JP2009259485A - Dye-sensitized solar battery, its manufacturing method and dye-sensitized solar battery module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar battery having a high fill factor and high conversion efficiency by reducing charge transport resistance inside a porous semiconductor layer, and to provide its manufacturing method and a dye-sensitized solar battery module. <P>SOLUTION: The dye-sensitized solar battery includes a first counter electrode base board 104 made of a translucent conductive layer 102 and a translucent catalyst layer 103 put on a first translucent base board 101, a second counter electrode base board 108 made of a conductive layer 106 and a catalyst layer 105 put on a second base board 107, a porous semiconductor electrode sheet 111 which consists of a conductive sheet 109 and a porous semiconductor sheet 110 with dye absorbed in the conductive sheet, and an electrolyte sheet 112. The first counter electrode base board and the second counter electrode base board function as identical poles and are faced with each other, and the porous semiconductor electrode sheet is arranged between the first counter electrode base board and the second counter electrode base board functioning as hetero poles, and the porous semiconductor layer is formed at least at the translucent catalyst layer and a region facing the catalyst layer at both sides of the conductive sheet. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dye-sensitized solar cell with improved solar cell characteristics, a method for producing the same, and a dye-sensitized solar cell module.

Dye-sensitized solar cells are attracting widespread attention because they exhibit high photoelectric conversion efficiency among organic solar cells. In a dye-sensitized solar cell, a semiconductor film in which a spectral dye is adsorbed on a surface and an absorption spectrum is provided in a visible light region is used as a photoelectric conversion material.
For example, Patent Document 1 describes a dye-sensitized solar cell using a metal oxide semiconductor film having a spectral dye made of a transition metal complex adsorbed on a surface as a photoelectric conversion material.
Patent Document 2 describes a dye-sensitized solar cell having a spectral dye layer such as a transition metal complex on the surface of a titanium oxide semiconductor film doped with metal ions.
Further, Patent Document 3 describes a dye-sensitized solar cell using a semiconductor film for a photoelectric conversion material obtained by heating and refluxing an ethanol solution of a spectral sensitizer on the surface of a semiconductor film.

The dye-sensitized solar cell generally has a structure in which the above-described photoelectric conversion semiconductor film and an electrolyte layer are disposed between electrodes of two glass substrates having electrodes formed on the surface. A dye-sensitized solar cell using an electrolytic solution as an electrolyte layer is generally produced as follows.
As shown in FIG. 13, first, a transparent conductor film 22 and a porous semiconductor film 23 such as titanium oxide are sequentially formed on a transparent support 21, and a dye is adsorbed on the obtained porous semiconductor film 23. Next, a catalyst layer 26 such as a platinum film is optionally formed (coated) on the counter electrode 25 on which a conductive film is formed on the support, and transparent so that the porous semiconductor film 23 and the catalyst layer 26 or the counter electrode 25 face each other. The support 21 and the counter electrode 25 are overlapped. Next, after the outer peripheral portion of the transparent support 21 and the counter electrode 25 is sealed with a sealing material 27 such as an epoxy resin, an electrolytic solution is injected between them to form an electrolytic solution layer 24, thereby dye sensitization. A solar cell is obtained.

In order to improve the short circuit current (Jsc) by the porous semiconductor film of the dye-sensitized solar cell, the porous semiconductor film is made thicker, and submicron particles are mixed as a light scattering material in the porous semiconductor film. There is a method of confining the light.
In order to improve the conversion efficiency by using a dye having low absorbance, it is necessary to increase the thickness of the porous semiconductor film to some extent. However, increasing the film thickness increases the internal resistance of the porous semiconductor film. In addition, since the charge transport distance in the pores of the porous semiconductor film is increased, the charge transport resistance is increased, and the reverse electron reaction is likely to occur.

In order to solve such a problem, Patent Document 4 describes a photoelectric conversion device in which a metal mesh structure made of metal is formed inside a porous semiconductor film on which a sensitizing dye is adsorbed.
Patent Document 5 discloses a dye-sensitized solar cell in which a conductive layer having a lattice shape, a mesh shape, or a stripe shape is formed on the opposite side of a transparent electrode of an oxide semiconductor film on which a dye is adsorbed.
In Patent Document 6, a porous oxide semiconductor layer in which a dye is adsorbed on both front and back surfaces of a metal electrode substrate is formed, and each of the porous oxide semiconductor layers on both front and back surfaces of the metal electrode substrate is opposed to each other. A photoelectric conversion element in which a counter electrode is arranged is described.

Japanese Patent Laid-Open No. 1-220380 Japanese Patent Publication No. 8-15097 JP 7-249790 A JP 2005-285473 A JP 2004-39471 A JP 2007-172917 A

However, in the photoelectric conversion elements described in Patent Document 4 and Patent Document 5, the internal resistance inside the porous semiconductor film can be reduced, but the charge transport resistance inside the pores of the porous semiconductor film can be reduced. It was difficult.
Moreover, since the photoelectric conversion element of patent document 6 has formed the porous oxide semiconductor layer in the front and back both surfaces of a metal substrate, the light which injected from the surface side or back surface side of a metal substrate reaches only a metal substrate. Therefore, the light-shielded porous oxide semiconductor layer does not contribute to power generation. Therefore, since the photoelectric conversion element of patent document 6 needs to irradiate light from the front and back both surfaces side of a metal substrate, when using it for the solar power generation utilized most, sunlight injects from one direction. Light cannot be used effectively and is not suitable for photovoltaic power generation.

  The present invention has been made in view of the above-described problems, and provides a dye-sensitized solar cell, a manufacturing method thereof, and a dye-sensitized solar cell module that improve the solar cell characteristics by effectively using light incident from one direction. The purpose is to do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the internal resistance inside the porous semiconductor layer is increased even when the thickness of the porous semiconductor layer is increased in order to improve the short circuit current (Jsc). It was found that the charge transport resistance was reduced by reducing the charge transport distance in the pores of the porous semiconductor film, and that a high fill factor (FF) was exhibited, leading to the present invention. .

  Thus, according to the present invention, the first counter electrode substrate in which the translucent conductive layer and the translucent catalyst layer are formed in this order on the translucent first substrate, and the conductive layer and the catalyst layer on the second substrate. Has a second counter electrode substrate formed in this order, a conductive sheet having a plurality of light transmitting openings, and a porous semiconductor layer formed on each side of the conductive sheet and adsorbed with a dye. A porous semiconductor electrode sheet, and an electrolyte layer impregnated in the porous semiconductor layer and covering the periphery of the porous semiconductor layer, the first counter electrode substrate and the second counter electrode substrate function as the same electrode and interact with each other The porous semiconductor electrode sheet functions as a different electrode and is disposed between the first counter electrode substrate and the second counter electrode substrate, and the porous semiconductor layer is disposed on both sides of the conductive sheet. At least the translucent catalyst layer and Dye-sensitized solar cell is formed in a region facing the catalyst layer.

  According to another aspect of the present invention, a conductive layer is formed on a first counter electrode substrate and a second substrate in which a light transmissive conductive layer and a light transmissive catalyst layer are formed in this order on the light transmissive first substrate. And a step (1) of forming a second counter electrode substrate in which the catalyst layers are formed in this order, and a porous material in which a dye is adsorbed on at least a part of each of both surfaces of a conductive sheet having a plurality of light-transmitting openings. Forming the porous semiconductor electrode sheet by forming a conductive semiconductor layer, and the porous layer between the translucent catalyst layer of the first counter electrode substrate and the catalyst layer of the second counter electrode substrate. And a step (3) of forming an electrolyte layer between each of the translucent catalyst layer and the catalyst layer and the porous semiconductor electrode sheet. A manufacturing method is provided.

  According to still another aspect of the present invention, there is provided a dye-sensitized solar cell module in which at least two or more of the dye-sensitized solar cells are electrically connected in series or in parallel.

The dye-sensitized solar cell of the present invention has a first counter electrode on both sides of a porous semiconductor electrode sheet in which a conductive sheet having a plurality of light-transmitting openings is arranged inside a porous semiconductor layer to which a dye is adsorbed. Since the substrate and the second counter electrode substrate are arranged via the electrolyte layer, the conductive sheet acts as a negative electrode side collecting electrode, and the light-transmitting conductive film and the conductive film of the first and second counter electrode substrates Acts as a positive collector electrode.
With this configuration, even when the thickness of the porous semiconductor layer is increased in order to improve the short-circuit current (Jsc), the movement distance of electrons generated in the porous semiconductor layer to the conductive sheet is reduced, so that the internal resistance And the charge transport distance in the pores of the porous semiconductor layer is shortened, thereby reducing the charge transport resistance. As a result, the fill factor (FF) is improved.
In the dye-sensitized solar cell of the present invention, the light incident from the translucent first substrate side enters the surface of the porous semiconductor layer on the first substrate side, and is not blocked by the conductive sheet. It can reach the surface on the second substrate side of the porous semiconductor layer through the portion. Therefore, light incident from one direction can be effectively used for power generation, and it is suitable as a solar cell that receives sunlight generated from one direction and generates power.

(Configuration of dye-increasing solar cell)
The dye-sensitized solar cell of the present invention includes a first counter electrode substrate in which a translucent conductive layer and a translucent catalyst layer are formed in this order on a translucent first substrate, and a conductive layer and a second substrate. A second counter electrode substrate having a catalyst layer formed in this order; a conductive sheet having a plurality of light-transmitting openings; and a porous semiconductor layer formed on each side of the conductive sheet and adsorbed with a dye. A porous semiconductor electrode sheet and an electrolyte layer impregnated in the porous semiconductor layer and covering the periphery of the porous semiconductor layer, the first counter electrode substrate and the second counter electrode substrate function as the same electrode. The porous semiconductor electrode sheet functions as a different electrode and is disposed between the first counter electrode substrate and the second counter electrode substrate, and the porous semiconductor layer is formed of the conductive sheet. At least the translucent catalyst layer on both sides Characterized in that it is formed in a region facing the fine catalyst layer.

That is, this dye-sensitized solar cell has a porous semiconductor electrode sheet in which a conductive sheet having a plurality of openings is disposed inside a porous semiconductor layer to which a dye is adsorbed, and the porous semiconductor electrode sheet The main feature is that the first counter electrode substrate and the second counter electrode substrate are arranged on both sides of the substrate with the electrolyte layer interposed therebetween.
Hereinafter, embodiments of the dye-sensitized solar cell and the module thereof according to the present invention will be described with reference to the drawings. In addition, this invention is not limited to the following embodiment.

(Embodiment 1)
FIG. 1 is a schematic sectional view showing Embodiment 1 of the dye-sensitized solar cell of the present invention.
This dye-sensitized solar cell (hereinafter sometimes abbreviated as “solar cell”) has a translucent conductive layer 102 and a translucent catalyst layer 103 formed in this order on a translucent first substrate 101. A first counter electrode 104, a second counter electrode 108 in which a conductive layer 106 and a catalyst layer 105 are formed in this order on a second substrate 107, and a light-transmitting catalyst layer 103 of the first counter electrode 104 facing each other; The porous semiconductor electrode sheet 111 disposed between the second counter electrode substrate 108 and the catalyst layer 105, and the light-transmitting catalyst layer 103 and the catalyst layer 105 disposed between the porous semiconductor electrode sheet 111. And an electrolyte layer 112.

The solar cell further includes a sealing portion 113 on the outer peripheral portion of the porous semiconductor electrode sheet 111 between the first counter electrode substrate 104 and the second counter electrode substrate 108 facing each other, and the porous semiconductor electrode sheet One end of the conductive sheet 109 111 is exposed to the outside through the sealing portion 113, and one end of the translucent conductive layer 102 and the conductive layer 106 is exposed to the outside outside the sealing portion 113. .
In addition, the second counter electrode substrate 108 is formed with injection holes 114 for injecting an electrolyte between the first and second counter electrode substrates 104 and 108 at a plurality of locations in a region where the catalyst layer 105 is not formed. The opening of each injection hole 114 is sealed with an injection hole sealing part 115 made of resin.
Hereinafter, each component of the dye-sensitized solar cell will be described.

(Translucent first counter electrode substrate)
The translucent first counter electrode substrate is not particularly limited as long as it transmits light having a wavelength having an effective sensitivity to at least a dye described later and has a catalytic action on the surface. In the first embodiment, as described above, a light-transmitting conductive layer 102 and a light-transmitting catalyst layer 103 are sequentially formed on a light-transmitting substrate 101 is used. However, if the translucent substrate 101 itself has sufficient conductivity and catalytic action, the translucent conductive layer and the translucent catalyst layer are not necessary, and the translucent catalyst layer has sufficient conductivity. If it does, a translucent conductive layer is unnecessary.

[Translucent substrate]
As the light-transmitting substrate 101, a substrate that can substantially transmit light having a wavelength having effective sensitivity to at least a dye described below and can support the light-transmitting conductive film 102 and the light-transmitting catalyst layer 103 is used. it can. For example, a glass substrate made of soda-lime float glass, quartz glass, tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PA), polyetherimide ( PEI), a transparent polymer sheet made of phenoxy resin and the like.
Although the thickness of the translucent board | substrate 101 is not specifically limited, About 0.5-8 mm is suitable.

[Translucent conductive layer]
The translucent conductive layer 102 may be a film formed from a material that has conductivity and can substantially transmit light having a wavelength that has at least an effective sensitivity to a dye described later. There is no need to be transparent to light in the wavelength region. Examples of such materials include indium tin complex oxide (ITO), tin oxide (SnO ₂ ), tin oxide doped with fluorine (FTO), zinc oxide (ZnO), titanium oxide doped with tantalum or niobium, and the like. Is mentioned.
The translucent conductive layer 102 can be formed on the translucent substrate 101 by a known method such as sputtering or spraying. The film thickness of the translucent conductive layer 102 is suitably about 0.02 to 5 μm, the film resistance is preferably as low as possible, and is preferably 40Ω / sq or less.
The translucent conductive layer 102 functions as a positive electrode side collecting electrode during power generation of the dye-sensitized solar cell.

[Translucent catalyst layer]
The translucent catalyst layer 103 may be any material that has a catalytic action and can substantially transmit light having a wavelength that has at least an effective sensitivity to a dye described later, and does not necessarily transmit light in all wavelength regions. It is not necessary to have transparency. The material constituting the translucent catalyst layer 103 is not particularly limited as long as it is generally used in the field, and examples thereof include platinum, carbon black, ketjen black, carbon nanotube, and fullerene.
For example, when platinum is used, the translucent catalyst layer 103 can be formed by a known method such as sputtering, thermal decomposition of chloroplatinic acid, or electrodeposition. Alternatively, the light-transmitting catalyst layer 103 can be formed by applying a commercially available platinum paste by a coating method such as a screen printing method. When carbon such as carbon black, ketjen black, carbon nanotube, fullerene is used, the light-transmitting catalyst layer 103 is formed by applying carbon paste dispersed in a solvent by the coating method. Is also possible.
The film thickness of the translucent catalyst layer 103 should just express a catalyst function, for example, about 1-500 nm is suitable.

[Second counter electrode substrate]
The second counter electrode substrate 108 only needs to have the same conductivity and catalytic action as the translucent first counter electrode substrate 104, and the presence or absence of translucency is not relevant. In the first embodiment, a structure in which a conductive layer 106 and a catalyst layer 105 are sequentially formed on a substrate 107 is used. However, the conductive layer 106 is unnecessary if the substrate 107 itself has sufficient conductivity like a metal plate, and the conductive layer 106 is unnecessary if the catalyst layer 105 has sufficient conductivity. Furthermore, if the substrate 107 itself has both conductivity and catalytic action like a platinum plate, the substrate 107 alone can be used as the second counter electrode substrate 108. The second counter electrode substrate 108 may be the same as the first counter electrode substrate 104.

[substrate]
The substrate 107 of the second counter electrode substrate 108 is not particularly limited as long as it can support the conductive layer 106 and the catalyst layer 105. For example, titanium, tantalum, tungsten, nickel, indium, aluminum, rhodium, gold, silver, Metal plates such as copper, zinc and iridium, ceramic plates such as alumina and magnetic plates, glass substrates such as soda lime float glass and quartz glass, tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyphenylene sulfide (PPS) And transparent polymer sheets such as polycarbonate (PC), polyarylate (PA), polyetherimide (PEI), and phenoxy resin.

[Conductive layer]
Examples of the material constituting the conductive layer 106 include metal foil films such as titanium, tantalum, tungsten, nickel, indium, aluminum, rhodium, gold, silver, copper, zinc, iridium, indium tin composite oxide (ITO), Examples thereof include tin oxide (SnO ₂ ), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), tantalum or niobium-doped titanium oxide.
The conductive layer 106 can be formed on the substrate 107 by a known method such as sputtering or spraying. The thickness of the conductive layer 106 is suitably about 0.02 to 5 μm, and the lower the film resistance, the better, preferably 40Ω / sq or less.
The conductive layer 106 also functions as a positive electrode side collecting electrode together with the translucent conductive layer 102 during power generation of the dye-sensitized solar cell.

[Catalyst layer]
The catalyst layer 105 is not particularly limited as long as it is generally used in the field. For example, the same material as the light-transmitting catalyst layer 103 such as platinum, carbon black, ketjen black, carbon nanotube, and fullerene is used. Can be mentioned. Further, the formation method of the catalyst layer 105 is the same as the formation method of the translucent catalyst layer 103.
The film thickness of the catalyst layer 105 should just be able to express a catalyst function, for example, about 1-2000 nm is suitable.

(Porous semiconductor electrode sheet)
The porous semiconductor electrode sheet 111 includes a conductive sheet 109 having a plurality of light-transmitting openings, and a porous semiconductor layer 110 formed on at least a part of each of both surfaces of the conductive sheet 109 and adsorbed with a dye. Have. In this porous semiconductor electrode sheet 111, at the time of power generation of the dye-sensitized solar cell, the porous semiconductor layer 110 on which the dye is adsorbed functions as a power generation unit, and the conductive sheet 109 functions as a negative electrode side collecting electrode.
The method for forming the porous semiconductor electrode sheet 111 will be described later in detail.

[Conductive sheet]
The conductive sheet 109 has a plurality of light-transmitting openings, and has a sheet shape that can carry the porous semiconductor layer 110 on at least a part of both the front and back surfaces. Further, even after the manufacturing process of the porous semiconductor layer 110 is performed. Others are not particularly limited as long as they are formed of a material that can maintain conductivity and is not corroded by an electrolytic solution containing iodine or the like.
Examples of the material of the conductive sheet 109 include titanium, nickel, tungsten, tantalum, or an alloy containing one or more of these metals.

Examples of the form of the conductive sheet 109 include a metal net and a metal film (metal foil) in which a plurality of small holes are formed in a matrix shape. The conductive sheet 109 has a plurality of light-transmitting openings, preferably a light-transmitting opening. Any form may be used as long as the parts have a uniform size and orderly arrangement.
The thickness of the conductive sheet 109 is preferably about 5 μm to 100 μm. If the thickness is larger than 100 μm, the thickness of the porous semiconductor layer 110 becomes too thick, and the charge transport distance in the pores becomes long. The conductive sheet 109 having a thickness of less than 5 μm may be used, but it is difficult to produce and may be damaged during and after the formation of the porous semiconductor layer because the strength is reduced.
Further, the opening ratio, which is the total area of the openings with respect to the entire area of the portion having the openings in the conductive sheet 109, is preferably 10% or more and 90% or less, and more preferably 30% or more and 90% or less. If the aperture ratio exceeds 90%, the strength of the conductive sheet tends to decrease, which is not preferable. If the aperture ratio is less than 10%, the area shielded by the conductive sheet 109 is too large, so that light can be used effectively. This is not possible and the solar cell characteristics (particularly the short-circuit current density) are reduced. In addition, the opening part should just be formed in the part in which the porous semiconductor layer 110 in the electroconductive sheet 109 is formed at least, and may be formed in the whole surface.

[Porous semiconductor layer]
The porous semiconductor layer 110 covers the conductive sheet 109 at a position approximately in the middle of its thickness. The thickness of the porous semiconductor layer 110 is preferably about 10 to 200 μm. When the thickness is greater than 200 μm, the movement distance of the electrons generated in the porous semiconductor layer 110 to the conductive sheet 109 is increased, so that the internal resistance tends to increase and the pores of the porous semiconductor layer 110 are increased. The charge transport resistance tends to increase because of the longer charge transport distance. Further, when the thickness is less than 10 μm, it is difficult to improve the short circuit current density (Jsc).

The material which comprises the porous semiconductor layer 110 will not be specifically limited if it is generally used for the photoelectric conversion material in the said field | area. Examples of such materials include titanium oxide, zinc oxide, tin oxide, iron oxide, niobium oxide, cerium oxide, tungsten oxide, barium titanate, strontium titanate, cadmium sulfide, lead sulfide, zinc sulfide, and indium phosphide. , Semiconductor compounds such as copper-indium sulfide (CuInS ₂ ), CuAlO ₂ , SrCu ₂ O ₂ , and combinations thereof. Among these, titanium oxide is particularly preferable from the viewpoint of stability and safety.

  This titanium oxide includes various narrowly defined titanium oxides such as anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, hydrous titanium oxide, etc. Or it can be used as a mixture. The two types of crystal systems, anatase type and rutile type, can be in any form depending on the production method and thermal history, but the anatase type is common. In the present invention, with respect to dye sensitization, those having a high anatase type content, for example, 80% or more are particularly preferred.

  In the present invention, the semiconductor layer is preferably a porous semiconductor layer obtained by sintering semiconductor fine particles. Others include thin-film semiconductor layers, fibrous semiconductor layers, and semiconductor layers made of acicular crystals obtained by the sol-gel method, sputtering method, spray pyrolysis method, etc. It can be appropriately selected depending on the shape of the material. However, a semiconductor layer having a large specific surface area such as a porous semiconductor layer or a needle-shaped semiconductor layer is preferable from the viewpoint of the amount of dye adsorption. In particular, a porous semiconductor layer formed from semiconductor fine particles is preferable from the viewpoint that the utilization factor of incident light and the like can be adjusted by the particle size of the semiconductor fine particles.

The semiconductor fine particles can be produced by a known method such as a sol-gel method such as a hydrothermal synthesis method, a sulfuric acid method, or a chlorine method, and is not particularly limited as long as the target semiconductor fine particles can be produced. Among these, the hydrothermal synthesis method is particularly preferable from the viewpoint of crystallinity.
The average particle size of the semiconductor fine particles is suitably about 1 nm to 500 nm, and preferably about 1 to 50 nm from the viewpoint of increasing the specific surface area of the porous semiconductor layer. Further, in order to efficiently use incident light in a solar cell, semiconductor fine particles having different average particle diameters may be mixed. For example, the semiconductor fine particles having the average particle diameter have an average particle diameter of about 200 to 400 nm. Large semiconductor particles may be added.

In order to improve the photoelectric conversion efficiency of the solar cell, it is necessary to adsorb more dye to the porous semiconductor layer 110. For this reason, the porous semiconductor layer 110 preferably has a specific surface area that is somewhat large, and is preferably about 10 to 200 m ² / g.
Further, the porosity of the porous semiconductor layer 110 is preferably about 40 to 80% from the viewpoints of dye adsorption and ion diffusion in the electrolyte layer described later, that is, charge transport. Here, the “porosity” means a value indicating the ratio of the total volume of the pores to the total volume of the porous semiconductor layer 110 including a large number of pores in%. The porosity was calculated by calculating the volume from the film thickness and area, calculating the filling rate from (weight of material) / {(volume) × (density of material)}, and subtracting the filling rate from 100%.

[Dye]
Examples of the dye that is adsorbed on the porous semiconductor layer 110 and functions as a photosensitizer include organic dyes and metal complex dyes having absorption in at least one of various visible light regions and infrared light regions. Then, one or more of these dyes can be selectively used.
Examples of organic dyes include azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes, porphyrin dyes, and phthalocyanines. And dyes, perylene dyes, indigo dyes, naphthalocyanine dyes and the like.
As metal complex dyes, Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb, Metals such as La, W, Pt, TA, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Te, Rh Examples include a form in which molecules are coordinated, and specific examples include ruthenium metal complex dyes such as ruthenium bipyridine metal complex dyes, ruthenium terpyridine metal complex dyes, and ruthenium quarter pyridine metal complex dyes. .

Moreover, in order to adsorb | suck a pigment | dye firmly to a porous semiconductor film, a carboxyl group (COOH group), an alkoxy group, a hydroxyl group, a hydroxyalkyl group, a sulfonic acid group, an ester group, a mercapto group, a phosphonyl group in a pigment molecule. Those having an interlock group such as are preferable, and among these, a carboxyl group is particularly preferable. In general, the interlock group provides an electrical bond that facilitates electron transfer between the excited state dye and the conduction band of the porous semiconductor film.
Examples of the dye having such an interlock group include the above organic dyes and metal complex dyes, and among these, ruthenium-based metal complex dyes represented by the following formulas (1) to (3) are particularly preferable.

[Dye adsorption method]
As a method for adsorbing the dye to the porous semiconductor layer 110, for example, a method of immersing the porous semiconductor layer 110 formed so as to cover the conductive sheet 109 in a solution in which the dye is dissolved (dye adsorption solution) is used. Can be mentioned.
The solvent for dissolving the dye may be any solvent that dissolves the dye. Examples thereof include alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran, nitrogen compounds such as acetonitrile, chloroform, and the like. Halogenated aliphatic hydrocarbons, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, esters such as ethyl acetate, and water. In the present invention, two or more of these solvents can be mixed and used.

The dye concentration in the dye solution can be adjusted as appropriate depending on the type of dye and solvent used, but it is preferable to have a high concentration to improve the adsorption function, for example, 5 × 10 ⁻⁵ mol. It is sufficient that the concentration is 1 / liter or more.
In addition, an organic compound such as deoxycholic acid may be added to the dye solution as a co-adsorbent in order to control the adsorption state of the dye, the surface of the porous semiconductor layer 110, and the like.
Conditions such as temperature, time, and atmosphere when the porous semiconductor layer 110 is immersed in the dye solution may be appropriately set depending on the material and state of the porous semiconductor layer 110, the constituent material of the dye solution, and the like. Immersion can be performed at about room temperature in an air atmosphere, for example. By immersing under heating, the dye can be efficiently adsorbed to the porous semiconductor layer 110.

(Electrolyte layer)
The electrolyte layer 112 is made of a conductive material that can transport ions, and is used in the form of, for example, a liquid electrolyte layer or a solid electrolyte layer.
The liquid electrolyte layer is not particularly limited as long as it is a liquid substance containing a redox species, and can be generally used in a battery or a solar battery. Specifically, a composition comprising a redox species and a solvent capable of dissolving the same is mentioned.
The redox species, e.g., LiI, NaI, KI, combinations of metal iodides and iodine, such as CaI _2, LiBr, NaBr, KBr, combinations of metal bromides and bromine, such as CaBr _2, a salt consisting of iodide ion A combination of iodine, a combination of a salt made of bromide ions and a bromine can be mentioned. Among these, a combination of LiI and iodine, and a combination of a salt made of iodide ions and iodine are preferable. These redox species can be used in combination of two or more.

To the liquid electrolyte layer, ionic compounds such as guanidine thiocyanate, nitrogen-containing heterocyclic compounds such as 4-tert-butylpyridine, and other organic compounds are added to improve characteristics by adsorption to the electrode surface. Also good.
Examples of the solvent capable of dissolving the redox species include carbonate compounds such as propylene carbonate, lactones such as γ-butyrolactone, nitrile compounds such as acetonitrile, alcohols such as ethanol, water, aprotic polar substances, and the like. Among these, carbonate compounds, lactones, and nitrile compounds are particularly preferable. Two or more of these solvents can be used in combination.

A molten salt can also be used as a solvent capable of dissolving the redox species, and a mixture with the above-described solvent can also be used.
The “molten salt” is a salt in a liquid state that does not contain a solvent and is composed only of ions.
Molten salts are described in, for example, Inorg. Chem., 1996, 35, p. 1168-1178 and Electrochemistry., 2002, 2, p. 130-136, and Japanese Patent Publication No. 9-507334 and It is not particularly limited as long as it can be generally used in a battery, a solar battery, or the like as described in patent documents such as 8-259543. In addition, the molten salt may be used regardless of whether it is involved in the production of redox species, or a mixture thereof.
As the molten salt, a salt having a melting point lower than room temperature (25 ° C.), or a liquid state at room temperature by dissolving with another molten salt or an electrolyte layer salt other than the molten salt even when having a melting point higher than room temperature. Salts are preferred.

Molten salt cations include ammonium, imidazolium, oxazolium, thiazolium, pyrazolium, isoxazolium, thiadiazolium, oxadiazolium, triazolium, pyrrolidinium, pyridinium, pyrimidinium, pyridazinium, pyrazinium, triazinium, phosphonium, sulfonium, carbazolium Indolium and its derivatives are preferable, and among these, ammonium, imidazolium, pyridinium, and sulfonium are particularly preferable.
Examples of the anion of the molten salt include metal chlorides such as AlCl ₄ ⁻ and Al ₂ Cl ₇ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , N (CF ₃ SO ₂ ) ₂ ⁻ , and N (SO ₂ Fluorine-containing materials such as F) ₂ ⁻ and F (HF) _n ⁻ , non-fluorine-containing materials such as NO ₃ ⁻ , CH ₃ COO ⁻ , C ₆ H ₁₁ COO ⁻ , SCN ⁻ and N (CN) ₂ ^— , iodine And halides such as bromine.
The molten salt can be synthesized by known methods described in the above-mentioned various documents and patent publications. Taking a quaternary ammonium salt as an example, a quaternization of an amine is performed using a tertiary amine as an alkylating agent as an alkylating agent as a first step, and an ion exchange from a halide anion to a target anion is performed as a second step. And a method of obtaining a target compound in one step by reacting a tertiary amine with an acid having a target anion.

When a solvent or molten salt that dissolves the redox species is used, a separator layer may be provided between the conductive sheet or porous semiconductor sheet and the counter electrode in order to prevent a short circuit.
The separator layer is not particularly limited as long as it is electrically insulating and stable with respect to the constituent material of the solar cell. Specifically, the separator layer is a porous layer formed from a metal oxide such as SiO ₂ or ZrO _2. Nonwoven fabrics formed from layers, polymer compounds, and the like.

As the solid electrolyte layer, a polymer electrolyte layer (gel electrolyte layer) obtained by solidifying an electrolyte solution containing a solvent with a polymer compound, an electrolyte layer obtained by solidifying an electrolyte solution containing a molten salt with fine particles, an organic P-type semiconductor And inorganic P-type semiconductors such as CuI.
The polymer compound used for forming the polymer electrolyte layer is not particularly limited as long as it is a polymer compound that can hold the mixed solvent and the electrolyte solution constituting the electrolyte layer. Examples of such a polymer compound include a poly (meth) acrylate polymer or copolymer obtained by polymerizing or copolymerizing a monomer unit represented by the following general formula (4), and a compound A having an isocyanate group. And an epoxy resin and the like. Among these, a poly (meth) acrylate polymer or copolymer, a compound A having an isocyanate group and an active hydrogen group are included. A compound obtained by polyaddition of the compound B is preferably used.

（式中、Ｒは水素原子またはメチル基であり、Ｘはエステル基と炭素原子で結合している残基であり、ｎは２〜４の整数である。）

(In the formula, R is a hydrogen atom or a methyl group, X is a residue bonded to an ester group with a carbon atom, and n is an integer of 2 to 4.)

  The polymerization method of the above-described polymer compound is not particularly limited, and may be appropriately set depending on the monomer material used, such as polymerization under normal temperature and normal pressure, thermal polymerization, and photopolymerization. However, when titanium oxide is used for the porous semiconductor layer 110, there is a problem that titanium oxide causes a photocatalytic reaction due to light irradiation in the ultraviolet region, and the dye adsorbed on the porous semiconductor layer 110 is decomposed. Polymerization of the polymer compound is preferably polymerization at normal temperature and pressure or thermal polymerization.

The method for forming the solid electrolyte layer may be appropriately selected according to the compound used for polymerizing the polymer compound.
For example, when using a compound containing isocyanate and an active hydrogen group that iodine does not affect polymerization, these compounds are mixed with a solution containing an electrolyte before polymerization, and the resulting mixture is polymerized. A gel electrolyte layer is obtained.
When (meth) acrylates are polymerized by radical polymerization in which iodine acts as a polymerization inhibitor, the polymer obtained is polymerized only in the polymer compound and the solvent, and the polymer obtained in the electrolyte solution consisting of the electrolyte and the solvent A gel electrolyte layer is obtained by soaking.

  The fine particles in the solid electrolyte layer obtained by solidifying an electrolytic solution containing a molten salt with fine particles are not particularly limited as long as they are compound fine particles capable of solidifying the electrolytic solution. Examples of such compounds include metal oxides such as silicon oxide and carbon nanotubes.

When the amount of electrolyte penetrating into the pores (micropores) of the porous semiconductor layer 110 is small, the photoelectric conversion efficiency of the resulting solar cell is lowered. Therefore, it is necessary to form more liquid electrolyte layers or solid electrolyte layers in the pores of the porous semiconductor layer 110.
If the liquid electrolyte layer has a low viscosity, it is possible to inject the liquid electrolyte layer into the porous semiconductor layer 110 even under normal temperature and pressure, but a high viscosity liquid electrolyte containing a large amount of a high viscosity solvent or molten salt. In the case of a layer, it becomes difficult to inject into the porous semiconductor layer 110 even under normal temperature and pressure. Therefore, the method of injecting the liquid electrolyte layer into the porous semiconductor layer 110 is preferably a vacuum injection method.
In the case where a polymer electrolyte layer is used as the electrolyte layer, for example, after impregnating the porous semiconductor layer 110 with a liquid prepolymer solution, the prepolymer may be polymerized. A method of injecting the prepolymer solution into the porous semiconductor layer 110 is preferably a vacuum injection method.
Also, when using a solid electrolyte layer that is formed by ion bonding or the like and causes a solid-liquid phase change reversibly by heat, for example, vacuum injection of the solid electrolyte layer that has been changed to a liquid state by heating or the like. It may be injected into the porous semiconductor layer 110 by a method.

(Sealing part)
The sealing portion 113 has a function of preventing leakage of the electrolyte inside the solar cell, a function of absorbing falling objects and stress (impact) acting on the support such as the first substrate 131 and the second substrate 136, and long-term use. Has a function of absorbing the deflection acting on the support.
Furthermore, when producing a solar cell module by connecting at least two or more of the solar cells of the present invention in series or in parallel, the sealing portion 113 is an inter-cell insulating layer in order to prevent the electrolyte from moving between the solar cells. It is important to function as.

The material which comprises the sealing part 113 will not be specifically limited if it is a material which can generally be used for a solar cell and can exhibit the said function. Examples of such materials include ultraviolet curable resins and thermosetting resins. Specific examples include silicone resins, epoxy resins, polyisobutylene resins, hot melt resins, and glass frit. The sealing portion 113 can also be formed by stacking two or more kinds of materials in two or more layers.
As the ultraviolet curable resin, manufactured by ThreeBond Co., Ltd., model number: 31X-101, and as the thermosetting resin, manufactured by ThreeBond Co., Ltd., model number: 31X-088, or a commercially available epoxy resin can be used.
The pattern of the sealing portion 113 can be formed by using a dispenser when using a silicone resin, an epoxy resin, or a glass frit. When using a hot melt resin, the pattern of the sealing portion 113 is formed on a sheet-like hot melt resin. It can be formed by opening a patterned hole.

(Method for producing dye-sensitized solar cell)
The dye-sensitized solar cell having the above-described configuration can be manufactured by the following manufacturing method.
That is, in this manufacturing method, the conductive layer is formed on the first counter electrode substrate 104 and the second substrate 107 in which the transparent conductive layer 102 and the transparent catalyst layer 103 are formed in this order on the transparent first substrate 101. 106 and the catalyst layer 105 are formed in this order, the step (1) for forming the second counter electrode substrate 108, and a dye on at least a part of each of both surfaces of the conductive sheet 109 having a plurality of light-transmitting openings. The step (2) of forming the porous semiconductor electrode sheet 111 by forming the adsorbed porous semiconductor layer 110, the translucent catalyst layer 103 of the first counter electrode substrate 104, and the catalyst layer 105 of the second counter electrode substrate 108. The porous semiconductor electrode sheet 111 is disposed between the transparent semiconductor electrode sheet 111 and an electrolyte layer is formed between each of the translucent catalyst layer 103 and the catalyst layer 105 and the porous semiconductor electrode sheet 111. And a step (3).

  In step (1), formation of the light-transmitting conductive layer 102 and the light-transmitting catalyst layer 103 on the light-transmitting first substrate 101 and formation of the conductive layer 106 and the catalyst layer 105 on the second substrate 107 are performed. Can be performed as described above.

[Method of forming porous semiconductor electrode sheet]
As one method for forming a porous semiconductor layer, first, a suspension is prepared by dispersing semiconductor fine particles in a solution in which a macromolecular organic compound, a dispersant, etc. are optionally added to an organic solvent or water. Apply the suspension to one side of the conductive sheet, dry and fire the resulting coating to form half of the porous semiconductor layer on one side, and then do the same for the other side of the conductive sheet It is conceivable to form the porous semiconductor layer so as to cover the conductive sheet by forming the remaining half of the porous semiconductor layer. However, if the suspension is applied as it is onto the conductive sheet, the suspension flows down from the opening, so that a hole is formed in the obtained porous semiconductor layer.
Therefore, in the step (2), it is preferable to form the porous semiconductor electrode sheet 111 by the following first to fourth methods.

The first forming method will be described with reference to FIG. 2. In this case, the step (2) is performed by forming a porous semiconductor on the thin film 2 of the heat resistant substrate 1 having a thin film 2 that can be dissolved in a stripping solution on the surface. A step of applying a layer material and baking to form a porous semiconductor layer first portion 110a (see FIG. 2A), and a conductive sheet 109 is placed on the first portion 110a (FIG. 2B). )), By applying a porous semiconductor layer material on the first portion 110a so as to cover the conductive sheet 109 and baking it to form the porous semiconductor layer second portion 110b, thereby forming the conductive sheet 109 therein. A step of forming a porous semiconductor layer 110 in which is disposed (see FIG. 2C), the heat-resistant substrate 1 is immersed in the peeling solution, thereby dissolving the thin film 2 to make the heat-resistant substrate 1 porous. A step of peeling from the conductive semiconductor layer 110 ( 2 (d) see), and a step (not shown) to a solution of the dye by immersing the porous semiconductor layer to adsorb the dye.
In this case, as the heat resistant substrate 1, for example, a glass substrate, a ceramic substrate, or the like can be used. Examples of the material for the thin film formed on the heat-resistant substrate 1 include metal oxides (such as zinc oxide) and metal films (such as copper and zinc), and the stripping solution is an acid capable of dissolving these thin films. A solution (an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, or an organic acid such as acetic acid or oxalic acid) can be used.
A method for forming a thin film on the heat-resistant substrate 1 can be performed by a known method and apparatus such as a coating method, a plating method, a CVD method, a sputtering method, and an SPD method. About 5 mm is appropriate.

The second forming method will be described with reference to FIG. 3. In this case, the step (2) includes a conductive sheet on the thin film 2 of the heat-resistant substrate 1 having a thin film 2 that can be dissolved in a peeling solution on the surface. 109. A step of applying a porous semiconductor layer material via 109 and baking to form a porous semiconductor layer first portion 110a (see FIG. 3A), and dipping the heat-resistant substrate 1 in the release solution A step of dissolving the thin film 2 to peel the heat-resistant substrate 1 from the porous semiconductor layer first portion 110a (see FIG. 3B), and so as to cover the conductive sheet 109 exposed to the outside. The porous semiconductor layer 110 having the conductive sheet 109 disposed therein is formed by applying a porous semiconductor layer material onto the semiconductor layer first portion 110a and baking it to form the porous semiconductor layer second portion 110b. Forming step (FIG. 3). c)), to a solution of the dye by immersing the porous semiconductor layer and a step (not shown) for adsorbing the dye.
In this case, the same heat-resistant substrate, thin film and stripping solution as in the first forming method can be used.

The third forming method will be described with reference to FIG. 4. In this case, in the step (2), the porous semiconductor layer material is applied onto the resin film 3 (see FIG. 4 (a)) and fired. Forming a porous semiconductor layer first portion 110a and burning out the resin film 3 (see FIG. 4B), placing a conductive sheet 109 on the first portion 110a, A porous semiconductor layer having a conductive sheet 109 disposed therein is formed by applying a porous semiconductor layer material on the first portion 110a and baking the first portion 110a so as to cover the first portion 110a. 110 (see FIG. 4C), and a step of immersing the porous semiconductor layer in a solution in which the dye is dissolved to adsorb the dye (not shown).
In this case, as a material for the resin film, a material that can be removed by baking such as polypropylene and nylon can be used, and the thickness of the resin film is suitably about 1 to 300 μm.

The fourth forming method will be described with reference to FIG. 5. In this case, the step (2) applies a porous semiconductor layer material to the resin film 3 via the conductive sheet 109 (FIG. 5 ( a)), firing to form the porous semiconductor layer first portion 110a and burning the resin film 3 (see FIG. 5B), so as to cover the conductive sheet 109 exposed to the outside. A porous semiconductor layer in which a conductive sheet 109 is disposed by forming a porous semiconductor layer second portion 110b by applying a porous semiconductor layer material onto the porous semiconductor layer first portion 110a and baking it. 110 (see FIG. 5C), and a step of immersing the porous semiconductor layer in a solution in which the dye is dissolved to adsorb the dye (not shown).
In this case, the same resin film as the third forming method can be used.

In any of the first to fourth methods, in order to form the porous semiconductor layer 110 thickly, a suspension (a material for the porous semiconductor layer) is formed during the formation of the first portion 110a and the second portion 110b. Since it is difficult to apply and fire the coating once, it is desirable to repeat the coating and firing several times. At this time, since the number of times of application and baking in the formation of the first portion 110a and the second portion 110b is substantially the same, the thickness of the first portion 110a and the thickness of the second portion 110b are made substantially the same. be able to. That is, the conductive sheet 109 can be disposed at a substantially intermediate position in the film thickness direction of the porous semiconductor layer 110.
As described above, when the conductive sheet 109 is disposed at a substantially intermediate position in the film thickness direction of the porous semiconductor layer 110, compared to the case where the conductive sheet 109 is disposed on the end surface of the porous semiconductor layer 110 in the film thickness direction, The distance that electrons generated in the porous semiconductor layer 110 move to the conductive sheet 109 serving as a current collecting electrode is shortened, and the charge transport distance in the pores is also shortened.
Note that the porous semiconductor layer 110 may be bent and cracked by firing, but as long as the porous semiconductor layer 110 is held in contact with the conductive sheet 109, there is no problem because the conductive sheet 109 functions as a current collecting electrode. .

The suspension for forming the porous semiconductor layer 110 contains an organic compound such as a polymer (resin) or an organic solvent in addition to the semiconductor fine particles, so that the organic compound burns or evaporates in the firing step. Thus, voids can be formed in the porous semiconductor layer 110. Further, the porosity of the porous semiconductor layer 110 can be changed by selecting the molecular weight or the addition amount of the organic compound.
Such a polymer as an organic compound is not particularly limited as long as it can be dissolved in a suspension and burned and removed in a baking step, and examples thereof include polyethylene glycol and ethyl cellulose.
Examples of the organic solvent include glyme solvents such as ethylene glycol monomethyl ether, alcohol solvents such as isopropyl alcohol, mixed solvents such as isopropyl alcohol / toluene, and water.
The type and amount of the organic compound may be appropriately set depending on the type of semiconductor fine particles used and the ratio to the total weight of the suspension. When the proportion of the semiconductor fine particles is too small, the desired strength as the porous semiconductor layer of the solar cell tends to be not obtained. When the proportion of the semiconductor fine particles is too large, the desired strength as the porous semiconductor layer is obtained. There is a tendency that porosity cannot be obtained. Therefore, the ratio of the semiconductor fine particles to the total weight of the suspension is, for example, about 10 to 40% by weight.

The porous semiconductor layer 110 was formed using not only a single layer film formed using a single semiconductor fine particle having a specific average particle diameter but also a suspension containing semiconductor fine particles of different types and average particle diameters. A single layer film or a multilayer film using individual suspensions containing semiconductor fine particles having different types and average particle diameters may be used.
The method for applying the suspension is not particularly limited, and examples thereof include known methods such as a doctor blade method, a squeegee method, a spin coating method, and a screen printing method.

  You may perform a drying process after baking and before baking. Conditions such as temperature, time, and atmosphere in drying and baking of the suspension coating film may be appropriately set depending on the material of the resin film used in the third and fourth forming methods, the kind of semiconductor fine particles, and the like. Drying and baking can be performed, for example, in an air atmosphere or an inert gas atmosphere within a range of about 50 to 800 ° C. for about 10 seconds to 12 hours. This drying and baking can be performed once at a single temperature or twice or more at different temperatures.

In the step (3), before the electrolyte layer 145 is formed, the sealing portion 113 is formed.
When forming the sealing portion 113, the resin material of the sealing portion 113 described above is applied to or installed on the outer peripheral portion of the first counter electrode substrate 104 and the outer peripheral portion of the second counter electrode substrate 108. The first counter electrode substrate 104 and the second counter electrode substrate 108 are overlapped so that the porous semiconductor layer 110 is sandwiched between the translucent catalyst layer 103 and the catalyst layer 105. Then, the sealing portion 113 is formed by curing the resin material by irradiating light or applying heat. Thus, one end of the conductive sheet 109 is held in a state where it penetrates the sealing portion 113 without a gap and is exposed to the outside. By covering the periphery of one end portion of the conductive sheet 109 with this sealing portion 113, it is possible to prevent a short circuit due to contact with the translucent conductive layer 102 and the conductive layer 106.

  Next, an electrolytic solution is injected between the first and second counter electrode substrates 104 and 108 from the injection hole sealing portion 115 of the second counter electrode substrate 108 to impregnate the porous semiconductor layer 110 with an electrolyte, and then each injection is performed. The dye-sensitized solar cell of Embodiment 1 is completed by sealing the opening of the hole 114 with an injection hole sealing part 115 (for example, photosensitive resin). In FIG. 1, the porous semiconductor layer 110 is illustrated as being separated from the translucent catalyst layer 103 and the catalyst layer 105 in order to represent the electrolyte layer 112, but actually the porous semiconductor layer 110 is translucent. The catalyst layer 103 and the catalyst layer 105 are brought into contact with each other.

The solar cell of Embodiment 1 manufactured in this way is connected to an external circuit using the transparent conductive layer 101 and the conductive layer 106 exposed to the outside as a positive electrode terminal and the conductive sheet 109 exposed to the outside as a negative electrode terminal. The light-transmitting first substrate 101 is used by being irradiated with light.
When light enters from the translucent first substrate 101 side, the light passes through the translucent first substrate 101, the translucent conductive layer 102, the translucent catalyst layer 103, and the electrolyte layer 112, so that the porous semiconductor layer 110 light receiving surface is reached. Further, the light reaching the light receiving surface of the porous semiconductor layer 110 passes through the inside of the porous semiconductor layer 110, passes through the opening of the conductive sheet 109, and reaches the back surface side of the porous semiconductor layer 110. Thereby, electrons are generated in the front side portion and the back side portion of the porous semiconductor layer 110, and the generated electrons move from the conductive sheet 109 through the external circuit to the translucent conductive layer 101 and the conductive layer 106. Charges are transported from the translucent catalyst layer 103 and the catalyst layer 105 by the electrolyte of the electrolyte layer 112 and return to the porous semiconductor layer 110.

(Embodiment 2)
FIG. 6 is a schematic sectional view showing Embodiment 2 of the dye-sensitized solar cell of the present invention.
The difference between the solar cell of the second embodiment and the solar cell of the first embodiment is that a collector electrode portion 146 that electrically connects the transparent conductive layer 102 and the conductive layer 106 exposed to the outside is provided. Other configurations in the second embodiment are the same as those in the first embodiment. In FIG. 6, the same components as those in the first embodiment of the second embodiment are denoted by the same reference numerals, and the description thereof is omitted. In FIG. 6, the injection hole 114 and the injection hole sealing portion 115 described in FIG. 1 are not shown.

The current collecting electrode portion 146 is a positive electrode terminal for electrical connection with an external circuit, and is made of, for example, carbon, Ag, In or the like, and is formed by applying paste or soldering. be able to.
By providing the current collecting electrode portion 146, connection to the external circuit of the positive electrode terminal of the solar cell is only required at one place.

(Embodiment 3)
FIG. 7 is a schematic cross-sectional view showing the dye-sensitized solar cell module of the present invention.
This solar cell module has a structure in which the solar cells (solar cells) of Embodiments 1 and 2 are electrically connected in series. In addition, although the case where two solar cells are connected in series is described here, it goes without saying that the number of solar cells may be three or more.

  In the solar cell module according to Embodiment 3, the translucent first counter electrode substrate 135 includes a translucent conductive layer 171 and a translucent catalyst layer 172 at two locations on the same translucent first substrate 170. The second counter electrode substrate 140 is formed by separating the laminated films of the conductive layer 174 and the catalyst layer 175 at two locations on the same second substrate 173, and the second counter electrode substrate 140 is disposed. The 1st counter electrode substrate 135 and the 2nd counter electrode substrate 140 are bonded together via the outer peripheral side sealing part 180a and the inner side sealing part 180b. Note that the two light-transmitting conductive layers 171 on the first substrate 170 and the two conductive layers 174 on the second substrate 173 are formed by forming a material film over the entire surface of the substrate, and then using a laser on the material film. The scribe line 176 is formed and electrically separated.

Each of the translucent conductive layer 171 and the conductive layer 174 is formed longer than the length of the translucent catalyst layer 172 and the catalyst layer 175 in the series connection direction, and the translucent light constituting one solar cell (left side in FIG. 7). The conductive conductive layer 171 and the conductive layer 174 are exposed to the outside.
The light-transmitting conductive layer 171 and the conductive layer 174 constituting the other (right side of FIG. 7) are close to the one light-transmitting conductive layer 171 and the conductive layer 174, and two places between them. The inner sealing portions 180b are spaced apart from each other.
In addition, between the two inner sealing portions 180b, a conductive sheet 177, which will be described later, penetrating the one inner sealing portion 180b is electrically connected to the opposing light-transmitting conductive layer 171 and conductive layer 174. A conductive connection 179 is provided. As a material for forming the conductive connection portion 179, for example, a commercially available silver paste or a paste material in which conductive fine particles are dispersed and mixed in the same resin material as the sealing portions 180a and 180b can be used. These conductive connection portion forming materials may or may not be cured.

In one solar cell, the porous semiconductor layer 178 of the porous semiconductor electrode sheet 143 is disposed between the translucent catalyst layer 172 and the catalyst layer 175, and one end of the conductive sheet 177 is sealed inside the one as described above. It penetrates the stop part 180b and is electrically connected to the conductive connection part 179. Further, a collecting electrode portion 182 that electrically connects them is formed between the transparent catalyst layer 172 and the catalyst layer 175 exposed to the outside. The current collecting electrode portion 182 serves as a positive terminal for electrical connection with an external circuit.
In the other solar cell, the porous semiconductor layer 178 of the porous semiconductor electrode sheet 143 is disposed between the translucent catalyst layer 172 and the catalyst layer 175, and one end of the conductive sheet 177 penetrates the outer peripheral sealing portion 180a. And exposed to the outside. A portion exposed to the outside of the conductive sheet 177 serves as a negative electrode terminal for electrical connection with an external circuit.

  The electrolyte layer 181 impregnated in each porous semiconductor layer 178 is formed by injecting an electrolyte into the region surrounded by the outer peripheral sealing portion 180a and the inner sealing portion 180b of the one and the other solar cells. ing. An injection hole (not shown) for injecting the electrolytic solution is formed at the position of, for example, the scribe line 176 in the second substrate 173, and the opening is sealed with resin.

Although this solar cell module can be manufactured according to the manufacturing method of the solar cell of Embodiment 1 and Embodiment 2, before bonding the 1st counter electrode 135 and the 2nd counter electrode 140, it is electroconductive previously. The connection part 179 needs to be formed.
Specifically, before or after applying or installing the resin material of the sealing portions 180a and 180b, screen printing is performed at predetermined positions on the outer peripheral side and the inner side of the first counter electrode substrate 170 and on the outer peripheral side and the inner side of the second counter electrode substrate 173. The conductive connecting portion forming material is applied by the method. Then, the first and second counter electrodes 135 and 140 are overlapped so as to sandwich the two porous semiconductor electrode sheets 143, and at least the resin material is cured. As a result, the conductive sealing portions 180a and 180b are sandwiched in a state where the conductive connection portion 179 is in electrical contact with the end portion of the conductive sheet 177 of the one porous semiconductor electrode sheet 143, and each conductive sheet The periphery of 177 is held without a gap.

The solar cell module according to the third embodiment manufactured in this way is connected to an external circuit using the current collecting electrode portion 182 as a positive electrode terminal and the conductive sheet 177 exposed to the outside as a negative electrode terminal. It is used by being irradiated with light.
When light enters from the translucent first substrate 170 side, the light passes through the translucent first substrate 170, each translucent conductive layer 171, each translucent catalyst layer 172, and each electrolyte layer 181. The light-receiving surface of each porous semiconductor layer 178 is reached. Further, the light reaching the light receiving surface of each porous semiconductor layer 178 passes through the inside of each porous semiconductor layer 178, passes through the opening of each conductive sheet 177, and reaches the back surface side of each porous semiconductor layer 178. Reach. As a result, electrons are generated in the front surface portion and the back surface portion of each porous semiconductor layer 178 and move to each conductive sheet 177. The electrons moved to the conductive sheet 177 of one (left side in FIG. 7) are transferred to the conductive connection portion 179, the translucent conductive layer 171 and the conductive layer 174 of the adjacent solar cell (right side in FIG. 7), The porous semiconductor layer 178 is reached through the photocatalytic layer 172, the catalyst layer 175, and the electrolyte layer 181, and moves to the conductive sheet 177. The electrons that have moved to the conductive sheet 177 move to the light-transmitting conductive layer 171 and the conductive layer 174 of one solar battery cell through an external circuit, and from the light-transmitting catalyst layer 172 and the catalyst layer 175 to the electrolyte layer 181. The charge is transported by the electrolyte and returns to the porous semiconductor layer 178.

(Embodiment 4)
The solar cell module of Embodiment 4 has a structure (not shown) in which a plurality of solar cells of Embodiment 1 (see FIG. 1) or Embodiment 2 (see FIG. 6) are electrically connected in parallel. And it can manufacture according to the manufacturing method of Embodiment 2.
The fourth embodiment is different from the third embodiment in that a plurality of photoelectric conversion element portions are arranged in the parallel connection direction between the same translucent first substrate and the same second substrate.
In this case, a plurality of conductive sheets exposed to the outside of the plurality of porous semiconductor electrode sheets may be electrically connected in parallel by, for example, metal wires. Further, in the plurality of photoelectric conversion element portions, the adjacent translucent conductive layers and the conductive layers may be electrically separated by a scribe line or may be integrated without being separated. . Further, in the plurality of photoelectric conversion element portions, when the light-transmitting conductive layer and the conductive layer are integrated, the adjacent light-transmitting catalyst layers and the catalyst layers may be integrated, and further, the adjacent photoelectric conversion elements are integrated. The inner sealing portion between the conversion element portions may be omitted. Further, in the plurality of photoelectric conversion element portions, when the adjacent translucent conductive layers and the conductive layers are electrically separated by a scribe line, the adjacent collector electrode portions may be integrated. .

(Embodiment 5)
Although not shown, a plurality of photoelectric conversion element portions are arranged in a plurality of rows in the vertical and horizontal directions between the same light-transmitting first substrate and the same second substrate, and the plurality of photoelectric conversion element portions arranged in the vertical direction are electrically connected to each other. A solar cell module having a structure in which a plurality of photoelectric conversion element portions that are connected in series with each other and that are arranged in the horizontal direction are electrically connected in parallel may be manufactured according to the manufacturing method of Embodiments 1 to 4.

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.
(Example 1)
A dye-sensitized solar cell having the structure of FIG. 6 was produced as follows.
First, as shown in FIG. 8, a conductive substrate having dimensions a20 mm × dimension b23 mm × thickness 1 mm in which a SnO ₂ film is formed on a transparent first substrate 101 made of glass (SnO, manufactured by Nippon Sheet Glass Co., Ltd.). _A light-transmitting first counter electrode substrate 104 was manufactured using a glass with _two films.
At this time, a laser scribing device (manufactured by Seishin Shoji Co., Ltd.) equipped with a YAG laser (fundamental wavelength: 1.06 μm) is used to irradiate the translucent first substrate 101 with a laser beam to place the SnO ₂ film at a predetermined position The light-transmitting conductive layer 102 was formed by forming a scribe line 121 having a width of 0.1 mm by cutting.

Next, a commercially available platinum paste is formed on the translucent conductive layer 102 using a screen plate having a translucent catalyst layer formation pattern and a screen printing machine (manufactured by Neurong Seimitsu Kogyo Co., Ltd., model number: LS-150). (Trade name: Pt-Catalyst T / SP, manufactured by Solaronix Co., Ltd.) was applied, and leveling was performed at room temperature for 1 hour. Then, the obtained coating film was dried in an oven set at 80 degrees for 20 minutes, and further baked in air using a baking furnace set at 450 ° C. (manufactured by Denken Co., Ltd., model number: KDF P-100). Thus, a light-transmitting catalyst layer 103 was formed, and a light-transmitting first counter electrode substrate 104 was obtained.
The dimensions of the obtained translucent first counter substrate 104 were a dimension c of 10 mm, a dimension d of 8 mm, a dimension e of 10 mm, and a dimension f of 5 mm (see FIG. 8).
Further, as the second counter electrode substrate 108, a substrate manufactured in the same manner as the light-transmitting first counter electrode substrate 104 and having the electrolyte solution injection hole 114 formed thereon was used.

Next, the porous semiconductor electrode sheet 111 was produced as follows.
First, as shown in FIG. 2A, a commercially available titanium oxide paste (product name: D / SP, manufactured by Solaronix) was applied on a ZnO film substrate having a ZnO thin film 2 on the surface of a glass substrate 1. Leveling was performed at room temperature for 1 hour. Then, the obtained coating film was dried in an oven set at 80 ° C. for 20 minutes, and further baked in the air for 60 minutes in an air using a baking furnace (model number: KDF P-100 manufactured by Denken Co., Ltd.) set at 450 ° C. did. Further, the steps of coating, leveling, drying and firing were repeated twice in the same manner to form the porous semiconductor layer first portion 110a.

Next, as shown in FIG. 2B, a 250-mesh wire mesh made of titanium wire having a wire diameter of 50 μm is installed as a conductive sheet 109 on the obtained porous semiconductor layer first portion 110a, The titanium oxide paste was applied to the plate, and leveling, drying and firing were performed in the same manner as described above. By repeating the same process twice more to form the porous semiconductor layer second portion 110b, the porous semiconductor layer 110 shown in FIG. 2C was formed.
Subsequently, by immersing the glass substrate 1 having the porous semiconductor layer 110 in a 0.1 M hydrochloric acid solution for 30 minutes to dissolve the ZnO thin film 2 and peeling the glass substrate 1 from the porous semiconductor layer 110, The porous semiconductor electrode sheet 111 shown in FIG. 2 (d) and FIG. 9 was obtained. In this porous semiconductor electrode sheet 11, the entire thickness of the porous semiconductor layer 110 was 40 μm, and the dimensions in FIG. 9 were a dimension g of 20 mm, a dimension h of 10 mm, and a dimension i of 10 mm.

Next, the porous semiconductor electrode sheet 111 is immersed in a dye solution prepared in advance at room temperature for 24 hours, and then the porous semiconductor electrode sheet 111 is washed with ethanol and dried at about 60 ° C. for about 5 minutes, A dye was adsorbed on the porous semiconductor layer 110.
The dye solution is a mixture of acetonitrile and t-butanol at a volume ratio of 1: 1 so that the dye of the formula (2) (manufactured by Solaronix, trade name: Ruthenium 620 1H3TBA) has a concentration of 4 × 10 ⁻⁴ mol / liter. It was prepared by dissolving in a solvent.

  Next, an ultraviolet curable resin (manufactured by Three Bond, model number: 31X-101) is applied to the outer peripheral portions of the translucent first counter electrode substrate 104 and the second counter electrode substrate 108 manufactured as described above, and the first and second counter electrodes The porous semiconductor electrode sheet 111 on which the dye was adsorbed between the substrates 104 and 108 was superposed so as to be sandwiched, and the ultraviolet curable resin was irradiated with ultraviolet light and cured to form the sealing portion 113.

Thereafter, the electrolyte prepared in advance is injected into the inside from the electrolyte injection hole 114 of the second counter electrode substrate 108, and the electrolyte is impregnated in the pores of the porous semiconductor layer 110 on which the dye is adsorbed, And the electrolyte layer 112 in which the electrolyte solution surrounds the porous semiconductor layer 110 is formed.
The electrolyte is acetonitrile as a solvent, LiI (manufactured by Aldrich) as a redox species at a concentration of 0.1 mol / liter, and I ₂ (manufactured by Kishida Chemical) at a concentration of 0.01 mol / liter. Furthermore, t-butylpyridine (manufactured by Aldrich) is added as an additive to a concentration of 0.5 mol / liter, and dimethylpropylimidazole iodide (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is added to a concentration of 0.6 mol / liter and dissolved. Prepared.

Thereafter, the electrolyte injection hole 114 is sealed using the ultraviolet curable resin, and an Ag paste (manufactured by Fujikura Kasei Co., Ltd., a product) is formed between the opposing transparent conductive layer 102 and the conductive layer 106 exposed to the outside. Name: Dotite) was applied and dried to form a collecting electrode portion 146, thereby obtaining a dye-sensitized solar cell (single cell).
A black mask having an opening area of 1.0 cm ² is placed on the light receiving surface, which is the surface of the first counter electrode substrate 104 of the obtained solar cell, and light (AM1) having an intensity of 1 kW / m ² is placed on the light receiving surface. .5 solar simulator) and various solar cell characteristics were measured. The results are shown in Table 1.

(Example 2)
In Example 2, a dye-sensitized solar cell (single cell) was produced in the same manner as in Example 1 except for the following points.
As the second counter electrode substrate, as shown in FIG. 10, the catalyst layer 151 is formed on the titanium plate 150 in the same manner as in Example 1, and then a short circuit does not occur when a conductive sheet is installed on the titanium plate 150. A protective film 152 was formed. The protective film 152 was formed by applying an ultraviolet curable resin (manufactured by Three Bond Co., Ltd., model number: 31X-101) on the titanium plate 150 and curing the resin with ultraviolet light.

A porous semiconductor electrode sheet was formed as follows.
First, as shown in FIG. 4 (a), a polypropylene film as the resin film 3 is used, and the steps of applying, leveling, drying and baking the titanium oxide paste on the resin film 3 are the same as in Example 1. 3 times, and the porous semiconductor layer first portion 110a was formed as shown in FIG. In addition, the resin film 3 was burned away by the 1st baking process.
Thereafter, the same conductive sheet 109 as that of Example 1 was placed on the porous semiconductor layer first portion 110a, and the steps of applying, leveling, drying and firing the titanium oxide paste were similarly repeated three times on the porous semiconductor layer 110a. By forming the semiconductor layer second portion 110b, a porous semiconductor electrode sheet 111 having a film thickness of 30 μm shown in FIG.

  For the obtained solar cell of Example 2, various solar cell characteristics were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3)
A solar cell was produced in the same manner as in Example 1 except that a 250-mesh wire mesh made of tungsten wire having a wire diameter of 30 μm was used instead of the conductive sheet used in Example 1.
For the obtained solar cell of Example 3, various solar cell characteristics were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1)
A solar cell having the structure of FIG. 13 was produced as follows.
On a conductive substrate (made by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) in which a transparent electrode 22 made of SnO ₂ film is formed on a transparent substrate 21 made of glass. A porous semiconductor layer 23 having a thickness of 40 μm was formed. The porous semiconductor layer 23 was formed by repeating the application, leveling, drying and firing of the titanium oxide paste five times under the same conditions as in Example 1.
Next, the ultraviolet curable resin used in Example 1 was applied to the outer periphery of the conductive substrate, and the second counter electrode substrate used in Example 1 was placed thereon, and the resin was cured by irradiating the resin with ultraviolet light. Then, the sealing portion 27 was formed, the electrolytic solution was injected into the inside from the electrolytic solution injection hole of the second counter electrode substrate, the injection hole was sealed, and the dye-sensitized solar cell of Comparative Example 1 was produced.

A black mask having an opening area of 1.0 cm ² is placed on the light receiving surface, which is the surface of the translucent substrate 21 of the obtained solar cell of Comparative Example 1, and the light receiving surface has an intensity of 1 kW / m ² . Were irradiated with light (AM1.5 solar simulator), and various solar cell characteristics were measured. The results are shown in Table 1.

Example 4
A dye-sensitized solar cell module having the structure shown in FIG. 7 was produced as follows.
As shown in FIG. 11, a conductive substrate (20 mm × 38 mm × thickness 1 mm) in which a SnO ₂ film is formed on a transparent first substrate 170 made of glass (Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) ) Was used to make a translucent first counter electrode substrate 135.
In this case, first, YAG laser (fundamental wavelength: 1.06 .mu.m) was irradiated with a laser beam to a predetermined position two places of SnO ₂ film using a laser scribe apparatus equipped with (manufactured by Seishin Trading Co., Ltd.), a SnO ₂ film By cutting to form a scribe line 176 having a width of 0.1 mm, two translucent conductive layers 171 arranged in series connection direction were formed.

Next, a commercially available platinum paste on each light-transmitting conductive layer 171 using a screen plate having a pattern for forming a light-transmitting catalyst layer and a screen printing machine (manufactured by Neurong Seimitsu Kogyo Co., Ltd., model number: LS-150). (Trade name: Pt-Catalyst T / SP, manufactured by Solaronix Co., Ltd.) was applied, and leveling was performed at room temperature for 1 hour. Then, the obtained coating film was dried in an oven set at 80 degrees for 20 minutes, and further baked in air for 60 minutes using a baking furnace set at 450 degrees (manufactured by Denken Co., Ltd., model number: KDF P-100). Thus, a light-transmitting catalyst layer 172 was formed, and a light-transmitting first counter electrode substrate 135 was obtained.
The dimensions of the translucent first counter substrate 135 shown in FIG. 16 are as follows: dimension o is 20 mm, dimension p is 38 mm, dimension q is 10 mm, dimension r is 8 mm, dimension s is 10 mm, dimension t is 5 mm, dimension u Was 5 mm.

Further, as the second counter electrode substrate 140, a substrate prepared in the same manner as the light-transmitting first counter electrode substrate 135 and having an electrolyte solution injection hole (not shown) was used.
Further, a contact electrode 179 for electrically connecting the conductive sheet 177, the transparent conductive layer 171 and the conductive film 175 of the porous semiconductor electrode sheet 143 is provided at predetermined positions on the transparent conductive layer 171 and the conductive layer 175. A commercially available silver paste was applied by screen printing.

  Next, two porous semiconductor electrode sheets 143 were produced according to Example 1. One porous semiconductor electrode sheet 143 (left side in FIG. 7) has the same size as in Example 1, and the other porous semiconductor electrode sheet 143 (right side in FIG. 7) has a dimension g of 4 mm in FIG. It is.

  Next, an ultraviolet curable resin (manufactured by Three Bond, model number: 31X-101) is applied to the outer peripheral side and the inner side of the translucent first counter substrate 135 and the second counter electrode substrate 140 manufactured as described above, and the first and first The porous semiconductor electrode sheets 143 having the dye adsorbed between the two counter electrode substrates 135 and 140 are stacked so as to be sandwiched, and the ultraviolet curable resin is irradiated with ultraviolet light and cured to form the sealing portions 180a and 180b. did.

Thereafter, an electrolyte prepared in advance is injected into the inside of the second counter electrode substrate 140 from an electrolyte injection hole (not shown), and the electrolyte is placed in the pores of the porous semiconductor layer 178 on which the dye is adsorbed. An electrolyte layer 181 that was impregnated and in which the electrolyte solution surrounded the porous semiconductor layer 178 was formed. In addition, the same electrolyte solution as Example 1 was used.
Then, the hole for electrolyte injection is sealed using the ultraviolet curable resin, and an Ag paste (trade name, manufactured by Fujikura Kasei Co., Ltd.) is formed between the opposing transparent conductive layer 171 and conductive layer 174 exposed to the outside. : Dotite) was applied and dried to form a collecting electrode portion 182 to obtain a dye-sensitized solar cell module in which two solar cells were electrically connected in series.

A black mask having an opening area of 2.5 cm ² (1.0 cm × 2.5 cm) is placed on the light receiving surface which is the surface of the first counter electrode substrate 1354 of the obtained solar cell module, Various solar cell characteristics were measured by irradiating light of 1 kW / m ² intensity (AM1.5 solar simulator). The results are shown in Table 2.

(Comparative Example 2)
A dye-sensitized solar cell module having the structure shown in FIG. 12 was produced as follows. The solar cell module of Comparative Example 2 has a structure in which two of the conventional solar cells shown in FIG. 13 are electrically connected in series.

First, a 20 mm × 38 mm × 1 mm thick conductive substrate (made by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) in which a SnO ₂ film was formed on a glass transparent substrate 190 was the same as in Example 4. The two transmissive conductive layers 191 were formed by forming a scribe line 192 by laser irradiation. Subsequently, a porous semiconductor layer having a film thickness of 40 μm is formed on each light-transmitting conductive layer 191 in the same pattern as the light-transmitting catalyst layer in Example 4 shown in FIG. 193 was formed, and a light-transmitting first counter electrode substrate 194 was obtained.
Next, a conductive contact portion 195 for electrically connecting to a second counter electrode substrate 196 described later is formed on the inner end portion of one of the light transmissive conductive layers 191 of the light transmissive first counter electrode substrate 194. It was formed by the same method. Then, a dye was adsorbed to the obtained porous semiconductor layer 193 according to Example 1.

As the second counter electrode substrate 196, the second counter electrode substrate having the electrolyte solution injection hole used in Example 4 was prepared, and the conductive contact was made to the inner end portion of the conductive layer 174 exposed inside the second counter electrode substrate 196. The part 197 was formed in the same manner as in Example 4.
Next, an ultraviolet curable resin (manufactured by ThreeBond, model number: 31X-101) is applied to the outer peripheral side and the inner side of the translucent first counter substrate 194 and the second counter substrate 196, and the first and second counter substrates 194, 196 And the sealing portions 198a and 198b were formed by irradiating and curing the ultraviolet curable resin with ultraviolet light. Thereby, the conductive connection part 195 of the translucent first counter substrate 194 and the conductive connection part 197 of the second counter electrode substrate 196 come into contact with each other.

  Next, the electrolyte solution 199 is formed by injecting the same electrolyte solution as in Example 4 from the electrolyte solution injection hole (not shown) of the second counter electrode substrate 196, and for injecting the electrolyte solution using the ultraviolet curable resin. The hole was sealed. Then, an Ag paste (product name: manufactured by Fujikura Kasei Co., Ltd.) is applied to a portion of the first counter electrode substrate 194 exposed to the outside of the translucent conductive layer 191 and a portion of the second counter electrode substrate 196 exposed to the outside of the conductive layer 174. The collector electrode part 200 was formed by applying and drying (doteite) to obtain a dye-sensitized solar cell module in which two solar cells were electrically connected in series.

A black mask having an opening area of 2.5 cm ² (1.0 cm × 2.5 cm) is placed on the light receiving surface which is the surface of the first counter electrode substrate 194 of the obtained solar cell module, Various solar cell characteristics were measured by irradiating light of 1 kW / m ² intensity (AM1.5 solar simulator). The results are shown in Table 2.

  From the above results, it can be seen that the dye-sensitized solar cells of Examples 1 to 3 and the dye-sensitized solar cell module of Example 4 exhibit higher FF than Comparative Examples 1 and 2. From this, in Examples 1 to 4, not only the internal resistance inside the porous semiconductor layer is reduced, but also the charge transport distance in the pores of the porous semiconductor layer is reduced and the charge transport resistance is reduced. it is conceivable that. In addition, since the thickness of the porous semiconductor layer up to the current collecting electrode is reduced, the distance of electron movement is shortened, so that the voltage drop due to the reverse electron reaction can be suppressed, so Voc is also considered to be improved. It is done.

It is a schematic sectional drawing which shows Embodiment 1 of the dye-sensitized solar cell of this invention. FIG. 3 is a schematic process diagram showing a first method for forming a porous semiconductor electrode sheet in Embodiment 1. FIG. 5 is a schematic process diagram showing a second method for forming a porous semiconductor electrode sheet in Embodiment 1. FIG. 5 is a schematic process diagram showing a third method for forming a porous semiconductor electrode sheet in Embodiment 1. FIG. 5 is a schematic process diagram showing a fourth method for forming a porous semiconductor electrode sheet in Embodiment 1. It is a schematic sectional drawing which shows the dye-sensitized solar cell of Embodiment 2 of this invention. It is a schematic sectional drawing which shows the dye-sensitized solar cell module of Embodiment 3 of this invention. 3 is a plan view showing a translucent first counter substrate in Example 1. FIG. 1 is a plan view showing a porous semiconductor electrode sheet in Example 1. FIG. 6 is a plan view showing a second counter electrode substrate in Example 2. FIG. 6 is a plan view showing a translucent first counter substrate in Example 4. FIG. It is a schematic sectional drawing which shows the dye-sensitized solar cell module of the comparative example 2. It is a schematic sectional drawing which shows the conventional dye-sensitized solar cell.

Explanation of symbols

101, 170 Translucent first substrate 102, 171 Translucent conductive layer 103, 172 Translucent catalyst layer 104, 135 Translucent first counter substrate 105, 175 Catalyst layer 106, 174 Conductive layer 107, 173 Second Substrate 108, 140 Second counter electrode 109, 177 Conductive sheet 110, 178 Porous semiconductor layer 111, 143 Porous semiconductor electrode sheet 112, 181 Electrolyte layer 113, 180a, 180b Sealing portion 114 Electrolyte injection hole 115 Injection hole Sealing part 120 Conductive substrate 134, 176 Scribe line 146, 182 Current collecting electrode part 179 Conductive connection part

Claims (12)

A first counter electrode substrate in which a translucent conductive layer and a translucent catalyst layer are formed in this order on a translucent first substrate, and a first counter electrode substrate in which a conductive layer and a catalyst layer are formed in this order on a second substrate. A porous semiconductor electrode sheet comprising a two counter electrode substrate, a conductive sheet having a plurality of light-transmitting openings, and a porous semiconductor layer formed on each side of the conductive sheet and adsorbed with a dye; An electrolyte layer impregnated in the porous semiconductor layer and covering the periphery of the porous semiconductor layer,
The first counter electrode substrate and the second counter electrode substrate function as the same electrode and are arranged opposite to each other, and the porous semiconductor electrode sheet functions as a different electrode, and the first counter electrode substrate and the second counter electrode substrate The dye-sensitized solar cell, wherein the porous semiconductor layer is disposed at least in a region facing both the light-transmitting catalyst layer and the catalyst layer on both surfaces of the conductive sheet.   The dye-sensitized solar cell according to claim 1, wherein the conductive sheet is made of a metal film or a metal film in which a plurality of small holes are formed in a matrix.   The dye-sensitized solar cell according to claim 1 or 2, wherein the conductive sheet is formed from titanium, nickel, tungsten, tantalum, or an alloy containing one or more of these metals.   The porous semiconductor electrode sheet further includes a sealing portion on an outer peripheral portion of the porous semiconductor electrode sheet between the first counter electrode substrate and the second counter electrode substrate facing each other, and one end of the conductive sheet of the porous semiconductor electrode sheet is The one part of the said translucent conductive layer and a conductive layer is exposed to the exterior outside the sealing part while penetrating the said sealing part, and being any one of Claims 1-3 The dye-sensitized solar cell described. A second electrode in which a conductive layer and a catalyst layer are formed in this order on a first counter electrode substrate and a second substrate in which a light transmissive conductive layer and a light transmissive catalyst layer are formed in this order on a light transmissive first substrate. Forming a counter electrode substrate (1);
A step (2) of forming a porous semiconductor electrode sheet by forming a porous semiconductor layer having a dye adsorbed on at least a part of each of both surfaces of the conductive sheet having a plurality of light-transmitting openings;
The porous semiconductor electrode sheet is disposed between the translucent catalyst layer of the first counter electrode substrate and the catalyst layer of the second counter electrode substrate, and each of the translucent catalyst layer and the catalyst layer and the And a step (3) of forming an electrolyte layer between the porous semiconductor electrode sheet and a method for producing a dye-sensitized solar cell.   The step (2) includes forming a porous semiconductor layer first portion by applying a porous semiconductor layer material onto the thin film of the heat-resistant substrate having a thin film that can be dissolved in a stripping solution on the surface and baking the material. The conductive sheet is placed on the first portion, the porous semiconductor layer material is applied on the first portion so as to cover the conductive sheet, and fired to form the second portion of the porous semiconductor layer. A step of forming a porous semiconductor layer having a conductive sheet disposed therein, and a step of immersing the heat-resistant substrate in the release solution to dissolve the thin film and thereby form the heat-resistant substrate into a porous semiconductor. The manufacturing method of the dye-sensitized solar cell of Claim 5 including the process of peeling from a layer, and the process of immersing a porous semiconductor layer in the solution which melt | dissolved the pigment | dye, and adsorb | sucking a pigment | dye.   In the step (2), the porous semiconductor layer first is applied by baking a porous semiconductor layer material on the thin film of the heat-resistant substrate having a thin film soluble in the stripping solution on the surface via a conductive sheet. Forming a portion, immersing the heat resistant substrate in the peeling solution, dissolving the thin film to peel the heat resistant substrate from the first portion of the porous semiconductor layer, and exposing to the outside By applying a porous semiconductor layer material on the first portion of the porous semiconductor layer so as to cover the conductive sheet and baking it to form the second portion of the porous semiconductor layer, the conductive sheet is disposed inside. The method for producing a dye-sensitized solar cell according to claim 5, comprising a step of forming a porous semiconductor layer, and a step of adsorbing the dye by immersing the porous semiconductor layer in a solution in which the dye is dissolved.   The step (2) includes applying a porous semiconductor layer material on a resin film and baking to form a porous semiconductor layer first portion, and burning the resin film; By installing the conductive sheet, coating the porous semiconductor layer material on the first portion so as to cover the conductive sheet, and baking it to form the second portion of the porous semiconductor layer, the conductive portion inside The production of a dye-sensitized solar cell according to claim 5, comprising a step of forming a porous semiconductor layer on which a sheet is disposed and a step of immersing the porous semiconductor layer in a solution in which the dye is dissolved to adsorb the dye. Method.   The step (2) is a step of applying a porous semiconductor layer material on a resin film via a conductive sheet and baking to form a porous semiconductor layer first portion, and burning out the resin film; A porous semiconductor layer material is applied onto the first portion of the porous semiconductor layer so as to cover the conductive sheet exposed to the outside, and then fired to form the second portion of the porous semiconductor layer. The production of a dye-sensitized solar cell according to claim 5, comprising a step of forming a porous semiconductor layer on which a sheet is disposed and a step of immersing the porous semiconductor layer in a solution in which the dye is dissolved to adsorb the dye. Method.   A dye-sensitized solar cell module in which at least two or more of the dye-sensitized solar cells according to any one of claims 1 to 4 are electrically connected in series or in parallel.   11. The dye-sensitized solar cell module according to claim 10, wherein the laminated film of the translucent conductive layer and the translucent catalyst layer is disposed at a plurality of locations on the same translucent first substrate.   The dye-sensitized solar cell module according to claim 10 or 11, wherein the laminated film of the conductive layer and the catalyst layer is disposed at a plurality of positions on the same second substrate.

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