WO2015033698A1 - Élément de conversion photovoltaïque, cellule photovoltaïque sensibilisée par colorant et inhibiteur de transfert d'électrons inverse pour un élément de conversion photovoltaïque - Google Patents

Élément de conversion photovoltaïque, cellule photovoltaïque sensibilisée par colorant et inhibiteur de transfert d'électrons inverse pour un élément de conversion photovoltaïque Download PDF

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WO2015033698A1
WO2015033698A1 PCT/JP2014/069654 JP2014069654W WO2015033698A1 WO 2015033698 A1 WO2015033698 A1 WO 2015033698A1 JP 2014069654 W JP2014069654 W JP 2014069654W WO 2015033698 A1 WO2015033698 A1 WO 2015033698A1
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group
atom
photoelectric conversion
dye
substituent
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PCT/JP2014/069654
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Japanese (ja)
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寛敬 佐藤
小林　克
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a photoelectric conversion element, a dye-sensitized solar cell, and a reverse electron transfer inhibitor for photoelectric conversion elements.
  • Photoelectric conversion elements are used in various optical sensors, copiers, solar cells and the like.
  • Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof.
  • a solar cell using non-depleting solar energy does not require fuel, and full-scale practical use is highly expected as it uses inexhaustible clean energy.
  • silicon-based solar cells have been researched and developed for a long time, and are spreading due to the policy considerations of each country.
  • silicon is an inorganic material, there is a limit to improving throughput and cost.
  • t-Butylpyridine is useful for improving the photoelectric conversion efficiency in terms of increasing the open-circuit voltage, but on the other hand, it reduces the short-circuit current, thus offsetting the improvement in photoelectric conversion efficiency due to the increase in voltage. A significant improvement in photoelectric conversion efficiency cannot be expected.
  • the electrolytic solution used in the dye-sensitized solar cell, its additive, and the like have been studied. As a result, even if the electrolyte solution described in Patent Documents 1 to 3 or its additive is used, It was found that the conversion efficiency is not sufficiently improved and there is room for improvement.
  • This invention makes it a subject to provide the photoelectric conversion element excellent in photoelectric conversion efficiency, a dye-sensitized solar cell, and the reverse electron transfer inhibitor for photoelectric conversion elements.
  • the present inventors examined the influence of the electrolyte additive on the photoelectric conversion efficiency.
  • the object of the present invention has been achieved by the following means.
  • a photoelectric conversion element having, in this order, a photoconductor layer having semiconductor fine particles carrying a dye, a charge transfer layer containing an electrolyte, and a counter electrode on a conductive support,
  • the photoelectric conversion element containing the compound represented by following formula (1) between a body and a counter electrode.
  • ring A represents a nitrogen-containing heteroaryl ring
  • X represents an N atom, an S atom or an O atom
  • m represents an integer of 1 or more, and when m is 2 or more, Xs may be different from each other.
  • Ac represents an acidic group
  • L represents a single bond or a linking group.
  • R is substituted with a branched alkyl group having 6 or more carbon atoms, an alkyl group substituted with a halogen atom, an alkenyl group or alkynyl group which may have a substituent, a branched alkoxy group having 6 or more carbon atoms, or a halogen atom.
  • the branched alkyl group, branched alkoxy group and branched alkylthio group may have a substituent other than a halogen atom.
  • R 1 and R 2 each independently represents a hydrogen atom or a substituent.
  • n1 represents an integer of 0 or more
  • n2 and n3 each independently represents an integer of 1 or more.
  • X 1 to X 5 each independently represent CR x (R x represents a hydrogen atom or a substituent) or an N atom, and X 1 to X 5 At least one represents an N atom.
  • X 6 represents NR X (R X represents a hydrogen atom or a substituent), S atom or O atom.
  • Ac, L, R, R 1 , R 2, n1, n2 and n3 have the same meanings Ac, L, R, and R 1, R 2, n1, n2 and n3 of the formula (1).
  • ⁇ 4> The photoelectric conversion element according to ⁇ 3>, wherein the compound is represented by the formula (9).
  • ⁇ 5> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 4>, wherein R is a branched alkyl group having 6 or more carbon atoms, an alkyl group substituted with a halogen atom, an alkenyl group, or an alkynyl group.
  • R is a branched alkyl group having 6 or more carbon atoms or an alkyl group substituted with a halogen atom.
  • ⁇ 7> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 6>, wherein the compound has at least one acidic group.
  • ⁇ 8> The photoelectric conversion element according to ⁇ 7>, wherein n1 is an integer of 1 or more, or at least one of R 1 and R 2 is a substituent having an acidic group.
  • n1 is an integer of 1 or more, or at least one of R 1 and R 2 is a substituent having an acidic group.
  • the acidic group is a carboxy group.
  • ⁇ 10> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 9>, wherein the compound is contained in at least one of an electrolyte and a surface of a semiconductor fine particle.
  • a dye-sensitized solar cell comprising the photoelectric conversion element according to any one of ⁇ 1> to ⁇ 10>.
  • a reverse electron transfer inhibitor for a photoelectric conversion element represented by the following formula (1).
  • ring A represents a nitrogen-containing heteroaryl ring
  • X represents an N atom, an S atom or an O atom
  • m represents an integer of 1 or more, and when m is 2 or more, Xs may be different from each other.
  • Ac represents an acidic group
  • L represents a single bond or a linking group.
  • R is substituted with a branched alkyl group having 6 or more carbon atoms, an alkyl group substituted with a halogen atom, an alkenyl group or alkynyl group which may have a substituent, a branched alkoxy group having 6 or more carbon atoms, or a halogen atom.
  • the branched alkyl group, branched alkoxy group and branched alkylthio group may have a substituent other than a halogen atom.
  • R 1 and R 2 each independently represents a hydrogen atom or a substituent.
  • n1 represents an integer of 0 or more
  • n2 and n3 each independently represents an integer of 1 or more.
  • the carbon-carbon double bond may be either E-type or Z-type in the molecule, or a mixture thereof.
  • substituents, linking groups, etc. hereinafter referred to as substituents, etc.
  • Each substituent group may be the same as or different from each other. The same applies to the definition of the number of substituents and the like.
  • substituents and the like when a plurality of substituents and the like are close to each other (especially when they are adjacent to each other), they may be connected to each other to form a ring unless otherwise specified.
  • a ring such as an alicyclic ring, an aromatic ring, or a hetero ring may be further condensed to form a condensed ring.
  • each substituent may be further substituted with a substituent unless otherwise specified.
  • the present invention it has become possible to provide a photoelectric conversion element excellent in photoelectric conversion efficiency, a dye-sensitized solar cell, and a reverse electron transfer inhibitor for photoelectric conversion elements.
  • the photoelectric conversion element of the present invention has, on a conductive support, a photosensitive layer having semiconductor fine particles carrying a dye, a charge transfer layer containing an electrolyte, and a counter electrode (counter electrode) in this order. Between the conductive support and the counter electrode, a compound represented by the following formula (1) (also referred to as the compound of the present invention) is included.
  • the compound of the present invention may be present anywhere between the conductive support and the counter electrode, and is preferably contained in at least one of the electrolyte (charge transfer layer) and the surface of the semiconductor fine particles.
  • the photoelectric conversion element of this invention has the said structure, another structure will not be specifically limited, The well-known structure regarding a photoelectric conversion element is employable.
  • Each layer in the photoelectric conversion element of the present invention may be a single layer or a multilayer, and may have layers other than the above-mentioned layers as necessary.
  • the dye-sensitized solar cell of the present invention includes the photoelectric conversion element of the present invention.
  • the photoelectric conversion element or the dye-sensitized solar cell of the present invention can be, for example, an embodiment shown in FIG.
  • the photoelectric conversion element 10 includes a conductive support 1, a photoreceptor layer 2 including semiconductor fine particles 22 sensitized by a dye 21, a charge transfer layer 3 that is a hole transport layer, and a counter electrode 4. Consists of.
  • the charge transfer body layer 3 contains a compound represented by the formula (1).
  • the compound or co-adsorbent of the present invention is adsorbed on the semiconductor fine particles 22 together with the dye 21.
  • the conductive support 1 provided with the photoreceptor layer 2 functions as a working electrode in the photoelectric conversion element 10.
  • the photoelectric conversion element 10 is shown as a system 100 using a dye-sensitized solar cell that can be used for a battery for causing an operating means (electric motor) M to work with an external circuit 6.
  • the light incident on the photoreceptor layer 2 excites the dye 21.
  • the excited dye has electrons with high energy, and these electrons are transferred from the dye 21 to the conduction band of the semiconductor fine particles 22 and further reach the conductive support 1 by diffusion. Due to this electron transfer, the dye 21 becomes an oxidant, but the electrons on the electrode work in the external circuit 6, while passing through the counter electrode 4 and the charge transfer body layer 3 in which the electrolyte is present, By returning to the photoreceptor layer 2 where the oxidant is present, it functions as a solar cell.
  • the material used for the photoelectric conversion element or the dye-sensitized solar cell and the method for producing each member may be the usual ones of this type, for example, US Pat. No. 4,927,721.
  • U.S. Pat.No. 4,684,537, U.S. Pat.No. 5,0843,65, U.S. Pat.No. 5,350,644, U.S. Pat.No. 5,463,057 Reference can be made to US Pat. No. 5,525,440, JP-A-7-249790, JP-A-2004-220974, and JP-A-2008-135197.
  • the outline of the compound of the present invention and the main member will be described.
  • the photoelectric conversion element of this invention contains the compound represented by following formula (1).
  • ring A represents a nitrogen-containing heteroaryl ring
  • X represents an N atom, an S atom or an O atom
  • m represents an integer of 1 or more, and when m is 2 or more, Xs may be different from each other.
  • Ac represents an acidic group
  • L represents a single bond or a linking group.
  • R is substituted with a branched alkyl group having 6 or more carbon atoms, an alkyl group substituted with a halogen atom, an alkenyl group or alkynyl group which may have a substituent, a branched alkoxy group having 6 or more carbon atoms, or a halogen atom.
  • the branched alkyl group, branched alkoxy group, and branched alkylthio group may have a substituent other than a halogen atom (hereinafter, also referred to as “specific substituent R”).
  • R 1 and R 2 each independently represents a hydrogen atom or a substituent.
  • n1 represents an integer of 0 or more
  • n2 and n3 each independently represents an integer of 1 or more.
  • the compound of the present invention is a nitrogen-containing heteroaryl ring compound having a nitrogen atom and at least one heteroatom of a nitrogen atom, a sulfur atom or an oxygen atom as a ring-forming heteroatom, comprising a specific substituent R and an amino group It has NR 1 R 2 .
  • it has a group “Ac-L” containing an acidic group Ac.
  • Such a compound of the present invention is preferably contained at least in the electrolyte or adsorbed on the surface of the semiconductor fine particles. Thereby, photoelectric conversion efficiency can be improved.
  • T-Butylpyridine which has been widely used conventionally, is adsorbed on the surface of semiconductor fine particles and recombines the semiconductor fine particles, that is, electrons transferred to the photoreceptor layer and oxide ions (for example, I 3 ⁇ ) of a redox pair. Is suppressed, and a voltage drop of the photoelectric conversion element is prevented. Further, the voltage is improved by reducing the Fermi level of the semiconductor fine particles due to the effect of the electron donating group. On the other hand, since the conduction band becomes shallow at the same time, the energy difference from the lowest empty orbital (LUMO) level of the dye is reduced. It is considered that this makes it difficult for electrons to move smoothly from the dye to the semiconductor fine particles, and the current of the photoelectric conversion element decreases.
  • LUMO lowest empty orbital
  • the compound of the present invention in addition to the ring-forming heteroatom, also functions as an adsorbing group for the semiconductor fine particles, so that the cation of the photoexcited dye existing in the vicinity of the dye can be stabilized quickly.
  • the presence of the compound of the present invention around the dye makes it difficult for the oxidant ions of the redox pair to approach the electrode surface.
  • both reverse electron transfer to the orbit (HOMO) and recombination can be suppressed. Therefore, it is considered that the electrons that have moved to the semiconductor fine particles are conducted in the semiconductor fine particles without reverse electron movement, and the electron transfer efficiency of the photoelectric conversion element is increased. As a result, it is considered that the photoelectric conversion element of the present invention containing the compound of the present invention increases the current due to the increase in electron transfer efficiency, and in some cases increases the voltage, thereby improving the photoelectric conversion efficiency.
  • the rearrangement energy of the surrounding solvent molecules with respect to the change in the dye charge during electron transfer from the photoexcitation of the dye to the semiconductor fine particles can be reduced.
  • the energy barrier at the time of electron movement is made small, and electron movement easily occurs. That is, it is considered that the current increases because the rearrangement energy is low and the electron transfer of the dye easily occurs.
  • Ring A in the compound of the present invention will be described.
  • Ring A may be a nitrogen-containing heteroaryl ring having a nitrogen atom and at least one hetero atom of a nitrogen atom, a sulfur atom or an oxygen atom as a ring-forming hetero atom.
  • X of ring A is an N atom, an S atom or an O atom, and preferably an N atom or an S atom.
  • m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. When m is an integer of 2 or more, X of 2 or more may be the same or different.
  • Ring A is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring in that it enters between the dyes adsorbed on the surface of the semiconductor fine particles or adsorbs and contributes to stabilization of the cation of the dye. For the same reason, ring A is preferably a single ring that is not condensed.
  • the compound of the present invention in which the ring A is a 5-membered ring or a 6-membered ring can be preferably represented by the following formula (2) or (3).
  • X 1 to X 5 each independently represent CR X or an N atom, and at least one of X 1 to X 5 represents an N atom.
  • X 6 represents NR X , S atom or O atom.
  • Ac, L, R, R 1 , R 2 , n1, n2, and n3 are synonymous with the formula (1).
  • R x represents a hydrogen atom or a substituent, and the substituent is not particularly limited, and examples thereof include a substituent W described later.
  • one or two of X 1 to X 5 are preferably N, and one is preferably N. Note that any of X 1 to X 5 may be N.
  • X 6 is preferably S or O, and more preferably S.
  • the six-membered ring A that is, the nitrogen-containing heteroaryl ring of the formula (2) is not particularly limited, and examples thereof include a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a tetrazine ring, and a quinazoline ring.
  • the 5-membered ring A that is, the nitrogen-containing heteroaryl ring of the formula (3) is not particularly limited.
  • the ring A is preferably a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, an oxazole ring or a thiazole ring, and the compounds of the present invention having these as a ring A are represented by the following formulas (4) to (9). be able to.
  • Ring A is more preferably an oxazole ring or a thiazole ring, and more preferably a thiazole ring. That is, the compound of the present invention is more preferably a compound represented by Formulas (8) and (9), and a compound represented by Formula (9) is more preferable.
  • Ac of the group represented by “Ac-L” is an acidic group, and specifically, any adsorbing group that adsorbs to the surface of the semiconductor fine particles may be used.
  • the acidic group is preferably a group having a dissociative proton, and specifically, one having a pKa of 11 or less is preferable.
  • the acidic group Ac may take the form of releasing a proton and dissociating, or may be a salt. When the compound of the present invention has an acidic group Ac, the photoelectric conversion efficiency can be increased.
  • the acidic group Ac is preferably a carboxy group (—CO 2 H), —SO 3 H, —PO 3 H 2 , —OH, —SH or a salt thereof, more preferably —CO 2 H, —OH or a salt thereof.
  • -CO 2 H or a salt thereof is particularly preferable.
  • L represents a single bond or a linking group.
  • the linking group may be a divalent group that links the ring A and the acidic group Ac, and examples thereof include a group in which the substituent W described later is divalent.
  • an alkylene group, an ethenylene group, an ethynylene group, an arylene group, a heteroaromatic ring group, and a group obtained by combining these are preferable.
  • L is preferably a single bond or an alkylene group.
  • the linking group represented by L may have a substituent, and examples of the substituent include the substituent W described later.
  • the specific substituent R may be any of the above groups, but is substituted with a branched alkyl group having 6 or more carbon atoms or a halogen atom in terms of photoelectric conversion efficiency.
  • An alkyl group, or an alkenyl group or alkynyl group which may have a substituent is preferable.
  • the specific substituent R is more preferably an alkyl group, an alkenyl group or an alkynyl group substituted with a halogen atom, more preferably an alkyl group substituted with a halogen atom, in that the effect of improving the photoelectric conversion efficiency due to an increase in current is great.
  • it is more preferably a branched alkyl group having 6 or more carbon atoms in that the effect of improving the photoelectric conversion efficiency by increasing the voltage is great.
  • the branched alkyl group having 6 or more carbon atoms is not particularly limited, but preferably has 6 to 40 carbon atoms, and preferably 6 to 35 carbon atoms because it is excellent in the effect of improving photoelectric conversion efficiency and is excellent in solubility in an organic solvent. More preferred is 6-30.
  • Examples of the branched alkyl group include 4-methylpentyl, 1-ethylpentyl, 2-ethylhexyl, 3-ethylheptyl, 3-decylpentadecyl and the like.
  • the alkyl group substituted with a halogen atom is not particularly limited as long as at least one hydrogen atom bonded to the carbon atom constituting the alkyl group is substituted with a halogen atom. It may be a branched alkyl group.
  • the halogen atom substituted for the hydrogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable in that the effect of improving the photoelectric conversion efficiency is excellent.
  • the number of hydrogen atoms substituted with halogen atoms and the bonding position of halogen atoms are not particularly limited, and both are appropriately set.
  • the bonding position of the halogen atom is preferably the terminal of the alkyl group.
  • the alkyl group is preferably 1 to 40 carbon atoms, more preferably 3 to 35 carbon atoms, and still more preferably 6 to 30 carbon atoms from the viewpoint of excellent photoelectric conversion efficiency improvement effect and excellent solubility in an organic solvent.
  • Examples of the linear alkyl group substituted with a halogen atom include trifluoromethyl, 6,6,6,5,5,4,4,3,3-nonafluoro-1-hexyl, and the like.
  • Examples of the branched alkyl group substituted with a halogen atom include 2-fluoro-2-propyl.
  • the substituent that the branched alkyl group may have is not particularly limited as long as it is other than a halogen atom, and examples thereof include the substituent W described later. Moreover, the alkyl group substituted with the halogen atom may have a substituent, and the substituent W mentioned later is mentioned as this substituent.
  • the alkenyl group is not particularly limited, and may be a linear alkenyl group or a branched alkenyl group.
  • the alkenyl group preferably has 5 to 40 carbon atoms, more preferably 6 to 35, and still more preferably 8 to 30.
  • Examples of the alkenyl group include 1-butenyl, 2-methyl-1-propenyl and the like.
  • the alkynyl group is not particularly limited, and may be a linear alkynyl group or a branched alkynyl group.
  • the alkynyl group preferably has 2 to 40 carbon atoms, more preferably 5 to 30 carbon atoms, and still more preferably 6 to 18 carbon atoms.
  • alkynyl group examples include ethynyl, butynyl, 3,3-dimethylbutynyl and the like.
  • the substituent that each alkenyl group and alkynyl group may have is not particularly limited, and examples thereof include a substituent W described later.
  • the branched alkoxy group having 6 or more carbon atoms and the branched alkylthio group having 6 or more carbon atoms each preferably have the same branched alkyl moiety as the branched alkyl group, and the preferred range is the same as the branched alkyl group.
  • the substituent that the branched alkoxy group and the branched alkylthio group may have is not particularly limited as long as it is other than a halogen atom, and examples thereof include the substituent W described later.
  • the alkyl portion is preferably the same as the alkyl group substituted with a halogen atom, and the preferred range is also the halogen group described above. Same as alkyl group substituted with an atom.
  • the substituent that the alkoxy group and the alkylthio group may have is not particularly limited, and examples thereof include a substituent W described later.
  • R 1 and R 2 in the amino group NR 1 R 2 each independently represents a hydrogen atom or a substituent.
  • the amide group, the substituent W mentioned later, and the substituent which has an acidic group are mentioned.
  • the substituent having an acidic group may be any substituent having the above acidic group Ac, and includes, for example, an acidic group Ac, a group represented by “Ac-L”, and an acidic group among the substituents W described later. Examples thereof include a substituent and a substituent W substituted with an acidic group Ac.
  • R 1 and R 2 are each preferably a substituent having a hydrogen atom, an amide group, an alkyl group or an acidic group.
  • the compound of the present invention may have a substituent in addition to the specific substituent R, the amino group NR 1 R 2 and the group represented by “Ac-L”.
  • substituents are not particularly limited.
  • a group other than the group represented by the specific substituent R, the amino group NR 1 R 2 and “Ac-L” Is mentioned.
  • One or more other substituents may be present.
  • Other substituents may be bonded to a group represented by the specific substituent R, amino group NR 1 R 2 or “Ac-L” to form a ring together with these, and there are a plurality of other substituents. Sometimes, they may combine with each other to form a ring.
  • n1 represents an integer of 0 or more, preferably 0 or more and 3 or less, more preferably 1 or more and 3 or less, and further preferably 1 or 2. is there.
  • n2 represents an integer of 1 or more, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 3 or less, and further preferably 1 or 2.
  • n3 represents an integer of 1 or more, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 3 or less, and further preferably 1 or 2.
  • n1, n2 and n3 are appropriately set.
  • the total of n1, n2 and n3 is preferably 1 or more, and more preferably an integer of 2 or more and 5 or less.
  • the compound of the present invention preferably has at least one acidic group in terms of adsorptivity to the surface of the semiconductor fine particles. Therefore, in formulas (1) to (9), the types of R 1 and R 2 in the amino group NR 1 R 2 are selected so that at least one acidic group is present, or n1 and n2 are It is selected from the above range.
  • n1 is preferably an integer of 1 or more, or at least one of R 1 and R 2 is a substituent having an acidic group, and n2 is preferably an integer of 1 or more.
  • the specific substituent R, the amino group NR 1 R 2 and the group represented by “Ac-L” are bonded to any ring constituent atom constituting the ring A. Also good.
  • the bonding position of the amino group NR 1 R 2 and the group represented by “Ac-L” is preferably a ring-constituting atom adjacent to the nitrogen atom of ring A, from the viewpoint of adsorptivity to the surface of the semiconductor fine particles.
  • the bonding position of the specific substituent R is (b) recombination with an oxidant ion and (c) recombination with a dye.
  • the nitrogen atom of the ring A is positioned at the 1-position and the amino group NR 1
  • the 4-position or 5-position is preferred when the bonding position of R 2 is 2- position for convenience.
  • a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • Preferred substituents include the following substituent W. In the present specification, when a substituent is simply described, the substituent W is referred to. When each group, for example, an alkyl group is only described, Preferred ranges and specific examples of the corresponding group of the group W are applied.
  • substituent W examples include the following.
  • An alkyl group preferably having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, trifluoromethyl, etc.
  • Alkenyl groups preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.
  • alkynyl groups preferably having 2 to 20 carbon atoms, such as ethynyl, butynyl, phenylethynyl, etc.
  • cycloalkyl groups preferably Has 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl and the like, cycloalkenyl group (preferably having 5 to 20 carbon atoms
  • alkoxycarbonyl group preferably having 2 to 20 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.
  • a cycloalkoxycarbonyl group preferably having 4 to 20 carbon atoms such as cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, etc.
  • Cyclohexyloxycarbonyl, etc. aryloxycarbonyl groups (preferably having 6 to 20 carbon atoms, such as phenyloxycarbonyl, naphthyloxycarbonyl, etc.)
  • amino groups preferably having 0 to 20 carbon atoms, alkylamino groups, alkenyls
  • An acyl group preferably having 1 to 20 carbon atoms such as acetyl, cyclohexylcarbonyl, benzoyl, etc.
  • an acyloxy group preferably having 1 to 20 carbon atoms such as acetyloxy, cyclohexylcarbonyloxy).
  • Benzoyloxy, etc. carbamoyl group (preferably an carbamoyl group having 1 to 20 carbon atoms, alkyl, cycloalkyl or aryl, such as N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.)
  • N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.
  • An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, cyclohexylcarbonylamino, benzoylamino, etc.), a sulfonamide group (preferably an alkyl, cycloalkyl or aryl sulfonamide having 0 to 20 carbon atoms) Groups such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-cyclohexylsulfonamide, N-ethylbenzenesulfonamide, etc., alkylthio groups (preferably having 1 to 20 carbon atoms, eg, methylthio , Ethylthio, isopropylthio, benzylthio, etc.), cycloalkylthio groups (preferably having 3 to 20 carbon atoms, such as cyclopropylthio, cyclopent
  • a silyl group (preferably a silyl group having 1 to 20 carbon atoms and substituted by alkyl, aryl, alkoxy and aryloxy, such as triethylsilyl, triphenylsilyl, diethylbenzylsilyl, dimethylphenylsilyl, etc.), silyloxy group ( Preferably, it is a silyloxy group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy, dimethylphenylsilyloxy, etc.), hydroxyl group , Cyano group, nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group, sulfo group, phosphonyl group, phosphoryl group, boric acid group, more
  • the compound or the substituent includes an alkyl group, an alkenyl group, etc.
  • these may be linear or branched, and may be substituted or unsubstituted.
  • an aryl group, a heterocyclic group and the like may be monocyclic or condensed, and may be substituted or unsubstituted.
  • the conductive support is preferably a support made of glass or plastic having a conductive film layer on the surface, such as a metal, which is conductive in itself.
  • the plastic support include a transparent polymer film described in paragraph No. 0153 of JP-A No. 2001-291534.
  • the support in addition to glass and plastic, ceramic (Japanese Patent Laid-Open No. 2005-135902) or conductive resin (Japanese Patent Laid-Open No. 2001-160425) may be used.
  • the surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated And a light guide function described in JP-A-2002-260746.
  • the thickness of the conductive film layer is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m.
  • the conductive support is substantially transparent.
  • substantially transparent means that the transmittance of light (wavelength 300 to 1200 nm) is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • a glass or plastic coated with a conductive metal oxide is preferable.
  • the metal oxide tin oxide (TO) is preferable, and fluorine-doped oxide such as indium-tin oxide (tin-doped indium oxide; ITO) and fluorine-doped tin oxide (FTO) is particularly preferable.
  • the coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the glass or plastic support. When a transparent conductive support is used, light is preferably incident from the support side.
  • the photoreceptor layer is designed according to the purpose and has semiconductor fine particles carrying a dye.
  • the dye 21 in the photoreceptor layer 2 may be a single type or a mixture of various types.
  • the photoreceptor layer preferably has semiconductor fine particles on which at least one of the compound of the present invention and the coadsorbent is supported together with a dye.
  • the light receiving electrode 5 includes the conductive support 1 and the photoreceptor layer 2.
  • the semiconductor fine particles are preferably metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or perovskite semiconductor fine particles.
  • metal chalcogenides for example, oxides, sulfides, selenides, etc.
  • perovskite semiconductor fine particles Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like.
  • Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide (titania), zinc oxide, tin oxide, and tungsten oxide are particularly preferable.
  • titania examples include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable. Titania nanotubes, nanowires, and nanorods may be mixed with titania semiconductor fine particles or used as a semiconductor electrode.
  • the particle diameters of the semiconductor fine particles are 0.001 to 1 ⁇ m as primary particles and 0.01 to 100 ⁇ m as the average particle diameter of the dispersion as the average particle diameter using the diameter when the projected area is converted into a circle. preferable.
  • a method of coating the semiconductor fine particles on the conductive support there are a dry method and other methods in addition to a wet method.
  • the semiconductor fine particles preferably have a large surface area so as to adsorb many dyes and, if desired, the compound of the present invention. For example, in a state where the semiconductor fine particles are coated on the support, the surface area is preferably 10 times or more, more preferably 100 times or more the projected area.
  • the thickness of the semiconductor fine particle layer which is a semiconductor fine particle layer (semiconductor layer) varies depending on the use of the photoelectric conversion element, but is typically 0.1 to 100 ⁇ m. When used as a dye-sensitized solar cell, the thickness is preferably 1 to 50 ⁇ m, more preferably 3 to 30 ⁇ m.
  • the semiconductor fine particles are preferably subjected to a baking treatment in order to adhere the particles to each other after being applied to the support.
  • the firing conditions can be, for example, 100 to 800 ° C. and 10 minutes to 10 hours.
  • the film forming temperature of the semiconductor fine particle layer is not particularly limited. For example, if the conductive support is glass, the film is preferably formed at 60 to 400 ° C.
  • the coating amount of semiconductor fine particles per 1 m 2 of support is preferably 0.5 to 500 g, more preferably 5 to 100 g.
  • a dye is used.
  • dye can use a normal thing in a photoelectric conversion element and a dye-sensitized solar cell, without being specifically limited.
  • Such dyes include Ru metal complex dyes, squarylium cyanine dyes, organic dyes, porphyrin dyes, and phthalocyanine dyes.
  • the organic dye is preferably a cyanine dye.
  • the Ru metal complex dye is preferably a dye represented by the following formula (DA), preferably a Ru metal complex dye coordinated with a ligand of a bipyridine or terpyridine skeleton, and an Ru metal complex having an amino group in the molecule. Dyes are also preferred.
  • L1 represents a monodentate ligand
  • L2 represents a bidentate ligand
  • L3 represents a tridentate ligand
  • CI represents a counter ion when a counter ion is required to neutralize the charge.
  • m1 represents an integer of 0 to 3
  • m2 represents an integer of 0 to 3
  • m3 represents an integer of 0 to 2.
  • m1 + m2 ⁇ 2 + m3 ⁇ 3 6.
  • the monodentate ligand in L1 is preferably a halogen ion, a cyanate anion, an isocyanate anion, a thiocyanate anion, an isothiocyanate anion, a selenocyanate anion, or an isoselenocyanate anion, and more preferably an isocyanate anion, an isothiocyanate anion, or an isoselenocyanate anion.
  • an isothiocyanate anion is particularly preferred.
  • bipyridine especially 2,2′-bipyridine
  • 1,3-diketone are preferred, bipyridine is more preferred, and bipyridine substituted with a carboxy group (particularly 4,4′-diketone).
  • Carboxy-2,2′-bipyridine) is more preferred.
  • the tridentate ligand in L3 is preferably a ligand in which three nitrogen-containing heteroaryl rings are bonded by a single bond between ring-constituting carbon atoms bonded to the ring-constituting nitrogen atom of the nitrogen-containing heteroaryl ring.
  • Preferred examples of the nitrogen-containing heteroaryl ring include the rings exemplified for the heteroaryl group in R.
  • L3 is particularly preferably terpyridine (particularly 2,2 ′: 6 ′, 2 ′′ -terpyridine).
  • nitrogen-containing heteroaryl rings are preferably those having a carboxy group substituted, more preferably two or more nitrogen-containing heteroaryl rings having a carboxy group substituted, and three nitrogen-containing heteroaryl rings having a carboxy group substituted. More preferred. Of these, 4,4 ′, 4 ′′ -tricarboxy-2,2 ′: 6 ′, 2 ′′ -terpyridine is preferable.
  • CI includes Cl ⁇ , I ⁇ , CF 3 SO 3 ⁇ (TfO ⁇ ), PF 6 ⁇ , H + , N (C 4 H 9 ) 4 + (NBu 4 + ), and Cl ⁇ , N (C 4 H 9 ) 4 + is preferred.
  • Ru metal complex dyes examples include Ru metal complex dyes described in JP-A-7-500630 (in particular, Examples 1 to 5 on page 5, lower left column, line 5 to page 7, upper right column, line 7).
  • the dye synthesized in Example 19 Ru metal complex dye described in JP-T-2002-512729 (especially synthesized in Examples 1 to 16 from the third line to the 29th line and the 23rd line from the bottom of page 20) Dyes), Ru metal complex dyes described in JP-A No. 2001-59062 (particularly dyes described in paragraph Nos. 0087 to 0104), Ru metal complex dyes described in JP-A No. 2001-6760 (particularly, paragraphs) Dyes described in JP-A Nos.
  • Ru metal complex dyes described in JP-A No. 2001-253894 particularly, dyes described in paragraph Nos. 0009 to 0010), and R described in JP-A No. 2003-212851 Metal complex dyes (especially the dyes described in paragraph 0005), Ru metal complex dyes described in WO 2007/91525 pamphlet (particularly the dyes described in [0067]), JP-A-2001-291534 Ru metal complex dyes described in the above (especially dyes described in paragraphs 0120 to 0144), Ru metal complex dyes described in JP2012-012570A (in particular, dyes described in paragraphs 0095 to 0103), JP Ru metal complex dyes described in JP 2013-084594 A (particularly dyes described in paragraphs 0072 to 0081), Ru metal complex dyes described in WO 2013/088888 (especially [0286] to [0 [0293].
  • Ru metal complex dye examples include butyl group.
  • Ru represents a butyl group.
  • some Os metal complex dyes other than Ru are also exemplified, but after Ru metal complex dyes, preferred metal complex dyes.
  • squarylium cyanine dyes described in JP-A No. 11-214730 particularly dyes described in paragraphs 0036 to 0047
  • squarylium cyanine dyes described in JP-A No. 2012-144688 in particular, And dyes described in paragraph numbers 0039 to 0046 and paragraph numbers 0054 to 0060
  • squarylium cyanine dyes described in JP 2012-84503 A in particular, dyes described in paragraph numbers 0066 to 0076 and the like.
  • organic dyes described in JP-A No. 2004-063274 particularly dyes described in paragraph Nos. 0017 to 0021
  • organic dyes described in JP-A No. 2005-123033 particularly paragraph numbers.
  • porphyrin dyes examples include Angew. Chem. Int. Ed. , 49, 1-5 (2010), and the like.
  • phthalocyanine dye for example, Angew. Chem. Int. Ed. , 46, 8358 (2007), and the like.
  • a plurality of dyes may be used in combination.
  • the dye used in combination include the aforementioned Ru metal complex dye, squarylium cyanine dye, or organic dye.
  • the total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and particularly preferably 0.1 to 10 mmol per 1 m 2 of the support.
  • the dye used in the present invention is preferably one that functions alone as a sensitizing dye of a dye-sensitized solar cell.
  • the adsorption amount of the dye to the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles. By using such a dye amount, the sensitizing effect in the semiconductor fine particles can be sufficiently obtained.
  • the counter ion is not particularly limited, and includes, for example, an alkali metal ion or a quaternary ammonium ion in addition to the CI.
  • the adsorption of the dye to the semiconductor fine particles is preferably performed using a dye solution containing the dye, as will be described later.
  • a semiconductor electrode in which a semiconductor fine particle layer (photoreceptor layer) is formed on a support can be performed by immersing it in a dye solution obtained by dissolving a dye.
  • the compound of the present invention is preferably used and contained in the electrolyte or adsorbed on the surface of the semiconductor fine particles together with the dye.
  • the compound of the present invention is preferably contained in at least one of the photosensitive layer, the surface of the photosensitive layer, the charge transfer layer, and the surface of the charge transfer layer.
  • a plurality of the compounds of the present invention may be used in combination.
  • the compound of this invention is as having mentioned above as a compound represented by Formula (1).
  • the amount of the compound used is not particularly limited.
  • the compound of the present invention is adsorbed on the semiconductor fine particles
  • the compound of the present invention can be adsorbed on the surface of the semiconductor fine particles.
  • the surface treatment liquid and the surface treatment method of the semiconductor fine particles will be described later.
  • a coadsorbent and adsorb it on the surface of the semiconductor fine particles together with the dye.
  • a co-adsorbent a co-adsorbent having at least one acidic group (preferably a carboxy group or a salt group thereof) is preferable, and examples thereof include compounds having a fatty acid or a steroid skeleton.
  • the fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include butanoic acid, hexanoic acid, octanoic acid, decanoic acid, hexadecanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.
  • Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, hyocholic acid, deoxycholic acid, lithocholic acid, ursodeoxycholic acid and the like.
  • cholic acid deoxycholic acid and chenodeoxycholic acid
  • more preferred are chenodeoxycholic acid Preferred are cholic acid, deoxycholic acid and chenodeoxycholic acid, and more preferred are chenodeoxycholic acid.
  • the compound described in paragraph No. 0107 of JP2012-012570A is preferred, and the description of paragraph No. 0107 in JP2012-012570A is preferably incorporated in the present specification as it is.
  • the co-adsorbent has an effect of suppressing inefficient association of the dye by adsorbing to the semiconductor fine particles and an effect of preventing reverse electron transfer from the surface of the semiconductor fine particles to the redox system in the electrolyte.
  • the amount of coadsorbent used is not particularly limited, but it is preferably 1 to 200 mol, more preferably 10 to 150 mol, and particularly preferably 20 to 50 mol with respect to 1 mol of the dye. It is preferable from the viewpoint of being expressed.
  • the charge transfer layer used in the photoelectric conversion element of the present invention is provided between the light receiving electrode and the counter electrode.
  • the charge transfer layer is a layer having a function of replenishing electrons to the dye oxidant.
  • the charge transfer layer has an electrolyte.
  • the charge transfer layer is made of an electrolyte.
  • the electrolyte include a liquid electrolyte obtained by dissolving a redox couple in an organic solvent, a so-called gel electrolyte obtained by impregnating a polymer matrix obtained by dissolving a redox couple in an organic solvent, and a molten salt containing the redox couple. .
  • a liquid electrolyte is preferred for increasing efficiency.
  • iodine and iodide iodide salt, ionic liquid is preferable, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, methylpropylimidazolium iodide are preferable
  • alkyl viologens for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
  • polyhydroxybenzenes for example, hydroquinone, naphthohydroquinone, etc.
  • divalent And trivalent iron complexes for example, red blood salt and yellow blood salt
  • divalent and trivalent cobalt complexes and the like.
  • a combination of iodine and iodide is preferable, and a combination of divalent and trivalent cobalt complexes is preferable, and a combination of iodine and iodide is particularly preferable.
  • the cobalt complex is preferably a complex represented by the formula (A) described in paragraphs 0060 to 0063 of JP2013-077449A, and described in paragraphs 0060 to 0077 of JP2013-077749A. Are preferably incorporated in the present specification as they are.
  • iodine and iodide When a combination of iodine and iodide is used as the electrolyte, it is preferable to further use an iodine salt of a 5-membered or 6-membered nitrogen-containing aromatic cation.
  • the electrolyte preferably has the compound of the present invention in addition to the redox couple.
  • the compounds of the present invention are as described above.
  • a conventionally known pyridine compound or aminopyridine compound, a benzimidazole compound other than the compound of the present invention, an aminotriazole compound other than the compound of the present invention, other than the compound of the present invention Aminothiazole compounds, imidazole compounds other than the compounds of the present invention, aminotriazine compounds other than the compounds of the present invention, urea derivatives, amide compounds, pyrimidine compounds other than the compounds of the present invention, and nitrogen-free heterocycles can be added. .
  • the organic solvent that dissolves the redox couple, the compound of the present invention that is suitably contained, and the additive that is optionally contained, is not particularly limited, but an aprotic polar solvent (for example, acetonitrile, propylene carbonate, carbonic acid, etc.). Ethylene, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone and the like are preferable.
  • the organic solvent of the liquid electrolyte is a nitrile compound, an ether compound, an ester compound or the like, preferably a nitrile compound, and particularly preferably acetonitrile or methoxypropionitrile.
  • Examples of the polymer (polymer matrix) used in the gel electrolyte matrix include polyacrylonitrile and polyvinylidene fluoride.
  • Examples of the molten salt include those imparted with fluidity at room temperature by mixing polyethylene oxide with lithium iodide and at least one other lithium salt (such as lithium acetate and lithium perchlorate). . In this case, the amount of the polymer added is 1 to 50% by mass.
  • ⁇ -butyrolactone may be included in the electrolytic solution, thereby increasing the diffusion efficiency of iodide ions and improving the photoelectric conversion efficiency.
  • a method of controlling the moisture of the electrolytic solution may be taken.
  • Preferred methods for controlling moisture include a method for controlling the concentration and a method in which a dehydrating agent is allowed to coexist.
  • an inclusion compound of iodine and cyclodextrin may be used, and conversely, a method of constantly supplying water may be used.
  • Cyclic amidine may be used, and an antioxidant, hydrolysis inhibitor, decomposition inhibitor, and zinc iodide may be added.
  • a molten salt may be used as the electrolyte, and preferred molten salts include ionic liquids containing imidazolium or triazolium type cations, oxazolium-based, pyridinium-based, guanidinium-based, and combinations thereof. These cationic systems may be combined with specific anions. Additives may be added to these molten salts. You may have a liquid crystalline substituent. Further, a quaternary ammonium salt-based molten salt may be used.
  • lithium iodide and at least one other lithium salt are mixed with polyethylene oxide to provide fluidity at room temperature. Etc.
  • the electrolyte may be quasi-solidified by adding a gelling agent to an electrolyte solution composed of an electrolyte and a solvent to cause gelation (hereinafter, the quasi-solid electrolyte is also referred to as “pseudo-solid electrolyte”).
  • the gelling agent include organic compounds having a molecular weight of 1000 or less, Si-containing compounds having a molecular weight in the range of 500 to 5000, organic salts made of a specific acidic compound and a basic compound, sorbitol derivatives, and polyvinylpyridine.
  • a method of confining the matrix polymer, the crosslinkable polymer compound or monomer, the crosslinking agent, the electrolyte, and the solvent in the polymer may be used.
  • a matrix polymer a polymer having a nitrogen-containing heterocyclic ring in the main chain or side chain repeating unit, a crosslinked product obtained by reacting these with an electrophilic compound, a polymer having a triazine structure, or having a ureido structure Inclusion of polymers, liquid crystal compounds, ether-bonded polymers, polyvinylidene fluoride, methacrylate / acrylate, thermosetting resins, crosslinked polysiloxane, polyvinyl alcohol (PVA), polyalkylene glycol and dextrin Examples thereof include compounds, systems to which oxygen-containing or sulfur-containing polymers are added, natural polymers, and the like.
  • the matrix polymer a system including a cross-linked polymer obtained by reacting a bifunctional or higher functional isocyanate with a functional group such as a hydroxyl group, an amino group, or a carboxy group may be used.
  • a crosslinking method in which a crosslinked polymer composed of a hydrosilyl group and a double bond compound, polysulfonic acid, polycarboxylic acid, or the like is reacted with a divalent or higher valent metal ion compound may be used.
  • Examples of the solvent that can be preferably used in combination with the quasi-solid electrolyte include a specific phosphate ester, a mixed solvent containing ethylene carbonate, and a solvent having a specific dielectric constant.
  • the liquid electrolyte solution may be held in a solid electrolyte membrane or pores, and preferred methods thereof include conductive polymer membranes, fibrous solids, and cloth solids such as filters.
  • a solid charge transport layer such as a p-type semiconductor or a hole transport material, for example, CuI, CuNCS, or the like can be used. Also, Nature, vol. 486, p. The electrolyte described in 487, 2012, or the like may be used. An organic hole transport material may be used as the solid charge transport layer.
  • the organic hole transport material is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole or polysilane, and a spiro compound in which two rings share a central element such as C or Si and a tetrahedral structure, an aromatic such as triarylamine Group amine derivatives, triphenylene derivatives, nitrogen-containing heterocyclic derivatives, and liquid crystalline cyano derivatives.
  • a conductive polymer such as polythiophene, polyaniline, polypyrrole or polysilane
  • a spiro compound in which two rings share a central element such as C or Si and a tetrahedral structure, an aromatic such as triarylamine Group amine derivatives, triphenylene derivatives, nitrogen-containing heterocyclic derivatives, and liquid crystalline cyano derivatives.
  • the redox couple becomes an electron carrier, it is preferably contained at a certain concentration.
  • a preferable concentration is 0.01 mol / L or more in total, more preferably 0.1 mol / L or more, and particularly preferably 0.3 mol / L or more.
  • the upper limit in this case is not particularly limited, but is usually about 5 mol / L.
  • the compound of this invention exhibits the function, it is preferable to contain in a certain amount of density
  • a preferred concentration is 0.01 mol / L or more, more preferably 0.1 mol / L or more, and particularly preferably 0.3 mol / L or more.
  • the upper limit in this case is not particularly limited, but is usually about 5 mol / L.
  • the counter electrode is preferably a positive electrode of a dye-sensitized solar cell (photoelectrochemical cell).
  • the counter electrode is usually synonymous with the conductive support described above, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained.
  • As the structure of the counter electrode a structure having a high current collecting effect is preferable.
  • at least one of the conductive support and the counter electrode described above must be substantially transparent.
  • the conductive support is preferably transparent, and sunlight is preferably incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light.
  • a counter electrode of the dye-sensitized solar cell glass or plastic on which metal or conductive oxide is vapor-deposited is preferable, and glass on which platinum is vapor-deposited is particularly preferable.
  • the dye-sensitized solar cell it is preferable to seal the side surface of the battery with a polymer, an adhesive or the like in order to prevent the constituents from evaporating.
  • the present invention is disclosed in Japanese Patent No. 4260494, Japanese Patent Application Laid-Open No. 2004-146425, Japanese Patent Application Laid-Open No. 2000-340269, Japanese Patent Application Laid-Open No. 2002-289274, Japanese Patent Application Laid-Open No. 2004-152613, and Japanese Patent Application Laid-Open No. 9-27352. It can apply to the described photoelectric conversion element and a dye-sensitized solar cell.
  • the reverse electron transfer inhibitor for a photoelectric conversion element of the present invention is a compound represented by the formula (1), and when used in a photoelectric conversion element, the effect of preventing voltage drop and the electron of the dye as described above. Demonstrate the effect of promoting movement.
  • the reverse electron transfer inhibitor for photoelectric conversion elements of the present invention is added to the electrolyte composition for photoelectric conversion elements, or the semiconductor fine particles of the photoelectric conversion elements or the surface treatment solution of the photoreceptor layer to produce, for example, a photoelectric conversion element. Used to do.
  • Electrolyte composition and surface treatment liquid are preferably produced by using at least one of an electrolyte composition and a semiconductor fine particle or a surface treatment solution for a photoreceptor layer.
  • the electrolyte composition and the surface treatment liquid preferably contain the compound of the present invention as a reverse electron transfer inhibitor for photoelectric conversion elements.
  • the compounds of the present invention are as described above.
  • the electrolyte composition is a material that becomes an electrolyte of a photoelectric conversion element.
  • the electrolyte composition may contain any of the liquid electrolyte, the gel electrolyte, and the molten salt as an electrolyte, but a liquid electrolyte is preferable.
  • the components, organic solvents, and contents of these electrolytes are as described above. Adjustment of the water content of the electrolyte composition in the photoelectric conversion element or the dye-sensitized solar cell is preferable for effectively achieving the effects of the present invention. For example, the water content (content) of the electrolyte composition is set to 0. It is more preferable to adjust to 0.1 mass%.
  • This electrolyte composition is provided between the photoreceptor layer and the counter electrode in the production of the photoelectric conversion element. For example, a liquid electrolyte can be injected or introduced between the photoreceptor layer and the counter electrode.
  • the surface treatment liquid only needs to contain the compound of the present invention, and is usually a composition containing a solvent. Although it does not specifically limit as a solvent, The same thing as what was illustrated with electrolyte can be mentioned. Examples of other components that may be contained in the surface treatment liquid include the above-mentioned additives such as aminopyridine compounds and coadsorbents.
  • the concentration of the compound of the present invention in the surface treatment liquid is not particularly limited, but is preferably 0.01 to 1.0 mol / L, and more preferably 0.05 to 0.5 mol / L, for example.
  • This surface treatment liquid is applied to semiconductor fine particles or a photoreceptor layer or used as an immersion liquid in the production of a photoelectric conversion element. Specific examples include a method of immersing a substrate having semiconductor fine particles adsorbed with a dye in an acetonitrile solution containing the compound of the present invention at a concentration of 0.05 mol / L for 30 minutes.
  • ⁇ Method for Producing Dye-Sensitized Solar Cell it is preferable to provide a charge transfer body layer using the electrolyte composition containing the compound of this invention.
  • the method for providing the charge transfer layer using the electrolyte composition is not particularly limited, and in the case of a liquid electrolyte, the above method can be used.
  • the method for surface-treating the semiconductor fine particles or the photoreceptor layer using the surface treatment liquid is as described above.
  • a dye adsorption electrode it is preferable to produce a dye adsorption electrode using a dye solution containing a dye.
  • the dye is dissolved in a solvent, and may contain a co-adsorbent and other components as necessary.
  • the solvent to be used include the solvents described in JP-A-2001-291534, but are not particularly limited.
  • an organic solvent is preferable, and alcohols, amides, nitriles, hydrocarbons, and a mixed solvent of two or more of these are preferable.
  • the mixed solvent a mixed solvent of an alcohol and a solvent selected from amides, nitriles or hydrocarbons is preferable.
  • alcohols and amides are further preferred.
  • mixed solvents of alcohols and hydrocarbons are particularly preferred.
  • mixed solvents of alcohols and amides are preferable. Specifically, methanol, ethanol, propanol, butanol, dimethylformamide, and dimethylacetamide are preferable.
  • the dye solution preferably contains a co-adsorbent.
  • the dye solution is preferably one in which the concentration of the dye or co-adsorbent is adjusted so that the solution can be used as it is when producing a photoelectric conversion element or a dye-sensitized solar cell.
  • the pigment is preferably contained in an amount of 0.001 to 0.1% by mass.
  • the water content of the dye solution is particularly preferably adjusted. Therefore, in the present invention, the water content (content ratio) is particularly preferably adjusted to 0 to 0.1% by mass.
  • a semiconductor electrode for a dye-sensitized solar cell in which a dye is supported on the surface of semiconductor fine particles provided in the semiconductor electrode using the dye solution is preferable. Moreover, it is preferable to manufacture a dye-sensitized solar cell by supporting a dye on the surface of semiconductor fine particles provided in the semiconductor electrode using the dye solution.
  • Example 1 Preparation of dye-sensitized solar cell> A dye-sensitized solar cell was prepared as described below, and the photoelectric conversion efficiency was measured.
  • N749 Black Dye
  • a photoelectrode having the same configuration as that of the photoelectrode 12 shown in FIG. 5 described in JP-A-2002-289274 is prepared by the following procedure, and further replaced with the photoelectrode in FIG.
  • a 10 ⁇ 10 mm scale dye-sensitized solar cell 20 having the same configuration as that of the dye-sensitized solar cell 20 of FIG. 3 was prepared except that the lever photoelectrode was used.
  • the specific configuration is shown in FIG. In FIG.
  • 41 is a transparent electrode
  • 42 is a semiconductor electrode
  • 43 is a transparent conductive film
  • 44 is a substrate
  • 45 is a semiconductor layer
  • 46 is a light scattering layer
  • 40 is a photoelectrode
  • 20 is a dye-sensitized solar cell
  • CE is The counter electrode
  • E is an electrolyte
  • S is a spacer.
  • Paste A A titania slurry was prepared by placing spherical TiO 2 particles (anatase, average particle size; 25 nm, hereinafter referred to as spherical TiO 2 particles A) in a nitric acid solution and stirring. Next, a cellulosic binder was added to the titania slurry as a thickener and kneaded to prepare paste A.
  • a titania slurry was prepared by stirring spherical TiO 2 particles A and spherical TiO 2 particles (anatase, average particle size: 200 nm, hereinafter referred to as spherical TiO 2 particles B) in a nitric acid solution. .
  • rod-like TiO 2 particles C anatase, diameter: 100 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO 2 particles C
  • a transparent electrode 41 (conductive support) in which a fluorine-doped SnO 2 conductive film 43 (transparent conductive film 43, film thickness: 500 nm) was formed on a glass substrate 44 (substrate 44) was prepared. Then, the SnO 2 conductive film, a paste 1 of the above screen printing and then dried. Then, it baked on the conditions of 450 degreeC in the air. Further, by repeating this screen printing and baking using the paste 2, a semiconductor electrode having the same configuration as the semiconductor electrode 42 shown in FIG. 2 (light-receiving surface area; 10 mm ⁇ 10 mm, layer) is formed on the SnO 2 conductive film.
  • Thickness 20 ⁇ m
  • layer thickness of semiconductor layer 15 ⁇ m
  • layer thickness of light scattering layer 5 ⁇ m
  • content of rod-like TiO 2 particles C contained in the light scattering layer 30% by mass
  • the dye (N749) was adsorbed to the photoelectrode prepared as described above.
  • N, N-dimethylformamide / t-BuOH 2/1 is used as a solvent, and a dye is dissolved in the solvent so as to have a concentration of 5 ⁇ 10 ⁇ 4 mol / L.
  • chenodeoxychol is used as a coadsorbent.
  • 20 mol of an equimolar mixture of acid and cholic acid was added to 1 mol of the dye to prepare a dye solution.
  • the water content of this dye solution was measured by Karl Fischer titration and found to be less than 0.01% by mass.
  • the semiconductor electrode prepared above was immersed in this solution, thereby completing the photoelectrode 40 in which the dye was adsorbed to the semiconductor electrode 42 by about 1.5 ⁇ 10 ⁇ 7 mol / cm 2 .
  • a platinum electrode thinness of Pt thin film; 100 nm having the same shape and size as the above-mentioned photoelectrode 40 as the counter electrode CE, and 1,2-dimethyl-3-propylimidazolium iodide (as the electrolyte E) 0.4M), iodine (0.1M) and lithium iodide (0.1M), and the compound of the present invention or the comparative compound (concentration 0.50 mol / L) dissolved in acetonitrile to prepare an electrolyte A composition (liquid electrolyte) was prepared. When the water content of this electrolyte composition was measured by Karl Fischer titration, it was less than 0.01% by mass.
  • a DuPont spacer S (trade name: “Surlin”) having a shape corresponding to the size of the semiconductor electrode 42 is prepared, as shown in FIG. 3 described in JP-A-2002-289274. Then, the photoelectrode 40, the counter electrode CE, and the spacer S were opposed to each other, and the inside was filled with the electrolyte composition to form an electrolyte E, thereby completing a dye-sensitized solar cell using the photoelectrode 40.
  • the battery characteristic test was performed by irradiating 1000 W / m 2 of pseudo-sunlight from a xenon lamp through an AM1.5 filter using a solar simulator (manufactured by WACOM, WXS-85H). The current-voltage characteristics were measured using an IV tester to determine the photoelectric conversion efficiency. The measured short-circuit current JSC and open circuit voltage V OC , and the obtained photoelectric conversion efficiency were evaluated based on the following criteria for the following comparative compound TA.
  • Comparative compound TA is t-butylpyridine (TBP, Comparative Example 2 described in Patent Document 2) which has been conventionally used.
  • Comparative compound TB is compound No. 1 described in Patent Document 1. 18.
  • Comparative compound TC is “2-amino-4-tert-butylthiazole” described in Patent Document 3.
  • the dye-sensitized solar cell of the present invention including the compounds of the present invention (Samples No.1 ⁇ 11) are short-circuit current J SC increases, is excellent in photoelectric conversion efficiency I understood it.
  • Sample No. From the comparison of 5 and 6, it was found that higher photoelectric conversion efficiency can be obtained when X in the formula (1) is an S atom than an O atom. This is because, in the HSAB (Hard and Soft Acids and Bases) rule, the inclusion of S atoms, which are relatively soft atoms, has a higher affinity for the cation of the dye, which is a soft acid. Yes.
  • HSAB Hard and Soft Acids and Bases
  • the specific substituent R included in the ring A is a branched alkyl group or an alkyl group substituted with a halogen atom
  • the short-circuit current JSC and / or the open-circuit voltage V OC are further increased, and further excellent photoelectric conversion efficiency is exhibited. I understood it. This is considered to be due to the fact that the compound of the present invention having the specific substituent R was localized in the vicinity of the cation of the dye due to the ring A, thereby exhibiting a reduction in rearrangement energy and a reverse electron transfer suppression effect. .
  • the compound of the present invention has an acidic group Ac in addition to the specific substituent R and the amino group NR 1 R 2 , the short-circuit current JSC and the open-circuit voltage V OC are further increased, and particularly excellent photoelectric conversion efficiency. It was found that It is considered that this is adsorbed on the surface of the semiconductor fine particles to effectively suppress the reverse electron transfer of electrons and further increase the photoelectric conversion efficiency.
  • the comparative compound is the pyridine ring to only one nitrogen atom as ring-constituting atoms as a basic skeleton TA (Sample No.C1), and comparative compounds TB (Sample No.C2) is short-circuit current J SC and The open circuit voltage V OC was small, and the photoelectric conversion efficiency was also small.
  • the compounds of the pyridine ring as a basic skeleton in particular short-circuit current J SC small, it was confirmed that not be obtained excellent photoelectric conversion efficiency. This is presumed to be due to the fact that the pyridine ring has a weak localizing force around the dye and / or on the electrode surface, and has no substituent that lowers the rearrangement energy.
  • comparative compound TC (Sample No.C3) number of carbon atoms in the branched alkyl group is 4, small short-circuit current J SC and the open circuit voltage V OC, photoelectric conversion efficiency was also small.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention porte sur un inhibiteur de transfert d'électrons inverse pour un élément de conversion photovoltaïque, qui est représenté par la formule (1). L'élément de conversion photovoltaïque est un élément de conversion photovoltaïque comportant, dans l'ordre suivant, sur un corps de support conducteur : une couche photosensible comprenant des particules fines de semi-conducteur transportant un colorant ; une couche de transfert de charge comprenant un électrolyte ; une contre-électrode. Un composé représenté par la formule (1) est présent entre le corps de support conducteur et la contre-électrode. Une cellule photovoltaïque sensibilisée par colorant est munie de l'élément de conversion photovoltaïque. Dans la formule (1), un cycle (A) représente un cycle hétéroaryle contenant de l'azote, et X représente un atome N, un atome S ou un atome O. m représente un nombre entier supérieur ou égal à 1, et lorsque m est supérieur ou égal à 2, chaque X peut être différent les uns des autres. Ac représente un groupe acide, et L représente une liaison unique ou un groupe de liaisons. R représente un C6 ou un groupe alkyle à ramification supérieure, un groupe alkyle remplacé par un atome d'halogène, ou un groupe alcényle ou un groupe alcynyle qui peut avoir un substituant, un C6 ou un groupe alkoxy à ramification supérieure ou un groupe alkoxy remplacé par un atome d'halogène, un C6 ou un groupe alkylthio à ramification supérieure ou un groupe alkylthio remplacé par un atome d'halogène, un atome de fluor ou un atome de cyano. Le groupe alkyle ramifié, le groupe alkoxy ramifié et le groupe alkylthio ramifié peuvent comprendre un substituant autre qu'un atome d'halogène. R1 et R2 représente chacun indépendamment un atome d'hydrogène ou un substituant. n1 représente un nombre entier supérieur ou égal à 0, et n2 et n3 représentent chacun indépendamment un nombre entier supérieur ou égal à 1.
PCT/JP2014/069654 2013-09-05 2014-07-25 Élément de conversion photovoltaïque, cellule photovoltaïque sensibilisée par colorant et inhibiteur de transfert d'électrons inverse pour un élément de conversion photovoltaïque WO2015033698A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000090991A (ja) * 1998-09-09 2000-03-31 Fuji Photo Film Co Ltd 光電気化学電池
JP2003331936A (ja) * 2002-05-13 2003-11-21 National Institute Of Advanced Industrial & Technology ピリジン及び／又はピリジン系化合物を含む電解質溶液を用いた光電変換素子及びそれを用いた色素増感型太陽電池
JP2004047229A (ja) * 2002-07-10 2004-02-12 National Institute Of Advanced Industrial & Technology アミノピリジン系化合物を含む電解質溶液を用いた光電変換素子及びそれを用いた色素増感型太陽電池
JP2005038711A (ja) * 2003-07-15 2005-02-10 National Institute Of Advanced Industrial & Technology 光電変換素子及びそれを用いた色素増感型太陽電池
JP2005108663A (ja) * 2003-09-30 2005-04-21 National Institute Of Advanced Industrial & Technology 光電変換素子及びそれを用いた色素増感型太陽電池
JP2006286203A (ja) * 2005-03-31 2006-10-19 Toshiba Corp 電解質組成物用原料キット、電解質組成物及び光増感型太陽電池
JP2009081074A (ja) * 2007-09-27 2009-04-16 Sony Corp 色素増感光電変換素子、電解質組成物、電解質用添加剤および電子機器
WO2011158922A1 (fr) * 2010-06-18 2011-12-22 ソニー株式会社 Élément de conversion photoélectrique et son procédé de production, et dispositif électronique
JP2012133962A (ja) * 2010-12-21 2012-07-12 Konica Minolta Business Technologies Inc 光電変換素子および色素増感型太陽電池
JP2012243527A (ja) * 2011-05-18 2012-12-10 Sony Corp 色素増感太陽電池および色素増感太陽電池用光電極

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000090991A (ja) * 1998-09-09 2000-03-31 Fuji Photo Film Co Ltd 光電気化学電池
JP2003331936A (ja) * 2002-05-13 2003-11-21 National Institute Of Advanced Industrial & Technology ピリジン及び／又はピリジン系化合物を含む電解質溶液を用いた光電変換素子及びそれを用いた色素増感型太陽電池
JP2004047229A (ja) * 2002-07-10 2004-02-12 National Institute Of Advanced Industrial & Technology アミノピリジン系化合物を含む電解質溶液を用いた光電変換素子及びそれを用いた色素増感型太陽電池
JP2005038711A (ja) * 2003-07-15 2005-02-10 National Institute Of Advanced Industrial & Technology 光電変換素子及びそれを用いた色素増感型太陽電池
JP2005108663A (ja) * 2003-09-30 2005-04-21 National Institute Of Advanced Industrial & Technology 光電変換素子及びそれを用いた色素増感型太陽電池
JP2006286203A (ja) * 2005-03-31 2006-10-19 Toshiba Corp 電解質組成物用原料キット、電解質組成物及び光増感型太陽電池
JP2009081074A (ja) * 2007-09-27 2009-04-16 Sony Corp 色素増感光電変換素子、電解質組成物、電解質用添加剤および電子機器
WO2011158922A1 (fr) * 2010-06-18 2011-12-22 ソニー株式会社 Élément de conversion photoélectrique et son procédé de production, et dispositif électronique
JP2012133962A (ja) * 2010-12-21 2012-07-12 Konica Minolta Business Technologies Inc 光電変換素子および色素増感型太陽電池
JP2012243527A (ja) * 2011-05-18 2012-12-10 Sony Corp 色素増感太陽電池および色素増感太陽電池用光電極

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