TWI707920B - 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

Method for manufacturing photosensitive dye dyeing liquid and photoelectrode

The present invention relates to a photosensitive dye dyeing solution for dyeing semiconductor layers with photosensitive dyes and a method for manufacturing a photoelectrode using the photosensitive dye dyeing solution.

This application claims priority based on Japanese Patent Application No. 2015-035674 filed in Japan on February 25, 2015, and the content is used herein.

The photosensitive dye is physically or chemically adsorbed on the surface of the oxide semiconductor layer of the Gratzel type dye photosensitive 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 with a semiconductor layer in a photosensitive dye dyeing solution is generally used (for example, Patent Document 1).

According to this dyeing method, the photosensitive dye dyeing solution can sufficiently penetrate into the porous semiconductor layer. On the other hand, the dyeing time usually requires 8 hours or more.

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

Patent Document 3 discloses a method for manufacturing a dye-sensitive photoelectric conversion element having the steps of bringing a dye solution into contact with the porous semiconductor layer so as to impregnate the dye solution into the porous semiconductor layer. It is generally believed that the dye solution is to dissolve the dye in a mixed solvent using two or any of aprotic polar solvent, lower alcohol and surfactant, and the weight percentage concentration of the dye is set to 0.5 wt% or more.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2006-196439 A

[Patent Document 2] JP 2013-65434 A

[Patent Document 3] JP 2010-182467 A

As shown in Comparative Example 2 below, by adding N,N-dimethylformamide (DMF) as one of the nitrogen-containing compounds disclosed in Patent Document 2 to the dyeing solution, the ruthenium-based photosensitive The concentration of dye was increased to 10mM. Therefore, the dyeing time can be greatly shortened, and the dyeing can be finished at a high speed in about 8 minutes to the extent that the dye adsorption reaches its peak.

However, there is a problem that it takes 8 hours to dye with a dyeing solution with a low dye concentration without adding DMF (comparative example 1 below), using a dyeing solution with a high dye concentration added DMF in a short time In the case of dyeing (Comparative Example 2 below), the photoelectric conversion efficiency was poor.

The present invention was made in view of the above situation, and its subject is to provide a photosensitive dye dyeing solution that dyes semiconductor films with photosensitive dyes in a short time and is equipped with a photoelectrode of the semiconductor film dyed in a short period of time with excellent photoelectric conversion efficiency. And the manufacturing method of the photoelectrode using the dyeing solution.

[1] A photosensitive dye dyeing solution comprising a mixed solvent and a photosensitive dye, wherein the mixed solvent contains (A) a nitrogen-containing solvent, (B) an alcohol solvent and (C) a sulfur-containing solvent, and the photosensitive dye is Dissolve at a concentration above 1mM.

[2] The photosensitive dye dyeing solution described in [1] above, wherein (A) the nitrogen-containing solvent is an amide-based solvent and/or a nitrile-based solvent, and (B) the alcohol-based solvent is an alcohol with 1 to 12 carbon atoms , (C) The sulfur-containing solvent is of the sub-sulphur series and/or the sulphur series.

[3] The photosensitive dye dyeing solution described in [2] above, wherein (A) the nitrogen-containing solvent is acetonitrile, (B) the alcohol-based solvent is tertiary butanol, and (C) the sulfur-containing solvent is dimethyl sulfoxide .

[4] The photosensitive dye dyeing liquid as described in any one of [1] to [3] above, wherein the content of the nitrogen-containing solvent in the mixed solvent is 20 to 75% by volume, and the content of the alcohol solvent is 20 ~75% by volume, and the content of sulfur-containing solvent is 1~60% by volume.

[5] The photosensitive dye dyeing solution according to any one of [1] to [4] above, wherein the photosensitive dye contains ruthenium.

[6] A method of manufacturing a photoelectrode, which has the following steps: by contacting the photosensitive dye dyeing solution described in any one of [1] to [5] above with a semiconductor film formed on a substrate, using The photosensitive dye dyes the above-mentioned semiconductor film.

[7] The method of manufacturing a photoelectrode as described in [6] above, wherein the semiconductor is formed on the surface The substrate of the body film is immersed in the above-mentioned photosensitive dye dyeing solution.

[8] The method for manufacturing a photoelectrode as described in [7] above, wherein the immersion time is less than 1 hour.

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

The photosensitive dye dyeing solution of the present invention can dissolve the metal complex-based photosensitive dye at a high concentration of 1 mM or more. According to the photoelectrode manufacturing method of the present invention using the photosensitive dye dyeing solution, since the semiconductor film is dyed with a high concentration of photosensitive dye, the dyeing time can be shortened to several minutes to tens of minutes, and the dyed dye can be reduced The photoelectric conversion efficiency of the photoelectrode of the semiconductor film remains the same as before. Therefore, it is possible to manufacture dye photosensitive solar cells with the same photoelectric conversion efficiency as before in a shorter time than before.

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

"Photosensitive dye dyeing liquid"

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

In the photosensitive dye dyeing solution of this embodiment, the aforementioned photosensitive dye is dissolved at a concentration of 1 mM or more.

(A) Nitrogen-containing solvents include, for example, amide series such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methylpyrrolidone; acetonitrile , Propionitrile and other nitrile series. Use one or more of these nitrogen-containing solvents.

(B) Alcohol-based solvents include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, and other saturated or non-carbon 1-12 solvents. Saturated alcohol. One or two or more of these alcohols are used.

(C) Sulfur-containing solvents include subsulfone series such as dimethylsulfoxide (DMSO), and trisulfide series such as cyclobutane. Use one or more of these sulfur-containing solvents. (C) The boiling point of the sulfur-containing solvent is preferably 300°C or lower, more preferably 200°C or lower.

As a preferred combination of the above A, B, and C, for example, acetonitrile and tertiary butanol and DMSO; acetonitrile and 2-propanol and DMSO; N,N-dimethylacetamide and tertiary butanol and DMSO; N-methylpyrrolidone, tertiary butanol and DMSO, etc.

Examples of solvents that can be added within a range that does not hinder the effects of the present invention include hydrocarbons such as pentane, hexane, and octane; aromatics such as benzene, toluene, and xylene; diethyl ether, methyl tertiary Ether series such as butyl ether; ester series such as ethyl acetate and butyl acetate; ketone series such as acetone and methyl ethyl ketone; amine series such as triethylamine and tributylamine; carboxylic acid series such as acetic acid and propionic acid; Halogen systems such as methyl chloride and chloroform; heterocyclic systems such as tetrahydrofuran and pyridine. One or two or more of these additional solvents can also be used. The total amount of the added solvents is preferably less than 10% by volume in 100% by volume of the mixed solvent.

As an example of a suitable photosensitive dye dyeing solution for the embodiment of the present invention, Enumerate those having a mixed solvent and a metal complex-based photosensitive dye. The mixed solvent is composed of at least one of an amide-based solvent and a nitrile-based solvent, an alcohol with a carbon number of 1 to 12, and at least one of a sulfite-based solvent and a sulfite-based solvent In one configuration, the metal complex photosensitive dye is dissolved at a concentration of 1 mM or more.

As a suitable photosensitive dye dyeing solution of the first embodiment of the present invention, one having a mixed solvent and a metal complex photosensitive dye, the mixed solvent consisting of acetonitrile, tertiary butanol and DMSO, the metal complex The photosensitive dye is dissolved at a concentration of 1 mM or more.

In the photosensitive dye dyeing solution of this embodiment, it is preferable that the total content of acetonitrile, tertiary butanol, and DMSO constituting the mixed solvent is 100% by volume, and the mixed solvent is only composed of the above three solvents. Among them, as long as the gist of the present invention is not impaired, the photosensitive dye dyeing liquid of this embodiment may contain a solvent other than the above-mentioned mixed solvent as an auxiliary optional component.

Preferably, in the above-mentioned mixed solvent 100% by volume, the content of (A) nitrogen-containing solvent is 20~75% by volume, (B) the content of alcoholic solvent is 20~75% by volume, and (C) the content of sulfur-containing solvent is 1~60% by volume.

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

More preferably, in the above-mentioned mixed solvent 100% by volume, (A) the content of nitrogen-containing solvent is 40~55% by volume, (B) the content of alcoholic solvent is 40~55% by volume, and (C) the content of sulfur-containing solvent It is 5-20% by volume.

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

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

If it is the above-mentioned suitable mixing ratio, the photosensitive dye can be reliably dissolved at a concentration of 1 mM or more, thereby preventing the precipitation or precipitation of the photosensitive dye in the dyeing solution during the dyeing step.

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

If it is the above-mentioned suitable mixing ratio, the photosensitive dye can be reliably dissolved at a concentration of 1 mM or more, thereby preventing the precipitation or precipitation of the photosensitive dye in the dyeing solution during the dyeing step.

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

If it is the above-mentioned suitable mixing ratio, the photosensitive dye can be reliably dissolved at a concentration of 1 mM or more, thereby preventing the precipitation or precipitation of the photosensitive dye in the dyeing solution during the dyeing step.

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

If it is 1 mM or more or the above-mentioned suitable concentration range, dyeing can be performed in a time shorter than the previous general dyeing time (such as 8 hours or more). There is a tendency that the higher the concentration of the photosensitive dye, the higher the dyeing efficiency, and the more the dyeing can be completed in a shorter time. Among them, if it is more than 20mM If the concentration of the dyeing liquid becomes higher, the effect of shortening the dyeing time reaches its peak, but the dyeing efficiency decreases.

The metal complexes used as photosensitive dyes in dye-sensitive solar cells are compounds that absorb sunlight in a specific wavelength range and become excited states. 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 above-mentioned compound has a nitrogen-containing aromatic ring coordinated with a metal, examples of the ring include nitrogen-containing aromatic rings such as pyridine, phenanthroline, and quinoline.

The type of photosensitive dye dissolved in the photosensitive dye dyeing solution of this embodiment is not particularly limited, and known photosensitive dyes can be used. There may be one kind of the above-mentioned photosensitive dye, or two or more kinds. In the case of dissolving two or more photosensitive dyes, the total concentration may be 1 mM or more. As the above-mentioned photosensitive dye, for example, a metal complex-based photosensitive dye coordinated with the above-mentioned metal is preferable, and more preferably a metal complex-based dye having any one or more of the nitrogen-containing aromatic rings coordinated with the above-mentioned metal Photosensitive dyes. In addition, the above-mentioned photosensitive dye preferably has one or more carboxyl groups, sulfonyl groups, or phosphonyl groups as functional groups bonded to the surface of the semiconductor film.

Hereinafter, an example of a suitable metal complex-based photosensitive dye is listed.

<Ruthenium-pyridine complex>

Cis-Dithiocyanobis(4,4'-dicarboxy-2,2'-bipyridine) ruthenium, Ru(dcbpy)2(NCS)2; Common name: N3, Ru(tctpy)2(NCS)3 , Common name: N714, Ru(dmipy)(dcbpyH)I, Ru(dcphenTBA(H))2(NCS)2, cis-Ru(dcbiqH)2(NCS)2(TBA)2

<Osmium-pyridine complex>

Cis-Dithiocyanobis(4,4'-dicarboxy-2,2'-bipyridine) osmium, Os(dcbpy)2(NCS)2

<Iron-pyridine complex>

Cis-Dithiocyanobis(4,4'-dicarboxy-2,2'-bipyridine) iron, Fe(dcbpy)2(NCS)2

<Copper-phenanthroline complexes>

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

啉系錯合物> <Platinum-quine

Morinoline complexes>

啉-2,3-二硫醇鹽] Pt(dcbpy)2(L)2[L: Quine

[Pholin-2,3-dithiolate]

<Rhenium-pyridine complex>

Re(bpy)(CO)3(ina)

As long as it does not impair the gist of the present invention, the photosensitive dye dyeing solution of this embodiment may contain optional components other than the above-mentioned mixed solvent and photosensitive dye.

"Manufacturing Method of Photoelectrode"

The manufacturing method of the photoelectrode of the second embodiment of the present invention has the following steps: the semiconductor film formed on the substrate is brought into contact with the photosensitive dye dyeing solution of the first embodiment to dye the semiconductor film with the photosensitive dye . The manufacturing method of this embodiment may have steps other than the dyeing step. In addition, in this specification and the scope of the patent application, the terms "semiconductor film" and "semiconductor layer" have the same meaning, and no distinction is made.

As the semiconductor film dyed with the above-mentioned photosensitive dye dyeing solution, the semiconductor film used in the conventional dye photosensitive solar cell can be used. For example, a porous semiconductor film in which semiconductor particles with an average particle diameter of 1 mm or less and transitions between energy gaps are joined to each other can be mentioned. As the type of 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 etc. These semiconductors are preferable because they have good dye adsorption and perform well as a photoelectrode supporting photosensitive dyes. From the viewpoint of irreversibly binding photosensitive dyes, metal oxide semiconductors such as titanium oxide, zinc oxide, strontium titanate, and tin dioxide having hydroxyl (-OH) on the surface are more suitable.

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

When the above-mentioned semiconductor film is a porous film, its porosity (sometimes referred to as porosity, porosity or porosity) is preferably 50% or more, more preferably 50 to 85%, and more preferably 50~75%, especially 50~65%.

If it is more than the lower limit of the above range, more photosensitive dyes can be supported. If 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 this embodiment is not particularly limited. For example, a thickness of about 0.1 μm to 100 μm can be mentioned.

The method of bringing the photosensitive dye dyeing solution into contact with the semiconductor film is not particularly limited. For example, a method of immersing the substrate on which the semiconductor film is formed in the photosensitive dye dyeing solution or the method of spraying the photosensitive dye dyeing solution onto the semiconductor film can be mentioned. . From the viewpoint of improving dyeing efficiency, the above-mentioned dipping method is preferred. Although the aforementioned contact time (dyeing time) also depends on the thickness of the semiconductor film, it can be sufficiently dyed in a shorter time than before, for example, it can be sufficiently dyed to the inside of the semiconductor film with a contact time of less than 1 hour. The dyeing time mentioned above can be shortened to several minutes (for example, about 5 minutes) to tens of minutes (for example, about 20 minutes).

The dyeing temperature, that is, the temperature of the photosensitive dye dyeing solution is not particularly limited, for example, Carry out in the range of 4℃~40℃. If it is a low temperature in the above-mentioned range, the evaporation of the above-mentioned mixed solvent can be suppressed. If it is a high temperature in the above range, the diffusion efficiency of the photosensitive dye may increase, and the dyeing time may be further shortened.

The method for forming the semiconductor film is not particularly limited. For example, a paste containing metal oxide particles and a binder resin is applied to a substrate and then fired to obtain a porous metal made by sintering the metal oxide particles. Oxide semiconductor film. Alternatively, by blowing oxide particles onto the substrate by aerosol deposition methods (AD method), a porous oxide semiconductor film in which oxide particles are joined to the substrate is obtained. The photosensitive dye dyeing solution of the present invention can be used to dye a semiconductor film obtained by a known method.

The type of the above-mentioned substrate supporting the semiconductor film is not particularly limited. The transparent substrate used in the conventional dye-sensitive solar cell is suitable, for example, glass substrates, transparent resin substrates, transparent resin films, and the like. In the case of using a transparent resin film, a so-called roll to roll method can be used to manufacture the photoelectrode of the dye-sensitive solar cell by rolling out a long transparent resin film from a roll. Specifically, for example, a long PET film can be unrolled from a roll, an oxide semiconductor film of a specific thickness can be formed by the AD method, and then the PET film can be immersed in the photosensitive dye dyeing solution of the present invention. After a specific time If necessary, the temporarily attached photosensitive dyes are appropriately washed with a cleaning solution, and then the PET film is dried to obtain a photoelectrode having an oxide semiconductor film with photosensitive dyes bonded to the PET film. A transparent conductive layer can also be provided on the surface of the substrate on which the semiconductor film is formed. The electrolyte is arranged between the photoelectrode and the opposite electrode prepared separately, and sealed in a way that the electrolyte does not leak out, thereby obtaining a film-type dye photosensitive solar cell.

The thickness of the transparent resin film is not particularly limited, and for example, 10 μm to 1000 μm can be cited. If it is more than the lower limit of the above range, the film strength is excellent, if it is the upper limit of the above range Below, it is excellent in light weight. Furthermore, in this specification and the scope of the patent application, the terms "membrane" and "sheet" 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. Examples include: acrylic polymer, polycarbonate, PET or PEN and other polyesters; polyimide, polystyrene, and polychloride Ethylene, polyamide, etc.

[Example]

Next, the present invention will be explained in more detail with examples, but the present invention is not limited by these examples. Hereinafter, the operation is performed in a nitrogen environment as necessary.

[Example 1]

Prepared in a mixed solvent with acetonitrile: tertiary butanol: DMSO=4.5:4.5:1 (volume ratio), the photosensitive dye N719 (2,2'-bipyridine-4,4'- Dicarboxylic acid (TBA) sensitive dye dyeing solution.

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

The substrate provided with the porous titanium oxide film was immersed in the photosensitive dye dyeing solution prepared above, and dyed at 25° C. in a nitrogen atmosphere. Use an absorbance meter to confirm the amount of dye adsorbed on the titanium oxide film, and dye until the adsorption amount reaches its peak. As a result, the adsorption amount reached its peak in the immersion time of 6 minutes, and a photoelectrode with a sufficient amount of N719 adsorbed was obtained. The active area of the photoelectrode is 0.16 cm ² .

[Comparative Example 1]

A dye solution prepared by dissolving the photosensitive dye N719 at a concentration of 0.3 mM in a mixed solvent of acetonitrile: tertiary butanol = 1:1 (volume ratio).

A photoelectrode was produced in the same manner as in Example 1, except that the above-mentioned dyeing solution was used. Among them, in order for the porous titanium oxide film immersed in the dyeing solution to fully adsorb the dye, it takes 8 hours for the dyeing time to reach its peak.

[Comparative Example 2]

Prepared in a mixed solvent of acetonitrile: tertiary butanol: DMF (N,N-dimethylformamide)=4.5:4.5:1 (volume ratio), and dyeing with the photosensitive dye N719 dissolved in a concentration of 10mM liquid.

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

<Preparation of Electrolyte>

Prepare iodine, alkaline additives, and iodide salt in appropriate amounts in acetonitrile solvent, and prepare by conventional methods.

<Production of Dye Photosensitive Solar Cell>

The above-mentioned electrolyte was injected into the cell to fabricate a dye-sensitive solar cell. The photoelectrode made in each test example was opposed to the Pt foil as the counter electrode, and a frame-shaped Himilan (registered (Trademark) made of separator (thickness 30μm) and sealed. At this time, the electrolyte is injected from an injection hole previously opened on the substrate of the counter electrode to seal the injection hole.

<Evaluation of Dye Photosensitive Solar Cells>

A solar simulator was used to irradiate simulated sunlight under AM1.5 conditions, and the photoelectric conversion efficiency (power generation performance) of the dye photosensitive solar cell of each test example produced above was measured. The results are shown in Table 1.

From the above results, it is confirmed that the mixed solvent constituting the photosensitive dye dyeing solution of Example 1 of the present invention can dissolve the ruthenium complex dye N719 at a high concentration of 6 mM, and the photosensitive dye dyeing solution of Example 1 can be used in a short time By dyeing the porous titanium oxide film, the photoelectrode obtained has the same excellent photoelectric conversion efficiency as before.

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

In addition, since the solvent constituting the dyeing solution of Comparative Example 2 contains DMF as an additive, it can dissolve N719 at a high concentration of 10 mM, and the dyeing solution of Comparative Example 2 can be used to dye the porous titanium oxide film in a short time. However, the photoelectric conversion efficiency is low.

The configurations and combinations of these in the embodiments described above are just examples, and additions, omissions, replacements, and other changes can be made to the configurations without departing from the scope of the present invention. In addition, the present invention is not limited by each embodiment, but is limited only by a claim.

[Industrial availability]

The invention can be widely used in the field of dye photosensitive solar cells.

Claims (4)

A method for manufacturing a photoelectrode using a photosensitive dye dyeing solution with a mixed solvent and photosensitive dye to dye the semiconductor film formed on the surface of the substrate. The content of (A) acetonitrile in the mixed solvent is 20~75% by volume , (B) the content of tertiary butanol is 20~75% by volume, and (C) the content of dimethylsulfoxide is 1~60% by volume. The photosensitive dye is dissolved at a concentration of 1mM or more and 20mM or less. The manufacturing method has The step of immersing the substrate with the semiconductor film formed on the surface in the photosensitive dye dyeing solution for less than 1 hour. For example, the method for manufacturing a photoelectrode in the scope of the patent application, wherein the photosensitive dye is a ruthenium-pyridine complex. For example, the manufacturing method of the photoelectrode of item 1 or 2 of the scope of patent application, wherein the substrate is a long resin film rolled from a roll. For example, the manufacturing method of the photoelectrode item 3 in the scope of patent application, wherein the thickness of the resin film is 10μm~1000μm.