JP2002246623A - Dye-sensitized solar cell and method of manufacturing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a full-solid dye-sensitized solar cell, which uses a copper thiocyanate layer as a carrier transport layer and is high in the long-term reliability, and to provide a method of manufacturing the solar cell, which raises the forming rate of the copper thiocyanate layer. SOLUTION: A dye-sensitized solar cell has a porous semiconductor layer with a dye adsorbed and a carrier transport layer constituted of a copper thiocyanate layer between a transparent conducting film formed on the surface of a transparent substrate and a conductive substrate and a method of manufacturing the solar cell is characterized in that the substrate formed with the porous semiconductor layer is dipped into the mixed solution of a copper salt selected from among a copper perchlorate, a copper chloride, a copper bronide, a copper nitrate, a copper sulfate, a copper acetate and a copper formic with a thiocyanate selected from between an alkali metallic salt thiocyanate and an ammonium thiocyanate and the copper thiocyanate layer, which is used as the carrier transport layer, is formed on the porous semiconductor layer by an electrochemical reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye-sensitized solar cell and a method for producing the same. More specifically, the present invention is a p-type oxide semiconductor as the carrier transport layer,
The present invention relates to a dye-sensitized solar cell using copper thiocyanate and a method for manufacturing a dye-sensitized solar cell using an electrochemical reaction (reduction method).

[0002]

2. Description of the Related Art Dye-sensitized solar cells (hereinafter referred to as "solar cells") have received widespread attention because of their high conversion efficiency among organic solar cells. A solar cell is composed of a carrier transport layer sandwiched between a semiconductor electrode and a counter electrode.When light is applied to the semiconductor electrode, electrons are excited on the electrode side, and the excited electrons form an electric circuit. Then, the electrons move to the counter electrode, and the electrons that have moved to the counter electrode move as ions in the carrier transport layer and return to the semiconductor electrode, and electric energy is extracted by repeating such a cycle.

As a semiconductor electrode used as a photoelectric conversion material of such a solar cell, a porous semiconductor having a surface to which a spectral sensitizing dye having absorption in a visible light region is adsorbed is used. As such a solar cell, for example, a solar cell using a metal oxide semiconductor in which a spectral sensitizing dye composed of a transition metal complex is adsorbed on a semiconductor surface is described (Japanese Patent No. 2664194).

FIG. 3 is a schematic sectional view of a main part showing a layer structure of a conventional solar cell. This solar cell is manufactured by the following procedure. First, a porous semiconductor layer (semiconductor electrode) 23 such as titanium oxide is formed on a transparent conductor 22 formed on the surface of a transparent support 21, and a dye is adsorbed on the porous semiconductor layer 23. As a specific method of forming the porous semiconductor layer 23, for example, a method of applying a suspension containing semiconductor particles on the transparent conductor 22, drying and firing at a high temperature, and the like can be mentioned. On the other hand, platinum 26
The transparent support 21 and the counter electrode 25 are overlapped so that the porous semiconductor layer 23 and the platinum 26 face each other, and an electrolytic solution 24 is injected as a carrier transport layer between the transparent support 21 and the platinum 26 so that the transparent support 21 and the platinum 25 is sealed with an epoxy resin 27 or the like.

Japanese Patent Application Laid-Open Nos. 8-236165 and 9-27352 disclose a general formula (1) for preventing electrolyte leakage.

[0006]

Embedded image

Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group; R ³ represents a hydrogen atom or a lower alkyl group; n is an integer of 1 or more; Is an integer, and m / n is in the range of 0 to 5). A solar cell is described, which is a polymer compound containing a structural unit formed from a monomer represented by the following formula: ing.

Specifically, a monomer solution obtained by dissolving a monomer represented by the general formula (1) in ethylene glycol is
Iodine compounds that are redox species (such as lithium iodide)
Is dissolved and impregnated in the porous semiconductor layer, and then polymerized by ultraviolet light or heat to form a polymer compound, and doping is performed by sublimating iodine, another redox species.

However, the solar cell using the polymer compound described in the above-mentioned publication is one in which a gel electrolyte is held in the polymer compound. Therefore, in manufacturing a solar cell, it is necessary to seal the transparent support 21 and the counter electrode 25 with an emphasis on hermeticity in order to protect the gel electrolyte.

On the other hand, a solar cell using a p-type oxide semiconductor, copper thiocyanate, as a carrier transport layer has also been reported (J. Appl. Phys. 80 (8), 15 Oct).
tober 1996, p. 4749-4754). Specifically, about 1 μm of SnO
_A titanium oxide thin film is formed by a spray pyrolysis method on a conductive glass substrate on which
The substrate was immersed in a mixed ethanol solution of uBF ₄ .3.5H ₂ O and 0.025 M-KSCN, and the electrolytic potential was −400 to −−.
A copper thiocyanate layer is formed on the titanium oxide thin film by an electrochemical reaction (electrodeposition or electrodeposition) applying 200 mV (vs. SCE). However, in the method described in the above document, it takes four days to form the copper thiocyanate layer, and there is a problem in terms of productivity and the like.

[0011]

SUMMARY OF THE INVENTION The present invention provides a completely solid-state solar cell using copper thiocyanate for the carrier transport layer and a solar cell with an improved production rate of copper thiocyanate. It is an object to provide a method.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the thiocyanate was electrochemically reacted using a mixed solution of a specific copper salt and thiocyanate. The inventors have found that a carrier transport layer made of copper oxide can be efficiently formed, and have completed the present invention.

Thus, according to the present invention, a porous semiconductor layer in which a dye is adsorbed and a carrier composed of copper thiocyanate are provided between the conductive film and the transparent conductive film formed on the surface of the transparent substrate. In the method for manufacturing a solar cell having a transport layer, the substrate on which the porous semiconductor layer is formed is formed of copper perchlorate, copper chloride, copper bromide, copper nitrate, copper sulfate, copper acetate, and copper formate selected from copper formate. Immersion in a mixed solution of a salt and a thiocyanate selected from an alkali metal salt of thiocyanic acid and ammonium thiocyanate, and forming copper thiocyanate to be a carrier transport layer on the porous semiconductor layer by an electrochemical reaction. A method for manufacturing a solar cell is provided. Further, according to the present invention, there is provided a solar cell obtained by the above manufacturing method.

[0014]

DETAILED DESCRIPTION OF THE INVENTION In general, copper thiocyanate is produced by chemically reacting a copper sulfate sol solution and a potassium thiocyanate sol solution in the presence of SO ₂ . To prepare a solar cell by mixing the obtained copper thiocyanate into a porous semiconductor, copper thiocyanate is dispersed in a solvent, and the copper thiocyanate is dropped on a heated porous semiconductor layer to evaporate the solvent. Can be produced. However, it is very difficult to inject copper thiocyanate into the inside of the porous semiconductor layer, which is a sintered body of fine particles, by such a method. Causes a decrease in

In the method of manufacturing a solar cell according to the present invention, a substrate having a porous semiconductor layer formed thereon is immersed in a mixed solution of a specific copper salt and thiocyanate, and thiocyanic acid serving as a carrier transport layer is formed by an electrochemical reaction. It is characterized in that copper is formed directly on the porous semiconductor layer.

Examples of the copper salt include inorganic salts such as copper perchlorate, copper chloride, copper bromide, copper nitrate, and copper sulfate, and organic acid salts such as copper acetate and copper formate. Copper acid is particularly preferred. Examples of the thiocyanate include lithium thiocyanate, sodium thiocyanate, and ammonium thiocyanate. Of these, lithium thiocyanate is particularly preferred.

Examples of the solvent for the mixed solution of a copper salt and a thiocyanate include alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran, cyanides such as acetonitrile, and water. Can be These solvents can be used as a mixture of two or more kinds.

A mixed solution of a copper salt and a thiocyanate can be prepared by mixing the respective solutions to a predetermined concentration. The concentration of the copper salt is preferably 0.001 mol / L or more (the upper limit is the saturation concentration), and
0.1 mol / l is particularly preferred. The concentration of the thiocyanate is preferably 0.001 mol / l or more (the upper limit is the saturation concentration), and particularly preferably 0.025 to 0.1 mol / l.

Next, the electrochemical reaction will be described. The substrate on which the porous semiconductor layer is formed, the counter electrode, and the reference electrode are immersed in a mixed solution of a copper salt and a thiocyanate, and the electrolytic potential is applied to reduce Cu (II) to Cu (I). Accordingly, copper thiocyanate adheres to the porous semiconductor layer.

The electrochemical reaction is carried out at an electrolytic potential of +0.1 to +
It is preferable to carry out in the range of 0.4 V (vs. SCE).
When the electrolytic potential is higher than the above range, no reaction occurs, and when the electrolytic potential is low, copper is deposited, which is not preferable.

The electrochemical reaction is carried out at a reaction temperature of 10-4.
It is preferable to carry out in the range of 0 ° C. When the reaction temperature is higher than the above range, the growth (crystallization) rate of copper thiocyanate is increased, and the adhesion to the substrate is deteriorated. On the other hand, when the reaction temperature is lower than the above range, the growth rate of copper thiocyanate becomes slow, and the productivity is unfavorably deteriorated.

The type of the electrochemical reaction may be either a bipolar type or a tripolar type. Examples of the reference electrode used in the case of the three-electrode type include SCE (saturated sweet electrode), NHE (standard hydrogen electrode), RHE (reversible hydrogen electrode at hydrogen pressure), NCE (standard sweet electrode).

When copper thiocyanate is formed by an electrochemical reaction, a by-product is generated in the mixed solution. For example, when a mixed solution of copper chloride and lithium thiocyanate is used, lithium chloride is generated. Since such a by-product may remain on the surface of copper thiocyanate or between copper thiocyanate and the porous semiconductor layer, it is preferable to wash the substrate with a solvent after the electrochemical reaction. As the solvent, a solvent having high solubility for by-products is preferable, and for example, ethanol and the like can be mentioned.

According to the manufacturing method of the present invention, a carrier transport layer made of copper thiocyanate is formed at a higher speed (specifically, in a time period of about 1/96) than the method described in the above-mentioned document. be able to.

As the porous semiconductor, various forms such as particles and films can be used, but a film-shaped porous semiconductor (porous semiconductor layer) formed on a substrate is preferable.
Examples of the substrate for forming the porous semiconductor layer include a glass substrate and a plastic substrate, among which a highly transparent substrate (transparent substrate) is particularly preferable. On this substrate, a transparent conductive film such as SnO ₂ is formed by a known method.

As a method for forming the porous semiconductor layer on the substrate, various known methods can be used. Specifically, a method of applying a suspension containing semiconductor particles on a substrate, drying and firing, a method of forming a semiconductor film by an electrochemical reaction, a CVD method using a desired source gas on the substrate, or A method of forming a semiconductor film by an MOCVD method or the like, a method of forming a semiconductor film by a PVD method using a raw material solid, an evaporation method, a sputtering method, a sol-gel method, or the like can be given.

The thickness of the porous semiconductor layer is not particularly limited, but may be selected from the viewpoints of permeability, conversion efficiency, and the like.
It is preferably about 0.5 to 20 μm. Further, in order to improve the conversion efficiency, it is necessary to adsorb a larger amount of a dye described later on the porous semiconductor layer. For this reason, the porous semiconductor layer preferably has a large specific surface area, specifically, about 10 to 200 m ² / g.

As a material constituting the porous semiconductor layer,
Known semiconductors such as titanium oxide, zinc oxide, tungsten oxide, barium titanate, strontium titanate, and cadmium sulfide are exemplified. These materials can be used as a mixture of two or more kinds. Among them, zinc oxide and titanium oxide are particularly preferable in terms of conversion efficiency, stability, and safety. As titanium oxide, anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide,
Examples include various titanium oxides such as metatitanic acid and orthotitanic acid, and titanium oxide-containing composites, and any of these may be used.

Drying and baking in the above-described method for forming a porous semiconductor layer are carried out by appropriately adjusting the temperature, time, atmosphere conditions, and the like, depending on the type of substrate and semiconductor particles used. For example, 50 in the atmosphere or in an inert gas atmosphere.
It can be performed for about 10 seconds to 12 hours within the range of about 800 ° C. The drying and firing are performed at a single temperature for 1
It can be carried out twice or more times or by changing the temperature.

As the semiconductor particles, commercially available particles of a single or compound semiconductor having an appropriate average particle size, for example, about 1 to 500 nm, may be mentioned. Also,
Solvents used for suspending the semiconductor particles include glyme solvents such as ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, alcohol solvents such as isopropyl alcohol, mixed solvents such as isopropyl alcohol / toluene, and water. No.

Next, a dye functioning as a photosensitizer (hereinafter, referred to as "dye") is adsorbed on the porous semiconductor.
As the method, for example, there is a method of immersing a porous semiconductor film formed on a substrate in a solution in which a dye is dissolved.

The dye used has an absorption in various visible light regions and infrared light regions, and a carboxyl group or a carboxyl group is contained in the dye molecule in order to strongly adsorb the semiconductor layer.
Those having an interlock group such as an alkoxy group, a hydroxyl group, a hydroxyalkyl group, a sulfonic acid group, an ester group, a mercapto group and a phosphonyl group are preferred.

The interlocking group provides an electrical bond that facilitates electron transfer between the dye in the excited state and the conduction band of the semiconductor. As the dye having such an interlock group, for example, ruthenium bipyridine dye, azo dye, quinone dye, quinone imine dye, quinacridone dye, squarylium dye, cyanine dye, merocyanine dye, triphenylmethane Dyes, xanthene dyes, porphyrin dyes, phthalocyanine dyes, perylene dyes, indigo dyes,
And naphthalocyanine dyes.

The solvent for dissolving the dye is not particularly limited as long as it can dissolve the dye, and examples thereof include alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran, and nitrogen such as acetonitrile. Compounds, halogenated aliphatic hydrocarbons such as chloroform, aliphatic hydrocarbons such as hexane,
Examples include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, and water. These solvents can be used as a mixture of two or more kinds.

The concentration of the dye in the solution can be appropriately adjusted depending on the type of the dye and the solvent to be used. However, in order to improve the adsorption function, it is preferable that the concentration is as high as possible. The dye concentration may be, for example, 5 × 10 ⁻⁵ mol / liter or more.

The conditions for immersing the solution in which the dye is dissolved in the semiconductor, such as the solution temperature, the ambient temperature and the pressure, are not particularly limited, and include, for example, about room temperature and atmospheric pressure. The immersion time can be appropriately adjusted depending on the type of the dye to be used, the type of solvent, the concentration of the solution, and the like. In order to effectively perform the immersion, the immersion may be performed under heating at or below the boiling point of the solvent used. This is preferable because the dye is easily adsorbed on the porous semiconductor.

Next, a method for forming the porous semiconductor layer will be described. In this method, for example, a porous semiconductor film is formed on a substrate by electrochemically reducing nitrate. Specifically, the substrate is immersed in a nitrate solution, and a porous semiconductor layer of a metal oxide is formed by an electrochemical reaction. The metal oxide formed by the nitrate used is determined, and zinc oxide is preferred as the metal oxide. Further, in this method, by using a mixed solution of nitrate and a dye, formation of the porous semiconductor layer and loading (adsorption) of the dye on the porous semiconductor layer can be performed simultaneously.

Examples of the dye include those described above, and those having a structure having an interlock group are preferable. Among these, xanthene dyes, triphenylmethane dyes, cyanine dyes, phthalocyanine dyes, porphyrin dyes, and polypyridine metal complex dyes are preferred.

When the nitrate solution is an aqueous zinc nitrate solution,
The concentration is preferably about 0.01 to 1 mol / l, particularly preferably 0.1 to 0.5 mol / l. The concentration of the dye is preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol / liter, and from 3 × 10 ^{−5 to} 6 × 10 ⁻⁵ mol / liter.
Liters are particularly preferred. The nitrate solvent may be a mixed solvent of water and an organic solvent.

Next, an electrochemical reaction using zinc nitrate will be described. By immersing the substrate on which the transparent conductive film is formed, the counter electrode, and the reference electrode in a mixed solution of a zinc nitrate aqueous solution and a dye, and applying an electrolytic potential, zinc oxide is formed on the transparent conductive film by the following reaction formula. You. NO ₃ ⁻ + H ₂ O + 2e ⁻ → NO ₂ ⁻ + 2OH ⁻ Zn ²⁺ + 2OH ⁻ → Zn (OH) ₂ Zn (OH) ₂ → ZnO + H ₂ O

The electrochemical reaction is carried out at an electrolytic potential of -0.7 to-
It is preferably performed in the range of 1.3 V (vs. SCE). When the electrolytic potential is higher than the above range, no reaction occurs, and when the electrolytic potential is low, zinc plating occurs, which is not preferable.

The electrochemical reaction is carried out at a reaction temperature of 0-10.
It is preferably carried out in the range of 0 ° C. If the reaction temperature is higher than the above range, the growth rate is increased and the adhesion to the substrate is deteriorated, which is not preferable. On the other hand, when the reaction temperature is lower than the above range, the reaction does not occur, which is not preferable.

The method of the electrochemical reaction may be any of a bipolar type and a tripolar type similarly to the formation of copper thiocyanate. In the case of the tripolar type, the reference electrode used is copper thiocyanate. What was illustrated in formation is mentioned. The counter electrode used is preferably zinc metal.

As shown in the above reaction formula, the formation of zinc oxide is due to the formation of a base accompanying the reduction of nitrate ions to nitrite ions. In the formation process, when a dye is mixed in the solution, the zinc oxide grows due to the chemical adsorption of the OH group on the surface of the zinc oxide and the functional group of the dye (a phthalocyanine dye containing a sulfonic acid group) and the dye molecule Get qualified. Here, the adsorption of the dye is determined by the zinc oxide (00
2) It occurs preferentially to the surface. As a result, the zinc oxide is suppressed from growing on the (002) plane and grows in the (100) direction. In this manner, a zinc oxide porous semiconductor layer carrying a dye can be produced. (Chem. Mate
r. 1999, 11, 2657-2667)

[0045]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples.

(Embodiment 1) Embodiment 1 of the present invention will be described with reference to FIG. 1 (a) to 1 (c) and 2 (d)
(F) to (f) are schematic cross-sectional views illustrating steps for manufacturing a solar cell of the present invention. 1 is a glass substrate, 2 is a transparent conductive film, 3 is a solution of (zinc nitrate + eosin Y dye), 4 is an eosin Y dye, 5 is a container, 6 is a zinc counter electrode, 7 is an SCE (saturated sweet kou electrode), 8 is Potentiostat, 9 is zinc oxide, 10
Denotes a (copper perchlorate + lithium thiocyanate) solution, 11 denotes a platinum counter electrode, 12 denotes copper thiocyanate, and 13 denotes a container.
(A) to (f) show the manufacturing procedure in order.

S is placed on a glass substrate 1 of 10 mm × 10 mm.
An nO ₂ transparent conductive film 2 was formed (FIG. 1A). Next, a lead wire is attached to the SnO ₂ transparent conductive film 2, connected to the working electrode of the potentiostat 8, a lead wire from the zinc counter electrode 6 is connected to its counter electrode, and SCE is used as a reference electrode.
(Saturated sweetfish electrode) 7 was connected to the reference. These were placed in a non-conductive container 5 made of glass. This container 5
Then, an aqueous solution 3 in which the eosin Y dye 4 was dispersed at a concentration of 5.5 × 10 ⁻⁶ mol / l in a 0.1 mol / l zinc nitrate aqueous solution was added (FIG. 1B).

The inside of the container 5 was set at 70 ° C., and an electrolytic potential of −0.7 V (vs. SC) was supplied by a stabilized power supply (not shown).
E) was applied for 60 minutes. By this electrolytic reaction, SnO
₍₂₎ A porous semiconductor layer of zinc oxide 6 supporting eosin Y dye 4 was formed on transparent conductive film 2 (FIG. 1 (c)).
Next, the porous semiconductor layer was dried in a dryer set at about 150 ° C. for 30 minutes (FIG. 2).
(D)).

Next, a lead wire is attached to the SnO ₂ transparent conductive film 2 and connected to the working electrode of the potentiostat 8.
A lead wire from a platinum counter electrode 11 was connected to the counter electrode, and an SCE (saturated sugar beet electrode) 7 was connected to the reference as a reference electrode. These were placed in a non-conductive container 13 made of glass. In this container 13, 5 × 10 ⁻² mol / liter of aqueous solution of copper perchlorate was charged with 5 × 10 ² lithium thiocyanate.
An aqueous solution dissolved at ^-2 mol / l was introduced (Fig. 2
(E)).

The inside of the container 13 was set at 25 ° C., and an electric potential of +0.25 V (vs. S.) was supplied by a stabilizing power supply (not shown).
CE) was applied for 60 minutes. By this electrolytic reaction, copper thiocyanate 12 was formed as a carrier transport layer on the porous semiconductor layer of zinc oxide 6 carrying eosin Y dye 4 (FIG. 2 (f)). Then, it was washed with an ethanol solvent and dried at 60 ° C. for 15 minutes.

Thereafter, as a counter electrode, gold was formed in a thickness of about 500 nm on the copper thiocyanate 12 by a sputtering method to complete a solar cell. When the obtained solar cell was evaluated under the measurement conditions: AM-1.5, the short-circuit current value was 8.8 mA / cm ² , the open-circuit voltage value was 0.54 V, the fill factor was 0.55, and the conversion efficiency was 2.42%. Was.

(Example 2) In Example 2, except that a porous semiconductor layer was formed by a method of applying a suspension containing semiconductor particles on a substrate, and drying and firing the suspension.
In the same manner as in the above, a solar cell was produced.

A coating liquid for forming a titanium oxide film to be a porous semiconductor layer was prepared as follows. Commercially available titanium oxide particles (manufactured by Teika Co., Ltd., trade name: AMT-600, anatase type crystal, average particle diameter 30 nm, specific surface area 50 m ² /
g) 4.0 g and 20 ml of diethylene glycol monomethyl ether were dispersed using a glass bead with a paint shaker for 6 hours to obtain a coating liquid (suspension) for forming a titanium oxide film.

Using a doctor blade, the obtained coating liquid for forming a titanium oxide film was applied to a thickness of about 10 μm and an area of 10 m.
It was applied on a SnO ₂ transparent conductive film formed on a glass substrate so as to have a size of about mx 10 mm. 100 ℃
Pre-drying for 30 minutes at 460 ° C in an oxygen atmosphere
By baking for 0 minutes, a titanium oxide film having a thickness of about 8 μm was obtained.

Next, a ruthenium dye (Solaroni)
x, trade name: Ruthenium 535) at a concentration of 4
Dissolve in absolute ethanol at × 10 ^-4 mol / l,
A dye solution for adsorption was prepared. A glass substrate provided with a transparent conductive film and a titanium oxide film was immersed in the obtained dye solution for adsorption for about 4 hours to allow the dye to permeate and adsorb to the titanium oxide film. Thereafter, the glass substrate was washed several times with anhydrous ethanol and dried at about 60 ° C. for about 20 minutes.

Next, a carrier transport layer made of copper thiocyanate was formed on the porous semiconductor layer in the same manner as in Example 1, and a counter electrode was formed to complete a solar cell. Example 1
In the same manner as described above, the obtained solar cell was measured under the following conditions:
When evaluated at 1.5, the short-circuit current value was 9.1 mA / cm.
² , open circuit voltage value 0.55V, fill factor 0.6,
The conversion efficiency was 3.0%.

[0057]

According to the present invention, the solar cell of the present invention having a porous semiconductor layer in which a dye is adsorbed and a carrier transport layer between a transparent conductive film formed on the surface of the transparent substrate and the conductive substrate. The layer is composed of all-solid copper thiocyanate. Therefore, the long-term reliability is higher than that of a conventional solar cell having a carrier transport layer composed of a solidified body such as a liquid and a gel. Further, in the method for manufacturing a solar cell of the present invention, an electrochemical reaction can be used in all steps, so that a flexible plastic substrate having low temperature durability can be used, and the solar cell can be adapted to various shapes. Can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a manufacturing process of a solar cell of the present invention ((a) to (c)).

FIG. 2 is a schematic cross-sectional view illustrating a manufacturing process of the solar cell of the present invention ((d) to (f)).

FIG. 3 is a schematic sectional view of a main part showing a layer configuration of a conventional dye-sensitized solar cell.

[Explanation of symbols]

 Reference Signs List 1 glass substrate 2 transparent conductive film 3 (zinc nitrate + eosin Y dye) solution 4 eosin Y dye 5, 13 container 6 zinc counter electrode 7 SCE (saturated sweet kou electrode) 8 potentiostat 9 zinc oxide 10 (copper perchlorate + Lithium thiocyanate) solution 11 Platinum counter electrode 12 Copper thiocyanate 21 Transparent support 22 Transparent conductor 23 Porous semiconductor layer 24 Electrolyte 25 Counter electrode 26 Platinum 27 Epoxy resin (epoxy sealant)

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tsukasa Yoshida 4-29-1, Minami-Kamishima, Gifu-shi, Gifu 501F Lions Garden Minami-Kamijima 501F Term (Reference) 5F051 AA14 AA20 FA03 FA06 GA03 5H032 AA06 AS16 EE16 EE17 HH06 HH08

Claims (7)

[Claims] 1. A dye having a porous semiconductor layer in which a dye is adsorbed and a carrier transport layer made of copper thiocyanate between a transparent conductive film formed on a surface of a transparent substrate and a conductive substrate. In a method for manufacturing a sensitized solar cell, a substrate on which a porous semiconductor layer is formed is formed by using copper perchlorate, copper chloride,
Immersed in a mixed solution of a copper salt selected from copper bromide, copper nitrate, copper sulfate, copper acetate and copper formate, and a thiocyanate selected from an alkali metal salt of thiocyanic acid and ammonium thiocyanate; A method for producing a dye-sensitized solar cell, comprising forming copper thiocyanate to be a carrier transport layer on a porous semiconductor layer by a reaction. 2. The method for producing a dye-sensitized solar cell according to claim 1, wherein the copper salt is copper perchlorate, and the thiocyanate is lithium thiocyanate. 3. The method according to claim 1, wherein the electrochemical reaction is carried out at an electrolytic potential of +0.1 to +
The method for producing a dye-sensitized solar cell according to claim 1, wherein the method is performed in a range of 0.4 V (vs. SCE). 4. An electrochemical reaction at a reaction temperature of 10 to 40 ° C.
The method for producing a dye-sensitized solar cell according to any one of claims 1 to 3, which is performed in the range of: 5. A method in which a substrate on which a transparent conductive film is formed is immersed in a mixed solution of zinc nitrate and a dye, and zinc oxide which becomes a porous semiconductor layer having the dye adsorbed by an electrochemical reaction is formed on the substrate. The method for producing a dye-sensitized solar cell according to claim 1, wherein: 6. The method for producing a dye-sensitized solar cell according to claim 1, wherein the porous semiconductor layer is made of titanium oxide. 7. A dye-sensitized solar cell obtained by the production method according to claim 1.