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WO2012099000A1 - Élément de conversion photoélectrique organique et photopile - Google Patents

Élément de conversion photoélectrique organique et photopile Download PDF

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WO2012099000A1
WO2012099000A1 PCT/JP2012/050549 JP2012050549W WO2012099000A1 WO 2012099000 A1 WO2012099000 A1 WO 2012099000A1 JP 2012050549 W JP2012050549 W JP 2012050549W WO 2012099000 A1 WO2012099000 A1 WO 2012099000A1
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photoelectric conversion
compound
general formula
organic photoelectric
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Japanese (ja)
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貴宗 服部
大久保　康
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Konica Minolta Inc
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Konica Minolta Inc
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    • H10K30/353—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising blocking layers, e.g. exciton blocking layers
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    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to an organic photoelectric conversion element and a solar cell, and more particularly to a bulk heterojunction type organic photoelectric conversion element and a solar cell using the organic photoelectric conversion element.
  • Non-Patent Document 2 discloses a specific band gap (p-type semiconductor). There is a need for compounds having bg) and LUMO levels.
  • this condition is a necessary condition, and in order to actually achieve a photoelectric conversion efficiency of 10%, it is necessary to satisfy a plurality of conditions.
  • two conditions that an external quantum efficiency (EQE) is 65% and a fill factor (FF) are 65% are set as a precondition.
  • the external quantum efficiency is a value indicating how many electrons can be generated from one photon of sunlight decomposed into a spectrum
  • the fill factor (FF) is the resistance inside the solar cell. It is a value concerned and is the ratio of the actual maximum power on the IV characteristic and the product of the open circuit voltage and the short circuit current. In other words, by setting a coefficient called a curve factor, if the irradiation light is sunlight, the efficiency of the solar cell is expressed by the following simple expression.
  • Photoelectric conversion efficiency (%) open circuit voltage (V) ⁇ short circuit current density (mA / cm 2 ) ⁇ fill factor (FF) Since the integration of external quantum efficiency ⁇ theoretical Jsc is the short-circuit current density, it can be seen that the external quantum efficiency (EQE) and the fill factor (FF) are very important factors for the efficiency of the solar cell.
  • the mobility of the p-type semiconductor material can be mentioned.
  • the open-circuit voltage is a difference between the HOMO level of the p-type semiconductor material used for the bulk heterojunction layer and the LUMO level of the n-type semiconductor material. It is said that there is a correlation, and it is considered that a higher open circuit voltage is obtained as the value of the difference is larger.
  • a suitable morphology is preferably formed in the bulk heterojunction layer in order to obtain higher power generation efficiency.
  • This invention is made
  • the objective is to provide the organic photoelectric conversion element excellent in photoelectric conversion efficiency, and a solar cell using the same.
  • An organic photoelectric conversion element having a transparent first electrode, a photoelectric conversion layer containing a p-type organic semiconductor material and an n-type organic semiconductor material, and a second electrode in this order on a transparent substrate,
  • the photoelectric conversion layer contains a compound having a partial structure represented by the following general formula (1) as the p-type organic semiconductor material.
  • Z 1 and Z 2 are each independently a cyano group, a fluoroalkyl group, —C ( ⁇ O) —R 1 , —C ( ⁇ O) —OR 2 , —C [ ⁇ C (CN 2 ] —R 3 , —C (R 4 ) ⁇ N—SO 2 R 5 , —C (R 6 ) ⁇ N—CN, represents an alkyl group, an aryl group or an alkoxy group, and represents at least one of Z 1 and Z 2
  • Z 1 and Z 2 may be bonded to each other to form a ring.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, —OH, —NHR 7 (R 7 represents a hydrogen atom or an alkyl group), or monovalent Represents an organic group.
  • Y 1 and Y 2 represent CH or N, and X represents a sulfur, oxygen or selenium atom.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in the general formula (1) are each independently a hydrogen atom, —OH, —NHR 7 (R 7 is a hydrogen atom or an alkyl group)
  • R 7 is a hydrogen atom or an alkyl group
  • At least one of Z 1 and Z 2 is —C ( ⁇ O) —OR 2 (R 2 represents an alkyl group).
  • R 2 represents an alkyl group.
  • A represents a saturated divalent linking group
  • Q 1 and Q 2 represent oxygen or a biscyanomethylene group.
  • Y 1 and Y 2 represent CH or N.
  • 7. 7 The organic photoelectric conversion device as described in 6 above, wherein in the general formula (2), Y 1 and Y 2 represent a nitrogen atom.
  • R 10 is an alkyl group having 6 to 10 carbon atoms.
  • Z represents an atom selected from carbon, silicon, and germanium
  • R 15 and R 16 represent a substituent selected from an alkyl group, a fluorinated alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and an alkylsilyl group. Represents a group, may further have a substituent, and may be bonded to each other to form a ring.
  • 12 12 The organic photoelectric conversion device according to any one of 1 to 11, wherein the photoelectric conversion layer is a photoelectric conversion layer produced by a solution coating method.
  • a solar cell comprising the organic photoelectric conversion device as described in any one of 1 to 13 above.
  • the above-described means of the present invention can provide an organic photoelectric conversion element having a high fill factor value and excellent photoelectric conversion efficiency, and a solar cell using the organic photoelectric conversion element.
  • the compound which has a partial structure represented by the said General formula (1) as a p-type organic-semiconductor material of the bulk heterojunction type photoelectric converting layer containing a p-type organic-semiconductor material and an n-type organic-semiconductor material especially By using this, it is possible to provide an organic photoelectric conversion element having a high fill factor value and high photoelectric conversion efficiency.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the organic photoelectric conversion element of the present invention.
  • the organic photoelectric conversion element 10 has a transparent first electrode 12 on a transparent substrate 11, a photoelectric conversion layer 14 on the first electrode 12, and a first electrode on the photoelectric conversion layer 14. Two electrodes 13 are provided.
  • a hole transport layer 17 described later is provided between the first electrode 12 and the photoelectric conversion layer 14, and an electron transport layer described later is provided between the photoelectric conversion layer 14 and the second electrode 13.
  • the substrate 11 and the first electrode 12 are transparent, and light used for photoelectric conversion enters from the direction of the arrow in FIG.
  • the photoelectric conversion layer 14 is a layer that converts light energy into electric energy, and contains a p-type semiconductor material and an n-type semiconductor material.
  • the p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.
  • the generated electric charge is generated between the electron acceptors due to the internal electric field, for example, when the work functions of the first electrode 12 and the second electrode 13 are different, due to the potential difference between the first electrode 12 and the second electrode 13. And the holes pass between the electron donors and are carried to different electrodes, and a photocurrent is detected.
  • the first electrode 12 functions as an anode (anode) and the second electrode functions as a cathode (cathode).
  • Figure 2 shows an example of another configuration.
  • the work function of the second electrode 13 is made larger than the work function of the first electrode 12, whereby electrons are transferred to the first electrode 12.
  • an electron transport layer 18 is provided between the first electrode 12 and the photoelectric conversion layer 14, and a hole transport layer 17 described later is provided between the photoelectric conversion layer 14 and the second electrode 13.
  • the first electrode functions as a cathode (cathode) and the second electrode functions as an anode (anode).
  • the configuration shown in FIG. 2 that is, the first electrode is a cathode (cathode) and the second electrode is an anode (anode) is a preferred embodiment.
  • the organic photoelectric conversion element of the present invention has a layer such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer. You may have.
  • FIG. 3 is a cross-sectional view illustrating an organic photoelectric conversion element including a tandem photoelectric conversion layer.
  • the first electrode 12 and the first photoelectric conversion layer 14 ′ are stacked on the substrate 11, the charge recombination layer 15 is stacked, the second photoelectric conversion layer 16, and then the second photoelectric conversion layer 16.
  • the electrodes 13 By stacking the electrodes 13, a tandem configuration can be obtained.
  • the second photoelectric conversion layer 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion layer 14 ′ or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. is there.
  • each photoelectric conversion layer preferably has a configuration as shown in FIG.
  • the photoelectric conversion layer contains a compound having a partial structure represented by the general formula (1) as a p-type organic semiconductor material.
  • the compound is an organic compound having semiconductor characteristics. Although it may only have the partial structure of the general formula (1), in order to obtain an organic compound having more preferable semiconductor characteristics as an organic thin film solar cell, it may be a compound having a structure combined with a donor unit described later. preferable.
  • X represents an oxygen atom, a sulfur atom or a selenium atom
  • Y represents —CH— or —N—.
  • Z 1 and Z 2 each independently represent a cyano group, a fluoroalkyl group, —C ( ⁇ O) —R 1 , —C ( ⁇ O) —OR 2 , —C [ ⁇ C (CN) 2 ] -R 3 , —CR 4 ⁇ N—SO 2 R 5 , —CR 6 ⁇ N—CN, an alkyl group, an aryl group or an alkoxy group, wherein at least one of Z 1 and Z 2 is a cyano group,
  • a fluoroalkyl group, —C ( ⁇ O) —R 1 , —C ( ⁇ O) —OR 2 , —C [ ⁇ C (CN) 2 ] —R 3 , —CR 4 ⁇ N—SO 2 R 5 , or -CR 6 is N-CN.
  • Z 1 and Z 2 may be bonded to each other to form a ring.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, —OH, —NHR 7 (R 7 represents a hydrogen atom or an alkyl group), or monovalent Represents an organic group.
  • the fluoroalkyl group in Z 1 and Z 2 is an alkyl group in which any one of a straight chain or branched alkyl group having 1 to 20 carbon atoms is substituted with a fluorine atom, and preferably has 1 to 10 carbon atoms. It is an alkyl group in which any hydrogen of a linear alkyl group is substituted with a fluorine atom.
  • halogenated alkyl examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,4 , 4,4-heptafluorobutyl group, 3,3,4,4,5,5,5-heptafluoropentyl group and the like.
  • the alkyl group for Z 1 and Z 2 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the aryl group in Z 1 and Z 2 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • a phenyl group, a p-methylphenyl group, Non-condensed hydrocarbon groups such as biphenyl group and terphenyl group; naphthyl group, pentarenyl group, indenyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group
  • condensed polycyclic hydrocarbon groups such as anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrycen
  • the alkoxy group (—OR) in Z 1 and Z 2 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • n-propoxy group iso-propyloxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-dodecyl
  • Examples thereof include an oxy group, a tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, and a nonadecyloxy group.
  • Z 1 and Z 2 may be bonded to each other to form a ring.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, —OH, —NHR 7 (R 7 represents a hydrogen atom or an alkyl group), or monovalent Represents an organic group.
  • NHR 7 for example, amino group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, methyl-tert-butylamino group, pentylamino group, dihexylamino group, dioctylamino group, didecylamino group, Examples include dihexadecylamino group, 2-ethylhexylamino group, di2-ethylhexylamino group, di2-hexyldecylamino group, dibenzylamino group and the like.
  • Examples of the monovalent organic group in R 1 to R 6 include alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, alkoxycarbonyl group, amino group, alkoxy group, cycloalkyloxy Group, aryloxy group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, silyl group, sulfonyl group, List sulfinyl group, ureido group, phosphoric acid amide group, halogen atom, hydroxyl group, mercapto group, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group
  • R 1 to R 6 are more preferably an alkyl group or an alkoxy group, and particularly preferably an alkyl group.
  • the alkyl group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl groups described above are Examples include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, and an n-hexadecyl group.
  • the cycloalkyl group in R 1 to R 6 preferably has 4 to 8 carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group.
  • the alkenyl group in R 1 to R 6 preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • a vinyl group an allyl group, 2-butenyl group Group, 3-pentenyl group and the like.
  • the alkynyl group in R 1 to R 6 preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a propargyl group and a 3-pentenyl group. Can be mentioned.
  • the aryl group in R 1 to R 6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • the aryl groups described above are Examples thereof include a phenyl group, a p-methylphenyl group, and a naphthyl group.
  • the heteroaryl group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.
  • the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, Examples thereof include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, thienyl and the like.
  • the acyl group (—COR) in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • the alkoxycarbonyl group (—COOR) in R 1 to R 6 preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms.
  • the amino group in R 1 to R 6 preferably has 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms.
  • the amino groups described above are Examples include amino group, methylamino group, dimethylamino group, diethylamino group, pentylamino group, 2-ethylhexylamino group, dibenzylamino group and the like.
  • the alkoxy group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkoxy groups described above are Examples thereof include methoxy group, ethoxy group, n-propoxy group, n-butoxy group and the like.
  • the cycloalkyloxy group in R 1 to R 6 preferably has 4 to 8 carbon atoms, and examples thereof include cyclopentyloxy and cyclohexyloxy.
  • the aryloxy group in R 1 to R 6 preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • phenyloxy, 2-naphthyloxy and the like Is mentioned.
  • the acyloxy group in R 1 to R 6 preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy.
  • the acylamino group (—NHCOR) in R 1 to R 6 preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
  • acetylamino benzoylamino Etc.
  • the alkoxycarbonylamino group in R 1 to R 6 preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like. .
  • the aryloxycarbonylamino group in R 1 to R 6 preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino and the like. Can be mentioned.
  • the sulfonylamino group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • methanesulfonylamino, benzenesulfonylamino, etc. Is mentioned.
  • the sulfamoyl group for R 1 to R 6 preferably has 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl. Famoyl, phenylsulfamoyl and the like can be mentioned.
  • the carbamoyl group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • carbamoyl methylcarbamoyl, diethylcarbamoyl, phenyl And carbamoyl.
  • the alkylthio group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio.
  • the arylthio group in R 1 to R 6 preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio.
  • the sulfonyl group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl.
  • the sulfinyl group in R 1 - R 6, preferably from 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, e.g., methanesulfinyl, benzenesulfinyl, and the like .
  • the ureido group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, phenylureido and the like. Can be mentioned.
  • the phosphoric acid amide group in R 1 to R 6 preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • diethylphosphoric acid amide, phenyl phosphorus Examples include acid amides.
  • halogen atom in R 1 to R 6 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, —OH, —NHR 7 (R 7 is a hydrogen atom or an alkyl group) Represents an alkyl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group, when Z 1 and Z 2 do not form a ring.
  • Z 1 and Z 2 do not form a ring, among the above substituents, Z 1 or Z 2 preferably has a cyano group or —C ( ⁇ O) —OR 2 , and Z 1 More preferably, both Z and Z 2 are cyano groups, or both Z 1 and Z 2 are —C ( ⁇ O) —OR 2 .
  • R 1 is selected from the group consisting of a hydrogen atom, —OH, and —NHR 7 (R 7 represents a hydrogen atom or an alkyl group). preferable.
  • the two R 1 groups of Z 1 and Z 2 are a combination of a hydrogen atom and —OH, and a combination of a hydrogen atom and NHR 7 (R 7 represents an alkyl group).
  • R 3 is selected from the group consisting of a hydrogen atom, —NHR 7 (R 7 represents a hydrogen atom or an alkyl group) and an alkyl group. preferable.
  • two R 3 groups of Z 1 and Z 2 are a combination of a hydrogen atom and an alkyl group, a combination of an alkyl group and an alkyl group, a hydrogen atom and —NHR 7 (R 7 represents an alkyl group), It is a combination.
  • R 4 ) ⁇ N—SO 2 R 5 R 4 and R 5 are preferably selected from the group consisting of a hydrogen atom or an alkyl group. More preferably, the two R 4 groups of Z 1 and Z 2 are a combination of an alkyl group and an alkyl group.
  • R 6 is preferably selected from the group consisting of a hydrogen atom and an alkyl group.
  • two R 6 of Z 1 and Z 2 is a combination of an alkyl group and an alkyl group.
  • Z 1 and Z 2 form a ring means that the carbon (C1) -hydrogen bond of Z 1 selected from the above substituents and the carbon of Z 2 selected from the above substituents. It means that (C2) -hydrogen bond forms a ring and becomes a C1-C2 bond.
  • the thienobenzene and thienopyrazine structures represented by the general formula (1) have a deep HOMO level and a narrow band gap, and an element having a high open-circuit voltage and a short-circuit current can be obtained. More preferred.
  • X is preferably a sulfur atom.
  • X is a sulfur atom, the conductivity is improved and high mobility is provided.
  • both Z 1 and Z 2 are the above cyano group, fluoroalkyl group, —C ( ⁇ O) —R 1 , —C ( ⁇ O) —OR 2 , —C [ ⁇ C (CN ) 2 ] —R 3 , —C (R 4 ) ⁇ N—SO 2 R 5 , and —C (R 6 ) ⁇ N—CN, the compound has a deeper HOMO level.
  • Z 1 and Z 2 are —C ( ⁇ O) —R 1 , —C ( ⁇ O) —OR 2 , —C [ ⁇ C (CN) 2 ] —R 3 , —C
  • the partial structure represented by the general formula (1) is a partial structure represented by the following general formula (4).
  • A represents —CH 2 CH 2 —, a connecting group of oxygen atom or nitrogen atom
  • Q 1 and Q 2 are oxygen atoms
  • ⁇ N (CN), ⁇ N—SO 2 R 5 , or C (CN) 2 is represented
  • Y 1 and Y 2 represent CH or N
  • X represents sulfur, oxygen or selenium atom.
  • the partial structure represented by the general formula (1) is more preferably a partial structure represented by the general formula (2).
  • A represents a nitrogen atom in the general formula (4) or (2)
  • the effect is improved and higher mobility is provided. That is, in the general formula (4) or (2), it is preferable that Y 1 and Y 2 represent a nitrogen atom.
  • R 10 is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 6 to 10 carbon atoms, and more preferably a branched alkyl group having 6 to 10 carbon atoms. It is an alkyl group. Specific examples of the alkyl group include the alkyl groups described above, and examples thereof include n-pentyl, n-hexyl, 2-ethylhexyl and the like. Of these, 2-ethylhexyl is preferred.
  • the solubility is improved and a polymer having a high molecular weight is easily obtained when a polymer containing the present compound is prepared.
  • the solubility is further improved, and a compound having a higher molecular weight can be obtained.
  • the structures represented by the general formulas (1), (4), and (2) are structures generally called acceptors (hereinafter, the partial structure is also referred to as an acceptor unit), and a unit that functions as a donor ( By combining with a donor unit), a narrow band gap material, that is, a material that can efficiently absorb sunlight up to a long wavelength. That is, the compound having a partial structure represented by the general formula (1) of the present invention preferably has an arbitrary donor unit.
  • any unit that has a LUMO level or a HOMO level shallower than a hydrocarbon aromatic ring (benzene, naphthalene, anthracene, etc.) having the same ⁇ electron number can be used without limitation. it can.
  • a thiophene ring More preferably, a thiophene ring, a furan ring, a pyrrole ring, a hetero 5-membered ring such as cyclopentadiene, silacyclopentadiene, a benzene ring, and a structure containing these as a condensed ring.
  • fluorene examples include fluorene, silafluorene, carbazole, dithienocyclopentadiene, dithienosilacyclopentadiene, dithienopyrrole, benzodithiophene, and structures containing these as condensed rings.
  • the donor unit is preferably a compound having a partial structure represented by the following general formula (3), (5), or (6).
  • Z represents an atom selected from carbon, silicon, and germanium. Of these, carbon and silicon are preferable, and silicon is more preferable.
  • R 15 and R 16 each represents a substituent selected from an alkyl group, a fluorinated alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and an alkylsilyl group, and further has a substituent. It may be bonded to each other to form a ring. Among these, an alkyl group is particularly preferable and used.
  • R 17 , R 18 , R 19 and R 20 are each independently an alkyl group, a fluorinated alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, or a heteroaryl group.
  • an alkyl group and an alkoxy group are preferable, and an alkoxy group is more preferably used.
  • the alkyl group in R 15 to R 20 is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a linear alkyl group having 1 to 10 carbon atoms. Specific examples include the alkyl groups described above.
  • the fluorinated alkyl group for R 15 to R 20 is an alkyl group in which any one of a straight chain or branched alkyl group having 1 to 20 carbon atoms is substituted with fluorine, and preferably has 1 to 10 carbon atoms. Any hydrogen in the linear alkyl group is an alkyl group substituted with fluorine. Specific examples include the fluorinated alkyl groups (fluoroalkyl groups) described above.
  • the cycloalkyl group in R 15 to R 20 is a cyclic alkyl group having 4 to 8 carbon atoms. Specific examples include the cycloalkyl groups described above.
  • the aryl group in R 15 to R 20 is an aromatic group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Specific examples include the aryl groups described above.
  • the heteroaryl group in R 15 to R 20 is a heteroaromatic group having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and the hetero atom is a nitrogen atom, an oxygen atom, or a sulfur atom.
  • Specific examples of the alkylsilyl group in R 15 to R 20 include the heteroaryl groups described above are silyl groups having an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. For example, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl and the like can be mentioned.
  • the alkoxy group for R 15 and R 16 is an oxyalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specific examples include the alkoxy groups described above. For example, n-octyloxy, n-dodecyloxy and the like are preferable.
  • the structure represented by the above general formulas (3) and (5) has a half surface having a larger ⁇ -conjugated plane by condensation of a highly mobile thiophene structure, and a substituent capable of imparting solubility. Therefore, both solubility and high mobility can be achieved, and higher photoelectric conversion efficiency can be expected.
  • a structure in which the atom represented by Z is a silicon atom is preferable. This is because, as described in AdvMatter 2010p367, when Z is a silicon atom, the crystallinity is high and high mobility tends to be obtained.
  • a polymer having a number average molecular weight of 10,000 to 100,000 is preferable, and a polymer having a number average molecular weight of 15,000 to 50,000 is more preferable.
  • the number average molecular weight can be measured by gel permeation chromatography (GPC).
  • the number average molecular weight is measured by the following method.
  • the combination of the acceptor unit exemplified above and the donor unit is not particularly limited, and an arbitrary acceptor unit and any donor unit may be appropriately combined to form a compound (conjugated system).
  • Molecular compounds can be synthesized and used.
  • a compound having an acceptor unit and a donor unit is synthesized and its performance is evaluated.
  • the technical scope of the present invention is not limited to these examples.
  • the proportion of the partial structure (1) in the compound having a partial structure according to the present invention is generally preferably 20 to 80% by mass, particularly preferably 25 to 60% by mass with respect to the compound.
  • the compound is preferably a high molecular weight compound as described above.
  • the compound has a partial structure as a repeating unit, and the entire compound including a repeating unit other than the partial structure is used. , Preferably in the range of 30 to 50 mol%.
  • the reason why the photoelectric conversion layer has the compound having the partial structure represented by the general formula (1) to achieve the effect of the present application is not clear, but is estimated as follows.
  • Non-Patent Document 3 and Non-Patent Document 4 do not have an electron withdrawing group.
  • the partial structure according to the present invention since the partial structure according to the present invention has an electron-attracting group, it is considered that the HOMO level of the compounds is lower than those of the compounds and gives a high open circuit voltage.
  • n is a value that falls within the above-described molecular weight.
  • n needs to be about 10 to 200 in order to fall within the range of the number average molecular weight of 10,000 to 100,000. There is.
  • Y 1 in the general formula (1) is carbon
  • the compound 301 and 401 is Y 1
  • Y 2 in the general formula (1) is carbon
  • the compound 301 and 401 is Y 1
  • Y 2 showing an example of the synthesis of the compounds 607,901,902 is N.
  • Exemplified compound 301 is synthesized by a polymerization reaction of the following compound (A) and compound (B).
  • Compound (B) Compound (B) can be synthesized with reference to Chemical Communications, 2009, 5570-5572.
  • the obtained precipitate was dissolved in chloroform and filtered to remove insoluble matters.
  • the resulting chloroform solution was purified by passing through an alumina column.
  • the obtained chloroform solution was concentrated under reduced pressure, added to 200 ml of methanol, and reprecipitated. This precipitate was dried under reduced pressure to obtain 0.12 g of Exemplified Compound 301.
  • Exemplified compound 401 can be synthesized by a polymerization reaction of the following compound (D) and compound (B).
  • the obtained precipitate was dissolved in chloroform and filtered to remove insoluble matters.
  • the resulting chloroform solution was purified by passing through an alumina column.
  • the obtained chloroform solution was concentrated under reduced pressure, added to 200 ml of methanol, and reprecipitated. This precipitate was dried under reduced pressure to obtain 0.24 g of Exemplified Compound 401.
  • Illustrative compound 607 can be synthesized by a polymerization reaction of the following compound (F) and compound (B).
  • Compound (F) can be synthesized from compound (G) according to the following route.
  • Synthesis of Compound (G) J. Org. Chem. Vol. 73, no. 21, 2008, 8531 can be used as a reference.
  • Synthesis of Compound (F) 3.97 g of Compound (G) and 1.74 g of n-octylboronic acid were placed in a nitrogen-substituted 100 ml three-necked flask, dissolved in 50 ml of toluene, and cooled on ice. 1.16 g of triphenylphosphine tetrakis palladium was added to the resulting solution, and the mixture was heated to reflux for 12 hours. Toluene was distilled off under reduced pressure and purified by silica gel column chromatography to obtain 3.0 g of compound (F).
  • the obtained precipitate was dissolved in chloroform and filtered to remove insoluble matters.
  • the resulting chloroform solution was purified by passing through an alumina column.
  • the obtained chloroform solution was concentrated under reduced pressure, added to 200 ml of methanol, and reprecipitated. This precipitate was dried under reduced pressure to obtain 0.30 g of Exemplified Compound 607.
  • Illustrative compound 610 can be synthesized by a polymerization reaction of the following compound (H) and compound (B).
  • Compound (H) can be synthesized from compound (J) according to the following route.
  • the obtained precipitate was dissolved in chloroform and filtered to remove insoluble matters.
  • the resulting chloroform solution was purified by passing through an alumina column.
  • the obtained chloroform solution was concentrated under reduced pressure, added to 200 ml of methanol, and reprecipitated. This precipitate was dried under reduced pressure to obtain 0.29 g of Exemplified Compound 610.
  • Example Compound 901 can be synthesized by a polymerization reaction of compound (K) and compound (B).
  • Compound (K) can be synthesized from compound (N) according to the following synthesis route.
  • Exemplified compound 902 can be synthesized by a polymerization reaction of the following compound (K) and compound (P).
  • the p-type organic semiconductor material contains a compound having a partial structure represented by the general formula (1), and preferably contains a compound having a structure combined with a donor unit.
  • p-type semiconductor materials may be added in addition to the compound having the partial structure.
  • examples of other p-type semiconductor materials used for the photoelectric conversion layer include various condensed polycyclic aromatic low molecular compounds and conjugated polymers.
  • condensed polycyclic aromatic low molecular weight compound examples include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthanthene, bisanthene, zeslene.
  • TTF tetrathiafulvalene
  • TCNQ tetracyanoquinodimethane
  • BEDTTTTF bisethylenetetrathiafulvalene
  • Examples of the derivative having the above condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A.
  • conjugated polymer for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and its oligomer, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer described in WO2008000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO2008000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160, Nature Mat. vol.
  • P3HT poly-3-hexylthiophene
  • polypyrrole and its oligomer polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as ⁇ -conjugated polymers such as polysilane and polygermane.
  • oligomeric materials not polymer materials, include thiophene hexamer ⁇ -seccithiophene ⁇ , ⁇ -dihexyl- ⁇ -sexualthiophene, ⁇ , ⁇ -dihexyl- ⁇ -kinkethiophene, ⁇ , ⁇ -bis (3 Oligomers such as -butoxypropyl) - ⁇ -sexithiophene can be preferably used.
  • an electron transport layer or a hole blocking layer is further formed on a photoelectric conversion layer (bulk hetero junction layer) by a solution process, it can be easily laminated if it can be further applied on the layer once applied.
  • a layer is further laminated by a solution process on a layer made of a material having a good solubility, there is a problem that it cannot be laminated because the underlying layer is dissolved. Therefore, the material which can be insolubilized after apply
  • Such materials include materials that can be insolubilized by polymerizing and crosslinking the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or a material in which soluble substituents react and become insoluble (pigmented) by applying energy such as heat, as described in US Patent Application Publication No. 2003/136964, and Japanese Patent Application Laid-Open No. 2008-16834 And so on.
  • the n-type organic semiconductor material used for the photoelectric conversion layer according to the present invention is not particularly limited. Fluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides and imidized compounds thereof Examples thereof include polymer compounds.
  • fullerene derivatives that can efficiently perform charge separation with various p-type semiconductor materials at high speed (up to 50 femtoseconds) are preferable.
  • Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Partially by hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, etc. Examples thereof include substituted fullerene derivatives.
  • N-methylfullropyrrolidine [6,6] -phenyl C61-butyric acid methyl ester (abbreviation PC61BM), [6,6] -phenyl C61-butyric acid-n-butyl ester (PC61BnB), [6,6]- Phenyl C61-butyric acid-isobutyl ester (PC61BiB), [6,6] -phenyl C61-butyric acid-n-hexyl ester (PC61BH), [6,6] -phenyl C71-butyric acid methyl ester (abbreviation) PC71BM), Adv. Mater. , Vol.
  • fullerene having a cyclic ether group such as Amer. Chem. Soc. , (2009) vol. 130, p15429, SIMEF, Appl. Phys. Lett. , Vol. 87 (2005), C60MC12 described in p203504, etc. It is preferable to use a fullerene derivative having a substituent and having improved solubility as described below.
  • the junction form of the p-type organic semiconductor and the n-type organic semiconductor in the photoelectric conversion layer is not particularly limited, and may be a planar heterojunction or a bulk heterojunction.
  • a planar heterojunction is a junction in which a p-type organic semiconductor layer containing a p-type organic semiconductor and an n-type organic semiconductor layer containing an n-type organic semiconductor are stacked, and the surface where these two layers contact is the pn junction interface. It is a form.
  • a bulk heterojunction is formed by applying a mixture of a p-type organic semiconductor and an n-type organic semiconductor. In this single layer, a domain of the p-type organic semiconductor and a domain of the n-type organic semiconductor are formed.
  • the junction between the p-type organic semiconductor and the n-type organic semiconductor in the photoelectric conversion layer is preferably a bulk heterojunction.
  • the photoelectric conversion layer (bulk heterojunction layer) is composed of a single layer (i layer) obtained by mixing a normal p-type organic semiconductor material and an n-type organic semiconductor layer. In some cases, it has a three-layer structure (pin structure) sandwiched between a p-layer made of a p-type organic semiconductor and an n-layer made of an n-type organic semiconductor. Such a pin structure has higher rectification of holes and electrons, reduces loss due to charge-separated hole-electron recombination, and can achieve higher photoelectric conversion efficiency. .
  • the mixing ratio of the p-type organic semiconductor and the n-type organic semiconductor contained in the photoelectric conversion layer is preferably in the range of 2: 8 to 8: 2, more preferably 4: 6 to 6: 4. Range.
  • the film thickness of one photoelectric conversion layer is preferably 50 to 400 nm, more preferably 80 to 300 nm, and particularly preferably 100 to 200 nm. In general, from the viewpoint of absorbing more light, it is preferable that the thickness of the photoelectric conversion layer is larger. However, as the film thickness increases, the extraction efficiency of carriers (holes / electrons) decreases, so the photoelectric conversion efficiency decreases. Tend to.
  • a compound having the partial structure of the formula (1) of the present invention when used as a p-type organic semiconductor material to form a photoelectric conversion layer, it is 100 nm as compared with a photoelectric conversion layer using a conventional p-type organic semiconductor material. Even in the case of the above film thickness, since the extraction efficiency of carriers (holes / electrons) is difficult to decrease, high photoelectric conversion efficiency can be maintained.
  • Examples of a method for forming a photoelectric conversion layer containing a p-type organic semiconductor material and an n-type organic semiconductor material include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • the coating method is preferable in order to increase the area of the interface where charge and electron separation of the above-described holes is performed and to produce a device having high photoelectric conversion efficiency. Also, the coating method is excellent in production speed. That is, the photoelectric conversion layer of the present invention is preferably produced by a solution coating method.
  • the application method used in this case is not limited, and examples thereof include spin coating, casting from a solution, dip coating, wire bar coating, gravure coating, and spray coating. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.
  • a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.
  • the photoelectric conversion layer can have an appropriate phase separation structure.
  • the photoelectric conversion layer may be composed of a single layer in which a p-type organic semiconductor material and an n-type organic semiconductor material are uniformly mixed.
  • the photoelectric conversion layer may be a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. It may be configured. In this case, it can be formed by using a material that can be insolubilized after application.
  • Electrode transport layer In the organic photoelectric conversion element of the present invention, by forming an electron transport layer in the middle of the photoelectric conversion layer and the cathode, it becomes possible to more efficiently extract charges generated in the photoelectric conversion layer. It is preferable to have.
  • the first electrode is a cathode.
  • the electron transport layer is a layer that is located between the cathode and the bulk heterojunction layer and can more efficiently transfer electrons between the bulk heterojunction layer and the electrode.
  • a compound having an LUMO level intermediate between the LUMO level of the n-type semiconductor material of the bulk heterojunction photoelectric conversion layer and the work function of the cathode is suitable as the electron transporting layer.
  • it is a compound having an electron mobility of 10 ⁇ 4 or more.
  • the electron transport layer having a HOMO level deeper than the HOMO level of the p-type semiconductor material used in the bulk heterojunction type photoelectric conversion layer includes a hole generated in the bulk heterojunction layer as a cathode.
  • a hole blocking function having a rectifying effect that does not flow to the side is provided.
  • Such an electron transport layer is also referred to as a hole blocking layer. More preferably, a material having a HOMO level deeper than the HOMO level of the n-type semiconductor is used for the electron transport layer. In addition, in view of the property of blocking holes, it is preferable to use a compound having a hole mobility lower than 10 ⁇ 6 .
  • the electron transport layer As the electron transport layer, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), carboline compounds described in International Publication No. 04/095889, and the like can be used.
  • the electron transport layer having a HOMO level deeper than the HOMO level of the p-type semiconductor material used for the photoelectric conversion layer has a rectifying effect so that holes generated in the photoelectric conversion layer do not flow to the cathode side.
  • the hole blocking function is imparted.
  • a material deeper than the HOMO level of the n-type semiconductor is used as the electron transport layer.
  • Such an electron transport layer is also called a hole blocking 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 materials 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 means for forming these layers may be either a vacuum vapor deposition method or a solution coating method, but is preferably a solution coating method.
  • the organic photoelectric conversion element of the present invention has a hole transport layer between the photoelectric conversion layer and the anode, and it is possible to extract charges generated in the photoelectric conversion layer more efficiently. It is preferable.
  • the present invention can be preferably applied when the second electrode is a hole transport layer.
  • PEDOT poly-3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • cyan compounds described in International Publication No. 06/019270, and the like can be used.
  • the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the photoelectric conversion layer has a rectifying effect that prevents electrons generated in the photoelectric conversion layer from flowing to the anode side. It has an electronic block function.
  • Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function.
  • unit used for the photoelectric converting layer can also be used.
  • the means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming a coating film in the lower layer before forming the photoelectric conversion layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.
  • it preferably has a hole mobility higher than 10 ⁇ 4 due to the property of transporting holes, and a compound with electron mobility lower than 10 ⁇ 6 due to the property of blocking electrons. It is preferable to use it.
  • Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.
  • the organic photoelectric conversion element of the present invention has the first electrode and the second electrode.
  • the tandem configuration can be achieved by using the intermediate electrode.
  • the first electrode is a transparent electrode.
  • Transparent means that the light transmittance is 50% or more.
  • the light transmittance is the total light transmittance in the visible light wavelength region measured by a method in accordance with “Testing method of total light transmittance of plastic-transparent material” of JIS K 7361-1 (corresponding to ISO 13468-1). Say.
  • the first electrode of the present invention is preferably a transparent cathode (cathode), and the second electrode is preferably an anode (anode).
  • first electrode transparent cathode
  • transparent metal oxides such as indium tin oxide (ITO), AZO, FTO, SnO 2 , ZnO, and titanium oxide, Ag, Al, Au, and Pt.
  • ITO indium tin oxide
  • AZO zinc oxide
  • FTO zinc oxide
  • SnO 2 zinc oxide
  • ZnO zirconium oxide
  • titanium oxide Ag, Al, Au
  • Pt platinum oxide
  • a very thin metal layer, a metal nanowire, a layer containing nanowires such as carbon nanotubes or a nanoparticle, a conductive polymer material such as PEDOT: PSS, polyaniline, or the like can be used.
  • Conductive polymers can also be used. Further, a plurality of these conductive compounds can be combined to form a cathode.
  • the second electrode may be a single conductive material layer, but in addition to a conductive material, a resin that holds these may be used in combination.
  • the work function of the transparent electrode which is the cathode
  • the built-in potential is necessary for carriers generated in the bulk heterojunction type photoelectric conversion layer to diffuse and reach each electrode. That is, it is preferable that the work function difference between the anode and the cathode is as large as possible.
  • the conductive material of the anode a material having a work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used.
  • an electrode material include gold, silver, copper, platinum, rhodium, indium, nickel, palladium, and the like.
  • silver is most preferable from the viewpoint of hole extraction performance, light reflectance, and durability against oxidation.
  • the anode 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 anode side is made light transmissive
  • a conductive material suitable for the anode such as aluminum and aluminum alloy
  • silver and silver compound is made thin with a film thickness of about 1 to 20 nm, and then the transparent electrode A light-transmitting anode can be obtained by providing the conductive light-transmitting material film mentioned in the description.
  • the so-called normal layer type (the first electrode is an anode and the second electrode is a cathode)
  • the relationship between the work functions of the first electrode and the second electrode may be reversed as described above, but the types of substantially transparent electrodes are limited, and the work functions are compared.
  • a normal layer type organic thin film solar cell can be obtained by using a metal having a shallow work function (less than ⁇ 4.0 eV) on the second electrode side. Examples of such a metal include aluminum, calcium, magnesium, lithium, sodium, potassium, and the like. In general, aluminum having high reflectivity and high conductivity is used.
  • the material of the intermediate electrode required in the case of the tandem configuration as shown in FIG. 3 is preferably a layer using a compound having both transparency and conductivity.
  • Transparent metal oxides such as ITO, AZO, FTO, SnO 2 , ZnO and titanium oxide, very thin metal layers such as Ag, Al, Au and Pt, or layers containing nanowires and nanoparticles such as metal nanowires and carbon nanotubes PEDOT: PSS, conductive polymer materials such as polyaniline, etc.
  • conductive polymer materials such as polyaniline, etc.
  • the substrate is a transparent substrate, and the term “transparent” has the same meaning as described above for the electrodes.
  • the substrate for example, a glass substrate, a resin substrate, and the like are preferably used, but it is desirable to use a transparent resin film from the viewpoint of light weight and flexibility.
  • a transparent resin film which can be preferably used as a transparent substrate by this invention,
  • the material, a shape, a structure, thickness, etc. can be suitably selected from well-known things.
  • polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc.
  • Resin films vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like.
  • the resin film transmittance of 80% or more at 80 ⁇ 800 nm) can be preferably applied to a transparent resin film according to the present invention.
  • biaxially stretched polyethylene terephthalate film preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film. More preferred are a stretched polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film.
  • the transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a conventionally well-known technique can be used about a surface treatment or an easily bonding layer.
  • the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.
  • a barrier coat layer may be formed in advance on the transparent substrate, or a hard coat layer may be formed in advance on the opposite side to which the transparent conductive layer is transferred. Good.
  • the organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight.
  • a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .
  • the antireflection layer can be provided as the antireflection layer.
  • the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ⁇ 1.63 because the transmittance can be improved by reducing the interface reflection between the film substrate and the easy adhesion layer.
  • the method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • the condensing layer for example, it is processed to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the light scattering layer examples include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.
  • the method and process for patterning each electrode, photoelectric conversion layer, hole transport layer, electron transport layer and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.
  • the electrode can be patterned by a known method such as mask vapor deposition during vacuum deposition or etching or lift-off.
  • the pattern may be formed by transferring a pattern formed on another substrate.
  • the solar cell of this invention has said organic photoelectric conversion element. That is, this invention provides the solar cell which comprises the said organic photoelectric conversion element.
  • the solar cell of the present invention comprises the above-described organic photoelectric conversion element, has a structure in which optimum design and circuit design are performed for sunlight, and optimum photoelectric conversion is performed when sunlight is used as a light source. .
  • the photoelectric conversion layer has a structure that can be irradiated with sunlight, and when the solar cell of the present invention is configured, the photoelectric conversion layer and each electrode are housed in a case and sealed, Alternatively, it is preferable to seal them entirely with resin.
  • a sealing method it is preferable to seal not only the organic photoelectric conversion element but also an organic electroluminescence element by a known method so that the produced organic photoelectric conversion element does not deteriorate due to oxygen, moisture, etc. in the environment. .
  • a method of sealing a cap made of aluminum or glass with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element with an adhesive For example, a method of sealing a cap made of aluminum or glass with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element with an adhesive.
  • Method of bonding spin coating of organic polymer materials with high gas barrier properties (polyvinyl alcohol, etc.), inorganic thin films with high gas barrier properties (silicon oxide, aluminum oxide, etc.) or organic films (parylene, etc.) deposited under vacuum And a method of laminating these in a composite manner.
  • AFPO-Green 5 used as a comparative example was synthesized with reference to Non-Patent Document 3.
  • the patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried by nitrogen blowing, and finally subjected to ultraviolet ozone cleaning.
  • the substrate was brought into a glove box (oxygen concentration 10 ppm, dew point temperature ⁇ 80 ° C.), and a 150 mM TiOx precursor solution prepared by the following procedure was spin coated (rotation speed 2000 rpm) on the transparent substrate under a nitrogen atmosphere. , Rotation time 60 s), and wiped off in a predetermined pattern.
  • the TiOx precursor was hydrolyzed by being left in the air, and then the TiOx precursor was heat-treated at 150 ° C. for 1 hour to obtain a 30 nm TiOx layer as an electron transport layer.
  • the mixed solution was heated at 80 ° C. for 2 hours and then refluxed for 1 hour. Finally, it was cooled to room temperature and adjusted to a predetermined concentration (150 ml) using methoxyethanol to obtain a TiOx precursor. The above steps were all performed in a nitrogen atmosphere.
  • photoelectric conversion layer (Preparation of photoelectric conversion layer) Next, photoelectric conversion by dissolving AFPO-Green5 as a p-type semiconductor material in 1.0% by mass and PC71BM (manufactured by Frontier Carbon, Nano Spectra E110H) as an n-type semiconductor material in 0.8% by mass in dichlorobenzene. A layer solution was prepared. The photoelectric conversion layer solution is spin-coated so as to have a film thickness of 150 nm after drying while being filtered with a 0.45 ⁇ m filter, and dried at room temperature for 30 minutes to obtain a photoelectric conversion layer on the TiOx layer. It was.
  • An organic solvent-based PEDOT: PSS dispersion (Enocoat HC200, manufactured by Kaken Sangyo Co., Ltd.) is spin-coated (2000 rpm, 60 s) on the obtained photoelectric conversion layer (also referred to as an organic semiconductor layer) to form a conductive polymer layer. Filmed and air dried to produce a hole transport layer.
  • Evaluation of the obtained organic photoelectric conversion element 1 was evaluated as a solar cell as follows.
  • the obtained organic photoelectric conversion element 1 was irradiated with light from a solar simulator (AM1.5G) at an irradiation intensity of 100 mW / cm 2 without sealing, and voltage-current characteristics were measured. Voltage), FF (fill factor) and photoelectric conversion efficiency were measured.
  • Organic photoelectric conversion elements 2-13 were prepared in the same manner except that AFPO-Green 5 was changed to the compounds shown in Table 1 in the production of organic photoelectric conversion element 1.
  • the compounds 301, 401, 607, 901, and 902 those described above were used.
  • Compounds 201, 203 and 504 were synthesized in the same manner as described above.
  • the molecular weights of the compounds 201, 203, and 504 are shown below.
  • the molecular weight is the number average molecular weight (Mn)
  • Synthesis of Compound 701 Compound 701 can be synthesized by changing ethylhexylamine used when compound 901 was synthesized to pentylamine.
  • Compound 801 can be synthesized by changing the ethylhexylamine used in the synthesis of compound 901 to hexylamine.
  • the obtained organic photoelectric conversion elements 2 to 13 were each sealed with an epoxy resin and a glass cap, and irradiated with solar simulator (AM1.5G) light at an irradiation intensity of 100 mW / cm 2 , and voltage-current characteristics. Were measured, and Voc (open circuit voltage), FF (fill factor) and photoelectric conversion efficiency were measured.
  • A1.5G solar simulator
  • the organic photoelectric conversion elements 2 to 13 of the present invention have high Voc (open voltage), FF (curve factor) and photoelectric conversion efficiency, and are excellent as solar cells. It was found to show the characteristics.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'objet de la présente invention est de fournir un élément de conversion photoélectrique organique présentant une excellente efficacité de conversion photoélectrique, et une photopile utilisant l'élément de conversion photoélectrique organique. A cet effet, un élément de conversion photoélectrique organique présente dans cet ordre sur un substrat transparent, une première électrode transparente, une couche de conversion photoélectrique contenant un matériau semi-conducteur organique de type p et un matériau semi-conducteur organique de type n, et une seconde électrode. L'élément de conversion photoélectrique organique est caractérisé en ce que la couche de conversion photoélectrique contient, comme matériau semi-conducteur organique de type p, un composé présentant une structure partielle exprimée par la formule générale (1).
PCT/JP2012/050549 2011-01-18 2012-01-13 Élément de conversion photoélectrique organique et photopile Ceased WO2012099000A1 (fr)

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JP2012162514A (ja) * 2011-01-20 2012-08-30 Kuraray Co Ltd ジチエノゲルモール重合体及びそれを含有した有機半導体デバイス
JP2012207104A (ja) * 2011-03-29 2012-10-25 Mitsubishi Chemicals Corp ヨウ素化縮合チオフェン化合物を用いたコポリマーの製造方法、及びヨウ素化ジオキソピロロチオフェン化合物
JP2013023572A (ja) * 2011-07-20 2013-02-04 Mitsubishi Chemicals Corp 新規コポリマー、有機半導体材料、及びこれを用いた有機電子デバイス、光電変換素子並びに太陽電池モジュール
JP2013170187A (ja) * 2012-02-17 2013-09-02 Fujifilm Corp 有機光電変換素子組成物、これを含む薄膜、光電池、これに用いられる有機半導体ポリマー、化合物およびポリマーの製造方法
WO2013168709A1 (fr) * 2012-05-07 2013-11-14 富士フイルム株式会社 Cellule solaire à couches minces organiques, monomères et composition de matière semi-conductrice utilisée dans une cellule solaire à couches minces organiques

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012162514A (ja) * 2011-01-20 2012-08-30 Kuraray Co Ltd ジチエノゲルモール重合体及びそれを含有した有機半導体デバイス
JP2012207104A (ja) * 2011-03-29 2012-10-25 Mitsubishi Chemicals Corp ヨウ素化縮合チオフェン化合物を用いたコポリマーの製造方法、及びヨウ素化ジオキソピロロチオフェン化合物
JP2013023572A (ja) * 2011-07-20 2013-02-04 Mitsubishi Chemicals Corp 新規コポリマー、有機半導体材料、及びこれを用いた有機電子デバイス、光電変換素子並びに太陽電池モジュール
JP2013170187A (ja) * 2012-02-17 2013-09-02 Fujifilm Corp 有機光電変換素子組成物、これを含む薄膜、光電池、これに用いられる有機半導体ポリマー、化合物およびポリマーの製造方法
US9680103B2 (en) 2012-02-17 2017-06-13 Fujifilm Corporation Organic photoelectric conversion element composition, thin film and photovoltaic cell each containing the same, organic semiconductor polymer and compound each for use in these, and method of producing the polymer
WO2013168709A1 (fr) * 2012-05-07 2013-11-14 富士フイルム株式会社 Cellule solaire à couches minces organiques, monomères et composition de matière semi-conductrice utilisée dans une cellule solaire à couches minces organiques
JP2013254943A (ja) * 2012-05-07 2013-12-19 Fujifilm Corp 有機薄膜太陽電池、これに用いられる有機半導体材料用組成物および単量体

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