JP2009043482A - Dye-sensitized solar cell, and dye-sensitized solar cell module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell of high performance with a non-power-generating part contracted and current generated per unit area increased, and to provide a dye-sensitized solar cell module using the same. <P>SOLUTION: Of the dye-sensitized solar cell having laminated in turn a transparent conductive layer, a porous semiconductor layer absorbing sensitizing dyes and containing electrolyte in the gap, and a catalyst layer, on a non-light-receiving face side of a translucent substrate to be a light-receiving face, and having a linear collector electrode, the linear collector electrode is fitted at a non-light-receiving face side of the catalyst layer, extended so as to be partially in electric contact with the transparent conductive layer penetrating through the porous semiconductor layer and the catalyst layer, and electrically insulated from the catalyst layer by the insulating layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dye-sensitized solar cell and a dye-sensitized solar cell module.

  As an energy source to replace fossil fuels, solar cells that can convert sunlight into electric power have attracted attention. At present, some solar cells and thin film silicon solar cells using a crystalline silicon substrate are beginning to be put into practical use. However, the former has a problem that the manufacturing cost of the silicon substrate is high, and the latter has a problem that the manufacturing cost becomes high because it is necessary to use various semiconductor manufacturing gases and complicated apparatuses. For this reason, efforts have been made to reduce the cost per power generation output by increasing the efficiency of photoelectric conversion in any of the solar cells, but they have not yet solved the above problem.

As a new type of solar cell, a wet solar cell using photo-induced electron transfer of a metal complex has been proposed (for example, see Japanese Patent No. 2664194: Patent Document 1).
In this wet solar cell, a photoelectric conversion material composed of a photoelectric conversion material having an absorption spectrum in the visible light region by adsorbing a photosensitizing dye between electrodes of two glass substrates having electrodes formed on the surface, and an electrolyte material. The conversion layer is sandwiched between them. When this wet solar cell is irradiated with light, electrons are generated in the photoelectric conversion layer, the generated electrons move to the opposing electrode through an external electric circuit, and the moved electrons are carried by the ions in the electrolyte. Return to the photoelectric conversion layer. Electrical energy is extracted by repeating such a series of electron movements.

  However, the basic structure of the dye-sensitized solar cell described in Patent Document 1 is a form in which an electrolytic solution is injected between the electrodes of two glass substrates, and even if a small-area solar cell can be prototyped, It is difficult to apply to a solar cell having a large area such as 1 m square. That is, when the area of one solar cell is increased, the generated current increases in proportion to the area, but the resistance in the in-plane direction of the transparent conductive layer used for the electrode portion increases, and as a result, the internal series electricity as a solar cell increases. Resistance increases. As a result, there arises a problem that the fill factor (FF) in the current-voltage characteristics at the time of photoelectric conversion, and further, the short-circuit current is lowered and the photoelectric conversion efficiency is lowered.

Therefore, in order to solve the above problem, a linear or grid electrode (hereinafter referred to as “grid electrode”) is laid on the transparent conductive layer using a low-resistance material such as metal, A method for compensating for high resistance has been proposed (see, for example, Japanese Patent Laid-Open No. 2000-285777: Patent Document 2).
In order to solve the above problem, a dye-sensitized solar cell module in which a plurality of dye-sensitized solar cells are connected in series has also been proposed. In this dye-sensitized solar cell module, an electrode (conductive layer) of a solar cell and an electrode (counter electrode) of an adjacent solar cell are electrically connected by a conductive layer (conductive connection layer) or a counter electrode material itself ( For example, refer to JP-A-11-514787: Patent Document 3 and JP-A-2001-357897: Patent Document 4.

Japanese Patent No. 2664194 JP 2000-285777 A JP-A-11-514787 JP 2001-357897 A

In the solar cell described in Patent Document 2, since the grid electrode (corresponding to the current collecting electrode) is provided on the transparent conductive layer serving as the light receiving surface, the laid portion becomes a non-power generating portion, and the generated current of the solar cell is reduced. is there.
Further, in the dye-sensitized solar cell module described in Patent Document 3, in order to prevent charge exchange between the conductive connection layer and the electrolyte layer, corrosion of the conductive connection layer, and the like, a conductive connection layer is formed using an inter-cell insulating layer. It is necessary to isolate the electrolyte layer.
Furthermore, in the dye-sensitized solar cell module described in Patent Document 4, in order to prevent contact (leakage) between electrodes in one solar cell and to prevent electrolyte migration, a porous insulating layer or an intermediate insulating layer is used. A layer is provided. However, there is a problem that the portion where these insulating layers and conductive connection layers are in contact with the substrate and the transparent conductive layer becomes a non-power generation portion, and the generated current of the dye-sensitized solar cell module is lowered.

  The present invention relates to a high-performance dye-sensitized solar cell (hereinafter also referred to as “solar cell”) in which a non-power generation portion is reduced and a generated current per unit area is increased, and a dye-sensitized solar cell module using the same Hereinafter, it is an object to provide a module.

  As a result of intensive studies to solve the above problems, the present inventors have provided a linear current collecting electrode on the non-light-receiving surface side of the catalyst layer, and penetrated the current collecting electrode through the porous semiconductor layer and the catalyst layer. The present invention has found that the above-mentioned problems can be solved by extending the transparent conductive layer so as to be in partial and electrical contact, and electrically insulating the collector electrode from the catalyst layer by the insulating layer. It came to complete.

  Thus, according to the present invention, the transparent conductive layer, the porous semiconductor layer containing the electrolyte in the gap, and the catalyst layer are sequentially laminated on the non-light-receiving surface side of the light-transmitting substrate serving as the light-receiving surface. A dye-sensitized solar cell having a linear collector electrode, wherein the linear collector electrode is provided on the non-light-receiving surface side of the catalyst layer, and penetrates the porous semiconductor layer and the catalyst layer to conduct transparent conduction. A dye-sensitized solar cell is provided which extends so as to be in partial and electrical contact with a layer and is electrically insulated from a catalyst layer by an insulating layer.

  In addition, according to the present invention, there is provided a dye-sensitized solar cell module, wherein at least two of the dye-sensitized solar cells are connected in series.

In the solar cell of the present invention, the portion of the current collecting electrode that extends through the porous semiconductor layer and the catalyst layer so as to partially and electrically contact the transparent conductive layer is transparent on the translucent substrate. It has a function to collect carriers (electrons) in the conductive layer, and the collector electrode part on the non-light-receiving surface side of the catalyst layer takes out the collected carriers to the outside or connects two or more solar cells In the case of modularization, it has a function of carrying a carrier to the adjacent solar cell.
In the solar cell of the present invention having such a collecting electrode, the non-power generation portion (non-power generation area) is reduced, and the generated current per unit area increases.

Further, a module in which at least two of the solar cells of the present invention are connected in series and integrated has a current collecting electrode and a catalyst layer (or a conductive layer laminated on the catalyst layer) on the non-light-receiving surface side. Can be connected.
That is, in the module of the present invention, the catalyst layer responsible for connection with the adjacent solar cell in the module described in Patent Document 3 and the conductive connection layer in the module described in Patent Document 4 do not appear on the light receiving surface side. That is, in the module of the present invention, only the inter-cell insulating layer that suppresses the movement of the electrolyte contained in the porous semiconductor layer appears on the light receiving surface side.
Therefore, the module of the present invention can reduce the non-power generation portion as compared with the solar cell modules described in Patent Document 3 and Patent Document 4, and can increase the generated current per unit area.

The solar cell of the present invention is formed by sequentially laminating a transparent conductive layer, a sensitizing dye, a porous semiconductor layer containing an electrolyte in the gap, and a catalyst layer on the non-light-receiving surface side of a light-transmitting substrate serving as a light-receiving surface. A linear current collecting electrode provided on the non-light-receiving surface side of the catalyst layer, penetrating the porous semiconductor layer and the catalyst layer and partially forming the transparent conductive layer It extends so that it may contact electrically and electrically, and is electrically insulated from the catalyst layer by the insulating layer.
The module of the present invention is characterized in that at least two or more of the solar cells of the present invention are connected in series.

A preferred embodiment of the solar cell of the present invention will be described with reference to the drawings. In addition, this embodiment is an example and implementation with a various form is possible within the scope of the present invention.
1-1 is (a) a schematic plan view of a light receiving surface and (b) (X) schematic sectional view of (a) in the solar cell of the present invention, and FIG. 1-2 is a schematic diagram of the solar cell of the present invention. (C) It is a schematic top view of a non-light-receiving surface, and (d) It is a schematic sectional drawing of the connection part at the time of setting it as a module.

FIG. 2-1 is (a) a schematic plan view of a light receiving surface and (b) (a) a schematic sectional view of XX in another solar cell of the present invention, and FIG. It is a schematic sectional drawing of the connection part at the time of setting it as a module (c) non-light-receiving surface in another solar cell of (d) module.
Note that the shapes of the various regions shown in the above figures are not necessarily shown in absolute or relative scale.

  1-1, FIG. 1-2, FIG. 2-1, and FIG. 2-2, 1 is a substrate, 2 is a transparent conductive layer (first conductive layer), 3 is a porous semiconductor layer, and 4 is a porous insulating layer. 5 is a catalyst layer, 6 is a conductive layer (second conductive layer), 7 is a current collecting electrode, 8 and 11 are insulating layers, 9 is a sealing portion (inter-cell insulating layer), and 10 is a sealing portion (resin). It is. A sensitizing dye (not shown) is adsorbed on the porous semiconductor layer, and an electrolyte (not shown) is contained in the porous semiconductor layer and an optional porous insulating layer.

(Collector electrode)
The solar cell of the present invention is a solar cell having a linear collector electrode, the linear collector electrode is provided on the non-light-receiving surface side of the catalyst layer, and penetrates the porous semiconductor layer and the catalyst layer. It extends so as to be in partial and electrical contact with the transparent conductive layer, and is electrically insulated from the catalyst layer by the insulating layer.
That is, the portion of the current collecting electrode that extends through the porous semiconductor layer and the catalyst layer so as to be in partial and electrical contact with the transparent conductive layer is in the transparent conductive layer on the translucent substrate. It has a function to collect carriers (electrons), and the collector electrode part on the non-light-receiving surface side of the catalyst layer takes out the collected carriers to the outside or connects two or more solar cells to make a module When it does, it has the function to carry a carrier to the next solar cell.
In the solar cell of the present invention having such a collecting electrode, the non-power generation portion (non-power generation area) is reduced, and the generated current per unit area increases.

The contact portions of the collector electrode extended so as to be in partial and electrical contact with the transparent conductive layer are regularly arranged on the transparent conductive layer, that is, discretely on the transparent conductive layer. Preferably it is present.
Further, in consideration of the isotropic property of carrier movement, the shape of the contact surface of the collector electrode, which is extended so as to be in partial and electrical contact with the transparent conductive layer, is circular. Is preferred.
In the case of a circle, the diameter r of the circle is calculated from the voltage drop calculation formula:
^{Jsc · L 2 · η / (} r 2 × 10 7) <0.05
(Where Jsc is the short-circuit current density of the solar cell, η is the light receiving area ratio (= (L ² −πr ² ) / L ² ), and L is the interval between the collector electrodes)
It is preferable to satisfy.

Furthermore, the linear collector electrode provided on the non-light-receiving surface side of the catalyst layer preferably has a shape having an opening in order to facilitate penetration of the dye adsorbing solution or the electrolyte into the porous semiconductor layer. .
In particular, the shape of the linear current collecting electrode is preferably a comb shape.

The material constituting the current collecting electrode includes indium tin composite oxide (ITO), tin oxide (SnO ₂ ), tin oxide doped with fluorine (F-doped SnO ₂ , FTO), zinc oxide (ZnO), Examples include gold, silver, copper, aluminum, nickel, titanium, and tantalum.
The collector electrode is formed on the catalyst layer or the second conductive layer by a known method such as a sputtering method or a spray method so as to extend partially and electrically in contact with the transparent conductive layer. Can do.

Among the materials constituting the current collecting electrode, a material having corrosion resistance to the electrolyte described later is preferable because it is not necessary to provide a layer for protecting the current collecting electrode on the non-light-receiving surface side. Examples of such a material include FTO, nickel, titanium, tantalum and the like, and a metal material selected from titanium, tantalum and nickel is particularly preferable.
In addition, when the material constituting the current collecting electrode is a material that does not have corrosion resistance to the electrolyte, for example, silver, copper, aluminum, etc., in order to protect the current collecting electrode, It is preferable to provide an insulating layer to be described later between the conductive semiconductor layer.

(Insulating layer)
The insulating layer electrically insulates the collecting electrode from the catalyst layer, and further to a conductive layer arbitrarily provided on the catalyst layer (the catalyst layer and the conductive layer are collectively referred to as a counter electrode).

Examples of the material constituting the insulating layer include inorganic materials such as zirconium oxide, silicon oxide, and aluminum oxide, and one or more of these materials can be selectively used.
Among the above inorganic materials, an inorganic material containing silicon oxide that is difficult to adsorb a sensitizing dye is particularly preferable, and a commercially available glass frit can be used.
The insulating layer using glass frit can be obtained, for example, by applying glass frit, drying and baking after leveling.

(Method of forming insulating layer)
It does not specifically limit as a method of forming an insulating layer, A well-known method is mentioned. For example, the method of apply | coating the suspension containing an inorganic material, and drying and / or baking is mentioned.
In the above method, first, the inorganic material fine particles are suspended in a suitable solvent to obtain a suspension. Examples of such solvents include glyme solvents such as ethylene glycol monomethyl ether, alcohols such as isopropyl alcohol, alcohol-based mixed solvents such as isopropyl alcohol / toluene, and water. In addition, an inorganic material paste may be used instead of such a suspension.

Next, the obtained suspension is applied by a known method such as a doctor blade method, a squeegee method, a spin coating method, or a screen printing method, and dried and / or baked to obtain an insulating layer.
What is necessary is just to set suitably the temperature, time, atmosphere, etc. which are required for drying and baking according to the kind of board | substrate and inorganic material fine particle to be used, for example, about 50-800 degreeC by air | atmosphere atmosphere or inert gas atmosphere. In the range of about 10 seconds to 12 hours. This drying and baking may be performed once at a single temperature or twice or more by changing the temperature.

When the current collecting electrode is formed of a material that does not have corrosion resistance to the electrolyte, the portion extending through the porous semiconductor layer and the catalyst layer of the linear current collecting electrode is an insulating layer. It is preferable to coat with.
Furthermore, the insulating layer is a portion of the collector electrode that extends through the porous semiconductor layer and the catalyst layer when the collector electrode is formed of a material that does not have corrosion resistance to the electrolyte. Has the function of inhibiting corrosion.

  An insulating layer that electrically insulates the catalyst layer and the current collecting electrode, and a porous semiconductor layer and a portion extending through the catalyst layer of the current collecting electrode and an insulating layer that insulates the catalyst layer have a number of processes. From the viewpoint, it is preferable that they are made of the same material and formed simultaneously.

The solar cell of FIGS. 1-1 and 1-2 is an example in which the collector electrode is formed of a material that does not have corrosion resistance to the electrolyte, and the collector electrode is covered with the insulating layer 8. And corrosion from the electrolyte is suppressed.
Moreover, the solar cell of FIGS. 2-1 and FIGS. 2-2 is an example in which the current collection electrode was formed with the material which has corrosion resistance with respect to electrolyte.

  Other components in the solar cell of the present invention will be described.

(Translucent substrate)
The material constituting the light-transmitting substrate is not particularly limited as long as it can substantially transmit light having a wavelength having effective sensitivity to at least a dye described later and can support a solar cell. For example, soda Glass such as lime float glass, quartz glass, tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PA), polyetherimide (PEI), phenoxy resin And transparent polymer sheets. Although glass is most commonly used, the transparent polymer sheet is advantageous in terms of cost in that it has flexibility.
Although the thickness of a translucent board | substrate is not specifically limited, Usually, it is about 0.5-8 mm.
A transparent conductive layer to be described later is formed on the translucent substrate.

(Transparent conductive layer, first conductive layer)
The material constituting the transparent conductive layer may be any material that can substantially transmit light having a wavelength having an effective sensitivity to a sensitizing dye described later, and is not necessarily transparent to light in all wavelength regions. There is no need to have. As such a material, e.g., indium-tin composite oxide (ITO), tin oxide (SnO _2), fluorine-doped tin oxide _{(F-doped SnO 2, FTO} ), and zinc oxide (ZnO) Can be mentioned.
The transparent conductive layer can be formed on the translucent substrate by a known method such as sputtering or spraying. The film thickness of the transparent conductive layer is about 0.02 to 5 μm, and the lower the film resistance, the better, preferably 40Ω / sq or less.
A translucent conductive substrate obtained by laminating FTO as a transparent conductive layer on soda-lime float glass as a translucent substrate is particularly preferable. In the present invention, a commercially available product of such a translucent conductive substrate may be used. Good.

(Porous semiconductor layer)
The material which comprises a porous semiconductor layer will not be specifically limited if it is generally used for a photoelectric conversion material. 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.

The form of the porous semiconductor may be either single crystal or polycrystal, but polycrystal is preferable from the viewpoint of stability, difficulty of crystal growth, production cost, and the like. The form of crystalline fine particles is particularly preferred.
Further, two or more kinds of particles having different particle sizes made of the same or different semiconductor compounds may be mixed and used. It is considered that particles having a large particle size scatter incident light and contribute to an improvement in the light capture rate, and particles having a small particle size contribute to an improvement in the amount of dye adsorbed by increasing the number of adsorption points. The ratio of the average particle sizes of different particle sizes is preferably 10 times or more, and the average particle sizes of the large particles and the small particles are about 100 to 500 nm and about 5 nm to 50 nm, respectively. In the case of mixed particles composed of different semiconductor compounds, it is effective to use a semiconductor compound having a strong adsorption action as a particle having a small particle size.

  The most preferable titanium oxide semiconductor fine particles can be produced by known methods described in various documents. For example, the method described in “The New Synthetic Method: Synthesis of Monodispersed Particles by Gel-Sol Method and Control of Size and Morphology” edited by the Japan Institute of Metals, the method of obtaining chloride developed by Degussa by high-temperature hydrolysis Etc.

(Method for forming porous semiconductor layer)
It does not specifically limit as a method of forming a porous semiconductor layer on a transparent conductive layer, A well-known method is mentioned. For example, the method of apply | coating the suspension containing a semiconductor particle on a transparent conductive layer, and drying and / or baking is mentioned.
In the above method, first, semiconductor fine particles are suspended in a suitable solvent to obtain a suspension. Examples of such solvents include glyme solvents such as ethylene glycol monomethyl ether, alcohols such as isopropyl alcohol, alcohol-based mixed solvents such as isopropyl alcohol / toluene, and water. Further, instead of such a suspension, a commercially available titanium oxide paste (eg, Solaronix, Ti-nanoxide, D, T / SP, D / SP) may be used.

Next, the obtained suspension is applied onto the transparent conductive layer by a known method such as a doctor blade method, a squeegee method, a spin coating method, or a screen printing method, and dried and / or baked to obtain a porous semiconductor layer. .
What is necessary is just to set suitably the temperature, time, atmosphere, etc. which are required for drying and baking according to the kind of transparent conductive layer and semiconductor particle to be used, for example, 50-800 degreeC under air | atmosphere atmosphere or inert gas atmosphere. The range is about 10 seconds to 12 hours. This drying and baking may be performed once at a single temperature or twice or more by changing the temperature.
The porous semiconductor layer may be composed of a plurality of layers. In such a case, a suspension of different semiconductor particles may be prepared, and coating, drying and / or firing may be repeated sequentially.

The film thickness of the porous semiconductor layer is not particularly limited, but is, for example, about 0.1 to 100 μm. From another viewpoint, the semiconductor layer preferably has a large surface area, for example, 10 to ²⁰⁰ m ^2. / G or so.

  After forming the porous semiconductor layer on the transparent conductive layer of the transparent substrate, for the purpose of improving the electrical connection between the semiconductor fine particles, improving the surface area of the porous semiconductor layer, reducing the defect level on the semiconductor fine particles, For example, when the porous semiconductor layer is a titanium oxide film, the semiconductor layer may be treated with an aqueous titanium tetrachloride solution.

(Porous insulation layer)
The porous insulating layer is a layer having a function of electrically insulating the porous semiconductor layer and the catalyst layer, and is formed by further laminating a porous insulating layer on the layer on the non-light-receiving surface side of the porous semiconductor layer. Is preferred.
Examples of the material constituting the porous insulating layer include niobium oxide, zirconium oxide, silicon oxide (silica glass, soda glass), aluminum oxide, barium titanate, and the like. One or more of these materials are used. Can be selectively used. These materials are preferably in the form of particles, and the average particle diameter is 5 to 500 nm, preferably 10 to 300 nm.

(Method for forming porous insulating layer)
The porous insulating layer can be formed in the same manner as the porous semiconductor layer. That is, fine particles for forming a porous insulating layer are dispersed in a suitable solvent, and a polymer compound such as ethyl cellulose and polyethylene glycol (PEG) is further mixed to obtain a paste. The obtained paste is placed on the porous semiconductor layer. The porous insulating layer is obtained by applying, drying and baking.

(Sensitizing dye)
Examples of the sensitizing dye that functions as a photosensitizer by being adsorbed on a porous semiconductor include organic dyes and metal complex dyes having absorption in various visible light regions and / or infrared light regions. 1 type, or 2 types or more 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 perylenes. And dyes such as indigo dyes and naphthalocyanine dyes. In general, the extinction coefficient of an organic dye is larger than that of a metal complex dye in which a molecule is coordinated to a transition metal.

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 among these, phthalocyanine dyes and ruthenium dyes are preferable, and ruthenium metal complex dyes are particularly preferable.
In particular, ruthenium-based metal complex dyes represented by the following formulas (1) to (3) are particularly preferable. Examples of commercially available ruthenium-based metal complex dyes include trade name Ruthenium 535 dye, Ruthenium 535-bisTBA dye, Ruthenium 620 manufactured by Solaronix. -1H3TBA dye and the like.

  In order to strongly adsorb the dye to the porous semiconductor, those having an interlock group such as a carboxyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, an ester group, a mercapto group, and a phosphonyl group in the dye molecule. preferable. In general, an interlock group is interposed when a dye is immobilized on a porous semiconductor, and provides an electrical bond that facilitates the transfer of electrons between the excited dye and the semiconductor conduction band.

(Dye adsorption method)
Examples of the method for adsorbing the dye to the porous semiconductor layer include a method of immersing the porous semiconductor layer formed on the transparent conductive layer in a solution in which the dye is dissolved (dye adsorption solution).
The solvent that dissolves the dye may be any solvent that dissolves the dye, and specifically includes alcohol, toluene, acetonitrile, tetrahydrofuran (THF), chloroform, dimethylformamide, and the like. These solvents are preferably purified, and two or more types can be mixed and used. The dye concentration in the dye adsorption solution can be appropriately set according to conditions such as the dye to be used, the type of solvent, and the dye adsorption step, and is preferably 1 × 10 ⁻⁵ mol / liter or more, for example. In preparing the dye adsorption solution, heating may be performed to improve the solubility of the dye.

(Catalyst layer)
The material which comprises a catalyst layer will not be specifically limited if it is generally used for a photoelectric conversion material. Examples of such a material include platinum, carbon black, ketjen black, carbon nanotube, fullerene and the like.
For example, when using platinum, the catalyst layer can be formed by a known method such as sputtering, thermal decomposition of chloroplatinic acid, or electrodeposition. The film thickness is, for example, about 0.5 nm to 1000 nm. In the case of using carbon such as carbon black, ketjen black, carbon nanotube, or fullerene, a catalyst layer can be formed by applying carbon paste dispersed in a solvent by a screen printing method or the like.

(Conductive layer, second conductive layer)
When the resistance of the catalyst layer is high, it is preferable that a conductive layer is further laminated on the non-light-receiving surface side of the catalyst layer. The catalyst layer alone or the catalyst layer and the (second) conductive layer are collectively referred to as a counter electrode.
The material constituting the conductive layer includes indium tin composite oxide (ITO), tin oxide (SnO ₂ ), tin oxide doped with fluorine (F-doped SnO ₂ , FTO), zinc oxide (ZnO), platinum Gold, silver, copper, aluminum, nickel, titanium and the like.
The second conductive layer can be formed on the catalyst layer by a known method such as a sputtering method or a spray method. The film thickness of the second conductivity is about 0.02 to 5 μm, the lower the film resistance, the better, and 40Ω / sq or less is preferable.

(Electrolytes)
The gap between the porous semiconductor layer and the porous insulating layer is filled.
The electrolyte is a liquid substance containing a redox species, and is not particularly limited as long as it is an electrolyte generally used for a battery, a solar battery or the like.
Examples of the redox species include I ⁻ / I ³⁻ series, Br ²⁻ / Br ³⁻ series, Fe 2 ⁺ / Fe ³⁺ series, and quinone / hydroquinone series. Specifically, a combination of metal iodide such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI ₂ ) and iodine (I ₂ ), tetraethylammonium ion Combinations of tetraalkylammonium salts and iodine such as dye (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), tetrahexylammonium iodide (THAI), and lithium bromide (LiBr); A combination of a metal bromide such as sodium bromide (NaBr), potassium bromide (KBr), calcium bromide (CaBr ₂ ) and bromine is preferable, and among these, a combination of LiI and I ₂ is particularly preferable.

  Examples of the electrolyte solvent include carbonate compounds such as propylene carbonate, nitrile compounds such as acetonitrile, alcohols such as ethanol, water, and aprotic polar substances. Among these, carbonate compounds and nitrile compounds are particularly preferable. Two or more of these solvents can be used in combination.

You may add an additive to said electrolyte as needed.
Examples of such additives include nitrogen-containing aromatic compounds such as t-butylpyridine (TBP), dimethylpropylimidazole iodide (DMPII), methylpropylimidazole iodide (MPII), ethylmethylimidazole iodide (EMII), Examples include imidazole salts such as ethylimidazole iodide (EII) and hexylmethylimidazole iodide (HMII).
The concentration of the electrolyte (redox species) in the electrolyte is preferably in the range of 0.001 to 1.5 mol / liter, and particularly preferably in the range of 0.01 to 0.7 mol / liter.

(Sealing part, sealing layer)
The solar cell of the present invention is preferably provided with a sealing portion (sealing layer) in order to prevent volatilization of the electrolyte and intrusion of water or the like into the battery.
The sealing portion is important for (1) absorbing falling objects and stresses (impacts) acting on the support, and (2) absorbing deflections acting on the support during long-term use.

  The material which comprises a sealing part will not be specifically limited if it is a material which can generally be used for a solar cell and can exhibit the effect of this invention. Examples of such materials include ultraviolet curable resins and thermosetting resins. Specific examples include silicone resins, epoxy resins, polyisobutylene resins, hot melt resins, glass frits, and the like. Two or more types can be used in two or more layers. Examples of the ultraviolet curable resin include Three Bond Co., Ltd., model numbers: 31X-088 and 31X-101, and examples of the thermosetting resin include commercially available epoxy resins.

  When using silicone resin, epoxy resin, or glass frit, the pattern of the sealing part is by using a dispenser, and when using hot melt resin, by opening a patterned hole in the sheet-like hot melt resin, Can be formed.

  According to the present invention, a module is provided in which at least two of the solar cells of the present invention are connected in series.

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.
The film thickness of each layer in Examples and Comparative Examples was measured using a product name: Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd. unless otherwise specified.

Example 1
The solar cell shown in FIGS. 1-1 and 1-2 was produced.
A glass substrate (made by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) in which a transparent conductive layer 2 made of SnO ₂ film was formed on a substrate 1 made of glass was prepared.

-Formation of sealing part (insulating layer between cells) Glass frit (manufactured by Noritake Co., Ltd., Ltd.) so that the inner frame is 32 mm x 52 mm and the line width is 0.5 mm in the part number 9 in FIG. ) Using a screen printing machine (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), the obtained coating film was pre-dried at 100 ° C. for 10 minutes, and then baked at 450 ° C. for 1 hour. An inter-cell insulating layer 9 was obtained. The film thickness was about 25 μm.

-Formation of porous semiconductor layer Screen plate and screen printing of commercially available titanium oxide paste (manufactured by Solaronix, trade name: Ti-Nanoxide D / SP, average particle size 13 nm) in the part of FIG. The coating was performed using a machine (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and leveling was performed at room temperature for 1 hour. As shown in FIG. 1A, the screen plate has a rectangular shape of 30 mm × 50 mm, a distance X from the end to the collecting electrode X = 4 mm, and a distance Y between the collecting electrodes Y = 8 mm. Layer 8) One having 3 rows × 5 columns = 15 φ = 2 mm was used.
Next, the obtained coating film was pre-dried at 80 ° C. for 20 minutes and then baked at 450 ° C. for 1 hour. This process was repeated to obtain a porous semiconductor layer (titanium oxide film) 3. The film thickness was 30 μm.

-Formation of porous insulating layer Zirconium oxide fine particles (particle size: 100 nm, manufactured by CI Kasei Co., Ltd.) were dispersed in terpineol, and ethyl cellulose was further mixed to prepare a paste. The obtained paste was applied onto the porous semiconductor layer 3 using the same screen plate and screen printer as the porous semiconductor layer 3 and leveled at room temperature for 1 hour.
Next, the obtained coating film was preliminarily dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour to obtain a porous insulating layer (zirconium oxide film) 4. The film thickness was 5 μm.

Formation of catalyst layer Platinum is deposited on the porous insulating layer 4 using an electron beam evaporator EVD-500A (manufactured by ANELVA) at a deposition rate of 0.1 Å / S, and a film thickness of about 5 nm. A catalyst layer 5 was obtained.

-Formation of the second conductive layer Titanium was deposited on the catalyst layer 5 by using an electron beam evaporator EVD-500A (manufactured by ANELVA) at a deposition rate of 0.5 Å / S. A second conductive layer 6 was obtained.

Formation of Insulating Layer Glass frit (Noritake Co., Ltd.) so that the insulating layer width Z = 2 mm, the insulating layer length U = 48 mm, and the insulating layer interval Y = 8 mm in the portion of the number 11 in FIG. (Limited) was applied using a screen printer (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and leveled at room temperature for 1 hour.
Next, the obtained coating film was preliminarily dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour to obtain insulating layers 8 and 11.

-Formation of current collecting electrode A silver paste (manufactured by Noritake Co., Ltd., Ltd.) on the insulating layer so that the current collecting electrode width Z = 1 mm, the current collecting electrode length U = 47 mm, and the current collecting electrode interval Y = 9 mm. ) Was applied using a screen printing machine (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and leveling was performed at room temperature for 1 hour.
Next, the obtained coating film was preliminarily dried at 150 ° C. for 5 minutes and baked at 450 ° C. for 1 hour to obtain a collecting electrode 7.

-Formation of insulating layer The insulating layer is made of glass frit (Noritake Company Limited) so that the insulating layer width Z = 2 mm, the insulating layer length U = 48 mm, and the insulating layer interval Y = 8 mm so as to cover the collecting electrode. Was applied using a screen printing machine (manufactured by Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and leveling was performed at room temperature for 1 hour.
Next, the obtained coating film was preliminarily dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour to obtain an insulating layer 11. The obtained insulating layers 8 and 11 have a function of suppressing corrosion of the collecting electrode due to the electrolytic solution.

Adsorption of sensitizing dye A sensitizing dye (manufactured by Solaronix, trade name: Ruthenium 620-1H3TBA) having a volume ratio of 1: 1 acetonitrile (manufactured by Aldrich Chemical Company) so as to have a concentration of 4 × 10 ⁻⁴ mol / liter. And a t-butyl alcohol (manufactured by Aldrich Chemical Company) were dissolved in a mixed solvent to obtain a dye adsorption solution.
The above laminate was immersed in the obtained dye adsorption solution at a temperature of 40 ° C. for 20 hours to adsorb the sensitizing dye to the porous semiconductor layer. Thereafter, the laminate was washed with ethanol (manufactured by Aldrich Chemical Company) and dried at about 80 ° C. for about 10 minutes.

- acetonitrile as prepared solvent of the electrolyte, LiI (Aldrich Chemical Company Ltd.) is a concentration of 0.1 mol / l, I ₂ (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is a concentration of 0.01 mol / liter as redox species As described above, t-butylpyridine (TBP, manufactured by Aldrich Chemical Company) was added at a concentration of 0.5 mol / liter, and dimethylpropylimidazole iodide (DMPII, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added at a concentration of 0.6 mol / liter. An electrolyte was obtained by adding and dissolving to a liter.

-Manufacture of solar cell On the insulating layer 9 between cells and the sealing part 10 (refer FIG.1 (c)), the ultraviolet curable material (Threebond company make, model number: 31X-088) was apply | coated, and 50 mm x 70 mm prepared separately. X A glass substrate for sealing having a thickness of 1.0 mm (manufactured by Corning, model number: 7059) and the substrate 1 were bonded together. The sealing glass substrate was previously provided with electrolyte injection holes. Next, the two substrates were fixed by irradiating the applied part with ultraviolet rays using an ultraviolet irradiation lamp (trade name: Novacure, manufactured by EFD) to cure the ultraviolet curable material.
Next, an electrolyte was injected from the electrolyte injection hole of the sealing glass substrate, and the electrolyte injection hole was sealed to complete the solar cell corresponding to FIG.

The obtained solar cell was irradiated with light having an intensity of 1 kW / m ² (AM1.5 solar simulator) to measure photoelectric conversion efficiency and the like. As a result, the short-circuit current I _sc = 27.2 A, the open circuit voltage V _OC = 0.701, the FF (fill factor) = 0.67, and the photoelectric conversion efficiency = 8.52%.
Note that the photoelectric conversion efficiency was obtained by multiplying the value obtained by dividing by the area of values aperture area of I _sc (area enclosed by connecting the outer frame of the photoelectric conversion element), V _OC, the FF.

(Example 2)
The solar cell shown in FIG. 2 was produced.
A glass substrate (made by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) in which a transparent conductive layer 2 made of SnO ₂ film was formed on a substrate 1 made of glass was prepared.

Formation of sealing part (insulating layer between cells) Glass frit (manufactured by Noritake Co., Ltd., Ltd.) so that the inner frame is 32 mm × 52 mm and the line width is 0.5 mm in the part number 9 in FIG. ) Using a screen printing machine (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), the obtained coating film was pre-dried at 100 ° C. for 10 minutes, and then baked at 450 ° C. for 1 hour. An inter-cell insulating layer 9 was obtained. The film thickness was about 25 μm.

Formation of porous semiconductor layer Screen plate and screen printing of commercially available titanium oxide paste (manufactured by Solaronix, trade name: Ti-Nanoxide D / SP, average particle size 13 nm) in the part of FIG. The coating was performed using a machine (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and leveling was performed at room temperature for 1 hour. As shown in FIG. 2A, the screen plate has a rectangular shape of 30 mm × 50 mm, a distance X from the end to the collecting electrode X = 4.5 mm, and a distance Y between the collecting electrodes Y = 9 mm. (Insulating layer) A layer having 15 × 3 rows × 5 columns = φ = 1 mm was used.
Next, the obtained coating film was pre-dried at 80 ° C. for 20 minutes and then baked at 450 ° C. for 1 hour. This process was repeated to obtain a porous semiconductor layer (titanium oxide film) 3. The film thickness was 30 μm.

-Formation of porous insulating layer Zirconium oxide fine particles (particle size: 100 nm, manufactured by CI Kasei Co., Ltd.) were dispersed in terpineol, and ethyl cellulose was further mixed to prepare a paste. The obtained paste was applied onto the porous semiconductor layer 3 using the same screen plate and screen printer as the porous semiconductor layer 3 and leveled at room temperature for 1 hour.
Next, the obtained coating film was preliminarily dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour to obtain a porous insulating layer (zirconium oxide film) 4. The film thickness was 5 μm.

Formation of catalyst layer Platinum is deposited on the porous insulating layer 4 using an electron beam evaporator EVD-500A (manufactured by ANELVA) at a deposition rate of 0.1 Å / S, and a film thickness of about 5 nm. A catalyst layer 5 was obtained.

-Formation of the second conductive layer Titanium was deposited on the catalyst layer 5 using an electron beam evaporator EVD-500A (manufactured by ANELVA) at a deposition rate of 0.5 Å / S. A second conductive layer 6 was obtained.
-Formation of insulating layer A glass frit (manufactured by Noritake Co., Ltd.), which is an insulating layer, is formed in a screen printing machine (manufactured by Neurong Seimitsu Co., Ltd. -150) and leveled at room temperature for 1 hour. Next, the obtained coating film was preliminarily dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour to obtain an insulating layer 8.

Adsorption of sensitizing dye A sensitizing dye (manufactured by Solaronix, trade name: Ruthenium 620-1H3TBA) having a volume ratio of 1: 1 acetonitrile (manufactured by Aldrich Chemical Company) so as to have a concentration of 4 × 10 ⁻⁴ mol / liter. And a t-butyl alcohol (manufactured by Aldrich Chemical Company) were dissolved in a mixed solvent to obtain a dye adsorption solution.
The above laminate was immersed in the obtained dye adsorption solution at a temperature of 40 ° C. for 20 hours to adsorb the sensitizing dye to the porous semiconductor layer. Thereafter, the laminate was washed with ethanol (manufactured by Aldrich Chemical Company) and dried at about 80 ° C. for about 10 minutes.

・ Installation of insulating layer (glass plate) On the insulating layer 9 between cells (see FIG. 2C), an ultraviolet curable material (manufactured by ThreeBond, model number: 31X-088) was applied, and 50 mm × 70 mm × prepared separately. A glass substrate (Corning 7059) having a thickness of 1.0 mm and the substrate 1 were bonded together. In the glass substrate, φ = 1 mm and 3 rows × 5 columns = 15 current collector electrode openings and electrolyte injection holes were provided. Next, the two substrates were fixed by irradiating the applied part with ultraviolet rays using an ultraviolet irradiation lamp (trade name: Novacure, manufactured by EFD) to cure the ultraviolet curable material. The glass plate corresponds to the insulating layer 11.

-Formation of current collecting electrode Titanium is an electron in the portion of the number 7 in FIG. 2 (c) so that the current collecting electrode width Z = 1 mm, the current collecting electrode length U = 47 mm, and the current collecting electrode interval Y = 9 mm. Using a beam evaporator EVD-500A (manufactured by ANELVA Co., Ltd.), a film was formed at a deposition rate of 0.5 Å / S to obtain a collecting electrode 7 having a film thickness of about 300 nm. Thereafter, a cover glass 12 (Corning 7059) having 52 mm × 72 mm × thickness 1.0 mm, in which an electrolyte injection hole is provided in advance, is overlaid on the non-light-receiving surface side of the laminate, and the surrounding is an ultraviolet curable material (ThreeBond) Manufactured, Model No .: 31X-088) was applied, and the applied portion was irradiated with ultraviolet rays using an ultraviolet irradiation lamp (manufactured by EFD, trade name: Novacure) to cure the ultraviolet curable material.

- acetonitrile as prepared solvent of the electrolyte, LiI (Aldrich Chemical Company Ltd.) is a concentration of 0.1 mol / l, I ₂ (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is a concentration of 0.01 mol / l redox species As described above, t-butylpyridine (TBP, manufactured by Aldrich Chemical Company) was added at a concentration of 0.5 mol / liter, and dimethylpropylimidazole iodide (DMPII, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added at a concentration of 0.6 mol / liter. An electrolyte was obtained by adding and dissolving to a liter.

-Production of solar cell By injecting an electrolyte from a hole for injecting an electrolyte provided in advance in a glass substrate corresponding to the insulating layer 11, and sealing the hole for injecting an electrolyte with a resin 31X101 (manufactured by Three Bond Co., Ltd.), A solar cell corresponding to FIG. 2 was completed.
The obtained solar cell was irradiated with light having an intensity of 1 kW / m ² (AM1.5 solar simulator), and the photoelectric conversion efficiency and the like were measured in the same manner as in Example 1. As a result, the short-circuit current I _sc = 27.4 A, the open circuit voltage V _OC = 0.702, FF (fill factor) = 0.68, and the photoelectric conversion efficiency = 8.72%.

(Comparative Example 1)
The solar cell shown in FIG. 4 was produced.
Substrate 1 transparent conductive layer 2 made of SnO ₂ film made of glass is deposited, 50 mm × 70 mm × thickness 4mm the glass substrate (Nippon Sheet Glass Co., Ltd., SnO ₂ glass with film) was prepared.

-Formation of current collecting electrode Silver paste (stock) so that current collecting electrode width Z '= 1 mm, current collecting electrode length U = 47 mm, current collecting electrode interval Y' = 9 mm is shown in FIG. Company Noritake Company Limited) was applied using a screen printer (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150) and leveled at room temperature for 1 hour.
Next, the obtained coating film was preliminarily dried at 150 ° C. for 5 minutes and baked at 450 ° C. for 1 hour to obtain a collecting electrode 7.

-Formation of insulating layer An insulating layer was formed to suppress the corrosion of the collecting electrode by the electrolyte.
4 is screened with glass frit (manufactured by Noritake Co., Ltd.) so that the insulating layer width Z = 2 mm, the insulating layer length U = 48 mm, and the insulating layer interval Y = 8 mm. It applied using the printing machine (Neurong Seimitsu Kogyo KK make and model: LS-150), and leveling was performed at room temperature for 1 hour.
Next, the obtained coating film was pre-dried at 80 ° C. for 20 minutes, and baked at 450 ° C. for 1 hour to obtain an insulating layer.

・ Formation of sealing part (inter-cell insulating layer) A glass frit (manufactured by Noritake Co., Ltd.) is attached to the portion of the number 9 in FIG. 4 so that the inner frame is 32 mm × 52 mm and the line width is 0.5 mm. It was applied using a screen printer (Neurong Seimitsu Kogyo Co., Ltd., Model: LS-150), and the resulting coating film was pre-dried at 100 ° C. for 10 minutes, and then baked at 450 ° C. for 1 hour, between cells An insulating layer 9 was obtained. The film thickness was about 25 μm.

Formation of porous semiconductor layer Commercially available titanium oxide paste (made by Solaronix, trade name: Ti-Nanoxide D / SP, average grain) in the portion of figure 3 in FIG. 4 (a) (within the frame of the insulating layer between cells) 13 nm in diameter) was applied using a screen plate and a screen printing machine (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and leveling was performed at room temperature for 1 hour. As shown in FIG. 4A, the screen plate has a rectangular shape of 30 mm × 50 mm, a distance X from the end to the collecting electrode X = 4 mm, a distance Y between the collecting electrodes Y = 8 mm, and a width Z of the collecting electrode = 1 mm. Those having 3 are used.
Next, the obtained coating film was pre-dried at 80 ° C. for 20 minutes and then baked at 450 ° C. for 1 hour. This process was repeated to obtain a porous semiconductor layer (titanium oxide film) 3. The film thickness was 30 μm.

-Porous insulating layer Zirconium oxide fine particles (particle size: 100 nm, manufactured by C-I Kasei Co., Ltd.) were dispersed in terpineol, and ethyl cellulose was further mixed to prepare a paste. The obtained paste was applied onto the porous semiconductor layer 3 using the same screen plate and screen printer as the porous semiconductor layer 3 and leveled at room temperature for 1 hour.
Next, the obtained coating film was preliminarily dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour to obtain a porous insulating layer (zirconium oxide film) 4. The film thickness was 5 μm.

Formation of catalyst layer Platinum is deposited on the porous insulating layer 4 using an electron beam evaporator EVD-500A (manufactured by ANELVA) at a deposition rate of 0.1 Å / S, and a film thickness of about 5 nm. A catalyst layer 5 was obtained.

-Formation of the second conductive layer Titanium was deposited on the catalyst layer 5 by using an electron beam evaporator EVD-500A (manufactured by ANELVA) at a deposition rate of 0.5 Å / S. A second conductive layer 6 was obtained.

Adsorption of sensitizing dye A sensitizing dye (manufactured by Solaronix, trade name: Ruthenium 620-1H3TBA) having a volume ratio of 1: 1 acetonitrile (manufactured by Aldrich Chemical Company) so as to have a concentration of 4 × 10 ⁻⁴ mol / liter. And a t-butyl alcohol (manufactured by Aldrich Chemical Company) were dissolved in a mixed solvent to obtain a dye adsorption solution.
The above laminate was immersed in the obtained dye adsorption solution at a temperature of 40 ° C. for 20 hours to adsorb the sensitizing dye to the porous semiconductor layer. Thereafter, the laminate was washed with ethanol (manufactured by Aldrich Chemical Company) and dried at about 80 ° C. for about 10 minutes.

- acetonitrile as prepared solvent of the electrolyte, LiI (Aldrich Chemical Company Ltd.) is a concentration of 0.1 mol / l, I ₂ (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is a concentration of 0.01 mol / liter as redox species As described above, t-butylpyridine (TBP, manufactured by Aldrich Chemical Company) was added at a concentration of 0.5 mol / liter, and dimethylpropylimidazole iodide (DMPII, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added at a concentration of 0.6 mol / liter. An electrolyte was obtained by adding and dissolving to a liter.

-Manufacture of solar cell An ultraviolet curable material (model number: 31X-088, manufactured by ThreeBond Co., Ltd.) is applied onto the inter-cell insulating layer 9 (see FIG. 4), and a separately prepared 50 mm × 70 mm × 1.0 mm thick seal The glass substrate for a stop (Corning company make, model number: 7059) and the board | substrate 1 were bonded together. The sealing glass substrate was previously provided with electrolyte injection holes. Next, the two substrates were fixed by irradiating the applied part with ultraviolet rays using an ultraviolet irradiation lamp (trade name: Novacure, manufactured by EFD) to cure the ultraviolet curable material.
Next, an electrolyte was injected from the electrolyte injection hole of the sealing glass substrate, and the electrolyte injection hole was sealed, thereby completing the solar cell corresponding to FIG.

The obtained solar cell was irradiated with light having an intensity of 1 kW / m ² (AM1.5 solar simulator), and the photoelectric conversion efficiency and the like were measured in the same manner as in Example 1. As a result, the short-circuit current I _sc = 23.9 A, the open circuit voltage V _OC = 0.701, FF (fill factor) = 0.65, and photoelectric conversion efficiency = 7.26%.

(Example 3)
FIG. 3 shows a manufacturing process of the solar cell module. 3A shows the state after the formation of the inter-cell insulating layer, FIG. 3B shows the state after the formation of the insulating layer (insulating the catalyst layer and the collector electrode), and FIG. 3C shows the state after the collector electrode is formed.
As shown in FIGS. 3A, 3 </ b> B, and 3 </ b> C, a solar cell module in which three solar cells in FIG. 2 were connected in series by the connection method in FIG.
A glass substrate (50 mm × 170 mm × 4.0 mm thick glass substrate made by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) in which a transparent conductive layer 2 made of SnO ₂ film was formed on a substrate 1 made of glass was prepared. .

Cutting of the transparent conductive layer The transparent conductive layer 2 in the D part of FIG. 3 was irradiated with laser light (YAG laser, fundamental wavelength: 1.06 μm, manufactured by Saishin Shoji Co., Ltd.) to evaporate SnO ₂ and scribe.

-Formation of sealing part (inter-cell insulating layer) Glass frit (stock) so that three patterns with an inner frame of 32 mm x 52 mm and a line width A of 0.5 mm are arranged in the part number 9 in FIG. Company Noritake Company Limited) was applied using a screen printer (Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and the resulting coating film was pre-dried at 100 ° C. for 10 minutes, and then at 450 ° C. The inter-cell insulating layer 9 was obtained by firing for 1 hour. The film thickness was about 25 μm.

-Formation of a porous semiconductor layer, a porous insulating layer, a catalyst layer, and a 2nd conductive layer It carries out similarly to Example 2, the porous semiconductor layer 3, the porous insulating layer 4, a catalyst in B part of Fig.3 (a). Layer 5 and second conductive layer 6 were formed.

-Adsorption of sensitizing dye In the same manner as in Example 2, the sensitizing dye was adsorbed on the porous semiconductor layer.

-Installation of insulating layer (glass plate) On the inter-cell insulating layer 9 (see FIG. 3 (b)), (manufactured by ThreeBond, model number: 31X-088) is applied, and 50 mm x 150 mm x thickness 1 prepared separately. A 0 mm glass substrate (Corning 7059) and the substrate 1 were bonded together. For the glass substrate, φ = 1 mm (3 rows × 5 columns = 15) × 3 current collecting electrode for the porous semiconductor layer, porous insulating layer, catalyst layer and second conductive layer in advance. An opening, an opening C for series connection, and an electrolyte injection hole were provided. Next, the two substrates were fixed by irradiating the applied part with ultraviolet rays using an ultraviolet irradiation lamp (trade name: Novacure, manufactured by EFD) to cure the ultraviolet curable material. The glass plate corresponds to the insulating layer 11.
Further, a cover glass 12 (Corning 7059) having a 52 mm × 152 mm × 1.0 mm thickness provided with an electrolyte injection hole in advance is superposed on the non-light-receiving surface side of the laminate, and the surrounding is an ultraviolet curable material (ThreeBond Co., Ltd.). Manufactured, Model No .: 31X-088) was applied, and the applied portion was irradiated with ultraviolet rays using an ultraviolet irradiation lamp (manufactured by EFD, trade name: Novacure) to cure the ultraviolet curable material.

・ Formation of current collecting electrodes In the part of FIG. 7 in FIG. 3 (c), titanium is electronized so that the current collecting electrode width Z = 1 mm, the current collecting electrode length U = 47 mm, and the current collecting electrode interval Y = 9 mm. Using a beam evaporator EVD-500A (manufactured by ANELVA Co., Ltd.), a film was formed at a deposition rate of 0.5 Å / S to obtain a collecting electrode 7 having a film thickness of about 300 nm. Thereafter, an ultraviolet curable material (manufactured by ThreeBond, model number: 31X-088) is applied to the portion corresponding to the opening, and the applied portion is irradiated with ultraviolet rays using an ultraviolet irradiation lamp (manufactured by EFD, product name: Novacure). The UV curable material was cured.

-Preparation of electrolyte In the same manner as in Example 2, an electrolyte was obtained.

-Production of solar cell module An electrolyte was injected from the electrolyte injection hole of the cover glass, and the electrolyte injection hole was sealed with 31X101 (manufactured by Three Bond Co., Ltd.) to complete the solar cell module corresponding to FIG. .
The obtained solar cell module was irradiated with light having an intensity of 1 kW / m ² (AM1.5 solar simulator), and the photoelectric conversion efficiency and the like were measured in the same manner as in Example 1. As a result, short-circuit current I _sc = 26.9A, open circuit voltage V _OC = 2.11, FF (fill factor) = 0.66, was photoelectric conversion efficiency = 8.32%.

(Comparative Example 2)
As shown in FIG. 5, a module in which three solar cells of FIG. 4 were connected in series by the connection method of FIG. 4B was produced.
A glass substrate (50 mm × 170 mm × 4.0 mm thick glass substrate made by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) in which a transparent conductive layer 2 made of SnO ₂ film was formed on a substrate 1 made of glass was prepared. .

Cutting of the transparent conductive layer The transparent conductive layer 2 in the D part of FIG. 5 was irradiated with laser light (YAG laser, fundamental wavelength: 1.06 μm, manufactured by Saishin Shoji Co., Ltd.) to evaporate SnO ₂ and scribe.

-Formation of current collection electrode and insulating layer The current collection electrode 7 and the insulation layer 8 were formed in the B part of FIG.

-Formation of sealing part (insulating layer between cells) In the part of FIG. 9 in FIG. 5, the inner frame is 32 mm × 51 mm, the line width A is 0.5 mm, and the width A ′ of the connecting part is 0.5 mm. A glass frit (manufactured by Noritake Co., Ltd.) was applied using a screen printing machine (manufactured by Neurong Seimitsu Kogyo Co., Ltd., model: LS-150), and the resulting coating film was pre-dried at 100 ° C. for 10 minutes. Then, it baked at 450 degreeC for 1 hour, and obtained the insulating layer 9 between cells. The film thickness was about 25 μm.

Formation of porous semiconductor layer, porous insulating layer, catalyst layer and second conductive layer In the same manner as in Comparative Example 1, porous semiconductor layer 3, porous insulating layer 4, catalyst layer 5 and A second conductive layer 6 was formed.

-Adsorption of sensitizing dye In the same manner as in Comparative Example 1, the sensitizing dye was adsorbed on the porous semiconductor layer.

-Preparation of electrolyte In the same manner as in Comparative Example 1, an electrolyte was obtained.

・ Installation of insulating layer (glass plate) On the insulating layer 9 between cells (see FIG. 5), an ultraviolet curable material (manufactured by ThreeBond, model number: 31X-088) was applied, and 50 mm × 150 mm × thickness 1 prepared separately. A 0 mm sealing glass substrate (Corning, model number: 7059) and the substrate 1 were bonded together. The sealing glass substrate was previously provided with electrolyte injection holes. Next, the two substrates were fixed by irradiating the applied part with ultraviolet rays using an ultraviolet irradiation lamp (trade name: Novacure, manufactured by EFD) to cure the ultraviolet curable material.

-Production of solar cell module An electrolyte was injected from the electrolyte injection hole of the glass substrate for sealing, and the electrolyte injection hole was sealed to complete a solar cell module corresponding to Fig. 4B.
The obtained solar cell module was irradiated with light having an intensity of 1 kW / m ² (AM1.5 solar simulator), and the photoelectric conversion efficiency and the like were measured in the same manner as in Example 1. As a result, the short-circuit current I _sc = 21.5 A, the open circuit voltage V _OC = 2.71, FF (fill factor) = 0.65, and the photoelectric conversion efficiency = 6.52%.

It is the schematic plan view of (a) light-receiving surface in the solar cell of this invention, and XX schematic sectional drawing of (b) (a). It is the schematic sectional drawing of the connection part at the time of setting it as (c) non-light-receiving surface in the solar cell of this invention, and (d) module. It is the schematic plan view of (a) light-receiving surface in another solar cell of this invention, and (b) XX schematic sectional drawing of (a). It is the schematic sectional drawing of the connection part at the time of setting it as (c) non-light-receiving surface in another solar cell of this invention, and (d) module. It is a schematic plan view which shows the manufacturing process of the solar cell module of this invention. (A) The schematic plan view of a light-receiving surface in the conventional solar cell, and (b) The schematic sectional drawing of the connection part at the time of setting it as a module. It is a schematic plan view which shows the manufacturing process of the conventional solar cell module.

Explanation of symbols

1 substrate 2 transparent conductive layer (first conductive layer)
DESCRIPTION OF SYMBOLS 3 Porous semiconductor layer 4 Porous insulating layer 5 Catalyst layer 6 2nd conductive layer 7 Current collecting electrode 8 Insulating layer 9 Sealing part (inter-cell insulating layer)
10 Sealing part (resin)
11 Insulating layer 12 Cover glass

Claims (11)

  A transparent conductive layer, a porous semiconductor layer containing a sensitizing dye and containing an electrolyte in the gap, and a catalyst layer are sequentially laminated on the non-light-receiving surface side of the light-transmitting substrate serving as the light-receiving surface. A dye-sensitized solar cell having an electrode, wherein a linear collector electrode is provided on the non-light-receiving surface side of the catalyst layer, penetrates the porous semiconductor layer and the catalyst layer, and partially and electrically A dye-sensitized solar cell, wherein the dye-sensitized solar cell is extended so as to be in contact with the catalyst and electrically insulated from the catalyst layer by an insulating layer.   The dye-sensitized sensitization according to claim 1, wherein a contact portion of a collecting electrode extended so as to be in partial and electrical contact with the transparent conductive layer is regularly arranged on the transparent conductive layer. Solar cell.   The dye-sensitized sun according to claim 1 or 2, wherein a shape of a contact surface of the collector electrode, which is extended so as to be in partial and electrical contact with the transparent conductive layer, is circular. battery.   The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the linear collector electrode has a comb shape.   The dye-sensitized solar cell according to any one of claims 1 to 4, wherein the current collecting electrode is formed of a metal material selected from titanium, tantalum, and nickel.   The portion of the linear collector electrode extending through the porous semiconductor layer and the catalyst layer is covered with an insulating layer, and is electrically insulated from the catalyst layer by the insulating layer. The dye-sensitized solar cell as described in any one of these.   The dye-sensitized sun according to any one of claims 1 to 6, wherein the insulating layer is formed of an inorganic material containing silicon oxide, or an organic polymer material containing an ultraviolet curable resin or a thermosetting resin. battery.   The insulating layer that electrically insulates the catalyst layer and the collector electrode, the porous semiconductor layer of the collector electrode and the portion extending through the catalyst layer, and the insulating layer that insulates the catalyst layer are made of the same material. The dye-sensitized solar cell according to claim 7 or 8, which is formed simultaneously.   The dye-sensitized solar cell according to any one of claims 1 to 8, wherein a porous insulating layer is further laminated on the non-light-receiving surface side layer of the porous semiconductor layer.   The dye-sensitized solar cell according to any one of claims 1 to 9, wherein a conductive layer is further laminated on a layer on the non-light-receiving surface side of the catalyst layer.   A dye-sensitized solar cell module comprising at least two dye-sensitized solar cells according to any one of claims 1 to 10 connected in series.

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