TW201638237A - Sensitizing dye-containing dyeing liquid and method for producing photoelectrode - Google Patents

Abstract

A sensitizing dye-containing dying liquid including a mixed solvent and a sensitizing dye, the mixed solvent including (A) a nitrogen-containing solvent, (B) an alcohol-type solvent, and (C) a sulfur-containing solvent, the sensitizing dye being dissolved at a concentration of 1 mM or more. A method for producing a photoelectrode, including a step of contacting the sensitizing dye-containing dying liquid with a semiconductor film formed on a substrate, thereby dying the semiconductor film with the sensitizing dye.

Description

Photosensitive dye dyeing liquid and photoelectrode manufacturing method

The present invention relates to a sensitizing dye staining solution for dyeing a semiconductor layer with a sensitizing dye and a method for producing a photoelectrode using the sensitizing dye staining liquid.

The present application claims priority based on Japanese Patent Application No. 2015-035674, filed on Jan.

A sensitizing dye is physically or chemically adsorbed on the surface of the oxide semiconductor layer of a Gratzel type dye-sensing solar cell.

As a method of adsorbing a photosensitive dye to a semiconductor layer in the production of a photoelectrode, a method of immersing a substrate on which a semiconductor layer is formed in a photosensitive dye dyeing liquid is generally used (for example, Patent Document 1).

According to this dyeing method, the dyeing liquid of the sensitizing dye can be sufficiently permeated into the inside of the porous semiconductor layer, and the dyeing time is usually required to be 8 hours or longer.

In Patent Document 2, as a method of shortening the dyeing time, it is disclosed that a nitrogen-containing compound having a gas or a liquid at 25 ° C and a boiling point of 200 ° C or less is added to the dyeing liquid. A dye solution containing a sensitizing dye at a high concentration.

Patent Document 3 discloses a method of producing a dye-sensitized photoelectric conversion element having a step of bringing a dye solution into contact with the porous semiconductor layer to impregnate a dye solution into a porous semiconductor layer. It is considered that the dye solution dissolves the dye in a mixed solvent using either or both of an aprotic polar solvent and a lower alcohol and a surfactant, and the weight percentage of the dye is set to 0.5% by weight or more.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-196439

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-65434

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-182467

As shown in the following Comparative Example 2, the lanthanide photosensitive can be obtained by adding N,N-dimethylformamide (DMF) which is one of the nitrogen-containing compounds disclosed in Patent Document 2 to the dyeing liquid. The concentration of the dye was increased to 10 mM. Therefore, the dyeing time can be greatly shortened, and the dyeing can be completed at a high speed to the extent that the dye adsorption reaches the apex in about 8 minutes.

However, there is a problem in that a dyeing liquid having a high dye concentration of DMF is added in a short time as compared with a case where dyeing with a low dye concentration is used for dyeing for 8 hours without adding DMF (Comparative Example 1 below). In the case of dyeing (Comparative Example 2 described below), the photoelectric conversion efficiency was poor.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sensitizing dyeing liquid which is excellent in photoelectric conversion efficiency of a photoelectrode having a semiconductor film which is dyed with a short-time dyeing film, and which has a short time for dyeing a semiconductor film. And a method of producing a photoelectrode using the dyeing liquid.

[1] A sensitizing dye dyeing liquid comprising a mixed solvent and a sensitizing dye, wherein the mixed solvent contains (A) a nitrogen-containing solvent, (B) an alcohol-based solvent, and (C) a sulfur-containing solvent, wherein the sensitizing dye is Dissolved at a concentration of 1 mM or more.

[2] The sensitizing dye dyeing liquid according to the above [1], wherein (A) the nitrogen-containing solvent is a guanamine-based solvent and/or a nitrile-based solvent, and (B) the alcohol-based solvent is an alcohol having 1 to 12 carbon atoms. (C) The sulfur-containing solvent is an Alonite and/or a lanthanide.

[3] The sensitizing dye dyeing liquid according to the above [2], wherein (A) the nitrogen-containing solvent is acetonitrile, (B) the alcohol-based solvent is the third butanol, and (C) the sulfur-containing solvent is dimethyl sulfoxide. .

[4] The sensitizing dye dyeing liquid according to any one of the above [1], wherein the content of the nitrogen-containing solvent in the mixed solvent is 20 to 75% by volume, and the content of the alcohol-based solvent is 20 ~75 vol%, the content of the sulfur-containing solvent is from 1 to 60% by volume.

[5] The sensitizing dye dyeing liquid according to any one of [1] to [4] wherein the sensitizing dye contains ruthenium.

[6] A method of producing a photoelectrode, comprising the step of: contacting a sensitizing dye dyeing liquid according to any one of the above [1] to [5] with a semiconductor film formed on a substrate The above-mentioned semiconductor film is dyed with a sensitizing dye.

[7] The method for producing a photoelectrode according to [6] above, wherein the above-described semiconductor is formed on the surface The substrate of the body film is immersed in the above-mentioned sensitizing dye staining solution.

[8] The method for producing a photoelectrode according to the above [7], wherein the immersion time is less than one hour.

[9] The method for producing a photoelectrode according to any one of the above [6], wherein the substrate is a long resin film wound from a roll.

The sensitizing dye dyeing liquid of the present invention can dissolve a metal complex-based sensitizing dye at a high concentration of 1 mM or more. According to the method for producing a photoelectrode of the present invention using the sensitizing dye liquid, since the semiconductor film is dyed with a high concentration of the sensitizing dye, the dyeing time can be shortened to several minutes to several tens of minutes, and the dyed film can be provided. The photoelectric conversion efficiency of the photoelectrode of the semiconductor film is maintained to be equivalent to the prior art. Therefore, it is possible to manufacture a dye-sensitized solar cell having photoelectric conversion efficiency equivalent to that of the prior time, which is shorter than the previous time.

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

"Sensitive dyeing solution"

The sensitizing dye dyeing liquid according to the first embodiment of the present invention has a mixed solvent and a sensitizing dye, and the mixed solvent contains (A) a nitrogen-containing solvent, (B) an alcohol-based solvent, and (C) a sulfur-containing solvent.

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

Examples of the (A) nitrogen-containing solvent include amide groups such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methylpyrrolidone; and acetonitrile. And nitrile such as propionitrile. One or two or more kinds of these nitrogen-containing solvents are used.

Examples of the (B) alcohol-based solvent include a saturated or non-carbon number of 1 to 12 such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol or tert-butanol. Saturated alcohol. One type or two or more types of these alcohols are used.

Examples of the (C) sulfur-containing solvent include an anthraquinone system such as dimethyl sulfoxide (DMSO), and an anthracene system such as cyclopentane. One type or two or more types of these sulfur-containing solvents are used. The boiling point of the (C) sulfur-containing solvent is preferably 300 ° C or lower, more preferably 200 ° C or lower.

As preferred combinations of the above A, B, and C, for example, acetonitrile and third butanol and DMSO; acetonitrile and 2-propanol and DMSO; N,N-dimethylacetamide and tert-butanol are exemplified. DMSO; N-methylpyrrolidone with tert-butanol and DMSO, and the like.

Examples of the solvent which can be added in a range which does not inhibit the effects of the present invention include hydrocarbons such as pentane, hexane, and octane; aromatic systems such as benzene, toluene, and xylene; and diethyl ether and methyl third. Ether such as butyl ether; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; amines such as triethylamine and tributylamine; and carboxylic acid such as acetic acid and propionic acid; Halogen such as methyl chloride or chloroform; heterocyclic ring such as tetrahydrofuran or pyridine. One or two or more of these added solvents may be used. The total amount of the added solvents is preferably less than 10% by volume in 100% by volume of the mixed solvent.

An example of a suitable sensitizing dye dyeing liquid according to an embodiment of the present invention is The mixed solvent and the metal complex-based photosensitive dye are at least one of a guanamine-based solvent and a nitrile-based solvent, an alcohol having 1 to 12 carbon atoms, and at least an anthraquinone solvent and an anthraquinone solvent. In one embodiment, the metal complex-based sensitizing dye is dissolved at a concentration of 1 mM or more.

The photosensitive dye dyeing liquid which is a suitable embodiment of the first embodiment of the present invention includes a mixed solvent and a metal complex dye, and the mixed solvent is composed of acetonitrile, third butanol, and DMSO. The sensitizing dye is dissolved at a concentration of 1 mM or more.

In the sensitizing dye dyeing liquid of the present embodiment, the total content of the acetonitrile, the third butanol, and the DMSO which constitute the mixed solvent is preferably 100% by volume, and the mixed solvent is composed only of the above three kinds of solvents. In addition, the solvent of the sensitizing dye of the present embodiment may contain a solvent other than the above-mentioned mixed solvent as an auxiliary component, as long as it does not impair the gist of the present invention.

Preferably, the content of the (A) nitrogen-containing solvent is 20 to 75% by volume, (B) the content of the alcohol-based solvent is 20 to 75% by volume, and the content of the (C) sulfur-containing solvent is preferably 100% by volume of the mixed solvent. 1 to 60% by volume.

More preferably, in 100% by volume of the above mixed solvent, (A) the content of the nitrogen-containing solvent is 30 to 65 vol%, (B) the content of the alcohol-based solvent is 30 to 65 vol%, and the content of the (C) sulphur-containing solvent is 5 to 30% by volume.

Further preferably, in 100% by volume of the mixed solvent, (A) the content of the nitrogen-containing solvent is 40 to 55% by volume, (B) the content of the alcohol-based solvent is 40 to 55% by volume, and (C) the content of the sulfur-containing solvent. It is 5 to 20% by volume.

When the content of each solvent is within the above-mentioned appropriate range, the sensitizing dye can be reliably dissolved at a concentration of 1 mM or more, thereby suppressing precipitation or precipitation of the sensitizing dye in the dyeing step in the dyeing step. condition.

The mixing ratio (volume basis) of the (A) nitrogen-containing solvent and the (B) alcohol-based solvent constituting the mixed solvent is preferably 6:1 to 1:6, more preferably 4:1 to 1:4, and further preferably It is 2:1~1:2.

According to the above-mentioned suitable mixing ratio, the sensitizing dye can be reliably dissolved at a concentration of 1 mM or more, thereby suppressing precipitation or precipitation of the sensitizing dye in the dyeing liquid in the dyeing step.

The mixing ratio (volume basis) of the (A) nitrogen-containing solvent and the (C) sulfur-containing solvent constituting the above mixed solvent is preferably from 10:1 to 1:1, more preferably from 8:1 to 2:1, and further preferably. It is 6:1~3:1.

According to the above-mentioned suitable mixing ratio, the sensitizing dye can be reliably dissolved at a concentration of 1 mM or more, thereby suppressing precipitation or precipitation of the sensitizing dye in the dyeing liquid in the dyeing step.

The mixing ratio (volume basis) of the (B) alcohol-based solvent and the (C) sulfur-containing solvent constituting the mixed solvent is preferably 10:1 to 1:1, more preferably 8:1 to 2:1, and further preferably It is 6:1~3:1.

According to the above-mentioned suitable mixing ratio, the sensitizing dye can be reliably dissolved at a concentration of 1 mM or more, thereby suppressing precipitation or precipitation of the sensitizing dye in the dyeing liquid in the dyeing step.

The concentration of the metal complex-based sensitizing dye dissolved in the dyeing solution of the sensitizing dye of the present embodiment is 1 mM or more, preferably 2 to 20 mM, more preferably 3 to 16 mM, still more preferably 4 to 12 mM, and particularly preferably 5 ~10 mM, preferably 6-10 mM.

If it is 1 mM or more or the above-mentioned suitable concentration range, it is possible to perform dyeing at a time shorter than the previous general dyeing time (for example, 8 hours or longer). The higher the concentration of the sensitizing dye becomes, the more the dyeing efficiency is improved, and the more the dyeing tendency is completed in a shorter time. Where, if it is more than 20mM At the concentration, the viscosity of the dyeing solution becomes high, and the effect of shortening the dyeing time reaches a peak, and the dyeing efficiency decreases.

A metal complex used as a sensitizing dye used in a dye-sensing solar cell is a compound that absorbs a specific wavelength band of sunlight and becomes an excited state. Examples of the metal constituting the metal complex include transition metals such as ruthenium, rhodium, iron, platinum, cobalt, zinc, magnesium, copper, ruthenium or chromium. In the case where the metal complex structure of the above compound has a nitrogen-containing aromatic ring coordinated to a metal, examples of the ring include a nitrogen-containing aromatic ring such as pyridine, phenanthroline or quinoline.

The type of the photosensitive dye to be dissolved in the dyeing liquid of the photosensitive dye of the present embodiment is not particularly limited, and a known photosensitive dye can be applied. The type of the sensitizing dye may be one type or two or more types. When two or more kinds of sensitizing dyes are dissolved, the total concentration may be 1 mM or more. The sensitizing dye is, for example, preferably a metal complex sensitizing dye in which the metal is coordinated, and more preferably any one or more metal complexes having the nitrogen-containing aromatic ring coordinated to the metal. Photosensitive dyes. Further, the sensitizing dye preferably has one or more carboxyl groups, a sulfonyl group or a phosphonyl group as a functional group bonded to the surface of the semiconductor film.

Hereinafter, an example of a suitable metal complex sensitizing dye will be listed.

<钌-pyridine-based complex>

Cis-dithiocyanobis(4,4'-dicarboxy-2,2'-bipyridyl) anthracene, Ru(dcbpy) 2 (NCS) 2; generic name: N3, Ru(tctpy) 2 (NCS) 3 , commonly known as: N714, Ru (dmipy) (dcbpyH) I, Ru (dcphenTBA (H)) 2 (NCS) 2, cis-Ru (dcbiqH) 2 (NCS) 2 (TBA) 2

<锇-pyridine-based complex>

Cis-dithiocyanobis(4,4'-dicarboxy-2,2'-bipyridyl) anthracene, Os(dcbpy)2(NCS)2

<Iron-pyridine-based complex>

Cis-dithiocyanobis(4,4'-dicarboxy-2,2'-bipyridyl) iron, Fe(dcbpy)2(NCS)2

<Copper-morpholine complex]

Bis(2,9-bis(4-carboxy)diphenyl-1,10-morpholine) copper

<platinum-quine Porphyrin complexes >

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

<铼-pyridine-based complex>

Re(bpy)(CO)3(ina)

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

"Method of Manufacturing Photoelectrodes"

The method for producing a photoelectrode according to the second embodiment of the present invention has the step of dyeing the semiconductor film with a sensitizing dye by bringing the sensitizing dye dyeing solution of the first embodiment into contact with a semiconductor film formed on a substrate. . The production method of this embodiment may have steps other than the dyeing step. Further, in the specification and the patent application, the terms "semiconductor film" and "semiconductor layer" have the same meaning and are not distinguished.

As the semiconductor film dyed using the above-mentioned sensitizing dye liquid, a semiconductor film used in a conventional dye-sensitized solar cell can be applied. For example, a porous semiconductor film in which semiconductor particles having an average particle diameter of 1 mm or less and having a transition between energy gaps are bonded to each other can be mentioned. Examples of the type of the semiconductor constituting the semiconductor film include TiO ₂ , TiSrO ₃ , BaTiO ₃ , Nb ₂ O ₅ , MgO, ZnO, WO ₃ , Bi ₂ O ₃ , CdS, CdSe, CdTe, and In ₂ O ₃ . SnO ₂ and the like. These semiconductors are preferred because they have good dye adsorption and good function as a photoelectrode carrying a sensitizing dye. From the viewpoint of irreversibly bonding the photosensitive dye, a metal oxide semiconductor such as titanium oxide, zinc oxide, barium titanate or tin dioxide having a hydroxyl group (-OH) on the surface is suitable.

The semiconductor film of the present embodiment may be a porous film or a dense film (non-porous film). However, from the viewpoint of increasing the amount of dye binding, a porous film is usually preferred.

In the case where the semiconductor film is a porous film, the void ratio (sometimes referred to as porosity, pore ratio or porosity) is preferably 50% or more, more preferably 50 to 85%, and further preferably 50~75%, especially 50~65%.

When it is more than the lower limit of the above range, the sensitizing dye can be more supported. When it is at most 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 examples thereof include a thickness of about 0.1 μm to 100 μm.

The method of bringing the dyeing liquid of the photosensitive dye into contact with the semiconductor film is not particularly limited, and examples thereof include a method of immersing a substrate having a semiconductor film formed on the surface thereof in a dyeing liquid of a photosensitive dye, or a method of spraying a dyeing liquid of a photosensitive dye onto a semiconductor film. . From the viewpoint of improving the dyeing efficiency, the above-mentioned method of impregnation is preferred. Although the contact time (dyeing time) depends on the thickness of the semiconductor film, the dyeing can be sufficiently performed in a shorter time than the previous time, and for example, it can be sufficiently dyed into the inside of the semiconductor film at a contact time of less than one hour. The above dyeing time can be shortened to a few 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 dyeing liquid of the sensitizing dye is not particularly limited, and for example, It is carried out in the range of 4 ° C to 40 ° C. If it is a low temperature in the above range, evaporation of the above mixed solvent can be suppressed. If it is a high temperature in the above range, the diffusion efficiency of the sensitizing dye is improved, and the dyeing time can be further shortened.

The method for forming the semiconductor film is not particularly limited. For example, a paste containing a metal oxide particle and a binder resin is applied to a substrate and then fired to obtain a porous metal obtained by sintering metal oxide particles. An oxide semiconductor film. Alternatively, the oxide particles are blown onto the substrate by an aerosol deposition method (AD method) to obtain a porous oxide semiconductor film in which oxide particles are bonded to each other on a substrate. The semiconductor film obtained by a known method can be dyed using the sensitizing dye staining solution of the present invention.

The type of the substrate supporting the semiconductor film is not particularly limited, and a transparent substrate used in a conventional dye-sensing 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, a photo-electrode of a dye-sensitized solar cell can be produced by a so-called roll-to-roll method using a long transparent resin film from a roll. Specifically, for example, an oxide film of a specific thickness can be formed by an AD method by rolling a long PET film from a roll, and the PET film can be immersed in the dyeing liquid of the sensitizing dye of the present invention, after a certain period of time. The photosensitive film which is temporarily attached is washed with a washing liquid as needed, and the PET film is dried to obtain a photoelectrode having an oxide semiconductor film in which a photosensitive dye is bonded to the PET film. A transparent conductive layer may be provided in advance on the surface of the substrate on which the semiconductor film is formed. The electrolyte is disposed between the photoelectrode and the separately prepared counter electrode, and sealed so that the electrolyte does not leak, thereby obtaining a film type dye photosensitive solar cell.

The thickness of the transparent resin film is not particularly limited, and examples thereof include 10 μm to 1000 μm. If it is more than the lower limit of the above range, the film strength is excellent, and if it is the upper limit of the above range Hereinafter, it is excellent in light weight. Furthermore, in the specification and the scope of the patent application, the terms "film" and "film" have the same meaning and are not distinguished.

The resin material constituting the transparent resin film and the transparent resin substrate is not particularly limited, and examples thereof include: acrylic polymer, polycarbonate, polyester such as PET or PEN; polyimine, polystyrene, and polychlorinated Ethylene, polyamine, and the like.

[Examples]

Next, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. Hereinafter, it is operated under a nitrogen atmosphere as needed.

[Example 1]

The sensitizing dye N719 (2,2'-bipyridyl-4,4'- was dissolved in a mixed solvent of acetonitrile:tertabutanol:DMSO=4.5:4.5:1 (volume ratio) at a concentration of 6 mM. Dyeing solution of sensitizing dye of dicarboxylic acid TBA).

Next, a paste containing titanium oxide particles was applied onto a glass substrate on which an FTO film was formed on the surface, and a porous titanium oxide film having a thickness of 9 to 10 μm was formed by firing at 150 °C. As the titanium oxide particles constituting the titanium oxide film, Ti-Nanoxide T/SP of SOLARONIX Corporation was used.

The substrate having the porous titanium oxide film was immersed in the dyeing liquid for dyeing prepared above, and dyed at 25 ° C in a nitrogen atmosphere. The amount of the dye adsorbed on the titanium oxide film was confirmed by an absorbance meter, and the amount of the dye was reached until the adsorption amount reached the peak. As a result, the amount of adsorption reached the peak at the immersion time of 6 minutes, and a photoelectrode having a sufficient amount of N719 adsorbed thereon was obtained. The area of action of the photoelectrode was 0.16 cm ² .

[Comparative Example 1]

The dyeing liquid of the sensitizing dye N719 was dissolved in a mixed solvent of acetonitrile:third butanol = 1:1 (volume ratio) at a concentration of 0.3 mM.

A photoelectrode was produced in the same manner as in Example 1 except that the above dye solution was used. Among them, in order to sufficiently adsorb the dye to the porous titanium oxide film immersed in the dyeing liquid, it takes 8 hours for the adsorption amount to reach the apex.

[Comparative Example 2]

The dyeing was carried out in a mixed solvent of acetonitrile: tert-butanol: DMF (N,N-dimethylformamide) = 4.5:4.5:1 (volume ratio) at a concentration of 10 mM to dissolve the sensitizing dye N719. liquid.

A photoelectrode was produced in the same manner as in Example 1 except that the above dye solution was used. Since the dye concentration of the dye solution used was a relatively high concentration of 10 mM, the adsorption of the dye reached its apex by dyeing for a short time of about 8 minutes.

<Preparation of electrolyte>

The iodine, the basic additive, and the iodide salt are respectively prepared in an appropriate amount in an acetonitrile solvent, and are prepared by a conventional method.

<Production of Dye Photosensitive Solar Cell>

The above electrolyte solution was injected into the cell to prepare a dye-sensing solar cell. The cell was made to face the photoelectrode produced in each test example and the Pt foil as the counter electrode, and the frame type Himilan was placed between the electrodes. A separator made of a trademark (thickness: 30 μm) and sealed. At this time, the electrolytic solution is injected from the injection hole previously formed on the substrate of the counter electrode, and the injection hole is sealed.

<Evaluation of dye-sensing solar cells>

The photoelectric conversion efficiency (power generation performance) of the dye-sensing solar cell of each of the test examples prepared above was measured by irradiating simulated sunlight under the conditions of AM 1.5 using a solar simulator. The results are shown in Table 1.

From the above results, it was confirmed that the yttrium complex dye N719 can be dissolved at a high concentration of 6 mM in the mixed solvent of the sensitizing dye dyeing liquid of Example 1 of the present invention, and the sensitizing dyeing solution of Example 1 can be used for a short time. The porous titanium oxide film was dyed, and the photoelectric conversion efficiency of the obtained photoelectrode was excellent as before.

On the other hand, since the solvent constituting the dyeing liquid of Comparative Example 1 could not dissolve N719 at a high concentration, it was necessary to use a dye solution having a low concentration, and as a result, a long-term dyeing step was required.

Further, since the solvent constituting the dyeing liquid 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 by the dyeing liquid of Comparative Example 2. However, the photoelectric conversion efficiency is low.

The present invention is not limited to the scope of the present invention, and may be added, omitted, replaced, or otherwise modified without departing from the spirit and scope of the invention. Further, the present invention is not limited to the embodiments, and is limited only by the claim.

[Industrial availability]

The present invention can be widely utilized in the field of dye-sensitized solar cells.

Claims (9)

A sensitizing dye dyeing liquid comprising a mixed solvent and a sensitizing dye, wherein the mixed solvent contains (A) a nitrogen-containing solvent, (B) an alcohol-based solvent, and (C) a sulfur-containing solvent, wherein the sensitizing dye is 1 mM or more The concentration is dissolved. The photosensitive dye dyeing liquid according to the first aspect of the invention, wherein the (A) nitrogen-containing solvent contains at least one solvent selected from the group consisting of a guanamine solvent and a nitrile solvent, and (B) the alcohol solvent is a carbon number. The alcohol of 1 to 12, (C) the sulfur-containing solvent contains at least one solvent selected from the group consisting of an anthraquinone solvent and an anthraquinone solvent. The sensitizing dye dyeing solution according to claim 2, wherein (A) the nitrogen-containing solvent is acetonitrile, (B) the alcohol-based solvent is third butanol, and (C) the sulfur-containing solvent is dimethyl sulfoxide. The photosensitive dye dyeing liquid according to any one of claims 1 to 3, wherein, in the mixed solvent, the content of the (A) nitrogen-containing solvent is 20 to 75% by volume, and the content of the (B) alcohol-based solvent is 20 to 75 vol%, (C) the content of the sulfur-containing solvent is 1 to 60% by volume. The sensitizing dye dyeing liquid according to any one of claims 1 to 4, wherein the sensitizing dye contains cerium. A method for producing a photoelectrode, comprising the steps of: contacting a semiconductor film formed on a substrate with a sensitizing dye dyeing liquid according to any one of claims 1 to 5, and using the sensitizing dye to the semiconductor The film was dyed. A method of producing a photoelectrode according to the sixth aspect of the invention, wherein the substrate on which the semiconductor film is formed is immersed in the dyeing liquid for the sensitizing dye. The method for producing a photoelectrode according to claim 7, wherein the immersion time is less than one hour. The method for producing a photoelectrode according to any one of claims 6 to 8, wherein the substrate is a long resin film wound from a roll.