WO2013121835A1 - Dérivé de spirobifluorène, colorant pour éléments de conversion photoélectrique, électrode de semi-conducteur l'utilisant, élément de conversion photoélectrique et cellule photoélectrochimique - Google Patents

Dérivé de spirobifluorène, colorant pour éléments de conversion photoélectrique, électrode de semi-conducteur l'utilisant, élément de conversion photoélectrique et cellule photoélectrochimique Download PDF

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WO2013121835A1
WO2013121835A1 PCT/JP2013/051121 JP2013051121W WO2013121835A1 WO 2013121835 A1 WO2013121835 A1 WO 2013121835A1 JP 2013051121 W JP2013051121 W JP 2013051121W WO 2013121835 A1 WO2013121835 A1 WO 2013121835A1
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photoelectric conversion
substituted
dye
compound
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Japanese (ja)
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前田　勝美
中村　新
輝昌 下山
静香 松永
中原　謙太郎
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日本電気株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells

Definitions

  • the present invention relates to a spirobifluorene derivative, a dye for a photoelectric conversion element, a semiconductor electrode using the same, a photoelectric conversion element, and a photoelectrochemical cell.
  • Solar cells that convert light energy into electrical energy include inorganic solar cells that use inorganic materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and organic solar cells that use organic dyes and conductive polymer materials. Solar cells have been proposed.
  • a Gretzel type solar cell includes a semiconductor electrode in which a semiconductor layer having a dye adsorbed thereon is formed on a conductive substrate, a counter electrode made of a conductive substrate opposite to the electrode, and an electrolyte layer held between the electrodes. And.
  • the adsorbed dye absorbs light and enters an excited state, and electrons are injected from the excited dye into the semiconductor layer.
  • the dye that is in an oxidized state due to the emission of electrons returns to the original dye by transferring electrons to the dye by the oxidation reaction of the redox agent in the electrolyte layer. Then, the redox agent that has donated electrons to the dye is reduced again on the counter electrode side. This series of reactions functions as a battery.
  • the effective reaction surface area increased about 1000 times by using porous titanium oxide in which fine particles were sintered in the semiconductor layer, and a photocurrent larger than the conventional one could be taken out. It is a big feature.
  • a metal complex such as a ruthenium complex is used as a sensitizing dye.
  • a metal complex such as a ruthenium complex
  • cis-bis (isothiocyanato) -bis- (2,2′-bipyridyl-4,4′-dicarboxylic acid) is used.
  • One type of complex is tris (isothiocyanato) (2,2 ′: 6 ′, 2 ′′ -terpyridyl-4,4 ′, 4 ′′ -tricarboxylic acid) ruthenium (II) tritetrabutylammonium complex.
  • organic dyes that do not contain noble metals such as ruthenium is required as sensitizing dyes in dye-sensitized solar cells.
  • organic dyes have a higher molar extinction coefficient than metal complexes such as ruthenium complexes, and further have a high degree of freedom in molecular design, so that development of dyes with high photoelectric conversion efficiency is expected.
  • the present invention has been made in order to solve the above-mentioned problems, and has a photoelectric conversion dye excellent in photoelectric conversion characteristics, a semiconductor electrode using the same, a photoelectric conversion element and a photoelectrochemical cell, and photoelectric conversion characteristics.
  • the object is to provide a compound having an excellent spirobifluorene skeleton.
  • the compound of the present invention is a compound having a spirobifluorene skeleton represented by the following general formula (1), a tautomer or a stereoisomer thereof.
  • R 1 and R 2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or an alkoxy group, a hydroxy group, or a substituted or unsubstituted aryl group. Represents a conjugated linking group, and X represents an organic group having an acidic group.
  • the dye for a photoelectric conversion device of the present invention includes at least one of the compound having a spirobifluorene skeleton of the present invention, a tautomer or a stereoisomer thereof.
  • the semiconductor electrode for photoelectric conversion elements of the present invention has a semiconductor layer containing the dye for photoelectric conversion elements of the present invention.
  • the photoelectric conversion element of the present invention has the semiconductor electrode for a photoelectric conversion element of the present invention.
  • the photoelectrochemical cell of the present invention has the photoelectric conversion element of the present invention.
  • skeleton excellent in the photoelectric conversion characteristic can be provided,
  • dye for photoelectric conversion elements excellent in the photoelectric conversion characteristic by using this compound, and semiconductor electrode using the same A photoelectric conversion element and a photoelectrochemical cell can be provided.
  • FIG. 3 is a diagram showing a current-voltage curve of cell 1 using the compound (SPF-1) of Example 1 according to the embodiment of the present invention.
  • FIG. 3 is a diagram showing a current-voltage curve of cell 2 using the compound (SPF-1) of Example 1 according to the embodiment of the present invention.
  • FIG. 3 is a diagram showing a current-voltage curve of cell 3 using the compound (SPF-1) of Example 1 according to the embodiment of the present invention.
  • a compound having a spirobifluorene skeleton suitable for the photoelectric conversion dye according to the present embodiment is a compound represented by the following general formula (1).
  • any isomer is present.
  • the body can also be used in the present invention.
  • compounds having a spirobifluorene skeleton, tautomers or stereoisomers thereof are collectively referred to as spirobifluorene derivatives.
  • R 1 and R 2 in the general formula (1) each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a hydroxy group, or a substituted or unsubstituted aryl group.
  • the substituted or unsubstituted alkyl group is an alkyl group having 1 to 20 carbon atoms in total, for example, methyl group, ethyl group, propyl group, n-butyl group, tert-butyl group, sec-butyl group, pentyl group A straight-chain, branched or cyclic unsubstituted alkyl group having 1 to 12 carbon atoms such as hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc.
  • Aralkyl groups such as benzyl groups substituted with groups, etc., hydroxyalkyl groups substituted with hydroxy groups on these alkyl groups, and alkoxyalkyl groups substituted with alkoxy groups (for example, alkoxy groups having 1 to 8 carbon atoms) on these alkyl groups Etc.
  • it is a linear or branched unsubstituted alkyl group having 1 to 8 carbon atoms.
  • the substituted or unsubstituted alkoxy group is an alkoxy group having 1 to 20 carbon atoms in total, for example, methoxy group, ethoxy group, propoxy group, n-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyl Straight, branched or cyclic unsubstituted alkoxy groups having 1 to 12 carbon atoms such as oxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group and n-dodecyloxy group An aralkyloxy group such as a benzyloxy group in which a phenyl group is substituted on the alkoxy group, a hydroxyalkoxy group in which a hydroxy group is substituted on the alkoxy group, an alkoxy group (for example, an alkoxy group having 1 to 8 carbon atoms) And al
  • a linear or branched unsubstituted alkoxy group having 1 to 8 carbon atoms is preferable.
  • substituent bonded to the aryl group include an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms), a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 8 carbon atoms), and the like.
  • the substituted or unsubstituted aryl group includes a phenyl group, a biphenyl group, a tolyl group, a 4-t-butylphenyl group, a 3,5-di-t-butylphenyl group, a 4-methoxyphenyl group, 4-hexyloxyphenyl group, 4-octyloxyphenyl group, 2,4-dihexyloxyphenyl group, 3,4,5-trihexyloxyphenyl group, 3,4,5-trioctyloxyphenyl group, 4- ( ⁇ , ⁇ -dimethylbenzyl) phenyl group, 9,9-dimethylfluoren-2-yl group, 2 ′, 4′-dihexyloxybiphenyl group, 2 ′, 4′-dibutoxybiphenyl group, etc. There are 30 substituted or unsubstituted aryl groups.
  • the linking group Z represents a ⁇ -conjugated linking group, specifically, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, a vinylene group (—CH ⁇ CH—), an ethynylene group (—C ⁇ C— ) Represents at least one linking group selected from the group consisting of
  • the linking group Z is not particularly limited, but is preferably an atomic group that can be conjugated with the spirobifluorene ring to which Z is bonded and the organic group X having an acidic group.
  • the linking group Z is preferably a linking group having a structure represented by at least the following general formula (2) or general formula (3).
  • R 3 and R 4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, and R 3 and R 4 are connected to each other.
  • a ring may be formed.
  • the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, a pentyl group, a neo-pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • Examples thereof include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, and examples of the substituent bonded to the alkyl group include a hydroxy group and an alkoxy group.
  • Examples of the unsubstituted alkoxy group include linear or branched alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an iso-propoxy group, a butoxy group, and a t-butoxy group. You may have the same substituent as the substituent to couple
  • examples of the ring formed by connecting R 3 and R 4 include a cycloheptane ring, a cyclohexane ring, a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, and a dioxepane ring. These rings may have a substituent which the alkyl group and alkoxy group may have.
  • Y represents an oxygen atom, a sulfur atom or NRa
  • Ra represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
  • the substituted or unsubstituted alkyl group include the same alkyl groups as the substituted or unsubstituted alkyl groups of R 1 and R 2 described above.
  • the substituent bonded to the aryl group include an alkyl group, a hydroxy group, an alkoxy group, and an N, N-dialkylamino group.
  • the substituted or unsubstituted aryl group includes a phenyl group, tolyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-methoxyphenyl group, 4- ( N, N-dimethylamino) phenyl group and the like. * Indicates a bond.
  • R 5 and R 6 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
  • A represents a carbon atom or a silicon atom.
  • Examples of the substituted or unsubstituted alkyl group include the same alkyl groups as the substituted or unsubstituted alkyl groups of R 3 and R 4 described above.
  • substituted or unsubstituted aryl group examples include phenyl group, biphenyl group, tolyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-methoxyphenyl group, and 4-hexyloxyphenyl.
  • linking group Z are shown in the chemical formulas (Z1) to (Z29), but are not limited thereto.
  • carbons constituting the rings are directly bonded to each other or bonded by forming a condensed ring.
  • a group in which a plurality of these linking groups are linked may be used.
  • the spirobifluorene ring is shown as being bonded to the left bond and the organic group X having an acidic group is bonded to the right bond, but it may be in the opposite direction.
  • X in the general formula (1) represents an organic group having an acidic group.
  • the acidic group of the organic group X include a carboxy group, a sulfonic acid group, a phosphonic acid group, or a salt thereof, and among them, a carboxy group or a salt thereof is particularly preferable.
  • a monovalent or divalent metal salt, ammonium salt or organic ammonium salt is preferred.
  • the monovalent or divalent metal salt include alkali metal salts such as Li, Na, K, and Cs, and alkaline earth metal salts such as Mg, Ca, and Sr.
  • the organic group of the organic ammonium salt include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
  • the spirobifluorene derivative represented by the general formula (1) preferably has a functional group that can be adsorbed to the semiconductor layer from the viewpoint of adsorbing to the semiconductor layer used in the semiconductor electrode, and the acidic group of the organic group X is the functional group. Can play a role.
  • Specific examples of the organic group X having an acidic group are shown by chemical formulas (X1) to (X16) in Tables 4 and 5, but are not limited thereto. These organic groups X have a carbon-carbon double bond in addition to the acidic group, and one bond of the linking group Z is bonded to one carbon of the carbon-carbon double bond, and the other carbon.
  • a cyano group, a carbonyl group, carbon of another carbon-carbon double bond, or carbon of a carbon-nitrogen double bond is bonded to.
  • the spirobifluorene derivative represented by the general formula (1) has two acidic groups that are functional groups that can be adsorbed to the semiconductor electrode in the molecular structure. Therefore, it can be expected that the adsorptive power becomes stronger compared to a dye having only one acidic group in the molecular structure, and as a result, improvement in the stability of the dye after the dye is adsorbed to the semiconductor electrode can be expected.
  • the organic group X having an acidic group is preferably a group represented by the following general formula (4).
  • M represents a hydrogen atom or a salt-forming cation.
  • Examples of the salt-forming cation include various cations capable of forming a salt with a carboxy group.
  • Examples of such a cation include an ammonium cation (NH 4+ ); an organic ammonium cation derived from an amine (A 1 A 2 A 3 A 4 N + , A 1 to A 4 represent a hydrogen atom or an organic group. At least one of which is an organic group); alkali metal ions such as Li + , Na + , K + and Cs + ; alkaline earth metal ions such as Mg 2+ , Ca 2+ and Sr 2+ .
  • Examples of the organic group represented by A 1 to A 4 of the organic ammonium cation include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
  • Examples of combinations of Z and X in the spirobifluorene derivative represented by the general formula (1) include, for example, the following a-1 to a-29, b-1 to b-29, and c-1 to c -29, d-1 to d-13, e-1 to e-13, f-1 to f-13, g-1 to g-13, h-1 to h-13, i-1 to i-13 But are not limited to these.
  • the spirobifluorene derivative of the present invention is particularly preferably a compound having a spirobifluorene skeleton represented by the following formula SPF-1, a tautomer or stereoisomer thereof, or a salt thereof.
  • compounds SPF-2 to SPF-13 shown in Tables 9 and 10 below are particularly preferable.
  • these compounds SPF-2 to SPF-13 can be prepared by referring to the production methods and examples described below, and by those skilled in the art without undue trial and error and complicated advanced experiments. It can be easily produced and used according to the production method of compound SPF-1.
  • the compound of this invention is not limited to these examples, The combination of R ⁇ 1 >, R ⁇ 2 >, Z, X can be made arbitrary within the defined range, respectively.
  • FIG. 1 schematically shows a cross-sectional structure of an example of the photoelectric conversion element according to the present embodiment.
  • the photoelectric conversion element shown in FIG. 1 includes a semiconductor electrode 4, a counter electrode 8, and an electrolyte layer (charge transport layer) 5 held between both electrodes.
  • the semiconductor electrode 4 includes a conductive substrate including the light transmissive substrate 3 and the transparent conductive layer 2, and the semiconductor layer 1.
  • the counter electrode 8 includes a catalyst layer 6 and a substrate 7.
  • the semiconductor layer 1 is adsorbed with a dye containing at least one spirobifluorene derivative according to the present invention.
  • the photoelectric conversion element When light is incident on this photoelectric conversion element, the dye adsorbed on the semiconductor layer 1 is excited and emits electrons. The electrons move to the conduction band of the semiconductor, and further move to the transparent conductive layer 2 by diffusion. The electrons in the transparent conductive layer 2 move to the counter electrode 8 via an external circuit (not shown). And the pigment
  • the photoelectric conversion element is configured to function as a photoelectrochemical cell, particularly a solar cell.
  • each component will be described by taking the photoelectric conversion element shown in FIG. 1 as an example.
  • the semiconductor electrode 4 includes a conductive substrate including the light transmissive substrate 3 and the transparent conductive layer 2, and the semiconductor layer 1. As shown in FIG. 1, a light transmissive substrate 3, a transparent conductive layer 2, and a semiconductor layer 1 are laminated in this order from the outside to the inside of the element. A dye (not shown) is adsorbed on the semiconductor layer 1.
  • the conductive substrate of the semiconductor electrode 4 may have a single layer structure in which the substrate itself has conductivity, or a two-layer structure in which a conductive layer is formed on the substrate.
  • the conductive substrate of the photoelectric conversion element shown in FIG. 1 has a two-layer structure in which a transparent conductive layer 2 is formed on a light transmissive substrate 3.
  • Examples of the substrate used for the conductive substrate include a glass substrate, a plastic substrate, a metal plate, and the like. Among them, a substrate having high light transmittance, for example, a transparent plastic substrate is particularly preferable.
  • Examples of the material for the transparent plastic substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polycycloolefin, polyphenylene sulfide, and the like.
  • the conductive layer (for example, the transparent conductive layer 2) formed on the substrate (for example, the light transmissive substrate 3) is not particularly limited, but for example, indium tin oxide (Indium-Tin-Oxide: ITO), A transparent conductive layer made of a transparent material such as fluorine-doped tin oxide (FTO), indium-zinc oxide (IZO), tin oxide (SnO 2 ), or the like is preferable.
  • the conductive layer formed over the substrate can be formed into a film shape over the entire surface or a part of the surface of the substrate.
  • the thickness of the conductive layer can be selected as appropriate, but is preferably about 0.02 ⁇ m or more and 10 ⁇ m or less. Such a conductive layer can be formed using a normal film formation technique.
  • the conductive substrate in this embodiment can also use a metal lead wire for the purpose of reducing the resistance of the conductive substrate.
  • the metal lead wire include metals such as aluminum, copper, gold, silver, platinum, and nickel.
  • the metal lead wire can be produced by vapor deposition, sputtering, or the like.
  • a conductive layer for example, transparent conductive layer 2 such as ITO or FTO
  • a metal lead wire may be formed on the conductive layer.
  • the following description of the present embodiment is based on an example in which a conductive substrate having a two-layer structure in which the transparent conductive layer 2 is formed on the light-transmitting substrate 3 is used as the conductive substrate of the semiconductor electrode. It is not limited to examples.
  • a semiconductor layer As a material constituting the semiconductor layer 1, a single semiconductor such as silicon or germanium, a compound semiconductor such as a metal chalcogenide, a compound having a perovskite structure, or the like can be used.
  • Metal chalcogenides include oxides such as titanium, tin, zinc, iron, tungsten, indium, zirconium, vanadium, niobium, tantalum, strontium, hafnium, cerium, lanthanum; cadmium, zinc, lead, silver, antimony, bismuth, etc. Sulfides; selenides such as cadmium and lead; tellurides of cadmium and the like.
  • Examples of other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium; gallium arsenide; copper-indium-selenide; copper-indium-sulfide, and the like.
  • Examples of the compound having a perovskite structure include commonly known semiconductor compounds such as barium titanate, strontium titanate, and potassium niobate. These semiconductor materials can be used alone or in combination of two or more.
  • a semiconductor material containing titanium oxide or zinc oxide is preferable, and a semiconductor material containing titanium oxide is more preferable.
  • titanium oxide include various types of titanium oxide such as anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, and a titanium oxide-containing complex can be used. .
  • anatase type titanium oxide is preferable from the viewpoint of further improving the stability of photoelectric conversion.
  • Examples of the form of the semiconductor layer include a porous semiconductor layer obtained by sintering semiconductor fine particles, a thin film semiconductor layer obtained by a sol-gel method, a sputtering method, a spray pyrolysis method, and the like. Moreover, it is good also as a semiconductor layer which consists of a fibrous semiconductor layer or an acicular crystal
  • the form of these semiconductor layers can be appropriately selected according to the purpose of use of the photoelectric conversion element. Among these, a semiconductor layer having a large specific surface area such as a porous semiconductor layer and a needle-like semiconductor layer is preferable from the viewpoint of the amount of dye adsorbed.
  • a porous semiconductor layer formed from semiconductor fine particles is preferable from the viewpoint that the utilization factor of incident light and the like can be adjusted by the particle size of the semiconductor fine particles.
  • the semiconductor layer may be a single layer or a multilayer. By forming a multilayer, a sufficiently thick semiconductor layer can be more easily formed.
  • the porous semiconductor layer formed from semiconductor fine particles is a multilayer, it may consist of a plurality of semiconductor layers having different average particle diameters of the semiconductor fine particles. For example, the average particle diameter of the semiconductor fine particles of the semiconductor layer closer to the light incident side (first semiconductor layer) may be smaller than that of the semiconductor layer farther from the light incident side (second semiconductor layer).
  • the first semiconductor layer absorbs a lot of light, and the light that has passed through the first semiconductor layer is efficiently scattered by the second semiconductor layer and returned to the first semiconductor layer, and the returned light is returned to the first semiconductor layer.
  • the whole optical absorptance can be improved further.
  • the film thickness of the semiconductor layer is not particularly limited, but can be set to, for example, not less than 0.5 ⁇ m and not more than 45 ⁇ m from the viewpoints of permeability and conversion efficiency.
  • the specific surface area of the semiconductor layer can be set to, for example, 10 m 2 / g or more and 200 m 2 / g or less from the viewpoint of adsorbing a large amount of dye.
  • the porosity of the porous semiconductor layer is, for example, 40% or more and 80 from the viewpoint that ions in the electrolyte are further sufficiently diffused and charge transport is performed. % Or less is preferable.
  • the porosity is a percentage of the volume of the semiconductor layer occupied by the pores in the semiconductor layer.
  • the porous semiconductor layer can be formed, for example, as follows.
  • a suspension is prepared by adding semiconductor fine particles together with an organic compound such as a resin and a dispersant to a dispersion medium such as an organic solvent and water. And this suspension is apply
  • an organic compound is added to the dispersion medium together with the semiconductor fine particles, the organic compound burns during firing, and it becomes possible to secure a further sufficient gap (void) in the porous semiconductor layer.
  • the porosity can be changed by controlling the molecular weight and the addition amount of the organic compound combusted during firing.
  • the organic compound to be used is not particularly limited as long as it can be dissolved in a suspension and burned and removed during firing.
  • polyethylene glycol, cellulose ester resin, cellulose ether resin, epoxy resin, urethane resin, phenol resin, polycarbonate resin, polyarylate resin, polyvinyl butyral resin, polyester resin, polyvinyl formal resin, silicon resin, styrene examples thereof include polymers and copolymers of vinyl compounds such as vinyl acetate, acrylic acid esters, and methacrylic acid esters.
  • the type and amount of the organic compound can be appropriately selected according to the type and state of the fine particles used, the composition ratio of the suspension, the total weight, and the like.
  • the ratio of the semiconductor fine particles is 10% by mass or more with respect to the total weight of the whole suspension, the strength of the prepared film can be further sufficiently increased, and the ratio of the semiconductor fine particles is If the total weight is 40% by mass or less, a porous semiconductor layer having a large porosity can be obtained more stably. Therefore, the ratio of the semiconductor fine particles is based on the total weight of the entire suspension. It is preferable that it is 10 mass% or more and 40 mass% or less.
  • semiconductor fine particles single or plural compound semiconductor particles having an appropriate average particle diameter, for example, an average particle diameter of about 1 nm to 500 nm can be used. Among these, from the viewpoint of increasing the specific surface area, those having an average particle diameter of about 1 nm to 50 nm are desirable. In order to increase the utilization factor of incident light, semiconductor particles having a relatively large average particle diameter of about 200 nm to 400 nm may be added.
  • Examples of the method for producing semiconductor fine particles include a sol-gel method such as a hydrothermal synthesis method, a sulfuric acid method, and a chlorine method.
  • the method is not limited as long as the method can produce the desired fine particles, but from the viewpoint of crystallinity. Is preferably synthesized by a hydrothermal synthesis method.
  • dispersion medium for the suspension examples include glyme solvents such as ethylene glycol monomethyl ether; alcohols such as isopropyl alcohol; mixed solvents such as isopropyl alcohol / toluene; water and the like.
  • the suspension can be applied by a usual application method such as a doctor blade method, a squeegee method, a spin coating method, or a screen printing method.
  • the conditions for drying and baking the coating film after application of the suspension can be, for example, about 10 seconds to 12 hours in the range of about 50 ° C. to 800 ° C. in the air or in an inert gas atmosphere. . This drying and baking can be performed once at a single temperature or twice or more at different temperatures.
  • semiconductor layers other than the porous semiconductor layer can be formed using a normal method for forming a semiconductor layer used in a photoelectric conversion element.
  • ⁇ Dye> As the dye in the photoelectric conversion device according to the present embodiment, at least one of the above-described spirobifluorene derivatives represented by the general formula (1) is used. Two or more kinds may be used in combination. Furthermore, other organic pigments can be combined.
  • adsorbing the dye to the semiconductor layer for example, a method in which a semiconductor substrate (that is, a conductive substrate having the semiconductor layer 1) is immersed in a solution in which the dye is dissolved, or a dye solution is applied to the semiconductor layer.
  • a semiconductor substrate that is, a conductive substrate having the semiconductor layer 1
  • a dye solution is applied to the semiconductor layer.
  • Solvents for this dye solution include nitrile solvents such as acetonitrile, propionitrile, methoxyacetonitrile; alcohol solvents such as methanol, ethanol, isopropyl alcohol, tert-butyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • Ketone solvents such as ethyl acetate and butyl acetate; ether solvents such as tetrahydrofuran and dioxane; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone And halogen solvents such as dichloromethane, chloroform, dichloroethane, trichloroethane, and chlorobenzene; hydrocarbon solvents such as toluene, xylene, and cyclohexane; and water. These may be used alone or in combination of two or more.
  • the solution can be stirred, heated to reflux, or ultrasonic waves can be applied.
  • the amount of the dye supported can be set in the range of 1 ⁇ 10 ⁇ 10 mol / cm 2 or more and 1 ⁇ 10 ⁇ 4 mol / cm 2 or less, and 1 ⁇ 10 ⁇ 9 mol / cm 2 or more and 9.0 ⁇ 10 ⁇ 6.
  • a range of less than mol / cm 2 is preferred. Within this range, the effect of improving the photoelectric conversion efficiency can be obtained economically and sufficiently.
  • one or more dyes other than the spirobifluorene derivative according to the present invention may be mixed and used, and in this case, the absorption wavelength of the dye It is preferable to appropriately select the type and ratio of the dye in consideration of the area and the intensity.
  • an additive may be used in combination when adsorbing the dye in order to suppress a decrease in conversion efficiency due to the association between the dyes.
  • additives include steroidal compounds having a carboxy group (for example, deoxycholic acid, cholic acid, chenodeoxycholic acid, etc.).
  • the counter electrode 8 in the photoelectric conversion element according to the present embodiment has the catalyst layer 6 on the substrate 7.
  • the counter electrode 8 efficiently annihilates electrons and holes.
  • the material There is no limit to the material as long as it can fulfill its function.
  • the catalyst layer 6 of the counter electrode 8 can be formed as a metal vapor deposition film on the substrate 7 by vapor deposition or the like.
  • a Pt layer formed on the substrate 7 may be used.
  • the catalyst layer 6 of the counter electrode 8 may contain a nanocarbon material.
  • the catalyst layer 6 of the counter electrode 8 may be formed by sintering a paste containing carbon nanotubes, carbon nanohorns, or carbon fibers on the porous insulating film. Nanocarbon materials have a large specific surface area and can improve the probability of annihilation of electrons and holes.
  • the substrate 7 examples include transparent substrates such as glass and polymer films, and metal plates (foil).
  • a glass with a transparent conductive film is selected as the substrate 7, and platinum, carbon, or the like is formed as the catalyst layer 6 using a vapor deposition method or a sputtering method. be able to.
  • the electrolyte layer 5 in the photoelectric conversion element according to the present embodiment has a function of transporting holes generated from the dye adsorbed on the semiconductor layer 1 due to incidence of light to the counter electrode 8.
  • an electrolyte layer an electrolyte solution in which a redox couple is dissolved in an organic solvent, a gel electrolyte in which a polymer matrix is impregnated with a liquid in which the redox couple is dissolved in an organic solvent, a molten salt containing the redox couple, a solid electrolyte Organic hole transport materials and the like can be used.
  • the electrolyte layer can be composed of an electrolyte, a solvent, and an additive.
  • the electrolyte LiI, NaI, KI, CsI , CaI 2 , etc. of the metal iodides, tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide iodide and I 2, such as iodine salts of quaternary ammonium compounds such as id
  • a bromide such as a bromide of a quaternary ammonium compound such as a metal bromide such as LiBr, NaBr, KBr, CsBr or CaBr 2 or a tetraalkylammonium bromide or pyridinium bromide with Br 2 ;
  • Metal complexes such as ferricyanate and ferrocene-ferricinium ions; sulfur compounds such as sodium polysulfide and alky
  • a combination of LiI, I 2 and imidazolium iodide, a combination of TEMPO radical and TEMPO cation, cobalt complex (II) and cobalt complex (III) are preferable.
  • said electrolyte may be used independently or may be used in mixture of 2 or more types.
  • a molten salt that is in a molten state at room temperature can be used as the electrolyte. In this case, a solvent need not be used.
  • Examples of the solvent used in the electrolyte layer include carbonate solvents such as ethylene carbonate, diethyl carbonate, dimethyl carbonate, and propylene carbonate; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; Nitrile solvents such as propionitrile, propionitrile, methoxyacetonitrile, acetonitrile; lactone solvents such as ⁇ -butyrolactone and valerolactone; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, ethylene glycol dialkyl ether; methanol, ethanol Alcohol solvents such as isopropyl alcohol; aprotic polar solvents such as dimethyl sulfoxide and sulfolane; 2-methyl-3-oxazolidinone, 2-methyl Heterocyclic compounds such as 1,3-dioxolane. These solvents may be used alone or in combination of two or more.
  • a basic compound may be added to the electrolyte layer in order to suppress dark current.
  • the type of basic compound is not particularly limited, and examples thereof include t-butylpyridine, 2-picoline, 2,6-lutidine and the like.
  • the addition concentration in the case of adding a basic compound can be, for example, about 0.05 mol / L or more and 2 mol / L or less.
  • a solid electrolyte can also be used.
  • a gel electrolyte or a completely solid electrolyte can be used.
  • a gelling agent to which an electrolyte or a room temperature molten salt is added can be used.
  • gelation can be performed by a technique such as addition of a polymer or an oil gelling agent, polymerization of coexisting polyfunctional monomers, or a crosslinking reaction of the polymer.
  • Examples of the polymer to be gelated by adding a polymer include polyacrylonitrile and polyvinylidene fluoride.
  • oil gelling agents dibenzylden-D-sorbitol, cholesterol derivatives, amino acid derivatives, alkylamide derivatives of trans- (1R, 2R) -1,2-cyclohexanediamine, alkylurea derivatives, N-octyl-D-gluconamide benzoate Double-headed amino acid derivatives, quaternary ammonium salt derivatives, and the like.
  • the monomer used is preferably a compound having two or more ethylenically unsaturated groups, such as divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, Examples include diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate.
  • a monofunctional monomer may be included in addition to the polyfunctional monomer.
  • Monofunctional monomers include esters derived from acrylic acid and ⁇ -alkyl acrylic acids such as acrylamide, N-isopropylacrylamide, methyl acrylate, and hydroxyethyl acrylate; amides; dimethyl maleate, diethyl fumarate, dibutyl maleate Esters derived from maleic acid and fumaric acid such as: Dienes such as butadiene, isoprene and cyclopentadiene; Aromatic vinyl compounds such as styrene, p-chlorostyrene and sodium styrenesulfonate; Vinyl esters such as vinyl acetate Nitriles such as acrylonitrile and methacrylonitrile; vinyl compounds having a nitrogen-containing heterocycle such as vinyl carbazole; vinyl compounds having a quaternary ammonium salt; other N-vinylformamide, vinyl sulfone , Vinylidene fluoride, vinyl alkyl ethers, N- phenylmaleimide, and the
  • Polymerization of the monomer for gelation can be performed by radical polymerization.
  • This radical polymerization can be carried out by heating, light, ultraviolet light or electron beam, or electrochemically.
  • the polymerization initiator used when forming a crosslinked polymer by heating include azo initiators such as 2,2′-azobis (isobutyronitrile) and 2,2′-azobis (dimethylvaleronitrile), Examples thereof include peroxide initiators such as benzoyl peroxide.
  • the addition amount of the polymerization initiator is preferably 0.01% by mass or more and 15% by mass or less, and more preferably 0.05% by mass or more and 10% by mass or less with respect to the total amount of monomers.
  • crosslinkable reactive groups are nitrogen-containing heterocycles such as pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring, and preferred crosslinkers are alkyl halides, halogenated alkyls.
  • Bifunctional or higher functional compounds capable of electrophilic substitution reaction with nitrogen atoms such as aralkyl, sulfonic acid ester, acid anhydride, acid chloride, isocyanate and the like can be mentioned.
  • a mixture of an electrolyte and an ion conductive polymer compound can be used.
  • the ion conductive polymer compound include polar polymer compounds such as polyethers, polyesters, polyamines, and polysulfides.
  • an inorganic hole transport material such as copper iodide or copper thiocyanide can be used as the charge transport material.
  • This inorganic hole transport material can be introduced into the electrode by a method such as a casting method, a coating method, a spin coating method, a dipping method, or electrolytic plating.
  • an organic hole transport material can be used instead of the electrolyte as the charge transport material.
  • organic hole transport materials include 2,2 ′, 7,7′-tetrakis (N, N-di-p-methoxyphenylamine) -9,9′-spirobifluorene (for example, Adv. Mater. 2005, 17). , 813), aromatic diamines such as N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (for example, Compounds described in US Pat. No.
  • the organic hole transport material can be introduced into the electrode by a method such as a vacuum deposition method, a cast method, a spin coating method, a dipping method, or an electrolytic polymerization method.
  • the production of the electrolyte layer 5 of the photoelectric conversion element of the present embodiment can be performed, for example, by the following two methods.
  • One is a method in which the counter electrode 8 is first bonded onto the semiconductor layer 1 on which the dye is adsorbed, and the liquid electrolyte layer 5 is introduced into the gap.
  • the other is a method of forming the electrolyte layer 5 directly on the semiconductor layer 1. In the latter case, the counter electrode 8 is formed on the electrolyte layer 5 after it is formed.
  • a photoelectrochemical cell can be provided using the photoelectric conversion element described above. This photoelectrochemical cell can be suitably used as a solar cell.
  • FIG. 2 shows an absorption spectrum curve of the obtained compound SPF-1 (dye) having a spirobifluorene skeleton in THF.
  • the maximum absorption wavelength ( ⁇ max) of the compound SPF-1 having the spirobifluorene skeleton was 486 nm.
  • a titanium oxide paste (semiconductor layer material) was prepared as follows.
  • Commercially available titanium oxide powder (trade name: P25, manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 21 nm) 5 g, 15 vol% acetic acid aqueous solution 20 ml, surfactant 0.1 ml (trade name: Triton (registered trademark) X- 100, manufactured by Sigma-Aldrich Co., Ltd.) and 0.3 g of polyethylene glycol (molecular weight 20000) (manufactured by Wako Pure Chemical Industries, Ltd., product code: 168-11285) were mixed, and this mixture was stirred with a stirring mixer for about 1 hour to oxidize. A titanium paste was obtained.
  • this titanium oxide paste was applied on a glass with FTO by a doctor blade method so that the film thickness was about 50 ⁇ m (application area: 10 mm ⁇ 10 mm). Thereafter, the glass with FTO coated with the titanium oxide paste was put in an electric furnace, baked at 450 ° C. for about 30 minutes in an air atmosphere, and naturally cooled to obtain a porous titanium oxide film on the glass with FTO. .
  • a light scattering layer was formed on the titanium oxide film as follows.
  • a titanium oxide paste having an average particle size of 400 nm (trade name: PST-400C, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was applied to the above-described titanium oxide film at a thickness of 20 ⁇ m by screen printing. Then, the light-scattering layer on the titanium oxide film was obtained by baking for about 30 minutes at 450 degreeC in air
  • a counter electrode was produced as follows. A platinum layer having an average film thickness of 1 ⁇ m was deposited as a catalyst layer on a soda lime glass plate (thickness: 1.1 mm) by a vacuum deposition method to obtain a counter electrode.
  • (C) Cell assembly The semiconductor electrode after the dye adsorption treatment and the counter electrode were arranged so that the semiconductor layer and the catalyst layer face each other, thereby forming a cell before electrolyte injection. Next, a thermosetting resin film in which the electrolyte was allowed to penetrate into the gap between the semiconductor electrode and the counter electrode was thermocompression bonded to the outer periphery of the cell.
  • (D) Injection of electrolyte An iodine-based electrolyte was injected into the above-described cell from the above-mentioned cut and allowed to penetrate between the semiconductor electrode and the counter electrode.
  • the iodine-based electrolyte uses acetonitrile as a solvent, the iodine concentration is 0.03 mol / L, the lithium iodide concentration is 0.05 mol / L, the 4-tert-butylpyridine concentration is 0.5 mol / L, 1, A solution having a concentration of 2-dimethyl-3-propylimidazolium iodide of 1.0 mol / L and a concentration of guanidine thiocyanate of 0.1 mol / L was used.
  • Example 3 A photoelectric conversion element (cell 2) was prepared in the same manner as in Example 2, except that an electrolyte composed of the following cobalt (II) complex / cobalt (III) complex was used instead of the iodine-based electrolyte. As a result of evaluating the photoelectric conversion characteristics of the obtained device, a photoelectric conversion efficiency of 4.0% was obtained. The current-voltage curve obtained at this time is shown in FIG.
  • composition of electrolyte using acetonitrile as a solvent, the concentration of cobalt (II) tris (2,2′-bipyridyl) tetracyanoborate is 0.22 mol / L, cobalt (III) tris (2,2′-bipyridyl) tetracyano
  • Example 4 A photoelectric conversion element (cell 3) was prepared in the same manner as in Example 2, except that an electrolyte composed of the following cobalt (II) complex / cobalt (III) complex was used instead of the iodine-based electrolyte. As a result of evaluating the photoelectric conversion characteristics of the obtained device, a photoelectric conversion efficiency of 4.8% could be obtained. The current-voltage curve obtained at this time is shown in FIG.
  • composition of electrolyte using acetonitrile as a solvent, a cobalt (II) complex having the following structure ([Co (py-py-pz) 2 ] (PF 6 ) 2 having a concentration of 0.22 mol / L, cobalt having the following structure (III ) Complex ([Co (py-py-pz) 2 ] (PF 6 ) 3 concentration is 0.05 mol / L, 4-tert-butylpyridine concentration is 0.2 mol / L, and lithium perchlorate concentration is A solution that is 0.1 mol / L.
  • a cobalt (II) complex having the following structure ([Co (py-py-pz) 2 ] (PF 6 ) 2 having a concentration of 0.22 mol / L
  • cobalt having the following structure (III ) Complex ([Co (py-py-pz) 2 ] (PF 6 ) 3 concentration is 0.05 mol / L
  • the spirobifluorene derivative according to the embodiment of the present invention as a dye for a photoelectric conversion element, it is possible to obtain a photoelectric conversion element excellent in photoelectric conversion efficiency and a semiconductor electrode used therefor. it can.
  • Such a photoelectric conversion element can be applied to a photoelectrochemical cell, and is particularly suitable for a solar cell. Further, the cost can be reduced compared to the case where a metal complex containing a noble metal is used.
  • the photoelectric conversion element according to the present invention is suitably used as a photoelectrochemical cell, and can be used not only as a photoelectrochemical cell but also as a photosensor.

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Abstract

Comme colorant pour éléments de conversion photoélectrique, qui a d'excellents caractéristiques de conversion photoélectrique, au moins un composé représenté par la formule générale (1) et ayant un squelette spirobifluorène est utilisé. (Dans la formule (1), chacun de R1 et R2 représente indépendamment un atome d'hydrogène, un groupe alkyle ou groupe alcoxy substitué ou non substitué, un groupe hydroxy ou un groupe aryle substitué ou non substitué ; Z représente un groupe de liaison d'un système π-conjugué ; et X représente un groupe organique ayant un groupe acide).
PCT/JP2013/051121 2012-02-15 2013-01-22 Dérivé de spirobifluorène, colorant pour éléments de conversion photoélectrique, électrode de semi-conducteur l'utilisant, élément de conversion photoélectrique et cellule photoélectrochimique WO2013121835A1 (fr)

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US10727414B2 (en) * 2015-06-25 2020-07-28 Ecole Polytechnique Federale De Lausanne (Epfl) Functional hole transport materials for optoelectronic and/or electrochemical devices
WO2021010425A1 (fr) 2019-07-16 2021-01-21 Ricoh Company, Ltd. Module de photopile, dispositif électronique et module d'alimentation électrique
EP3839994A1 (fr) 2019-11-28 2021-06-23 Ricoh Company, Ltd. Élément de conversion photoélectrique, module de conversion photoélectrique, dispositif électronique et module d'alimentation électrique
EP4064355A1 (fr) 2021-03-23 2022-09-28 Ricoh Company, Ltd. Module de cellule solaire
WO2023008085A1 (fr) 2021-07-29 2023-02-02 Ricoh Company, Ltd. Élément de conversion photoélectrique et module de cellules solaires
WO2023175466A1 (fr) 2022-03-18 2023-09-21 Ricoh Company, Ltd. Élément de conversion photoélectrique, module de conversion photoélectrique, dispositif électronique et module de cellule solaire
JP7460259B2 (ja) 2021-05-17 2024-04-02 エルジー・ケム・リミテッド 樹脂およびその製造方法

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10727414B2 (en) * 2015-06-25 2020-07-28 Ecole Polytechnique Federale De Lausanne (Epfl) Functional hole transport materials for optoelectronic and/or electrochemical devices
WO2021010425A1 (fr) 2019-07-16 2021-01-21 Ricoh Company, Ltd. Module de photopile, dispositif électronique et module d'alimentation électrique
EP3839994A1 (fr) 2019-11-28 2021-06-23 Ricoh Company, Ltd. Élément de conversion photoélectrique, module de conversion photoélectrique, dispositif électronique et module d'alimentation électrique
EP4064355A1 (fr) 2021-03-23 2022-09-28 Ricoh Company, Ltd. Module de cellule solaire
JP7460259B2 (ja) 2021-05-17 2024-04-02 エルジー・ケム・リミテッド 樹脂およびその製造方法
WO2023008085A1 (fr) 2021-07-29 2023-02-02 Ricoh Company, Ltd. Élément de conversion photoélectrique et module de cellules solaires
WO2023175466A1 (fr) 2022-03-18 2023-09-21 Ricoh Company, Ltd. Élément de conversion photoélectrique, module de conversion photoélectrique, dispositif électronique et module de cellule solaire

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