JP2013058424A - Photosensitizing dye, dye sensitized photoelectric conversion element, electronic apparatus and building - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitizing dye capable of preventing deterioration in photoelectric conversion efficiency when used for a thermo dye sensitized photoelectric conversion element, and a dye sensitized photoelectric conversion element including the photosensitizing dye.SOLUTION: In a dye sensitized photoelectric conversion element, an electrolyte layer is provided between a porous photo electrode and a counter electrode, and a photosensitizing dye is bonded to the porous photo electrode. For the photosensitizing dye, a dye having a carboxyl group as a functional group represented by the following formula or the like, and a ruthenium polypyridine complex having two thiocyanate ligands, at least one of which is substituted by an N-butyl benzimidazole group, as a ligand, is used.

Description

  The present disclosure relates to a photosensitizing dye, a dye-sensitized photoelectric conversion element, an electronic device, and a building, and particularly, a photosensitizing dye suitable for use in a dye-sensitized solar cell, and a dye-sensitized dye using the photosensitizing dye. The present invention relates to a photoelectric conversion element, an electronic apparatus using the dye-sensitized photoelectric conversion element, and a building using the dye-sensitized photoelectric conversion element.

  Solar cells, which are photoelectric conversion elements that convert sunlight into electrical energy, use sunlight as an energy source, and therefore have very little influence on the global environment, and are expected to become more widespread.

  Conventionally, crystalline silicon solar cells using single crystal or polycrystalline silicon and amorphous silicon solar cells are mainly used as solar cells.

  On the other hand, the dye-sensitized solar cell proposed by Gretzell et al. In 1991 can obtain high photoelectric conversion efficiency, and unlike a conventional silicon-based solar cell, it does not require a large-scale device for production, and has a low It is attracting attention because it can be manufactured at low cost (for example, see Non-Patent Document 1).

  This dye-sensitized solar cell generally has a porous electrode made of titanium oxide or the like to which a photosensitizing dye is bound and a counter electrode made of platinum or the like facing each other, and an electrolyte layer made of an electrolytic solution is interposed between them. Has a filled structure. As the electrolytic solution, a solution obtained by dissolving an electrolyte containing oxidation / reduction species such as iodine or iodide ions in a solvent is often used.

や、Ｎ７１９と呼ばれる光増感色素

や、Ｃ１０６と呼ばれる光増感色素

や、Ｚ９９１と呼ばれる光増感色素

などがある。 In conventional dye-sensitized solar cells, a polypyridine ruthenium (Ru) complex-based photosensitizing dye is mainly used as the photosensitizing dye to be bonded to the porous electrode. This polypyridine ruthenium complex-based photosensitizing dye generally has a plurality of thiocyanate ligands (—NCS groups) as ligands. As a representative example, a photosensitizing dye called Z907 represented by the following formula:

And a photosensitizing dye called N719

And a photosensitizing dye called C106

And a photosensitizing dye called Z991

and so on.

  In addition to these dyes, various photosensitizing dyes have been proposed in order to improve the photoelectric conversion performance of dye-sensitized solar cells (see, for example, Patent Document 1).

JP 2009-200028 A

Nature, 353, p.737-740,1991

  Further, it is also known that an additive is effectively added to the electrolytic solution for improving the photoelectric conversion performance of the dye-sensitized solar cell. Examples of the additive for the electrolytic solution include rubenzimidazole (NBB). In particular, when N-butylbenzimidazole is added to the electrolyte solution of a dye-sensitized solar cell in which a photosensitizing dye is a polypyridine ruthenium complex-based dye, the photoelectric conversion efficiency is increased over time as compared with a conventional dye-sensitized solar cell. It is known that deterioration is suppressed.

  However, although the dye-sensitized solar cell having the above structure has improved durability over time, it cannot be said that the dye-sensitized solar cell has sufficient durability over time for practical use.

  Therefore, the problem to be solved by the present invention is that it is stable against heat, electrolyte, etc., and when used in a dye-sensitized photoelectric conversion element such as a dye-sensitized solar cell, the photoelectric conversion efficiency decreases due to deterioration with time. It is to provide a novel photosensitizing dye that can be prevented.

  Another problem to be solved by the present invention is to provide a dye-sensitized photoelectric conversion element using the excellent photosensitizing dye as described above.

  Still another problem to be solved by the present invention is to provide a high-performance electronic device using the excellent photoelectric conversion element as described above.

  Still another problem to be solved by the present invention is to provide a building using the excellent photoelectric conversion element as described above.

In order to solve the above problems, this disclosure
It is a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand.

The polypyridine ruthenium complex in this disclosure preferably has a carboxy group as a functional group and has at least one thiocyanate ligand as a ligand, and has a carboxy group as a functional group, Those having at least two thiocyanate ligands are more preferred, and specific examples include bipyridine ruthenium complexes and terpyridine ruthenium complexes. In the case of a bipyridine ruthenium complex, 4,4′-dicarboxy-2,2′-bipyridine or 4,4 ′, 4 ″ -tricarboxy-2,2 ′, 2 ″ terpyridine is used as a ligand for surface fixation. It is preferable to have at least one. In particular, when the bipyridine ruthenium complex has one 4,4′-dicarboxy-2,2′-bipyridine as a ligand and two thiocyanate ligands, the remaining two coordinations. It is preferable to coordinate a 2,2′-bipyridine derivative having functional groups R1 and R2 at positions 4, 4 ′ at the position, and specifically, for example, represented by the following formula (1) or the like.

The functional groups R1 and R2 in the formula (1) may be basically any one, but specifically, for example, functional groups represented by the following formulas (2) to (7) Groups. The reason why the dye of formula (1) does not depend on the functional groups R1 and R2 is that the reactivity between the functional groups R1 and R2 and the thiocyanate ligand is low. This is because it is considered that the functional groups R1 and R2 are not involved in the substitution with the ligand.

The polypyridine ruthenium complex may be, for example, a bipyridine ruthenium complex (trade name: Black Dye) having three thiocyanate ligands as a ligand, as represented by the following formula (8). However, the polypyridine ruthenium complex is not limited to those listed above.

The neutral ligand in this disclosure is a heterocyclic compound containing at least one nitrogen atom, and satisfies any one of the following conditions.
(1) It contains at least one 5-membered heterocyclic ring or 6-membered heterocyclic ring.
(2) The heterocyclic skeleton contains at least one unsaturated bond.
(3) The molecular weight of the cyclic portion forming the heterocyclic skeleton is in the range of 68 to 136.

Typical examples of the neutral ligand that satisfies any one of the above-mentioned conditions include N-butylbenzimidazole and derivatives thereof, but the neutral ligand is limited to this. Specifically, for example, heterocyclic compounds represented by the following formulas (9) to (33) may be mentioned.

Further, the photosensitizing dye of this disclosure is specifically represented by, for example, the following formula (34).

  The functional groups R1 and R2 in the formula (34) may be basically any one, specifically, for example, from the functional groups represented by the formulas (2) to (7). It is selected appropriately.

One of the ligands R3 and R4 in the formula (34) is a neutral ligand, and the other is either a thiocyanate ligand or a neutral ligand. Specifically, the neutral ligand is appropriately selected from, for example, neutral ligands represented by formulas (9) to (33). When a plurality of neutral ligands are coordinated, the plurality of neutral ligands may be the same or different, and are appropriately selected and combined from those listed above . Specific examples of the photosensitizing dye represented by the formula (34) include a photosensitizing dye represented by the following formula (35).

  The photosensitizing dye represented by the formula (35) has one of the thiocyanate ligands of a bipyridine ruthenium complex having a carboxy group as a functional group and two thiocyanate ligands as a ligand. It is a photosensitizing dye formed by substituting with an N-butylbenzimidazole group which is a functional ligand.

  Depending on the conformation of the ligands R3 and R4, stereoisomers such as geometric isomers and optical isomers may be generated even if the compounds have the same molecular formula. In this case, only a compound having the same structure may be used as the photosensitizing dye, or a mixture of compounds having different structures may be used as the photosensitizing dye. As a case where a geometric isomer is generated, specifically, for example, a thiocyanate ligand and a neutral ligand are coordinated one by one to the ligands R3 and R4 in the formula (34). There are cases.

Further, the photosensitizing dye of this disclosure is specifically represented by, for example, the following formula (36).

Of the ligands R5, R6, and R7 in the formula (36), at least one is a neutral ligand, and the remainder is either a thiocyanate ligand or a neutral ligand. The neutral ligand is specifically selected from, for example, neutral ligands represented by formulas (9) to (33). Here, when a plurality of neutral ligands are coordinated, the plurality of neutral ligands may be the same or different. These are selected and combined as appropriate from those listed. Specific examples of the photosensitizing dye represented by the formula (36) include photosensitizing dyes represented by the following formulas (37), (38), and (39).

  The photosensitizing dye represented by the formula (37) has one of the thiocyanate ligands of a polypyridine ruthenium complex having a carboxy group as a functional group and three thiocyanate ligands as a ligand. It is a photosensitizing dye formed by substitution with an N-butylbenzimidazole group which is a neutral ligand.

  The photosensitizing dye represented by the formula (38) includes two of thiocyanate ligands of a polypyridine ruthenium complex having a carboxy group as a functional group and three thiocyanate ligands as a ligand. It is a photosensitizing dye formed by substitution with an N-butylbenzimidazole group which is a neutral ligand.

  In the photosensitizing dye represented by the formula (39), one of the neutral ligands of the photosensitizing dye represented by the formula (38) is different from the N-butylbenzimidazole group. It is a rank.

  Depending on the conformation of the ligands R5, R6, and R7, stereoisomers such as geometric isomers and optical isomers may be generated even if the compounds have the same molecular formula. In this case, only a compound having the same structure may be used as the photosensitizing dye, or a mixture of compounds having different structures may be used as the photosensitizing dye.

This disclosure also
It has a structure in which an electrolyte layer is provided between the porous electrode and the counter electrode,
Dye sensitization in which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand is bonded to the porous electrode. It is a photoelectric conversion element.

This disclosure also
Having at least one photoelectric conversion element;
The photoelectric conversion element is
It has a structure in which an electrolyte layer is provided between the porous electrode and the counter electrode,
Dye sensitization in which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand is bonded to the porous electrode. This is an electronic device that is a photoelectric conversion element.

This disclosure also
Having at least one photoelectric conversion element;
The photoelectric conversion element is
It has a structure in which an electrolyte layer is provided between the porous electrode and the counter electrode,
Dye sensitization in which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand is bonded to the porous electrode. It is a building that is a photoelectric conversion element.

  In this disclosure, an electrolytic solution is typically used as the electrolyte layer. A conventionally well-known thing can be used as electrolyte solution, It selects as needed. From the viewpoint of preventing the volatilization of the electrolytic solution, the electrolytic solution is preferably a low-volatile electrolytic solution, for example, an ionic liquid electrolytic solution using an ionic liquid as a solvent. A conventionally well-known thing can be used as an ionic liquid, and it selects as needed.

The porous electrode is composed of fine particles made of a semiconductor. The semiconductor preferably comprises titanium oxide (TiO ₂ ), especially anatase TiO ₂ .

  The dye-sensitized photoelectric conversion element is most typically configured as a solar cell. However, the dye-sensitized photoelectric conversion element may be other than a solar cell, for example, an optical sensor.

  Electronic devices may be basically any type, including both portable and stationary types, but specific examples include mobile phones, mobile devices, robots, personal computers. , In-vehicle equipment, various home appliances. In this case, the photoelectric conversion element is a solar cell used as a power source for these electronic devices, for example.

  Buildings are typically large buildings such as buildings and condominiums, but are not limited to this. Basically, any building having an outer wall surface may be used. Also good. Specific examples of the building include a detached house, an apartment, a station building, a school building, a government building, a stadium, a stadium, a hospital, a church, a factory, a warehouse, a shed, a garage, and a bridge. The structure is preferably a built structure having two window parts (for example, glass windows) or a daylighting part, but the building is not limited to those mentioned above.

  Among photoelectric conversion elements provided in buildings and / or photoelectric conversion element modules in which a plurality of photoelectric conversion elements are electrically connected, those provided in a window or daylighting section are sandwiched between two transparent plates However, it is preferable to fix and configure as necessary. Typically, the photoelectric conversion element and / or the photoelectric conversion element module is assembled between two glass plates and fixed as necessary. Is done.

  The transparent material constituting the transparent plate may be basically any material as long as it is transparent and easily transmits light. Specifically, transparent materials such as transparent inorganic materials and transparent resins may be used. Examples of the transparent inorganic material include quartz glass, borosilicate glass, phosphate glass, and soda glass. Examples of the transparent resin include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. , Acetyl cellulose, tetraacetyl cellulose, polyphenylene sulfide, polycarbonate, polyethylene, polypropylene, polyvinylidene fluoride, brominated phenoxy, aramids, polyimides, polystyrenes, polyarylates, polysulfones, polyolefins, etc. This is the only material Not intended to be.

  In addition, what sandwiches the photoelectric conversion element and / or the photoelectric conversion element module is not limited to the transparent plate, and may be a sphere, an ellipsoid, a polyhedron, a cone, a frustum, a column, a lens body, or the like made of a transparent material There may be.

  In the photosensitizing dye according to the present disclosure configured as described above, the N-butylbenzimidazole group as an alternative ligand for the thiocyanate ligand is more stable than the thiocyanate ligand, and therefore, heat and electrolysis A decrease in photoelectric conversion efficiency due to deterioration with time of the liquid can be prevented.

  According to this disclosure, it is possible to obtain a photosensitizing dye that is stable against heat and an electrolytic solution. By using this photosensitizing dye for a dye-sensitized photoelectric conversion element, it is possible to prevent a decrease in photoelectric conversion efficiency. By using this excellent dye-sensitized photoelectric conversion element, a high-performance electronic device or the like can be realized.

It is sectional drawing which shows the dye-sensitized photoelectric conversion element by 2nd Embodiment of this indication.

  The present inventors have intensively studied to solve the above-described problems. Of these, attention was paid to a dye-sensitized solar cell having a polypyridine ruthenium complex-based dye as a photosensitizing dye and an electrolytic solution added with N-butylbenzimidazole.

  In the course of the research, the present inventors have found that the photosensitizing dye is modified with a decrease in the photoelectric conversion efficiency of the dye-sensitized solar cell. Furthermore, it has also been found that this modification is caused by exchanging N-butylbenzimidazole in the electrolytic solution with at least one thiocyanate ligand which is an auxiliary ligand of the polypyridine ruthenium complex.

  However, it cannot be said that the modified photosensitizing dye itself directly contributes to the decrease in photoelectric conversion efficiency of the dye-sensitized solar cell. The reason is that there was not much change in the light absorption ability between the photosensitizing dye before modification and the photosensitizing dye after modification.

  Therefore, the present inventors have further studied, and the cause of the decrease in the photoelectric conversion efficiency of the dye-sensitized solar cell is not due to the modification of the photosensitizing dye, but the electrolytic solution accompanying the modification of the photosensitizing dye. It was found to be a modification of The modification of the electrolytic solution occurs when the thiocyanate ligand of the photosensitizing dye elutes in the electrolytic solution and N-butylbenzimidazole in the electrolytic solution decreases. In order to prevent this, it is necessary to prevent elimination of the thiocyanate ligand in the photosensitizing dye.

  Therefore, the present inventors have proposed photosensitization by substituting at least one of a plurality of thiocyanate ligands coordinated to a photosensitizing dye with another ligand, particularly an N-butylbenzimidazole group. It has been found that the ligand binding in the photosensitizing dye can be stabilized while maintaining the light absorption capability of the dye itself. Furthermore, when the above-described photosensitizing dye is used in a dye-sensitized solar cell, it has been found that the above-described modification of the electrolytic solution can be effectively suppressed, and this finding has led to the present disclosure.

Hereinafter, modes for carrying out the invention (hereinafter referred to as “embodiments”) will be described. The description will be given in the following order.
1. First embodiment (photosensitizing dye)
2. Second Embodiment (Dye-sensitized photoelectric conversion element and manufacturing method thereof)

<1. First Embodiment>
[Photosensitizing dye]
The photosensitizing dye according to the first embodiment is represented by the formula (35).

<Example 1>
A photosensitizing dye represented by the formula (35) was synthesized as follows.
First, 0.9 g of Z907 and 3.8 g of N-butylbenzimidazole are mixed in a 3% by weight tetrabutylammonium hydroxide aqueous solution, and heated to reflux at an oil bath temperature of 115 ° C. for 24 hours to prepare a reaction solution. did. Thereafter, the reaction solution was allowed to cool to room temperature, neutralized with 150 ml of 0.1 M nitric acid, extracted with a pigment, and reprecipitated to obtain 0.8 g of a target crude product of the pigment. This was purified by a column chromatography method or a reprecipitation method to obtain 0.3 g of a photosensitizing dye represented by the formula (35).

  According to the first embodiment, the photosensitizing dye represented by the formula (35) has a thiocyanate ligand and an —N-butylbenzimidazole group as a ligand. While the benzimidazole group is stably bonded to the photosensitizing dye, the bond of the thiocyanate ligand which is the other ligand can also be stabilized. Thereby, it is stable with respect to electrolyte solution etc., and when it uses for a dye-sensitized photoelectric conversion element, the fall of a photoelectric conversion efficiency can be prevented over a long period of time.

<2. Second Embodiment>
[Dye-sensitized photoelectric conversion element]
FIG. 1 is a cross-sectional view of an essential part showing a dye-sensitized photoelectric conversion element according to a first embodiment.
As shown in FIG. 1, in this dye-sensitized photoelectric conversion element, a transparent electrode 2 is provided on one main surface of a transparent substrate 1 and has a predetermined planar shape smaller than the transparent electrode 2 on the transparent electrode 2. A porous electrode 3 is provided. At least one or two or more photosensitizing dyes containing the photosensitizing dye represented by the formula (35) are bonded to the porous electrode 3. On the other hand, a conductive layer 5 is provided on one main surface of the counter substrate 4, and a counter electrode 6 is provided on the conductive layer 5. The counter electrode 6 has the same planar shape as the porous electrode 3. An electrolyte layer 7 is provided between the porous electrode 3 on the transparent substrate 1 and the counter electrode 6 on the counter substrate 4. The outer peripheral portions of the transparent substrate 1 and the counter substrate 4 are sealed with a sealing material 8. The sealing material 8 is in contact with the transparent electrode 2 and the conductive layer 5, but the transparent electrode 2 may be in contact with the transparent substrate 1 by forming the transparent electrode 2 in the same planar shape as the porous electrode 3. 6 may be formed on the entire surface of the conductive layer 5 so as to be in contact with the conductive layer 5.

As the porous electrode 3, a porous semiconductor layer in which semiconductor fine particles are sintered is typically used. The photosensitizing dye is adsorbed on the surface of the semiconductor fine particles. As a material for the semiconductor fine particles, an elemental semiconductor typified by silicon, a compound semiconductor, a semiconductor having a perovskite structure, or the like can be used. These semiconductors are preferably n-type semiconductors in which conduction band electrons become carriers under photoexcitation and generate an anode current. Specifically, for example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), strontium titanate (SrTiO ₃ ), tin oxide (SnO ₂ ). Such semiconductors are used. Among these semiconductors, it is preferable to use TiO ₂ , especially anatase TiO ₂ . However, the types of semiconductors are not limited to these, and two or more types of semiconductors can be mixed or combined as needed. Further, the shape of the semiconductor fine particles may be any of granular, tube-like, rod-like and the like.

  The particle size of the semiconductor fine particles is not particularly limited, but the average particle size of primary particles is preferably 1 nm or more and 200 nm or less, particularly preferably 5 nm or more and 100 nm or less. It is also possible to improve the quantum yield by mixing particles having a size larger than that of the semiconductor fine particles and scattering incident light with these particles. In this case, the average size of the separately mixed particles is preferably 20 nm or more and 500 nm or less, but is not limited thereto.

  The porous electrode 3 preferably has a large actual surface area including the surface of fine particles facing pores inside the porous semiconductor layer made of semiconductor fine particles so that as many photosensitizing dyes as possible can be bonded. . For this reason, it is preferable that the actual surface area in the state which formed the porous electrode 3 on the transparent electrode 2 is 10 times or more with respect to the area (projection area) of the outer surface of the porous electrode 3, 100 times More preferably, it is the above. There is no particular upper limit to this ratio, but it is usually about 1000 times.

  Generally, as the thickness of the porous electrode 3 increases and the number of semiconductor fine particles contained per unit projected area increases, the actual surface area increases, and the amount of photosensitizing dye that can be held in the unit projected area increases. Since it increases, the light absorption rate becomes high. On the other hand, when the thickness of the porous electrode 3 is increased, the distance that electrons transferred from the photosensitizing dye to the porous electrode 3 are diffused before reaching the transparent electrode 2, so that the charge in the porous electrode 3 is increased. Electron loss due to recombination also increases. Therefore, there is a preferable thickness in the porous electrode 3, but this thickness is generally 0.1 μm or more and 100 μm or less, more preferably 1 μm or more and 50 μm or less, and more preferably 3 μm or more and 30 μm or less. It is particularly preferred.

Examples of the electrolytic solution constituting the electrolyte layer 7 include a solution containing a redox system (redox couple). The redox system is not particularly limited as long as it is a substance having an appropriate redox potential. Specifically, as the redox system, for example, a combination of iodine (I ₂ ) and a metal or organic iodide salt, a combination of bromine (Br ₂ ) and a metal or organic bromide salt, or the like is used. . Examples of the cation constituting the metal salt include lithium (Li ⁺ ), sodium (Na ⁺ ), potassium (K ⁺ ), cesium (Cs ⁺ ), magnesium (Mg 2+), and calcium (Ca 2+). Further, as the cation constituting the organic salt, quaternary ammonium ions such as tetraalkylammonium ions, pyridinium ions and imidazolium ions are suitable. These may be used alone or in combination of two or more. Can be used.

  In addition to the above, the electrolyte solution constituting the electrolyte layer 7 includes a combination of an oxidant / reducer of an organometallic complex composed of a transition metal such as cobalt, iron, copper, nickel, platinum, sodium polysulfide, alkylthiol, Sulfur compounds such as combinations with alkyl disulfides, viologen dyes, combinations of hydroquinone and quinone, and the like can also be used.

Among the above, the electrolyte of the electrolyte solution constituting the electrolyte layer 7 includes iodine (I ₂ ), quaternary ammonium compounds such as lithium iodide (LiI), sodium iodide (NaI), imidazolium iodide, among others. An electrolyte in combination with is preferable. The concentration of the electrolyte salt is preferably 0.05 M or more and 10 M or less, more preferably 0.2 M or more and 3 M or less with respect to the solvent. The concentration of iodine (I ₂ ) or bromine (Br ₂ ) is preferably 0.0005M or more and 1M or less, more preferably 0.001 or more and 0.5M or less.

As the electrolyte of the electrolytic solution, in particular, an electrolyte combining iodine (I ₂ ) and a quaternary ammonium compound such as lithium iodide (LiI), sodium iodide (NaI), imidazolium iodide, among the above is used. Is preferred. The concentration of the electrolyte salt is preferably 0.05 M or more and 10 M or less, more preferably 0.2 M or more and 3 M or less with respect to the solvent. The concentration of iodine I ₂ or bromine Br ₂ is preferably 0.0005 M or more and 1 M or less, and more preferably 0.001 or more and 0.5 M or less. Various additives such as 4-tert-butylpyridine and benzimidazoliums may be added for the purpose of improving the open circuit voltage and the short circuit current.

  When an additive is added to the electrolytic solution, it is preferable to select a neutral ligand to be introduced into the photosensitizing dye in advance according to the component of the additive. When an alkylbenzimidazole, an alkylpyridine derivative or the like is used as an additive in the liquid, the photosensitizing dye to be adsorbed on the porous electrode 3 is preferably a dye represented by the formula (35). However, the neutral ligand previously introduced into the photosensitizing dye is not limited by the additive component added to the electrolytic solution, and the neutral ligand is listed above regardless of the electrolytic solution component. Can be appropriately selected from the above.

  As the solvent constituting the electrolytic solution, generally, 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 are used.

  As a solvent constituting the electrolytic solution, an ionic liquid may be used, and by doing so, the problem of volatilization of the electrolytic solution can be improved. A conventionally well-known thing can be used as an ionic liquid, Although it chooses as needed, a specific example is as follows.

EMImTCB: 1-ethyl-3-methylimidazolium tetracyanoborate
EMImTFSI: 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfone) imide
EMImFAP: 1-ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate
EMImBF ₄ : 1-ethyl-3-methylimidazolium tetrafluoroborate
EMImOTf (1-ethyl-3-methylimidazolium trifluorometanesulfonate)
・ P22 ₂ MOMTFSI (triethyl (methoxymethyl) phosphonium bis (trifluoromethylsufonyl) imide)

  The transparent substrate 1 is not particularly limited as long as it has a material and a shape that easily transmit light, and various substrate materials can be used, but a substrate material that has a particularly high visible light transmittance is used. Is preferred. In addition, a material having a high blocking performance for blocking moisture and gas from entering the dye-sensitized photoelectric conversion element from the outside, and excellent in solvent resistance and weather resistance is preferable. Specifically, as the material of the transparent substrate 1, transparent inorganic materials such as quartz and glass, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetylcellulose, bromo Examples thereof include transparent plastics such as modified phenoxy, aramids, polyimides, polystyrenes, polyarylates, polysulfones, and polyolefins. The thickness in particular of the transparent substrate 1 is not restrict | limited, It can select suitably considering the light transmittance and the performance which interrupts | blocks the inside and outside of a photoelectric conversion element.

The transparent electrode 2 provided on the transparent substrate 1 is more preferable as the sheet resistance is smaller, specifically 500Ω / □ or less, more preferably 100Ω / □ or less. A known material can be used as the material for forming the transparent electrode 2 and is selected as necessary. Specifically, the material for forming the transparent electrode 2 is indium-tin composite oxide (ITO), fluorine-doped tin oxide (IV) SnO ₂ (FTO), tin oxide (IV) SnO ₂ , oxidation Zinc (II) ZnO, indium-zinc composite oxide (IZO), etc. are mentioned. However, the material which forms the transparent electrode 2 is not limited to these, It can also use combining 2 or more types.

  When the porous electrode 3 is combined with one or two or more other photosensitizing dyes in addition to the photosensitizing dye represented by the formula (35), the photosensitizing dye exhibits a sensitizing action. There is no particular limitation as long as it is an organic metal complex, an organic dye, metal / semiconductor nanoparticles, and the like, and those having an acid functional group adsorbed on the surface of the porous electrode 3 are preferable. In general, the photosensitizing dye preferably has a carboxy group, a phosphoric acid group, and the like, and among them, a dye having a carboxy group is particularly preferable. Specific examples of the photosensitizing dye include, for example, xanthene dyes such as rhodamine B, rose bengal, eosin, erythrosine, cyanine dyes such as merocyanine, quinocyanine, and cryptocyanine, phenosafranine, fog blue, thiocin, and methylene blue. Basic dyes, porphyrin compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, and others include azo dyes, phthalocyanine compounds, coumarin compounds, pyridine complex compounds, anthraquinone dyes, polycyclic quinone dyes, Examples thereof include π-conjugated polymers such as triphenylmethane dyes, indoline dyes, perylene dyes, polythiophenes, and dimers to 20-mers of monomers, and quantum dots such as CdS and CdSe. Among these, the ligand (ligand) includes a pyridine ring or an imidazolium ring, and a dye of at least one metal complex selected from the group consisting of Ru, Os, Ir, Pt, Co, Fe, and Cu is High quantum yield is preferable. In particular, cis-bis (isothiocyanato) -N, N-bis (2,2′-dipyridyl-4,4′-dicarboxylic acid) -ruthenium (II) or tris (isothiocyanato) -ruthenium (II) — A dye molecule having 2,2 ': 6', 2 "-terpyridine-4,4 ', 4" -tricarboxylic acid as a basic skeleton has a wide absorption wavelength range and is preferable. However, the photosensitizing dye is not limited to these.

  The method for adsorbing the photosensitizing dye to the porous electrode 3 is not particularly limited. For example, the photosensitizing dye may be an alcohol, nitrile, nitromethane, halogenated hydrocarbon, ether, dimethyl sulfoxide, amide, It is dissolved in a solvent such as N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates, ketones, hydrocarbons, water, and the porous electrode 3 is immersed in the solution. A solution containing a photosensitizing dye can be applied onto the porous electrode 3. Further, deoxycholic acid or the like may be added for the purpose of reducing association between molecules of the photosensitizing dye. If necessary, an ultraviolet absorber can be used in combination.

  After the photosensitizing dye is adsorbed on the porous electrode 3, the surface of the porous electrode 3 may be treated with amines for the purpose of promoting the removal of the excessively adsorbed photosensitizing 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.

  Any material can be used as the material for the counter electrode 6 as long as it is a conductive substance. However, if a conductive layer is formed on the side facing the electrolyte layer 7 of the insulating material, this can also be used. Is possible. As the material of the counter electrode 6, it is preferable to use an electrochemically stable material. Specifically, it is desirable to use platinum, gold, carbon, a conductive polymer, or the like.

  Further, in order to improve the catalytic action for the reduction reaction at the counter electrode 6, it is preferable that the surface of the counter electrode 6 in contact with the electrolyte layer 7 is formed so that a fine structure is formed and the actual surface area is increased. . For example, the surface of the counter electrode 6 is preferably formed in a platinum black state if it is platinum, or in a porous carbon state if it is carbon. Platinum black can be formed by anodization of platinum or chloroplatinic acid treatment, and porous carbon can be formed by a method such as sintering of carbon fine particles or firing of an organic polymer.

  The counter electrode 6 is formed on the conductive layer 5 formed on one main surface of the counter substrate 4, but is not limited thereto. As the material of the counter substrate 4, opaque glass, plastic, ceramic, metal, or the like may be used, or a transparent material such as transparent glass or plastic may be used. As the conductive layer 5, the same material as that of the transparent electrode 2 can be used, and one formed of an opaque conductive material can also be used.

  As a material of the sealing material 8, it is preferable to use a material having light resistance, insulation, moisture resistance, and the like. Specific examples of the material for the sealing material include epoxy resin, ultraviolet curable resin, acrylic resin, polyisobutylene resin, EVA (ethylene vinyl acetate), ionomer resin, ceramic, and various heat-sealing films.

[Method for producing dye-sensitized photoelectric conversion element]
Next, the manufacturing method of this dye-sensitized photoelectric conversion element is demonstrated.
First, the transparent electrode 2 is formed by forming a transparent conductive layer on one main surface of the transparent substrate 1 by sputtering or the like.

  Next, the porous electrode 3 is formed on the transparent electrode 2 of the transparent substrate 1. The method for forming the porous electrode 3 is not particularly limited, but in consideration of physical properties, convenience, production cost, etc., it is preferable to use a wet film forming method. In the wet film forming method, a paste-form dispersion liquid in which semiconductor fine particle powder or sol is uniformly dispersed in a solvent such as water is prepared, and this dispersion liquid is applied or printed on the transparent electrode 2 of the transparent substrate 1. Is preferred. There is no restriction | limiting in particular in the application method or printing method of a dispersion liquid, A well-known method can be used. Specifically, as a coating method, for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or the like can be used. Moreover, as a printing method, 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, etc. can be used.

When anatase-type TiO ₂ is used as the material for the semiconductor fine particles, this anatase-type TiO ₂ may be a commercially available product in the form of powder, sol, or slurry, or is known such as hydrolyzing titanium oxide alkoxide. A material having a predetermined particle diameter may be formed by a method. When using a commercially available powder, it is preferable to eliminate secondary agglomeration of the particles, and it is preferable to pulverize the particles using a mortar, ball mill or the like when preparing the paste-like dispersion. At this time, acetylacetone, hydrochloric acid, nitric acid, a surfactant, a chelating agent, and the like can be added to the paste-like dispersion in order to prevent the particles from which secondary aggregation has been eliminated from aggregating again. In addition, in order to increase the viscosity of the paste-like dispersion, polymers such as polyethylene oxide and polyvinyl alcohol, or various thickeners such as a cellulose-based thickener can be added to the paste-like dispersion.

  The porous electrode 3 is formed by applying or printing the semiconductor fine particles on the transparent electrode 2 and then electrically connecting the semiconductor fine particles to improve the mechanical strength of the porous electrode 3, thereby improving the adhesion with the transparent electrode 2. In order to improve, baking is preferable. There is no particular limitation on the range of the firing temperature, but if the temperature is raised too much, the electrical resistance of the transparent electrode 2 increases, and further the transparent electrode 2 may melt. 40 ° C. or higher and 650 ° C. or lower is more preferable. Moreover, although there is no restriction | limiting in particular in baking time, Usually, it is about 10 minutes or more and 10 hours or less.

  For example, a dip treatment with a titanium tetrachloride aqueous solution or a titanium oxide ultrafine particle sol having a diameter of 10 nm or less may be performed for the purpose of increasing the surface area of the semiconductor fine particles or increasing the necking between the semiconductor fine particles. When a plastic substrate is used as the transparent substrate 1 that supports the transparent electrode 2, the porous electrode 3 is formed on the transparent electrode 2 using a paste-like dispersion containing a binder, and the transparent electrode 2 is heated by pressing. It is also possible to pressure-bond to.

  Next, the transparent substrate 1 on which the porous electrode 3 is formed is immersed in a photosensitizing dye solution in which the photosensitizing dye represented by the formula (35) is dissolved in a predetermined organic solvent, thereby making the porous substrate 1 porous. A photosensitizing dye is bonded to the electrode 3.

  On the other hand, after the conductive layer 5 is formed on the entire surface of the counter substrate 4 by sputtering, for example, a counter electrode 6 having a predetermined planar shape is formed on the conductive layer 5. The counter electrode 6 can be formed, for example, by forming a film to be the material of the counter electrode 6 on the entire surface of the conductive layer 5 by sputtering, for example, and then patterning the film by etching.

Next, the transparent substrate 1 and the counter substrate 4 are arranged so that the porous electrode 3 and the counter electrode 6 face each other at a predetermined interval, for example, 1 μm to 100 μm, preferably 1 μm to 50 μm. Then, a sealing material 8 is formed on the transparent substrate 1 and the counter substrate 4 to create a space in which the electrolyte layer 7 is enclosed, and a liquid injection port (not shown) previously formed on the transparent substrate 1 is formed in this space, for example. An electrolyte solution is injected to form the electrolyte layer 7. Thereafter, the liquid injection port is closed.
Thus, the target dye-sensitized photoelectric conversion element is manufactured.

[Operation of dye-sensitized photoelectric conversion element]
Next, the operation of this dye-sensitized photoelectric conversion element will be described.
When light is incident, the dye-sensitized photoelectric conversion element operates as a battery having the counter electrode 6 as a positive electrode and the transparent electrode 2 as a negative electrode. The principle is as follows. Here, it is assumed that FTO is used as the material of the transparent electrode 2, TiO ₂ is used as the material of the porous electrode 3, and the redox species of I ⁻ / I ₃ ⁻ is used as the redox pair. It is not limited to this. Further, it is assumed that one type of photosensitizing dye represented by the formula (35) is bonded to the porous electrode 3.

When a photosensitizing dye that has passed through the transparent substrate 1 and the transparent electrode 2 and has entered the porous electrode 3 and has been bonded to the porous electrode 3 absorbs the photons, the electrons in the photosensitizing dye are released from the ground state (HOMO). Excited to an excited state (LUMO). The electrons thus excited are drawn out to the conduction band of TiO ₂ constituting the porous electrode 3 through the electrical coupling between the photosensitizing dye and the porous electrode 3, and pass through the porous electrode 3. It reaches the transparent electrode 2.

On the other hand, the photosensitizing dye that has lost electrons receives electrons from the reducing agent in the electrolyte layer 7, for example, I ^−, by the following reaction, and the oxidant, for example, I ₃ ⁻ (I ₂ and I ⁻ To form a conjugate).
2I ⁻ → I ₂ + 2e ^{−
_{I 2 + I - → I 3}} -

The oxidant thus generated reaches the counter electrode 6 by diffusion, receives electrons from the counter electrode 6 by the reverse reaction of the above reaction, and is reduced to the original reducing agent.
^{_{I 3 - → I 2 + I}} -
I ₂ + 2e ^- → 2I ^-

  The electrons sent from the transparent electrode 2 to the external circuit return to the counter electrode 6 after performing electrical work in the external circuit. In this way, light energy is converted into electrical energy without leaving any change in the photosensitizing dye or the electrolyte layer 7.

<Example 2>
A dye-sensitized photoelectric conversion element was produced as follows.
The paste-like dispersion of TiO ₂ that is a raw material for forming the porous electrode 3 is referred to “the latest technology of dye-sensitized solar cells” (supervised by Hironori Arakawa, 2001, CMC Co., Ltd.). Produced. That is, first, 125 ml of titanium isopropoxide was gradually added dropwise to 750 ml of 0.1 M nitric acid aqueous solution while stirring at room temperature. After dropping, the mixture was transferred to a constant temperature bath at 80 ° C. and stirring was continued for 8 hours. As a result, a cloudy translucent sol solution was obtained. The sol solution was allowed to cool to room temperature, filtered through a glass filter, and a solvent was added to make the solution volume 700 ml. The obtained sol solution was transferred to an autoclave, subjected to a hydrothermal reaction at 220 ° C. for 12 hours, and then subjected to dispersion treatment by ultrasonic treatment for 1 hour. Next, this solution was concentrated at 40 ° C. using an evaporator to prepare a TiO ₂ content of 20 wt%. To the concentrate sol solution was added to 20% content of polyethylene glycol of TiO ₂ weight (molecular weight 500,000), 30% of the grain diameter 200nm of TiO ₂ by weight and anatase TiO _2, stirring deaerator Were mixed uniformly to obtain a paste-like dispersion of TiO ₂ with increased viscosity.

The paste dispersion of TiO ₂ was applied onto the FTO layer as the transparent electrode 2 by a blade coating method to form a fine particle layer having a size of 5 mm × 5 mm and a thickness of 200 μm. Thereafter, the TiO ₂ fine particles were sintered on the FTO layer by holding at 500 ° C. for 30 minutes. A 0.1 M titanium chloride (IV) TiCl ₄ aqueous solution was added dropwise to the sintered TiO ₂ film, kept at room temperature for 15 hours, washed, and fired again at 500 ° C. for 30 minutes. Thereafter, the ultraviolet light irradiation apparatus is used to irradiate the TiO ₂ sintered body with ultraviolet light for 30 minutes, and impurities such as organic substances contained in the TiO ₂ sintered body are oxidatively decomposed and removed by the photocatalytic action of TiO _2. The porous electrode 3 was obtained by performing a treatment for increasing the activity of the TiO ₂ sintered body.

  As a photosensitizing dye, 23.8 mg of a sufficiently purified photosensitizing dye represented by formula (35) was dissolved in 50 ml of a mixed solvent in which acetonitrile and tert-butanol were mixed at a volume ratio of 1: 1, A photosensitizing dye solution was prepared.

Next, the porous electrode 3 was immersed in this photosensitizing dye solution at room temperature for 24 hours to hold the photosensitizing dye on the surface of the TiO ₂ fine particles. Next, the porous electrode 3 was washed sequentially with an acetonitrile solution of 4-tert-butylpyridine and acetonitrile, and then the solvent was evaporated in the dark and dried.

On the other hand, to 3-methoxypropionitrile (MPN) as a solvent, 1.0 M 1-propyl-3-methylimidazolium iodide (MPImI), 0.1 M iodine I ₂ , and 0.3 M as an additive Of N-butylbenzimidazole was dissolved to prepare an electrolytic solution.

  The counter electrode 6 is formed by sequentially depositing a 50 nm-thick chromium layer and a 100 nm-thick platinum layer on a FTO layer, in which a liquid injection port having a diameter of 0.5 mm is formed in advance, by sputtering. An isopropyl alcohol (2-propanol) solution was spray coated and formed by heating at 385 ° C. for 15 minutes.

  Next, the transparent substrate 1 and the counter substrate 4 are arranged so that the porous electrode 3 and the counter electrode 6 face each other, and the outer periphery is sealed with an ionomer resin film having a thickness of 30 μm and an acrylic ultraviolet curable resin. .

  Next, the electrolyte solution was injected from a liquid injection port of a dye-sensitized photoelectric conversion element prepared in advance using a liquid feed pump, and the pressure was reduced to expel bubbles inside the element. Thus, the electrolyte layer 7 is formed. Thereafter, the liquid inlet was sealed with an ionomer resin film, an acrylic resin, and a glass substrate to complete a dye-sensitized photoelectric conversion element.

  As described above, according to the second embodiment, by using a novel photosensitizing dye that is stable with respect to the electrolytic solution represented by the formula (35) in the porous electrode 3, Since the thiocyanate derived from the photosensitizing dye is not mixed into the electrolytic solution, and the N-butylbenzimidazole in the electrolytic solution is not reduced, deterioration of the electrolytic solution with time can be prevented, such as Z907. As compared with a conventional dye-sensitized photoelectric conversion element using the above, a decrease in photoelectric conversion efficiency can be prevented over a long period of time. Further, by using this excellent dye-sensitized photoelectric conversion element, a high-performance electronic device or the like can be realized.

Although the embodiments and examples have been specifically described above, the present disclosure is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present disclosure are possible. .
For example, the numerical values, structures, configurations, shapes, materials, and the like given in the above-described embodiments and examples are merely examples, and different numerical values, structures, configurations, shapes, materials, etc. are used as necessary. Also good.

（４）上記光増感色素の官能基Ｒ１、Ｒ２が、下記式（２）〜（７）で表される官能基のうちのいずれかである（３）記載の色素増感光電変換素子。

（５）上記光増感色素が、下記式（３５）で表される光増感色素である（１）〜（４）のいずれか記載の色素増感光電変換素子。

（６）上記光増感色素が、下記式（３６）で表され、３つの配位子Ｒ５、Ｒ６、Ｒ７のうち、少なくとも１つは中性配位子であり、残りの配位子はチオシアネート配位子および中性配位子のいずれかである（１）または（２）記載の色素増感光電変換素子。

（７）上記光増感色素が、下記式（３７）で表される光増感色素である（５）記載の色素増感光電変換素子。

（８）少なくとも１つの光電変換素子を有し、上記光電変換素子が、多孔質電極と対極との間に電解質層が設けられた構造を有し、上記多孔質電極に、少なくとも１つのチオシアネート配位子を有するポリピリジンルテニウム錯体のチオシアネート配位子のうち、少なくとも１つを中性配位子で置換してなる光増感色素が結合した色素増感光電変換素子である電子機器。
（９）官能基としてカルボキシ基を有する（８）記載の電子機器。
（１０）上記光増感色素が、下記式（３４）で表され、配位子Ｒ３、Ｒ４のうち、一方は中性配位子であり、もう一方はチオシアネート配位子および中性配位子のいずれかである（８）または（９）記載の電子機器。

（１１）上記光増感色素の官能基Ｒ１、Ｒ２が、下記式（２）〜（７）で表される官能基のうちのいずれかである（１０）記載の電子機器。

（１２）上記光増感色素が下記式（３５）で表される光増感色素である（１１）記載の電子機器。

（１３）上記光増感色素が、下記式（３６）で表され、
３つの配位子Ｒ５、Ｒ６、Ｒ７のうち、少なくとも１つは中性配位子であり、残りの配位子はチオシアネート配位子および中性配位子のいずれかである（８）または（９）記載の電子機器。

（１４）上記光増感色素が、下記式（３７）で表される光増感色素である（１３）記載の電子機器。

（１５）少なくとも１つのチオシアネート配位子を有するポリピリジンルテニウム錯体のチオシアネート配位子のうち、少なくとも１つを中性配位子で置換してなる光増感色素。
（１６）下記式（３４）で表され、
配位子Ｒ３、Ｒ４のうち、一方は中性配位子であり、もう一方はチオシアネート配位子および中性配位子のいずれかである（１５）記載の光増感色素。

（１７）上記光増感色素の官能基Ｒ１、Ｒ２が、下記式（２）〜（７）で表される官能基のうちのいずれかである（１６）記載の光増感色素。

（１８）上記光増感色素が、下記式（３５）で表される光増感色素である（１５）記載の光増感色素。

（１９）少なくとも１つの光電変換素子を有し、上記光電変換素子が、多孔質電極と対極との間に電解質層が設けられた構造を有し、上記多孔質電極に、少なくとも１つのチオシアネート配位子を有するポリピリジンルテニウム錯体のチオシアネート配位子のうち、少なくとも１つを中性配位子で置換してなる光増感色素が結合した色素増感光電変換素子である建築物。
（２０）上記光電変換素子および／または上記光電変換素子モジュールのうち、少なくとも１つは２枚の透明板の間に挟持されている（１９）に記載の建築物。 In addition, this technique can also take the following structures.
(1) A thiocyanate ligand of a polypyridine ruthenium complex having a structure in which an electrolyte layer is provided between a porous electrode and a counter electrode, and having at least one thiocyanate ligand on the porous electrode, A dye-sensitized photoelectric conversion element having a photosensitizing dye formed by substituting at least one with a neutral ligand.
(2) The dye-sensitized photoelectric conversion device according to (1), which has a carboxy group as a functional group.
(3) The photosensitizing dye is represented by the following formula (34), and one of the ligands R3 and R4 is a neutral ligand, and the other is a thiocyanate ligand and a neutral ligand. The dye-sensitized photoelectric conversion element according to (1) or (2), wherein

(4) The dye-sensitized photoelectric conversion element according to (3), wherein the functional groups R1 and R2 of the photosensitizing dye are any one of functional groups represented by the following formulas (2) to (7).

(5) The dye-sensitized photoelectric conversion element according to any one of (1) to (4), wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (35).

(6) The photosensitizing dye is represented by the following formula (36), and at least one of the three ligands R5, R6, and R7 is a neutral ligand, and the remaining ligands are The dye-sensitized photoelectric conversion device according to (1) or (2), which is any of a thiocyanate ligand and a neutral ligand.

(7) The dye-sensitized photoelectric conversion element according to (5), wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (37).

(8) having at least one photoelectric conversion element, wherein the photoelectric conversion element has a structure in which an electrolyte layer is provided between a porous electrode and a counter electrode, and at least one thiocyanate is disposed on the porous electrode. An electronic device which is a dye-sensitized photoelectric conversion element to which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having a ligand with a neutral ligand is bound.
(9) The electronic device according to (8), which has a carboxy group as a functional group.
(10) The photosensitizing dye is represented by the following formula (34), and one of the ligands R3 and R4 is a neutral ligand, and the other is a thiocyanate ligand and a neutral coordination. The electronic device according to (8) or (9), which is one of children.

(11) The electronic device according to (10), wherein the functional groups R1 and R2 of the photosensitizing dye are any one of functional groups represented by the following formulas (2) to (7).

(12) The electronic device according to (11), wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (35).

(13) The photosensitizing dye is represented by the following formula (36):
Of the three ligands R5, R6, R7, at least one is a neutral ligand and the remaining ligand is either a thiocyanate ligand or a neutral ligand (8) or (9) The electronic device according to (9).

(14) The electronic device according to (13), wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (37).

(15) A photosensitizing dye obtained by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand.
(16) It is represented by the following formula (34),
The photosensitizing dye according to (15), wherein one of the ligands R3 and R4 is a neutral ligand, and the other is either a thiocyanate ligand or a neutral ligand.

(17) The photosensitizing dye according to (16), wherein the functional groups R1 and R2 of the photosensitizing dye are any one of functional groups represented by the following formulas (2) to (7).

(18) The photosensitizing dye according to (15), wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (35).

(19) having at least one photoelectric conversion element, wherein the photoelectric conversion element has a structure in which an electrolyte layer is provided between a porous electrode and a counter electrode, and at least one thiocyanate is disposed on the porous electrode. A building which is a dye-sensitized photoelectric conversion element to which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having a ligand with a neutral ligand.
(20) The building according to (19), wherein at least one of the photoelectric conversion element and / or the photoelectric conversion element module is sandwiched between two transparent plates.

  DESCRIPTION OF SYMBOLS 1 ... Transparent substrate, 2 ... Transparent electrode, 3 ... Porous electrode, 4 ... Opposite substrate, 5 ... Conductive layer, 6 ... Counter electrode, 7 ... Electrolyte layer, 8 ... Sealing material.

Claims (20)

It has a structure in which an electrolyte layer is provided between the porous electrode and the counter electrode,
Dye sensitization in which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand is bonded to the porous electrode. Photoelectric conversion element.   The dye-sensitized photoelectric conversion element according to claim 1, which has a carboxy group as a functional group. The photosensitizing dye is represented by the following formula (34):
3. The dye-sensitized photoelectric conversion element according to claim 2, wherein one of the ligands R3 and R4 is a neutral ligand and the other is either a thiocyanate ligand or a neutral ligand.

The dye-sensitized photoelectric conversion element according to claim 3, wherein the functional groups R1 and R2 of the photosensitizing dye are any one of functional groups represented by the following formulas (2) to (7).

The dye-sensitized photoelectric conversion element according to claim 4, wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (35).

The photosensitizing dye is represented by the following formula (36),
2. At least one of the three ligands R5, R6, and R7 is a neutral ligand, and the remaining ligand is either a thiocyanate ligand or a neutral ligand. Dye-sensitized photoelectric conversion element.

The dye-sensitized photoelectric conversion element according to claim 6, wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (37).

Having at least one photoelectric conversion element;
The photoelectric conversion element is
It has a structure in which an electrolyte layer is provided between the porous electrode and the counter electrode,
Dye sensitization in which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand is bonded to the porous electrode. An electronic device that is a photoelectric conversion element.   The electronic device of Claim 8 which has a carboxy group as a functional group. The photosensitizing dye is represented by the following formula (34):
The electronic device according to claim 9, wherein one of the ligands R3 and R4 is a neutral ligand, and the other is either a thiocyanate ligand or a neutral ligand.

The electronic device according to claim 10, wherein the functional groups R1 and R2 of the photosensitizing dye are any one of functional groups represented by the following formulas (2) to (7).

The electronic device according to claim 11, wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (35).

The photosensitizing dye is represented by the following formula (36),
9. At least one of the three ligands R5, R6, and R7 is a neutral ligand, and the remaining ligand is either a thiocyanate ligand or a neutral ligand. Electronic equipment.

The electronic device according to claim 13, wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (37).

  A photosensitizing dye obtained by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand. It is represented by the following formula (34),
The photosensitizing dye according to claim 15, wherein one of the ligands R3 and R4 is a neutral ligand, and the other is either a thiocyanate ligand or a neutral ligand.

The photosensitizing dye according to claim 16, wherein the functional groups R1 and R2 of the photosensitizing dye are any one of functional groups represented by the following formulas (2) to (7).

The photosensitizing dye according to claim 17, wherein the photosensitizing dye is a photosensitizing dye represented by the following formula (35).

Having at least one photoelectric conversion element;
The photoelectric conversion element is
It has a structure in which an electrolyte layer is provided between the porous electrode and the counter electrode,
Dye sensitization in which a photosensitizing dye formed by substituting at least one of thiocyanate ligands of a polypyridine ruthenium complex having at least one thiocyanate ligand with a neutral ligand is bonded to the porous electrode. A building that is a photoelectric conversion element.   The building according to claim 19, wherein at least one of the photoelectric conversion element and / or the photoelectric conversion element module is sandwiched between two transparent plates.

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