JP5482290B2 - Photoelectric conversion element - Google Patents

Description

  The present invention relates to a photoelectric conversion element.

  Conventionally, dyes are widely used in various technical fields. As an example, in the field of photoelectric conversion elements that convert light energy such as sunlight into electrical energy, for example, a dye having a photosensitizing action is used as a working electrode of a dye-sensitized solar cell.

  A dye-sensitized solar cell generally has an electrode having a dye that performs a sensitizing action and an oxide semiconductor as a carrier for the dye, and is excited by absorbing light incident on the dye. The excited dye injects electrons into the carrier to perform photoelectric conversion. In addition, this type of dye-sensitized solar cell can theoretically be expected to have high photoelectric conversion efficiency among organic solar cells, and is lower in price than a solar cell using a conventional silicon semiconductor that is widely used. It is considered that it is very advantageous in terms of cost.

  As dyes used for photoelectric conversion elements, organic dyes such as ruthenium complex dyes and cyanine dyes are widely known. In particular, organic dyes are relatively stable and can be easily synthesized, and thus various studies have been made.

For example, Patent Document 1 discloses an oxidation sensitized by an organic dye having a methine (—CH═) chain, a rhodanine skeleton bonded to one end of the methine chain, and a phenylamine skeleton bonded to the other end of the methine chain. A photoelectric conversion element using physical semiconductor fine particles is disclosed. More specifically, an organic dye in which a —CH ₂ COOH group or a —COOH group is introduced into a nitrogen atom of rhodanine as an anchor group for adsorbing to an oxide semiconductor electrode is disclosed.

JP 2004-014175 A

  However, the photoelectric conversion element using the above-mentioned conventional organic dye easily peels off the organic dye from the carrier. In particular, when used for a long period of time, moisture remaining in the element or enters the element from the outside. There was a problem that the organic dye was easily peeled off from the support by the moisture, and as a result, the photoelectric conversion efficiency was lowered.

  The present invention has been made in view of such a situation, and an object of the present invention is to suppress the peeling of an organic dye from a metal oxide as a support, thereby improving photoelectric conversion characteristics and durability. It is to provide a conversion element.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by using an organic dye having a specific structure having two to three rhodanine structure portions, and have completed the present invention. It was.

That is, the present invention provides the following <1> to <4>.
<1> In a photoelectric conversion element comprising a working electrode having a dye-supported metal oxide electrode in which a dye is supported on a metal oxide layer,
As the dye, the following general formula (1):
(In Formula (1), R1 and R2 are each independently a hydrogen atom, a terminal aryl group, a terminal alkyl group, or a terminal alkoxy group, and at least one of R1 and R2 is a terminal aryl group, a terminal alkyl group. Or a terminal alkoxy group, and R1 and R2 may combine to form a ring).
Including a compound having a structure represented by:
Photoelectric conversion element.

<2> In the general formula (1), R1 is a terminal aryl group or a terminal alkyl group.
The photoelectric conversion element as described in <1> above.

<3> In the general formula (1), R1 is 1-1 diphenylethylene.
The photoelectric conversion element according to <1> or <2>.

<4> The metal oxide layer is substantially composed of zinc oxide.
The photoelectric conversion element according to any one of <1> to <3> above.

  ADVANTAGE OF THE INVENTION According to this invention, the peeling of the organic pigment | dye from the metal oxide which is a support body is suppressed, and the photoelectric conversion element with which the photoelectric conversion characteristic and durability were improved is implement | achieved.

1 is a cross-sectional view showing a schematic configuration of a dye-sensitized solar cell 100. FIG.

  Embodiments of the present invention will be described below. In addition, the same code | symbol is attached | subjected to the same element and the overlapping description is abbreviate | omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios in the drawings are not limited to the illustrated ratios. The following embodiments are examples for explaining the present invention, and the present invention is not limited only to the embodiments.

The dye of this embodiment is used for a photoelectric conversion element such as a dye-sensitized solar cell, and has a structure represented by the following general formula (1) (hereinafter, “the rhodanine compound of this embodiment”). It is also called.) The dye according to the present embodiment has an adsorptivity (bonding property) to a metal oxide layer (support) including a metal oxide semiconductor material, and is excited by absorbing light, and becomes a nitrogen atom in the rhodanine structure portion. It is a compound that can inject electrons into the carrier through the introduced —CH ₂ CH ₂ COOH group.

(In Formula (1), R1 and R2 are each independently a hydrogen atom, a terminal aryl group, a terminal alkyl group, or a terminal alkoxy group, and at least one of R1 and R2 is a terminal aryl group, a terminal alkyl group. Or a terminal alkoxy group, and R1 and R2 may combine to form a ring).

  Here, the above-mentioned “rhodanine structure portion” means a 5-membered ring (thiazolidine ring) skeleton having a sulfur atom and a nitrogen atom as heteroatoms, an oxo group (═O) bonded to the 4-position of the thiazolidine ring skeleton, And a thioxo group (═S) bonded to the 2-position of the thiazolidine ring skeleton.

The rhodanine compound of this embodiment is characterized in that two rhodanine structure parts are linked via a methine chain, and a —CH ₂ CH ₂ COOH group is introduced into the nitrogen atom of each rhodanine structure part. And The part where the two rhodanine structural parts are linked is the main part that constitutes the chromophore, and the light absorption peak is broadened by the spread of π conjugation as a whole molecule, and the light absorption wavelength range is expanded. This contributes to an improvement in the efficiency of electron injection into the metal oxide layer that is the carrier. In addition, two —CH ₂ CH ₂ COOH groups introduced into the molecule function as anchor groups that are adsorbed to the metal oxide as a support. The “anchor group” means a substituent having chemical or electrostatic affinity or binding ability to the carrier.

  In the general formula (1), the “terminal aryl group” means a monovalent substituent whose terminal is an aryl group, and more specifically, via a linking group such as a single bond, an alkylene group or an alkenylene group. Means a monovalent substituent to which an aryl group is linked. Specific examples of the terminal aryl group include, for example, aromatic hydrocarbons having 6 to 12 carbon atoms (for example, phenyl, naphthyl, etc.), and these aromatic hydrocarbons may be a linking group such as an alkylene group or an alkenylene group. (For example, phenylmethyl, diphenylethyl, triphenylmethyl, 1-phenylethylene, 1,1-diphenylethylene, etc.) are not limited to these. Among these, as the terminal aryl group, 1-phenylethylene, 1,1-diphenylethylene and the like are preferable.

  In the general formula (1), “terminal alkyl group” means a monovalent substituent whose terminal is an alkyl group, and more specifically, via a linking group such as a single bond, an aryl group or an alkenylene group. Means a monovalent substituent to which an alkyl group is linked. Specific examples of the terminal alkyl group include linear, branched or cyclic hydrocarbons having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl). Tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, 2-hexyl, dimethylbutyl, ethylbutyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) Examples include, but are not limited to, those in which hydrogen is linked through a linking group such as an aryl group or an alkenylene group (methylphenyl, ethylphenyl, dimethylphenyl, etc.). Among these, as the terminal alkyl group, a linear or branched hydrocarbon having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl) Butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, 2-hexyl, dimethylbutyl, ethylbutyl, heptyl, octyl, etc.) are preferred.

  In the general formula (1), the “terminal alkoxy group” means a monovalent substituent whose terminal is an alkoxy group, and more specifically, via a linking group such as a single bond, an aryl group or an alkenylene group. Means a monovalent substituent to which an alkoxy group is linked. Specific examples of the terminal alkoxy group include, for example, an alkoxy group having 1 to 20 carbon atoms (for example, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, etc.) Examples include, but are not particularly limited to, those in which an alkoxy group is linked via a linking group such as an aryl group or an alkenylene group (methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, methoxyphenylethylene, ethoxyphenylethylene, etc.). Among these, as a terminal alkoxy group, a C1-C20 linear or branched hydrocarbon (for example, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy) Etc.) is preferred.

  In general formula (1), R1 and R2 may combine to form a ring. Specific examples of the ring formed by combining R1 and R2 include, but are not limited to, pyran, dioxin, dioxane and the like.

  In the general formula (1), from the viewpoint of improving the photoelectric conversion characteristics, at least one of R1 and R2 is required to be the above-described terminal aryl group, terminal alkyl group, or terminal alkoxy group. Therefore, both R1 and R2 may be the terminal aryl group, terminal alkyl group, or terminal alkoxy group described above, but one of R1 and R2 is the terminal aryl group, terminal alkyl group, or terminal described above. It is preferably an alkoxy group and the other is a hydrogen atom. In particular, from the viewpoint of improving photoelectric conversion characteristics, it is more preferable that R1 is a terminal aryl group or a terminal alkyl group, and R2 is a hydrogen atom.

According to the knowledge of the present inventors, the organic dye described in Patent Document 1 in which a —CH ₂ COOH group is introduced into the nitrogen atom of rhodanine has low adhesion (adsorption) to the metal oxide layer, Photoelectric conversion efficiency was insufficient as a dye used for the photoelectric conversion element. In contrast, in the rhodanine compound of the present embodiment, _two —CH ₂ CH ₂ COOH groups are introduced as anchor groups, and the content of COOH groups per molecule is increased. In addition, since the rhodanine compound of the present embodiment employs —CH ₂ CH ₂ COOH groups as anchor groups, two —COOH groups are easily oriented in the same direction due to its three-dimensional structure, in other words, two The —COOH group is designed to be easily adsorbed on the metal oxide layer at the same time. Therefore, the rhodanine compound of the present embodiment has improved adhesion (adsorbability) to the metal oxide layer as compared with the conventional organic dye. In addition, the rhodanine compound of the present embodiment can adsorb perpendicularly to the metal oxide layer due to the orientation direction of the two —COOH, so that the dye adsorption amount per unit area of the metal oxide layer is increased. Can be. Therefore, even when the metal oxide layer is exposed to an environment containing a large amount of moisture, the rate at which the pigment peels from the metal oxide layer is reduced. As a result of a combination of these actions, in the photoelectric conversion element using the rhodanine compound of the present embodiment, the peeling of the dye from the metal oxide as the support is suppressed, and as a result, the photoelectric conversion characteristics are enhanced, It is inferred that durability has been improved.

Here, the anchor group introduced into the nitrogen atom of each rhodanine structure portion is required to be a —CH ₂ CH ₂ COOH group. For example, when an alkyl group or the like is employed instead of the anchor group as in the prior art, the adsorptivity to the metal oxide layer becomes insufficient, the film easily peels off from the metal oxide layer, and the photoelectric conversion characteristics are remarkably deteriorated. On the other hand, when a short anchor group such as —CH ₂ COOH group is employed, the metal oxide layer is caused by the steric hindrance of the dye molecule such that the —CH ₂ COOH group can be oriented perpendicular to the dye plane and opposite to each other. Adsorption to the resin becomes insufficient, it is easy to peel off from the metal oxide layer, and the photoelectric conversion characteristics deteriorate. In addition, when a long anchor group such as a —CH ₂ CH ₂ CH ₂ COOH group is employed, the efficiency of electron injection from the dye into the metal oxide layer is lowered, and the photoelectric conversion characteristics are lowered.

  In addition, the same effect is acquired even if the rhodanine-type compound which has a structure represented by said General formula (1) is a stereoisomer. Moreover, the rhodanine-type compound which has a structure represented by said General formula (1) is a compound which can take a resonance structure. Therefore, the rhodanine-based compound of the present embodiment is not limited to the structure shown in the general formula (1), but includes its resonance structure.

  Specific examples of the rhodanine compound having the structure represented by the general formula (1) include compounds represented by the chemical formulas (1-1) to (1-10).

  Next, a photoelectric conversion element using a rhodanine compound having a structure represented by the general formula (1) will be described.

FIG. 1 is a cross-sectional view showing a schematic configuration of a dye-sensitized solar cell 100 which is a photoelectric conversion element of the present embodiment.
The dye-sensitized solar cell 100 according to this embodiment includes a working electrode 11, a counter electrode 21, and an electrolyte 31 provided between the working electrode 11 and the counter electrode 21. At least one of the working electrode 11 and the counter electrode 21 is an electrode having optical transparency. The working electrode 11 and the counter electrode 21 are arranged to face each other via a spacer 41, and an electrolyte 31 is enclosed in a sealing space defined by the working electrode 11, the counter electrode 21, the spacer 41, and a sealing member (not shown). Has been.

  The working electrode 11 functions as a negative electrode for the external circuit. The working electrode 11 includes a porous metal oxide layer 13 containing a metal oxide (metal oxide semiconductor material) on the conductive surface 12a of the base 12, and the metal oxide layer 13 has the general formula ( The dye-supporting metal oxide electrode 14 is formed by supporting (adsorbing) the rhodanine compound (dye) having the structure represented by 1). In other words, in the working electrode 11 of the present embodiment, the rhodanine compound having the structure represented by the general formula (1) described above is carried on the surface of the metal oxide (metal oxide semiconductor material) of the metal oxide layer 13. The (adsorbed) composite structure is laminated on the conductive surface 12a of the substrate 12 (dye-supported metal oxide electrode 14).

  The type and size of the substrate 12 are not particularly limited as long as at least the metal oxide layer 13 can be supported. For example, a plate-like or sheet-like material is preferably used. Specific examples thereof include glass substrates, polyethylene, polypropylene, polystyrene, tetraacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), and polyphenylene sulfide (PPS). , Polycarbonate (PC), polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin or brominated phenoxy plastic substrate, metal substrate or alloy substrate, ceramic substrate Or these laminated bodies etc. are mentioned. Moreover, it is preferable that the base | substrate 12 has translucency, and the thing excellent in the translucency in visible region is more preferable. Further, the base 12 is preferably flexible. In this case, it is possible to provide various types of structures utilizing the flexibility.

The conductive surface 12a can be applied to the base 12 by, for example, forming a transparent conductive film on the base 12 like a conductive PET film. Here, when forming the conductive surface 12a, for example, a binder such as acrylic resin, polyester resin, phenol resin, epoxy resin, cellulose, melamine resin, fluoroelastomer, or polyimide resin may be used. Moreover, the process which provides the electroconductive surface 12a to the base | substrate 12 can be skipped by using the base | substrate 12 which has electroconductivity. Specific examples of the transparent conductive film include, for example, a metal thin film containing gold (Au), silver (Ag), platinum (Pt) or the like, a conductive polymer or the like, and an indium-tin oxide ( ITO), indium - zinc oxide (IZO), other SnO _2, InO _3, although FTO fluorine-doped SnO ₂ (F-SnO _2), and the like, not particularly limited thereto. These may be used alone or in combination. The formation method of a transparent conductive film is not specifically limited, For example, well-known methods, such as a vapor deposition method, CVD method, a spray method, a spin coat method, or an immersion method, are applicable. Moreover, the film thickness of a transparent conductive film can be set suitably. The conductive surface 12a of the substrate 12 may be subjected to appropriate surface modification treatment as necessary. Specifically, for example, a known surface treatment such as a degreasing treatment with a surfactant, an organic solvent or an alkaline aqueous solution, a mechanical polishing treatment, an immersion treatment in an aqueous solution, a preliminary electrolytic treatment with an electrolytic solution, a water washing treatment, a drying treatment, etc. However, it is not particularly limited to these.

  The metal oxide layer 13 is a carrier that carries a dye. The metal oxide layer 13 generally has a porous structure with many voids and a large surface area, and is preferably dense and has few voids, and preferably has a film shape. More preferred. In particular, the metal oxide layer 13 preferably has a structure in which porous fine particles are attached.

  The metal oxide layer 13 of this embodiment is mainly composed of a metal oxide such as titanium oxide, zinc oxide, tin oxide, niobium oxide, indium oxide, zirconium oxide, tantalum oxide, vanadium oxide, yttrium oxide, aluminum oxide, or magnesium oxide. It is a porous semiconductor layer as a component. These metal oxides may be used alone or in combination of two or more (mixed, mixed crystal, solid solution, etc.). For example, a combination of zinc oxide and tin oxide, titanium oxide and niobium oxide, or the like can be used. From the viewpoint of enhancing photoelectric conversion efficiency and durability, the metal oxide layer 13 is preferably a layer substantially made of zinc oxide. Here, “consisting essentially of zinc oxide” means containing 95 wt% or more of zinc oxide. The metal oxide layer 13 is made of a metal such as titanium, tin, zinc, iron, tungsten, zirconium, strontium, indium, cerium, vanadium, niobium, tantalum, cadmium, lead, antimony, bismuth, these metal oxides and These metal chalcogenides may be included. In addition, although the thickness of the metal oxide layer 13 is not specifically limited, It is preferable that it is 0.05-50 micrometers.

  As a method for forming the metal oxide layer 13, for example, a method of applying a metal oxide dispersion on the conductive surface 12a of the substrate 12 and then drying, a metal oxide dispersion or paste (metal oxide slurry) Is applied to the conductive surface 12a of the substrate 12 and then sintered at a high temperature. After the metal oxide dispersion or paste is applied to the conductive surface 12a of the substrate 12, a low temperature treatment of about 50 to 150 ° C. is performed. In addition to the method, a method of cathodic electrodeposition from an electrolytic solution containing a metal salt onto the conductive surface 12a of the substrate 12 is exemplified, but the method is not particularly limited thereto. Here, when a method that does not require high-temperature sintering is employed, a plastic material having low heat resistance can be used as the base 12, and thus the working electrode 11 having high flexibility can be manufactured.

  The metal oxide layer 13 has a structure represented by the above-described general formula (1) as a dye (sensitizing dye) capable of injecting electrons into the metal oxide by being excited by absorbing light. A rhodanine-based compound having the above is supported (adsorbed). As described above, by using the rhodanine compound having the structure represented by the general formula (1), the rate at which the pigment peels from the metal oxide layer 13 is lowered even when exposed to an environment containing a lot of moisture. Therefore, durability is improved.

  In addition, as a pigment | dye, other pigment | dye (sensitizing pigment | dye) other than the rhodanine-type compound which has the structure represented by General formula (1) mentioned above may be included. Depending on the performance required for the photoelectric conversion element, one having a desired light absorption band / absorption spectrum can be applied.

  Specific examples of other dyes include, for example, eosin Y, dibromofluorescein, fluorescein, rhodamine B, pyrogallol, dichlorofluorescein, erythrosine B (erythrocin is a registered trademark), fluorescin, mercurochrome, cyanine dye, merocyanine disazo dye, trisazo Dyes, anthraquinone dyes, polycyclic quinone dyes, indigo dyes, diphenylmethane dyes, trimethylmethane dyes, quinoline dyes, benzophenone dyes, naphthoquinone dyes, perylene dyes, fluorenone dyes, squarylium dyes, Examples thereof include organic dyes such as azulenium dyes, perinone dyes, quinacridone dyes, metal-free phthalocyanine dyes, and metal-free porphyrin dyes. Moreover, it is preferable that these other pigment | dyes have an anchor group which can be couple | bonded or adsorb | sucked with a metal oxide. Here, specific examples of the anchor group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, but are not particularly limited thereto. These other dyes may be used alone or in combination.

  In addition, for example, an organometallic complex compound can be used as the other dye. Specific examples of the organometallic complex compound include, for example, an ionic coordination bond formed between a nitrogen anion and a metal cation in an aromatic heterocyclic ring, and a nitrogen atom or a chalcogen atom formed between the metal cation. Between a nitrogen atom or a chalcogen atom and a metal cation, and an organometallic complex compound having both a nonionic coordinate bond and an ionic coordinate bond formed by an oxygen or sulfur anion and a metal cation. And organometallic complex compounds having both nonionic coordination bonds formed on the surface. More specifically, metal phthalocyanine dyes such as copper phthalocyanine and titanyl phthalocyanine, metal naphthalocyanine dyes, metal porphyrin dyes, bipyridyl ruthenium complexes, terpyridyl ruthenium complexes, phenanthroline ruthenium complexes, ruthenium bicinchonirate complexes, azo Examples include ruthenium complexes such as ruthenium complexes and quinolinol ruthenium complexes. These may be used alone or in combination.

  Moreover, the pigment | dye may contain the 1 type (s) or 2 or more types of additive. Examples of the additive include an association inhibitor that suppresses association of the dye, and specifically, a cholic acid compound represented by the chemical formula (2). These may be used alone or in combination of two or more.

(In the above formula (2), R91 is an alkyl group having an acidic group. R92 represents a group bonded to any of the carbon atoms constituting the steroid skeleton in the chemical formula, and represents a hydroxyl group, a halogen group, an alkyl group, an alkoxy group. A group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an oxycarbonyl group, an oxo group, an acidic group, or a derivative thereof, which may be the same or different, and t is 1 or more. (It is an integer of 5 or less. The bond between the carbon atoms constituting the steroid skeleton in the chemical formula may be a single bond or a double bond.)

  The method for supporting the dye on the metal oxide layer 13 is not particularly limited. Specific examples thereof include a method of immersing the metal oxide layer 13 in a solution containing a dye and a method of applying a solution containing a dye to the metal oxide layer 13. The solvent of the dye-containing solution used here may be appropriately selected from known solvents such as water, ethanol solvents, nitrile solvents, ketone solvents, etc., depending on the solubility or compatibility of the dyes used. it can.

  Here, when the metal oxide layer 13 is formed by the cathode electrodeposition method, by using an electrolytic solution containing a metal salt and a dye, the metal oxide layer 13 is formed and the dye is supported at the same time. The dye-supported metal oxide electrode 14 supported (adsorbed) on the metal oxide surface of the oxide layer 13 can also be formed immediately. The electrolysis conditions may be appropriately set according to the characteristics of the material used in accordance with a conventional method. For example, when forming the dye-supported metal oxide electrode 14 composed of ZnO and a dye, the reduction electrolysis potential is about −0.8 to −1.2 V (vs. Ag / AgCl), the pH is about 4 to 9, The bath temperature of the electrolytic solution is preferably about 0 to 100 ° C. Further, the metal ion concentration in the electrolytic solution is preferably about 0.5 to 100 mM, and the dye concentration in the electrolytic solution is preferably about 50 to 500 μM. Furthermore, in order to further improve the photoelectric conversion characteristics, the dye may be once desorbed from the metal oxide layer 13 on which the dye is supported, and then another dye may be adsorbed again.

  The working electrode 11 (dye-supported metal oxide electrode 14) may have an intermediate layer between the conductive surface 12a of the base 12 and the metal oxide layer 13. Although the material of an intermediate | middle layer is not specifically limited, For example, the metal oxide etc. which were demonstrated by said transparent conductive film 12a are preferable. The intermediate layer is formed by depositing or depositing a metal oxide on the conductive surface 12a of the substrate 12 by a known method such as vapor deposition, CVD, spraying, spin coating, dipping, or electrodeposition. Can be formed. Note that the intermediate layer preferably has translucency, and more preferably has conductivity. The thickness of the intermediate layer is not particularly limited, but is preferably about 0.1 to 5 μm.

  The counter electrode 21 functions as a positive electrode for the external circuit. The counter electrode 21 includes a base body 22 having a conductive surface 22 a, and is disposed so as to face the metal oxide layer 13 of the working electrode 11. As the base body 22 and the conductive surface 22a, well-known ones can be appropriately employed as in the case of the base body 12 and the conductive surface 12a. For example, in addition to the base body 12 having conductivity, a transparent conductive material is formed on the base body 12. A film having a film 12a, and a film of a metal such as platinum, gold, silver, copper, aluminum, indium, molybdenum, titanium, rhodium, ruthenium, or magnesium, carbon, or a conductive polymer on the transparent conductive film 12a of the substrate 12 ( A plate, foil, or the like can be used. When forming the conductive surface 22a, for example, a binder such as acrylic resin, polyester resin, phenol resin, epoxy resin, cellulose, melamine resin, fluoroelastomer, or polyimide resin may be used.

  As the electrolyte 31, a redox electrolyte having a redox pair, a semi-solid electrolyte obtained by gelling the redox electrolyte, or a film formed of a p-type semiconductor solid hole transport material, or the like, which is generally used in batteries, solar cells, etc., is appropriately used. Can be used. In addition, the electrolyte 31 may be used individually by 1 type, or may use 2 or more types together.

Examples of the redox electrolyte include I ⁻ / I ₃ ⁻ system, Br ⁻ / Br ₃ ⁻ system, and quinone / hydroquinone system. Specifically, a combination of an iodide salt and a simple substance of iodine, a combination of a bromide salt and bromine, a combination of a halide salt and a simple substance of halogen, or the like. The content of the redox agent is not particularly limited, but is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol / g with respect to the total amount of the electrolyte, and 1 × 10 ⁻³ to 1 × 10 ⁻² mol / g. g is more preferable.

  Examples of the halide salts include cesium halides, quaternary alkyl ammonium halides, imidazolium halides, thiazolium halides, oxazolium halides, quinolinium halides, pyridinium halides, and the like. Is mentioned. More specifically, as these iodide salts, for example, cesium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetrahexylammonium iodide, Quaternary alkylammonium iodides such as tetraheptylammonium iodide or trimethylphenylammonium iodide; imidazolium iodides such as 3-methylimidazolium iodide or 1-propyl-2,3-dimethylimidazolium iodide 3-ethyl-2-methyl-2-thiazolium iodide, 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium iodide or 3-ethyl-2-methylbenzothia Zorium iodide, etc. Thiazolium iodides, oxazolium iodides such as 3-ethyl-2-methyl-benzoxazolium iodide, and quinolinium iodides such as 1-ethyl-2-methylquinolinium iodide And pyridinium iodides. Examples of the bromide salt include quaternary alkyl ammonium bromide. Among the combinations of halide salts and simple halogens, combinations of at least one of the above-described iodide salts and simple iodine are preferable.

  The redox electrolyte may be, for example, a combination of an ionic liquid and a halogen simple substance. In this case, the above-described halide salt and the like may be further included. What is generally used in a battery, a solar cell, etc. can be used suitably as an ionic liquid, and it does not specifically limit. Specific examples of the ionic liquid include, for example, “Inorg. Chem.” 1996, 35, p 1168 to 1178, “Electrochemistry” 2002, 2, p 130 to 136, JP-A-9-507334, or JP-A-8 Examples disclosed in JP-A No. 259543.

  The ionic liquid is preferably a salt having a melting point lower than room temperature (25 ° C.), or a salt that has a melting point higher than room temperature and liquefies at room temperature by dissolving with other molten salts. Specific examples of such an ionic liquid include the following anions and cations.

  Examples of the cation of the ionic liquid include ammonium, imidazolium, oxazolium, thiazolium, oxadiazolium, triazolium, pyrrolidinium, pyridinium, piperidinium, pyrazolium, pyrimidinium, pyrazinium, triazinium, phosphonium, sulfonium, carbazolium, indolium, and their Derivatives. These may be used alone or in combination. Specific examples include 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-ethyl-3-methylimidazolium, and the like. .

Examples of the anion of the ionic liquid include metal chlorides such as AlCl ₄ ⁻ or Al ₂ Cl ₇ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , N (CF ₃ SO ₂ ) ₂ ⁻ , Fluorine-containing ions such as F (HF) _n ⁻ or CF ₃ COO ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , C ₆ H ₁₁ COO ⁻ , CH ₃ OSO ₃ ⁻ , CH ₃ OSO ₂ ⁻ , CH ₃ SO Non-fluorine compound ions such as ₃ ⁻ , CH ₃ SO ₂ ⁻ , (CH ₃ O) ₂ PO ₂ ⁻ , N (CN) ₂ ⁻ or SCN ⁻ , and halide ions such as iodide ions or bromide ions can be mentioned. . These may be used alone or in combination. Among these, iodide ions are preferable as the anions of the ionic liquid.

  Even if the electrolyte 31 is a liquid electrolyte (electrolytic solution) in which the above-described redox electrolyte is dissolved, dispersed or suspended in a solvent, the solid polymer electrolyte in which the above-described redox electrolyte is held in a polymer substance. It may be. Further, it may be a quasi-solid (paste-like) electrolyte containing a redox electrolyte and a particulate conductive carbon material such as carbon black. Here, in the present specification, “pseudo-solid” means a concept including a solid solid or a gel-like solid or a clay-like solid that hardly deforms but is deformable by application of stress. Specifically, it means that there is no change in shape due to its own weight or a slight change in shape after standing for a certain period of time. Note that in a quasi-solid electrolyte containing a conductive carbon material, the conductive carbon material has a function of catalyzing the oxidation-reduction reaction, and therefore the halogen may not be contained in the electrolyte.

  The electrolyte 31 may include an organic solvent that dissolves, disperses, swells, or suspends the above-described halide salt, ionic liquid, and the like. The organic solvent can be used without any particular limitation as long as it is electrochemically inactive, but preferably has a melting point of 20 ° C. or lower and a boiling point of 80 ° C. or higher. Durability tends to be increased by using a material having a melting point and a boiling point within this range. In addition, the organic solvent preferably has a high viscosity. Since the boiling point is increased due to the high viscosity, leakage of the electrolyte tends to be suppressed even when exposed to a high temperature environment. Furthermore, the organic solvent preferably has a high electrical conductivity. High photoelectric conversion efficiency tends to be obtained due to high electrical conductivity.

  Specific examples of the organic solvent include hexane, benzene, toluene, quinoline, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, methylene chloride, acetone, acetonitrile, methoxyacetonitrile, propionitrile, butyronitrile, benzonitrile, 3-methoxy. Propionitrile, valeronitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, acetic acid, formic acid, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, pentanol, methyl ethyl ketone, dimethyl carbonate, ethyl methyl carbonate , Ethylene carbonate, propylene carbonate, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene Ren glycol monoalkyl ether, polypropylene glycol monoalkyl ether, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, dioxane, 1,4-dioxane, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene Examples include glycol dialkyl ether, N-methylpyrrolidone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, and 3-methyl-γ-valerolactone. Among these, the organic solvent has at least one of a nitrile group, a carbonate ester structure, a cyclic ester structure, a lactam structure, an amide group, an alcohol group, a sulfinyl group, a pyridine ring, and a cyclic ether structure as a functional group. Is preferred. This is because an organic solvent having such a functional group can provide a higher effect as compared with those not containing any of these functional groups. Examples of the organic solvent having such a functional group include acetonitrile, propyl nitrile, butyronitrile, methoxyacetonitrile, methoxypropionitrile, dimethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, pentanol, Examples include quinoline, N, N-dimethylformamide, γ-butyrolactone, dimethyl sulfoxide, or 1,4-dioxane. Among them, methoxypropionitrile, propylene carbonate, N-methylpyrrolidone, pentanol, quinoline, N, N-dimethylformamide, γ-butyrolactone, dimethyl sulfoxide, 1,4-dioxane, methoxyacetonitrile and butyronitrile are exemplified. These organic solvents may be used alone or in combination. Further, the content of the organic solvent is preferably 10 to 80 wt% with respect to the total amount of the electrolyte 31.

  The electrolyte 31 may contain various additives depending on the required performance. As the additive, those generally used in batteries, solar cells and the like can be appropriately used. Specific examples thereof include, for example, p-type conductive polymers such as polyaniline, polyacetylene, polypyrrole, polythiophene, polyphenylene, polyphenylene vinylene, and derivatives thereof; imidazolium ions, pyridinium ions, triazolium ions, derivatives thereof, and halogen ions. Examples include, but are not limited to, a molten salt comprising a combination of the following: a gelling agent; an oil gelling agent; a dispersant; a surfactant;

  The method for disposing the electrolyte 31 between the working electrode 11 and the counter electrode 21 is not particularly limited, and can be performed using various known methods. For example, the dye-carrying metal oxide electrode 14 of the working electrode 11 and the conductive surface 22a of the counter electrode 21 are disposed to face each other with a predetermined interval through a spacer as necessary. The whole is sealed using a sealant or the like, and then the whole is sealed. Subsequently, the electrolyte 31 can be formed by injecting an electrolyte from the injection port between the working electrode 11 and the counter electrode 21 and then sealing the injection port.

  When a solid charge transfer material is employed as the electrolyte 31, it is preferable to use an electron transport material, a hole transport material, or the like.

  As the hole transport material, for example, aromatic amines and triphenylene derivatives are preferably used. Specific examples thereof include, for example, oligothiophene compounds, polypyrrole, polyacetylene or derivatives thereof, poly (p-phenylene) or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, polythienylene vinylene or derivatives thereof, polythiophene or Examples thereof include, but are not limited to, organic conductive polymers such as polyaniline or derivatives thereof, polytoluidine or derivatives thereof, and the like.

  Further, as the hole transport material, for example, a p-type inorganic compound semiconductor can be used. In this case, a p-type inorganic compound semiconductor having a band gap of 2 eV or more is preferably used, and a p-type inorganic compound semiconductor having 2.5 eV or more is more preferable. In addition, the ionization potential of the p-type inorganic compound semiconductor needs to be smaller than the ionization potential of the working electrode 11 from the condition that the holes of the dye can be reduced. The preferable range of the ionization potential of the p-type inorganic compound semiconductor varies depending on the dye used, but the ionization potential is preferably in the range of 4.5 eV or more and 5.5 eV or less, and 4.7 eV or more and 5.3 eV or less. More preferably within the following range.

As the p-type inorganic compound semiconductor, for example, a compound semiconductor containing monovalent copper is preferably used. Specific examples of the compound semiconductor containing monovalent copper include, for example, CuI, CuSCN, CuInSe ₂ , Cu (In, Ga) Se ₂ , CuGaSe ₂ , Cu ₂ O, CuS, CuGaS ₂ , CuInS ₂ , CuAlSe ₂ , Examples include GaP, NiO, CoO, FeO, Bi ₂ O ₃ , MoO ₂ , and Cr ₂ O _3, but are not particularly limited thereto.

  The method for forming the electrolyte 31 from the solid charge transfer material is not particularly limited, and can be performed using various known methods. When using a hole transport material containing an organic conductive polymer, for example, a technique such as a vacuum deposition method, a cast method, a coating method, a spin coating method, a dipping method, an electrolytic polymerization method, or a photoelectrolytic polymerization method may be employed. it can. Moreover, when using an inorganic solid compound, methods, such as a casting method, the apply | coating method, a spin coat method, the immersion method, the electrolytic plating method, can be employ | adopted, for example.

  Now, when the dye-sensitized solar cell 100 of this embodiment is irradiated with light (sunlight or ultraviolet light, visible light, or near infrared light equivalent to sunlight) to the working electrode 11, The dye that has been excited by absorbing the light injects electrons into the metal oxide layer 13. The injected electrons move to the adjacent conductive surface 12a and then reach the counter electrode 21 via an external circuit. On the other hand, the electrolyte 31 is oxidized so as to return (reduce) the dye that has been oxidized (the dye that has emitted electrons) as the electrons move. The oxidized electrolyte 31 is reduced by receiving the electrons. As described above, the movement of electrons between the working electrode 11 and the counter electrode 21 and the accompanying oxidation-reduction reaction of the electrolyte 31 are repeated, whereby continuous movement of electrons occurs, and photoelectric conversion is constantly performed. Is done.

Here, in the dye-sensitized solar cell 100 of the present embodiment, since the rhodanine compound having the structure represented by the general formula (1) is used, a dye having only one carboxylic acid group is used. When used, when using a dye having a plurality of carboxylic acid groups but having no rhodanine structure (for example, a phthalocyanine dye), a short anchor group such as —CH ₂ COOH group, or —CH ₂ CH Compared to the case of using a dye having a rhodanine structure part into which a long anchor group such as ₂ CH ₂ COOH group is introduced, the adsorptivity of the dye to the metal oxide layer 13 is enhanced. Therefore, even when moisture remains in the element or when moisture enters the element from the outside, the rate at which the pigment peels from the metal oxide layer 13 is low. Therefore, according to the dye-sensitized solar cell 100 of this embodiment, even if it is used for a long time, the fall of the photoelectric conversion efficiency by peeling of a pigment | dye can be suppressed, and durability can be improved. Moreover, in the dye-sensitized solar cell 100 of this embodiment, the electrons to the metal oxide layer 13 in the case of being excited by absorbing light as compared with the case where a dye having no rhodanine structure portion is used. Since the injection efficiency is excellent, the photoelectric conversion efficiency is excellent. In particular, in the dye-sensitized solar cell 100 in which the metal oxide layer 13 employs the working electrode 11 substantially made of zinc oxide, the photoelectric conversion efficiency and the durability are further improved.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
The dye-sensitized solar cell 100 described in the above embodiment was manufactured by the following procedure.

First, the working electrode 11 was produced according to the following procedure.
First, as a substrate 12 having a conductive surface 12a, a conductive glass substrate (F-SnO ₂ ) having a length of 2.0 cm, a width of 1.5 cm, and a thickness of 1.1 mm using fluorine-doped SnO as a transparent conductive film. Prepared. Subsequently, a masking tape having a thickness of 70 μm is pasted on the conductive surface 12a so as to surround a square of 0.5 cm in length and 0.5 cm in width, and 3 cm ^{3 of the} metal oxide slurry is uniformly applied to this portion. It was applied and dried. At this time, as the metal oxide slurry, zinc oxide powder (surface area 60 m ² / g, average primary particle size 50 nm or less; FINEX-30 manufactured by Sakai Chemical Industry Co., Ltd.) is used as a nonionic surface active so as to be 10% by weight. An agent prepared by suspending in water to which 1 drop of Triton X-100 (Triton is a registered trademark) was added was used. Subsequently, the masking tape on the conductive surface 12 a was peeled off, and the substrate 12 was baked at 450 ° C. in an electric furnace to form a zinc oxide film having a thickness of about 5 μm as the metal oxide layer 13.

Subsequently, the rhodanine compound of formula (1-1) and deoxycholic acid were dissolved in absolute ethanol so as to have concentrations of 3 × 10 ⁻⁴ mol / dm ³ and 1 × 10 ⁻³ mol / dm ³ , respectively. A dye-containing solution was prepared. And the base | substrate 12 with which the metal oxide layer 13 was formed in this pigment | dye containing solution was immersed, and the rhodanine compound of Chemical formula (1-1) was carry | supported by the metal oxide layer 13, and the pigment | dye carrying | support metal oxide electrode 14 was carried out. By forming, the working electrode 11 was obtained.

Next, the counter electrode 21 was produced according to the following procedure.
First, as a base 22 having a conductive surface 22a, a conductive glass substrate (F-SnO ₂ ) having a length of 2.0 cm, a width of 1.5 cm, and a thickness of 1.1 mm using fluorine-doped SnO as a transparent conductive film is prepared. did. Subsequently, a counter electrode 21 was obtained by forming a Pt layer having a thickness of 100 nm on the conductive surface 22a by sputtering. In this case, two holes (φ1 mm) for injecting the electrolyte were previously formed in the base 22 having the conductive surface 22a.

Then, with respect to acetonitrile, dimethyl hexyl imidazolium iodide (0.6mol / dm ^3), lithium iodide (0.1mol / dm ^3), iodine (0.05mol / dm ^3), each predetermined concentration It mixed so that electrolyte solution might be prepared.

Then, the dye-sensitized solar cell 100 was produced according to the following procedure using the working electrode 11, the counter electrode 21, and the electrolytic solution.
First, a spacer having a thickness of 50 μm is arranged so as to surround the metal oxide layer 13, and then the dye-supported metal oxide electrode 14 of the working electrode 11 and the Pt layer of the counter electrode 21 are arranged to face each other, and the spacer is arranged. Pasted together. Thereafter, an electrolyte solution was injected from an injection hole opened in the counter electrode 21 to form an electrolyte 31. Finally, the entire periphery of the cell and the injection hole were sealed to obtain the dye-sensitized solar cell 100 of Example 1.

(Examples 2 to 7)
The same treatment as in Example 1 was conducted except that the rhodanine compounds of chemical formulas (1-2) to (1-6) and (1-11) were used instead of the rhodanine compound of chemical formula (1-1). The dye-sensitized solar cells 100 of Examples 2 to 7 were obtained.

(Comparative Examples 1-6)
Comparative Example 1 was carried out in the same manner as in Example 1 except that the rhodanine compounds of the following chemical formulas (3-1) to (3-6) were used instead of the rhodanine compound of the chemical formula (1-1). -6 dye-sensitized solar cells 100 were obtained.

<Measurement of photoelectric conversion efficiency>
The battery characteristics of the dye-sensitized solar cells 100 of Examples 1 to 7 and Comparative Examples 1 to 6 were measured using an AM-1.5 (1000 W / m ² ) solar simulator. The evaluation results are shown in Table 1.
The photoelectric conversion efficiency (η:%) is the maximum output that is the product of the voltage and current obtained by measuring the response current by sweeping the voltage of the dye-sensitized solar cell 100 with a source meter. Is calculated by dividing the result by the light intensity per 1 cm ² and multiplying this calculation result by 100 to display a percentage. That is, the photoelectric conversion efficiency (η:%) is expressed by (maximum output / 1 light intensity per 1 cm ² ) × 100.

<Peel test>
In order to evaluate the adsorptivity (adhesiveness) of the dye, a peeling test was performed on the working electrode 11 of the dye-sensitized solar cell 100 of Examples 1 to 7 and Comparative Examples 1 to 6. The evaluation results are shown in Table 1.
The peel test was performed according to the following procedure. First, the absorption spectrum (measurement wavelength was in the range of 350 nm to 850 nm) of the surface of the dye-supported metal oxide layer 14 of the working electrode 11 was measured with a UV spectrometer, and the initial absorbance at the peak wavelength was determined. Next, after immersing the working electrode 11 in 100 cm ³ of an acetonitrile mixed solution containing water at a ratio of 10% by weight for 2 hours, the absorption spectrum was measured in the same manner, and 10% by weight of acetonitrile containing water at the peak wavelength was immersed for 2 hours. Absorbance was determined. Finally, from the initial absorbance at the peak wavelength and the absorbance after immersion in acetonitrile containing 10 wt% water for 2 hours, the residual ratio of dye (%) = (absorbance after immersion in acetonitrile containing 10 wt% water / initial absorbance) × 100 was calculated. The series of absorption spectra was measured using a Shimadzu UV-3101PC with a slit width of 5 nm.

As shown in Table 1, the dye-sensitized solar cells 100 of Examples 1 to 7 both have both photoelectric conversion efficiency and dye residual ratio as compared to the dye-sensitized solar cells 100 of Comparative Examples 1 to 6. High performance was confirmed.
Further, from the comparison between Comparative Example 1 and Example 1 and Comparative Examples 2 to 6, only one carboxylic acid group was introduced by using a rhodanine compound into which a plurality of carboxylic acid groups functioning as anchor groups were introduced. It was confirmed that the dye residual ratio was remarkably improved as compared with the case where the rhodanine compound was used. On the other hand, from the comparison between Comparative Example 1 and Comparative Examples 2 to 6, it was confirmed that the use of a rhodanine compound in which a plurality of carboxylic acid groups functioning as anchor groups were introduced tends to cause a decrease in photoelectric conversion efficiency. . On the other hand, from the comparison between Example 1 and Comparative Examples 2 to 6, only when two —CH ₂ CH ₂ COOH groups were introduced as carboxylic acid groups that function as anchor groups, the photoelectric conversion efficiency was significantly increased. It was confirmed that it could be increased.
Furthermore, from the comparison with Examples 1 to 7 and Comparative Example 1, the compound having the structure represented by the general formula (1) does not greatly depend on the types of substituents R1 and R2 of the phenylamine skeleton, It was confirmed that the high-performance dye-sensitized solar cell 100 can be realized in both the photoelectric conversion efficiency and the dye residual ratio.

(Examples 8-14 and Comparative Examples 7-12)
When forming the metal oxide layer 13 by the firing method, Examples 1 to 6 and Comparative Example 1 were used except that a metal oxide slurry containing titanium oxide (TiO ₂ ) powder was used instead of the zinc oxide powder. The dye-sensitized solar cells 100 of Examples 8 to 14 and Comparative Examples 7 to 12 were obtained by processing in the same manner as in.
In addition, what was prepared as follows was used as metal oxide slurry containing said titanium oxide powder. First, titanium isopropoxide 125 cm ^3, was added with stirring to 0.1 mol / dm ³ aqueous solution of nitric acid 750 cm ^3, and 8 hours vigorously stirred at 80 ° C.. The obtained liquid was poured into a pressure vessel made of Teflon (registered trademark), and the pressure vessel was treated in an autoclave at 230 ° C. for 16 hours. Thereafter, the liquid (sol solution) containing the precipitate subjected to autoclaving was resuspended by stirring. Subsequently, this suspension was subjected to suction filtration to remove precipitates that were not resuspended, and the sol-like filtrate was concentrated with an evaporator until the titanium oxide concentration became 11% by mass. Thereafter, one drop of Triton X-100 was added to the concentrated solution in order to improve the paintability to the substrate. Subsequently, titanium oxide powder having an average particle size of 30 nm (P-25 manufactured by Nippon Aerosil Co., Ltd.) was added to the sol-like concentrated solution so that the total content of titanium oxide was 33% by mass, and rotation revolution was utilized. Centrifugal stirring was performed for 1 hour to disperse.

  The photoelectric conversion efficiency and the dye residual ratio of the obtained dye-sensitized solar cells 100 of Examples 8 to 14 and Comparative Examples 7 to 12 were measured by the same method as described above. The evaluation results are shown in Table 2.

As shown in Table 2, the dye-sensitized solar cells 100 of Examples 8 to 14 both have both photoelectric conversion efficiency and dye residual ratio as compared to the dye-sensitized solar cells 100 of Comparative Examples 7 to 12. High performance was confirmed.
From these results, also in the dye-sensitized solar cells 100 of Examples 8 to 14 using the metal oxide layer 13 substantially made of titanium oxide, the metal oxide layer 13 substantially made of zinc oxide was used. It was confirmed that the same tendency as the dye-sensitized solar cell 100 of Examples 1 to 7 appeared.
Further, from the comparison between Examples 1 to 7 and Examples 8 to 14, the compound having the structure represented by the general formula (1) is substantially more effective than the metal oxide layer 13 substantially made of titanium oxide. In the dye-sensitized solar cell 100 which is excellent in adsorptivity with the metal oxide layer 13 made of zinc oxide and adopts the metal oxide layer 13 made substantially of zinc oxide, the photoelectric conversion efficiency and durability are remarkably increased. It was confirmed that

  In addition, as above-mentioned, this invention is not limited to the said embodiment and Example, In the range which does not deviate from the summary, it can add suitably.

  As described above, the present invention is widely and effective for electronic / electrical materials, electronic / electrical devices related to photoelectric conversion elements such as dye-sensitized solar cells and optical sensors, and various devices, facilities, systems, and the like equipped with them. Is available.

  DESCRIPTION OF SYMBOLS 11 ... Working electrode, 12 ... Base | substrate, 12a ... Conductive surface, 13 ... Metal oxide layer, 14 ... Dye carrying | support metal oxide electrode, 21 ... Counter electrode, 22a ... Conductive surface, 22 ... Base | substrate, 31 ... Electrolyte, 41: spacer, 100: photoelectric conversion element.

Claims (4)

In a photoelectric conversion element comprising a working electrode having a dye-supported metal oxide electrode in which a dye is supported on a metal oxide layer,
As the dye, the following general formula (1):
(In Formula (1), R1 and R2 are each independently a hydrogen atom, a terminal aryl group, a terminal alkyl group, or a terminal alkoxy group, and at least one of R1 and R2 is a terminal aryl group, a terminal alkyl group. Or a terminal alkoxy group, and R1 and R2 may combine to form a ring).
Including a compound having a structure represented by:
Photoelectric conversion element. In the general formula (1), R1 is a terminal aryl group or a terminal alkyl group.
The photoelectric conversion element according to claim 1. In the general formula (1), R1 is 1-1 diphenylethylene.
The photoelectric conversion element according to claim 1. The metal oxide layer is substantially composed of zinc oxide;
The photoelectric conversion element as described in any one of Claims 1-3.