JP2002353483A - Dye sensitizing solar cell and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye sensitizing solar cell, where a metal oxide semiconductor is laminated at a low temperature using the same material as in prior art. SOLUTION: In the manufacturing method of dye sensitizing solar cells where at least a transparent conductive layer, a metal oxide semiconductor layer where a dye is made to adsorb, a change transportation layer, a conductive layer, and/or conductive catalyst layer are formed successively, the metal oxide semiconductor layer should be formed by applying metal alkoxide or metal oxide gel to the transparent conductive layer on the substrate prior to plasma treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye-sensitized solar cell that absorbs light and converts it into electricity by using a sensitizing dye adsorbed on a metal oxide semiconductor.

[0002]

2. Description of the Related Art In general, single-crystal silicon solar cells, amorphous silicon solar cells, compound semiconductor solar cells, and the like are known as solar cells. However, it is difficult to reduce manufacturing costs and raw material costs, which hinders the spread of solar cells. Had become. Under these circumstances, it is known that a dye-sensitized solar cell using an electrode constituted by supporting a dye on the surface of a semiconductor layer has features of low cost and high conversion efficiency. For example, Japanese Patent No. 2664194 Or Patent No. 2101
No. 079 is described in each specification.

The structure of a dye-sensitized solar cell is as follows. As the photoelectrode, a porous metal oxide semiconductor electrode obtained by applying a metal oxide semiconductor sol on a transparent conductive film and sintering is usually used. Furthermore, by immersing these metal oxide semiconductor electrodes in a solution in which the dye is dissolved, the dye is monomolecularly adsorbed on the porous metal oxide semiconductor surface to form a dye layer, whereby the photoelectrode is manufactured. You. Further, a dye-sensitized solar cell is manufactured by forming a transparent conductive film as a counter electrode and a conductive film serving as a catalyst, and then sandwiching the photoelectrode and the counter electrode via a charge transport layer.

The principle of operation of a dye-sensitized solar cell is as follows. Light incident from the photoelectrode side is absorbed by the dye carried on the surface of the metal oxide semiconductor through the transparent conductive film and the metal oxide semiconductor, and the sensitizing dye absorbing the light is excited. The excited dye quickly passes electrons to the metal oxide semiconductor, and the electrons travel through the metal oxide semiconductor and flow to the transparent conductive film. After emitting electrons, the positively charged dye returns to neutral by receiving electrons from the charge transport layer. As described above, the dye-sensitized solar cell operates using the photoelectrode and the counter electrode as the negative electrode and the positive electrode, respectively.

For the charge transport layer, an electrolyte in which iodine and lithium or potassium iodide are dissolved in an organic solvent such as acetonitrile is generally used. When using a liquid, sealing to prevent liquid leakage is very important from the viewpoint of environmental considerations at the time of destruction and the life of the solar cell, but it is difficult to maintain the sealing for a long time It is. Therefore, in recent years, dye-sensitized solar cells using polymer gels that do not have to worry about spillage in place of electrolyte solvents, p-type semiconductors that transport holes without using solvents instead of charge transport layers, and organic materials with electron conductivity are used. An all-solid-state dye-sensitized solar cell using a solid substance or the like has also been proposed.

[0006]

The metal oxide semiconductor in the dye-sensitized solar cell needs to have a surface area as large as possible in order to sufficiently increase the amount of light absorbed by the dye layer in which the dye is monomolecularly adsorbed. Therefore, by using the sol-gel method, it is possible to reduce the size of semiconductor fine particles of 40 nm by 40 nm.
Sintered at 0 ° C to 500 ° C to increase the surface area.
However, in this case, a substrate such as glass that can withstand firing at 400 ° C. or higher must be used, which is naturally limited. In addition, when ITO, which is generally used for a transparent conductive film laminated on a base material, is used, heating at 400 ° C. or more doubles the resistance value or more before heating, and reduces the photoelectric conversion efficiency of the solar cell. Was one of the causes of the decline.

As described above, the conventional dye-sensitized solar cell has a 400
A high temperature of from 500C to 500C is required, but a substrate such as a plastic film cannot withstand this temperature. The use of a flexible substrate such as a plastic film is very important in that the solar cell can be fixed to the windows and walls of personal computers, mobile terminals, watches, automobiles and buildings, and the cost of materials is low. There is great significance in adopting a dye-sensitized solar cell that can be manufactured as a general-purpose solar cell. Therefore, the present invention provides a dye-sensitized solar cell using a means for laminating a metal oxide semiconductor from a material similar to the conventional one at a low temperature, and further provides a flexible dye-sensitized solar cell using a base material such as a plastic film. Provide solar cells.

[0008]

According to the present invention, at least a transparent conductive layer, a metal oxide semiconductor layer having a dye adsorbed thereon, a charge transport layer, a conductive layer and / or a conductive catalyst layer are provided on a substrate. In the method of manufacturing a dye-sensitized solar cell formed in order, the metal oxide semiconductor layer is formed by applying a metal alkoxide or a metal oxide gel to a transparent conductive layer on a substrate, and then performing a plasma treatment on the metal alkoxide or the metal oxide gel. This is a method for producing a dye-sensitized solar cell.

A second aspect of the present invention is the method for producing a dye-sensitized solar cell according to the first aspect, wherein the plasma treatment is performed under atmospheric pressure.

The invention according to claim 3 is that the metal oxide semiconductor is an oxide of at least one metal selected from zinc, niobium, tin, titanium, vanadium, indium, tungsten, tantalum, zirconium, molybdenum and manganese. The method for producing a dye-sensitized solar cell according to claim 1, wherein the method comprises:

A fourth aspect of the present invention is the method for producing a dye-sensitized solar cell according to any one of the first to third aspects, wherein the charge transport layer contains a solid electrolyte or a p-type semiconductor.

[0012] The invention of claim 5 is the method of manufacturing a dye-sensitized solar cell according to any one of claims 1 to 4, wherein the substrate is a plastic film.

According to a sixth aspect of the present invention, there is provided a dye-sensitized solar cell manufactured by the manufacturing method according to any one of the first to sixth aspects.

[0014]

Embodiments of the present invention will be described below in detail. FIG. 1 and FIG. 2 are cross-sectional views each showing the configuration of one embodiment of the dye-sensitized solar cell of the present invention. Photoelectrode 7 in dye-sensitized solar cell 10 of the present invention
Is composed of a substrate 1, a transparent conductive layer 2, a metal oxide semiconductor 3, and a dye 4 carried on the metal oxide semiconductor 3, as shown in FIG. On the photoelectrode, a counter electrode 8 composed of the charge transport layer 5, the substrate 1, and the conductive catalyst layer 6
Are formed. The counter electrode 8 may have the transparent conductive layer 2 formed between the substrate 1 and the conductive catalyst layer 6 as in the dye-sensitized solar cell 20 shown in FIG. In the dye-sensitized solar cell of the present invention, at least one of the two electrodes is transparent.

As the substrate 1 used in the present invention, a glass or plastic film such as polymethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyether sulfone, polyolefin, polyethylene terephthalate (P
ET), polyethylene naphthalate, triacetyl cellulose and the like can be used, but the material is not particularly limited as long as it is an insulating and transparent substrate. Furthermore, from the viewpoint of the environment in which the solar cell is used and its life, light resistance,
Substrates with heat resistance are preferred. In order to effectively take in incident light, an antireflection layer may be provided on the surface of the substrate used for the photoelectrode on which the transparent conductive layer is not laminated.

The transparent conductive layer 2 in the present invention includes:
Tin oxide and zinc oxide doped with fluorine, indium, or the like, and other conductive transparent conductors that have low absorption in the visible light region are preferable.

The transparent conductive layer 2 can be formed by vacuum deposition, reactive deposition, ion beam assisted deposition, sputtering, ion plating, plasma C
Although a vacuum film forming process such as a VD method can be used, any film forming method may be used.

As the metal oxide semiconductor 3 forming the metal oxide semiconductor layer in the present invention, a metal oxide exhibiting the properties of an n-type semiconductor can be used. Specifically, zinc, niobium, tin, titanium, vanadium, indium,
Tungsten, tantalum, zirconium, molybdenum,
Oxides of manganese may be mentioned. Also, SrTiO ₃ ,
CaTiO ₃ , BaTiO ₃ , MgTiO ₃ , SrNb ₂ O
A perovskite such as ₆ , or a composite oxide or oxide mixture thereof can also be used.

The surface of the metal oxide semiconductor has a diameter of 5 nm to 200 nm in order to increase the amount of the dye carried thereon.
It is a porous body in which about m fine particles are laminated. By forming the porous body, the surface area per unit area is increased, and the amount of adsorbed dye is increased, so that the light absorption amount can be sufficiently increased. Depending on the application, the thickness of the laminated film can be reduced if transparency is required, and can be increased if high photoelectric conversion efficiency is required.
２０20 μm.

In the present invention, when these metal oxide semiconductor layers are obtained, a metal halide, a metal alkoxide, or a metal oxide sol obtained by hydrolyzing the metal halide or metal alkoxide is applied onto a transparent conductive film and dried. It is formed by performing a plasma treatment. Through the above operation without a heating step, a metal oxide semiconductor having the same performance as that obtained by using the sol-gel method by heating at 400 ° C. or higher can be obtained. The diameter of the metal oxide semiconductor fine particles obtained by the present invention is about 5 nm to 100 nm.
Met. In the process of the plasma treatment for forming the metal oxide semiconductor layer in the present invention, the temperature of the substrate is kept low. Therefore, a metal oxide semiconductor can be stacked even on a substrate having insufficient heat resistance, such as a plastic film.

When the metal oxide sol is applied to a substrate,
Coating machines such as dipping, spin coater, bar coater, blade coater, knife coater, reverse roll coater, gravure roll coater, squeeze coater, curtain coater, spray coater and die coater can be used, but continuous coating is possible Is more preferable.

The method is performed when forming a metal oxide semiconductor layer.
The plasma treatment may be performed before the coated metal oxide sol is dried, during the drying, at any stage after the drying,
Further, not only one-stage processing but also two or more-stage processing may be performed.

The conditions for the plasma treatment include the type, concentration, pressure, sealing conditions, electric field strength, discharge conditions, etc. of the gas used, and these can be appropriately selected.

As a gas used for the plasma treatment, a reactive gas such as oxygen, hydrogen, nitrogen, carbon dioxide, a fluorine-containing compound or the like, or an inert gas such as helium or argon can be used. When performing the plasma treatment in a vacuum, the pressure is set to 0.0 to stabilize the plasma discharge.
The range is 15 to 2500 Pa.

When the plasma treatment is performed under atmospheric pressure, a known technique can be used.
Phys. D: Appl. Phys. 21 (1988)
838-840 and the method described in Japanese Patent No. 3040358 can be used. According to this method, plasma processing in an open system or a low airtight system is possible, and a continuous metal oxide semiconductor layer can be formed.

As the dye 4 in the present invention, any dye can be selected as long as it absorbs light capable of generating an electromotive force. Such dyes include, for example, ruthenium-tris, ruthenium-bis, osmium-tris, osmium-bis transition metal complexes, or ruthenium-cis-diaqua-bipyridyl complexes, or phthalocyanine, porphyrin, dithiolate complexes, acetylacetonate So-called metal chelate complexes such as complexes, and cyanidin dyes, merocyanine dyes,
Organic dyes such as rhodamine dyes, and oxadiazole derivatives, benzothiazole derivatives, coumarin derivatives,
Stilbene derivatives, organic compounds having an aromatic ring, and others are preferred. These dyes preferably have a large extinction coefficient and are stable against repeated oxidation-reduction. The dye molecule may be a low molecular compound,
Further, a polymer having a repeating unit may be used.

The dye is preferably chemically adsorbed on the metal oxide semiconductor and has a functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amide group, an amino group, a carbonyl group, and a phosphine group. It is preferred to have. Further, it is preferable that a plurality of such functional groups are present in the dye molecule.

In the present invention, the dye 4 is supported on the metal oxide semiconductor by an aqueous solvent,
After preparing a dye solution in which a dye is dissolved in an organic solvent arbitrarily selected, the metal oxide semiconductor is immersed in the dye solution. After a lapse of time sufficient for the dye to be adsorbed on the metal oxide semiconductor, the metal oxide semiconductor can be removed from the dye solution, washed, and dried. When the metal oxide semiconductor is immersed in the dye solution as necessary, heating may be performed, or the dye solution may be made acidic or basic. Alternatively, the metal oxide semiconductor may be treated with an acid or a base and then immersed in a dye solution.

In the dye-sensitized solar cell of the present invention, as the electrolyte contained in the charge transporting layer 5, any material generally used for the charge transporting layer of the dye-sensitized battery can be used arbitrarily, and includes, for example, iodine. An iodide, a bromide, a quinone complex, a tetracyanoquinonedimethane (TCNQ) complex, a dicyanoquinonediimine complex, or the like can be used.

Further, in the charge transport layer 5 of the present invention,
A solid charge transport layer containing a solid electrolyte or a p-type semiconductor can be used. Such a charge transport layer is preferable because there is no possibility of liquid leakage that may occur when a liquid charge transport layer is used.

Specific examples of the material which can be used for the solid charge transporting layer include aromatic amine compounds such as triphenylamine, diphenylamine, and phenylenediamine as a donor skeleton, and condensed polycyclic hydrocarbons such as naphthalene, anthracene, and biylene. , An azo compound such as azobenzene, a compound having a structure in which aromatic rings such as stilbene are connected by an ethylene bond or an acetylene bond, a heteroaromatic ring compound substituted with an amino group, porphyrins, phthalocyanines, and the like. Examples thereof include quinones, tetracyanoquinodimethanes, dicyanoquinonediimines, tetracyanoethylene, viologens, and dithiol metal complexes. Other materials that can be used for the solid charge transport layer include Cu.
I, AgI, TiI, and other metal iodides, C
There are uBr, CuSCN and the like. Further, a polymer gel such as a polyalkylene ether may be used by impregnating an iodide, a quinone complex, or the like. These materials can be used in any combination as needed.

The conductive catalyst layer 6 used for the counter electrode of the present invention
Any conductive material can be used, and examples thereof include metals such as platinum, gold, silver, and copper, and carbon. When these are formed, a vacuum film forming method similar to that for the transparent conductive layer 2 or a method of wet coating a paste of fine particles of these materials can be used.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Example 1 A dye-sensitized solar cell 10 having the layer structure shown in FIG. 1 was produced as follows. First, the photoelectrode 7 used PET (100 μm thick) as the substrate 1, and indium tin oxide (ITO) was formed thereon as the transparent conductive layer 2 by vacuum sputtering. And on top of this,
Titanium oxide was formed as the metal oxide semiconductor layer 3. Titanium oxide is synthesized using a sol-gel method by hydrolyzing titanium tetra-t-butoxide with nitric acid, and after applying the obtained titanium oxide sol on the transparent conductive layer, plasma treatment is performed under atmospheric pressure. It was formed by doing. The plasma treatment is performed in an oxygen atmosphere of 101.32 kPa, a pulse rise time is 10 μs, a peak value is 9 kV, a frequency is 3.5 kHz, and a pulse width is 180 μs.
By applying a pulse voltage of, a plasma discharge was performed. Subsequently, the laminate obtained above was replaced with a screw (4, 4
-Dicarboxy-2,2-bipyridyl) dithiocyanate by immersion in a solution of ruthenium in ethanol
As the dye 4, bis (4,4-dicarboxy-2,2-
Bipyridyl) dithiocyanate ruthenium was supported.
As the counter electrode 8, an electrode formed by forming platinum formed as a conductive catalyst layer 6 on a PET (100 μm thick) film by a vacuum evaporation method was used. The above photoelectrode 7 and counter electrode 8 are overlapped so that the film forming surfaces face each other, and 0.5 M LiI,
A dye-sensitized solar cell was produced by impregnating an electrolyte comprising 0.05 M I ₂ and methoxyacetonitrile as the charge transport layer 5. The current-voltage characteristics of the dye-sensitized solar cell obtained above were measured. M. 1.
5, when using simulated sunlight of 100 mW / cm ² , short-circuit current J _SC = 22 mA / cm ² and open-circuit voltage V _OC = 0.68
V, the fill factor FF = 0.69, and the photoelectric conversion efficiency was η = 10.3%.

Example 2 A dye-sensitized solar cell 20 having the layer structure shown in FIG. 2 was produced as follows. First, the photoelectrode 7 used PET (100 μm thick) as the substrate 1, and indium tin oxide (ITO) was formed thereon as the transparent conductive layer 2 by vacuum sputtering. And on top of this,
Titanium oxide was formed as the metal oxide semiconductor layer 3. Titanium oxide is synthesized using a sol-gel method by hydrolyzing titanium tetra-t-butoxide with nitric acid, and after applying the obtained titanium oxide sol on the transparent conductive layer, plasma treatment is performed under atmospheric pressure. It was formed by doing. The plasma treatment is performed in an oxygen atmosphere of 101.32 kPa, a pulse rise time is 10 μs, a peak value is 9 kV, a frequency is 3.5 kHz, and a pulse width is 180 μs.
By applying a pulse voltage of, a plasma discharge was performed. Subsequently, the laminate obtained above was replaced with a screw (4, 4
-Dicarboxy-2,2-bipyridyl) dithiocyanate by immersion in a solution of ruthenium in ethanol
As the dye 4, bis (4,4-dicarboxy-2,2-
Bipyridyl) dithiocyanate ruthenium was supported.
The photoelectrode 7 was formed by impregnating the charge transport layer 5 with CuI in an acetonitrile solution and heating it on a hot plate at 120 ° C. to evaporate acetonitrile as a solvent. The opposite electrode 8 is made of PET
(100 μm thick), indium tin oxide (ITO) was formed by vacuum sputtering, and gold formed by vacuum evaporation was used as the conductive catalyst layer 6. A dye-sensitized solar cell was produced by stacking the photoelectrode 7 and the counter electrode 8 such that the film-forming surfaces face each other. The current-voltage characteristics of the dye-sensitized solar cell obtained above were measured. M. 1.5, 100mW /
When simulated sunlight of cm ² is used, short-circuit current J _SC = 20 m
A / cm ² , open-circuit voltage V _OC = 0.65 V, fill factor FF = 0.71, and photoelectric conversion efficiency η = 9.2%.

Example 3 A dye-sensitized solar cell 20 having the layer structure shown in FIG. 2 was produced as follows. First, the photoelectrode 7 is made of glass (trade name: Corning 7059,
(Thickness: 1.1 mm), and zinc oxide doped with aluminum was formed thereon as a transparent conductive layer 2 by a vacuum sputtering method. Then, titanium oxide was formed thereon as the metal oxide semiconductor layer 3. Titanium oxide synthesizes titanium oxide sol using a sol-gel method by hydrolyzing titanium tetra-t-butoxide with nitric acid,
The obtained titanium oxide sol was applied on the transparent conductive layer, and then formed by performing a plasma treatment under an oxygen atmosphere of 10 Pa. The plasma treatment is performed at 13.56 MHz R
Plasma discharge was performed for 10 seconds at an output of 500 W using an F power source. Subsequently, the laminate obtained above was immersed in an acetic acid solution of cyanidin to carry cyanidin as Dye 4. As the counter electrode 8,
A film of zinc oxide doped with aluminum is formed on PET (100 μm thick) by vacuum sputtering, and platinum formed by vacuum sputtering is coated on the conductive catalyst layer 6.
What was formed as was used. The above photoelectrode 7 and counter electrode 8 are overlapped so that the film formation surfaces face each other,
A dye-sensitized solar cell was prepared by impregnating a gel electrolyte comprising LiI, 0.05 M I ₂ , methoxyacetonitrile, and polyethylene glycol. The current-voltage characteristics of the dye-sensitized solar cell obtained above were measured. M. When simulated sunlight of 1.5 and 100 mW / cm ² was used, the short-circuit current J _SC = 20 mA / cm ² ,
Open circuit voltage V _OC = 0.67 V, fill factor FF =
At 0.70, the photoelectric conversion efficiency was η = 9.4%.

<Comparative Example> A dye-sensitized solar cell 10 having the layer structure shown in FIG. 1 was produced as follows. First, the photoelectrode 7 is made of glass (Corning 7059, 1.1 mm
), And indium tin oxide (ITO) was formed thereon as a transparent conductive layer 2 by a vacuum sputtering method. Then, titanium oxide was formed thereon as the metal oxide semiconductor layer 3. Titanium oxide synthesizes a titanium oxide sol using a sol-gel method by hydrolyzing titanium tetra-t-butoxide with nitric acid, and after applying the obtained titanium oxide sol on the transparent conductive layer, it is baked at 450 ° C. for 30 minutes. Formed by things. Subsequently, the laminate obtained above was replaced with bis (4,4-dicarboxy-2,2
By immersing it in an ethanol solution of -bipyridyl) dithiocyanate ruthenium, bis (4,4-dicarboxy-2,2-bipyridyl) dithiocyanate ruthenium was supported as Dye 4. As the counter electrode 8, an electrode in which platinum formed as a film on a PET (100 μm thick) by a vacuum evaporation method was formed as the conductive catalyst layer 6 was used. The above photoelectrode 7 and counter electrode 8 are overlapped so that the film forming surfaces face each other, and 0.5M LiI, 0.05M
A dye-sensitized solar cell was prepared by impregnating an electrolyte comprising I ₂ and methoxyacetonitrile as the charge transport layer 5. The current-voltage characteristics of the dye-sensitized solar cell obtained above were measured. M. 1.5, 100mW
/ Cm ² simulated sunlight, short-circuit current J _SC = 21
mA / cm ² , open-circuit voltage V _OC = 0.64 V, fill factor FF = 0.68, and the photoelectric conversion efficiency was η = 9.1%. The dye-sensitized solar cell of the present invention forms the metal oxide semiconductor by the plasma treatment, and is the same as the dye-sensitized solar cell using the metal oxide semiconductor fired at 450 ° C. even though the temperature is low. It has been shown to provide a degree of photoelectric conversion efficiency.

[0038]

According to the present invention, the metal oxide semiconductor layer is formed by applying a metal oxide semiconductor sol to a transparent conductive layer on a substrate and then performing a plasma treatment on the transparent conductive layer. A metal oxide semiconductor layer can be stacked at a low temperature with a material similar to the conventional one without performing a high temperature treatment of ° C.
Further, since high-temperature treatment is not performed, a flexible dye-sensitized solar cell using a substrate such as a plastic film and a method for producing the same can be provided.

[0039]

[Brief description of the drawings]

FIG. 1 is a layer configuration diagram of a dye-sensitized solar cell of the present invention.

FIG. 2 is a layer configuration diagram of the dye-sensitized solar cell of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Transparent conductive layer 3 ... Metal oxide semiconductor 4 ... Dye 5 ... Charge transport layer 6 ... Conductive catalyst layer 7 ... Photoelectrode 8 ... Counter electrode 10, 20 ... Dye-sensitized solar cell

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5F051 AA14 BA15 CB13 EA04 FA02 GA03 GA05 5H032 AA06 AS16 BB05 BB10 CC11 CC17 EE02 EE16

Claims (6)

[Claims] 1. A dye-sensitized solar cell comprising at least a transparent conductive layer, a metal oxide semiconductor layer having a dye adsorbed thereon, a charge transport layer, a conductive layer and / or a conductive catalyst layer formed on a substrate in this order. In the manufacturing method, the metal oxide semiconductor layer is formed by applying a metal alkoxide or a metal oxide gel to a transparent conductive layer on a substrate and then performing a plasma treatment on the metal alkoxide or the metal oxide gel. Battery manufacturing method. 2. The method for manufacturing a dye-sensitized solar cell according to claim 1, wherein said plasma treatment is performed under atmospheric pressure. 3. The method according to claim 1, wherein the metal oxide semiconductor is zinc, niobium,
Tin, titanium, vanadium, indium, tungsten,
The method for producing a dye-sensitized solar cell according to claim 1, wherein the method is an oxide of at least one metal selected from tantalum, zirconium, molybdenum, and manganese. 4. The method for producing a dye-sensitized solar cell according to claim 1, wherein said charge transport layer contains a solid electrolyte or a p-type semiconductor. 5. The method for manufacturing a dye-sensitized solar cell according to claim 1, wherein said substrate is a plastic film. 6. A dye-sensitized solar cell manufactured by the manufacturing method according to claim 1.