KR20170118692A - Sensitizing-dye dyeing solution and method for producing photoelectrode - Google Patents

Abstract

Wherein the mixed solvent comprises (A) a nitrogen-containing solvent, (B) an alcohol-based solvent and (C) a sulfur-containing solvent, wherein the sensitizing dye has a concentration of 1 mM or more Dissolving color enhancer dye. And dyeing the semiconductor film with the sensitizing dye by bringing the dye sensitizing dye into contact with the semiconductor film formed on the substrate.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a dye-

The present invention relates to a dye sensitizing dye for dyeing a semiconductor layer with an increasing dye, and a method for producing a photoelectrode using the dye sensitizing dye.

The present application claims priority based on Japanese Patent Application No. 2015-035674 filed on February 25, 2015, the contents of which are incorporated herein by reference.

Sensitized dye is physically or chemically adsorbed on the surface of the oxide semiconductor layer in the graze-type dye-sensitized solar cell.

As a method of adsorbing a sensitizing dye to a semiconductor layer in the production of a photo-electrode, a method of immersing a substrate on which a semiconductor layer has been formed in a sensitizing dye dye solution is generally used (for example, Patent Document 1).

According to this dyeing method, the coloring dye solution can be sufficiently penetrated into the porous semiconductor layer, but it is usually required that the dyeing time is 8 hours or more.

Patent Document 2 discloses a dye solution containing a sensitizing dye at a high concentration by adding a nitrogen-containing compound having a boiling point of 200 캜 or less to a dyeing solution as a gas or liquid at 25 캜 .

Patent Document 3 discloses a method of manufacturing a dye-sensitized photoelectric conversion device comprising a step of bringing a dye solution and a porous semiconductor layer into contact with each other to allow a dye solution to penetrate into a porous semiconductor layer. The coloring matter solution is prepared by dissolving the coloring matter in a mixed solvent using an aprotic polar solvent, a lower alcohol and / or a surfactant, so that the concentration of the coloring matter in the weight percentage is 0.5 wt% or more.

Japanese Patent Application Laid-Open No. 2006-196439 Japanese Patent Application Laid-Open No. 2013-65434 Japanese Patent Application Laid-Open No. 2010-182467

As shown in Comparative Example 2 to be described later, increasing the concentration of the ruthenium-based sensitizing dye to 10 mM by adding N, N-dimethylformamide (DMF), which is one of the nitrogen-containing compounds disclosed in Patent Document 2, It was possible. As a result, the dyeing time was drastically shortened, and dyeing was completed at a high speed as the dye adsorption reached the limit in about 8 minutes.

However, compared with the case of dyeing for 8 hours in the dye solution of low pigment concentration without addition of DMF (Comparative Example 1 to be described later), when dyeing with high dye concentration using DMF was used for a short time There is a problem that the photoelectric conversion efficiency of Comparative Example 2 described later is not excellent.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has an object of providing a dye sensitizing dye dye having excellent photoelectric conversion efficiency of a photoelectrode having a semiconductor film having a short time for dyeing with a sensitizing dye, And a method of manufacturing a used optical electrode.

[1] A sensitizing dye dye having a mixed solvent and a sensitizing dye, wherein the mixed solvent comprises (A) a nitrogen-containing solvent, (B) an alcoholic solvent and (C) a sulfur-containing solvent, Of the total amount of the coloring matter.

(2) A process for producing a sulfur-containing compound, wherein the nitrogen-containing solvent is an amide solvent and / or a nitrile solvent, (B) the alcohol solvent is an alcohol having 1 to 12 carbon atoms, (C) A sensitizing dyestuff solution according to [1] above, wherein

[3] The sensitizing dye described in [2] above, wherein the nitrogen-containing solvent is acetonitrile, (B) the alcoholic solvent is t-butanol, and (C) the sulfur-containing solvent is dimethylsulfoxide.

[4] The method according to any one of [1] to [5], wherein the content of the nitrogen-containing solvent in the mixed solvent is 20 to 75% by volume, the content of the alcoholic solvent is 20 to 75% 3] or [3].

[5] The sensitizing dye according to any one of [1] to [4], wherein the sensitizing dye comprises ruthenium.

[6] A manufacturing method of a photoelectrode having a step of dyeing the semiconductor film with a sensitizing dye by contacting the semiconductor film formed on the substrate with the sensitizing dye described in any one of [1] to [5] .

[7] The method of manufacturing a photoelectrode according to [6] above, wherein the substrate on which the semiconductor film is formed is immersed in the dye sensitizing dye.

[8] The method of manufacturing a photoelectrode according to [7], wherein the immersion time is less than 1 hour.

[9] The method for producing a photo-electrode as described in any one of [6] to [8], wherein the substrate is a long resin film extruded from a roll.

The sensitizing dyes of the present invention can dissolve the sensitizing dye of the metal complex system at a high concentration of 1 mM or more. According to the method for producing a photoelectrode according to the present invention using this dye sensitizing dye, dyeing time can be shortened to several minutes to several tens of minutes in order to dye a semiconductor film with a dye sensitizing dye having a high concentration, The photoelectric conversion efficiency of the photoelectrode can be kept equal to the conventional one. Therefore, a dye-sensitized solar cell having photoelectric conversion efficiency equivalent to that of the prior art can be manufactured in a shorter time than in the prior art.

Hereinafter, the present invention will be described based on preferred embodiments of the present invention, but the present invention is not limited to these embodiments.

"Increasing coloring dye solution"

The dye sensitizing dye according to the first embodiment of the present invention is a dye sensitizing dye having a mixed solvent and a sensitizing dye, and the mixed solvent is (A) a nitrogen-containing solvent, (B) an alcohol- Containing solvent.

In the sensitizing dye solution of the present embodiment, the sensitizing dye is dissolved at a concentration of 1 mM or more.

Examples of the nitrogen-containing solvent (A) include amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide and N-methylpyrrolidone, nitriles such as acetonitrile and propionitrile . One or two or more of these nitrogen-containing solvents are used.

Examples of the alcoholic solvent (B) include saturated or unsaturated alcohols having 1 to 12 carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and t-butanol. One or more of these alcohols are used.

Examples of the sulfur-containing solvent (C) include sulfoxides such as dimethyl sulfoxide (DMSO) and sulfone such as sulfolane. One or two or more of these sulfur-containing solvents are used. The boiling point of the sulfur-containing solvent (C) is preferably 300 占 폚 or lower, more preferably 200 占 폚 or lower.

Preferred combinations of A, B and C above include, for example, acetonitrile, t-butanol and DMSO; Acetonitrile and 2-propanol and DMSO; N, N-dimethylacetamide, t-butanol and DMSO; N-methylpyrrolidone and t-butanol and DMSO; And the like.

Examples of the solvent which may be added within the range not impairing the effect of the present invention include hydrocarbon such as pentane, hexane and octane, aromatic type such as benzene, toluene and xylene, diethyl ether, methyl-t- Such as acetone, methyl ethyl ketone and the like, amine type, such as triethylamine and tributylamine, carboxylic acids such as acetic acid and propionic acid, methylene chloride, chloroform and the like Halogen-based, tetrahydrofuran, and heterocyclic systems such as pyridine. One or more of these addition solvents may be used. The total amount of these addition solvents to be added is preferably less than 10% by volume in 100% by volume of the mixed solvent.

As an example of a preferable colorimetric / increasing dye solution of the embodiment of the present invention, a mixed solution comprising at least one of an amide solvent and a nitrile solvent, an alcohol having 1 to 12 carbon atoms and at least one of a sulfoxide solvent and a sulfone solvent Solvent and a sensitizing dye of a metal complex system dissolved at a concentration of 1 mM or more.

Preferred examples of the enhancement dye coloring solution of the first embodiment of the present invention include mixed solvents composed of acetonitrile, t-butanol and DMSO, and those having a sensitizing dye of a metal complex system dissolved at a concentration of 1 mM or more.

In the color enhancing dye solution of the present embodiment, the total content of acetonitrile, t-butanol and DMSO constituting the mixed solvent is 100% by volume, and the mixed solvent is preferably composed of only the above three solvents . However, the sensitizing dyes of the present embodiment may contain a solvent other than the mixed solvent as an auxiliary optional ingredient, so long as the effect of the present invention is not impaired.

(A) the content of the nitrogen-containing solvent is 20 to 75% by volume, (B) the content of the alcoholic solvent is 20 to 75% by volume, (C) the content of the sulfur- And preferably 60 vol.%.

(A) the content of the nitrogen-containing solvent is 30 to 65% by volume, (B) the content of the alcoholic solvent is 30 to 65% by volume, (C) the content of the sulfur-containing solvent is 5 to 100% by volume, More preferably 30% by volume.

(A) the content of the nitrogen-containing solvent is 40 to 55% by volume, (B) the content of the alcoholic solvent is 40 to 55% by volume, (C) the content of the sulfur-containing solvent is 5 to 100% by volume, More preferably 20% by volume.

When the content of each solvent is within the above preferable range, it is possible to reliably dissolve the sensitizing dye in a concentration of 1 mM or more, and to prevent the sensitizing dye from precipitating or precipitating in the dyeing solution in the dyeing step.

The mixing ratio (by volume) of the nitrogen-containing solvent and the alcohol-based solvent constituting the mixed solvent is preferably 6: 1 to 1: 6, more preferably 4: 1 to 1: 4, More preferably from 2: 1 to 1: 2.

With the above preferable mixing ratio, it is possible to reliably dissolve the sensitizing dye in a concentration of 1 mM or more, and to prevent the sensitizing dye from precipitating or precipitating in the dyeing solution in the dyeing step.

The mixing ratio (by volume) of the nitrogen-containing solvent and the sulfur-containing solvent constituting the mixed solvent is preferably 10: 1 to 1: 1, more preferably 8: 1 to 2: 1, More preferably from 6: 1 to 3: 1.

With the above preferable mixing ratio, it is possible to reliably dissolve the sensitizing dye in a concentration of 1 mM or more, and to prevent the sensitizing dye from precipitating or precipitating in the dyeing solution in the dyeing step.

The mixing ratio (by volume) of the alcohol solvent (B) and the sulfur-containing solvent (B) constituting the mixed solvent is preferably 10: 1 to 1: 1, more preferably 8: 1 to 2: More preferably from 6: 1 to 3: 1.

With the above preferable mixing ratio, it is possible to reliably dissolve the sensitizing dye in a concentration of 1 mM or more, and to prevent the sensitizing dye from precipitating or precipitating in the dyeing solution in the dyeing step.

The concentration of the enhancer dye of the metal complex system dissolved in the sensitizing dye solution of the present embodiment is preferably 1 mM or more, more preferably 2 to 20 mM, still more preferably 3 to 16 mM, still more preferably 4 to 12 mM, Most preferably 10 mM, most preferably 6 to 10 mM.

When the concentration is in the range of 1 mM or more or in the above-mentioned appropriate range, the dyeing can be performed in a shorter time than the conventional dyeing time (for example, 8 hours or more). As the increase / decrease dye concentration increases, the dyeing efficiency improves, and dyeing tends to be completed in a shorter time. However, when the concentration exceeds 20 mM, the viscosity of the dyeing solution becomes high, so that the effect of shortening the dyeing time may reach the limit, or the dyeing efficiency may be lowered inversely.

A metal complex as a sensitizing dye used in a dye-sensitized solar cell is a compound which absorbs a specific wavelength band of sunlight to become an excited state. Examples of the metal constituting the metal complex include transition metals such as ruthenium, osmium, iron, platinum, cobalt, zinc, magnesium, copper, rhenium or chromium. When the metal complex structure of the compound has a nitrogen-containing aromatic ring coordinated to the metal, examples of the ring include a nitrogen-containing aromatic ring such as pyridine, phenanthroline, quinoline, and the like.

The kinds of the sensitizing dyes dissolved in the sensitizing dyes of the present embodiment are not particularly limited, and known sensitizing dyes can be used. The types of the sensitizing dyes may be one kind or two or more kinds. When two or more kinds of sensitizing dyes are dissolved, the total concentration may be 1 mM or more. As the sensitizing dye, for example, a metal complex system sensitizing dye for embedding the metal is preferable, and a metal complex dye sensitizing dye having any one or more of the nitrogen containing aromatic rings coordinated to the metal is more preferable. It is preferable that the sensitizing dye has at least one of a carboxyl group, a sulfonyl group, and a phosphonyl group as a functional group bonding to the surface of the semiconductor film.

Examples of preferred metal complex dye sensitizing pigments are listed below.

≪ Ruthenium-pyridine type complex >

Cis-dithiocyano bis (4, 4'-dicarboxy-2,2'-bipyridine) ruthenium]; cis-dithiocyano bis (4,4'- dcbpy) 2 (NCS) 2; generic name: N3,

Ru (tctpy) 2 (NCS) 3, generic name: N714,

Ru (dmipy) (dcbpyH) I,

Ru (dcphenTBA (H)) 2 (NCS) 2,

cis-Ru (dcbiqH) 2 (NCS) 2 (TBA) 2

≪ Osmium-pyridine-based complex >

Cis-dithiocyano bis (4,4'-dicarboxy-2,2'-bipyridine) osmium] Os (dcbpy ) 2 (NCS) 2

≪ Iron-pyridine complex >

Cis-dithiocyano bis (4,4'-dicarboxy-2,2'-bipyridine) iron]; Fe (dcbpy ) 2 (NCS) 2

≪ Copper-phenanthroline complex >

Bis (2,9-di (4-carboxy) diphenyl-1,10-phenanthroline) copper]

≪ Platinum-quinoxaline complex >

Pt (dcbpy) 2 (L) 2 [L: quinoxaline -2,3-dithiolate]

≪ Rhenium-pyridine-based complex &

Re (bpy) (CO) 3 (ina)

The dye sensitizing dye of the present embodiment may contain any component other than the above-mentioned mixed solvent and the sensitizing dye, so long as the effect of the present invention is not impaired.

&Quot; Method of manufacturing photoelectrode "

The method of manufacturing a photoelectrode according to the second embodiment of the present invention has a step of dyeing the semiconductor film with a sensitizing dye by contacting the semiconductor film formed on the substrate with the sensitizing dye solution of the first embodiment described above. The manufacturing method of the present embodiment may have a step other than this dyeing step. In this specification and claims, the terms "semiconductor film" and "semiconductor layer" are synonymous and not distinguished.

As the semiconductor film to be dyed by using the above-described increase / decrease coloring solution, a semiconductor film used in a conventional dye-sensitized solar cell can be applied. For example, a porous semiconductor film in which semiconductor grains having an average particle diameter of 1 mm or less and in which transition occurs between band gaps are bonded to each other. As the kind of the semiconductor constituting the semiconductor film, for example, TiO ₂ , TiSrO ₃ , BaTiO ₃ , Nb ₂ O ₅ , MgO, ZnO, WO ₃ , Bi ₂ O ₃ , CdS, CdSe, CdTe, In ₂ O ₃ , SnO ₂ , and the like. These semiconductors are preferable because they have good dye adsorption and function well as photoelectrodes carrying a sensitizing dye. From the viewpoint of irreversibly bonding the sensitizing dye, a metal oxide semiconductor such as titanium oxide, zinc oxide, strontium titanate, or stannic oxide having a hydroxyl group (-OH) on its surface is preferable.

The semiconductor film in the present embodiment may be a porous film or a dense film (non-porous film), but it is usually preferable to be a porous film from the viewpoint of increasing the dye binding amount.

When the semiconductor film is a porous film, the porosity (sometimes referred to as porosity, porosity or porosity) of the porous film is preferably 50% or more, more preferably 50 to 85%, further preferably 50 to 75% , And particularly preferably from 50 to 65%.

If it is not less than the lower limit of the above range, the sensitizing dye can be supported more. Below the upper limit of the above range, the strength of the porous film can be made stronger.

The thickness of the semiconductor film in the present embodiment is not particularly limited and may be, for example, about 0.1 to 100 m.

There is no particular limitation on the method of bringing the dye sensitizing dye into contact with the semiconductor film. For example, there are a method of immersing a substrate in which a semiconductor film is formed on a surface thereof in a dye sensitizing dye solution, a method of spraying a dye sensitizing dye in a semiconductor film . From the viewpoint of enhancing the dyeing efficiency, the above-mentioned immersion method is preferable. The time of the contact (dyeing time) varies depending on the thickness of the semiconductor film, but it can be sufficiently dyed in a shorter time than in the prior art. For example, the inside of the semiconductor film can be sufficiently dyed with a contact time of less than one hour. The dyeing time may be shortened to several minutes (for example, about 5 minutes) to several tens of minutes (for example, about 20 minutes).

The dyeing temperature, that is, the temperature of the increasing and decreasing dyeing solution is not particularly limited and may be, for example, in the range of 4 ° C to 40 ° C. When the temperature is low in the above range, evaporation of the mixed solvent can be suppressed. When the temperature is in the above range, the diffusion efficiency of the sensitizing dye increases, and the dyeing time can be shortened in some cases.

The method for forming the semiconductor film is not particularly limited, and for example, a porous metal oxide semiconductor film obtained by sintering metal oxide particles can be obtained by applying a paste containing metal oxide particles and a binder resin to a substrate and further baking. Alternatively, by spraying oxide particles onto a substrate by an aerosol deposition method (AD method), a porous oxide semiconductor film in which oxide particles are bonded to each other on a substrate can be obtained. The semiconductor film obtained by the known method can be dyed using the dye sensitizing dye according to the present invention.

The type of the substrate for supporting the semiconductor film is not particularly limited and a transparent substrate used in a conventional dye-sensitized solar cell is preferable, and examples thereof include a glass substrate, a transparent resin substrate, and a transparent resin film. In the case of using a transparent resin film, the photoelectrode of the dye-sensitized solar cell can be produced in a so-called roll-to-roll system using a long transparent resin film wound from a roll. Specifically, for example, a long PET film is taken out from a roll, an oxide semiconductor film of a predetermined thickness is formed by the AD method, the PET film is dipped in the dye sensitizing dye according to the present invention, After that, if necessary, the sensitizing dye temporarily adhered to the PET film is cleaned with an appropriate cleaning liquid, and the PET film is dried to obtain a photoelectrode having an oxide semiconductor film having a sensitizing dye bonded to the PET film.

A transparent conductive layer may be formed in advance on the surface of the substrate on which the semiconductor film is to be formed. A film type dye-sensitized solar cell is obtained by disposing an electrolyte between the photoelectrode and the counter electrode separately prepared and sealing the electrolyte so as not to leak.

The thickness of the transparent resin film is not particularly limited, and may be 10 탆 to 1000 탆, for example. When the lower limit of the above range is more than the lower limit, the film strength is excellent. When the lower limit is above the upper limit, the lightness is excellent. In the present specification and claims, the terms "film" and "sheet" are synonymous and not to be distinguished.

The transparent resin film and the resin material constituting the transparent resin substrate are not particularly limited and examples thereof include polyacryl, polycarbonate, polyester such as PET and PEN, polyimide, polystyrene, polyvinyl chloride, polyamide and the like .

Example

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, it was operated in a nitrogen atmosphere if necessary.

[Example 1]

(2,2'-bipyridyl-4,4'-dicarboxylic acid TBA) [((2, 2'-bipyridyl-4,4'-dicarboxylic acid TBA)] was added to a mixed solvent prepared by mixing acetonitrile, t-butanol and DMSO at a ratio of 4.5: 2,2'-bipyridyl-4,4'-dicarboxylic acid TBA) was dissolved at a concentration of 6 mM to prepare a sensitizing dye staining solution.

Then, a paste containing titania particles was coated on the glass substrate having the FTO film formed on its surface, and a porous titanium oxide film having a thickness of 9 to 10 탆 was formed by firing at 150 캜. Ti-Nanoxide T / SP manufactured by SOLARONIX Co., Ltd. was used as the titania particles constituting the titanium oxide film.

The substrate provided with the porous titanium oxide film was immersed in the dye sensitizing dye solution prepared above and dyed at 25 캜 in a nitrogen atmosphere. The amount of the dye adsorbed on the titanium oxide film was confirmed by an absorbance meter, and the dye was stained until the adsorption amount reached the limit. As a result, the adsorption amount became a critical point in the soaking time of 6 minutes, and a sufficient amount of N719 adsorbed photo-electrode was obtained. The working area of the photoelectrode was 0.16 cm 2.

[Comparative Example 1]

And a mixture of acetonitrile and t-butanol in a volume ratio of 1: 1 (volume ratio), to obtain a dyeing solution in which a sensitizing dye N719 was dissolved at a concentration of 0.3 mM.

A photo electrode was produced in the same manner as in Example 1 except that the dyeing solution was used. However, the pigment was sufficiently adsorbed on the porous titanium oxide film immersed in the dyeing solution, and a dyeing time of 8 hours was required so that the adsorption amount thereof reached the limit.

[Comparative Example 2]

A sensitizing dye N719 at a concentration of 10 mM was dissolved in a mixed solvent of acetonitrile: t-butanol: DMF (N, N-dimethylformamide) = 4.5: 4.5: 1 (volume ratio).

A photo electrode was produced in the same manner as in Example 1 except that the dyeing solution was used. Since the dye concentration of the dyeing solution used was a relatively high concentration of 10 mM, the amount of adsorption of the dye reached a critical point with a short dyeing time of about 8 minutes.

<Preparation of electrolytic solution>

An appropriate amount of iodine, a basic additive, and an iodine salt were added to an acetonitrile solvent, respectively, and these were prepared by a conventional method.

<Fabrication of dye-sensitized solar cell>

A frame-type Hi-Milan (registered trademark) separator (thickness: 30 mu m) was placed between the both electrodes and the photoelectrode fabricated in each test example was opposed to the Pt foil as a counter electrode. To prepare a dye-sensitized solar cell. At this time, the electrolytic solution was injected into the substrate of the counter electrode through the injection hole previously vacated, and the injection hole was sealed.

&Lt; Evaluation of dye-sensitized solar cell &

Photovoltaic conversion efficiency (power generation performance) of the dye-sensitized solar cell in each of the test examples prepared above was measured using a solar simulator under the condition of AM 1.5. The results are shown in Table 1.

From the above results, it can be concluded that the mixed solvent constituting the sensitizing dye solution of Example 1 according to the present invention can dissolve the ruthenium complex-system dye N719 at a high concentration of 6 mM, a porous titanium oxide film as the sensitizing dye solution of Example 1 It was confirmed that the dye could be dyed in a short time and that the photoelectric conversion efficiency of the obtained photoelectrode was equal to that of the conventional one.

On the other hand, since the solvent constituting the dyeing solution of Comparative Example 1 can not dissolve N719 at a high concentration, it has to be used as a low-concentration dyeing solution, and as a result, a long-time dyeing step is required.

Further, since the solvent constituting the dyeing solution of Comparative Example 2 contains DMF as an additive, N719 can be dissolved at a high concentration of 10 mM, and the porous titanium oxide film can be dyed in a short time with the dyeing solution of Comparative Example 2. However, the photoelectric conversion efficiency was low.

The configurations and combinations of the above-described embodiments are merely examples, and additions, omissions, substitutions, and other modifications are possible without departing from the scope of the present invention. The present invention is not limited to the embodiments, but is limited only by the scope of claims (claims).

The present invention is widely available in the field of dye-sensitized solar cells.

Claims (9)

A sensitizing dye coloring liquid having a mixed solvent and a sensitizing dye,
Wherein the mixed solvent comprises (A) a nitrogen-containing solvent, (B) an alcohol-based solvent and (C) a sulfur-containing solvent, wherein the increase / decrease dye is dissolved at a concentration of 1 mM or more. The positive resist composition according to claim 1, wherein (A) the nitrogen-containing solvent comprises at least one solvent selected from the group consisting of amide solvents and nitrile solvents, (B) the alcohol solvent is an alcohol having 1 to 12 carbon atoms, (C) the sulfur-containing solvent comprises at least one solvent selected from the group consisting of a sulfoxide-based solvent and a sulfone-based solvent. The sensitizing dyeing liquid according to claim 2, wherein the (A) nitrogen-containing solvent is acetonitrile, (B) the alcoholic solvent is t-butanol, and (C) the sulfur-containing solvent is dimethylsulfoxide. 4. The method according to any one of claims 1 to 3, wherein in the mixed solvent
(A) the content of the nitrogen-containing solvent is 20 to 75% by volume,
(B) the content of the alcoholic solvent is 20 to 75% by volume,
(C) the content of the sulfur-containing solvent is 1 to 60% by volume,
Phosphorus coloring agent. 5. The dye sensitizing dye according to any one of claims 1 to 4, wherein the sensitizing dye comprises ruthenium. A method of manufacturing a photoelectrode, comprising the step of dyeing the semiconductor film with an increasing dye by bringing the dye sensitizing dye described in any one of claims 1 to 5 into contact with the semiconductor film formed on the substrate. 7. The method of manufacturing a photoelectrode according to claim 6, wherein the substrate having the semiconductor film formed on its surface is immersed in the dye sensitizing dye. The method according to claim 7, wherein the immersion time is less than 1 hour. The method of manufacturing a photoelectrode according to any one of claims 6 to 8, wherein the substrate is a long resin film wound from a roll.