JP2011134532A - Method of manufacturing action pole, action pole, and photoelectric conversion element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve photoelectric conversion efficiency in an action pole with a structure in which a plurality of conductive wires each composed by forming titanium at least at the outermost peripheral part thereof are knitted in a mesh state. <P>SOLUTION: A method of manufacturing the action pole 3 has: a process of forming a nitrogen-containing site 32 in a surface skin part of the conductive wire 31; and a process of forming a porous oxide semiconductor layer 12 on which sensitized dye is carried. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a working electrode that constitutes a photoelectric conversion element, and more specifically, a method for producing a working electrode that can efficiently flow electrons excited on titanium oxide particles into titanium, and the working electrode. Further, the present invention relates to a photoelectric conversion element provided with this working electrode.

The dye-sensitized solar cell has been proposed by a group such as Gretzel et al. In Switzerland, and has attracted attention as a photoelectric conversion element that can obtain high conversion efficiency (see, for example, Non-Patent Document 1).
Dye-sensitized solar cells can be significantly reduced in price compared to silicon-based conventional solar cells, but the price of conductive substrates used in power generation units is an obstacle to lower prices It has become. In a dye-sensitized solar cell having a conventional structure, the electrode (window electrode) on which light enters is particularly required to have visible light transmission and high conductivity. A substrate coated with a transparent conductive metal oxide such as indium oxide or fluorine-doped tin oxide has been used. Therefore, if a dye-sensitized solar cell having a completely new structure that does not use such a transparent conductive substrate is realized, research and development are being carried out on the assumption that the cost of solar cells can be greatly reduced. (See Non-Patent Documents 2 and 3).

As a solution to these problems, a novel element structure (see Patent Documents 1, 2, 3, and 4) using a metal wire as a working electrode of a power generation unit has been proposed. However, in these structures, since a metal wire is used for the working electrode, it is difficult to configure a large-area solar cell module, and it is easy to increase the area that a dye-sensitized photoelectric conversion element originally has. As a result, the advantage was lost. Therefore, development of a photoelectric conversion element having a structure that does not impair the above-described advantages is required.
In order to enable a large-area element, as described in Patent Document 5 and Patent Document 6, photoelectric conversion elements that employ a textile structure in which metal wires are knitted in a mesh shape as a working electrode have also been proposed. .

  However, in the case where the working electrode using the metal wire is adopted, the metal wire needs to have corrosion resistance to the electrolyte, so that only a limited metal such as titanium (Ti) or tungsten (W) is used as the material. Could not be used. Since these metals generally have low electrical conductivity and are expensive, there has been a problem of high costs.

For this problem, photoelectric conversion using a metal wire (hereinafter referred to as Ti-coated Cu wire) in which the outer side of a linear base material (eg, Cu wire) having excellent conductivity is coated with an alloy (eg, Ti) having excellent corrosion resistance. The inventors are developing a device. The metal wire having this structure has excellent properties as a working electrode of the photoelectric conversion element as a metal wire having both high conductivity of Cu and high corrosion resistance of Ti.
Use of a Ti-coated Cu wire as the metal wire and use of a working electrode having the metal wire as a textile structure provides a photoelectric conversion element having a flexible structure, having a large area element, having excellent conductivity and corrosion resistance. Is possible.

JP 2008-181690 A JP 2008-181691 A JP 2005-196982 A JP 2005-516370 gazette JP 2001-283941 A JP 2001-283944 A

O'Regan B., Graetzel M., Alow cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films, Nature, 1991, 353, 737-739 Japan Patent Office: Standard Technology Collection: “Dye-sensitized solar cell” Japan Patent Office: Patent application technology trend survey: FY 2005 “Dye-sensitized solar cell”

By the way, in order for the photoelectric conversion element as described above to function as a working electrode, titanium oxide (TiO ₂ ) is applied as a porous oxide semiconductor on a Ti-coated Cu wire. More finely, it has a structure in which fine particles of titanium oxide are sintered on titanium constituting the surface portion of the Ti-coated Cu wire. That is, the structure of the interface is a structure of titanium / titanium oxide in order from the inside.

However, in practice, a natural oxide film of several tens of nanometers exists on titanium constituting the Ti-coated Cu wire. Therefore, the microstructure of the interface has a structure of titanium / titanium natural oxide film / titanium oxide particles in the inner order. That is, a titanium natural oxide film is interposed between the titanium layer of the Ti-coated Cu wire and the porous oxide semiconductor layer (titanium oxide).
Therefore, when electrons excited on the titanium oxide particles by sunlight flow into titanium, they inevitably pass through a titanium natural oxide film existing on titanium. This natural oxide film of titanium hinders the inflow of electrons, and as a result, there is a problem that the power generation efficiency is lowered.

  The present invention has been made in consideration of such circumstances. The purpose of the working electrode composed of a conductive wire coated with titanium is that it does not hinder the inflow of electrons when the electrons excited on the titanium oxide particles flow into titanium during power generation. An object of the present invention is to provide a working electrode with high power generation efficiency, and a photoelectric conversion element including the working electrode.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1 of the present invention is a method for producing a working electrode having a structure in which a plurality of conductive wires each having titanium formed at least on the outermost periphery are knitted in a mesh shape, A working electrode comprising at least a step A for forming a site containing nitrogen on a skin portion of a conductive wire and a step B for forming a porous oxide semiconductor layer carrying a sensitizing dye. It is a manufacturing method.
The invention according to claim 2 of the present invention is characterized in that the step A forms a portion containing nitrogen in the skin portion of the conductive wire by performing a heat treatment in a nitrogen atmosphere. 1. A method for producing a working electrode according to 1.
Further, in the invention according to claim 3 of the present invention, in the step A, the portion containing nitrogen is formed in the skin portion of the conductive wire using an ion implantation method. It is a manufacturing method of the working electrode of description.
Further, in the invention according to claim 4 of the present invention, in the step A, the working electrode according to claim 1 is characterized in that the portion containing nitrogen is formed in a skin portion of the conductive wire by using a sputtering method. It is a manufacturing method.

The invention according to claim 5 of the present invention is a working electrode having a structure in which a plurality of conductive wires each having titanium formed at least on the outermost peripheral portion are knitted in a mesh shape, and the conductive wires In this working electrode, a part containing nitrogen is formed and a porous oxide semiconductor layer carrying a sensitizing dye is formed on the outer periphery thereof.
The invention according to claim 6 of the present invention is sealed between the working electrode according to claim 5, a counter electrode arranged to face the working electrode, and the working electrode and the counter electrode. It is a photoelectric conversion element characterized by including an electrolyte.

  The present invention provides a method for producing a working electrode of a photoelectric conversion element, comprising the step of forming a portion containing nitrogen in a skin portion of a conductive wire formed with titanium at least on the outermost peripheral portion constituting the working electrode. It is characterized by that. The photoelectric conversion element provided with the working electrode manufactured by this manufacturing method can efficiently flow electrons excited on the titanium oxide particles into titanium.

It is a top view which shows the outline of the dye-sensitized photoelectric conversion element which concerns on this invention. It is sectional drawing which follows the BB cross section of FIG. It is an enlarged view of the electroconductive wire which comprises the working electrode of the dye-sensitized photoelectric conversion element which concerns on this invention.

(Embodiment)
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a plan view schematically illustrating a photoelectric conversion element according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view taken along line BB in FIG. FIG. 3 is an enlarged view of the conductive wire constituting the working electrode.

As shown in the plan view of FIG. 1 and the cross-sectional view of FIG. 2, the photoelectric conversion element 1 of this embodiment includes a working electrode 3 (3a), a counter electrode 4 disposed so as to face the working electrode 3, The current collector 5 is electrically connected to the working electrode 3, and a bag body 10 that houses the working electrode 3 and the counter electrode 4.
The working electrode 3 has a cloth structure (textile structure) having a rectangular shape in plan view, in which a plurality of conductive wires 31 are knitted in a mesh shape. The conductive wire 31 is knitted so that the overlapping portions are in sufficient contact with each other.
In addition, the working electrode 3 is configured to be overlapped with a plate-shaped counter electrode 4 having a rectangular shape in plan view and a separator 6.

The working electrode 3 of the textile structure is composed of a plurality of conductive wires 31 having conductivity, and a porous oxide semiconductor layer 12 that is arranged around the conductive wires 31 and carries a dye. The oxide semiconductor layer 12 is impregnated with the electrolyte 13 together with the sensitizing dye.
The conductive wire 31 in the present embodiment is a metal wire obtained by coating a Cu wire with Ti (hereinafter, Ti-coated Cu wire). Ti covers the Cu wire in order to improve the corrosion resistance of the conductive wire 31.

  The counter electrode 4 is a plate-like conductive base material, and is overlapped with the working electrode 3 through a separator 6. The counter electrode 4 has an extraction electrode 4 a that is paired with the current collector 5, and the extraction electrode 4 a extends outside the bag body 10 when the counter electrode 4 is accommodated in the bag portion 10. Is formed. The separator 6 is not necessary if the insulation between the working electrode 3 and the counter electrode 4 is ensured.

At least a part of the plurality of conductive wires 31 constituting the working electrode 3 is extended from the working electrode 3 to form a current collecting wiring.
The current collector 5 includes an extended conductive wire 31 and a plurality of outer peripheral wires 51 having conductivity. The outer peripheral wire 51 has a linear shape, and constitutes a cloth-like current collecting portion 52 formed by meshing with the conductive wire 31.
A Ti foil 53 is stacked on the cloth-shaped current collector 52, and the cloth-shaped current collector 52 and the Ti foil 53 are electrically connected by spot welding. A part of the Ti foil 53 is drawn to the outside, and current can be collected from this part.

  The inside of the bag body 10 is filled with the electrolyte 13, and the opening of the bag body 10 is sealed with an adhesive.

The working electrode 3 according to the present invention has a portion 32 containing nitrogen in the skin portion of the conductive wire 31 constituting the working electrode 3 as shown in FIG. It is a feature. In FIG. 3, reference numeral 12 denotes a porous oxide semiconductor layer. That is, the nitrogen-containing portion 32 includes a titanium layer and a porous oxide semiconductor layer 12 formed on the outermost peripheral portion of the conductive wire 31. Between the two.
The portion 32 containing nitrogen is preferably a TiN film provided over the entire skin portion of the Ti-coated Cu wire. The TiN film can be formed by heat-treating a Ti-coated Cu wire and modifying the skin portion of the Ti-coated Cu wire. Moreover, the site | part 32 containing nitrogen does not need to be formed in the whole skin part of Ti covering Cu wire, for example, the TiN film | membrane may have an island-like structure.

  By forming the portion 32 containing nitrogen on the conductive wire 31 constituting the working electrode 3, a natural oxide film is formed on the exposed portion of the titanium layer formed on the outermost peripheral portion of the conductive wire 31. Nothing will happen. Therefore, when electrons excited in the porous oxide semiconductor layer 12 flow into the titanium layer of the conductive wire 31 by the natural oxide film, the flow of electrons is not hindered. Therefore, the electrons excited on the porous oxide semiconductor layer 12 can efficiently flow into the conductive wire 31.

Hereinafter, each component will be described in detail.
The conductive wire 31 and the outer peripheral wire 51 are Ti-coated Cu wires having a diameter of 0.05 mm. Hereinafter, an example of a method for producing a Ti-coated Cu wire will be described.
First, Ti is formed into a pipe shape by extrusion molding or the like, and Cu is formed into a linear shape by extrusion molding or the like, and a Cu copper wire is inserted into the Ti pipe while running the Ti pipe and the Cu wire simultaneously. These are squeezed to bring them into close contact with each other to obtain a Ti-coated Cu wire.

The conductive wire 31 and the outer peripheral wire 51 are not limited to Ti-coated Cu wires, and wires that are corrosive to the electrolyte, such as W-coated Cu wires, can also be used. Wires with high conductivity such as Ti-coated Al wires can also be used.
The thickness (diameter) of such a wire is preferably 10 μm to 10 mm, for example. However, in order to fully exhibit flexibility, the thinner the substrate, the better.

As described above, a TiN film is formed on the portion of the conductive wire 31 that forms the textile structure of the working electrode 3.
Further, a porous oxide semiconductor layer 12 is disposed on the outside, and a sensitizing dye and an electrolyte 13 are supported at least partially on the surface.
The semiconductor that forms the porous oxide semiconductor layer 12 is titanium oxide (TiO ₂ ). The thickness of the titanium oxide is about 5 μm, but is not particularly limited, and may be, for example, 1 μm to 50 μm.
The semiconductor that forms the porous oxide semiconductor layer 12 is not limited to titanium oxide, and is generally zinc oxide (ZnO), tin oxide (SnO ₂ ), oxidation, as long as it is used in dye-sensitized solar cells. Various semiconductor electrodes such as zinc (ZnO), niobium oxide (Nb ₂ O ₅ ), and tungsten oxide (WO ₃ ) can be used without limitation.

  Examples of the sensitizing dye include ruthenium complexes such as N719, N3, and black dye, metal-containing complexes such as porphyrin and phthalocyanine, and organic dyes such as eosin, rhodamine, and merocyanine. From the above, it is only necessary to appropriately select one having an excitation behavior suitable for the application and the semiconductor used.

  The porous oxide semiconductor layer 12 is impregnated with an electrolytic solution, and this electrolytic solution also constitutes a part of the electrolyte 13. In this case, the electrolyte 13 in the porous oxide semiconductor layer 12 is formed by impregnating the porous oxide semiconductor layer 12 with the electrolytic solution, or impregnating the porous oxide semiconductor layer 12 with the electrolytic solution. Then, the electrolytic solution is gelled (pseudo-solidified) using an appropriate gelling agent and formed integrally with the porous oxide semiconductor layer 12, or based on an ionic liquid. Further, a gel electrolyte containing oxide semiconductor particles and conductive particles is used.

As said electrolyte solution, what melt | dissolved electrolyte components, such as an iodine, iodide ion, and tertiary butyl pyridine, in organic solvents and ionic liquids, such as ethylene carbonate and methoxyacetonitrile, is used.
Examples of the gelling agent used for gelling the electrolytic solution include polyvinylidene fluoride, a polyethylene oxide derivative, and an amino acid derivative.
Moreover, if it replaces with a volatile electrolyte solution and is generally used for a dye-sensitized solar cell, not only what a solvent is an ionic liquid or the gelatinized thing but a p-type inorganic semiconductor and an organic hole transport layer Even solids such as these can be used without limitation.

Although it does not specifically limit as said ionic liquid, It is a liquid at room temperature, For example, the normal temperature molten salt which used the compound which has the quaternized nitrogen atom as a cation is mentioned.
Examples of the cation of the room temperature molten salt include quaternized imidazolium derivatives, quaternized pyridinium derivatives, and quaternized ammonium derivatives.
Examples of the anion of the room temperature molten salt include BF ₄ ⁻ , PF ₆ ⁻ , (HF) _n ⁻ , bistrifluoromethylsulfonylimide [N (CF ₃ SO ₂ ) ₂ ⁻ ], and iodide ions.
Specific examples of the ionic liquid include salts composed of quaternized imidazolium-based cations and iodide ions or bistrifluoromethylsulfonylimide ions.

  The oxide semiconductor particles are not particularly limited in terms of the type and particle size of the substance, but are excellent in miscibility with an electrolyte mainly composed of an ionic liquid and gel the electrolyte. Is used. In addition, the oxide semiconductor particles are required to have excellent scientific stability against other coexisting components contained in the electrolyte 13 without reducing the semiconductivity of the electrolyte 13. In particular, even when the electrolyte 13 includes a redox pair such as iodine / iodide ions or bromine / bromide ions, the oxide semiconductor particles are preferably those that do not deteriorate due to an oxidation reaction.

Examples of such oxide semiconductor particles include TiO ₂ , SnO ₂ , SiO ₂ , ZnO, Nb ₂ O ₅ , In ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ , WO ₃ , SrTiO ₃ , Ta ₂ O ₅ , One or a mixture of two or more selected from the group consisting of La ₂ O ₃ , Y ₂ O ₃ , Ho ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ is preferable, and the average particle size is about 2 nm to 1000 nm. preferable.

As the conductive fine particles, conductive particles such as a conductor and a semiconductor are used.
Further, the type and particle size of the conductive particles are not particularly limited, and those that are excellent in miscibility with an electrolytic solution mainly composed of an ionic liquid and that gel the electrolytic solution are used. Furthermore, it is necessary to be excellent in chemical stability against other coexisting components contained in the electrolyte 13.
In particular, even when the electrolyte 13 includes a redox pair such as iodine / iodide ions or bromine / bromide ions, an electrolyte that does not deteriorate due to an oxidation reaction is preferable.

  Examples of such conductive fine particles include those composed mainly of carbon, and specific examples include particles such as carbon nanotubes, carbon fibers, and carbon black. All methods for producing these substances are known, and commercially available products can also be used.

The counter electrode 4 is formed of a Ti plate having a thickness of 0.1 mm that has a conductive plate shape and the surface thereof is nonconductive. The counter electrode 4 has a catalyst film (not shown) made of Pt on the surface. In addition, the extraction electrode 4a is provided in the edge part for current collection.
In order to prevent a short circuit between the working electrode 3 and the counter electrode 4, a separator 6 made of a nonconductive material and having a thickness of 20 μm is inserted between the working electrode 3 and the counter electrode 4.

  The bag 10 that accommodates the working electrode 3, the counter electrode 4, and the separator 6 is formed of a material made of PET or PEN (polyethylene naphthalate). The material used for the bag body 10 is not limited to PET and PEN, and can be appropriately changed as long as the material has translucency and can withstand the electrolytic solution.

(Method for manufacturing working electrode)
Hereinafter, the manufacturing method of the working electrode 3 according to the present invention will be described.
In the manufacturing method of this embodiment, first, a textile structure is formed by knitting a predetermined number of conductive wires 31 (Ti-coated Cu wires) in a mesh shape. Next, the plurality of conductive wires 31 having the textile structure are washed. This cleaning is for removing the oxide film naturally formed on the Ti surface of the Ti-coated Cu wire.
The oxide film is removed with a chemical solution. Hydrofluoric acid is preferable as the chemical solution, but hydrochloric acid or the like may be used, for example, as long as it can remove the oxide film.
Further, the cleaning (removal) method is not limited as long as the oxide film on Ti can be removed without being limited to chemical removal by a chemical solution. For example, a mechanical removal method such as a blast method may be employed.

  Next, heat treatment is performed for 3 hours in a state where the conductive wire 31 having a textile structure after washing is heated to 500 ° C. in a furnace in a nitrogen atmosphere. With this heat treatment, nitrogen (N) diffuses into Ti on the surface of the Ti-coated Cu wire, thereby generating TiN and forming a TiN film (site containing nitrogen) 32. The TiN film 32 includes not only uniformly containing N but also non-uniformly containing N. In the present invention, these are collectively referred to as the TiN film 32.

  After the heat treatment, the conductive wire 31 is taken out from the furnace, and it is confirmed that the surface of the conductive wire 31 is yellow. Thereby, it can be confirmed that the skin portion of the conductive wire 31 is modified and the TiN film 32 is formed on the inside of the surface of the conductive wire 31.

  The formation method of the TiN film 32 is not limited to the heat treatment in the nitrogen atmosphere, and may be formed by using, for example, a sputtering method. The TiN film is formed by sputtering using a sputtering apparatus (for example, a direct current magnetron sputtering apparatus) including a Ti disk as a target, and sputtering is performed using a sputtering gas mixed with nitrogen. As a result, the TiN film 32 is formed outside the surface of the conductive wire 31.

  Further, the TiN film 32 can be formed by modifying the skin portion of the conductive wire 31 using the ion implantation method. The TiN film 32 is formed on the inner side of the surface of the conductive wire 31.

Next, TiO ₂ paste (catalyst conversion, PST-21NR) was applied to the conductive wire 31 by a squeegee method, and sintered in an electric furnace at 500 ° C. for 1 hour. The film thickness of TiO ₂ after sintering was approximately 15 μm.

After the adsorbed water is evaporated by holding the conductive wire 31 in an oven at 120 ° C. for 10 minutes, 0.3 mM of a ruthenium dye (Solaronix, RutheAlum535-bisTBA, generally called N719), It was immersed in an acetonitrile / tert-butanol = 1: 1 solution and allowed to stand at room temperature for 24 hours to carry the dye on the TiO ₂ surface. After lifting from the dye solution, it was washed with the above mixed solvent, and this was used as working electrode 3.

(Example)
A dye-sensitized photoelectric conversion element 1 having the structure shown in FIG. 1 was produced.
First, a Ti-coated Cu wire drawn to a diameter of 0.050 mm was woven into a dense plain weave textile structure using a loom. The size of the rectangular part (textile part, the part constituting the working electrode 3) on which the vertical and horizontal Ti-coated Cu wires are woven is 10 cm × 10 cm, and the number of Ti-coated Cu wires is 1500 to 2000 in the vertical and horizontal directions. On the other hand, the collector electrode was configured to have a width of 1 cm.

  The TiN film 32 and the porous oxide semiconductor layer 12 carrying the dye were formed on the textile part by the above method.

  A Ti foil 53 was welded to the collector electrode by resistance welding. The collector electrode and the Ti foil 53 are preferably continuously welded. For example, a spot welded multi-point or a seam welded one is preferable. Laser welding may also be used.

Next, a protective part 54 was formed on the collector electrode. The protection part 54 is made of resin, and is formed by impregnating a collecting electrode in the resin. The resin is required to withstand the electrolytic solution and to have adhesiveness with titanium. Specific examples include polyimide, fluororesin, and PET resin. During impregnation, defoaming was performed in a vacuum so that the resin completely penetrated into the structure of the current collector.
Alternatively, a low-viscosity adhesive may be applied without impregnating the resin. However, since the water molecules adsorbed on the titanium oxide surface layer are evaporated before the titanium oxide is immersed in the pigment, a drying process is performed at 120 ° C., and therefore a resin that can withstand that temperature is preferable.

On the other hand, the counter electrode 6 was obtained by depositing Pt on a Ti foil having a size of 10 cm × 10 cm and a thickness of 0.1 mm using a ternary RF sputtering apparatus. The thickness of Pt was 200 nm. In order to collect current, the counter electrode 4 was provided with an extraction electrode 4a.
The working electrode 3 and the counter electrode 4 were superposed via a separator 10 made of polyolefin (Asahi Kasei Chemicals, Hypore) having a thickness of 20 μm.

  The bag 10 for housing the working electrode 3, the counter electrode 4, and the separator 6 was produced. If the bag body 10 can accommodate the working electrode 3, the counter electrode 4, and the separator 6, the smaller one is preferable. Moreover, as a material used as the bag body 10, what has translucency and can endure electrolyte solution is preferable.

  In 10 mL of methoxypropionitrile (MPN), the electrolyte was 0.3777 g (0.15 M) of I2, 2.128 g (0.8 M) of DMPImI, 0.1182 g (0.1 M) of GuSCN, and NMBI. It was prepared by dissolving 0.6609 g (0.5 M).

  Next, the working electrode 3, the counter electrode 4, and the separator 6 were inserted into the bag body 10. After the insertion, the electrolytic solution is injected into the bag body 10, and the opening of the bag body 10 with the current collector 5 of the working electrode 3 and the extraction electrode 4 a of the counter electrode 4 extending outside the bag body 10. Was sealed. Although an adhesive was used for sealing, the material of the adhesive is preferably a material that can withstand the electrolytic solution and obtain a good adhesive force with the bag body 14 and Ti.

  Each dye-sensitized photoelectric conversion element manufactured as described above is irradiated with light using a solar simulator (AM1.5, 100 mW / cm2), a current-potential curve is measured, and the photoelectric conversion efficiency thereof Asked. The conversion efficiency of this photoelectric conversion element was 4.6%.

(Comparative example)
The photoelectric conversion element was produced with the manufacturing method which does not perform the process which heat-processes in the nitrogen atmosphere with respect to the electroconductive wire which comprises a working electrode. Therefore, no TiN film is formed around the conductive wire.
Except for this step, a photoelectric conversion element was produced by the same production method as in the embodiment of the present invention. The conversion efficiency of this photoelectric conversion element was 3.2%.

  From the above results, it was found that the power generation efficiency of the photoelectric conversion element was improved by forming the TiN film. This is because the TiN film allows electrons to flow more easily than the natural oxide film formed on titanium, so that the electrons excited by the titanium oxide efficiently flow into the titanium through the TiN film. It is believed that there is.

  The present invention is widely applicable to photoelectric conversion elements using metal wires as electrodes.

DESCRIPTION OF SYMBOLS 1 ... Dye-sensitized photoelectric conversion element, 2 ... Power generation part, 3 ... Working electrode, 4 ... Counter electrode, 5 ... Current collection part, 6 ... Separator, 10 ... Bag body, 12 ... Porous oxide semiconductor layer, 13 ... Electrolyte, 31 ... conductive wire, 32 ... site containing nitrogen.

Claims (6)

A method of manufacturing a working electrode having a structure in which a plurality of conductive wires formed of titanium at least on the outermost periphery is knitted in a mesh shape,
Forming a portion containing nitrogen in the skin portion of the conductive wire; and
And a step B of forming a porous oxide semiconductor layer carrying a sensitizing dye, and a method for producing a working electrode, comprising:   The method for manufacturing a working electrode according to claim 1, wherein the step A forms a portion containing nitrogen in a skin portion of the conductive wire by performing a heat treatment in a nitrogen atmosphere.   The method of manufacturing a working electrode according to claim 1, wherein the step A uses an ion implantation method to form a portion containing the nitrogen in a skin portion of the conductive wire.   The method for producing a working electrode according to claim 1, wherein the step A uses a sputtering method to form a portion containing the nitrogen in a skin portion of the conductive wire. A working electrode having a structure in which a plurality of conductive wires formed of titanium at least on the outermost periphery is knitted in a mesh shape,
A working electrode characterized in that a portion containing nitrogen is formed in the skin portion of the conductive wire, and a porous oxide semiconductor layer carrying a sensitizing dye is formed on the outer peripheral portion thereof. A working electrode according to claim 5;
A counter electrode disposed opposite to the working electrode;
A photoelectric conversion element comprising an electrolyte sealed between the working electrode and the counter electrode.

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