WO2013168709A1 - Cellule solaire à couches minces organiques, monomères et composition de matière semi-conductrice utilisée dans une cellule solaire à couches minces organiques - Google Patents

Cellule solaire à couches minces organiques, monomères et composition de matière semi-conductrice utilisée dans une cellule solaire à couches minces organiques Download PDF

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WO2013168709A1
WO2013168709A1 PCT/JP2013/062847 JP2013062847W WO2013168709A1 WO 2013168709 A1 WO2013168709 A1 WO 2013168709A1 JP 2013062847 W JP2013062847 W JP 2013062847W WO 2013168709 A1 WO2013168709 A1 WO 2013168709A1
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寛記 杉浦
中井　義博
野村　公篤
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富士フイルム株式会社
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Definitions

  • the present invention relates to an organic thin film solar cell, a composition for an organic semiconductor material used therefor, and a monomer.
  • Organic semiconductor polymers have been actively researched in recent years in the electronics field. For example, it is used for an organic electroluminescence element that emits light when electricity is passed, an organic photoelectric conversion element that generates power by light irradiation, an organic thin film transistor element that controls the amount of current and voltage, and the like.
  • an organic semiconductor material in which a p-type conductivity / semiconductor material as an electron donating material and an n-type conductivity / semiconductor material as an electron-accepting material are combined is used as in the case of the inorganic semiconductor material.
  • fossil energy such as petroleum has a problem of releasing carbon dioxide into the atmosphere
  • demand for solar cells is increasing in order to protect the global environment by suppressing global warming.
  • Known organic solar cells using organic photoelectric conversion elements include wet-type dye-sensitized solar cells (Gretzel cells) and all-solid-state organic thin-film solar cells. Since the latter does not use an electrolytic solution, there is no need to consider evaporation or leakage of the electrolytic solution. Moreover, it is possible to give flexibility, and the structure and manufacture of the solar cell become simpler than the former.
  • the photoelectric conversion efficiency of the organic thin film solar cell is still insufficient.
  • the photoelectric conversion efficiency is calculated by short circuit current density (Jsc) ⁇ open circuit voltage (Voc) ⁇ fill factor (FF).
  • Jsc short circuit current density
  • Voc open circuit voltage
  • FF fill factor
  • the open-circuit voltage is said to be related to the difference between the HOMO level of the p-type conductivity / semiconductor material and the LUMO level of the n-type conductivity / semiconductor material. Increasing this difference increases the open-circuit voltage. .
  • Patent Document 1 proposes a polymer having a specific thienoisothiazole structure.
  • Patent Document 2 and Non-Patent Document 1 disclose thienopyrazine structural units
  • Non-Patent Documents 2 and 3 disclose compounds having an isothianaphthene structural unit.
  • the inventors of the present invention focused on a technology for stabilizing product quality in view of further improvement in performance as an organic thin film solar cell, mass production and widespread use.
  • the object of the present invention is to provide an organic thin-film solar cell that is excellent in various characteristics relating to photoelectric conversion and has little variation in product quality. Furthermore, an object of the present invention is to provide a composition useful as a semiconductor material used in the solar cell and the like, and a monomer for polymer synthesis.
  • An organic thin-film solar cell comprising a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, wherein the photoelectric conversion layer has the following formulas (1) to (4):
  • the organic thin-film solar cell containing the polymer which has a structural unit represented by either.
  • R 11 represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group or a group represented by —CR c ⁇ CR a R b .
  • R a and R b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group
  • R c represents a hydrogen atom or an alkyl group.
  • one of R a and R b is a cyano group, an alkoxycarbonyl group, or an acyl group.
  • R 12 represents a hydrogen atom or a substituent.
  • X A represents an oxygen atom, a sulfur atom, a selenium atom, SiR 2 (R is a hydrogen atom or a substituent), a tellurium atom,>C ⁇ O,> SO 2 or> NR N ( RN is a hydrogen atom or a substituent).
  • X 11 represents an oxygen atom, a sulfur atom, or> NR N ( RN is a hydrogen atom or a substituent).
  • X 12 represents an oxygen atom, a sulfur atom or ⁇ NR n (R n is a substituent).
  • X 21 represents an oxygen atom, a sulfur atom, a divalent group represented by ⁇ NR n or ⁇ CR 201 R 202 .
  • R 201 and R 202 each independently represent a substituent.
  • R 201 and R 202 may be connected to each other to form a ring.
  • Is R n is as defined in the formula (1).
  • Ring A represents an aromatic ring.
  • X B is as defined above X A.
  • Ring B represents a monocyclic or bicyclic aromatic ring or alicyclic ring.
  • X 31 and X 32 each independently represent a nitrogen atom or ⁇ CR 31 —.
  • R 31 represents a hydrogen atom or a substituent.
  • the ring B represents a monocyclic aromatic ring, a monocyclic alicyclic ring containing no nitrogen atom, or a bicyclic aromatic ring or alicyclic ring.
  • the X C have the same meanings as defined above X A.
  • R 41 and R 42 each independently represent a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, An acyloxy group having 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 24 carbon atoms, an alkoxysulfonyl group having 1 to 24 carbon atoms, a nitro group, a perfluoroalkyl group having 1 to 24 carbon atoms, and a perfluoroalkyl group having 1 to 24 carbon atoms.
  • Fluoroalkoxy group carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 carbon atoms
  • R 45 represents a hydrogen atom or an alkyl group.
  • R 46 and R 47 each independently represents a hydrogen atom, an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group.
  • R 46 and R 47 is a cyano group, an alkoxycarbonyl group or an acyl group.
  • R 43 represents a substituent.
  • X 41 represents a nitrogen atom or ⁇ CR 44 —.
  • R 44 represents a hydrogen atom or a substituent.
  • * in the formulas (1) to (4) represents a bond forming a polymer main chain.
  • the organic thin film solar cell according to any one of X A is a sulfur atom in the formula (1) [1] to [3].
  • X 21 has the same meaning as in Formula (2).
  • * indicates a bond forming a polymer main chain.
  • R 22 represents> NR N or> C ⁇ O.
  • R 23 to R 26 each independently represents a hydrogen atom or a substituent.
  • X E and X F have the same meaning as in formula (2-1).
  • RN is synonymous with the formula (1).
  • * indicates a bond forming a polymer main chain.
  • R 33 represents a hydrogen atom or a substituent.
  • X 33 represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR N.
  • X 35 represents a divalent group represented by> CR b R c ,> C ⁇ CR d R e or> NR N.
  • R b to R e each independently represents a hydrogen atom or a substituent.
  • R 34 to R 37 each independently represents a hydrogen atom or a substituent.
  • X B has the same meaning as in the above formula (3).
  • R N and R M have the same meanings as those in the above formulas (1) and (2-1), respectively.
  • * indicates a bond forming a polymer main chain.
  • [8] The organic thin-film solar cell according to [1], wherein the structural unit represented by the formula (3) is a structural unit represented by any of the following formulas (3-4) to (3-6) .
  • R 33 represents a hydrogen atom or a substituent.
  • X 33 represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR N.
  • R b to R e each independently represents a hydrogen atom or a substituent.
  • R 64 and R 65 each independently represents a hydrogen atom or a substituent.
  • X B is as defined X B in the formula (3).
  • R N and R M have the same meanings as those in the above formulas (1) and (2-1), respectively.
  • * indicates a bond forming a polymer main chain.
  • R 33 represents a hydrogen atom or a substituent.
  • X 33 represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR N.
  • X 35 represents a divalent group represented by> CR b R c ,> C ⁇ CR d R e or> NR N.
  • R b to R e each independently represents a hydrogen atom or a substituent.
  • R 74 to R 77 each independently represents a hydrogen atom or a substituent.
  • X B has the same meaning as in the above formula (3).
  • R N and R M have the same meanings as those in the above formulas (1) and (2-1), respectively.
  • * indicates a bond forming a polymer main chain.
  • X C in Formula (4) an organic thin film solar cell according to a sulfur atom [1].
  • R 41 and R 42 in the formula (4) are each independently a formyl group, a fluorine atom, a chlorine atom, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, or 2 carbon atoms.
  • R 46 and R 47 are a cyano group, an alkoxycarbonyl group or an acyl group.
  • a composition comprising a polymer having a structural unit represented by any one of the following formulas (1) to (4) in an organic solvent.
  • R 11 represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group or a group represented by —CR c ⁇ CR a R b .
  • R a and R b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group
  • R c represents a hydrogen atom or an alkyl group.
  • one of R a and R b is a cyano group, an alkoxycarbonyl group, or an acyl group.
  • R 12 represents a hydrogen atom or a substituent.
  • X A represents an oxygen atom, a sulfur atom, a selenium atom, SiR 2 (R is a hydrogen atom or a substituent), a tellurium atom,>C ⁇ O,> SO 2 or> NR N ( RN is a hydrogen atom or a substituent).
  • X 11 represents an oxygen atom, a sulfur atom or> NR N (R N is a hydrogen atom or a substituent).
  • X 12 represents an oxygen atom, a sulfur atom or ⁇ NR n (R n is a substituent).
  • X 21 represents an oxygen atom, a sulfur atom, a divalent group represented by ⁇ NR n or ⁇ CR 201 R 202 .
  • R 201 and R 202 each independently represent a substituent.
  • R 201 and R 202 may be connected to each other to form a ring.
  • Is R n is as defined in the formula (1).
  • Ring A represents an aromatic ring.
  • X B is as defined above X A.
  • Ring B represents a monocyclic or bicyclic aromatic ring or alicyclic ring.
  • X 31 and X 32 each independently represent a nitrogen atom or ⁇ CR 31 —.
  • R 31 represents a hydrogen atom or a substituent.
  • ring B represents a monocyclic aromatic ring, a monocyclic alicyclic ring containing no nitrogen atom, or a bicyclic aromatic ring or alicyclic ring.
  • the X C have the same meanings as defined above X A.
  • R 41 and R 42 each independently represent a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, An acyloxy group having 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 24 carbon atoms, an alkoxysulfonyl group having 1 to 24 carbon atoms, a nitro group, a perfluoroalkyl group having 1 to 24 carbon atoms, and a perfluoroalkyl group having 1 to 24 carbon atoms.
  • Fluoroalkoxy group carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 carbon atoms
  • R 45 represents a hydrogen atom or an alkyl group.
  • R 46 and R 47 each independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group or an acyl group.
  • R 46 and R 47 is a cyano group, an alkoxycarbonyl group or an acyl group.
  • R 43 represents a substituent.
  • X 41 represents a nitrogen atom or ⁇ CR 44 —.
  • R 44 represents a hydrogen atom or a substituent.
  • * in the formulas (1) to (4) represents a bond forming a polymer main chain.
  • R a and R b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group
  • R c represents a hydrogen atom or an alkyl group.
  • one of R a and R b is a cyano group, an alkoxycarbonyl group, or an acyl group.
  • R 12 represents a hydrogen atom or a substituent.
  • X A represents an oxygen atom, a sulfur atom, a selenium atom, SiR 2 (R is a hydrogen atom or a substituent), a tellurium atom,>C ⁇ O,> SO 2 or> NR N ( RN is a hydrogen atom or a substituent).
  • X 11 represents an oxygen atom, a sulfur atom, or> NR N ( RN is a hydrogen atom or a substituent).
  • X 12 represents an oxygen atom, a sulfur atom or ⁇ NR n (R n is a substituent).
  • R 201 and R 202 each independently represent a substituent.
  • R 201 and R 202 may be connected to each other to form a ring.
  • Is R n is as defined in the formula (1).
  • Ring A represents an aromatic ring.
  • X B is as defined above X A.
  • Ring B represents a monocyclic or bicyclic aromatic ring or alicyclic ring.
  • X 31 and X 32 each independently represent a nitrogen atom or ⁇ CR 31 —.
  • R 31 represents a hydrogen atom or a substituent.
  • the ring B represents a monocyclic aromatic ring, a monocyclic alicyclic ring containing no nitrogen atom, or a bicyclic aromatic ring or alicyclic ring.
  • X C has the same meaning as X A above.
  • R 41 and R 42 each independently represent a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, An acyloxy group having 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 24 carbon atoms, an alkoxysulfonyl group having 1 to 24 carbon atoms, a nitro group, a perfluoroalkyl group having 1 to 24 carbon atoms, and a perfluoroalkyl group having 1 to 24 carbon atoms.
  • Fluoroalkoxy group carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 carbon atoms
  • R 45 represents a hydrogen atom or an alkyl group.
  • R 46 and R 47 each independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group or an acyl group.
  • R 46 and R 47 is a cyano group, an alkoxycarbonyl group or an acyl group.
  • R 43 represents a substituent.
  • X 41 represents a nitrogen atom or ⁇ CR 44 —.
  • R 44 represents a hydrogen atom or a substituent.
  • Ya and Yb each independently represent a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a boronic ester group or a boronic acid group.
  • aromatic ring is used to mean an aromatic ring and an aromatic heterocyclic ring, and may be monocyclic or bicyclic.
  • An alicyclic ring represents a non-aromatic ring structure which may contain a hetero atom, and may be monocyclic or multicyclic.
  • the organic thin film solar cell of the present invention is excellent in various characteristics relating to photoelectric conversion. Furthermore, there is an excellent effect that there is little variation in quality when considering mass production and actual use. Further, the polymer synthesis monomer of the present invention and the composition containing the same are novel and useful as a semiconductor material used in the solar cell and the like.
  • FIG. 1 is a side view schematically showing the configuration of a preferred embodiment of the organic thin film solar cell of the present invention.
  • the organic thin film solar cell of the present invention uses a polymer having a structural unit represented by any one of the following formulas (1) to (4) in the photoelectric conversion layer.
  • a polymer having a structural unit represented by any one of the following formulas (1) to (4) in the photoelectric conversion layer is described.
  • FIG. 1 is a side view schematically showing an example of the organic thin film solar cell of the present invention.
  • the solar cell 10 of the present embodiment includes a photoelectric conversion layer (bulk hetero bond layer) 3 including a polymer having the following specific structural unit.
  • Organic thin film solar cells are generally classified into pin junction type organic thin film solar cells having a pin three-layer structure and bulk heterojunction type organic thin film solar cells. I do not care. Since high power generation efficiency can be easily obtained, it is particularly preferably applied to a bulk heterojunction organic thin film solar cell as shown in FIG.
  • the photoelectric conversion layer 3 is composed of the p-type semiconductor phase that is an electron donating compound and the n-type semiconductor phase that is an electron accepting compound made of the specific polymer.
  • the photoelectric conversion layer 3 is provided between the first electrode 11 and the second electrode 12.
  • the hole transport layer 21 is preferably provided between the first electrode and the photoelectric conversion layer
  • the electron transport layer 22 is preferably provided between the second electrode and the photoelectric conversion layer.
  • the distinction between the upper and lower sides is not particularly important, but if necessary for convenience, the first electrode 11 side is positioned as the “up” or “top” side, and the second electrode 12 side is defined as “ Position it as “bottom” or “bottom”.
  • the configuration of the substrate, the positive electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the negative electrode is referred to as the forward configuration
  • the substrate, the negative electrode, the electron transport layer, the photoelectric conversion layer, and the hole transport in order from the upper layer.
  • the configuration of the layer and the positive electrode is referred to as a reverse configuration, and in the present invention, both the forward configuration and the reverse configuration are preferably applied.
  • the p-type semiconductor phase and the n-type semiconductor phase are mixed in a specific form as described above, and photoelectric conversion is performed at the interface.
  • the form is not particularly limited, but as an ideal example, a state in which the phases are interdigitated in the order of nanometers as illustrated is preferable.
  • the p-type semiconductor polymer preferably has a specific compatibility or incompatibility with the n-type semiconductor polymer.
  • the material that becomes the p-type semiconductor is not determined only by the specific physical properties, but is specified by the relative relationship with the material that becomes the n-type semiconductor.
  • a material having a higher electron donating property can be a p-type semiconductor material. According to the following specific polymer, the above requirements can be satisfied satisfactorily.
  • a polymer having a structural unit represented by any of the following formulas (1) to (4) (hereinafter sometimes referred to as a specific structural unit) is applied to the photoelectric conversion layer of the organic thin film solar cell.
  • R 11 represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR c ⁇ CR a R b .
  • R 12 represents a hydrogen atom or a substituent.
  • Preferable examples of R 12 include examples of the substituent T described later, and include a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group (preferably having 1 to 24 carbon atoms), a hydroxyl group, and an acyloxy group (having 2 to 24 carbon atoms).
  • R 11 is preferably a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, or a group represented by —CR c ⁇ CR a R b .
  • R a and R b each independently represents an alkyl group (preferably having 1 to 24 carbon atoms), a cyano group, an alkoxycarbonyl group (preferably having 2 to 24 carbon atoms), or an acyl group (preferably having 2 to 24 carbon atoms).
  • R c represents a hydrogen atom or an alkyl group (preferably having 1 to 24 carbon atoms).
  • one of R a and R b is a cyano group, an alkoxycarbonyl group, or an acyl group.
  • X A is an oxygen atom, a sulfur atom, a selenium atom, SiR 2 (R represents a hydrogen atom or a substituent), a tellurium atom,>C ⁇ O,> SO 2 or> NR N ( RN is a hydrogen atom or a substituent) Represents).
  • R N and R are substituents, preferred examples of the substituent include the examples of substituent T described later, and include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (carbon number). 2-24 are preferred), alkynyl groups (preferably having 2-24 carbon atoms) are preferred, and alkyl groups are more preferred.
  • a preferable range of the carbon number of the alkyl group and the like exemplified in the substituent T is not particularly specified, but is the same as that described for the substituent T throughout the present specification.
  • X A is preferably a sulfur atom, a selenium atom,>C ⁇ O,> SO 2 , or> NR N, and more preferably a sulfur atom.
  • X 11 represents an oxygen atom, a sulfur atom or> NR N.
  • the R N wherein has the same meaning as R N, and their preferable ranges are also the same.
  • X 11 is preferably an oxygen atom.
  • X 12 represents an oxygen atom, a sulfur atom or ⁇ NR n (R n represents a substituent).
  • R n represents a substituent
  • substituent for R n include the examples of substituent T described later, and include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), and an alkynyl group. (C2-C24 is preferred).
  • X 12 is preferably an oxygen atom.
  • X 21 represents an oxygen atom, a sulfur atom, a divalent group represented by ⁇ NR n or ⁇ CR 201 R 202 .
  • R 201 and R 202 represent a substituent.
  • R n has the same meaning as described above.
  • Examples of the substituent of R 201 and R 202 include the examples of the substituent T described later, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), an alkynyl group (having a carbon number) 2-24 are preferred), acyl groups (preferably having 2-24 carbon atoms), alkoxycarbonyl groups (preferably having 2-24 carbon atoms), and cyano groups are preferred.
  • R 201 and R 202 may be bonded to each other to form a ring.
  • Ring A represents an aromatic ring.
  • the aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocycle, and examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
  • the aromatic heterocycle is preferably a 5- or 6-membered ring, and the ring-constituting heteroatom is preferably a nitrogen atom, oxygen atom, sulfur atom, selenium atom or tellurium atom.
  • a ring in which a benzene ring is condensed is also preferable.
  • Preferred aromatic rings include benzene ring, naphthalene ring, benzothiophene ring, benzothiazole ring, benzoisothiazole ring, benzoxazole ring, benzisoxazole ring, pyridine ring, pyridazine ring, among them, benzene ring, pyridine ring A pyridazine ring is preferred.
  • Ring A may be substituted with a substituent T described later.
  • the structural unit represented by the formula (2) is preferably a structural unit represented by the following formula (2-1).
  • X 21 have the same meanings as those in formula (2).
  • R M represents a hydrogen atom or a substituent) or a nitrogen atom.
  • substituent T preferably an alkyl group (having 1 to 24 carbon atoms is preferred), 2 alkenyl group (carbon-24 ), An alkynyl group (preferably having 2 to 24 carbon atoms), an acyl group (preferably having 2 to 24 carbon atoms), an acyloxy group (preferably having 2 to 24 carbon atoms), an alkoxycarbonyl group (having 2 to 24 carbon atoms).
  • a fluorine atom a chlorine atom, and a cyano group.
  • the structural unit represented by the formula (2-1) is preferably a structural unit represented by the following formula (2-2).
  • R 22 represents> NR N or> C ⁇ O.
  • RN has the same meaning as defined above.
  • R 23 to R 26 each independently represent a hydrogen atom or a substituent.
  • X E and X F have the same meaning as in formula (2-1).
  • examples of the substituent include the examples of substituent T described later, and include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkoxy group (carbon number). 1 to 24 are preferred), an alkoxycarbonyl group (preferably having 2 to 24 carbon atoms), and an aryl group (preferably having 6 to 24 carbon atoms) are preferred.
  • X B is as defined above X A.
  • ⁇ Ring B Ring B represents a monocyclic or bicyclic aromatic ring or alicyclic ring.
  • the ring B represents a monocyclic aromatic ring, a monocyclic alicyclic ring containing no nitrogen atom, or a bicyclic aromatic ring or alicyclic ring.
  • the aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocycle, and examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.
  • the aromatic heterocycle is preferably a 5- or 6-membered ring, and the ring-constituting heteroatom is preferably a nitrogen atom, oxygen atom, sulfur atom, selenium atom or tellurium atom.
  • the ring-constituting heteroatom is preferably a nitrogen atom, oxygen atom, sulfur atom, selenium atom or tellurium atom.
  • the alicyclic ring is a ring other than an aromatic ring, including a cycloalkane or a hetero ring, and a 5- or 6-membered ring is preferable.
  • the cycloalkane include cyclopentane, cyclopentanone, 1,3-cyclopentanedione, cyclohexane, cyclohexanone, and 1,4-cyclohexanedione
  • examples of the heterocyclic ring include pyrrolidinone and 2,5-pyrrolidinedione.
  • Ring B may be substituted with a substituent T described later.
  • the ring B is benzene, naphthalene, 2,5-pyrrolidinedione, 1,3-cyclopentanedione, thiophene, selenophene, pyrrole, thiazole, isothiazole, imidazole.
  • ⁇ X 31, X 32 X 31 and X 32 each represent a nitrogen atom or ⁇ CR 31 —.
  • R 31 include a substituent T described later, preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom or a fluorine atom.
  • the structural unit represented by the formula (3) is preferably a structural unit represented by any of the following formulas (3-1) to (3-3).
  • R 33 represents a hydrogen atom or a substituent.
  • substituents include the substituent T described later.
  • alkoxycarbonyl groups preferably having 2 to 24 carbon atoms
  • acyl groups preferably having 2 to 24 carbon atoms
  • alkylsulfonyl groups preferably having 1 to 24 carbon atoms
  • X 33 represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR N.
  • X 33 is preferably a sulfur atom or> NR N, more preferably a sulfur atom.
  • RN is synonymous with that defined in Formula (1), and the preferred range is also the same.
  • R M has the same meaning as defined above, and the preferred range is also the same.
  • X 35 represents a divalent group represented by> CR b R c ,> C ⁇ CR d R e or> NR N.
  • X 35 is preferably> CR b R c or> NR N.
  • RN has the same meaning as defined above.
  • R b to R e each independently represents a hydrogen atom or a substituent.
  • substituents include the substituent T described later, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms) An alkynyl group (preferably having 2 to 24 carbon atoms) is preferred, and an alkyl group is more preferred.
  • R 34 to R 37 each independently represents a hydrogen atom or a substituent.
  • substituent include the examples of substituent T described later.
  • R 34 to R 37 are each independently an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), alkynyl. Group (preferably having 2 to 24 carbon atoms), acyl group (preferably having 2 to 24 carbon atoms), alkoxycarbonyl group (preferably having 2 to 24 carbon atoms), acyloxy group (preferably having 2 to 24 carbon atoms), fluorine atom A chlorine atom is preferred.
  • At least one of R 34 to R 37 is preferably an electron withdrawing group.
  • R 34 and R 37 are preferably a halogen atom among the electron-attracting groups, and more preferably a fluorine atom or a chlorine atom.
  • R 35 and R 36 are preferably an alkoxycarbonyl group or an acyl group among electron withdrawing groups.
  • ⁇ X B X B is as defined in the formula (3).
  • the structural unit represented by the formula (3) is a structural unit represented by the following formulas (3-4) to (3-6).
  • R 33 , X 33 , X 34 , and X B are as defined in formulas (3-1) to (3-3).
  • R b to R e have the same meanings as (3-2) R b to R e .
  • R 64, R 65 and R M is preferably an electron withdrawing group.
  • R 64 and R 65 is preferably an alkoxycarbonyl group or an acyl group, R M is preferably a halogen atom, a fluorine atom or a chlorine atom is more preferable.
  • the structural unit represented by the formula (3) is a structural unit represented by the following formulas (3-7) to (3-9).
  • R 33 , X 33 , X 34 , X 35 , and X B are as defined in the above formulas (3-1) to (3-3).
  • R 74 to R 77 in the formula (3-9) have the same meanings as R 34 to R 37 in the formula (3-3).
  • the notation of a repeating unit means that this includes an isomer having a structure that is horizontally reversed. In other words, the structural unit represented by the structural formula may be introduced into the polymer in an inverted form.
  • X C has the same meaning as defined above X A, the preferred range is also the same.
  • R 41 , R 42 R 41 and R 42 each independently represents a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms (preferably having 4 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), carbon An acyl group having 2 to 24 carbon atoms (preferably 4 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), an alkoxycarbonyl group having 3 to 25 carbon atoms (preferably having 5 to 25 carbon atoms, and having 7 to 25 carbon atoms) More preferably), an acyloxy group having 2 to 24 carbon atoms (preferably 4 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), an alkylsulfonyl group having 1 to 24 carbon atoms (preferably 4 to 24 carbon atoms, carbon 6 to 24 are more preferable), an alkoxysulfonyl group having 2 to 24 carbon atoms (preferably 4 to 24 carbon atoms,
  • An alkyl group (preferably having 1 to 16 carbon atoms, more preferably 1 to 6 carbon atoms), a perfluoroalkoxy group having 1 to 24 carbon atoms (preferably having 1 to 16 carbon atoms, more preferably 1 to 6 carbon atoms), A carbamoyl group having 1 to 24 carbon atoms (preferably 4 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), a sulfamoyl group having 1 to 24 carbon atoms (preferably having 4 to 24 carbon atoms, and having 6 to 24 carbon atoms) More preferably), a perfluoroalkylcarbonyl group having 2 to 24 carbon atoms (preferably 2 to 16 carbon atoms, more preferably 2 to 6 carbon atoms), a perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms (2 carbon atoms).
  • CR 46 R 47 It represents a CR 46 R 47.
  • the number of carbons in the above groups excluding perfluoroalkyl groups, perfluoroalkoxy groups, perfluoroalkylcarbonyl groups, and perfluoroalkylcarbonyloxy groups is preferably 4 to 24, more preferably 6 to 24.
  • the perfluoroalkyl group, perfluoroalkoxy group and perfluoroalkylcarbonyl group preferably have 1 to 16 carbon atoms, more preferably 1 to 6 carbon atoms.
  • -CR 45
  • R 45 represents a hydrogen atom or an alkyl group (preferably having 1 to 24 carbon atoms).
  • R 46 and R 47 each independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group (preferably having 2 to 24 carbon atoms) or an acyl group (preferably having 2 to 24 carbon atoms). However, either one of R 46 and R 47 is a cyano group, an alkoxycarbonyl group or an acyl group.
  • R 43 represents a hydrogen atom or a substituent. Examples of the substituent include the substituent T described later, and a hydrogen atom and a fluorine atom are preferable.
  • X 41 represents a nitrogen atom or ⁇ CR 44 —.
  • R 44 represents a hydrogen atom or a substituent.
  • substituents include a substituent T described later, a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), an alkynyl group ( (Preferably having 2 to 24 carbon atoms) is preferred, and a hydrogen atom or a fluorine atom is more preferred.
  • the specific structural unit in the specific polymer can be synthesized from a compound represented by any of the following formulas (M1) to (M4).
  • R 11 , R 12 , R 41 , R 42 , R 43 , X A , X B , X C , X 11 , X 12 , X 21 , X 31 , X 32 , X 41 , Ring A, Ring B Is as defined in the above formulas (1) to (4).
  • ⁇ Ya, Yb Ya and Yb each independently represent a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a boronic ester group or a boronic acid group.
  • the polymer used in the present invention is preferably a copolymer having the specific structural unit and two or more other copolymer components.
  • copolymerization components benzene structural unit, naphthalene structural unit, anthracene structural unit, phenanthrene structural unit, benzodithiophene structural unit, naphthodithiophene structural unit, carbazole structural unit, silacyclopentadithiophene structural unit, cyclopentadithiazole Structural unit, benzothiadiazole structural unit, thiadiazoloquinoxaline structural unit, cyclopentadithiophene structural unit, oxidized cyclopentadithiophene structural unit, benzisothiazole structural unit, benzothiazole structural unit, oxidized thiophene structural unit, thienothiophene structural unit , Thienothiophene oxide unit, dithienothiophene unit,
  • ⁇ Xb Xb in the formulas (II-1) to (II-23) represents NH, NRb, O or S.
  • Xc represents CRa or N.
  • Ra Ra represents a hydrogen atom or a substituent, and may be connected to each other to form a ring. When a plurality of substituents are indicated by a specific code, they may be different from each other. Further, when the substituent Ra is condensed to form an aromatic ring or an aromatic heterocyclic ring, it may have a structure different from the resonance structure shown above. Examples of Ra include the substituent T described later, a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), alkynyl.
  • alkoxy group preferably having 1 to 24 carbon atoms
  • acyl group preferably having 2 to 12 carbon atoms
  • acyloxy group preferably having 2 to 24 carbon atoms
  • alkoxycarbonyl group An alkylsulfonyl group (preferably having 1 to 24 carbon atoms) is preferred (preferably having 2 to 24 carbon atoms).
  • Rb Rb represents a hydrogen atom or a substituent, and examples of the substituent include the substituent T described later, a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms). ) And alkynyl groups (preferably having 2 to 24 carbon atoms) are preferred.
  • Rb is a substituent, they may be connected to each other to form a ring.
  • Rc Rc represents a hydrogen atom substituent, and examples of the substituent include the substituent T described later, a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms).
  • An alkynyl group preferably having 2 to 4 carbon atoms
  • an alkoxycarbonyl group preferably having 2 to 24 carbon atoms
  • an acyl group preferably having 2 to 24 carbon atoms
  • a cyano group are preferred.
  • the structural units of the formulas (II-1) to (II-23) are preferably those represented by the formulas (1) to (61).
  • Ra and Rb are the same as described above.
  • Examples of the monomer forming the specific structural unit of the present invention include the following examples.
  • Me represents —CH 3
  • Bu represents —C 4 H 9
  • M + represents a metal ion such as Na + or K + .
  • Examples of the polymer that forms the specific structural unit of the present invention include the following examples.
  • Me represents —CH 3 .
  • the polymers of the present invention can be used in coupling reactions such as Chemical Reviews, 2002, 102, 1358, Chemical Reviews, 2011, 111, 1493, Journal of Materials of Chemistry, 2004, 14, 11 and the like. Can be synthesized using the method described in 1. above. In other words, Negishi coupling using a transition metal catalyst, zinc reaction agent, Ueda-Kosugi-Still coupling using tin reactant, Suzuki-Miyaura coupling using boron reactant, Kumada-tama using magnesium reactant It can be synthesized by using cross-coupling such as tail-Coriu coupling, Kashiyama coupling using silicon reagent, Ullmann reaction using copper, Yamamoto polymerization using nickel, and the like.
  • metals such as palladium, nickel, copper, cobalt, and iron (Journal of the American Chemical Society, 2007, Vol. 129, page 9844) can be used.
  • the metal may have a ligand, such as a phosphorus ligand such as PPh 3 or P (t-Bu) 3 , an N-heterocyclic carbene ligand (Angewandte Chemie International Edition, 2002, 41, 1290) and the like are preferably used.
  • a method for synthesizing a metal reactant such as a tin reactant and a boron reactant as a raw material is not particularly limited, and can be synthesized according to various known methods.
  • the tin reactant is Journal of the American Chemistry, 2009, 131, 7792, the Journal of the American Chemistry, 2008, 130, 16144, the European Patent Application No. 2407465, and the boron reactant is Journal. It can be synthesized with reference to American Chemistry, pages 2012, 134, 539 and the like.
  • the reaction may be performed under microwave irradiation as described in Macromolecular Rapid Communications, 2007, 28, 387.
  • the molecular weight of the polymer having the specific structural unit is not particularly limited, but the mass average molecular weight (weight average molecular weight) is preferably 5,000 to 50,000, more preferably 10,000 to 500,000.
  • the molecular weight and the degree of dispersion are values measured using a GPC (gel filtration chromatography) method, and the molecular weight is a weight average molecular weight in terms of polystyrene.
  • the gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. Two to six columns are preferably connected and used.
  • the solvent used include ether solvents such as tetrahydrofuran, amide solvents of N-methylpyrrolidone, halogen solvents such as chloroform, and aromatic solvents such as chlorobenzene and 1,2-dichlorobenzene.
  • the measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently.
  • the measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C. Measurement can also be performed at 50 ° C. to 200 ° C. using a column having a high usable temperature and a solvent having a high boiling point.
  • the column and carrier to be used can be appropriately selected according to the physical properties of the polymer compound to be measured.
  • the copolymerization ratio is not particularly limited, but the specific structural unit is preferably 10 to 90 mol%, and preferably 40 to 60 mol% of the total molar ratio. preferable.
  • the copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a periodic copolymer, but is preferably an alternating copolymer or a periodic copolymer. More preferably, it is an alternating copolymer.
  • a substituent for which substitution / non-substitution is not specified means that the group may have an arbitrary substituent. This is also the same for compounds and polymers that do not specify substitution / non-substitution.
  • Preferred substituents include the following substituent T.
  • substituent T examples include the following.
  • An alkyl group preferably an alkyl group having 1 to 24 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2 -Methylheptyl, 2-ethylhexyl, n-nonyl, n-decyl, 3,7-dimethyloctyl, isodecyl, n-undecyl, n-dodecyl, 2-butyloctyl, n-tridecyl, 3-butylnonyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-hexyldecyl, n-heptadecyl
  • a cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., an aryl group (preferably an aryl group having 6 to 26 carbon atoms such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl) , 3-methylphenyl, etc.),
  • a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocyclic group having at least one oxygen atom, sulfur atom, or nitrogen atom is preferable.
  • An acyl group (preferably an acyl group having 1 to 24 carbon atoms such as acetyl, propionyl, butyryl, benzoyl, hexanoyl, 2-ethylhexanoyl, octanoyl, 3,7-dimethyloctanoyl, 2-butyloctanoyl, 2- Hexyldecanoyl, 2-decyltetradecanoyl, etc.), acyloxy groups (preferably acyloxy groups having 1 to 24 carbon atoms, such as acetyloxy, benzoyloxy, hexanoyloxy, 2-ethylhexanoyloxy, octanoyloxy, 3,7-dimethyloctanoyloxy, 2-butyloctanoyloxy, 2-hexyldecanoyloxy, 2-decyltetradecanoyloxy, etc.), a carbamoyl group (
  • a alkyl group or an arylsulfonyloxy group (preferably an alkyl or arylsulfonyloxy group having 1 to 24 carbon atoms, such as methanesulfonyloxy, ethanesulfonyloxy).
  • alkoxy or aryloxysulfonyl group preferably an alkoxy or aryloxysulfonyl group having 1 to 24 carbon atoms, such as methoxysulfonyl, ethoxysulfonyl, phenoxysulfonyl, etc.
  • hydroxyl group preferably an alkoxy or aryloxysulfonyl group having 1 to 24 carbon atoms, such as methoxysulfonyl, ethoxysulfonyl, phenoxysulfonyl, etc.
  • hydroxyl group preferably an alkoxy or aryloxysulfonyl group having 1 to 24 carbon atoms, such as methoxysulfonyl, ethoxysulfonyl, phenoxysulfonyl, etc.
  • hydroxyl group preferably an alkoxy or aryloxysulfonyl group having 1 to 24 carbon atoms, such as methoxysulf
  • the compound or substituent / linking group contains an alkyl group / alkylene group, alkenyl group / alkenylene group, etc.
  • these may be cyclic or chain-like, and may be linear or branched, and substituted as described above. It may be substituted or unsubstituted.
  • an aryl group, a heterocyclic group, etc. may be monocyclic or condensed and may be similarly substituted or unsubstituted.
  • Organic semiconductor polymer is a polymer of an organic compound capable of exhibiting properties as a semiconductor, and the polymer of the present invention is particularly useful as a p-type organic semiconductor polymer.
  • a p-type organic semiconductor compound containing a polymer is generally a ⁇ -electron conjugated compound having a highest occupied orbital (HOMO) level of 4.5 to 6.0 eV.
  • Organic semiconductor polymers are used in the field of organic electronics, organic electroluminescence elements that emit light when electricity is passed, organic photoelectric conversion elements that generate electricity when irradiated with light, organic thin film transistor elements that control the amount of current and voltage, electrochemical sensors, and printables Used in circuits.
  • a photovoltaic cell especially an organic thin-film solar cell.
  • composition for organic semiconductor material The composition for organic semiconductor materials of the present invention will be described.
  • the polymer (specific polymer) having the specific structural unit of the present invention is useful as a p-type organic semiconductor polymer, and the composition for an organic semiconductor material preferably contains the specific polymer in an organic solvent.
  • the composition further preferably contains an n-type semiconductor compound, and particularly preferably contains an n-type organic semiconductor compound.
  • a p-type organic semiconductor compound other than a polymer having a specific structural unit a compound other than a semiconductor (for example, poly-3-hexylthiophene (P3HT), poly [2-HT Methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene (MEH-PPV), poly [2-methoxy-5- (3 ′, 7′-dimethyloctyloxy) -1,4-phenylene vinylene ] (MDMO-PPV), poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -alt- (benzo [2,1,3] thiadiazole-4,8-diyl)] (F8BT) etc.
  • P3HT poly-3-hexylthiophene
  • MEH-PPV poly [2-HT Methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene
  • the organic solvent applied to the composition is not particularly limited, but ether solvents such as tetrahydrofuran, 1,4-dioxane, cyclopentylmethyl ether, benzene, toluene, ethylbenzene, xylene, mesitylene, anisole, thioanisole, pyridine, picoline , Aromatic solvents such as lutidine, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, bromo Aromatic halogen solvents such as benzene, iodobenzene, trifluoromethylbenzene, fluorobenzene, difluorobenzene, thioanisole, 1-chloronaphthalene, etc. are mentioned. Tetrahydrofuran,
  • additives include diiodoalkanes (for example, 1,8-diiodooctane, 1,6-diiodohexane, 1,10-diiododecane, etc.), alkanedithiols (for example, 1,8-octanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.) and 1-chloronaphthalene.
  • diiodoalkanes for example, 1,8-diiodoctane, 1,6-diiodohexane, 1,10-diiododecane, etc.
  • alkanedithiols for example, 1,8-octanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.
  • 1-chloronaphthalene for example, 1,8-diiodoct
  • the content of the polymer having the specific structural unit is not particularly limited, but when the total mass of the composition is 100, it is preferable to contain 0.01 to 90% by mass of the polymer having the specific structural unit, More preferably, 70% by mass is contained.
  • the n-type organic semiconductor compound is preferably contained in an amount of 0.01 to 90% by mass, more preferably 0.1 to 70% by mass, when the total mass of the composition is 100.
  • Any p-type organic semiconductor compound other than the polymer having a specific structural unit is preferably contained in an amount of 0 to 50% by mass, more preferably 0 to 30% by mass.
  • a compound other than a semiconductor may be contained in an amount of about 0 to 50% by mass, depending on the component.
  • the composition means that two or more components exist substantially uniformly in a specific composition.
  • substantially uniform means that each component may be unevenly distributed within the range where the effects of the invention are exerted.
  • the composition is not particularly limited as long as the above definition is satisfied, is not limited to a fluid liquid or a paste, and includes a solid or powder composed of a plurality of components. Furthermore, even when there is a sediment, it means that the composition maintains a dispersion state for a predetermined time by stirring.
  • the n-type organic semiconductor compound is not particularly limited, but is generally a ⁇ -electron conjugated compound having a lowest unoccupied orbital (LUMO) level of 3.5 to 4.5 eV, such as fullerene or Perfluoro derivatives (eg, perfluoropentacene or perfluorophthalocyanine) in which hydrogen atoms of p-type organic semiconductor compounds are substituted with fluorine atoms, such as derivatives thereof, octaazaporphyrins, naphthalene tetracarboxylic acid anhydrides, naphthalene tetracarboxylic acid diimides, Examples thereof include aromatic carboxylic acid anhydrides such as perylene tetracarboxylic acid anhydride and perylene tetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton.
  • LUMO lowest unoccupied orbital
  • Perfluoro derivatives eg, per
  • fullerene or a derivative thereof is preferable because charge separation can be performed at high speed and efficiently from the organic semiconductor polymer (p-type organic semiconductor compound) having the specific structural unit of the present invention.
  • fullerenes and derivatives thereof C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, C 84 fullerene, C 240 fullerene, C 540 fullerene, mixed fullerene, fullerene nanotube, and a part of them are hydrogen atoms.
  • Fullerene derivatives substituted by halogen atoms substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Can be mentioned.
  • Preferred fullerene derivatives are phenyl-C 61 -butyric acid ester, diphenyl-C 62 -bis (butyric acid ester), phenyl-C 71 -butyric acid ester, phenyl-C 85 -butyric acid ester or thienyl-C 61 -butyric acid ester,
  • the preferred number of carbon atoms in the alcohol portion of the butyric acid ester is 1-30, more preferably 1-8, even more preferably 1-4, and most preferably 1.
  • Examples of preferred fullerene derivatives include phenyl-C 61 -butyric acid methyl ester ([60] PCBM), phenyl-C 61 -butyric acid n-butyl ester ([60] PCBnB), phenyl-C 61 -butyric acid isobutyl ester ([60 PCBiB), phenyl-C 61 -butyric acid n-hexyl ester ([60] PCBH), phenyl-C 61 -butyric acid n-octyl ester ([60] PCBO), diphenyl-C 62 -bis (butyric acid methyl ester) ( Bis [60] PCBM), phenyl-C 71 -butyric acid methyl ester ([70] PCBM), phenyl-C 85 -butyric acid methyl ester ([84] PCBM), thienyl-C 61 -butyric acid methyl ester (
  • composition for an organic semiconductor material of the present invention contains another p-type semiconductor compound (for example, a condensed polycyclic aromatic low molecular weight compound, oligomer or polymer) together with the polymer having the specific structural unit of the present invention. Also good.
  • another p-type semiconductor compound for example, a condensed polycyclic aromatic low molecular weight compound, oligomer or polymer
  • Examples of the condensed polycyclic aromatic low-molecular compound that is a p-type semiconductor compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumcam Compounds such as anthracene, bisanthene, zeslen, heptazesulene, pyranthrene, violanthene, isoviolanthene, sacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bis Examples thereof include ethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, and derivative
  • the composition for an organic semiconductor material is preferably used as a coating composition for a photoelectric conversion layer (particularly a bulk hetero layer).
  • the mixing ratio of the p-type organic semiconductor compound that is an electron-donating material and the n-type semiconductor compound that is an electron-accepting material is preferably adjusted so as to increase the photoelectric conversion efficiency. It is selected from the range of ⁇ 90: 10, preferably 20:80 to 80:20.
  • a co-evaporation method is used.
  • a coating method is preferable in order to increase the area of the interface where holes and electrons are separated by charge and to have high photoelectric conversion efficiency.
  • the method for the purpose of promoting the phase separation of the electron donating region (donor) and the electron accepting region (acceptor) in the photoelectric conversion layer, crystallization of the organic material contained in the photoelectric conversion layer, and transparency of the electron transport layer, etc.
  • You may heat-process (anneal) by the method.
  • a dry film forming method such as vapor deposition
  • a wet film forming method such as printing or coating
  • heating may be performed at 50 ° C. to 250 ° C. after the subsequent step, for example, the formation of the metal negative electrode is completed.
  • the photoelectric conversion element according to the present invention has at least a first electrode and a second electrode.
  • One of the first electrode and the second electrode is a positive electrode, and the rest is a negative electrode.
  • the tandem configuration can be achieved by using an intermediate electrode.
  • an electrode through which holes mainly flow is referred to as a positive electrode
  • an electrode through which electrons mainly flow is referred to as a negative electrode.
  • an electrode having translucency is referred to as a transparent electrode
  • an electrode having no translucency is referred to as a counter electrode or a metal electrode.
  • the positive electrode is a translucent transparent electrode
  • the negative electrode is a non-translucent counter electrode or metal electrode, but both the first electrode and the second electrode can be transparent electrodes.
  • the first electrode is a positive electrode. In the case of a solar cell having a forward configuration, it is preferably a transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm).
  • transparent conductive metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), tin oxide, zinc oxide, and indium oxide, magnesium, aluminum, calcium, Ultrathin films of metal and metal alloys such as titanium, chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth, metal nanowires, and carbon nanotubes can be used.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • IWO indium tungsten oxide
  • tin oxide zinc oxide
  • magnesium aluminum, calcium
  • Ultrathin films of metal and metal alloys such as titanium, chromium, manganese, iron, copper, zinc, strontium, silver,
  • a mesh electrode in which a metal such as silver is meshed to ensure light transmission.
  • a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene.
  • a functional polymer can also be used.
  • a plurality of these conductive compounds can be combined to form a positive electrode.
  • the transmittance of the positive electrode is the thickness used for solar cells (eg, 0.2 ⁇ m thickness), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more. If light transmittance is not required in the reverse configuration, metals such as chromium, cobalt, nickel, copper, molybdenum, palladium, silver, tantalum, tungsten, platinum, and gold, alloys thereof, transparent conductive oxide, polyaniline
  • the positive electrode can be formed of a conductive polymer such as polythiophene or polypyrrole.
  • Suitable conductive polymer layers are disclosed in JP 2012-43835 A, polythiophene derivatives are preferable, and polyethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) is more preferable.
  • PEDOT-PSS polyethylenedioxythiophene-polystyrene sulfonic acid
  • These metals, transparent conductive oxides, and conductive polymers may be used alone, or two or more kinds may be mixed or laminated.
  • the second electrode is a negative electrode.
  • the negative electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination.
  • a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used.
  • Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of these metals and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the negative electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the second electrode is a transparent electrode.
  • a transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm) is preferable, and examples thereof include metals, metal oxides, conductive polymers, mixtures thereof, and laminated structures.
  • transparent conductive oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and indium tungsten oxide (IWO), magnesium, aluminum, calcium, titanium
  • transparent conductive oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and indium tungsten oxide (IWO)
  • magnesium aluminum, calcium, titanium
  • ultrathin films of metals and metal alloys such as chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth
  • conductive polymers such as polyaniline, polythiophene, and polypyrrole.
  • the transparent conductive oxide is ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), and gallium-doped oxide.
  • Zinc (GZO) can be used.
  • the transmittance of the negative electrode is the thickness used for solar cells (eg, 0.2 ⁇ m thickness), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more.
  • the metal electrode may be a metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure.
  • a dispersion is preferable because a transparent and highly conductive negative electrode can be formed by a coating method.
  • the metal electrode side is made light transmissive, for example, a conductive material suitable for the negative electrode such as aluminum and aluminum alloy, silver and silver compound is formed in a thin film thickness of about 1 to 20 nm, and then the positive electrode is formed.
  • a light-transmitting negative electrode can be obtained by providing the conductive light-transmitting material film mentioned in the description.
  • hole transport layer In the present invention, it is preferable to provide a hole transport layer between the first electrode and the photoelectric conversion layer.
  • the conductive polymer that forms the hole transport layer include polythiophene, polypyrrole, polyaniline, polyphenylene vinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having a plurality of these conductive skeletons. Can be mentioned. Among these, polythiophene and its derivatives are preferable, and polyethylenedioxythiophene and polythienothiophene are particularly preferable. These polythiophenes are usually partially oxidized in order to obtain conductivity.
  • the electrical conductivity of the conductive polymer can be adjusted by the degree of partial oxidation (doping amount). The larger the doping amount, the higher the electrical conductivity.
  • polythiophene becomes cationic by partial oxidation, a counter anion for neutralizing the charge is required.
  • polythiophenes include polyethylene dioxythiophene (PEDOT-PSS) with polystyrene sulfonic acid as a counter ion and polyethylene dioxythiophene (PEDOT-TsO) with p-toluenesulfonic acid as a counter anion.
  • an electron transport layer is preferably provided between the second electrode and the photoelectric conversion layer, a hole transport layer is provided between the first electrode and the photoelectric conversion layer, and the photoelectric conversion layer and the second It is particularly preferable to provide an electron transport layer between the electrodes.
  • the electron transporting material that can be used for the electron transporting layer include an n-type semiconductor compound that is the electron accepting material mentioned in the above photoelectric conversion layer, and Electron ⁇ in Chemical Review Vol. 107, pages 953 to 1010 (2007). Examples thereof include those described as Transporting and Hole-Blocking Materials.
  • alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride are preferable.
  • Various metal oxides are preferably used as materials for electron transport layers having high stability.
  • relatively stable aluminum oxide, titanium oxide, and zinc oxide are more preferable.
  • the film thickness of the electron transport layer is 0.1 to 500 nm, preferably 0.5 to 300 nm.
  • the electron transport layer can be suitably formed by any of a wet film formation method by coating or the like, a dry film formation method by PVD method such as vapor deposition or sputtering, a transfer method, or a printing method.
  • holes generated in the photoelectric conversion layer do not flow to the negative electrode side in the electron transport layer having a HOMO level deeper than the HOMO level of the p-type semiconductor compound used in the photoelectric conversion layer.
  • a hole blocking function having a rectifying effect is provided.
  • a material deeper than the HOMO level of the n-type semiconductor compound is used as the electron transport layer.
  • Such an electron transport layer is also referred to as a hole block layer, and it is preferable to use an electron transport layer having such a function.
  • Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor compounds such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide.
  • n-type semiconductor compounds such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide.
  • N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.
  • unit used for the photoelectric converting layer can also be used.
  • the support constituting the photovoltaic cell includes at least a first electrode (positive electrode), a photoelectric conversion layer, a second electrode (metal negative electrode), and in a more preferred embodiment, a first electrode (positive electrode), a hole. It is not particularly limited as long as it can form and hold a transport layer, a photoelectric conversion layer, an electron transport layer, and a second electrode (metal negative electrode). For example, glass, plastic film, etc. You can choose.
  • a conventional layer may be applied to provide an easy adhesion layer / undercoat layer, functional layer, recombination layer, other semiconductor layer, protective layer, gas barrier layer, UV absorption layer, antireflection layer, etc. Good.
  • the specific polymer can be used in other devices and systems.
  • field effect transistors eg, photodetectors (eg, infrared photodetectors), photovoltaic detectors, imaging devices (eg, RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (eg, Organic LEDs, or infrared or near-infrared LEDs), laser elements, conversion layers (eg, layers that convert visible emission into infrared emission), amplifiers and radiators for telecommunications (eg, fiber dopants),
  • LEDs light emitting diodes
  • conversion layers eg, layers that convert visible emission into infrared emission
  • amplifiers and radiators for telecommunications eg, fiber dopants
  • These polymers can be used in suitable organic semiconductor elements such as storage elements (eg, holographic storage elements), as well as electrochromic elements (eg, electrochromic displays).
  • Example 1 (Polymer synthesis) The polymer of the present invention was synthesized as follows.
  • the concentrate was purified by silica gel column chromatography, crystallized from chloroform-methanol, and collected by filtration.
  • the solid collected by filtration was extracted with acetone for 10 hours by Soxhlet and then dried under reduced pressure to obtain 669 mg (yield 82%) of the polymer (101).
  • the compound (2-2) was obtained in the same manner as the synthesis of the compound (1-5) except that the cyanoacetic acid ester (1-4) was changed to the malonic acid ester (2-1).
  • the compound (1-5) was changed to the compound (2-2) and the same procedure as in the synthesis of the compound (1-6) was performed to obtain the compound (2-3).
  • the polymer (102) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-7) was replaced with the compound (2-4) and the compound (1-6) was replaced with the compound (2-3). Of 658 mg (yield 79.9%).
  • the cyanoacetate ester (1-4) was changed to the acetoacetate ester (3-1) and the same procedure as in the synthesis of the compound (1-5) was carried out to obtain the compound (3-2).
  • the compound (1-5) was replaced with the compound (3-2) and the same procedure as in the synthesis of the compound (1-6) was performed to obtain the compound (3-3).
  • the polymer (103) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-7) was replaced with the compound (3-4) and the compound (1-6) was replaced with the compound (3-3). 643 mg (yield 80.2%) was obtained.
  • Compound (6-2) was prepared as described in Journal of Organic Chemistry, 1991, 56, p.
  • the compound (6-3) was obtained by reacting with iodooctane according to the method described in 4223-4233.
  • Compound (6-3) was treated with ion exchange resin Amberlite resin IRA-401 (OH ⁇ form) according to the method described in the same document to obtain compound (6-4).
  • compound (9-4) and compound (9-3) were reacted to obtain compound (9-5).
  • Compound (9-8) was synthesized from compound (9-5) according to the method described in Macromolecules, 2001, 34, 1810-1816. Compound (9-8) was hydrolyzed and esterified, and then compound (9-9) was brominated in the same manner as in polymer (101) to give compound (9-10).
  • the polymer (302) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-6) was replaced with the compound (9-10) and the compound (1-7) was replaced with the compound (9-11). 652 mg (yield 81.9%) was obtained.
  • the polymer (303) was prepared in the same manner as the synthesis of the polymer (101) except that the compound (1-6) was replaced with the compound (10-4) and the compound (1-7) was replaced with the compound (10-5). 643 mg (yield 83.1%) was obtained.
  • the compound (11-7) was synthesized with reference to the method described in 756-762.
  • the compound (11-8) is fluorinated according to the method described in US Pat. No. 4,782,180, and the thiophene ring is converted according to the method described in Journal of American Chemical Society, 2009, 131, 7792-7799.
  • Compound (11-12) was synthesized by construction and bromination.
  • the polymer (305) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-6) was replaced with the compound (12-3) and the compound (1-7) was replaced with the compound (2-4). Of 659 mg (yield 80.2%).
  • the polymer (406) was synthesized in the same manner as the polymer (405).
  • Comparative polymer (C-1) is a polymer described in Chemistry of Materials, 2009, 21, 3618-3628. Comparative polymers (C-2) and (C-3) are described in Macromolecules, Vol. 45, 2012, 4069-4074.
  • PEDOT-PSS HC Stark CleviosP VP AI4083
  • HC Stark CleviosP VP AI4083 used as a hole transport layer was spin-coated (3000 rpm) on a glass-ITO substrate that had been cleaned and UV-ozone treated, and dried at 140 ° C. for 30 minutes.
  • a mixture of 10 mg of the polymer (101) and 10 mg of PC 71 BM was dissolved in 2 mL of 3% by mass of 1,8-diiodooctane-containing o-dichlorobenzene and filtered through a 0.45 ⁇ m polytetrafluoroethylene filter (one The amount and mass ratio of the polymer and the fullerene derivative, and the kind and amount of the solvent were changed for some of the exemplified compounds.)
  • the filtrate was applied onto the PEDOT-PSS layer by spin coating (1000 rpm, 40 seconds) and dried to produce a photoelectric conversion layer. The operation so far was performed in a glove box under a nitrogen atmosphere / yellow light. Lithium fluoride and aluminum were sequentially deposited on the photoelectric conversion layer to form an upper electrode to obtain a 2 mm square element. This is element A.
  • annealing was performed at 80 ° C., 90 ° C., 100 ° C., 110 ° C., and 120 ° C. for 10 minutes. Three elements were produced for each temperature, and a total of 15 element C groups were obtained.
  • Elements E group was obtained in the same manner as Element A except that the photoelectric conversion layer was applied and dried under a fluorescent lamp.
  • Sample No. 102 to 406 and comparative sample Nos. C01 to C03 Sample No.
  • the polymer (101) is converted into an equal mass of the polymers (102), (103), (201) to (204), (301) to (310), (401) to (406), the comparative polymer ( Sample No. 1 except that C-1) to (C-3) were replaced.
  • Sample No. 102, 103, 201 to 204, 301 to 310, 401 to 406, and comparative samples C01 to C03 were prepared.
  • the solar cell using the polymer of the present invention as a p-type semiconductor has high photoelectric conversion efficiency, and the polymers [polymers (201) to (204)] represented by formula (2) Polymers represented by (1) [Polymers (101) to (103)] and polymers represented by Formula (3) [Polymers (301) to (310)] and polymers represented by Formula (4) [Polymer The photoelectric conversion ability is improved in the order of (401) to (406)]. Further, all of the polymers (101) to (103) have a small variation in photoelectric conversion ability during device fabrication under fluorescent lamp irradiation. All of the polymers (201) to (204) have small variations with respect to the annealing temperature. All of the polymers (301) to (310) have small variations during device fabrication in the atmosphere.
  • All of the polymers (401) to (406) have small variations due to the spin coat rotation speed. As described above, it can be seen that all the polymers of the present invention have high photoelectric conversion ability, small variation in photoelectric conversion ability with respect to fluctuations in production conditions, and high quality stability during production.

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Abstract

L'invention concerne une cellule solaire à couches minces organiques comportant une première électrode, une deuxième électrode et une couche de conversion photoélectrique, placée entre celles-ci, la couche de conversion photoélectrique incluant des polymères qui comprennent des motifs structuraux représentés par les formules (1)-(4) ; une composition de solvant organique ; un film formé à partir de cette composition ; et des monomères. R11, R12, R41, R42 et R43 représentent des groupes substituants univalents spécifiques, XA, XB, XC, X11, X31, X32 et X41 représentent des groupes divalents ou trivalents spécifiques, et X12 et X21 représentent des groupes divalents spécifiques. Le noyau A représente un noyau aromatique, et le noyau B représente un noyau aromatique ou alicyclique simple ou double. Dans la decription, * représente une liaison formant une chaîne principale polymère.
PCT/JP2013/062847 2012-05-07 2013-05-07 Cellule solaire à couches minces organiques, monomères et composition de matière semi-conductrice utilisée dans une cellule solaire à couches minces organiques WO2013168709A1 (fr)

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CN113264948A (zh) * 2021-04-22 2021-08-17 华南师范大学 一种含酯基取代的芳香杂环共轭骨架及其聚合物材料和应用
WO2023282605A3 (fr) * 2021-07-07 2023-03-02 (주)피엔에이치테크 Élément électroluminescent organique à haut rendement commandé par basse tension ayant une couche monotrou multifonctionnelle

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EP3790918A4 (fr) 2018-05-05 2022-03-16 Jason D. Azoulay Conducteurs polymères conjugués à couche ouverte, composites, et compositions
KR102675085B1 (ko) * 2018-06-20 2024-06-13 (주)피엔에이치테크 유기발광 화합물 및 이를 포함하는 유기발광소자
WO2020106361A2 (fr) 2018-09-21 2020-05-28 Joshua Tropp Post-modification à base de thiol de polymères conjugués
US11781986B2 (en) 2019-12-31 2023-10-10 University Of Southern Mississippi Methods for detecting analytes using conjugated polymers and the inner filter effect
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