JP2012216483A - Dye-sensitized solar cell and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell whose conversion efficiency can be improved by a simple process.SOLUTION: The dye-sensitized solar cell comprises a photoelectrode, an electrolyte layer, and a counter electrode. The photoelectrode has a current collecting material containing a metal or a metal oxide as a main component. The current collecting material has a surface on which an adsorption compound is adsorbed.

Description

  The present technology relates to a dye-sensitized solar cell and a method for manufacturing the same. In detail, it is related with the dye-sensitized solar cell which can improve conversion efficiency.

In a dye-sensitized solar cell using a metal current collector substrate or metal current collector wiring for the negative electrode, the size of the cell can be easily increased because the metal has a low resistance. For example, Non-Patent Document 1 proposes a dye-sensitized solar cell using a TiO ₂ layer as a metal oxide semiconductor layer and a SUS mesh as a metal current collecting base material. However, reverse electron transfer occurs from the negative electrode metal current collector substrate or metal current collector wiring to the electrolyte, and the conversion efficiency of the dye-sensitized solar cell is low.

Therefore, a technique for improving the conversion efficiency by applying a surface coating treatment to the metal current collector substrate or metal current collector wiring has been proposed. For example, in Non-Patent Document 2, a TiO ₂ layer is used for the metal oxide semiconductor layer, SUS316 mesh (wire diameter 25 μm, opening 25 μm) is used for the metal current collector, and the SUS316 mesh surface is coated with a laminated film. Thus, a technique for improving the conversion efficiency has been proposed. In this technique, the laminated film is formed by forming a Ti layer (200 nm thickness) on the surface of SUS316 mesh by sputtering and then forming a TiO _x layer (200 nm thickness) by arc plasma deposition.

Appl. Phys. Lett. 2007, 90, 073501.

Appl. Phys. Lett. 2009, 94, 093301.

However, in the technique described in Non-Patent Document 2, since the Ti layer and the TiO _x layer are formed by a vacuum process, the productivity of the dye-sensitized solar cell is lowered. Therefore, it is desired to improve the conversion efficiency by a simpler process.

  Therefore, the objective of this technique is to provide the dye-sensitized solar cell which can improve conversion efficiency by a simple process, and its manufacturing method.

In order to solve the above-mentioned problem, the first technique is:
A photoelectrode, an electrolyte layer, and a counter electrode;
The photoelectrode has a current collector mainly composed of metal or metal oxide,
The current collector is a dye-sensitized solar cell having a surface on which an adsorbing compound is adsorbed.

The second technology is
A step of adsorbing an adsorbing compound to the surface of the current collector of the photoelectrode;
The current collector is a method for producing a dye-sensitized solar cell mainly containing a metal or a metal oxide.

In the present technology, the adsorption compound is preferably one represented by the following general formula (1).
RX (1)
(However, R contains at least one of a saturated or unsaturated alkyl group, an aromatic ring, an alicyclic ring, and a heterocyclic ring. X can be coordinated to an adsorptive functional group or a metal or metal oxide. Is a simple atom.)

  In the present technology, the adsorptive functional group may be a carboxylic acid group, a sulfo group, an amino group, a phosphoric acid group, a phosphino group, a silanol group, an epoxy group, an isocyanate group, a cyano group, a vinyl group, a thiol group, or a hydroxyl group. preferable.

  In the present technology, the current collecting material is preferably a porous electrode, a current collecting electrode, a current collecting base material, a transparent conductive layer, or a current collecting wiring. In this case, it is preferable that the current collecting material is a porous electrode, a current collecting electrode, a current collecting base material, or a current collecting wiring whose main component is a metal. Moreover, it is preferable that a current collection material is a transparent conductive layer which has a metal oxide which has transparency as a main component.

  In the present technology, the photoelectrode includes a porous metal electrode, a porous metal oxide layer carrying a sensitizing dye, and a porous intermediate layer provided between the porous metal electrode and the porous metal oxide layer It is preferable that the porous intermediate layer includes conductive fine particles, and the current collector is a porous metal electrode.

  In this technology, in a photoelectrode that uses a current collector mainly composed of metal or metal oxide on the negative electrode side, an adsorbed compound is adsorbed on the surface of the current collector, so that the reverse of the current collector surface to the electrolyte solution occurs. Electron transfer can be suppressed. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved.

  As described above, according to the present technology, the conversion efficiency of the dye-sensitized solar cell can be improved only by adsorbing the adsorbing compound on the surface of the current collector. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved by a simple process.

FIG. 1 is a cross-sectional view illustrating an example of the configuration of the dye-sensitized solar cell according to the first embodiment of the present technology. FIG. 2 is a schematic diagram for explaining the action of the adsorbing compound adsorbed on the surface of the back contact electrode. FIG. 3 is a schematic diagram showing an enlarged surface of the back contact electrode shown in FIG. FIG. 4 is a cross-sectional view illustrating an example of the configuration of the dye-sensitized solar cell according to the second embodiment of the present technology. FIG. 5 is a cross-sectional view illustrating an example of the configuration of the dye-sensitized solar cell according to the third embodiment of the present technology. FIG. 6A is a cross-sectional view illustrating an example of a configuration of a dye-sensitized solar cell according to a fourth embodiment of the present technology. FIG. 6B is a perspective view showing an example of the configuration of the photoelectrode of the dye-sensitized solar cell shown in FIG. 6A. FIG. 7A is a cross-sectional view illustrating an example of a configuration of a dye-sensitized solar cell according to a fifth embodiment of the present technology. FIG. 7B is a perspective view showing an example of the configuration of the photoelectrode of the dye-sensitized solar cell shown in FIG. 7A. FIG. 8 is a graph showing current-voltage characteristic curves of back contact type dye-sensitized solar cells of Examples 1 to 4 and Comparative Example 1. 9A is a graph showing current-voltage characteristic curves of back contact type dye-sensitized solar cells of Comparative Examples 1 and 2. FIG. FIG. 9B is a graph showing current-voltage characteristic curves of back contact type dye-sensitized solar cells of Comparative Examples 2 and 3.

Embodiments of the present technology will be described in the following order with reference to the drawings. In all the drawings of the following embodiments, the same or corresponding parts are denoted by the same reference numerals.
1. First embodiment (example of back contact type dye-sensitized solar cell)
2. Second Embodiment (Example of Back Contact Type Dye-Sensitized Solar Cell with Porous Intermediate Layer)
3. Third Embodiment (Example of dye-sensitized solar cell using metal substrate as current collecting substrate)
4). Fourth Embodiment (Example of dye-sensitized photoelectric conversion element module using current collecting electrode)
5. Fifth embodiment (example of dye-sensitized photoelectric conversion element module using current collecting wiring)

<1. First Embodiment>
[Configuration of dye-sensitized solar cell]
FIG. 1 is a cross-sectional view illustrating an example of the configuration of the dye-sensitized solar cell according to the first embodiment of the present technology. This dye-sensitized solar cell is a so-called back contact type dye-sensitized solar cell. As shown in FIG. 1, a photoelectrode substrate 1 and a counter electrode substrate 2 disposed opposite to the photoelectrode substrate 1 And an electrolyte layer 3 interposed between the photoelectrode substrate 1 and the counter electrode substrate 2. The photoelectrode substrate 1 includes a substrate 12 and a photoelectrode 11 formed on one main surface of the substrate 12, and the photoelectrode 11 is disposed so as to face the counter electrode substrate 2. The counter electrode substrate 2 includes a substrate 22 and a counter electrode 21 formed on one main surface of the substrate 22, and the counter electrode 21 is disposed so as to face the photoelectrode substrate 1. An outer peripheral portion of a region sandwiched between the photoelectrode substrate 1 and the counter electrode substrate 2 is sealed with, for example, a sealing material 4. The photoelectrode substrate 1 and the counter electrode substrate 2 are electrically connected to the load 5 via, for example, a linear member such as a lead wire.

[Configuration of photoelectrode]
As shown in FIG. 1, the photoelectrode 11 includes a porous metal electrode (hereinafter referred to as a back contact electrode) 31 and a porous metal oxide layer 32 on which a dye is supported. In addition, the photoelectrode 11 may further include a porous insulating layer 33 on the main surface opposite to the side on which the porous metal oxide layer 32 is provided, of both main surfaces of the back contact electrode 31 as necessary. You may make it prepare.

  Hereinafter, the back contact electrode 31, the porous metal oxide layer 32, the counter electrode 21, the base materials 12 and 22, the dye, the electrolyte layer 3, and the porous that constitute the dye-sensitized solar cell according to the first embodiment of the present technology. The insulating material layer 33 will be described sequentially.

(Back contact electrode)
The back contact electrode 31 has a function as a current collector. The back contact electrode 31 is a porous electrode, for example, and is preferably composed mainly of a metal having excellent conductivity, but is not limited thereto. As the metal, for example, one or more selected from the group consisting of Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, and Fe can be used. Specifically, for example, as the metal, for example, a simple substance such as Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, Fe, or an alloy containing two or more of these can be given. As the alloy, nickel alloys such as stainless steel (SUS), NiCu alloy, NiCr alloy, etc. are preferably used. As the stainless steel, SUS304, SUS30d4L, SUS310S, SUS316, SUS316L, SUS317L, SUS321, SUS347, or the like is preferably used.

  As the structure of the back contact electrode 31, for example, when the electrolyte is dropped on the surface of the back contact electrode, a structure in which the electrolyte can penetrate in the electrode depth direction and reach the back side is preferable. A film with a hole, a sheet, a foil, a substrate, or the like can be used. More specifically, a foil (for example, plain weave, twill weave, plain tatami mat, twill mat weave, etc.), porous body, non-woven fabric, fiber sintered body, expanded metal, punching metal, foil with holes made by etching, etc. However, it is not limited to these. As the back contact electrode 31, an electrode in which the surface of a base material made of a plastic material or the like is covered with a conductive material such as a metal may be used. The thickness of the back contact electrode 31 is preferably as thin as possible in consideration of, for example, that ions in the electrolytic solution move efficiently and the movement of electrons associated therewith is not hindered, specifically 0.5 mm. The following is preferable.

(Adsorption compound)
An adsorbed compound is adsorbed on the surface of the back contact electrode 31. As the adsorption compound, for example, a compound having a functional group that adsorbs to a metal and / or metal oxide can be used. For example, when the back contact electrode 31 has a metal as a main component, a compound having a functional group that adsorbs to the metal can be used.

The adsorbing compound can be represented by, for example, the following general formula (1).
RX (1)
(However, R contains at least one of a saturated or unsaturated alkyl group, an aromatic ring, an alicyclic ring, and a heterocyclic ring. X is coordinated to an adsorptive functional group, or a metal and / or a metal oxide. Possible atoms.)

The adsorbing compound may be a compound that adsorbs to a metal and / or metal oxide, and the size of R and the like are not limited. In general, the distance between the electron passing side (for example, the back contact electrode 31 existing on the negative electrode side) and the electron receiving side (for example, I ₃ ⁻ in the electrolyte layer 3) is the electron transfer. It affects the speed (the likelihood of electronic movement) (HB Gray and JR Winkler, PNAS 2005, 102 3534-3539). The details of such a phenomenon are explained by the Marcus theory, and the electron movement speed becomes exponentially slower as the distance between the two parties becomes longer. Therefore, in the case of the present embodiment, it is considered that the effect of preventing the reverse electron transfer increases as the distance at which I ₃ ⁻ is separated from the surface of the back contact electrode 31 on the negative electrode side by the adsorbing compound increases.

  However, it is not known what form the adsorbing compound takes when adsorbed on the surface of the back contact electrode 31 (for example, it is not known whether the adsorbing compound is vertically or horizontally with respect to the surface of the back contact electrode 31). Therefore, the larger the size of the molecule, the greater the effect of preventing reverse electron transfer. Further, when compared with reverse electron transfer from the surface of the back contact electrode 31 on which nothing is adsorbed, the reverse electron prevention effect should appear if any small adsorbed compound is adsorbed. Considering these points, it is considered that the size of R of the adsorption compound is not limited.

  Examples of the adsorptive functional group include a carboxylic acid group (including carboxylate), a sulfo group (including sulfonate), an amino group, a phosphate group (including phosphate and phosphate ester), a phosphino group, a silanol group, Examples thereof include an epoxy group, an isocyanate group, a cyano group, a vinyl group, a thiol group, and a hydroxyl group.

  As an atom that can be coordinated to a metal and / or metal oxide, for example, N, S, O, and the like can be used. When the atom capable of coordinating to the metal and / or metal oxide is an atom such as N, S, or O, the above general formula (1) means a compound having a heterocyclic ring.

  As the adsorbing compound, a compound that can be dissolved in a predetermined concentration in the solvent to be used and adsorbs to the metal and / or metal oxide to be used can be appropriately selected and used. Examples of the adsorbing compound having a carboxylic acid group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid. Oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4-butylbenzoic acid, 4-tert-butylbenzoic acid, 3,5-di-tert-butylbenzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 2-ethoxybenzoic acid, 3-ethoxybenzoic acid, 4-ethoxybenzoic acid, 4-n-but Xylbenzoic acid, 2-phenoxybenzoic acid, 3-phenoxybenzoic acid, 4-phenoxybenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, phenylacetic acid, diphenylacetic acid, (±) -2-phenylpropanoic acid, 3-phenylpropanoic acid, 2,2-diphenylpropanoic acid, 3,3-diphenylpropanoic acid, 4-biphenylacetic acid, triphenylacetic acid, phenoxyacetic acid, biphenyl-2-carboxylic acid, biphenyl-4-carboxylic acid, 1- Naphthoic acid, 2-naphthoic acid, 1-naphthylacetic acid, 2-naphthylacetic acid, (2-naphthylthio) acetic acid, fluorene-1-carboxylic acid, fluorene-4-carboxylic acid, fluorene-9-carboxylic acid, 9-anthracenecarbon Acid, 1-pyrenecarboxylic acid, pyrrole-2-carboxylic acid, 2-thiophenecarboxylic acid, 3-thiol Carboxylic acid, 3- (2-thienyl) acrylic acid, 4-thiazole carboxylic acid, indole-2-carboxylic acid, indole-3-carboxylic acid, indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6 -Carboxylic acid, benzo [b] thiophene-2-carboxylic acid, benzothiazole-6-carboxylic acid, 4-dibenzothiophenecarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid Oxocarboxylic acid, pyruvic acid, lactic acid, malic acid, citric acid, fumaric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, amino acid nitrocarboxylic acid and the like can be used.

  Examples of the adsorbing compound having a phosphate group include phosphoric acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, 2- Ethylhexylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, hexadecylphosphonic acid, octadecylphosphonic acid, eicosylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid group, phenethylphosphonic acid, α- Methylbenzylphosphonic acid, 1-methyl-1-phenethylphosphonic acid, diphenylmethylphosphonic acid, biphenylphosphonic acid, benzylphenylphosphonic acid, α-cumylphosphonic acid, toluylphosphonic acid, xylylphosphonic acid, ethyl Phenylphosphonic acid, cumenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, heptylphenylphosphonic acid, octylphenylphosphonic acid, nonylphenylphosphonic acid, phenyl phosphate, benzyl phosphate, phenethyl phosphate, α-methylbenzyl phosphate 1-methyl-1-phenethyl phosphate, diphenylmethyl phosphate, biphenyl phosphate, benzylphenyl phosphate, α-cumyl phosphate, toluyl phosphate, xylyl phosphate, ethylphenyl phosphate, cumenyl phosphate, phosphoric acid Propylphenyl, butylphenyl phosphate, heptylphenyl phosphate, octylphenyl phosphate, nonylphenyl phosphate, methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, pentyl phosphate, hexyl phosphate, heptyl phosphate ,phosphoric acid Octyl, 2-ethylhexyl phosphate, octyl phosphate, nonyl phosphate, decyl phosphate, undecyl phosphate, dodecyl phosphate, hexadecyl phosphate, octadecyl phosphate, eicosyl phosphate, and the like can be used.

  Examples of the adsorbing compound having a sulfo group include benzenesulfonic acid, n-butylbenzenesulfonic acid, n-octylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, and 2,5-dimethylbenzenesulfonic acid. 2,5-dibutylbenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 5-amino-2-methylbenzene Sulfonic acid, 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, hydroxynitrobenzenesulfonic acid, Aminotoluenesulfonic acid, p -Phenolsulfonic acid, aminophenolsulfonic acid, cumenesulfonic acid, xylenesulfonic acid, o-cresolsulfonic acid, m-cresolsulfonic acid, p-cresolsulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 1- Naphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, naphtholsulfonic acid, naphthylaminesulfonic acid, sulfanilamide, sulfaguanidine, dinonylnaphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 2 , 7-Naphthalenedisulfonic acid, aminohydroxynaphthalenedisulfonic acid, 4,4-biphenyldisulfonic acid, anthraquinonesulfonic acid, m-benzenedisulfonic acid, 2,5-diamino-1 3-benzenedisulfonic acid, naphthol disulfonic acid, aniline-2,4-disulfonic acid, anthraquinone-1,5-disulfonic acid, polystyrene sulfonic acid, catechol disulfonic acid, aromatic disulfonic acid such as phenol disulfonic acid, methanesulfonic acid, Ethanesulfonic acid, 1-propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, n-octylsulfonic acid, nonanesulfonic acid, decanesulfonic acid, undecylsulfonic acid, dodecylsulfonic acid, tri Decylsulfonic acid, tetradecylsulfonic acid, pentadecylsulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, methanedisulfonic acid, 1,2-ethanedisulfonic acid, 1,3-propanedisulfonic acid, pig Sulfonic acid, 2-hydroxyethane sulfonic acid, sulfo acid, aliphatic sulfonic acids, such as taurine, cyclopentane sulfonic acid, and alicyclic acid such as cyclohexane sulfonic acid, and camphorsulfonic acid.

  Examples of the adsorbing compound having an amino group include ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine. Decylamine, laurylamine, mystyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, Aminohexanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3 Primary amines such as (2-ethylhexyloxy) propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine, furfurylamine; ethylenediamine, 1 , 2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis -(3 -Aminopropoxy) -2,2'-dimethylpropane, aminoethylethanolamine, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4 -Aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, menthanediamine, 1,4-bisamino Propyl piperazine, o-, m- Or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, 2,4-toluenediamine, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-, or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, benzidine, 4,4'-bis (o-toluidine), Dianisidine, 4,4′-diaminodiphenylmethane, 2,2- (4,4′-diaminodiphenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-thiodianiline, 4,4′-diaminodiphenylsulfone, 4 , 4′-diaminoditolylsulfone, methylenebis (o-chloroaniline), 3,9-bi (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylene Pentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis ( Primary polyamines such as 3,4-diaminophenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexyl Amine, o Cutylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2,4-, 2,6-, 3,5-lupetidine, diphenylamine, N- Secondary amines such as methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine; N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2, -Diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane, N, N ' -Dimethyl-1,4-diaminobutane, N, N'-dimethyl-1,5-diaminopentane, N, N'- Methyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'-diethyl-1,2-diaminopropane, N, N'- Diethyl-1,3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane N, N′-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, Secondary polyamines such as 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- (4-piperidyl) butane; , Triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n-butylamine, tri-iso-butylamine, tri- sec-butylamine, tri-pentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine, tri-dodecylamine, tri-laurylamine, dicyclohexylethylamine, Cyclohexyldiethylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N-diethylethanolamine, N, N -Dimethylethanolamine, N-ethyldiethanolamine, triethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethyl Aminomethylphenol, 2- (N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2- Tertiary amines such as dimethylaminoethoxy) -4-methyl-1,3,2-dioxabornane; tetramethylethylenediamine, pyrazine, N, N′-dimethylpiperazine, N, N′-bis ((2-hydroxy) propyl) Piperazine, hexamethylenetetramine, N N, N ′, N′-tetramethyl-1,3-butaneamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4, Tertiary polyamines such as 6-tris (N, N-dimethylaminomethyl) phenol and heptamethylisobiguanide; imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole 4-ethylimidazole, N-butylimidazole, 2-butylimidazole, N-undecylimidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 2- Mercap Imidazole, 2-mercapto-N-methylimidazole, 2-mercaptobenzimidazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-mercapto-1-methyl-tetrazole, 2,5-dimercapto -1,3,4-thiadiazole 1-benzyl-2-methylimidazole, N- (2′-cyanoethyl) -2-methylimidazole, N- (2′-cyanoethyl) -2-undecylimidazole, N- (2 Various imidazoles such as' -cyanoethyl) -2-phenylimidazole, 3,3-bis- (2-ethyl-4-methylimidazolyl) methane, an adduct of alkylimidazole and isocyanuric acid; 1,8-diazabicyclo (5 , 4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5 And amidines such as 6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7.

  Examples of the adsorbing compound having a hydroxyl group include anisyl alcohol, anis alcohol, aminophenylethyl alcohol, aminophenethyl alcohol, aminobenzyl alcohol, allyl alcohol, isobutyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, isopentyl alcohol, n-un. Decyl alcohol, n-eicosyl alcohol, 2-ethylhexyl alcohol, enanth alcohol, n-octadecyl alcohol, octyl alcohol, oleyl alcohol, cumin alcohol, chrysanthemyl alcohol, crotyl alcohol, cinnamic alcohol, coniferyl alcohol, salicyl alcohol , Α-cyclopropyl-4-fluorobenzyl alcohol, diacetone alcohol, dinitrobe Dil alcohol, difluorobenzyl alcohol, dimethoxybenzyl alcohol, stearyl alcohol, cetyl alcohol, tetradecyl alcohol, tetrahydrofurfuryl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, (trifluoromethyl) benzyl alcohol, (trifluoromethoxy) benzyl Alcohol, nitrobenzyl alcohol, nonyl alcohol, vanillyl alcohol, perfluoro-tert-butyl alcohol, 4-hydroxyphenethyl alcohol, o-hydroxybenzyl alcohol, 4-hydroxy-3-methoxybenzyl alcohol, hydrocinnamic alcohol, 3, 5-bis (trifluoromethyl) benzyl alcohol, 2-phenylethyl alcohol, phenylpropyl alcohol Coal, phenethyl alcohol, fluorophenethyl alcohol, fluorobenzyl alcohol, 4-fluoro-α-methylbenzyl alcohol, furfuryl alcohol, butyl alcohol, propargyl alcohol, propyl alcohol, propylbenzyl alcohol, hexadecyl alcohol, hexyl alcohol, heptyl alcohol, Benzyl alcohol, benzyloxybenzyl alcohol, benzylbenzyl alcohol, perillyl alcohol, n-pentadecyl alcohol, 2,3,4,5,6-pentafluorobenzyl alcohol, pentyl alcohol, polyvinyl alcohol, myristyl alcohol, 4- (methylthio) ) Benzyl alcohol, methyl (trifluoromethyl) benzyl alcohol, methyl butyl alcohol, , 4-methylenedioxybenzyl alcohol, methoxybenzyl alcohol, lauryl alcohol, 3-allyloxy-1,2-propanediol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 2-ethyl-1 , 3-hexanediol, octafluorooctanediol, octanediol, quinolinediol, propanediol, cyclohexanediol, 2,2-diethyl-1,3-propanediol, ethanediol, diphenylethanediol, diphenylsilanediol, dimethylpropanediol , Tetradecanediol, tetraphenyl-1,2-ethanediol, tetrafluorobutanediol, decanediol, trimethylpentanediol, dodecanediol, naphthalenediol, biphenyl Diol, pinanediol, pyrimidinediol, phenylethanediol, phenylpropanediol, phenoxypropanediol, butanediol, hexynediol, benzenediol, pentanediol, butanetriol, propanetriol, benzenetriol and the like.

  Examples of the adsorption compound having an isocyanate group include methyl isocyanate, ethyl isocyanate, propyl isocyanate, iso-propyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, dodecyl. Monoisocyanates such as isocyanate, cyclohexyl isocyanate, phenyl isocyanate, toluyl isocyanate, diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4 -Screw Isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine diisocyanate, 4, 4'-diphenylmethane diisocyanate, diphenyl ether diisocyanate, 3- (2'-isocyanatocyclohexyl) propyl isocyanate, tris (phenylisocyanate) thiophosphate, isopropylidenebis (cyclohexylisocyanate), 2,2'-bis (4-isocyanatophenyl) propane , Triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ′, 4 ″ -triisocyanate To-2,5-dimethoxyphenylamine, 3,3′-dimethoxybenzidine-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diisocyanatobiphenyl, 4 , 4′-diisocyanato-3,3′-dimethylbiphenyl, dicyclohexylmethane-4,4′-diisocyanate, 1,1′-methylenebis (4-isocyanatobenzene), 1,1′-methylenebis (3-methyl-4) -Isocyanatobenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanato-1-methylethyl) Benzene, 1,3-bis (2-isocyanato-2-propyl) ben Zen, 2,6-bis (isocyanatomethyl) naphthalene, 1,5-naphthalene diisocyanate, bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene, bis (isocyanatomethyl) tetrahydrothiophene, 2, Polyisocyanates such as 5-diisocyanatomethylnorbornene, bis (isocyanatomethyl) adamantane, dimer acid diisocyanate, 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, and the like by burette type reaction of these polyisocyanates. Isomers, cyclized trimers of these polyisocyanates, and isocyanates such as adducts of these polyisocyanates and alcohols.

  Examples of the adsorbing compound having a thiol group include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, allyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, iso-propyl mercaptan, tert-butyl mercaptan, tert-nonyl mercaptan, tert-dodecyl mercaptan, phenyl mercaptan, benzyl mercaptan, 3-methylphenyl Mercaptan, 4-methylphenyl mercaptan, 4-chlorobenzyl mercaptan, 4-vinylbenzyl mercapta , 3-vinylbenzyl mercaptan, methyl mercaptopropionate, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, mercaptoacetic acid, mercaptoglycolic acid, mercaptopropionic acid Methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercapto Hexane, bis (2-mercaptoethyl) ether, bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethyloxy) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 2, 3-dimercapto-1-propanol, 1,3-dimer Put-2-propanol, 1,2,3-trimercaptopropane, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 2- (2-mercaptoethylthio) ) -1,3-dimercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, 4,8-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaundecane, 1,1,1-tris (mercaptomethyl) propane, teto Lakis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1 , 4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropio) Nate), pentaerythritol tetrakis (2-mercaptocetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-dimercaptocyclohexane, 1,3-dimercap Cyclohexane, 1,4-dimercaptocyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2, 5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethylthiomethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, Aliphatic mercaptans such as 2,5-bis (2-mercaptoethyl) -1-thian and 2,5-bis (mercaptomethyl) thiophene, and 1,2-dimercaptobenzene, 1,3-dimercaptobenzene 1,4-dimercaptobenzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, 2,2-bis (4-mercaptophenyl) propane, bis (4-mercaptophenyl) ether, Bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, bis (4-mercaptomethylphenyl) methane, 2,2-bis (4-mercaptomethylphenyl) propane, bis (4-mercaptomethylphenyl) Aromatic cyclic mercaptans such as ether, bis (4-mercaptomethylphenyl) sulfide, 4-hydroxythiophenol, mercaptobenzoic acid and the like can be mentioned.

  Examples of the adsorption compound having a cyano group include acetonitrile, propionitrile, isobutyronitrile, 2-ethylhexonitrile, lauronitrile, stearonitrile, cyclohexylnitrile, phenylacetonitrile, phenylpropionitrile, benzonitrile, and methyl. Examples include benzonitrile, dimethylbenzonitrile, methoxybenzonitrile, dimethoxybenzonitrile, naphthonitrile, cyanopyridine, malonnitrile, adiponitrile, phthalonitrile, dicyanodiphenyl, 1,4-dicyanobutane, and the like.

  As the adsorption compound having a silanol group, for example, a compound that hydrolyzes to produce a silanol group can be used. For example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) Propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryl Rooxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meta ) Acryloxypropyltriethoxysilane, butyltrimethoxy Silane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropyl Propyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxy Silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-me Examples include lucaptopropyltrimethoxysilane, trimethylsilanol, and methyltrichlorosilane.

  Examples of the adsorbing compound having a phosphino group include monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, and dibutyl Dihydrocarbon-substituted phosphines such as phosphine, dihexylphosphine, dicyclohexylphosphine, and dioctylphosphine; Alkyl phosphines, vinyl phosphines, propenyl phosphines Monoalkenylphosphine such as cyclohexenylphosphine and dialkenylphosphine in which two alkenyl hydrogen atoms are substituted; trialkenylphosphine in which three alkenyl hydrogen atoms are substituted; benzylphosphine, phenylethylphosphine, phenylpropylphosphine Arylalkyl phosphines such as diarylalkyl phosphine or aryl dialkyl phosphine in which three hydrogen atoms of phosphine are substituted with aryl or alkenyl; Phosphine, naphthyl phosphine, methyl naphthyl phosphine, anthracenyl phosphine Phosphine, phenanthonylphosphine; di (alkylaryl) phosphine in which two hydrogen atoms of phosphine are substituted with alkylaryl; arylphosphine such as tri (alkylaryl) phosphine in which three hydrogen atoms of phosphine are substituted with alkylaryl Is mentioned.

  Examples of the adsorbing compound having a vinyl group include aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and other α-olefins. Alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene; Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene and indene. Aromatic vinyl hydrocarbons: styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methyl styrene, vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, And butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

Examples of the adsorption compound having an epoxy group include propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylphenyl) -propan-1-one, and 1-phenyl-2. -Dimethylamino-2-methyl-3- (4-methoxyphenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (3,4-dimethoxyphenyl) -propane-1 -One, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylthiophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-fluoro Phenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (2-chlorophenyl) -propan-1-one, 1-phenyl-2-di Tylamino-2-methyl-3- (4-chlorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-bromophenyl) -propan-1-one, 1- Phenyl-2-dimethylamino-2-methyl-3- (4-benzoylphenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-benzyl-propan-1-one, 1,3-diphenyl 2-dimethylamino-2-benzyl-propan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-fluorophenyl) -2 -Dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-benzoylphenyl) -2-dimethylamino-2-benzyl-propane- -One, 1- (4-methylthiophenyl) -2-morpholino-2-methyl-propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-methyl) Phenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-methoxyphenyl) -propan-1-one, 1- (4-methylthiophenyl) 2-dimethylamino-2-methyl-3- (3,4-dimethoxyphenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4- Fluorophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (2-chlorophenyl) -propan-1-one, 1- ( 4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-chlorophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- ( 4-Bromophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-benzoylphenyl) -propan-1-one, 1,3-bis (4-Methylthiophenyl) -2-dimethylamino-2-methyl-propan-1-one, 1- (4-butylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one 1- (4-cyclohexylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-benzylthiophenyl) 2-dimethylamino-2-benzyl-propan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-dimethylaminophenyl)- 2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (2-chloropentenyl) -propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (N-methylindoline-5-yl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (N-butylphenoxazine-2 Yl) -2-morpholino-2-benzyl-propan-1-one, butan-1-one, 1-phenyl-2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylphenyl) 2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,5-dimethyl-4 -Methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,4-dimethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3 , 4,5-trimethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-hydroxyphenyl) -2-dimethylamino-2-benzyl-butane-1-one 1- [4- (2-hydroxyethoxy) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-allyloxyphenyl) -2-dimethylamino-2-benzyl- Butan-1-one, 1- (4-ethoxycarbonylmethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (1,1,2-trimethylpropyldimethylsilyloxy) Phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-chlorophenyl)- 2-dimethylamino-2-benzyl-butan-1-one, 1- (2,4-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, -(3,4-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,5-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1 -(4-bromophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-mercaptophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- ( 4-methylthiophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylthiophenyl) -2-dibutylamino-2-benzyl-butan-1-one, 1- (4- Methylthiophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butan-1-one, 1- [4- (2-methoxyethylthio) phenyl] -2-dimethyla No-2-benzyl-butan-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-octylthiophenyl) ) -2-Dimethylamino-2-benzyl-butan-1-one, 1- (4-methylsulfonylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (4- Methylphenylsulfonyl) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-benzenesulfonylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- ( 4-methylsulfinylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-aminophenyl) -2-dimethylamino-2-benzyl- Butan-1-one, 1- (4-methylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl- Butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-methylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino 2- (4-Isopropylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -butan-1-one, 1- (4 -Dimethylaminophenyl) -2-dimethylamino-2- (1-chlorohexenylmethyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethyla No-2- (2-pinen-10-yl) -butan-1-one, 1- (4-dimethylamino-2-methylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1 -(4-Dimethylamino-3-ethylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-diethylaminophenyl) -2-dimethylamino-2-benzyl-butane-1- ON, 1- (4-Isopropylaminophenyl) -2-dimethylamino-2-butyl-butan-1-one, 1- [4- (2-methoxyethylamino) phenyl] -2-dimethylamino-2-benzyl -Butan-1-one, 1- [4- (3-methoxypropylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-acetylaminophenyl) Nyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (N-acetylmethylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (N-acetyl-3-methoxypropylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-piperidinophenyl) -2-dimethylamino-2- Benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (3 , 4-Dimethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-ethylbenzyl) -butan-1-one, 1- (4-morphol Linophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-butylbenzyl) -butane-1- ON, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-isobutylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4- Dodecylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-hydroxymethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2 -Dimethylamino-2- (4-acetoxyethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4- Toxibenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-butoxybenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2- Dimethylamino-2- [4- (2-hydroxyethoxy) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2-methoxyethoxy) benzyl] -Butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- (2-methoxyethoxy) ethoxy) benzyl] -butan-1-one, 1- (4 -Morpholinophenyl) -2-dimethylamino-2- [4- (2- (2-methoxyethoxy) ethoxycarbonyl) benzyl] -butan-1-one, 1- (4-morpholino Enyl) -2-dimethylamino-2- [4- (2- (2- (2-methoxyethoxy) ethoxycarbonyl) ethyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2- Dimethylamino-2- [4- (2-bromoethyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2-diethylaminoethyl) benzyl]- Butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-trifluoroacetate, 1- (4-morpholinophenyl) -2-dimethylamino-2- Benzyl-butan-1-one-dodecylbenzenesulfonate, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butane-1- On-p-toluenesulfonate, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-camphorsulfonate, 1- (4-morpholinophenyl) -2-diethylamino-2-benzyl -Butan-1-one, 1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-butylmethyl Amino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) 2-dibutylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2- N-butane-1-one, 1- (3-chloro-4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2,6-dimethylmorpholine-4 -Yl) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,4-dimethyl-1,2,3,4-tetrahydroquinoxalin-6-yl) -2-dimethylamino 2-benzyl-butan-1-one, 1- (N-butylcarbazol-3-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,3-benzodioxy Sole-5-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,3-dihydrobenzofuran-5-yl) -2-dimethylamino-2-benzyl-butane-1- ON, 1- ( Santen-2-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,3-dihydro-2,3-dimethylbenzothiazol-5-yl) -2-dimethylamino-2 -Benzyl-butan-1-one, 2- (2-dimethylamino-2-benzyl-butanoyl) -fluorenone, 2- (2-dimethylamino-2-benzyl-butanoyl) -dibenzosuberone, 3,6-di (2-dimethylamino-2-benzyl-butanoyl) -9-butyl-carbazole and the like.

(Method for confirming adsorbed compounds)
Whether or not the above-mentioned adsorption compound is adsorbed on the surface of the back contact electrode 31 can be confirmed by, for example, the following method. First, the photoelectrode 11 to be analyzed is immersed in an alkaline solution for about several hours to several tens of hours, and the adsorbing compound adsorbed on the surface of the back contact electrode 31 is extracted. Next, the extract component is concentrated by removing the solvent from the extract by heating or reducing the pressure. In addition, you may perform the separation by chromatography as needed. Alternatively, the photoelectrode 11 to be analyzed may be immersed in a solution in which a reducing agent is dissolved for several hours to several tens of hours, and the adsorbed compound adsorbed on the surface of the back contact electrode 31 may be extracted.

  Next, the presence or absence of the adsorbed compound on the surface of the back contact electrode 31 can be determined by performing gas chromatograph (GC) analysis on the above-described extracted components and confirming the molecules of the adsorbed compound and fragments thereof. The extraction operation can also be confirmed by NMR analysis using a deuterium substitution solvent.

(Porous metal oxide layer)
For example, the porous metal oxide layer 32 is formed on the back contact electrode 31. A part of the back contact electrode surface may be exposed from the porous metal oxide layer 32. Further, the porous metal oxide layer 32 may partially penetrate in the thickness direction of the back contact electrode 31. Generally, as the thickness of the porous metal oxide layer 32 increases and the number of metal oxide fine particles contained per unit projected area increases, the actual surface area increases and the amount of dye that can be held per unit projected area increases. Therefore, the light absorptance with respect to incident light becomes high. On the other hand, when the thickness of the porous metal oxide layer 32 increases, the distance that electrons transferred from the sensitizing dye to the porous metal oxide layer 32 diffuse until reaching the back contact electrode 31 increases. Electron loss due to charge recombination in the metal oxide layer 32 also increases. Therefore, the porous metal oxide layer 32 has a preferable thickness, but generally it is preferably in the range of 0.1 μm to 100 μm, more preferably in the range of 1 μm to 30 μm. .

  The porous metal oxide layer 32 includes, for example, metal oxide fine particles as a main component, and may further include a binder as necessary. As the binder, for example, at least one of an organic binder and an inorganic binder can be used. As the inorganic binder, for example, a metal alkoxide or a hydrolyzate thereof, a metal salt, or the like can be used. As the organic binder, for example, polyvinyl alcohol, polyamideimide, polyvinylidene fluoride, or the like can be used. The kind of binder is not limited to these, Moreover, these can also be used in combination of 2 or more types.

As the metal alkoxide or a hydrolyzate thereof, for example, one represented by the following general formula (2) can be used.

  In the general formula (2), the metal alkoxide or a hydrolyzate thereof may be any of a monomer (m = 0), an oligomer (m = 1 to 10), and a polymer (m> 10). A mixture of more than one can also be used. M is a metal ion, titanium (Ti) ion, aluminum (Al) ion, silicon (Si) ion, vanadium (V) ion, zirconium (Zr) ion, niobium (Nb) ion, tantalum (Ta) ion, magnesium Preferably, it is at least one selected from the group consisting of (Mg) ions, silicon (Si) ions, boron (B) ions, tungsten (W) ions, tin (Sn) ions, and strontium (Sr) ions. . Examples of the alkoxy group include a methoxy group (n = 1), an ethoxy group (n = 2), an n-propoxy group, an i-propoxy group (n = 3), an n-butoxy group, an i-butoxy group, A sec-butoxy group, a tert-butoxy group (above, n = 4), a 2-ethylhexoxy group, and other alkoxy groups derived from lower and higher alcohols can be used. The alkoxide may be modified with β-diketones such as acetylacetone. A part of the alkoxy group may be substituted with a hydroxy group.

The metal oxide particles are preferably semiconductor fine particles. As a material for the semiconductor fine particles, for example, various compound semiconductors, compounds having a perovskite structure, and the like can be used in addition to an elemental semiconductor represented by silicon. These semiconductors are preferably n-type semiconductors in which conduction band electrons become carriers under photoexcitation and give an anode current. Specific examples of such semiconductors include titanium oxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), titanium strontium oxide (SrTiO ₃ ), And tin oxide (SnO ₂ ). Among these, anatase-type titanium oxide (TiO ₂ ) is particularly preferable. The kind of semiconductor is not limited to these, Moreover, these 2 types or more can also be mixed and used.

  Examples of the shape of the metal oxide particles include a spherical shape, an ellipsoidal shape, a needle shape, a plate shape, a scale shape, a tube shape, a rod shape, and an indefinite shape, but are not particularly limited thereto. In order to increase the specific surface area of the porous metal oxide layer 32, it is preferable that the average particle diameter of the primary particles is 1 nm or more and 100 nm or less. In order to impart a light diffusing function to the porous metal oxide layer 32, the primary particles may contain fine particles having an average particle diameter of more than 100 nm and 10000 nm or less. In order to improve the conductivity of the porous metal oxide layer 32, the primary particles have a needle shape, the average minor axis diameter of which is preferably greater than 0.1 μm and less than 1 μm, and the average Fine particles having a major axis length of preferably 1 μm or more and 10 μm or less may be contained. Moreover, it is preferable to add the organic filler or organic compound comprised only from organic substance to the composition for porous metal oxide layer formation. The porous property of the porous metal oxide layer 32 can be improved by burning off in the baking step described later. As a result, ions in the electrolytic solution can move more smoothly and conversion efficiency is improved. As the organic filler to be added, for example, a PMMA filler or a polystyrene filler having a particle size of 100 nm to 20 μm can be used. As the organic compound, for example, ethyl cellulose can be used.

(Counter electrode)
Any material can be used for the counter electrode 21 as long as it is a conductive material, but an insulating material can also be used if a conductive catalyst layer is provided on the side facing the photoelectrode 11. Is possible. However, as the material of the counter electrode 21, it is preferable to use an electrochemically stable material. Specifically, it is desirable to use platinum, gold, carbon, a conductive polymer, or the like. For the purpose of improving the catalytic effect of redox, it is preferable that the side facing the photoelectrode 11 has a fine structure and an increased surface area. In this case, it is desired to be in a porous state. The platinum black state can be formed by a method of anodizing platinum, a reduction treatment of a platinum compound, or the like, and the porous carbon can be formed by a method such as sintering of carbon fine particles or firing of an organic polymer. Moreover, it can also be used as a transparent counter electrode by wiring a metal having a high redox catalyst effect such as platinum on a transparent conductive substrate, or by reducing the surface of a platinum compound.

(Base material)
The substrate 12 for photoelectrodes is not particularly limited as long as it has transparency, and various substrates can be used. For example, a transparent inorganic substrate or plastic substrate is used. Can be used. Among these base materials, it is preferable to use a transparent plastic substrate in consideration of processability, lightness and the like. As the shape of the substrate, for example, a transparent film, sheet, substrate or the like can be used. As a material for this base material, a material excellent in barrier properties such as moisture and gas entering from the outside of the dye-sensitized solar cell, solvent resistance, and weather resistance is preferable. Examples of the material of the inorganic base material include quartz, sapphire, and glass. As a material for the plastic substrate, for example, a known polymer material can be used. Specific examples of known polymer materials include triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyamide (PA), and aramid. , Polyethylene (PE), polyacrylate, polyether sulfone, polysulfone, polypropylene (PP), diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin, urea resin, urethane resin, melamine resin And cycloolefin polymer (COP). Among these inorganic base materials and plastic base materials, it is particularly preferable to use a base material having a high transmittance in the visible light region, but is not limited thereto.

  The thickness of the substrate 12 is not particularly limited, and can be freely selected depending on the light transmittance, the shielding property between the inside and the outside of the dye-sensitized solar cell, and the like. Specifically, when a plastic substrate is used as the substrate 12, the thickness is preferably 38 μm to 500 μm from the viewpoint of productivity, but is not particularly limited to this range.

  The substrate 22 for the counter electrode is not particularly limited to a substrate having transparency, and an opaque substrate can be used, for example, an inorganic substrate or a plastic substrate having transparency or transparency. Various base materials can be used. As the material for the inorganic base material or the plastic base material, for example, those exemplified as the material for the above-mentioned photoelectrode base material 12 can be used in the same manner. It is also possible to use materials.

(Dye)
The dye to be carried on the porous metal oxide layer 32 is not particularly limited as long as it exhibits a sensitizing action. Cyanine dyes such as cryptocyanine, basic dyes such as phenosafranine, fog blue, thiocin, and methylene blue, and porphyrin compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, and others include azo dyes, phthalocyanine compounds, Examples include coumarin compounds, Ru bipyridine complex compounds, Ru terpyridine complex compounds, anthraquinone dyes, polycyclic quinone dyes, squarylium, and the like. Among these, Ru bipyridine complex compounds are particularly preferable because of their high quantum yield. However, the sensitizing dyes are not limited to these, and two or more kinds of these sensitizing dyes may be mixed and used. In consideration of the combination with the above-mentioned adsorption compound, it is preferable to use a dye that does not have a linear alkyl-based adsorption site. This is because the conversion efficiency can be improved by employing such a combination of an adsorbing compound and a dye. Examples of the dye having no linear alkyl-based adsorption site include ruthenium-based N719, Z991, Z907, organic dye-based D102, D149, D205 (manufactured by Mitsubishi Paper Industries), NKX-2587, NKX- One or more selected from the group consisting of 2677 (manufactured by Hayashibara Biochemical) and the like can be used.

  The method for adsorbing the dye to the porous metal oxide layer 32 is not particularly limited. For example, the sensitizing dye may be selected from alcohols, nitriles, nitromethane, halogenated hydrocarbons, ethers, dimethyl sulfoxide, amides, N -Dissolve in a solvent such as methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates, ketones, hydrocarbons, water, etc. and immerse the porous metal oxide layer 32 in this Or a dye solution can be applied onto the porous metal oxide layer 32. In addition, when a dye having high acidity is used, deoxycholic acid or the like may be added for the purpose of reducing association between the dye molecules. After adsorbing the sensitizing dye, the surface of the porous metal oxide layer 32 may be treated with amines for the purpose of promoting the removal of the excessively adsorbed sensitizing dye. Examples of amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine, and the like. When these are liquid, they may be used as they are, or may be used after being dissolved in an organic solvent.

(Electrolyte layer)
For example, the electrolyte layer 3 is provided between the porous metal oxide layer 32 and the counter electrode 21, but the porous metal oxide layer 32 and the counter electrode 21 may be impregnated with the electrolyte layer 3. The electrolyte layer 3 is composed of an electrolyte solution composed of an electrolyte and a solvent, for example. The electrolyte may be a combination of iodine (I ₂ ) and metal iodide or organic iodide, bromine (Br ₂ ) and metal bromide or organic bromide, ferrocyanate / ferricyanate, ferrocene / ferricene. Metal complexes such as sinium ion, sodium polysulfide, sulfur compounds such as alkyl thiol / alkyl disulfide, viologen dye, hydroquinone / quinone, and the like can be used. Lithium, Na, K, Mg, Ca, Cs and the like are preferable as the cation of the metal compound, and quaternary ammonium compounds such as tetraalkylammonium, pyridinium, and imidazolium are preferable as the cation of the organic compound. It is not limited, and two or more of these can be mixed and used. Among this, I ₂ and LiI, is NaI and imidazolium iodide electrolyte layer 3 that combines a quaternary ammonium compound such as preferred. The concentration of the electrolyte salt is preferably 0.05 to 5M, more preferably 0.2 to 3M with respect to the solvent. The concentration of I ₂ or Br ₂ is preferably 0.0005 to 1M, more preferably 0.001 to 0.3M. Moreover, you may add the additive which consists of an amine type compound represented by 4-tert- butyl pyridine for the purpose of improving an open circuit voltage.

  Examples of the solvent include water, alcohols, ethers, esters, carbonate esters, lactones, carboxylic acid esters, phosphate triesters, heterocyclic compounds, nitriles, ketones, amides, Nitromethane, halogenated hydrocarbons, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, hydrocarbons and the like, but are not limited thereto, A mixture of two or more of these can also be used. Furthermore, an ionic liquid of a tetraalkyl, pyridinium, or imidazolium quaternary ammonium salt can be used as the solvent.

  For the purpose of reducing leakage of dye-sensitized solar cells and volatilization of the electrolyte layer 3, in addition to dissolving the gelling agent, polymer, cross-linking monomer, etc. in the electrolyte, inorganic ceramic particles are dispersed and used as a gel electrolyte It is also possible to do. The ratio between the gel matrix and the electrolyte solution is that the ionic conductivity increases if the electrolyte solution is large, but the mechanical strength decreases. Conversely, if the electrolyte solution is too small, the mechanical strength increases but the ionic conductivity decreases. Therefore, the electrolytic solution is preferably 50 to 99% by mass, and more preferably 80 to 97% by mass of the gel electrolyte. It is also possible to realize an all-solid type dye-sensitized solar cell by dissolving the electrolyte solution and the plasticizer in a polymer and volatilizing and removing the plasticizer.

(Porous insulation layer)
The porous insulating layer 33 performs an insulating function with respect to the counter electrode 21. The porous insulating layer 33 is formed on the back contact electrode 31 on the side opposite to the side on which the porous metal oxide layer 32 is formed. The porous insulating layer 33 may partially penetrate in the thickness direction of the back contact electrode 31. The porous insulating layer 33 is made of, for example, oxide fine particles, and may further include a binder as necessary. As the binder, for example, at least one of an organic binder and an inorganic binder can be used. As the inorganic binder, for example, a metal alkoxide or a hydrolyzate thereof, a metal salt, or the like can be used. As the organic binder, for example, polyvinyl alcohol, polyamideimide, polyvinylidene fluoride, or the like can be used. The kind of binder is not limited to these, Moreover, these can also be used in combination of 2 or more types.

As a metal alkoxide or its hydrolyzate, what is shown by following General formula (3) can be used, for example.

  In the above general formula (3), the metal alkoxide or a hydrolyzate thereof may be any of a monomer (m = 0), an oligomer (m = 1 to 10), and a polymer (m> 10), and two or more types may be used. It can also be used as a mixture. M is a metal ion, titanium (Ti) ion, aluminum (Al) ion, silicon (Si) ion, vanadium (V) ion, zirconium (Zr) ion, niobium (Nb) ion, tantalum (Ta) ion, magnesium Preferably, it is at least one selected from the group consisting of (Mg) ions, silicon (Si) ions, boron (B) ions, tungsten (W) ions, tin (Sn) ions, and strontium (Sr) ions. . Examples of the alkoxy group include a methoxy group (n = 1), an ethoxy group (n = 2), an n-propoxy group, an i-propoxy group (n = 3), an n-butoxy group, an i-butoxy group, A sec-butoxy group, a tert-butoxy group (above, n = 4), a 2-ethylhexoxy group, and other alkoxy groups derived from lower and higher alcohols can be used. Moreover, the alkoxide may be modified with β-diketones such as acetylacetone. A part of the alkoxy group may be substituted with a hydroxy group.

As a material for the oxide fine particles, for example, at least one selected from the group consisting of silicon oxide (SiO ₂ ), zirconium oxide (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), and boron oxide (B ₂ O ₃ ). Types can be used. Further, the metal oxide material exemplified as the material of the porous metal oxide layer 32 may be used similarly as the material of the oxide fine particles. Examples of the shape of the oxide fine particles include a spherical shape, an ellipsoidal shape, a needle shape, a plate shape, a scale shape, a tube shape, a rod shape, and an indefinite shape, but are not particularly limited to these shapes. The particle diameter of the oxide fine particles can be, for example, in the range of 1 nm to 100 μm, but is not particularly limited to this range. Two or more kinds of fine particles having different particle diameters may be mixed and used.

  The thickness of the porous insulating layer 33 is not particularly limited as long as the insulating function with respect to the counter electrode 21 can be achieved. Usually, it is 10 nm or more and 500 μm or less. The porous insulating layer 33 only needs to perform an insulating function, and may not completely cover the back contact surface. Moreover, it is preferable to add the organic filler or organic compound comprised only from organic substance to the composition for porous insulating layer formation. The porous property of the porous insulating layer 33 can be improved by burning off in the baking step described later. As a result, ions in the electrolytic solution can move more smoothly and conversion efficiency is improved. As the organic filler to be added, for example, a PMMA filler or a polystyrene filler having a particle size of 100 nm to 20 μm can be used. As the organic compound, for example, ethyl cellulose can be used. The formation of the porous insulating layer 33 may be omitted. When the formation of the porous insulating layer 33 is omitted in this way, a separator is disposed on the back contact electrode 31 in order to avoid contact between the counter electrode 21 and the back contact electrode 31, or a spacer is provided in the electrolyte layer 3. It is preferable to add a filler.

[Operation of dye-sensitized solar cell]
Next, the operation of this dye-sensitized solar cell will be described.
The light L incident from the substrate 12 side for the photoelectrode passes through the substrate 12 and is absorbed by the dye of the porous metal oxide layer 32. The dye that has absorbed light becomes excited and can emit electrons. The electrons emitted from the dye are immediately injected from the dye into the metal oxide fine particle conduction band of the porous metal oxide layer 32, and then travel toward the back contact electrode 31. Next, the electrons pass through the back contact electrode 31 and go to the counter electrode 21 via the load 5. Then, the ions contained in the electrolyte layer 3 receive electrons, while the dye that has lost the electrons receives electrons from the ions in the electrolyte layer 3, and the ions that have released the electrons again receive electrons on the surface of the counter electrode 21. Due to this series of reactions, an electromotive force is generated between the photoelectrode 11 and the counter electrode 21. In this way, photoelectric conversion is performed.

[Action of adsorbed compound]
Next, the action of the adsorbing compound will be described.
FIG. 2 is a schematic diagram for explaining the action of the adsorbing compound adsorbed on the surface of the back contact electrode. FIG. 3 is a schematic diagram showing an enlarged surface of the back contact electrode shown in FIG. As shown in FIG. 2, the back contact electrode 31 has a mesh structure composed of a plurality of linear members 31a. On the surface of the linear member 31a, as shown in FIG. 3, dodencan which is an adsorption compound 31b. The acid is adsorbed. When the porous metal oxide layer 32 partially penetrates in the thickness direction of the back contact electrode 31, metal oxide particles 32a are present on the surface of the linear member 31a and in the vicinity thereof. A pigment 32b is supported on the surface of the metal oxide particles 32a. For example, a binder 32c is interposed between the linear member 31a and the metal oxide particles 32a.

Since the adsorption compound 31b is adsorbed on the surface of the linear member 31a, the approach of I ₃ ⁻ in the electrolyte layer to the surface of the linear member 31a can be suppressed. When the adsorbed compound has a structure represented by the above general formula (1), “X” is adsorbed on the surface of the linear member 31a, and “R” suppresses the approach of I ₃ ⁻ in the electrolyte layer. Fulfills the function of Therefore, reverse electron transfer from the back contact electrode 31 to the electrolyte layer 3 can be suppressed. Here, the case where the back contact electrode 31 has a mesh structure and the adsorption compound 31b is dodencanic acid has been described as an example, but the back contact electrode 31 and the adsorption compound 31b are not limited to this example.

[Production Method of Photoelectrode]
Next, an example of a method for manufacturing a photoelectrode according to the first embodiment of the present technology will be described.

(Formation of porous metal oxide layer)
First, metal oxide fine particles are dispersed in a solvent to prepare a metal oxide fine particle dispersion that is a composition for forming a porous metal oxide layer. Examples of the solvent include lower alcohols having 4 or less carbon atoms such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, t-butanol, ethylene glycol, propylene glycol (1,3-propanediol), 1, Aliphatic glycols such as 3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, ketones such as methyl ethyl ketone, dimethylethylamine Such amines can be used alone or in admixture of two or more, but are not particularly limited thereto. As the dispersion method, for example, a known method can be used. Specifically, for example, stirring treatment, ultrasonic dispersion treatment, bead dispersion treatment, kneading treatment, homogenizer treatment, etc. can be used. It is not limited to.

  Next, if necessary, the metal oxide fine particle dispersion is mixed with a binder and an organic filler or an organic compound to prepare a metal oxide fine particle dispersion containing the binder. In order to adjust the viscosity, a viscosity adjusting agent such as polyvinyl alcohol may be further added. However, when adding a viscosity modifier, it is preferable to bake off the viscosity modifier in a baking process, which is a subsequent step.

  Next, the prepared metal oxide fine particle dispersion is applied or printed on one of both surfaces of the back contact electrode 31, and then dried to volatilize the solvent. Thereby, the porous metal oxide layer 32 is formed on one surface of the back contact electrode 31. Examples of the coating method include a micro gravure coating method, a wire bar coating method, a direct gravure coating method, a die coating method, a dip method, a spray coating method, a reverse roll coating method, a curtain coating method, a comma coating method, a knife coating method, and a spin coating method. A coating method or the like can be used, but is not particularly limited thereto. Further, as the printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method and the like can be used, but not particularly limited thereto. .

(Formation of porous insulation layer)
First, oxide fine particles are dispersed in a solvent to prepare an oxide fine particle dispersion that is a composition for forming a porous insulating layer. Examples of the solvent include lower alcohols having 4 or less carbon atoms such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, t-butanol, ethylene glycol, propylene glycol (1,3-propanediol), 1, Aliphatic glycols such as 3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, ketones such as methyl ethyl ketone, dimethylethylamine Such amines can be used singly or in combination of two or more, but are not particularly limited thereto, and are not particularly limited thereto. As the dispersion method, for example, a known method can be used, and specifically, for example, stirring treatment, ultrasonic dispersion treatment, bead dispersion treatment, kneading treatment, homogenizer treatment, and the like can be used. Is not to be done.

  Next, if necessary, the oxide fine particle dispersion is mixed with a binder and an organic filler or an organic compound to prepare an oxide fine particle dispersion containing the binder. Next, the prepared oxide fine particle dispersion is applied or printed on the other side of the back contact electrode 31 opposite to the side on which the porous metal oxide layer 32 is formed, and then dried. As a result, the solvent is volatilized. Thereby, the porous insulating layer 33 is formed on the other surface of the back contact electrode 31. Examples of the coating method include a micro gravure coating method, a wire bar coating method, a direct gravure coating method, a die coating method, a dip method, a spray coating method, a reverse roll coating method, a curtain coating method, a comma coating method, a knife coating method, and a spin coating method. A coating method or the like can be used, but is not particularly limited thereto. Further, as the printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method and the like can be used, but not particularly limited thereto. .

(Baking)
Next, the photoelectrode 11 produced as described above is fired to improve the electronic connection between the metal oxide fine particles in the porous metal oxide layer 32. If the temperature is too high, the back contact electrode 31 may be deteriorated by heat. Therefore, the firing temperature is preferably 40 to 1000 ° C., more preferably about 40 to 600 ° C., particularly in this temperature range. It is not limited. The firing time is preferably about 30 seconds to 10 hours, but is not particularly limited to this time range.

  An organic filler or an organic compound composed only of an organic substance is added to at least one of the porous metal oxide layer 32 or the porous metal oxide layer 32 and the porous insulating layer 33 constituting the photoelectrode 11. It is preferable. By baking off in the main firing step, the porosity of the layer containing the organic filler or organic compound can be improved. As a result, ions in the electrolytic solution can move more smoothly and conversion efficiency is improved.

(Dye support)
Next, for example, a sensitizing dye is adsorbed on the porous metal oxide layer 32. As a method for adsorbing a sensitizing dye, for example, a solution in which a dye molecule is dissolved is prepared, and the photoelectrode 11 is immersed in the dye solution, or a dye solution is applied on the porous metal oxide layer 32. A method of evaporating the solvent after spraying or dripping the dye metal solution into the porous metal oxide layer 32 and then evaporating the solvent can be mentioned, but it is not particularly limited to these methods. A sensitizing dye may be adsorbed on the porous insulating layer 33.

(Preparation of treatment solution)
A treatment solution is prepared by dissolving the adsorbed compound in a solvent. Further, when the adsorbing compound is in a liquid state at room temperature or in a liquid state after being subjected to heat treatment or the like, the adsorbing compound can be used as it is as a treatment solution. When this treatment solution approaches the metal and / or metal oxide in the photoelectrode 11, for example, the adsorption compound in the treatment solution forms a covalent bond or a coordination bond with the surface of the back contact electrode 31, and the adsorption compound Adsorbed on the surface of the back contact electrode 31. Increasing the amount of adsorbed compound in the treatment solution improves the adsorption rate, so that the adsorbed compound concentration is preferably larger. Specifically, the concentration of the adsorbed compound with respect to the treatment solution is preferably in the range of 0.1 mM or more, more preferably 100 mM or more.

  As the solvent, a solvent capable of dissolving the adsorption compound at a predetermined concentration can be appropriately selected and used. Specifically, for example, acetonitrile, 3-methoxypropionitrile, 3,3-dimethoxypropionitrile ethoxypropionitrile, 3-ethoxypropionitrile, 3,3′-oxydipropionitrile, 3-aminopropyl Pionitrile, propionitrile, propyl cyanoacetate, 3-methoxypropyl isothiocyanate, 3-phenoxypropionitrile, p-anisidine 3- (phenylmethoxy) propanenitrile, methanol, ethanol, propanol, isopropyl alcohol, n-butanol, 2-butanol, isobutanol, t-butanol, ethylene glycol, triethylene glycol, 1-methoxy-ethanol, 1,1-dimethyl-2-methoxyethanol, 3-methoxy-1-propanol, dimethylformamide Benzene, toluene, o- xylene, m- xylene, p- xylene, chlorobenzene, dichlorobenzene, butyl acetate, ethyl acetate, cyclohexane, cyclohexanone, ethyl methyl ketone, acetone, and dimethylformamide. These solvents can be used alone or in combination.

(Photoelectrode surface treatment)
By treating the photoelectrode 11 with the treatment solution, the adsorbed compound is adsorbed on the photoelectrode 11, specifically, the back contact electrode 31. Examples of the processing method include a method of immersing the photoelectrode 11 in a processing solution, and a method of applying or printing a certain amount of the processing solution on the photoelectrode 11. Examples of the coating method include a micro gravure coating method, a wire bar coating method, a direct gravure coating method, a die coating method, a dip method, a spray coating method, a reverse roll coating method, a curtain coating method, a comma coating method, a knife coating method, and a spin coating method. A coating method or the like can be used, but is not particularly limited thereto. As the printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method, and the like can be used, but not particularly limited thereto.

  In the case of using the dipping method, a treatment solution is prepared so that the photoelectrode 11 is sufficiently immersed, and the photoelectrode 11 is immersed for 0.1 second to 48 hours. After the immersion, if necessary, the photoelectrode 11 may be washed with a good solvent for the adsorbed compound, and the unadsorbed compound remaining on the photoelectrode 11 may be washed away. Thereafter, the photoelectrode 11 is dried to complete. Further, while the photoelectrode 11 is immersed, heating and / or ultrasonic treatment may be performed to increase the adsorption rate of the adsorbing compound.

  When the coating method is used, a certain amount of processing solution is applied to the photoelectrode 11. At this time, the photoelectrode 11 may be used together with a treatment such as heating or ultrasonic waves. After application, the photoelectrode 11 may be washed with a non-adsorbed adsorbing compound with a good solvent for the adsorbing compound, if necessary. Thereafter, the photoelectrode 11 is naturally dried or dried in a heating device. Further, the application amount of the adsorbing compound does not need to be achieved by one application, and a desired application amount of the adsorbing compound may be achieved by repeating the above-described application process and washing process a plurality of times. The surface treatment step of the photoelectrode is preferably after the dye carrying step. If the surface treatment step of the photoelectrode is performed before the dye supporting step, the adsorbed compound is first adsorbed on the porous metal oxide layer 32, and it is difficult to adsorb the dye on the porous metal oxide layer 32. Because it becomes.

(assembly)
Next, the sealing material 4 is formed on the peripheral edge of the counter electrode base material 2. As a material of the sealing material 4, for example, a thermoplastic resin, a photocurable resin, a glass frit, or the like can be used, but the material is not limited to this. Next, the electrolyte layer 3 is formed in a region surrounded by the sealing material 4. Next, the counter electrode substrate 2 and the photoelectrode substrate 1 are bonded together via the sealing material 4. Thereby, the target dye-sensitized solar cell is obtained.

  According to the first embodiment, in the photoelectrode 11 that uses the back contact electrode 31 mainly composed of metal on the negative electrode side, the adsorbed compound is adsorbed on the surface of the back contact electrode 31. The reverse electron transfer from the surface to the electrolyte layer 3 can be suppressed. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved.

  Further, the reverse electron transfer from the surface of the back contact electrode 31 to the electrolyte layer 3 can be suppressed only by treating the photoelectrode 11 with the treatment solution containing the adsorption compound and causing the adsorption compound to be adsorbed on the surface of the back contact electrode 31. Can do. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved by a simple process.

<2. Second Embodiment>
FIG. 4 is a cross-sectional view illustrating an example of the configuration of the dye-sensitized solar cell according to the second embodiment of the present technology. As shown in FIG. 4, the dye-sensitized solar cell according to the second embodiment is different in that it further includes a porous intermediate layer 34 between the back contact electrode 31 and the porous metal oxide layer 32. It differs from that of one embodiment.

(Porous intermediate layer)
For example, the porous intermediate layer 34 is formed on the back contact electrode 31. The porous intermediate layer 34 may penetrate in the thickness direction of the back contact electrode 31 or may penetrate completely to the back side of the back contact electrode 31. The porous intermediate layer 34 improves the conversion efficiency by guiding the photocurrent generated in the porous metal oxide layer 32 to the back contact electrode 31 without loss. Therefore, the porous intermediate layer 34 must be a conductor. In order to improve the conversion efficiency, it is preferable to match the energy levels of the porous metal oxide layer 32 and the porous intermediate layer 34. From the viewpoint of improving the conversion efficiency, the porous intermediate layer 34 is preferably formed continuously over the entire interface between the back contact electrode 31 and the porous metal oxide layer 32. It may be distributed discontinuously in the form of islands at the interface.

  On the other hand, when the porous intermediate layer 34 is not formed, the photocurrent from the porous metal oxide layer 32 present at the opening portion present in the back contact electrode 31 is lost. When the opening is large, the effect of suppressing the current collection loss due to the formation of the porous intermediate layer 34 is particularly remarkable.

  The difference in work function between the porous intermediate layer 34 and the porous metal oxide layer 32 after the firing step described later is preferably within a range of 0.9 eV or less. This is because if it exceeds 0.9 eV, the photoelectric conversion efficiency tends to deteriorate.

  The work function of each layer of the porous intermediate layer 34 and the porous metal oxide layer 32 is obtained by, for example, separately preparing samples formed up to the respective layers, and performing ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, or Auger electron spectroscopy. Evaluate by law. Alternatively, the photoelectrode 11 may be sliced with a microtome or the like, and each layer may be evaluated by ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, or Auger electron spectroscopy. Moreover, the cross section of the photoelectrode 11 may be produced by a microtome or the like, and this may be used as a test piece to evaluate each layer by Auger electron spectroscopy. When the photoelectrode 11 is loaded with a dye, the evaluation may be performed after the dye is detached from the photoelectrode 11. For example, the dye is detached by immersing the dye-supported photoelectrode 11 in a 10-4 M NaOH ethanol solution for a predetermined time.

  The porous intermediate layer 34 is made of conductive fine particles, and may further include a binder (binder) as necessary. As the binder, for example, at least one of an organic binder and an inorganic binder can be used. As the inorganic binder, for example, a metal alkoxide or a hydrolyzate thereof, a metal salt, or the like can be used. As the organic binder, for example, polyvinyl alcohol, polyamideimide, polyvinylidene fluoride, or the like can be used. The kind of binder is not limited to these, Moreover, these can also be used in combination of 2 or more types.

As a metal alkoxide or its hydrolyzate, what is shown by following General formula (4) can be used, for example.

  In the general formula (4), the metal alkoxide or a hydrolyzate thereof may be any of a monomer (m = 0), an oligomer (m = 1 to 10), and a polymer (m> 10), and two or more types Can also be used in combination. M is a metal ion, titanium (Ti) ion, aluminum (Al) ion, silicon (Si) ion, vanadium (V) ion, zirconium (Zr) ion, niobium (Nb) ion, tantalum (Ta) ion, magnesium Preferably, it is at least one selected from the group consisting of (Mg) ions, silicon (Si) ions, boron (B) ions, tungsten (W) ions, tin (Sn) ions, and strontium (Sr) ions. . Examples of the alkoxy group include a methoxy group (n = 1), an ethoxy group (n = 2), an n-propoxy group, an i-propoxy group (n = 3), an n-butoxy group, an i-butoxy group, sec- A butoxy group, a tert-butoxy group (n = 4), a 2-ethylhexoxy group, and other alkoxy groups derived from lower and higher alcohols can be used. Moreover, the alkoxide may be modified with β-diketones such as acetylacetone. A part of the alkoxy group may be substituted with a hydroxy group.

The conductor fine particles are, for example, selected from the group consisting of metal fine particles mainly composed of metal, metal oxide fine particles mainly composed of metal oxide, and metal oxide-coated fine particles coated with metal oxide. More than seeds can be used. Specifically, for example, metal fine particles, metal oxide fine particles, or metal oxide-coated fine particles can be used as the conductive fine particles. Two or more kinds of metal fine particles may be used as the metal fine particles. Two or more kinds of metal oxide fine particles may be used as the metal oxide fine particles. Two or more kinds of metal oxide fine particles may be used as the metal oxide-coated fine particles. As the metal material of the metal fine particles, for example, one or more selected from the group consisting of Ti, W, Ta, Nb, Zr, Zn, Ni, Cu, Cr and Fe can be used. Specifically, for example, as the metal material of the metal fine particles, a simple substance such as Ti, W, Ta, Nb, Zr, Zn, Ni, Cu, Cr, Fe, or an alloy containing two or more of these can be used. . As the alloy, it is preferable to use stainless steel (SUS), NiCu alloy, NiCr alloy or the like. As stainless steel, it is preferable to use SUS304, SUS304L, SUS310S, SUS316, SUS316L, SUS317L, SUS321, SUS347, or the like. As the metal oxide material of the metal oxide fine particles and the metal oxide-coated fine particles, conductive metal oxides are preferably used. For example, indium-tin composite oxide (ITO), fluorine-doped SnO ₂ (FTO), antimony 1 selected from the group consisting of doped SnO ₂ (ATO), SnO ₂ , ZnO, indium-zinc composite oxide (IZO), aluminum-zinc composite oxide (AZO), and gallium-zinc composite oxide (GZO). What consists of more than a kind can be used.

  Although the thickness of the porous intermediate | middle layer 34 is 10 nm or more and 500 micrometers or less, for example, what is necessary is just the thickness which can show | play the said function, and it does not specifically limit. The particle diameter of the conductive fine particles is, for example, 1 nm or more and 100 μm or less, but is not particularly limited, and two or more kinds of conductive fine particles having different particle diameters may be mixed and used. Moreover, it is preferable to add the organic filler or organic compound comprised only from organic substance to the composition for porous intermediate | middle layer formation. The porous property of the porous intermediate layer 34 can be improved by baking off in a baking step described later. As a result, ions in the electrolytic solution can move more smoothly and conversion efficiency is improved. As the organic filler to be added, for example, a PMMA (polymethyl methacrylate) filler having a particle size of 100 nm to 20 μm, a polystyrene filler, and the like can be used. As the organic compound, for example, ethyl cellulose can be used. The adsorbing compound may be adsorbed on the porous intermediate layer 34. Specifically, for example, an adsorbing compound may be adsorbed on the surface of the conductive fine particles contained in the porous intermediate layer 34. Thereby, reverse electron transfer from the porous intermediate layer 34 to the electrolyte layer 3 can be suppressed. As the adsorbing compound, the same one as in the first embodiment can be used.

(Method for forming porous intermediate layer)
First, conductive fine particles are dispersed in a solvent to prepare a conductive fine particle dispersion that is a composition for forming a porous intermediate layer. Examples of the solvent include lower alcohols having 4 or less carbon atoms such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, t-butanol, ethylene glycol, propylene glycol (1,3-propanediol), 1, Aliphatic glycols such as 3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, ketones such as methyl ethyl ketone, dimethylethylamine Such amines can be used singly or in combination of two or more, but are not particularly limited thereto, and are not particularly limited thereto. As the dispersion method, for example, a known method can be used. Specifically, for example, stirring treatment, ultrasonic dispersion treatment, bead dispersion treatment, kneading treatment, homogenizer treatment, etc. can be used. It is not limited to.

  Next, if necessary, a binder and an organic filler or an organic compound are mixed with the conductor fine particle dispersion to prepare a conductor fine particle dispersion containing the binder. Next, the prepared conductive fine particle dispersion is applied or printed on one of both surfaces of the back contact electrode 31, and then dried to volatilize the solvent. Thereby, the porous intermediate layer 34 is formed on one surface of the back contact electrode 31. Examples of the coating method include a micro gravure coating method, a wire bar coating method, a direct gravure coating method, a die coating method, a dip method, a spray coating method, a reverse roll coating method, a curtain coating method, a comma coating method, a knife coating method, and a spin coating method. A coating method or the like can be used, but is not particularly limited thereto. Further, as the printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method and the like can be used, but it is not particularly limited thereto. .

  Other than the above are the same as in the dye-sensitized solar cell according to the first embodiment.

  According to the second embodiment, since the porous intermediate layer 34 is formed between the back contact electrode 31 and the porous metal oxide layer 32 of the photoelectrode 11, the opening existing in the back contact electrode 31 is formed. Current collection loss at the eyes can be suppressed. When the photoelectrode 11 having the above configuration is applied to a dye-sensitized solar cell, the conversion efficiency can be improved.

  The porous intermediate layer 34 and the porous metal oxide layer 32 can be formed by a coating process. That is, the photoelectrode 11 having the above-described configuration can be manufactured by a coating manufacturing process, specifically, for example, a roll to roll coating manufacturing process. Therefore, since all the photoelectrodes 11 can be formed by a wet process, productivity improvement and cost reduction of the dye-sensitized solar cell can be realized.

<3. Third Embodiment>
FIG. 5 is a cross-sectional view illustrating an example of the configuration of the dye-sensitized solar cell according to the third embodiment of the present technology. As shown in FIG. 5, the current collector base material mainly composed of metal is used as the base material 12, and the light is taken into the dye-sensitized solar cell from the counter electrode base material 2 side. Is different.

  The photoelectrode substrate 1 includes a substrate 12 and a porous metal oxide layer 32 formed on the substrate 12. The photoelectrode substrate 1 may further include a porous insulating layer 33 on the porous metal oxide layer 32 as necessary.

  Examples of the metal of the base material 12 include simple substances such as Al, Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, and Fe, or alloys containing two or more of these. As the alloy, nickel alloys such as stainless steel (SUS), NiCu alloy, NiCr alloy, etc. are preferably used. As stainless steel, it is preferable to use SUS304, SUS304L, SUS310S, SUS316, SUS316L, SUS317L, SUS321, SUS347, or the like.

  The adsorption compound is adsorbed on the surface of the substrate 12 on which the porous metal oxide layer 32 is formed. As this adsorption compound, the same compound as that used for the surface of the back contact electrode 31 in the first embodiment can be used.

  As the material of the counter electrode 21, a metal having catalytic ability such as platinum or palladium can be used, and it is preferable to use these materials in consideration of light transmittance. As a method for forming the counter electrode 21, for example, a vapor deposition method, a sputtering method, or the like can be used, and the thickness thereof is preferably in the range of several nm to several hundred nm, for example, but is not limited thereto. Absent. The counter electrode 21 may have a mesh structure or a stripe structure.

  The substrate 22 is not particularly limited as long as it has transparency, for example, and various substrates can be used. For example, the substrate 12 of the photoelectrode substrate 1 in the first embodiment. The same can be used.

When the sheet resistance of the counter electrode 21 having catalytic ability is high, a transparent conductive layer may be further formed between the counter electrode 21 and the substrate 22. As the material of the transparent conductive layer, known materials can be used. For example, it is preferable to use a metal oxide or carbon having good conductivity. Examples of the metal oxide include indium-tin composite oxide (ITO), fluorine-doped SnO ₂ (FTO), antimony-doped SnO ₂ (ATO), SnO ₂ , ZnO, indium-zinc composite oxide (IZO), and aluminum. -One or more types selected from the group consisting of zinc composite oxide (AZO) and gallium-zinc composite oxide (GZO) can be used.

  Further, the wiring may be formed in a mesh shape or a stripe shape instead of the transparent conductive layer. As the wiring material, for example, one or more selected from the group consisting of Al, Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, and Fe can be used. Specifically, examples of the metal include, for example, a simple substance such as Al, Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, Fe, or an alloy containing two or more of these. . As the alloy, it is preferable to use a nickel alloy such as a NiCu alloy or a NiCr alloy.

  Other than the above are the same as in the dye-sensitized solar cell according to the first embodiment.

  According to the third embodiment, since the current collecting base material containing metal as a main component is used as the base material 12 and the adsorbing compound is adsorbed on the surface of the current collecting base material, the base as the current collecting base material is used. Reverse electron transfer from the surface of the material 12 to the electrolyte layer 3 can be suppressed. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved.

<4. Fourth Embodiment>
FIG. 6A is a cross-sectional view illustrating an example of a configuration of a dye-sensitized solar cell according to a fourth embodiment of the present technology. FIG. 6B is a perspective view showing an example of the configuration of the photoelectrode of the dye-sensitized solar cell shown in FIG. 6A. This dye-sensitized solar cell is a so-called dye-sensitized photoelectric conversion element module. In this dye-sensitized solar cell, a plurality of stripe-shaped transparent conductive layers 35 are formed in parallel with each other on a substrate 12. Further, a plurality of striped transparent conductive layers 23 are formed on the base material 22 so as to face the transparent conductive layer 35 in parallel to the transparent conductive layer 35 and in parallel to each other with the same width as the transparent conductive layer 35. ing. In this case, the transparent conductive layer 35 and the transparent conductive layer 23 are shifted from each other by a predetermined distance in a direction perpendicular to the extending direction. Between the transparent conductive layer 35 and the transparent conductive layer 23 facing each other, a porous metal oxide layer 32 and a counter electrode 21 as a catalyst electrode layer are provided to face each other with the electrolyte layer 3 therebetween. A dye-sensitized photoelectric conversion element is formed. The porous metal oxide layer 32 and the counter electrode 21 have a long rectangular shape in a direction parallel to the transparent conductive layer 35 and the transparent conductive layer 23.

  The porous metal oxide layer 32 is in electrical contact with the transparent conductive layer 35, and the counter electrode 21 is in electrical contact with the transparent conductive layer 23. In a portion between two adjacent dye-sensitized photoelectric conversion elements, the transparent conductive layer 35 of one dye-sensitized photoelectric conversion element and the transparent conductive layer 23 of another dye-sensitized photoelectric conversion element are the same. The terminal portions are electrically connected to each other by the collecting electrode 6. As a result, the plurality of dye-sensitized photoelectric conversion elements are electrically connected to each other in series. The number of dye-sensitized photoelectric conversion elements connected in series is selected as necessary. In this case, the current collecting electrode 6 is provided along one side in the longitudinal direction of the porous metal oxide layer 32.

  The current collecting electrode 6 may include a first current collecting electrode 6a and a second current collecting electrode 6b, and the current collecting electrode 6 may be formed by electrically joining the tip portions thereof. . In this case, the first collector electrode 6a is formed in advance on the photoelectrode substrate 1, the second collector electrode 6b is formed in advance on the counter electrode substrate 2, and the photoelectrode substrate 1 and the counter electrode substrate 2 are connected. In the combining step, the first current collecting electrode 6a and the second current collecting electrode 6b are electrically connected.

  The current collecting electrode 6 is mainly composed of metal, for example. Examples of the metal include simple substances such as Al, Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, and Fe, or alloys containing two or more of these. As the alloy, nickel alloys such as stainless steel (SUS), NiCu alloy, NiCr alloy, etc. are preferably used. As stainless steel, it is preferable to use SUS304, SUS304L, SUS310S, SUS316, SUS316L, SUS317L, SUS321, SUS347, or the like.

  An adsorbed compound is adsorbed on the surface of the current collecting electrode 6 that contacts the electrolyte layer 3. Further, the adsorption compound may be adsorbed on the surface of the transparent conductive layer 35 on which the porous metal oxide layer 32 is formed. As the adsorbing compound, the same compound as that used for the surface of the back contact electrode 31 in the first embodiment can be used.

As the material of the transparent conductive layers 23 and 35, known materials can be used. For example, it is preferable to use a metal oxide having good conductivity. Examples of the metal oxide include indium-tin composite oxide (ITO), fluorine-doped SnO ₂ (FTO), antimony-doped SnO ₂ (ATO), SnO ₂ , ZnO, indium-zinc composite oxide (IZO), and aluminum. -One or more types selected from the group consisting of zinc composite oxide (AZO) and gallium-zinc composite oxide (GZO) can be used.

  Further, instead of the transparent conductive layers 23 and 35, the wiring may be formed in a mesh shape or a stripe shape. As the wiring material, for example, one or more selected from the group consisting of Al, Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, and Fe can be used. Specifically, examples of the metal include, for example, a simple substance such as Al, Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, Fe, or an alloy containing two or more of these. . As the alloy, it is preferable to use a nickel alloy such as a NiCu alloy or a NiCr alloy.

  Other than the above are the same as in the dye-sensitized solar cell according to the first embodiment.

  According to the fourth embodiment, the adsorbed compound is adsorbed on the surface of the current collecting electrode 6 that is in contact with the electrolyte layer 3, so that the back electrons from the surface of the current collecting electrode 6 to the electrolyte layer 3 are absorbed. Movement can be suppressed. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved.

  Further, when an adsorbing compound is adsorbed on the surface of the transparent conductive layer 35 on which the porous metal oxide layer 32 is formed, reverse electron transfer from the surface of the transparent conductive layer 35 to the electrolyte layer 3 is suppressed. can do. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved.

  It is preferable that the adsorbed compound is adsorbed on at least one of the surface of the collecting electrode 6 that contacts the electrolyte layer 3 and the surface of the transparent conductive layer 35 on which the porous metal oxide layer 32 is formed. From the viewpoint of improving the conversion efficiency, it is preferable to adsorb the adsorbing compound on both surfaces described above.

<5. Fifth Embodiment>
FIG. 7A is a cross-sectional view illustrating an example of a configuration of a dye-sensitized solar cell according to a fifth embodiment of the present technology. FIG. 7B is a perspective view showing an example of the configuration of the photoelectrode of the dye-sensitized solar cell shown in FIG. 7A. This dye-sensitized solar cell is a so-called dye-sensitized photoelectric conversion element module. In this dye-sensitized solar cell, a transparent conductive layer 35 is formed on a substrate 12, and a plurality of stripe-shaped porous metal oxide layers 32 are formed on the transparent conductive layer 35 in parallel with each other. A transparent conductive layer 23 is formed on the substrate 22, and a striped counter electrode 21 is formed on the transparent conductive layer 23. The porous metal oxide layer 32 and the counter electrode 21 are formed at opposing positions. On the surface of the porous metal oxide layer 32, the current collector wiring 7 is formed at a portion between the adjacent porous metal oxide layers 32. The current collector wiring 7 is formed in parallel with the striped porous metal oxide layer 32.

  The current collector wiring 7 is mainly composed of metal, for example. Examples of the metal include simple substances such as Al, Ti, W, Mo, Ta, Nb, Zr, Zn, Ni, Cr, and Fe, or alloys containing two or more of these. As the alloy, nickel alloys such as stainless steel (SUS), NiCu alloy, NiCr alloy, etc. are preferably used. As stainless steel, it is preferable to use SUS304, SUS304L, SUS310S, SUS316, SUS316L, SUS317L, SUS321, SUS347, or the like.

  An adsorbing compound is adsorbed on the surface of the current collector wiring 7 that contacts the electrolyte layer 3. Further, the adsorption compound may be adsorbed on the surface of the transparent conductive layer 35 on which the porous metal oxide layer 32 is formed. As the adsorbing compound, the same compound as that used for the surface of the back contact electrode 31 in the first embodiment can be used.

  Except for the above, this is the same as the dye-sensitized solar cell according to the fourth embodiment.

  According to the fifth embodiment, the adsorbed compound is adsorbed on the surface of the current collector wiring 7 that is in contact with the electrolyte layer 3, so that the back electrons from the surface of the current collector wiring 7 to the electrolyte layer 3 are absorbed. Movement can be suppressed. Therefore, the conversion efficiency of the dye-sensitized solar cell can be improved.

  It is preferable that the adsorbing compound is adsorbed on at least one of the surface of the current collector wiring 7 in contact with the electrolyte layer 3 and the surface of the transparent conductive layer 35 on which the porous metal oxide layer 32 is formed. From the viewpoint of improving the conversion efficiency, it is preferable to adsorb the adsorbing compound on both surfaces described above.

  Hereinafter, the present technology will be specifically described by way of examples. However, the present technology is not limited only to these examples.

Example 1
(Formation of Ti porous intermediate layer)
The Ti porous intermediate layer was produced as follows.
First, Ti powder with a particle size of 45 μm (trade name: TS-450, manufactured by Toho Titanium Co., Ltd.) is used with a paint shaker and SUS beads of φ3 mm so that the content of Ti powder is 30% by mass. Dispersed in (IPA). The bead dispersion treatment time was 24 hours. Next, butoxy titanium dimer (Mitsubishi Gas Chemical Co., Ltd., trade name: DBT) was mixed with this so that the mass ratio of Ti powder and butoxy titanium dimer was 1: 1, and stirred to make it uniform. . Thereby, a Ti fine particle dispersion was prepared. Next, SUS316 mesh (manufactured by Taiyo Wire Mesh Co., Ltd., 400 mesh, twill, wire diameter 30 μm, opening 34 μm) was prepared as a back contact electrode. Next, after the prepared Ti fine particle dispersion was applied on a SUS316 mesh with a coil bar of count 44, it was heated in air at 150 ° C. for 30 minutes. Thereby, a Ti porous intermediate layer was formed on the SUS316 mesh.

(Formation of TiO ₂ porous layer)
The TiO ₂ porous layer was produced as follows.
First, first TiO ₂ fine particles (manufactured by Degussa, trade name: P25, a mixture of anatase type crystal (80% by mass) and rutile type crystal (20% by mass), average particle size of primary particles: about 21 nm), A first TiO ₂ dispersion was prepared by mixing with ethanol so that the content of TiO ₂ fine particles was 30% by mass, and performing bead dispersion treatment using agitator and zirconia beads having a diameter of 0.65 mm for 24 hours. . Next, the second TiO ₂ fine particles (manufactured by Fuji Titanium Industry Co., Ltd., trade name: TA-300, anatase type crystal, average particle size of primary particles: about 390 nm), titanium oxide content becomes 20% by mass. In this way, the mixture was mixed with ethanol and subjected to bead dispersion treatment using agitator and zirconia beads having a diameter of 0.65 mm for 24 hours to prepare a _second TiO ₂ dispersion. Next, the first TiO ₂ dispersion, the second TiO ₂ dispersion, butoxytitanium dimer (trade name: DBT, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and ethanol are mixed to be uniform. A TiO ₂ fine particle dispersion was prepared by stirring. The concentration of the first TiO ₂ fine particles (P25) is 8.75% by mass, the concentration of the second TiO ₂ fine particles (TA-300) is 8.75% by mass, and the concentration of butoxytitanium dimer (DBT) is 2.5. It was set as mass%. Next, the prepared TiO ₂ fine particle dispersion was applied onto the Ti porous intermediate layer with a coil bar having a count of 44, and then dried in the atmosphere at 80 ° C. for 2 minutes. As a result, a TiO ₂ porous layer was formed on the Ti porous intermediate layer.

(Formation of TiO ₂ porous insulating layer)
The TiO ₂ porous insulating layer was produced as follows.
First, a TiO ₂ fine particle dispersion was prepared in the same manner as the TiO ₂ porous layer forming step. Next, the prepared TiO ₂ fine particle dispersion was applied on the SUS316 mesh on the side opposite to the side on which the Ti porous intermediate layer and the TiO ₂ porous layer were laminated with the coil bar of the count 44, and then in the atmosphere 80 A TiO ₂ porous insulating layer was formed by drying at 2 ° C. for 2 minutes.
Thus, a photoelectrode composed of a TiO ₂ porous insulating layer, a SUS mesh, a Ti porous intermediate layer, and a TiO ₂ porous layer was obtained.

(Baking, dye support)
Next, the photoelectrode obtained as described above was baked at 500 ° C. for 30 minutes in the atmosphere. Next, a sensitizing dye (Z991) represented by the following structural formula (5) and dodecylphosphonic acid were dissolved in a solvent at a ratio of 0.1 mM and 0.025 mM, respectively, to prepare a dye solution. As the solvent, a mixed solvent in which acetonitrile and t-butanol were mixed at a volume ratio of 1: 1 was used. Next, the sensitizing dye was supported on the photoelectrode by immersing the photoelectrode in the prepared dye solution for 18 hours. As described above, the dye solution contains dodecylphosphonic acid, but it is considered that dodecylphosphonic acid is almost adsorbed on the TiO ₂ porous layer. This concentration of dodecyl phosphonic acid dye solution is very thin and, dodecyl phosphonic acid, when compared to the SUS mesh (metal) TiO ₂ porous layer (metal oxide), TiO ₂ porous It is because it is thought that it adsorb | sucks preferentially to a layer.

(surface treatment)
Next, after taking out the photoelectrode from the dye solution, it was immediately rinsed with acetonitrile to remove the unsupported dye and allowed to dry naturally. Next, dodecanoic acid (CH ₃ (CH ₂ ) ₁₀ COOH) as an adsorbing compound is dissolved to a concentration of 100 mM in a solvent in which acetonitrile and t-butanol are mixed at a volume ratio of 1: 1. Thus, a treatment solution was prepared. Dodecanoic acid was adsorbed on the photoelectrode by immersing the photoelectrode in this treatment solution for 4 hours. Thereby, the target photoelectrode was obtained.

(assembly)
Next, the photoelectrode obtained as described above was cut into a size of 15 mm × 25 mm using scissors. Next, a counter electrode was prepared by sequentially stacking a chromium (Cr) layer having a thickness of 50 nm and a platinum (Pt) layer having a thickness of 100 nm on a glass substrate in advance by sputtering. Next, a silicone rubber sheet having a thickness of 50 μm and having a 7 mm × 10 mm square hole was stuck on the platinum (Pt) layer.

Next, as the electrolyte, methoxyacetonitrile, 1.4 M iodide (1-propyl-3-methylimidazolium), 0.15 M iodine, 0.1 M sodium iodide, 0.2 M 4 A gel electrolyte in which a solution in which -tert-butyl-pyridine is dissolved and SiO ₂ fine particles (manufactured by Degussa, trade name: R805, BET specific surface area 150 ± 25 m ² / g) are mixed at a mass ratio of 92: 8 Prepared. An appropriate amount of this was deposited on the Pt layer in the square hole portion of the silicone rubber sheet.

Next, the photoelectrode was arrange | positioned so that the square hole of the silicone rubber sheet on Pt layer might be covered. Here, the TiO ₂ porous insulating layer and the Pt layer face each other. A glass substrate was placed on the TiO ₂ porous layer of the photoelectrode, and the glass substrate and the glass substrate of the counter electrode were clipped. Thereby, the target back contact type dye-sensitized solar cell was obtained.

(Example 2)
A back contact type dye-sensitized solar cell was obtained in the same manner as in Example 1 except that caproic acid “CH ₃ (CH ₂ ) ₄ COOH” as an adsorbing compound was dissolved in a solvent to a concentration of 100 mM.

(Example 3)
A back contact type dye-sensitized solar cell was obtained in the same manner as in Example 1 except that stearic acid “C ₁₇ H ₃₅ COOH” as an adsorbing compound was dissolved in a solvent to a concentration of 66 mM.

Example 4
A back contact type dye-sensitized solar cell was obtained in the same manner as in Example 1 except that dodecylphosphonic acid “C ₁₂ H ₂₅ PO (OH) ₂ ” as an adsorbing compound was dissolved in a solvent to a concentration of 66 mM.

(Comparative Example 1)
A back contact type dye-sensitized solar cell was obtained in the same manner as in Example 1 except that the surface treatment of the photoelectrode with the treatment solution was omitted.

(Comparative Example 2)
(Formation of Ti porous intermediate layer)
The Ti porous intermediate layer was produced as follows.
First, Ti powder with a particle size of 45 μm (trade name: TS-450, manufactured by Toho Titanium Co., Ltd.) is used with a paint shaker and SUS beads of φ3 mm so that the content of Ti powder is 30% by mass. Dispersed in (IPA). The bead dispersion treatment time was 24 hours. Next, butoxy titanium dimer (Mitsubishi Gas Chemical Co., Ltd., trade name: DBT) was mixed with this so that the mass ratio of Ti powder and butoxy titanium dimer was 1: 1, and stirred to make it uniform. . Thereby, a Ti fine particle dispersion was prepared. Next, SUS316 mesh (manufactured by Taiyo Wire Mesh Co., Ltd., 400 mesh, twill, wire diameter 30 μm, opening 34 μm) was prepared as a back contact electrode. Next, after the prepared Ti fine particle dispersion was applied on a SUS316 mesh with a coil bar of count 44, it was heated in air at 150 ° C. for 30 minutes. Thereby, a Ti porous intermediate layer was formed on the SUS316 mesh.

(Formation of TiO ₂ porous layer)
The TiO ₂ porous layer was produced as follows.
First, first TiO ₂ fine particles (manufactured by Degussa, trade name: P25, a mixture of anatase type crystal (80% by mass) and rutile type crystal (20% by mass), average particle size of primary particles: about 21 nm), A first TiO ₂ dispersion was prepared by mixing with ethanol so that the content of TiO ₂ fine particles was 30% by mass, and performing bead dispersion treatment using agitator and zirconia beads having a diameter of 0.65 mm for 24 hours. . Next, the second TiO ₂ fine particles (manufactured by Fuji Titanium Industry Co., Ltd., trade name: TA-300, anatase type crystal, average particle size of primary particles: about 390 nm), titanium oxide content becomes 20% by mass. In this way, the mixture was mixed with ethanol and subjected to bead dispersion treatment using agitator and zirconia beads having a diameter of 0.65 mm for 24 hours to prepare a _second TiO ₂ dispersion. Next, the first TiO ₂ dispersion, the second TiO ₂ dispersion, butoxytitanium dimer (trade name: DBT, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and ethanol are mixed to be uniform. A TiO ₂ fine particle dispersion was prepared by stirring. The concentration of the first TiO ₂ fine particles (P25) is 8.75% by mass, the concentration of the second TiO ₂ fine particles (TA-300) is 8.75% by mass, and the concentration of butoxytitanium dimer (DBT) is 2.5. It was set as mass%. Next, the prepared TiO ₂ fine particle dispersion was applied onto the Ti porous intermediate layer with a coil bar having a count of 44, and then dried in the atmosphere at 80 ° C. for 2 minutes. As a result, a TiO ₂ porous layer was formed on the Ti porous intermediate layer.

(Formation of TiO ₂ porous insulating layer)
The TiO ₂ porous insulating layer was produced as follows.
First, a TiO ₂ fine particle dispersion was prepared in the same manner as the TiO ₂ porous layer forming step. Next, the prepared TiO ₂ fine particle dispersion was applied on the SUS316 mesh on the side opposite to the side on which the Ti porous intermediate layer and the TiO ₂ porous layer were laminated with the coil bar of the count 44, and then in the atmosphere 80 A TiO ₂ porous insulating layer was formed by drying at 2 ° C. for 2 minutes.
Thus, a photoelectrode composed of a TiO ₂ porous insulating layer, a SUS mesh, a Ti porous intermediate layer, and a TiO ₂ porous layer was obtained.

(Baking, dye support)
The photoelectrode obtained as described above was baked at 500 ° C. for 30 minutes in the atmosphere. This is a solution (concentration: 0.5 mM, solvent: acetonitrile / t-butanol = 1/1 (v) of a sensitizing dye (manufactured by Mitsubishi Paper Industries Co., Ltd., trade name: D358) represented by the following structural formula (6). / V)) was immersed for 12 hours to produce a photoelectrode.

(assembly)
Next, the photoelectrode obtained as described above was cut into a size of 15 mm × 25 mm using scissors. Next, a counter electrode was prepared by sequentially stacking a chromium (Cr) layer having a thickness of 50 nm and a platinum (Pt) layer having a thickness of 100 nm on a glass substrate in advance by sputtering. Next, a silicone rubber sheet having a thickness of 50 μm and having a 7 mm × 10 mm square hole was pasted on the Pt layer. Next, as an electrolyte, a solution obtained by dissolving 0.6 M iodide (1-propyl-3-methylimidazolium) and 0.1 M iodine in 3-methoxypropionitrile and SiO ₂ fine particles (manufactured by Degussa) , Trade name: R805, BET specific surface area 150 ± 25 m ² / g) was prepared in a mass ratio of 92: 8 to prepare a gel electrolyte. An appropriate amount of this was deposited on a square hole Pt layer of a silicone rubber sheet. Next, the photoelectrode was arrange | positioned so that the square hole of the silicone rubber sheet on Pt layer might be covered. Here, the TiO ₂ porous insulating layer and the Pt layer face each other. A glass substrate was placed on the TiO ₂ porous layer of the photoelectrode, and the glass substrate and the glass substrate of the counter electrode were clipped. Thereby, the target back contact type dye-sensitized solar cell was obtained.

(Comparative Example 3)
First, a TiO ₂ fine particle dispersion was prepared in the same manner as in the TiO ₂ porous layer forming step of Comparative Example 2. As the back contact electrode, the same SUS316 mesh (400 mesh, twill, wire diameter 30 μm, opening 34 μm) as in Comparative Example 2 was prepared. Next, the prepared TiO ₂ fine particle dispersion was applied onto a SUS316 mesh with a coil bar of count 44, and then dried in the atmosphere at 80 ° C. for 2 minutes to form a TiO ₂ porous layer. In the drying step, the dispersion liquid wraps around the back side of the SUS316 mesh, and a TiO ₂ porous insulating layer is formed at the same time.

  The photoelectrode obtained as described above was baked at 500 ° C. for 30 minutes in the atmosphere. This was immersed in a solution (concentration: 0.5 mM, solvent: acetonitrile / t-butanol = 1/1 (v / v)) of a sensitizing dye (Mitsubishi Paper Co., Ltd., trade name: D358) for 12 hours. This produced the target photoelectrode.

  Next, a back contact type dye-sensitized solar cell was obtained in the same manner as in Comparative Example 2 except that the produced photoelectrode was used.

(Evaluation of dye-sensitized solar cell)
The performance of the back contact type dye-sensitized solar cells obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was evaluated as follows. That is, opening of the back contact type dye-sensitized solar cell produced while irradiating pseudo sunlight (AM1.5, 100 mW / cm ² ) using a square mask with a square hole of 4.5 mm × 4.5 mm. Voltage V _OC , short circuit current density J _SC , fill factor FF, and photoelectric conversion efficiency Eff. Was evaluated at 24 ° C. The results are shown in Table 1, FIG. 8, FIG. 9A and FIG. 9B.

Table 1 shows the evaluation results of the back contact type dye-sensitized solar cells of Examples 1 to 4 and Comparative Examples 1 to 3.

The following can be understood from the above evaluation results.
In Examples 1 to 4 in which the photoelectrode was treated with the treatment solution containing the adsorbing compound, the conversion efficiency was improved as compared with Comparative Example 1 in which the photoelectrode was not treated with such a treatment solution.
Also in Examples 1 to 3 using an adsorption compound having a carboxyl group as an adsorption functional group and in Example 4 using an adsorption compound having a phosphate group as an adsorption functional group, the conversion efficiency is improved. When using adsorption functional groups other than carboxyl groups and phosphate groups (for example, sulfo groups, amino groups, phosphino groups, silanol groups, epoxy groups, isocyanate groups, cyano groups, vinyl groups, thiol groups, or hydroxyl groups) However, it can be estimated that the conversion efficiency is improved.
In Comparative Example 1 using Z991 as the sensitizing dye, the conversion efficiency tends to be lower than that in Comparative Example 2 using D358 as the adsorbing dye. However, in Examples 1 and 4 in which the photoelectrode was treated with a treatment solution containing an adsorbing compound, even when Z991 was used as the sensitizing dye, a higher conversion efficiency was obtained than in Comparative Example 2 using D358 as the adsorbing dye. ing.
In Comparative Example 2 in which the porous intermediate layer is formed between the back contact electrode and the porous metal oxide layer, the conversion efficiency is improved as compared with Comparative Example 3 in which such a porous intermediate layer is not formed. ing.

As described above, the conversion efficiency of the back contact type dye-sensitized solar cell can be improved by treating the photoelectrode with the treatment solution containing the adsorbing compound and adsorbing the adsorbing compound on the surface of the back contact electrode.
In addition, a porous intermediate layer is formed between the back contact electrode and the porous metal oxide layer, and the photoelectrode is treated with a treatment solution containing an adsorbing compound to adsorb the adsorbing compound on the surface of the back contact electrode. Thus, the conversion efficiency of the back contact type dye-sensitized solar cell can be further improved.

  As mentioned above, although embodiment of this technique was described concretely, this technique is not limited to the above-mentioned embodiment, Various deformation | transformation based on the technical idea of this technique is possible.

  For example, the configurations, methods, processes, shapes, materials, numerical values, and the like given in the above-described embodiments are merely examples, and different configurations, methods, processes, shapes, materials, numerical values, and the like are used as necessary. Also good.

  The configurations, methods, processes, shapes, materials, numerical values, and the like of the above-described embodiments can be combined with each other without departing from the gist of the present technology.

DESCRIPTION OF SYMBOLS 1 Photoelectrode base material 2 Counter electrode base material 3 Electrolyte layer 4 Sealing material 5 Load 6 Current collection electrode 6a 1st current collection electrode 6b 2nd current collection electrode 7 Current collection wiring 11 Photoelectrode 12, 22 Base material 21 Counter electrode 31 Back contact electrode 31a Linear member 32 Porous metal oxide layer 32a Metal oxide particle 32b Dye 33 Porous insulating layer 34 Porous intermediate layer 35, 23 Transparent conductive layer

Claims (8)

A photoelectrode, an electrolyte layer, and a counter electrode;
The photoelectrode has a current collector mainly composed of metal or metal oxide,
The current collector is a dye-sensitized solar cell having a surface on which an adsorbing compound is adsorbed. The dye-sensitized solar cell according to claim 1, wherein the adsorption compound is represented by the following general formula (1).
RX (1)
(However, R contains at least one of a saturated or unsaturated alkyl group, an aromatic ring, an alicyclic ring, and a heterocyclic ring. X can be coordinated to an adsorptive functional group or a metal or metal oxide. Is a simple atom.)   The adsorbing functional group is a carboxylic acid group, a sulfo group, an amino group, a phosphoric acid group, a phosphino group, a silanol group, an epoxy group, an isocyanate group, a cyano group, a vinyl group, a thiol group, or a hydroxyl group. Dye-sensitized solar cell.   The dye-sensitized solar cell according to claim 1, wherein the current collector is a porous electrode, a current collector electrode, a current collector substrate, a transparent conductive layer, or a current collector wiring.   The dye-sensitized solar cell according to claim 1, wherein the current collecting material is a porous electrode, a current collecting electrode, a current collecting base material, or a current collecting wiring whose main component is a metal.   The dye-sensitized solar cell according to claim 1, wherein the current collector is a transparent conductive layer mainly composed of a metal oxide having transparency. The photoelectrode is
A porous metal electrode;
A porous metal oxide layer carrying a sensitizing dye;
A porous intermediate layer provided between the porous metal electrode and the porous metal oxide layer,
The porous intermediate layer contains conductive fine particles,
The dye-sensitized solar cell according to claim 1, wherein the current collector is the porous metal electrode. A step of adsorbing an adsorbing compound to the surface of the current collector of the photoelectrode;
The said current collection material is a manufacturing method of the dye-sensitized solar cell which has a metal or a metal oxide as a main component.

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