JP2009231285A - Method of manufacturing dye sensitized solar battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a dye-sensitized solar battery which has a resistance against an external impact and damage and achieves airtightness having a high strength and has a high durability. <P>SOLUTION: The method of manufacturing the dye sensitized solar battery includes a step in which glass frit is coated on an upper plate or on a bonding surface of a bonding plate for bonding with the upper plate along an airtight line of a dye-sensitized solar battery, a step in which a light curing resin composition is coated on the upper plate or on the bonding surface of the bonding plate for bonding with the upper plate, on a position surrounding an outer enclosure by keeping a distance from the airtight line, a step in which the upper plate and the bonding plate are bonded to form a bonded body, a step in which the bonded body is cured by being irradiated by light for curing the light curing resin composition, and a step in which laser is irradiated along the glass frit of the bonded body for calcination. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a dye-sensitized solar cell (DSSC), and in particular, by applying a low-melting glass frit composition and a photocurable resin composition, low-temperature firing of a laser can be achieved. Possible to reduce damage to heat-sensitive elements, and pre-sealing with photo-curing resin can increase the efficiency of glass frit sealing and increase process efficiency, which makes it a harsh external environment It can prevent the electrolyte of solar cells used by being exposed to air from evaporating from the airtight part, extend the life, provide resistance to external impact and damage, and provide high strength airtightness Thus, the present invention relates to a method for producing a dye-sensitized solar cell, which can obtain the effect of extending the life of the dye-sensitized solar cell and increasing the durability.

  Much work has been done in this field since the dye-sensitized nanoparticle titanium oxide solar cells were developed by the Michael Gratzel research team at the Swiss National Institute of Advanced Technology (EPFL) in 1991. Dye-sensitive solar cells have a significantly lower unit price than existing silicon-based solar cells, so they have the potential to replace existing amorphous silicon solar cells. Unlike silicon solar cells, dye-sensitive solar cells The battery is a photoelectrochemical solar cell mainly composed of a dye molecule capable of generating an electron-hole pair by absorbing visible light and a transition metal oxide that transmits the generated electrons.

The unit cell structure of a typical dye-sensitized solar cell is based on a transparent substrate on the top and bottom and a conductive transparent electrode formed on the surface of the transparent substrate. A transition metal oxide porous layer having a dye adsorbed on its surface is formed on the electrode, and a catalyst thin film electrode is formed on the other conductive transparent electrode corresponding to the second electrode. The object is, for example, TiO ₂ and has a structure in which an electrolyte is filled between the porous electrode and the catalyst thin film electrode.

  Therefore, in order to stably maintain the electrolyte filled between the first electrode and the second electrode, a thermoplastic polymer film is placed between the first electrode and the second electrode, and the thermocompression bonding process is performed. These are joined to form and maintain a certain space where electrolyte is injected and stored between the first electrode and the second electrode.

  However, in the case of the thermoplastic polymer film, the structure is not precise, and it deteriorates due to high temperature, intense sunlight, thermal cycling, etc., and the electrolyte volatilizes through thermal cycling such as night / daytime or winter / summer, so that the solar cell. This is a factor that lowers the efficiency of the film and eventually ends its life, and there is a problem that damage occurs due to external impact due to the limit of the mechanical strength of the polymer film. The fact is that the lifespan of the battery is shortened, which is a fatal problem in its durability.

  The present invention is for solving such problems of the prior art, and by applying a low-melting glass frit composition and a photocurable resin composition, low-temperature firing of a laser is possible, The damage to heat-sensitive elements can be reduced, and by pre-sealing the photo-curing resin, the efficiency of glass frit sealing can be improved and the production efficiency can be increased, so that it is exposed to a harsh external environment. The electrolyte of the solar cell used can be prevented from volatilizing from the hermetic part and the life can be extended, it is resistant to external impact and damage, and provides a high strength airtight, An object of the present invention is to provide a method for producing a dye-sensitized solar cell capable of extending the life of the dye-sensitized solar cell and improving the durability.

  In order to achieve such an object, the present invention provides a method for manufacturing a dye-sensitized solar cell including bonding of an upper plate and a bonding plate bonded to the upper plate, and the upper plate or the bonding plate bonded to the upper plate. Applying a glass frit along the airtight line of the dye-sensitized solar cell to the joint surface of the dye; the airtight line being separated from the airtight line on the joint surface of the upper plate or the joint plate to be joined to the upper plate and surrounding the outer shell A step of applying a photocurable resin composition to a position; a step of bonding the upper plate and a bonding plate to produce a bonded body; a light for curing the photocurable resin composition on the bonded bonded body And a method of producing a dye-sensitized solar cell, comprising: a step of irradiating a laser along the glass frit of the bonded body and baking it.

  The present invention also provides a dye-sensitized solar cell manufactured by the manufacturing method.

  According to the method for producing a dye-sensitized solar cell of the present invention, by applying a low-melting glass frit composition and a photocurable resin composition, laser can be fired at a low temperature and damage to heat-sensitive elements can be reduced. By pre-sealing with a photocurable resin, the efficiency of glass frit sealing can be improved and the production efficiency can be increased. In addition, volatilization from the airtight part of the electrolyte of the solar cell used by being exposed to a harsh external environment is prevented, it has resistance to external impact and damage, and a high strength airtightness is obtained. The life of the dye-sensitized solar cell is extended, and the effect of increasing the durability can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram schematically illustrating a process of a method for producing a dye-sensitized solar cell according to an embodiment of the method for producing a dye-sensitized solar cell of the present invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  A method for manufacturing a dye-sensitized solar cell according to the present invention includes a method for manufacturing a dye-sensitized solar cell including a bonding of an upper plate and a bonding plate bonded to the upper plate. Applying a glass frit to the bonding surface of the lower plate) along the airtight line of the dye-sensitized solar cell; separating the outer wall from the airtight line on the bonding surface of the upper plate or the bonding plate bonded to the upper plate; A step of applying a photocurable resin composition to a position that surrounds; a step of bonding the upper plate and a bonding plate to produce a bonded body; and curing the photocurable resin composition to the bonded bonding body Irradiating and curing the light; and irradiating and firing a laser along the glass frit of the bonded body.

A general dye-sensitized solar cell is opposed to a first electrode (corresponding to a lower plate-bonding plate in FIG. 1) having a porous film containing a dye on one side and the first electrode (lower plate). And the second electrode (the upper plate in FIG. 1) and the electrolyte filled between these electrodes. In the case of the present invention, in order to stably store the electrolyte for a long period of time between the first electrode and the second electrode, the first electrode and the second electrode are spaced apart from each other. The air-tight space is sealed with a glass frit fired body so that the electrolyte is filled in the air-tight space formed in this manner, and the porous film has a variety of known porous materials to which a dye is bound (adsorbed). A specific example of this is a porous film obtained by applying a transition metal oxide porous material, for example, TiO ₂ having a size of 10 to 15 nm and baking it. The translucent plate on which the porous film is formed is not necessarily limited to a flat plate, and includes a plate having a bent surface, and transmits visible light or a wave (light wave) of a certain wavelength band that deviates from this. This includes various known light-transmitting plates applied to solar cells such as a plate made of a material such as glass. What has conductivity is preferable in order to serve as an electrode. Specific examples of the light-transmitting plate include known light-transmitting glass, light-transmitting resin, PET (polyethylene terephthalate), ITO (indium tin oxide), FTO (fluorine-doped tin oxide), and the like. In addition to the above material, a conductive film or a coating layer (ITO, FTO, or conductive polymer) is additionally included between the porous film and the plate in order to have a property. can do. The second electrode (upper plate) disposed opposite to the first electrode in a pair includes a plate applied to a well-known solar cell second electrode, and is not necessarily limited to a flat plate. In this case, a plate having a bent surface is also included, and it is preferable that the plate is made of a material that transmits visible light or waves in a certain wavelength band that deviates from the visible light. For this purpose, it can be composed of a material such as a known translucent glass, PET glass, ITO glass or FTO glass, preferably a conductive film or a selective film on the material in order to have conductivity. A coating layer (ITO, FTO, or conductive polymer) can be additionally included, and the first catalyst metal layer such as platinum is used to increase the efficiency of sunlight absorption and activate the reaction. It can be further included in the outermost surface on the electrode side.

  In the dye-sensitized solar cell, the upper plate is made of a glass substrate, and the lower plate or the bonding plate can be made of a glass substrate as shown in FIG. (As shown in FIG. 1, when the structure is composed of only the upper and lower plates, the lower plate becomes a coupling plate, and when it has a multilayer structure having more layers than this, it is coupled to the lower surface of the upper plate. The plate can be joined and an additional plate can be further joined below it).

  In such a dye-sensitized solar cell, as shown in FIG. 1, a large number of dye-sensitive solar cells (2 × 2 in the case of FIG. 1) can be formed on one substrate. Only one cell can be produced. Since each cell needs to maintain hermeticity at its bonding surface, the glass frit composition is applied along a hermetic line that hermetically seals the outer shell of the cell with a closed curve as shown in FIG. The airtight line may be formed in various shapes according to the shape of the device, and a glass frit is applied to the bonding surface along the airtight line as shown in FIG. In the coupling surface, the lower surface of the upper plate can be a coupling surface, and the upper surface of the lower plate (or the coupling plate coupled to the upper plate) can be a coupling surface. This ultimately serves to maintain the tightness of the binding site. The glass frit can be applied through various known methods. For example, the glass frit can be manufactured as a glass paste and printed and dried by a screen printing method.

As the glass frit, a known glass frit can be used. Preferably, P ₂ O ₅ 0~30 mol%; V ₂ O ₅ 0~50 mol%; ZnO 0 to 20 mole%; BaO 0 to 15 mole%; As ₂ O ₃ 0~20 mol%; Sb ₂ O ₃ 0-20 mole%; In ₂ O ₃ 0~5 mole%; Fe ₂ O ₃ 0~10 mol%; Al ₂ O ₃ 0~5 mole%; B ₂ O ₃ 0 to 20 mole%; Bi ₂ O _{It is} preferred to use a glass frit containing 30-10 mol%; and 0-10 mol% TiO ₂ .

  Preferably, a glass frit paste containing the glass frit is applied along the periphery, and the glass frit paste composition includes (a) the glass frit, (b) an organic binder, and (c) an organic solvent. it can. Preferably, (a) 60 to 90 parts by mass of the glass frit, (b) 0.1 to 5 parts by mass of an organic binder, and (c) 5 to 35 parts by mass of an organic solvent may be included.

Preferably, the glass frit is P ₂ O ₅ 10 to 25 mole%; V ₂ O ₅ 40~50 mol%; ZnO 10 to 20 mole%; BaO 1 to 15 mol%; Sb ₂ O ₃ 1~10 mol Fe ₂ O ₃ 1-10 mol%; Al ₂ O ₃ 0.1-5 mol%; B ₂ O ₃ 0.1-5 mol%; Bi ₂ O ₃ 1-10 mol%; and TiO ₂ 0 good to contain .1～5 mol%, more preferably, P ₂ O ₅ 15 to 20 mole%; V ₂ O ₅ 40~50 mol%; ZnO 10 to 20 mole%; BaO 5 to 10 mol% ; Sb ₂ O ₃ 3~7 mole%; Fe ₂ O ₃ 5~10 mol%; Al ₂ O ₃ 0.1~5 mol%; B ₂ O ₃ 0.1~5 mol%; Bi ₂ O ₃ 1 5 mol%; and it may comprise a TiO ₂ 0.1 to 5 mol%.

  When the content of the glass frit component constituting the present invention is out of the above range, vitrification may not occur, water resistance may be significantly reduced, or laser firing may not be performed.

  Preferably, the glass frit has a glass transition temperature (Tg) of 300 to 400 ° C. and a softening temperature (Tdsp) of 300 to 400 ° C. When it is within the above range, excellent firing stability is exhibited at a low temperature.

  The glass frit preferably has a particle size of 0.1 to 20 μm. When it is within the above range, low-temperature processing is possible and suitable for hermetic sealing of heat-sensitive elements, laser processing is possible, and the sealing efficiency of electric elements can be improved.

  In the glass frit paste composition, (a) the glass frit is as described above, and (b) the organic binder can be a commercially available organic binder. As a specific example of the organic binder, an ethyl cellulose-based or acrylic copolymer can be used. Further, as the organic solvent (c), it is possible to use an organic solvent compatible with the organic binder used in the glass frit paste composition of the present invention. As a specific example, the organic binder is an ethyl cellulose type. In this case, butyl carbitol acetate (BCA), terpineol (TPN), and dibutyl phthalate (DBP) can be used alone or in admixture of two or more. Preferably, a vehicle is manufactured by first mixing an organic binder with 30 to 70 parts by mass of an organic solvent in 100 parts by mass of the organic solvent used, and then the remaining amount of the organic solvent and glass frit are added to the manufactured vehicle. It is preferable to produce a glass frit paste composition by mixing. In this case, the dispersibility of the glass frit paste composition can be further improved. More preferably, at the time of manufacturing the vehicle, 30 to 70 parts by mass of the organic solvent may contain 20 to 55 parts by mass of BCA, 3 to 10 parts by mass of TPN, and 1 to 5 parts by mass of DBP, and is used when mixing with glass frit. BCA is preferably used as the solvent.

  The glass frit paste composition may further include a filler for adjusting a thermal expansion coefficient. As a specific example of the filler, 0.1 to 20 μm cordierite can be used, and the content thereof is preferably 0.1 to 30 parts by mass.

  The glass frit paste composition preferably has a viscosity of 500 to 50,000 cps. More preferably, it is 2000-35000 cps. When the viscosity is within the above range, it is possible to further improve workability by enabling application by a screen printing technique.

  In the method for producing a dye-sensitized solar cell according to the present invention, the photocurable resin composition is then placed at a position surrounding the outer wall of the upper plate or a bonding surface of the bonding plate bonded to the upper plate so as to be separated from the hermetic line. Apply. By this application, the sealing efficiency of the glass frit can be further improved. As shown in FIG. 1, the photo-curable resin composition can be applied to the upper plate together with the glass frit at the same location, or can be applied to the upper surface of the lower plate, preferably from the alignment side. It is good to apply together on one side. That is, the lower plate (or coupling plate) as the first electrode includes a porous film containing an electrode and a dye as shown in FIG. 1 (additional connection lines connecting unit cells are added if necessary) The glass frit and the photocurable resin composition are coated on one side as shown in the figure, as the upper plate as the second electrode. Here, during the coating, the glass frit and the resin composition are not hermetically sealed over the entire hermetic line, and a part thereof is opened so that the space between the bonding surfaces of the bonded body can be filled with an electrolyte later. It is preferable to prepare as follows.

  The photo-curable resin composition can be applied by various known methods, and examples thereof include screen printing and gravure printing.

  As such a photocurable resin composition, an ordinary photocurable resin composition can be used. Preferably, the photocurable resin composition used in the present invention is (a) 100 parts by mass of an epoxy resin. (B) 0.01-20 parts by weight of a photopolymerization initiator, (c) 0.01-10 parts by weight of a coupling agent, (d) 0.01-100 parts by weight of an inorganic filler, and (e) a photoacid. 0.05-10 mass parts of generating agents can be contained.

  The photocurable resin composition of the present invention has a viscosity (at 25 ° C.) of 5,000 to 150,000 cps, preferably 10,000 to 100,000 cps, so that a screen printing process is possible, and the process time is reduced. It has the advantage that it can be shortened and the cost of entering the process can be reduced.

  Hereinafter, preferable specific components of the photocurable resin composition will be described.

  The epoxy resin of (a) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, glycidylamine type epoxy resin, naphthol novolak type epoxy resin, diester. Cyclopentadiene type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, prepolymer of the epoxy resin, polyether modified epoxy resin, silicone modified epoxy resin, co-polymerization of the epoxy resin with other polymers A coalescence etc. can be used individually or in mixture of 2 or more types.

  As the photopolymerization initiator (b), aromatic diazonium salts, aromatic sulfonium salts, aromatic iodoaluminum salts, aromatic sulfonium aluminum salts, metallocene compounds, iron arene compounds, and the like can be used. .

  In particular, an aromatic sulfonium salt is preferable from the viewpoint of photocuring, and an aromatic sulfonium hexafluorophosphate compound, an aromatic sulfonium hexafluoroantimonate, or a mixture thereof is used from the aspects of curability and adhesiveness. Is preferred.

  The photopolymerization initiator is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 1 to 6 parts by weight, based on 100 parts by weight of the epoxy resin. Is done. When the content exceeds 20 parts by mass, it does not participate in the reaction of the composition, and the remaining components may act as a factor for reducing the physical properties of the photocurable resin composition.

  The coupling agent (c) is an additive for increasing adhesive strength (adhesion properties), and is a silane coupling agent such as trimethoxysilylbenzoic acid or γ-glycidoxypropyltrimethoxysilane, titanium These coupling agents, silicone compounds and the like can be used alone or in admixture of two or more.

  The coupling agent is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and most preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the epoxy resin. Is done. When the content exceeds 10 parts by mass, it does not participate in the reaction of the composition, and the remaining components may act as a factor that lowers the physical properties of the photocurable resin composition.

  Examples of the inorganic filler (d) include silica, talc, magnesium oxide (MgO), mica, montmorillonite, alumina, graphite, and beryllium oxide. Plate-type or spherical inorganic fillers such as oxide, aluminum nitride, silicon carbide, mullite, silicon, etc. can be used.

  In particular, as the inorganic filler, it is preferable to use talc which is excellent in moisture barrier property and light transmittance and prevents shrinkage after photocuring.

  In addition, the inorganic filler may be used by introducing a substituent into the inorganic filler in order to increase the dispersion characteristics and the adhesive strength with the epoxy resin in the photocurable resin composition.

  The inorganic filler is preferably used in an amount of 0.01 to 100 parts by weight, more preferably 0.1 to 80 parts by weight, based on 100 parts by weight of the epoxy resin. When the content exceeds 100 parts by mass, the reaction of the photocurable resin composition may be hindered to act as a factor for reducing physical properties. The inorganic filler is better if particles having an average particle diameter of 0.1 to 50 μm are used.

  The photoacid generator (e) is not limited as long as it is a compound capable of generating a Lewis acid and Bronsted acid component by exposure and generating an acid by light. For example, as the photoacid generator, a sulfide salt compound such as organic sulfonic acid, an onium salt compound such as onium salt, and a mixture thereof can be used. Non-limiting examples of photoacid generators include phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone, naphthylimido trifluoromethane sulfonate (naphthylimido trifluoromethane sulfonate). ), Diphenyliodo salt (iodonium salt) hexafluorophosphate, diphenyliodo salt hexafluoroarsenate, diphenyliodo salt hexafluoroantimonate, diphenylparamethoxyphenylsulfonium triflate, diphenylparatolenylsulfonium triflate, diphenylparaisobutylphenylsulfonium Triflate, triphenylsulfonium hexafluoroarsenate, triphenylsulfoniu Hexafluoroantimonate, triphenylsulfonium triflate, and the like dibutyl Luna borderless Le triflate.

  The photoacid generator is preferably contained in an amount of 0.05 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. When the content exceeds 10 parts by mass, the photoacid generator may absorb a lot of far ultraviolet rays, and a large amount of acid may be generated, thereby reducing the physical properties of the photocurable resin composition.

  The photocurable resin composition may further include a spacer selectively. The spacer applicable to the photocurable resin composition is not particularly limited as long as the thickness of the panel after curing can be kept constant, and the thickness of the panel is 5 to 50 μm, preferably 5 to 25 μm. What can be maintained is good. The spacer has a spherical shape, a log shape, and the like, and the shape of the spacer is not particularly limited as long as the thickness of the panel can be kept constant. It is preferable that the content of the spacer is 0.01 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin.

  The photocurable resin composition of the present invention composed of such components preferably has an epoxy change rate of 85% or more in the cured product.

  Next, the upper plate prepared in this way and the bonding plate bonded to the upper plate are bonded together to prepare a combined body. In the case of FIG. 1, the bonding plate corresponds to the lower plate, and after the bonding is performed as the bonded body, further internal approach is restricted, so that the glass frit or the resin composition is applied. The upper plate and the bonding plate must be joined after all the necessary processing steps in the cell configuration are completed before and after the process. For this, an electrode formation, a dye adsorption process and the like as shown in FIG. 1 are applied.

  Further, in the application of the glass frit and the photocurable resin composition, when applying along the airtight line, it can be applied completely so that the airtightness can be maintained. This can also be applied by leaving the connection port connected to the electrode, and in the case of the dye-sensitized solar cell of the present invention, it is necessary to fill the electrolyte, so for this purpose the electrolyte injection port is left and applied. be able to.

  Since the glass frit and the photocurable resin composition of the bonded body thus bonded are not yet cured, the light that cures the photocurable resin composition is then applied to the bonded bonded body. A step of curing by irradiation is performed. As shown in a specific example in FIG. 1, when the applied photocurable resin composition is cured to UV, it is cured by irradiating with ultraviolet rays as illustrated. Next, since it is necessary to harden the glass frit of the bonded bonded body, for this purpose, a step of firing by irradiating a laser along the applied glass frit is performed. As described above, the glass frit may preferably be a low melting glass frit, so that the irradiated laser can use a laser having a low output, and therefore, the thermal damage to the device is prevented. It can be minimized. In this case, the resin composition layer that is already cured and surrounds the glass frit serves to block gas generation and contact with oxygen during firing of the glass frit, and serves to support the bonded body during firing of the glass frit. Therefore, it is possible to improve glass frit sealing efficiency through pre-sealing and to increase the process efficiency.

  Through this, the airtightness of the dye-sensitized solar cell is maintained by the glass frit and the resin composition, and the airtight line and the photocurable resin composition are used as shown in FIG. By cutting between the object application portions, the portion where the photocurable resin composition is cured can be separated. In particular, in the case of FIG. 1, since a large number of cells are provided on a single substrate, a dicing operation is performed by cutting each of the cells into a large number of cells. Further, after the glass frit firing step or after the dicing operation, the electrolyte is injected into the electrolyte injection port, and the airtight operation is finally performed using the glass frit or the like to complete the airtightness. It can also be done.

  The present invention described above is not limited by the foregoing embodiments and the accompanying drawings, but is within the scope of the technical field within the scope of the spirit and scope of the present invention described in the claims below. It goes without saying that various modifications and changes made by a trader are also included in the scope of the present invention.

Claims (12)

  In a method for manufacturing a dye-sensitized solar cell including bonding of an upper plate and a bonding plate bonded to the upper plate, an airtight line of the dye-sensitive solar cell is formed on a bonding surface of the upper plate or a bonding plate bonded to the upper plate. A step of applying a glass frit along the step; a step of applying a photocurable resin composition to a position surrounding the outer wall of the upper plate or a bonding surface of the bonding plate bonded to the upper plate, spaced from the hermetic line; Bonding the upper plate and the bonding plate to produce a bonded body; irradiating the bonded bonded body with light for curing the photocurable resin composition; and curing the bonded body; A method for producing a dye-sensitized solar cell, comprising a step of firing by irradiating a laser along the glass frit of the bonded body.   The dye-sensitive sun according to claim 1, further comprising a step of cutting between the airtight line and the photocurable resin composition application portion and separating a portion where the photocurable resin composition is cured as a post-process. Battery manufacturing method. Said glass frit, P ₂ O ₅ 0~30 mol%; V ₂ O ₅ 0~50 mol%; ZnO 0 to 20 mole%; BaO 0 to 15 mole%; As ₂ O ₃ 0~20 mol%; Sb ₂ O ₃ 0 to 20 mol%; In ₂ O ₃ 0 to 5 mol%; Fe ₂ O ₃ 0 to 10 mol%; Al ₂ O ₃ 0 to 5 mol%; B ₂ O ₃ 0 to 20 mol%; _{2. The} method for producing a dye-sensitized solar cell according to claim 1, comprising 0 to 10 mol% of O ₃ ; and 0 to 10 mol% of TiO ₂ .   The method for producing a dye-sensitized solar cell according to claim 1, wherein the glass frit is applied by applying a glass frit paste composition containing (a) the glass frit; (b) an organic binder; and (c) an organic solvent.   5. The glass frit paste according to claim 4, wherein the glass frit paste comprises (a) 60 to 90 parts by mass of the glass frit; (b) 0.1 to 5 parts by mass of an organic binder; and (c) 5 to 35 parts by mass of an organic solvent. A method for producing a dye-sensitized solar cell.   The photocurable resin composition comprises: (a) 100 parts by mass of an epoxy resin; (b) 0.01 to 20 parts by mass of a photopolymerization initiator; (c) 0.01 to 10 parts by mass of a coupling agent; The method for producing a dye-sensitized solar cell according to claim 1, comprising 0.01 to 100 parts by mass of an inorganic filler; and (e) 0.05 to 10 parts by mass of a photoacid generator.   The epoxy resin (a) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, glycidylamine type epoxy resin, naphthol novolac type epoxy resin, di Cyclopentadiene type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, prepolymer of the above epoxy resin, polyether modified epoxy resin, silicone modified epoxy resin and co-use of the epoxy resin with other polymers The method for producing a dye-sensitized solar cell according to claim 6, which is at least one selected from the group consisting of polymers.   The photopolymerization initiator (b) is at least one selected from the group consisting of aromatic diazonium salts, aromatic sulfonium salts, aromatic iodoaluminum salts, aromatic sulfonium aluminum salts, metallocene compounds, and iron arene compounds. A method for producing a dye-sensitized solar cell according to claim 6.   The method for producing a dye-sensitized solar cell according to claim 6, wherein the coupling agent (c) is one or more selected from the group consisting of a silane coupling agent, a titanium coupling agent, and a silicone compound.   The inorganic filler (d) is one or more selected from the group consisting of silica, talc, magnesium oxide, mica, montmorillonite, alumina, graphite, beryllium oxide, aluminum nitride, silicon carbide, mullite, and silicon. A method for producing a dye-sensitized solar cell as described in 1 above.   The method for producing a dye-sensitized solar cell according to claim 6, wherein the photoacid generator (e) is selected from the group consisting of a sulfide-based compound, an onium salt-based compound, and a mixture thereof.   The dye-sensitized solar cell manufactured by the manufacturing method of the dye-sensitive solar cell of any one of Claims 1-11.

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