WO2012111811A1 - Élément de conversion photoélectrique organique et photopile - Google Patents

Élément de conversion photoélectrique organique et photopile Download PDF

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WO2012111811A1
WO2012111811A1 PCT/JP2012/053836 JP2012053836W WO2012111811A1 WO 2012111811 A1 WO2012111811 A1 WO 2012111811A1 JP 2012053836 W JP2012053836 W JP 2012053836W WO 2012111811 A1 WO2012111811 A1 WO 2012111811A1
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photoelectric conversion
carbon atoms
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organic photoelectric
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大久保　康
貴宗 服部
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コニカミノルタホールディングス株式会社
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Priority to JP2012558038A priority Critical patent/JP5838975B2/ja
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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.
  • an electron donor layer p-type semiconductor layer
  • an electron acceptor layer p-type semiconductor layer
  • a bulk heterojunction photoelectric conversion element sandwiching a photoelectric conversion layer mixed with an n-type semiconductor layer) has been proposed, and an efficiency exceeding 5% has been reported (for example, see Non-Patent Document 1).
  • Solar cells using these bulk heterojunction type photoelectric conversion elements can be formed by coating other than the anode and cathode, so that they can be manufactured at high speed and at low cost, and the above-mentioned problem of power generation cost can be solved.
  • Non-Patent Document 2 requires a compound having a specific band gap (bg) and LUMO level as a p-type semiconductor. According to this document, the band gap is required to be 1.3 to 1.7 eV, and the LUMO level is required to be ⁇ 3.9 to ⁇ 4.0 eV (Non-patent Document 2).
  • this condition is a necessary condition, and it is necessary to satisfy other conditions in order to actually obtain a photoelectric conversion efficiency of 10%.
  • 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. This value 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.
  • This curve factor and external quantum efficiency are said to be related to the mobility of the semiconductor material in the power generation layer. If the mobility is high, the series resistance inside the solar cell is low, and the fill factor can be improved. In addition, since the length of the carrier that can be taken out is the product of mobility, carrier life, and built-in electric field, ideally a material with higher mobility can produce a thicker power generation layer and can increase absorbance, High external quantum efficiency can be aimed at.
  • one of the important conditions is to have high mobility.
  • the mobility is generally higher in a crystalline material than amorphous, it is important to select a crystalline p-type semiconductor material.
  • a compound having a deeper LUMO level and a larger ⁇ conjugate length small band gap and high crystallinity is required.
  • Non-Patent Document 1 In order to obtain such a deep LUMO level, as in Non-Patent Document 1, a donor unit (thiophene, etc.) having a high electron donating property and an acceptor unit (nitrogen-containing aromatic ring, etc.) having a high electron attractive property are used. Many copolymers have been studied.
  • Non-Patent Document 3 discloses a structure in which a dicyanomethylene group is added to a thiophene ring, but the dicyanomethylene group causes steric hindrance with the adjacent thiophene ring and twists the ⁇ -conjugated surface, or the mobility is insufficient. The conversion efficiency was also low, less than 1%.
  • Non-Patent Document 4 discloses a structure in which an ester group is added to thiophene. Similarly, an ester group also causes steric hindrance with the adjacent thiophene ring and twists the ⁇ -conjugated surface, so that a vinylene group is sandwiched between them. To ensure flatness. However, the level was not deep enough and the conversion efficiency was as low as 2%.
  • Non-Patent Document 5 discloses a p-type polymer material into which a thiazolothiazole group, which is known as an acceptor nucleus of relatively high mobility even in organic TFTs, is introduced as a donor-acceptor type polymer. However, the level was not deep enough and the conversion efficiency was as low as 2%.
  • Non-Patent Document 5 the alkynyl group does not cause twisting of the main chain even in a structure in which thiophene is continuous, and is a weak electron-withdrawing substituent, so that the LUMO level is slightly deepened. It is a structure that can. With such a structure, it is expected that the above requirement (a crystalline compound having a deeper LUMO level and a larger ⁇ -conjugated area) will be observed. Properties have not been evaluated. In these documents, only polymerization with thiophenes and benzenes is carried out. Further, donor-acceptor type polymers are not synthesized, and polymers with deep LUMO levels as described above are obtained. There wasn't.
  • Patent Document 1 a material capable of providing high photoelectric conversion efficiency in a reverse layer structure has been demanded.
  • the present invention has been made in view of the above problems, and an object thereof is to provide an organic photoelectric conversion element having high photoelectric conversion efficiency and excellent durability, and a solar cell using the organic photoelectric conversion element.
  • 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, An organic photoelectric conversion element, wherein the photoelectric conversion layer contains a compound having a partial structure represented by the following general formula 1 or general formula 1 ′ as the p-type organic semiconductor material.
  • each X 1 independently represents —S—, —O—, —NR 2 —, and each Y 1 independently represents —CR 3 ⁇ or —N ⁇ .
  • R 1 -R 3 each independently represents a hydrogen atom, an alkyl group that may have a substituent, a fluorinated alkyl group that may have a substituent, or a cycloalkyl group that may have a substituent.
  • L 1 is independently selected from a single bond, an arylene group, a heteroarylene group, a carbonyl group, —COO—, and —CONR′— (wherein R ′ represents a hydrogen atom or an alkyl group).
  • A represents a divalent acceptor unit
  • D 1 and D 2 represent a donor unit
  • m and n represent an integer of 0 to 2.
  • the above-described means of the present invention can provide an organic photoelectric conversion element having high photoelectric conversion efficiency and excellent durability, and a solar cell using the organic photoelectric conversion element.
  • the schematic sectional drawing which shows the example of a structure of the organic photoelectric conversion element of this invention.
  • the schematic sectional drawing which shows the other example of a structure of the organic photoelectric conversion element of this invention.
  • the schematic sectional drawing which shows the example of the organic photoelectric conversion element of this invention provided with the tandem type photoelectric conversion layer.
  • the present invention is 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 general formula 1 as a p-type organic semiconductor material.
  • a compound having a partial structure represented by the above general formula 1 is used as a p-type organic semiconductor material of a bulk heterojunction photoelectric conversion layer that contains a p-type organic semiconductor material and an n-type organic semiconductor material.
  • an organic photoelectric conversion element having a high fill factor value, high photoelectric conversion efficiency, and excellent durability can be provided.
  • 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 work function of the first electrode 12 is deeper (larger) than the work function of the second electrode 13, so that holes are transported to the first electrode 12 and electrons are transported to the second electrode 13. Is done.
  • the second electrode 13 is made of a metal that has a shallow (small) work function and is easily oxidized.
  • the first electrode 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, so that 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 15.
  • 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 following general formula 1 or 1 ′ as a p-type organic semiconductor material.
  • a compound having a partial structure represented by the following general formula 1 or 1 ′ can provide an organic photoelectric conversion element having high photoelectric conversion efficiency, excellent durability, and preferably a high fill factor, and a solar cell using the organic photoelectric conversion element.
  • the compound includes one or more partial structures represented by the general formula 1 or 1 ′.
  • X 1 and Y 1 between the partial structures are present.
  • R 1 to R 3 , L 1 and A, and D 1 , D 2 , m and n may be the same as or different from each other.
  • each X 1 independently represents —S—, —O—, —NR 2 —
  • each Y 1 independently represents —CR 3 ⁇ or —N ⁇ .
  • R 1 -R 3 each independently represents a hydrogen atom, an alkyl group that may have a substituent, a fluorinated alkyl group that may have a substituent, or a cycloalkyl group that may have a substituent.
  • L 1 represents a substituent independently selected from a single bond, an arylene group, a heteroarylene group, a carbonyl group, —COO—, and —CONR′— (wherein R ′ is a hydrogen atom or an alkyl group).
  • A represents a divalent acceptor unit
  • D 1 and D 2 represent a donor unit
  • m and n represent an integer of 0 to 2.
  • the position of substitution with the adjacent unit in the unit represented by the chemical formula 1 or 1 ′ represents that it is substituted at either the 2-position or 5-position, respectively. That is, the partial structure of the general formula 1 includes the following acceptor unit -A- and left and right X 1 :
  • bonding position is not limited, and actually includes all of the following four isomers, and any of these may be used.
  • the partial structure of the general formula 1 ′ includes the following structure including a left donor unit —D 1 — and left X 1 and Y 1 :
  • bonding position of is not limited, and actually includes all of the following two isomers, and any of these may be used.
  • the p-type semiconductor material in the photoelectric conversion layer has a compound having a partial structure represented by the general formula 1 or 1 ′, (1) an electron-withdrawing alkynyl group is substituted. The HOMO / LUMO level is deepened and the open circuit voltage is expected to be improved. (2) The ⁇ -conjugated area is increased by the alkynyl group, the crystallinity is improved, and the mobility is improved. (3) The alkynyl group is linear. The steric hindrance to other aromatic rings connected to the general formula 1 or 1 ′ in the state is less likely to occur, so that the planarity of the main chain is maintained, and further improvement in crystallinity and mobility is expected.
  • the oligomer and polymer of the present invention have a very high planarity, and are easily ⁇ -stacked between molecules as described above. Therefore, donor materials also form a network structure by interaction with each other in the bulk heterojunction layer. However, it is presumed that even with a thick film thickness, it is possible to form a highly continuous morphology without a dead end (a region where carriers cannot be extracted).
  • R 1 to R 3 may have a hydrogen atom, an alkyl group that may have a substituent, a fluorinated alkyl group that may have a substituent, or a substituent. Represents a cycloalkyl group.
  • R 1 s there are two R 1 s , and each R 1 may be the same or different, but the same from the viewpoint of symmetry and synthesis. Preferably there is.
  • the alkyl group represented by R 1 to R 3 is preferably a linear or branched alkyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. It is.
  • the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, Isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n -Heptyl group, 1,4-dimethylpentyl group,
  • the fluorinated alkyl group is a fluorinated alkyl group in which part or all of the alkyl group is fluorinated.
  • it may be a fluorinated alkyl group in which the position close to the mother nucleus is an alkyl group and the terminal portion is a fluorinated alkyl group. preferable. For example, — (CH 2 CH 2 ) —C 4 F 9 , — (CH 2 CH 2 ) —C 7 F 15 , etc.
  • the cycloalkyl group preferably has 4 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl and the like.
  • R 1 and R 2 are preferably C 6 or more and C 16 or less alkyl groups. This is because the p-type semiconductor material to be obtained needs to have a certain level of solubility in order to be formed with a sufficiently thick film, and in terms of imparting solubility, a material substituted with these substituents It is preferable that In particular, in the case of a polymer material, in addition to imparting solubility, a linear alkyl group may provide alignment and may provide high mobility (also referred to as a fastener effect). A p-type material substituted with an alkyl group is preferred.
  • Substituents optionally present in the alkyl group, fluorinated alkyl group, or cycloalkyl group include alkyl groups, fluorinated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, acyl groups, alkoxycarbonyl groups, (Alkyl) amino group, alkoxy group, cycloalkyloxy group, aryloxy group, aryloxycarbonyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, Arylthio group, silyl group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, halogen atom, hydroxyl group, mercapto group, cyano group, sul
  • substituent which exists depending on the case is not the same as the substituent to be substituted.
  • R 1 or R 2 is an alkyl group, it is not further substituted with an alkyl group.
  • the alkyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and specific examples thereof include the alkyl groups described above.
  • fluorinated alkyl group examples include the fluorinated alkyl groups described above.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. .
  • the alkynyl group 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 propargyl and 3-pentenyl.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, a biphenyl group, and a terphenyl group.
  • Non-condensed hydrocarbon group pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptalenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl And condensed polycyclic hydrocarbon groups such as a group, an acephenanthrenyl group, an aceanthrylenyl group, a triphenylenyl group, a pyrenyl group, a chrycenyl group, and a naphthacenyl group.
  • the heteroaryl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.
  • the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, a pyridyl group.
  • the acyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • the acyl group is represented by the formula: —C (O) R.
  • R is preferably an alkyl group having 1 to 24 carbon atoms, and examples of the alkyl group include the alkyl groups described above.
  • the alkoxycarbonyl group preferably has 2 to 25 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms.
  • the alkoxycarbonyl group is represented by the formula: —C (O) OR.
  • R is preferably an alkyl group having 1 to 24 carbon atoms, and examples of the alkyl group include the alkyl groups described above.
  • the (alkyl) amino group preferably has 0 to 24 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms.
  • the alkoxy group is preferably a group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, specifically a group represented by the formula: —OR;
  • R is preferably an alkyl group having 1 to 24 carbon atoms, and examples of the alkyl group in this case include the alkyl groups described above.
  • the cycloalkyloxy group preferably has 4 to 8 carbon atoms, and examples thereof include cyclopentyloxy and cyclohexyloxy.
  • the aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy.
  • the aryloxycarbonyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl.
  • the acylamino group preferably has 2 to 21 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
  • the acylamino group is a group represented by the formula: —NHCOR;
  • R is preferably an alkyl group having 1 to 24 carbon atoms, and examples of the alkyl group in this case include the alkyl groups described above.
  • the alkoxycarbonylamino group preferably has 2 to 24 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino.
  • the aryloxycarbonylamino group preferably has 7 to 24 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino.
  • the sulfonylamino group preferably has 1 to 24 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino.
  • the sulfamoyl group preferably has 0 to 24 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms.
  • sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamo Moyl etc. are mentioned.
  • the carbamoyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like.
  • the alkylthio group preferably has 1 to 24 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio.
  • the arylthio group 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 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 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 methanesulfinyl and benzenesulfinyl.
  • the ureido group preferably has 1 to 24 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, and phenylureido.
  • the phosphoric acid amide group preferably has 1 to 24 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide. .
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • L 1 represents a substituent selected from a single bond, an arylene group, a heteroarylene group, a carbonyl group, —COO—, and —CONR′— (wherein R ′ represents a hydrogen atom or an alkyl group). Since these substituents can deepen the HOMO / LUMO level of the structure represented by the general formula 1 and increase the ⁇ conjugate area, higher open-circuit voltage and higher mobility, that is, higher fill factor External quantum efficiency can be expected.
  • L 1 is preferably a single bond or —COO—, and more preferably —COO— because the photoelectric conversion efficiency is improved and the durability is also improved.
  • there are two L 1 s there are two L 1 s , and each L 1 may be the same or different, but the same from the viewpoint of symmetry and synthesis. Preferably there is.
  • the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 24 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • the heteroarylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • Examples of the alkyl group when R ′ in —CONR′— is an alkyl group include those described in the above R 1 to R 3 columns.
  • X 1 represents —S—, —O—, —NR 2 —.
  • X 1 is preferably —S— or —O—. More preferred is —S— from the viewpoint of durability.
  • there are two X 1 s there are two X 1 s , and each X 1 may be the same or different, but the same from the viewpoint of symmetry and synthesis. Preferably there is.
  • the group represented by Y 1 represents —CR 3 ⁇ or —N ⁇ .
  • Y 1 is preferably —CR 3 ⁇ , more preferably —CH ⁇ .
  • X 1 is -S-
  • there are two Y 1 s and each Y 1 may be the same or different, but the same from the viewpoint of symmetry and synthesis. Preferably there is.
  • the partial structure represented by the general formula 1 may further have a donor unit or an acceptor unit.
  • Specific partial structures include: the partial structure of the general formula 1 -D-, -general Examples include the partial structure of formula 1 -DAD-, the partial structure of general formula 1 -A-, and the like.
  • A indicates an acceptor unit
  • D indicates a donor unit.
  • the acceptor unit represented by A in the formula is generally a partial structure in which the LUMO level or the HOMO level is deeper than a hydrocarbon aromatic ring having the same number of ⁇ electrons (benzene, naphthalene, anthracene, etc.) Unit).
  • the acceptor unit included in the compound that is a conjugated polymer of this embodiment is a partial structure represented by the following among the acceptor units included in the conjugated polymer. It is preferable to contain.
  • the number of partial structures represented below is preferably 50% or more, more preferably 70% or more, based on the total number of acceptor units contained in the conjugated polymer. 90% or more, more preferably 95% or more, and most preferably 100%.
  • R is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted fluorinated alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkoxy group or a substituted group.
  • the aryl group which may be sufficient is shown.
  • examples of the alkyl group, the fluorinated alkyl group, and the cycloalkyl group include those described in the above R 1 to R 3 columns.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • Non-condensed hydrocarbon group pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptalenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl And condensed polycyclic hydrocarbon groups such as a group, an acephenanthrenyl group, an aceanthrylenyl group, a triphenylenyl group, a pyrenyl group, a chrycenyl group, and a naphthacenyl group.
  • Non-condensed hydrocarbon group pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptalenyl group, biphenyleny
  • the alkoxy group is preferably a group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, specifically a group represented by the formula: —OR;
  • R is preferably an alkyl group having 1 to 24 carbon atoms, and examples of the alkyl group in this case include those described in the above R 1 to R 3 column.
  • substituent optionally present in the alkyl group, fluorinated alkyl group, cycloalkyl group, alkoxy group or aryl group include those described in the above R 1 to R 3 columns.
  • R is preferably a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, more preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms. .
  • each R when there are a plurality of R, each R may be the same or different substituent.
  • the unit represented by A is preferably a nitrogen-containing heteroaromatic ring group.
  • the unit is preferably a unit having a large ⁇ -conjugated area by condensation, and the unit represented by A is preferably a condensed polycyclic group in which two or more rings are condensed.
  • the unit is preferably a unit having a large ⁇ -conjugated area by condensation.
  • the units are A-1 to A-19 and A-33 to 38.
  • condensed polycyclic group in which two or more units are condensed include the following structures.
  • R 4 , R 5 , R 5 ′ , R 6 , R A and R B are each independently a hydrogen atom, an alkyl group which may have a substituent, or a fluorinated alkyl which may have a substituent Or a cycloalkyl group which may have a substituent.
  • the alkyl group which may have a substituent, the fluorinated alkyl group which may have a substituent, or the cycloalkyl group which may have a substituent has been described in the above R 1 to R 3 columns. It is the same as that.
  • X 2 is preferably —S— or —O—, more preferably —S—.
  • a p-type organic semiconductor material having thiazolothiazole as an acceptor unit is preferable because it can provide high mobility.
  • the above formula R 7 and R 8 are the same as R 7 and R 8 in the following general formulas 4A and 4B, separately described in detail below.
  • the structure represented by the general formula 1 is preferably a structure represented by the following general formula 2 in terms of durability.
  • a p-type organic semiconductor material in which X 2 is S in General Formula 2 has thiazolothiazole as an acceptor unit, and thus can provide high mobility and is preferable.
  • the compound containing the structural unit represented by the general formula 2 further has any of the acceptor units represented by the following general formula 4A or 4B.
  • Such a structure can absorb longer wavelengths and can provide a high short-circuit current.
  • Y 3 and Y 4 each independently represent —O—, —NR 10 —, —S—, —C (R 11 ) ⁇ C (R 11 ′ ) —, or —N ⁇ C (R 12 ) —, wherein R 10 , R 11 , R 11 ′ and R 12 are each independently an alkyl group, a fluorinated alkyl group or a cyclo group which may have a hydrogen atom or a substituent. Represents an alkyl group.
  • R 7 to R 8 each independently represents a hydrogen atom, a halogen atom (F, Cl, Br, or I), a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, or 1 carbon atom.
  • a halogen atom F, Cl, Br, or I
  • R 7 to R 8 each independently represents a hydrogen atom, a halogen atom (F, Cl, Br, or I), a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, or 1 carbon atom.
  • R 7 s there are two R 7 s
  • R 8 s there are two R 7 s .
  • Each R 7 , R 8 may be the same or different, but they are symmetrical. From the viewpoints of properties and synthesis, the same is preferable.
  • the compound preferably contains one or more partial structures represented by the general formula 4A or 4B.
  • Y 3 , Y in each partial structure 4 and R 10 to R 12 may be the same as or different from each other.
  • R 7 to R 8 are preferably a hydrogen atom or a halogen atom (preferably a fluorine atom).
  • Y 3 and Y 4 are preferably —S— and —O—, and more preferably because they can provide high mobility. Is -S-.
  • examples of the alkyl group, fluorinated alkyl group or cycloalkyl group which may be substituted in R 7 to R 8 and R 10 to R 12 include those described in the above R 1 to R 3 column. .
  • Examples of the fluorinated cycloalkyl group in R 7 to R 8 include groups in which at least one hydrogen atom contained in the cycloalkyl group exemplified above is substituted with a fluorine atom.
  • the alkoxy group having 1 to 24 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an n-octyloxy group, an n-decyloxy group, and an n-hexadecyl group. Examples thereof include an oxy group, 2-ethylhexyloxy group, and 2-hexyldecyloxy group.
  • Examples of the fluorinated alkoxy group include a group in which at least one hydrogen atom contained in the alkoxy group exemplified above is substituted with a fluorine atom.
  • the aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include non-condensed hydrocarbon groups such as a phenyl group, a biphenyl group, and a terphenyl group; a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, Heptalenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylenyl group,
  • the fluorinated aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a group in which at least one hydrogen atom contained in the aryl group exemplified above is substituted with a fluorine atom.
  • the heteroaryl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include pyridyl group, pyrimidyl group, pyrazinyl group, triazinyl group, furanyl group, pyrrolyl group, thiophenyl group (thienyl group), quinolyl group, Furyl group, piperidyl group, coumarinyl group, silafluorenyl group, benzofuranyl group, benzimidazolyl group, benzoxazolyl group, benzthiazolyl group, dibenzofuranyl group, benzothiophenyl group, dibenzothiophenyl group, indolyl group, carbazolyl group, pyrazolyl Group,
  • the compound contained in the p-type organic semiconductor material of the present invention is preferably a copolymer of the structure represented by the general formula 1 and a donor unit.
  • a copolymer of the structure represented by the general formula 1 and a donor unit at least one of m and n is one or more forms, which is a preferable form because it has a donor unit.
  • the donor unit that can be included in the conjugated polymer compound of the present embodiment has a LUMO level or a HOMO level rather than a hydrocarbon aromatic ring (benzene, naphthalene, anthracene, etc.) having the same number of ⁇ electrons. If it is a shallow unit, it can be used without restriction.
  • thiophene examples include thiophene, thienothiophene, bithiophene, fluorene, silafluorene, carbazole, dithienocyclopentadiene, dithienosylcyclopentadiene, dithienopyrrole, and benzodithiophene.
  • thiophene thienothiophene
  • bithiophene fluorene
  • silafluorene carbazole
  • dithienocyclopentadiene dithienosylcyclopentadiene
  • dithienopyrrole dithienopyrrole
  • benzodithiophene examples include thiophene, thienothiophene, bithiophene, fluorene, silafluorene, carbazole, dithienocyclopentadiene, dithienosylcyclopentadiene, dithienopyrrole, and benzodithiophene.
  • R may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a fluorinated alkyl group which may have a substituent, or a substituent.
  • a cycloalkyl group, an alkoxy group which may have a substituent, a fluorinated alkoxy group which may have a substituent, a cycloalkoxy group which may have a substituent, an alkoxycarbonyl which may have a substituent A group, an acyl group which may have a substituent, an alkylaminocarbonyl group which may have a substituent, or an acylamino group which may have a substituent.
  • a hydrogen atom or an alkyl group which may have a substituent is preferable.
  • the halogen atom, an alkyl group that may have a substituent, a fluorinated alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, and an alkoxy group that may have a substituent examples include those described in the above R 7 to R 8 columns.
  • each R may be the same substituent and may be different substituents.
  • the alkoxycarbonyl group is preferably an alkoxycarbonyl group (—COOR) having 2 to 30 carbon atoms, more preferably 2 to 24 carbon atoms, and still more preferably 6 to 24 carbon atoms.
  • the acyl group (—COR) is preferably an alkoxycarbonyl group (—COOR) having 2 to 30 carbon atoms, more preferably 2 to 24 carbon atoms, and still more preferably 6 to 25 carbon atoms.
  • the alkylaminocarbonyl group (—CONHR or —CONRR ′) is preferably an alkylaminocarbonyl having 2 to 40 carbon atoms, more preferably 9 to 40 carbon atoms, and still more preferably 13 to 24 carbon atoms.
  • Groups such as dimethylaminocarbonyl group, diethylaminocarbonyl group, diisopropylaminocarbonyl group, methyl-tert-butylaminocarbonyl group, dihexylaminocarbonyl group, dioctylaminocarbonyl group, didecylaminocarbonyl group, dihexadecylaminocarbonyl Group, di2-ethylhexylaminocarbonyl group, di2-hexyldecylaminocarbonyl group and the like.
  • the acylamino group (—NHCOR) is preferably an acylamino group having 2 to 30 carbon atoms, and examples thereof include an acetamide group, an ethylamide group, and a propylamide group.
  • a unit represented by the general formula 3 is preferable.
  • each R 9 independently has a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a fluorinated alkyl group which may have a substituent, or a substituent.
  • R 9 substituents are the same as those described in the column of R in the above D1 to D18.
  • each R 9 may be the same or different, but is preferably the same from the viewpoint of symmetry and synthesis.
  • the compound preferably contains one or more partial structures represented by the general formula 3, but when there are two or more partial structures, R 9 in each partial structure is the same as each other. It may be different or different.
  • the donor unit having such a structure has high crystallinity and can obtain higher conversion efficiency.
  • the compound having the structure represented by the general formula 1 is preferably a polymer compound having a number average molecular weight of 10,000 or more.
  • the low-molecular compound (fullerene derivative) is widely used as the n-type organic semiconductor which is the other component constituting the bulk heterojunction type photoelectric conversion layer. This is because a microphase-separated structure is formed, and it is easy to generate carrier paths that respectively carry holes and electrons generated in the bulk heterojunction photoelectric conversion layer.
  • the number average molecular weight of the compound is preferably 100,000 or less. More preferably, it is in the range of 15,000 to 50,000.
  • the molecular weight can be measured by gel permeation chromatography (GPC).
  • the number average molecular weight can be measured by the following method.
  • purification according to molecular weight can be performed by preparative gel permeation chromatography (GPC).
  • the ratio of the partial structure according to the present invention to the compound having the partial structure according to the present invention is generally preferably 20 to 80% by mass and 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 number of repetitions (polymerization degree) of each unit is a value that falls within the above-mentioned molecular weight.
  • a number average molecular weight of 10,000 to 100,000 approximately 10 to 200 is required. It needs to be about.
  • thiazolothiazole ring and the like are described in Adv. Mater. Can be synthesized with reference to 2007, 19, 4160, etc.
  • Example Compound 11-1 3.0 g, rubeanic acid 0.4 g, and dimethylformamide (DMF) 60 ml were added and stirred at 150 ° C. for 8 hours. After completion of the reaction, the organic phase was separated with water / ethyl acetate, and then the organic phase was distilled off to obtain a crude product. Further purification by silica gel column chromatography gave Exemplified Compound 11-2 (0.69 g, 20%).
  • Exemplified Compound 11-2 (0.69 g) was dissolved in 30 ml of chloroform, 0.39 g of N-bromosuccinimide was added, reacted for 5 hours under reflux, water was added and the phases were separated to extract the organic phase. The solvent was distilled off to obtain a crude product, which was then purified by silica gel column chromatography to obtain Exemplified Compound 11-3 (0.64 g, 75%).
  • Example Compound 12-1 2.1 g, rubeanic acid 0.4 g, and dimethylformamide (DMF) 60 ml were added and stirred at 150 degrees for 8 hours. After completion of the reaction, the organic phase was separated with water / ethyl acetate, and then the organic phase was distilled off to obtain a crude product. Further purification by silica gel column chromatography gave Exemplified Compound 12-2 (0.50 g, 20%).
  • Example Compound 12-2 0.5 g of 1N aqueous sodium hydroxide solution 0.5 g and 10 ml of tetrahydrofuran was stirred at room temperature for 2 hours, and then ethyl acetate was added to extract the organic layer to deprotect the trimethylsilyl group. .
  • This compound was dissolved in 20 ml of dehydrated tetrahydrofuran, cooled to ⁇ 78 ° C., 1.0 ml of 2.0 M lithium diisopropylamine solution was added dropwise, and the mixture was stirred for 1 hour. After raising the temperature of the reaction solution to 0 ° C., dodecyl chloroformate (1.33 g) was added, and the reaction was further continued at room temperature for 5 hours.
  • Exemplified Compound 12-3 (0.65 g) was dissolved in 30 ml of chloroform, 0.35 g of N-bromosuccinimide was added and reacted for 5 hours under reflux, followed by addition of water and liquid separation to extract the organic phase. The solvent was distilled off to obtain a crude product, which was then purified by silica gel column chromatography to obtain Exemplified Compound 12-4 (0.67 g, 80%).
  • 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 C 60 , fullerene C 70 , fullerene C 76 , fullerene C 78 , fullerene C 84 , fullerene C 240 , fullerene C 540 , mixed fullerene, fullerene nanotube, multi-wall nanotube, single-wall nanotube, nanohorn (cone Type), etc., and some of these are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, The fullerene derivative substituted by the amino group, the silyl group, etc. can be mentioned.
  • fullerene having a cyclic ether group such as Amer. Chem. Soc. , (2009) vol. 130, p15429, SIMEF, Appl. Phys. Lett. , Vol. 87 (2005), C 60 MC12 described in p203504, etc. It is preferable to use a fullerene derivative having a substituent and having improved solubility as described below.
  • 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.
  • 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.
  • a coating liquid composed of three types of p-type semiconductor material, n-type semiconductor material, and solvent for at least the photoelectric conversion layer coating liquid As the solvent, a solvent capable of dissolving both the p-type semiconductor material and the n-type semiconductor material which are solutes is preferable.
  • a solvent for example, aromatic solvents such as toluene, xylene and tetralin, and halogen solvents such as chloroform, dichloroethane, chlorobenzene, dichlorobenzene and trichlorobenzene are preferable.
  • the total concentration of the solute in these solvents varies depending on the film thickness to be obtained and the film forming method, but is preferably about 1 to 3% by mass in the spin coating method and the blade coating method. More preferably, the content is 1.5 to 2% by mass.
  • a photoelectric conversion layer having a film thickness of about 100 to 200 nm can be formed by spin coating and blade coating, which are typical film forming methods.
  • the mass ratio of the p-type semiconductor and the n-type semiconductor, which are solutes can be any value such as 1: 4 to 4: 1, but in practice, the mass ratio is about 1: 1 to 1: 2. A value is preferred.
  • 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.
  • a p-type semiconductor material that can be insolubilized after coating for example, the coating film is polymerized after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225.
  • n-type semiconductor material that can be insolubilized after application include Adv. Mater. , Vol. 20 (2008), p2116, phenyl-C61-glycidyl butyrate (PCBG), and the like.
  • 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 present invention can be particularly preferably applied when 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.
  • 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 can more efficiently extract the charge generated in the photoelectric conversion layer, it may have a hole transport layer between the photoelectric conversion layer and the anode. 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.
  • a compound having a hole mobility higher than 10 ⁇ 4 because of the property of transporting holes, and from the property of blocking electrons, the electron mobility is higher than 10 ⁇ 6. It is preferable to use a low compound.
  • 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 in the visible wavelength range measured by a method in accordance with “Testing method of total light transmittance of plastic-transparent material” of JIS K 7361-1: 1997 (corresponding to ISO 13468-1). It refers to transmittance.
  • 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 nanowire such as a carbon nanotube or a layer containing nanoparticles, 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 cathode 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, and potassium. 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.
  • 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 by bonding 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 are pasted with an adhesive.
  • Method, spin coating of organic polymer material with high gas barrier property (polyvinyl alcohol, etc.), inorganic thin film with high gas barrier property (silicon oxide, aluminum oxide, etc.) or organic film (parylene etc.) are deposited under vacuum. Examples thereof include a method and a method of laminating these in a composite manner.
  • Example 1 Evaluation of photoelectric conversion efficiency [Preparation of organic photoelectric conversion element 1] With reference to Japanese Patent Application Laid-Open No. 2009-146981, a reverse layer type organic photoelectric conversion element was produced.
  • an indium tin oxide (ITO) transparent conductive film deposited with a thickness of 110 nm (surface resistivity 13 ⁇ / ⁇ ) is patterned to a width of 2 mm using a normal photolithography technique and hydrochloric acid etching, A transparent electrode was formed.
  • ITO indium tin oxide
  • 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, and a 150 mmol / L (liter) TiO x precursor solution prepared by the following procedure was spin-coated (rotation speed 2000 rpm, rotation time 60 s) on the transparent substrate in a nitrogen atmosphere. A predetermined pattern was wiped off.
  • the TiO x precursor was hydrolyzed by being left in the air.
  • the TiO x precursor was heat-treated at 150 ° C. for 1 hour to obtain a 30 nm TiO x layer.
  • Comparative Compound 1 As a p-type semiconductor material and 0.9% by mass (total solid content concentration: 1.8% by mass) of PCBM (manufactured by Frontier Carbon, Nano Spectra E100H) as an n-type semiconductor material were dissolved. A solution was prepared, and a solution filtered through a 0.45 ⁇ m filter was applied by a blade coater and dried at 100 ° C. for 30 minutes to obtain a photoelectric conversion layer having a dry film thickness of 220 nm. Comparative compound 1 was synthesized based on Non-Patent Document 3.
  • an organic solvent-based PEDOT: PSS dispersion (Enocoat HC200, manufactured by Kaken Sangyo) was blade coated on the organic semiconductor layer and air-dried to form a hole transport layer having a dry film thickness of 30 nm.
  • a reverse layer type organic photoelectric conversion element was produced by performing a heat treatment at 150 ° C. for 10 minutes.
  • the obtained organic photoelectric conversion element 1 is a transparent barrier film GX made of relief printing using a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) under a nitrogen atmosphere (water vapor transmission rate 0.05 g / m 2). / D) and sealed and taken out to the atmosphere.
  • a UV curable resin manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1
  • nitrogen atmosphere water vapor transmission rate 0.05 g / m 2). / D
  • the obtained organic photoelectric conversion element 1 was sealed and then irradiated with solar simulator (AM1.5G) light at an irradiation intensity of 100 mW / cm 2 to measure voltage-current characteristics, and to obtain an initial conversion efficiency.
  • solar simulator AM1.5G
  • Organic photoelectric conversion elements 2 to 15 were obtained in the same manner as the comparative organic photoelectric conversion element 1 except that the p-type semiconductor material was changed to the material shown in Table 1 in the production of the organic photoelectric conversion element 1.
  • n in the table represents the mass ratio of the p-type semiconductor (polymer) and the n-type semiconductor (PCBM).
  • the compound of the present invention can provide better photoelectric conversion efficiency than the comparative compound in the reverse layer solar cell. Moreover, it turns out that durability can also be improved. In particular, it can be seen that a compound having —COO— introduced has a high effect of improving durability.
  • Example 2 Durability evaluation About the organic photoelectric conversion elements 8 and 11 produced in Example 1, the following normal layer type
  • the substrate was brought into the glove box and worked in a nitrogen atmosphere.
  • the substrate was again heat-treated at 140 ° C. for 10 minutes in a nitrogen atmosphere.
  • a p-type semiconductor material 0.6% by mass of the comparative compound 4 and 0.9% by mass of PCBM as an n-type semiconductor material are dissolved in chlorobenzene to prepare a 1.2% by mass chlorobenzene solution. While being filtered through a 45 ⁇ m filter, spin coating was performed at 700 rpm for 60 seconds, then at 2200 rpm for 1 second, and left at room temperature for 30 minutes.
  • the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus without being exposed to the atmosphere.
  • the element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁇ 3 Pa or less, and then 0.6 nm of lithium fluoride was deposited and 100 nm of aluminum was deposited as a counter electrode.
  • heating was performed at 120 ° C. for 30 minutes to obtain a comparative organic photoelectric conversion element 8 ′.
  • the deposition rate was 2 nm / second, and the size was 2 mm square.
  • the obtained organic photoelectric conversion element 4 ′ was obtained by using a transparent barrier film GX (water vapor transmission rate: 0.05 g / mm) using a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) under a nitrogen atmosphere. m2 / d) and sealed and taken out to the atmosphere.
  • GX water vapor transmission rate: 0.05 g / mm
  • UV curable resin manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1
  • Photoelectric conversion elements prepared above was irradiated with light having an intensity of 100 mW / cm 2 solar simulator (AM1.5G filter), a superposed mask in which the effective area 4.0 mm 2 on the light receiving portion, the short circuit current density Jsc ( The four light-receiving portions formed on the same element were measured for mA / cm 2 ), open-circuit voltage Voc (V), and fill factor (fill factor) FF, and the average value was obtained.
  • the photoelectric conversion efficiency ⁇ (%) was obtained from Jsc, Voc, and FF according to Equation 1.
  • Formula 1 ⁇ (%) Jsc (mA / cm 2 ) ⁇ Voc (V) ⁇ FF (Durability Evaluation) Store in a container kept at a temperature of 80 ° C and a humidity of 80%, periodically take it out, measure the voltage-current characteristics, set the initial conversion efficiency as 100, and reduce the time to 80% of the initial efficiency. It was evaluated as LT80.
  • Comparison of organic photoelectric conversion elements 4 and 12 in Table 2 shows that the compound 12 of the present invention has higher durability.
  • the value of LT80 increased at 4 and 4 ′ and the value of LT80 increased at 12 and 12 ′ were compared, the former value using the compound according to the present invention was significantly more durable than the latter value. It can be understood that the effect of the present invention is particularly great in a so-called reverse layer type organic photoelectric conversion element.

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Abstract

La présente invention a pour objectif de proposer : un élément de conversion photoélectrique organique ayant un haut rendement de conversion photoélectrique et une excellente durabilité ; et une photopile équipée de l'élément de conversion photoélectrique organique. Pour ce faire, elle propose un élément de conversion photoélectrique organique qui comprend une première électrode transparente, une couche de conversion photoélectrique comprenant un matériau semi-conducteur organique de type p et un matériau semi-conducteur organique de type n et une seconde électrode qui sont agencées dans cet ordre sur un substrat transparent, et qui est caractérisé en ce que la couche de conversion photoélectrique contient un composé ayant une structure partielle représentée par la formule générale (1) ou (1') en tant que matériau semi-conducteur organique de type p. (Dans les formules, les X1 représentent indépendamment -S-, -O- ou -NR2- ; les Y1 représentent indépendamment -CR3= ou -N= ; R1 à R3 représentent indépendamment un atome d'hydrogène, un groupe alkyle qui peut comporter un substituant, un groupe alkyle fluoré qui peut comporter un substituant, ou un groupe cycloalkyle qui peut comporter un substituant ; les L1 représentent indépendamment une simple liaison ou un substituant choisi parmi un groupe arylène, un groupe hétéroarylène, un groupe carbonyle, -COO- et -CONR'- (où R' représente un atome d'hydrogène ou un groupe alkyle) ; A représente un motif accepteur bivalent ; D1 et D2 représentent indépendamment un motif donneur ; et m et n représentent indépendamment un entier de 0 à 2).
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