group (C1 to C12 alkyl represents an alkyl having 1 to 12 carbon atoms, and the C1 to C12 alkyl is preferably a C1 to C8 alkyl. More preferably, C1 to C6 alkyl, C1 to C8 alkyl represents alkyl having 1 to 8 carbon atoms, and C1 to C6 alkyl represents alkyl having 1 to 6 carbon atoms.
  • C1 to C12 alkyl, C1 to C8 alkyl and C1 to C6 alkyl include those described and exemplified for the above alkyl group, the same applies to the following), C1 to C12 alkylphenyl group, 1- Examples thereof include a naphthyl group, a 2-naphthyl group, and a pentafluorophenyl group.
  • the aryloxy group usually has 6 to 60 carbon atoms.
  • the aryloxy group examples include a phenoxy group, a C1-C12 alkoxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenoxy group.
  • the arylthio group usually has 6 to 60 carbon atoms.
  • Specific examples of the arylthio group include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.
  • the substituted arylthio group include And pentafluorophenylthio group.
  • the arylalkyl group usually has 7 to 60 carbon atoms.
  • Specific examples of the arylalkyl group include phenyl-C1-C12 alkyl group, C1-C12 alkoxyphenyl-C1-C12 alkyl group, C1-C12 alkylphenyl-C1-C12 alkyl group, and 1-naphthyl-C1-C12 alkyl group. 2-naphthyl-C1-C12 alkyl group.
  • the arylalkoxy group usually has 7 to 60 carbon atoms.
  • the arylalkoxy group examples include a phenyl-C1-C12 alkoxy group, a C1-C12 alkyloxyphenyl-C1-C12 alkoxy group, a C1-C12 alkylphenyl-C1-C12 alkoxy group, and a 1-naphthyl-C1-C12 alkoxy group. And a 2-naphthyl-C1-C12 alkoxy group.
  • the arylalkylthio group usually has 7 to 60 carbon atoms.
  • the arylalkylthio group examples include a phenyl-C1-C12 alkylthio group, a C1-C12 alkyloxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, and a 1-naphthyl-C1-C12 alkylthio group.
  • the acyl group usually has 2 to 20 carbon atoms.
  • the acyl group examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.
  • the acyloxy group usually has 2 to 20 carbon atoms.
  • acyloxy group examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.
  • the amide group usually has 1 to 20 carbon atoms.
  • An amide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid amide.
  • an imide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid imide.
  • the imide group include succinimide group and phthalimide group.
  • the substituted amino group usually has 1 to 40 carbon atoms.
  • the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino
  • examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, and tri-p-xylylsilyl group.
  • examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, Examples thereof include a tri-p-xylylsilyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.
  • examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, triisopropylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, Examples thereof include a tri-p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.
  • examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, Tri-p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group , Di (tri-n-propylsilyl) amino group, di (triisopropylsilyl) amino group, di (tert-butyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p-
  • the monovalent heterocyclic group includes furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, Thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene , Chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimi
  • the heterocyclic oxy group examples include a group represented by the formula (4) in which an oxygen atom is bonded to the monovalent heterocyclic group.
  • the heterocyclic thio group examples include a group represented by the formula (5) in which a sulfur atom is bonded to the monovalent heterocyclic group.
  • Ar 7 Represents a monovalent heterocyclic group.
  • the heterocyclic oxy group usually has 2 to 60 carbon atoms.
  • heterocyclic oxy group examples include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group.
  • examples include a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.
  • the heterocyclic thio group usually has 2 to 60 carbon atoms.
  • heterocyclic thio group examples include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.
  • the arylalkenyl group usually has 8 to 20 carbon atoms, and specific examples of the arylalkenyl group include a styryl group.
  • an arylalkynyl group usually has 8 to 20 carbon atoms, and specific examples of the arylalkynyl group include a phenylacetylenyl group.
  • a structural unit represented by Formula (2) a structural unit represented by Formula (2-11) and a structural unit represented by Formula (2-12) are preferable.
  • the polymer compound of the present invention may further contain a structural unit represented by the formula (2 ′) in addition to the structural unit represented by the formula (1).
  • Ar 3 Represents an arylene group different from the structural unit represented by Formula (1) or a heteroarylene group different from the structural unit represented by Formula (1).
  • the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, and a fluorenediyl group.
  • the heteroarylene group include a flangyl group, a pyrrole diyl group, and a pyridinediyl group.
  • a preferred embodiment of the structural unit represented by the formula (1) is a group represented by the formula (3).
  • Ar 11 And Ar 21 Are the same or different and each represents a trivalent heterocyclic group.
  • R 4 , R 5 , R 6 , R 7 , R 8 And R 9 are the same or different, hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, Amide group, imide group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, aryl An alkenyl group, an arylalkynyl group, a carboxyl group or a cyano group is represented.
  • R 50 And R 51 are the same or different and are a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide Group, imide group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl Represents a group, an arylalkynyl group, a carboxyl group or a cyano group.
  • Ar 11 And Ar 21 are the same or different and each represents a trivalent heterocyclic group.
  • a trivalent heterocyclic group refers to the remaining atomic group obtained by removing three hydrogen atoms from a heterocyclic compound.
  • a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Refers to a compound.
  • R ′ is the same or different and is a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl.
  • An alkoxy group, an arylalkylthio group, a substituted amino group, an acyloxy group, an amide group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group, or a cyano group is represented.
  • R ′′ is the same or different and represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.
  • Ar 11 And Ar 21 Is preferably a group obtained by removing three hydrogen atoms from a thiophene ring, and more preferably a group obtained by removing three hydrogen atoms from a thiophene ring.
  • the trivalent heterocyclic group is preferably a heterocyclic group containing a sulfur atom, more preferably a group represented by the formula (268) or the formula (273). And more preferably a group represented by the formula (273).
  • R 50 And R 51 are preferably the same or different, and are an alkyl group having 6 or more carbon atoms, an alkoxy group having 6 or more carbon atoms, an alkylthio group having 6 or more carbon atoms, an aryl group having 6 or more carbon atoms, or an aryl having 6 or more carbon atoms Oxy group, arylthio group having 6 or more carbon atoms, arylalkyl group having 7 or more carbon atoms, arylalkoxy group having 7 or more carbon atoms, arylalkylthio group having 7 or more carbon atoms, acyl group having 6 or more carbon atoms, or 6 or more carbon atoms More preferably an alkyl group having 6 or more carbon atoms, an alkoxy group having 6 or more carbon atoms, an aryl group having 6 or more carbon atoms, or an aryloxy group having 6 or more carbon atoms, particularly preferably 6 carbon atoms.
  • polymer compound having the structural unit represented by the formula (1) polymer compound A is exemplified.
  • the high molecular compound A has the following repeating unit.
  • n represents the number of repeating units.
  • the polymer compound containing the structural unit represented by the formula (1) may be contained in the active layer as an electron donating compound or may be contained in the active layer as an electron accepting compound. It is preferable that it is contained in the active layer as a functional compound.
  • the electron-donating compound in addition to the polymer compound containing the structural unit represented by the formula (1), for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinyl Carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amine residues in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythieny Examples include lenvylene and derivatives thereof.
  • oligothiophene and derivatives thereof, and a polymer compound containing the structural unit represented by the formula (1) are preferable, and poly (3-hexylthiophene) (P3HT) is preferable.
  • the polymer compound which has a structural unit represented by Formula (2-1) to (2-10) from a viewpoint of improving a photoelectric conversion efficiency is preferable.
  • the electron donating compound may be used alone in the active layer, or two or more types may be used in combination in the active layer.
  • 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 derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, C 60 And the like, and phenanthrene derivatives such as bathocuproine, metal oxides such as titanium oxide, and carbon nanotubes.
  • oxadiazole derivatives anthraquinodimethane and its derivatives
  • benzoquinone and its derivatives naphthoquinone and its derivatives
  • anthraquinone and its derivatives
  • fullerene derivatives As the electron-accepting compound, titanium oxide, carbon nanotubes, fullerenes, and fullerene derivatives are preferable, and fullerenes and fullerene derivatives are particularly preferable.
  • the fullerene derivative represents a compound in which at least a part of fullerene is modified. Examples of fullerenes include C60 fullerene, C70 fullerene, C76 fullerene, C78 fullerene, C84 fullerene and the like. Examples of the fullerene derivative include a compound represented by the formula (6), a compound represented by the formula (7), a compound represented by the formula (8), and a compound represented by the formula (9).
  • R a Is a group having an alkyl group, an aryl group, a heteroaryl group or an ester structure. Multiple R a May be the same or different.
  • R b Represents an alkyl group or an aryl group. Multiple R b May be the same or different.
  • R a Examples of the group having an ester structure represented by the formula (10) include a group represented by the formula (10). (Wherein u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, R c Represents an alkyl group, an aryl group or a heteroaryl group.
  • heteroaryl group examples include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
  • fullerenes and fullerene derivatives are C 60 , C 70 , C 76 , C 78 , C 84 And derivatives thereof.
  • C 60 Fullerene derivative, C 70 Examples of fullerene derivatives include the following compounds.
  • fullerene derivatives include [5,6] -phenyl C61 butyric acid methyl ester ([5,6] -PCBM), [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6).
  • the amount of the fullerene derivative in the active layer is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the electron donating compound, and 20 to 500 parts. More preferred are parts by weight.
  • the electron-accepting compound one kind of compound may be used for the active layer, or two or more kinds of compounds may be used in combination for the active layer.
  • the active layer of the organic photoelectric conversion element is formed from a liquid containing a polymer compound and a fluorine-containing solvent. In the liquid, a solvent containing no fluorine atom may be mixed.
  • the fluorine-containing solvent may be a solvent containing a fluorine atom in the molecule, and a solvent having two or more fluorine atoms in one molecule is preferable.
  • the fluorine-containing solvent preferably has 5 or more fluorine atoms, more preferably 7 or more, and particularly preferably 9 or more fluorine atoms.
  • fluorine-containing solvent for example, CF 3 CF 2 CHCl 2 , CClF 2 CF 2 CHClF, CF 3 CH 2 OCF 2 CHF 2 , C 3 F 7 OCH 3 , C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , C 2 F 5 CF (OCH 3 ) C 3 F 7 , C 3 HF 6 -CH (CH 3 ) O-C 3 HF 6 Is mentioned.
  • Asahi Clin AK-225 * (CF manufactured by Asahi Glass Co., Ltd.) 3 CF 2 CHCl 2 / CCIF 2 CF 2 CHClF), Asahiklin AK-225AES, Asahiklin AE-3000 (CF 3 CH 2 OCF 2 CHF 2 ), AE-3100E, Sumitomo 3M Novec7000 (C 3 F 7 OCH 3 ), Novec7100 (C 4 F 9 OCH 3 ), Novec7200 (C 4 F 9 OC 2 H 5 ), Novec7300 (C 2 F 5 CF (OCH 3 ) C 3 F 7 ), Novec7600 (C 3 HF 6 -CH (CH 3 ) O-C 3 HF 6 ) Can also be used.
  • a fluorine-containing solvent and a solvent not containing a fluorine atom can be mixed and used.
  • the solvent containing no fluorine atom is appropriately selected depending on the kind of the electron donating compound and the electron accepting compound, and examples thereof include water and organic solvents.
  • organic solvent examples include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, 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, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, tetrahydrofuran And ether solvents such as tetrahydropyran.
  • unsaturated hydrocarbon solvents such as toluene, xylene,
  • halogenated unsaturated hydrocarbon solvents are preferred, dichlorobenzene is more preferred, and orthodichlorobenzene is more preferred.
  • the amount of the fluorinated solvent in the liquid containing the polymer compound and the fluorinated solvent is usually 99.9 wt (wt)% to 0.001 wt%, preferably 50 wt% to 0.01%. More preferably, it is 30 wt% to 0.05 wt%, and particularly preferably 15 wt% to 0.1 wt%.
  • the amount of the polymer compound in the liquid containing the polymer compound and the fluorine-containing solvent is not particularly limited and can be appropriately selected within an optimal range, and is usually 0.1 wt% or more and 10 wt% or less, Preferably they are 0.3 weight% or more and 5 weight% or less, More preferably, they are 0.5 weight% or more and 3 weight% or less.
  • the amount of the electron-donating compound and the amount of the electron-accepting compound in the liquid contains an electron-accepting compound and an electron-donating compound that is a polymer compound
  • the amount of the electron-donating compound and the amount of the electron-accepting compound in the liquid is usually 0.2 wt% or more and 20 wt% or less, preferably 0.5 wt% or more and 10 wt% or less, more preferably 1 wt% or more and 5 wt% or less.
  • the compounding ratio of the electron donating compound and the electron accepting compound is usually 1 to 20:20 to 1, preferably 1 to 10:10 to 1, and more preferably 1 to 5: 5 to 1. It is.
  • the electron donating compound or the electron accepting compound is usually 0.4% by weight or more, preferably 0.6% by weight. More preferably, 2% by weight or more is added.
  • the liquid containing the polymer compound and the fluorine-containing solvent is preferably a liquid containing the polymer compound containing the structural unit represented by the formula (1) and the fluorine-containing solvent.
  • One aspect of the method for producing an organic photoelectric conversion element of the present invention is a method for producing an organic photoelectric conversion element having an active layer between a pair of electrodes and a pair of electrodes, It is a manufacturing method including a step of applying a liquid containing a molecular compound and a fluorine-containing solvent to form an active layer, and a step of forming the other electrode on the active layer.
  • Application methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, gravure printing, flexographic printing. Examples thereof include a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, and a capillary coating method.
  • the spin coating method flexographic printing method, gravure printing method, ink jet printing method, and dispenser printing method are preferable, and the spin coating method is more preferable.
  • An active layer can be formed by applying a later solution on the electrode and volatilizing the solvent.
  • an organic photoelectric conversion element having an active layer of pn heterojunction is manufactured, for example, a solution containing an electron donating compound and a solution containing an electron accepting compound are mixed at least twice with different frequencies.
  • a solution containing the electron-donating compound after treatment is applied onto the electrode, and the solvent is volatilized to form an electron-donating layer.
  • a solution containing the electron-accepting compound after the treatment is applied on the electron-donating layer, and the solvent is volatilized to form an electron-accepting layer.
  • 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 still more preferably 20 nm to 200 nm.
  • the substrate may be any substrate that does not chemically change when the electrode is formed and the organic layer is formed.
  • the material for the substrate include glass, plastic, polymer film, and silicon.
  • the opposite electrode that is, the electrode farther from the substrate of the pair of electrodes
  • the electrode material constituting the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, it is manufactured 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.
  • a film made of a conductive material made of ITO, indium / zinc / oxide, tin oxide or the like is preferable, and a metal thin film such as gold, platinum, silver, or copper is used.
  • the electrode manufacturing method 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.
  • the electrode paired with the transparent or translucent electrode may be transparent or translucent, but may be transparent or not translucent.
  • a metal, a conductive polymer, or the like can be used as an electrode material constituting the electrode.
  • the electrode material include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like.
  • 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.
  • alkali metal or alkaline earth metal halide or oxide such as lithium fluoride (LiF)
  • inorganic semiconductor fine particles such as titanium oxide, metal alkoxide, PEDOT (poly (3,4) ethylene) Dioxythiophene) is exemplified.
  • the intermediate layer on the anode side is preferably a layer made of PEDOT.
  • the intermediate layer on the cathode side is a layer made of alkali metal halide (more preferably LiF), a titania thin film layer made of titanium isopropoxide is preferred, a layer made of lithium fluoride (LiF), titanium isopropoxide
  • a thin film layer of titania formed from is more preferable.
  • the organic photoelectric conversion element manufactured by the manufacturing method of the present invention is operated as an organic thin film solar cell by generating a photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. be able to. 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 thin film solar cell can basically have the same module structure as a conventional solar cell module.
  • the solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light 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.
  • the module structure of the organic thin film solar cell of the present invention 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 treated with antireflection, and adjacent cells are connected by metal leads or flexible wiring.
  • the current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside.
  • Various types of 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 protective 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 a sealing material is hermetically sealed between the support substrate and the frame.
  • 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.
  • a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 may be used.
  • a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.
  • Synthesis example 1 (Synthesis of Compound 1) A 1000 mL four-necked flask in which the gas in the flask was replaced with argon was charged with 13.0 g (80.0 mmol) of 3-bromothiophene and 80 mL of diethyl ether to obtain a uniform solution. While maintaining the solution at ⁇ 78 ° C., 31 mL (80.6 mmol) of 2.6M n-butyllithium (n-BuLi) in hexane was added dropwise. After reacting at ⁇ 78 ° C.
  • reaction solution was cooled to ⁇ 25 ° C., and a solution in which 60 g (236 mmol) of iodine was dissolved in 1000 mL of diethyl ether was added dropwise over 30 minutes. After dropping, the mixture was stirred at room temperature (25 ° C.) for 2 hours, and 50 mL of 1N aqueous sodium thiosulfate solution was added to stop the reaction. After extracting the reaction product with diethyl ether, the reaction product was dried with magnesium sulfate, filtered, and the filtrate was concentrated to obtain 35 g of a crude product. The crude product was purified by recrystallization using chloroform to obtain 28 g of Compound 1.
  • NBS N-bromosuccinimide
  • the flask was kept at 0 ° C., and 2.31 g (1.30 mmol) of N-bromosuccinimide (hereinafter sometimes referred to as NBS) was added over 15 minutes. Then, it stirred at 0 degreeC for 2 hours, the depositing solid was filtered and collect
  • NBS N-bromosuccinimide
  • the filtrate was concentrated to recover the precipitated solid.
  • the obtained solid is referred to as crude product 4-B.
  • the crude product 4-A and the crude product 4-B were combined and purified by silica gel column chromatography where the developing solvent was chloroform to obtain 17.3 g of compound 4. The operation so far was performed several times.
  • Synthesis of Compound 5 A homogeneous solution was prepared by adding 25.0 g (71.4 mmol) of Compound 4, 250 mL of chloroform, and 160 mL of trifluoroacetic acid to a 1000 mL four-necked flask equipped with a mechanical stirrer and replacing the gas in the flask with argon. .
  • the reaction solution was warmed to room temperature (25 ° C.), 1000 mL of THF was distilled off with an evaporator, and 100 mL of acetic acid was added.
  • the reactive organism was extracted with chloroform, and then the chloroform solution was dried over sodium sulfate. After the chloroform solution was filtered, the solvent of the filtrate was distilled off with an evaporator. The obtained solid was washed with hexane and dried under reduced pressure to obtain 10.9 g of Compound 6.
  • the solution was kept at ⁇ 78 ° C., and 4.37 mL (11.4 mmol) of a 2.6M n-butyllithium hexane solution was added dropwise to the solution over 10 minutes. After the addition, the reaction solution was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 2 hours. Thereafter, the flask was cooled to ⁇ 78 ° C., and 4.07 g (12.5 mmol) of tributyltin chloride was added. After the addition, the mixture was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 3 hours.
  • Synthesis example 2 (Synthesis of Compound 10) In a 500 ml flask, 10.5 g (70.8 mmol) of 4,5-difluoro-1,2-diaminobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 mL of pyridine were added to obtain a homogeneous solution. While maintaining the flask at 0 ° C., 16.0 g (134 mmol) of thionyl chloride was dropped into the flask. After dropping, the flask was warmed to 25 ° C. and reacted for 6 hours. Thereafter, 250 ml of water was added, and the reaction product was extracted with chloroform.
  • the obtained solution was poured into 300 mL of 5 wt% aqueous sodium sulfite solution and stirred for 1 hour.
  • the organic layer of the obtained mixture was separated with a separatory funnel, and the aqueous layer was extracted with chloroform three times.
  • the obtained extract was combined with the organic layer separated earlier and dried over sodium sulfate. After filtration, the filtrate was concentrated with an evaporator and the solvent was distilled off.
  • the obtained yellow solid was dissolved in 90 mL of methanol heated to 55 ° C., and then cooled to 25 ° C. The precipitated crystals were collected by filtration and then dried under reduced pressure at room temperature (25 ° C.) to obtain 1.50 g of compound 11.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours each using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 100 mL of toluene, 2 g of sodium diethyldithiocarbamate and 40 mL of water were added, and the mixture was stirred under reflux for 8 hours. After removing the aqueous layer, the organic layer is washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water and then with 5% fluoride.
  • polymer compound A This was washed twice with 50 mL of an aqueous potassium chloride solution and then twice with 50 mL of water, and the resulting solution was poured into methanol to precipitate a polymer.
  • the polymer was filtered and dried, and the obtained polymer was dissolved again in 50 mL of o-dichlorobenzene and passed through an alumina / silica gel column.
  • the obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 185 mg of a purified polymer.
  • this polymer is referred to as polymer compound A.
  • the high molecular compound A has the following repeating unit. In the formula, n represents the number of repeating units.
  • Example 1 preparation of an organic photoelectric conversion element
  • a glass substrate on which ITO with a thickness of about 150 nm formed by sputtering was patterned was washed with an organic solvent, an alkaline detergent, and ultrapure water, and dried.
  • the glass substrate was subjected to ultraviolet ozone (UV-O 3 ) treatment using an ultraviolet ozone (UV-O 3 ) apparatus.
  • a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid dissolved in water (HC Starck B-Tech, Bytron P TP AI 4083) was filtered through a filter having a pore size of 0.5 ⁇ m.
  • the suspension after filtration was spin-coated on the ITO side of the substrate to form a film with a thickness of 70 nm. Subsequently, it was dried on the hot plate at 200 ° C. for 10 minutes in the air to form an organic layer.
  • a mixed solution was prepared by mixing orthodichlorobenzene and hydrofluoroether which is a fluorine-containing solvent (manufactured by Sumitomo 3M, ⁇ Novec> HFE7200) at a weight ratio of 99.4: 0.6.
  • polymer compound A and [6,6] -phenyl C71-butyric acid methyl ester were added to the mixed solution so that the weight ratio was 1: 2.
  • a coating solvent was prepared.
  • the polymer compound A was added so that the amount added was 0.5% by weight with respect to the weight of the mixed solvent.
  • the polymer compound A had a polystyrene equivalent weight average molecular weight of 29000 and a polystyrene equivalent number average molecular weight of 14,000.
  • the light absorption edge wavelength of the polymer compound A was 890 nm.
  • a stirrer chip was introduced into the coating solution, and stirring and mixing were performed at a rotation speed of 300 rpm to 1000 rpm.
  • the stirring and mixing was performed on a hot stirrer with a temperature variable function, and the set temperature was set to 70 ° C.
  • the coating solution was filtered with a filter having a pore size of 0.5 ⁇ m, and the obtained filtrate was spin-coated on the organic layer, followed by drying in a nitrogen atmosphere to form an active layer.
  • 97% of Titanium (IV) isopropoxide purchased from SIGMAS ALDRICH was mixed with isopropanol to a concentration of 1 wt (wt), and the resulting solution was spin-coated on the active layer to a thickness of 10 nm.
  • Comparative Example 1 (Production of organic photoelectric conversion element) An organic photoelectric conversion device was produced in the same manner as in Example 1 except that orthodichlorobenzene was used as a coating solvent in place of the mixed solution of orthodichlorobenzene and hydrofluoroether.
  • the shape of the organic thin film solar cell which is the organic photoelectric conversion element obtained in Example 1 and Comparative Example 1 was a square of 2 mm ⁇ 2 mm. These organic thin film solar cells are irradiated with a certain amount of light using a solar simulator (trade name: CEP-2000, manufactured by Spectrometer Co., Ltd., irradiance: 100 mW / cm 2 ), and the generated current and voltage are measured. Conversion efficiency was calculated. The results are shown in Table 1.
  • an organic photoelectric conversion element having excellent photoelectric conversion efficiency can be produced.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un élément de conversion photoélectrique organique équipé d'une paire d'électrodes et d'une couche active comportant un composé polymère entre la paire d'électrodes, la couche active étant formée à partir d'une solution comprenant le composé polymère et un solvant contenant du fluor. Un élément de conversion photoélectrique organique affichant un excellent rendement de conversion photoélectrique peut ainsi être fabriqué.
PCT/JP2012/053733 2011-02-14 2012-02-10 Procédé de fabrication d'un élément de conversion photoélectrique organique Ceased WO2012111782A1 (fr)

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JP2011028260 2011-02-14

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US9876184B2 (en) 2013-08-28 2018-01-23 Taiwan Semiconductor Manufacturing Company, Ltd. Organic photosensitive device with an electron-blocking and hole-transport layer

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WO2009063850A1 (fr) * 2007-11-12 2009-05-22 Konica Minolta Holdings, Inc. Procédé de fabrication d'élément électronique organique
WO2009113450A1 (fr) * 2008-03-12 2009-09-17 東レ株式会社 Dispositif photovoltaïque, matériau en couche active, et procédé de fabrication du dispositif photovoltaïque
JP2010074127A (ja) * 2008-02-18 2010-04-02 Sumitomo Chemical Co Ltd 組成物およびそれを用いた有機光電変換素子

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JP2006063334A (ja) * 2004-07-30 2006-03-09 Sumitomo Chemical Co Ltd 高分子化合物、高分子薄膜およびそれを用いた高分子薄膜素子
JP5046492B2 (ja) * 2005-03-29 2012-10-10 シャープ株式会社 光電変換素子及び太陽電池
WO2007121252A2 (fr) * 2006-04-11 2007-10-25 Konarka Technologies, Inc. Cellules photovoltaïques montées en tandem
TW200937656A (en) * 2008-02-29 2009-09-01 Univ Nat Chiao Tung An organic active-layer solution for a polymer solar cell and a method for preparing the same
EP2327116A1 (fr) * 2008-08-20 2011-06-01 Plextronics, Inc. Système de solvants amélioré pour la fabrication de cellules solaires organiques

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WO2009063850A1 (fr) * 2007-11-12 2009-05-22 Konica Minolta Holdings, Inc. Procédé de fabrication d'élément électronique organique
JP2010074127A (ja) * 2008-02-18 2010-04-02 Sumitomo Chemical Co Ltd 組成物およびそれを用いた有機光電変換素子
WO2009113450A1 (fr) * 2008-03-12 2009-09-17 東レ株式会社 Dispositif photovoltaïque, matériau en couche active, et procédé de fabrication du dispositif photovoltaïque

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Publication number Priority date Publication date Assignee Title
US9876184B2 (en) 2013-08-28 2018-01-23 Taiwan Semiconductor Manufacturing Company, Ltd. Organic photosensitive device with an electron-blocking and hole-transport layer
US10818857B2 (en) 2013-08-28 2020-10-27 Taiwan Semiconductor Manufacturing Co., Ltd. Organic photosensitive device with an electron-blocking and hole-transport layer
WO2016076213A1 (fr) * 2014-11-13 2016-05-19 住友化学株式会社 Composition d'encre et élément de conversion photoélectrique produit à l'aide de celle-ci
JPWO2016076213A1 (ja) * 2014-11-13 2017-06-29 住友化学株式会社 インク組成物およびそれを用いて製造した光電変換素子

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