JP6338458B2 - Photoelectric conversion element, photoelectric conversion module, and method for manufacturing photoelectric conversion element - Google Patents

Description

  The present invention relates to a photoelectric conversion element, a photoelectric conversion module, and a method for manufacturing a photoelectric conversion element.

  Sunlight has attracted attention as an energy source to replace fossil fuels, and solar cells that can convert sunlight into electric power have attracted attention. Among them, the dye-sensitized solar cell has been attracting attention as a new type of solar cell because it has an advantage that the manufacturing cost can be reduced.

  For example, Patent Document 1 discloses a dye-sensitized photoelectric conversion element in which an electrolyte is filled between a porous electrode on which a photosensitizing dye is adsorbed and a counter electrode. The dye-sensitized photoelectric conversion element of Patent Document 1 includes a transparent electrode provided with a porous electrode and a counter electrode provided so as to face the transparent electrode with a gap in order to prevent leakage of the electrolyte to the outside. The sealing body which surrounds the outer periphery of the area | region between is included.

  However, since the dye-sensitized photoelectric conversion element of Patent Document 1 is provided with only a single sealing body, leakage of the electrolyte could not be sufficiently prevented.

  Therefore, for example, in Patent Document 2, for the purpose of preventing leakage of the electrolyte, a porous oxide semiconductor layer containing a dye sensitizer and an oxide semiconductor of a counter substrate facing the oxide semiconductor layer are disclosed. Dye-sensitized solar cell module in which an outer seal portion is further provided around an element seal portion for sealing the electrolyte layer provided around the electrolyte layer between the counter electrode layer formed on the surface on the layer side Is disclosed.

  Further, for example, in Patent Document 3, two inner main seals and outer main seals are provided on the outer periphery of a region between the photoelectrode-side transparent conductive film and the counter electrode-side conductive film that are provided so as to face each other with a space therebetween. A dye-sensitized solar cell in which an electrolyte solution is sealed by providing a heavy seal is disclosed.

JP2013-122874A JP 2007-220606 A JP 2010-92762 A

  However, the dye-sensitized solar cell module described in Patent Document 2 is provided with an element seal portion and an external seal portion along the outer peripheral portion of the oxide semiconductor layer of the electrode base material, and the electrode base material and the counter electrode base It is formed by bonding materials together by thermocompression bonding (paragraph [0101] of Patent Document 2). Therefore, in the dye-sensitized solar cell module described in Patent Document 2, there is a problem that the dye sensitizer is deteriorated by being heated and the conversion efficiency is lowered.

Moreover, the dye-sensitized solar cell module described in Patent Document 3 is manufactured as follows. That is, first, an ultraviolet curable resin is applied annularly as an inner main seal on the photoelectrode-side transparent conductive film on the photoelectrode-side transparent substrate so as to surround the TiO ₂ porous film carrying the sensitizing dye, The inner main seal is cured by irradiating with ultraviolet rays in a state where the counter electrode side substrate is overlapped via the inner main seal. Next, by injecting UV curable resin having a low viscosity as an outer main seal into the gap between the peripheral edge of the photoelectrode side transparent substrate and the counter electrode side substrate using capillary action, and curing by irradiating with UV rays, The photoelectrode side transparent substrate and the counter electrode side substrate are joined to each other (paragraphs [0089] to [0091] in Patent Document 3).

  In Patent Document 3, when ultraviolet rays are irradiated from the counter electrode side substrate side, since the ultraviolet rays are blocked by the counter electrode on the counter electrode side substrate, the ultraviolet curable resin as the inner main seal and the outer main seal is cured. I can't. On the other hand, when ultraviolet rays are irradiated from the photoelectrode-side transparent substrate, there has been a problem that the sensitizing dye is deteriorated by the irradiation of ultraviolet rays and the conversion efficiency is lowered.

  Therefore, conventionally, there has been a problem that even if leakage of the electrolyte to the outside can be suppressed, high conversion efficiency cannot be realized.

  The embodiment disclosed herein is provided on a first substrate, a second substrate facing the first substrate with a space therebetween, a first conductive layer provided on the first substrate, and a first conductive layer. A photoelectric conversion layer, a porous insulating layer provided on the photoelectric conversion layer, a second conductive layer provided on the porous insulating layer, and a region between the first substrate and the second substrate. And an electrolyte disposed in a region surrounded by the first substrate, the second substrate, and the sealing material, the photoelectric conversion layer comprising a porous semiconductor layer, a porous material A photosensitizer provided on the semiconductor layer, and the second conductive layer is provided on the porous insulating layer so as to face the second substrate at a distance from the second substrate. The material includes a first sealing material and one or more second sealing materials provided outside the first sealing material. The first sealing material is ultraviolet A photoelectric conversion element comprising a cured resin.

  An embodiment disclosed herein includes a first substrate, a second substrate facing the first substrate with a space therebetween, and a plurality of photoelectric conversion cells electrically connected between the first substrate and the second substrate. Each of the plurality of photoelectric conversion cells includes a first conductive layer provided on the first substrate, a photoelectric conversion layer provided on the first conductive layer, and a photoelectric conversion A porous insulating layer provided on the layer, a second conductive layer provided on the porous insulating layer, and an electrolyte between the first substrate and the second substrate, wherein the photoelectric conversion layer is porous A semiconductor layer and a photosensitizer provided on the porous semiconductor layer are provided, and the second conductive layer is provided on the porous insulating layer so as to face the second substrate at a distance from the second substrate. The photoelectric conversion module includes a plurality of photoelectric conversion cells between the first substrate and the second substrate. Including a sealing material provided so as to surround the first sealing material and one or more second sealing materials provided outside the first sealing material, The first sealing material is a photoelectric conversion module containing an ultraviolet curable resin.

  The embodiment disclosed herein includes a step of forming a stacked body including a photoelectric conversion layer and a second conductive layer in this order on a first conductive layer on a first substrate, and a stacked body on the first substrate. A step of installing a first encapsulant precursor containing an ultraviolet curable resin so as to surround the substrate, and one or more second encapsulant precursors outside the first encapsulant precursor on the first substrate. A step of installing, a step of installing the second substrate on the first sealing material precursor and the second sealing material precursor so as to face the first substrate, and a first state in which the second substrate is installed. And a step of curing the first sealing material precursor by irradiating the sealing material precursor with ultraviolet rays from the second substrate side.

  According to the embodiment disclosed herein, leakage of the electrolyte to the outside can be suppressed, and high conversion efficiency can be realized.

2 is a schematic cross-sectional view of the photoelectric conversion element of Embodiment 1. FIG. 2 is a flowchart of an example of a method for manufacturing the photoelectric conversion element of Embodiment 1. FIG. 3 is a schematic cross-sectional view illustrating a part of the manufacturing process of the example of the method for manufacturing the photoelectric conversion element according to the first embodiment. It is typical sectional drawing illustrating the case where the photoelectric conversion element of the structure where the 2nd conductive layer facing a 1st board | substrate was provided in contact with the 2nd board | substrate was produced. 6 is a schematic cross-sectional view of a photoelectric conversion element according to Embodiment 2. FIG. 6 is a schematic cross-sectional view of a photoelectric conversion element according to Embodiment 3. FIG. 6 is a schematic cross-sectional view of a photoelectric conversion module according to Embodiment 4. FIG. 10 is a schematic cross-sectional view of a photoelectric conversion module of Example 8. FIG. 6 is a schematic cross-sectional view of a photoelectric conversion element of Comparative Example 2. FIG.

  Hereinafter, embodiments will be described. In the drawings used to describe the embodiments, the same reference numerals represent the same or corresponding parts.

[Embodiment 1]
<Structure of photoelectric conversion element>
FIG. 1 is a schematic cross-sectional view of the photoelectric conversion element of Embodiment 1. The photoelectric conversion element of Embodiment 1 includes a first substrate 1, a first conductive layer 3 provided on the first substrate 1, a photoelectric conversion layer 4 provided on the first conductive layer 3, and a photoelectric conversion layer. 4, the porous insulating layer 12 provided on the porous insulating layer 12, the catalyst layer 10 provided on the porous insulating layer 12, the second conductive layer 5 provided on the catalyst layer 10, and the distance between the second conductive layer 5. And a second substrate 2 provided so as to face the second conductive layer 5.

  The first substrate 1 and the second substrate 2 are joined by a sealing material 41, and the electrolyte 6 is disposed in a region surrounded by the first substrate 1, the second substrate 2, and the sealing material 41. . The sealing material 41 includes an inner first sealing material 7 and a second sealing material 8 outside the first sealing material 7.

  The first conductive layer 3 is formed with a strip-shaped dividing groove 13 extending so as to divide the first conductive layer 3, and the dividing groove 13 is filled with the porous insulating layer 12 to divide the first conductive layer 3. The conductive layers 3 are electrically insulated from each other by the porous insulating layer 12.

  The photoelectric conversion layer 4 is based on the porous semiconductor layer 14 provided on the first conductive layer 3, and a photosensitizer (not shown) is formed on the surface of the porous semiconductor layer 14 inside and outside the hole. It is comprised by installing.

  One end of the second conductive layer 5 is electrically connected to the first conductive layer 3 on the left side of the first conductive layer 3 divided into the right side and the left side in FIG. The other end of the second conductive layer 5 is electrically connected to the catalyst layer 10.

  The sealing material 41 is provided on the first conductive layer 3 on the first substrate 1, and the first substrate 1 and the second substrate 2 are bonded by bonding the first conductive layer 3 and the second substrate 2. Are joined.

  In FIG. 1, the electrolyte 6 is illustrated as being disposed only in a region between the second substrate 2 and the second conductive layer 5. However, in Embodiment 1, since the second conductive layer 5, the catalyst layer 10, the porous insulating layer 12, and the photoelectric conversion layer 4 each have a plurality of holes, the electrolyte 6 includes the second conductive layer 5, The catalyst layer 10, the porous insulating layer 12, and the photoelectric conversion layer 4 are also present inside the plurality of holes.

<Method for producing photoelectric conversion element>
In FIG. 2, the flowchart of an example of the manufacturing method of the photoelectric conversion element of Embodiment 1 is shown. As shown in FIG. 2, the manufacturing method of the photoelectric conversion element of Embodiment 1 includes a first conductive layer forming step (S10), a porous semiconductor layer forming step (S20), and a porous insulating layer forming step. (S30), catalyst layer formation step (S40), second conductive layer formation step (S50), photosensitizer installation step (S60), and first sealing material precursor installation step ( S70), a second sealing material precursor installation step (S80), a second substrate installation step (S90), an ultraviolet irradiation step (S100), and an electrolyte injection step (S110). S10, S20, S30, S40, S50, S60, S70, S80, S90, S100 and S110 are performed in this order. In addition, it cannot be overemphasized that the process other than S10-S110 may be included in the manufacturing method of the photoelectric conversion element of Embodiment 1, and the order of a process is not limited to the order of the process demonstrated below.

(First conductive layer forming step)
The step of forming the first conductive layer (S10) can be performed by forming the first conductive layer 3 on the first substrate 1. As a method of forming the first conductive layer 3, for example, a method such as a sputtering method or a spray method can be used. Further, a substrate in which the first conductive layer 3 is previously provided on the first substrate 1 may be prepared.

  As the first substrate 1, for example, a translucent substrate having translucency can be used. For example, the first substrate 1 is formed of a material that substantially transmits light having a wavelength having effective sensitivity to a sensitizing dye described later. It is not necessary to have translucency with respect to light in all wavelength regions. It is preferable that the thickness of the 1st board | substrate 1 is 0.2 mm or more and 5 mm or less.

  As the first substrate 1, for example, a glass substrate such as soda glass, fused silica glass or crystalline quartz glass, or a heat resistant resin plate such as a flexible film can be used.

The first conductive layer 3 is not particularly limited as long as it has conductivity and translucency, for example, indium tin composite oxide (ITO), tin oxide (SnO ₂ ), tin oxide doped with fluorine. At least one selected from the group consisting of prepared (FTO) and zinc oxide (ZnO) can be used.

  The thickness of the first conductive layer 3 is preferably 0.02 μm or more and 5 μm or less. The electric resistance of the first conductive layer 3 is preferably as low as possible, and is preferably 40Ω / □ or less.

(Porous semiconductor layer formation process)
The step of forming the porous semiconductor layer (S20) can be performed by forming the porous semiconductor layer 14 on the first conductive layer 3. The method for forming the porous semiconductor layer 14 is not particularly limited, and for example, a conventionally known method can be used. For example, a method of applying a suspension containing the above-described semiconductor fine particles on the first conductive layer 3 and performing at least one of drying and baking can be used.

The porous semiconductor layer 14 is not particularly limited as long as it is generally used for photoelectric conversion materials. For example, titanium oxide, zinc oxide, tin oxide, iron oxide, niobium oxide, cerium oxide, tungsten oxide, titanate Use of at least one selected from the group consisting of barium, strontium titanate, cadmium sulfide, lead sulfide, zinc sulfide, indium phosphide, copper-indium sulfide (CuInS ₂ ), CuAlO ₂ and SrCu ₂ O ₂ Among them, it is preferable to use titanium oxide from the viewpoint of high stability.

Although the thickness of the porous semiconductor layer 14 is not specifically limited, For example, it can be 0.1 micrometer or more and 100 micrometers or less. The surface area of the porous semiconductor layer 14 is preferably 10 m ² / g or more and 200 m ² / g or less.

(Porous insulating layer formation process)
The step of forming the porous insulating layer (S30) can be performed by forming the porous insulating layer 12 on the porous semiconductor layer. Although the formation method of the porous insulating layer 12 is not specifically limited, For example, it can form by the method similar to said porous semiconductor layer 14. FIG.

  As the porous insulating layer 12, for example, at least one selected from the group consisting of silicon oxide such as titanium oxide, niobium oxide, zirconium oxide, silica glass or soda glass, aluminum oxide, and barium titanate can be used. .

(Catalyst layer formation process)
The catalyst layer forming step (S <b> 40) can be performed by forming the catalyst layer 10 on the porous insulating layer 12. As the catalyst layer 10, for example, at least one selected from the group consisting of platinum, carbon black, ketjen black, carbon nanotube, and fullerene can be used.

  The formation method of the catalyst layer 10 is not specifically limited, For example, a conventionally well-known method can be used. When platinum is used as the catalyst layer 10, as a method for forming the catalyst layer 10, for example, a method such as sputtering, thermal decomposition or electrodeposition of chloroplatinic acid can be used. Further, when carbon such as carbon black, ketjen black, carbon nanotube, and fullerene is used as the catalyst layer 10, the catalyst layer 10 may be formed by, for example, a screen printing method using a paste in which carbon is dispersed in a solvent. The method etc. which apply | coat to the porous insulating layer 12 using etc. can be used.

(Second conductive layer forming step)
In the second conductive layer forming step (S50), one end of the second conductive layer 5 is electrically connected to the first conductive layer 3, and the other end is electrically connected to the catalyst layer 10. This can be done by forming the second conductive layer 5. Although the formation method of the 2nd conductive layer 5 is not specifically limited, For example, methods, such as a sputtering method or a spray method, can be used.

  A material that does not transmit ultraviolet rays is used for the second conductive layer 5. As the material that does not transmit ultraviolet rays, a material that does not transmit at least part of ultraviolet rays, preferably a material that does not transmit all of ultraviolet rays, is used. As a material that does not transmit at least a part of ultraviolet rays, preferably a material that does not transmit all of ultraviolet rays, a metal material including at least one selected from the group consisting of titanium, tungsten, gold, silver, copper, aluminum and nickel, etc. Is mentioned. In addition, ultraviolet rays are electromagnetic waves with a wavelength of 1 nm or more and 400 nm or less.

  The thickness of the second conductive layer 5 is preferably 0.02 μm or more and 5 μm or less. The electrical resistance of the second conductive layer 5 is preferably as low as possible, and is preferably 40Ω / □ or less.

(Installation process of photosensitizer)
The installation step (S60) of the photosensitizer can be performed, for example, by installing a photosensitizer on the porous semiconductor layer 14. As the photosensitizer, for example, a sensitizing dye such as an organic dye and a metal complex dye can be used. By adsorbing the sensitizing dye to the porous semiconductor layer 14, the photosensitization is performed on the porous semiconductor layer 14. The photoelectric conversion layer 4 in which an agent is installed can be formed.

  As a method of adsorbing the sensitizing dye to the porous semiconductor layer 14, for example, a method of immersing the porous semiconductor layer 14 in a dye adsorbing solution in which the sensitizing dye is dissolved can be used. When the porous semiconductor layer 14 is immersed in the dye adsorption solution in which the sensitizing dye is dissolved, the dye adsorption solution is used to penetrate the interior of the pores of the porous semiconductor layer 14. You may heat.

  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. In addition, at least one selected from the group consisting of perylene dyes, indigo dyes, and naphthalocyanine dyes can be used. In general, the extinction coefficient of an organic dye is larger than the extinction coefficient of a metal complex dye in which a molecule is coordinated to a transition metal.

  In addition, the metal complex dye is constituted by a metal coordinated to a molecule. Examples of the molecule include porphyrin dyes, phthalocyanine dyes, naphthalocyanine dyes, ruthenium dyes, and the like. Examples of the metal include Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb, La, W, Pt, TA, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Te and Rh The at least 1 sort (s) selected from these can be mentioned. Among these, as the metal complex dye, it is preferable to use a phthalocyanine dye or a ruthenium dye with a metal coordinated, and it is particularly preferable to use a ruthenium metal complex dye.

  As the ruthenium-based metal complex dye, for example, a commercially available ruthenium-based metal complex dye such as a trade name Ruthenium 535 dye, Ruthenium 535-bisTBA dye, or Ruthenium 620-1H3TBA dye manufactured by Solaronix can be used.

(Installation process of first sealing material precursor)
The installation process (S70) of a 1st sealing material precursor can be performed by apply | coating the 1st sealing material precursor containing the ultraviolet curable resin before hardening. In addition, a 1st sealing material precursor is a material used as the 1st sealing material 7 by the ultraviolet irradiation in the below-mentioned ultraviolet irradiation process (S100). The method for applying the first sealing material precursor is not particularly limited. For example, using a dispenser, the porous semiconductor layer 14, the porous insulating layer 12, the catalyst layer 10, and the second conductive layer 5 stacked as described above are used. It can apply | coat on the 1st conductive layer 3 so that a laminated body may be surrounded.

  The ultraviolet curable resin contained in the first encapsulant precursor is not particularly limited as long as it is a resin that is cured by ultraviolet irradiation described later, but the first encapsulant 7 is in contact with the electrolyte 6, so It is preferable to use a material in which one sealing material 7 does not chemically react with the electrolyte 6. As a material in which the first sealing material 7 after curing hardly reacts chemically with the electrolyte 6, it is preferable to use at least one of a radical resin or a cationic resin, and an acrylic resin which is a kind of radical resin. It is more preferable to use an ultraviolet curable resin containing a resin.

  The radical resin is a resin that is cured by radical polymerization (chain polymerization using free radicals as growth active species) or a cured resin. The cationic resin is a resin that cures or cures through cationic polymerization (chain polymerization using a cation as a growth active species). An acrylic resin is a kind of radical resin, and is a resin containing an acrylic resin such as a methacrylic resin as a main component (50% by mass or more of the entire acrylic resin). Including state.

(Installation process of second sealing material precursor)
The installation process (S80) of the second sealing material precursor can be performed by applying the second sealing material precursor to the outside of the first sealing material precursor. In addition, a 2nd sealing material precursor is a material used as the 2nd sealing material 8 by hardening of a 2nd sealing material precursor. The method for applying the second sealing material precursor is not particularly limited, but it can be applied on the first conductive layer 3 so as to surround the first sealing material precursor using, for example, a dispenser.

  The second sealing material precursor is not particularly limited as long as it is a material that can form the second sealing material 8 by curing because the curing method is not particularly limited. However, since the second sealing material 8 after the curing of the second sealing material precursor is in contact with the atmosphere, the second sealing material precursor has low permeability such as moisture or oxygen, and the first conductive layer 3 It is preferable to use a resin having high adhesiveness with the second substrate 2. Examples of such a resin include a resin containing at least one selected from the group consisting of epoxy resins, silicone resins, fluorine resins, hot melt resins, radical resins, cationic resins, and olefin resins. It is preferable to use it.

  The epoxy resin is a resin that is cured by an epoxy group ring-opening reaction. The silicone resin is a resin having a repeating unit of silicon having an organic group and oxygen as a main skeleton. A fluorine-based resin is a resin containing fluorine. The hot melt resin is a resin that is solid at normal temperature (25 ° C.) and melts by heating. For example, synthetic rubber resin, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, ethylene-propylene copolymer Examples include coalesced and linear polyester. The olefin resin is a resin obtained by polymerizing ethylene hydrocarbon. In the present specification, the first sealing material precursor and the second sealing material precursor each mean a resin before curing, and the first sealing material and the second sealing material are respectively , Meaning a cured resin.

  Moreover, when producing a photoelectric conversion element by hardening a 2nd sealing material precursor with a 1st sealing material precursor by the ultraviolet irradiation in the below-mentioned ultraviolet irradiation process (S100), a photoelectric conversion element is made efficient. Therefore, it is preferable that the second sealing material precursor contains an ultraviolet curable resin.

  As the ultraviolet curable resin contained in the second sealing material precursor, it is preferable to use at least one of a radical resin or a cationic resin, as in the case of the first sealing material precursor. It is more preferable to use a certain acrylic resin.

  Since the second sealing material 8 is not limited to one and may be two or more, when two or more second sealing materials 8 are formed, the first sealing material precursor is surrounded. Two or more second sealing material precursors can be applied to the substrate. When applying a second or more second encapsulant precursor, at least one different type of material may be applied as the second encapsulant precursor, and all the same type of material may be applied. It may be applied.

(Installation process of the second substrate)
The second substrate placement step (S90) can be performed by placing the second substrate 2 on the first sealing material precursor and the second sealing material precursor so as to face the first substrate 1. it can.

  As the second substrate 2, a material capable of sealing the electrolyte 6 and transmitting at least a part, preferably all of the ultraviolet rays is used. As such a material, for example, a substrate made of ordinary glass or the like can be used, and among these, it is preferable to use a substrate made of acrylic glass. When a substrate made of acrylic glass is used, the photoelectric conversion element of Embodiment 1 can be reduced in weight.

Acrylic glass is a transparent solid material of polymethyl methacrylate resin.
(UV irradiation process)
In the ultraviolet irradiation step (S100), for example, as shown in the schematic cross-sectional view of FIG. 3, the first sealing material made of an uncured ultraviolet curable resin bonding the first substrate 1 and the second substrate 2 together. This can be performed by irradiating the precursor 7a with ultraviolet rays 11 from the second substrate 2 side. Thereby, the 1st sealing material 7 is hardened by hardening the 1st sealing material precursor 7a containing uncured ultraviolet curing resin installed at the above-mentioned installation process (S70) of the 1st sealing material precursor. It is formed.

  In the case where the second sealing material precursor 8a contains an ultraviolet curable resin, in this step, by irradiating the second sealing material precursor 8a with the ultraviolet light 11 together with the first sealing material precursor 7a, The second sealing material 8 can be formed together with the first sealing material 7. Moreover, when the 2nd sealing material precursor 8a contains a thermosetting resin, the 2nd sealing material precursor 8a is heated locally after hardening of the 1st sealing material precursor 7a by irradiation of the ultraviolet-ray 11. FIG. Thus, the second sealing material 8 can be formed by curing.

  As described above, the first sealing material precursor 7a and the second sealing material precursor 8a are cured to form the first sealing material 7 and the second sealing material 8, respectively. A sealing material 41 composed of the material 7 and the second sealing material 8 can be formed.

(Electrolyte injection process)
The electrolyte injection step (S110) can be performed by injecting the electrolyte 6 into the space partitioned by the sealing material 41 between the first substrate 1 and the second substrate 2, for example, the second substrate 2. An injection method for injecting the electrolyte 6 into the hole and injecting the electrolyte 6 from the hole can be performed. Alternatively, the second substrate 2 may be provided by an ODF method in which the second substrate 2 is not provided with a hole for injecting the electrolyte 6 but the electrolyte 6 is injected before the second substrate 2 is installed. As described above, the photoelectric conversion element of Embodiment 1 can be manufactured.

  As the electrolyte 6, an electrolyte having at least fluidity can be used. For example, a liquid electrolyte such as an electrolytic solution can be preferably used. The liquid electrolyte may be a liquid material containing redox species. For example, a liquid electrolyte composed of a redox species and a solvent capable of dissolving the redox species can be used.

As the redox species, for example, I ⁻ / I ³⁻ series, Br ²⁻ / Br ³⁻ series, Fe 2 ⁺ / Fe ³⁺ series, quinone / hydroquinone series and the like can be used. More specifically, examples of the redox species include metal iodides such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI ₂ ), and iodine (I ₂ ) Can be used. Also, use a combination of tetraalkylammonium salt such as tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), tetrahexylammonium iodide (THAI) and iodine. You can also. Further, a combination of a metal bromide such as lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), calcium bromide (CaBr ₂ ) and bromine can be used. Among these, it is particularly preferable to use a combination of LiI and I ₂ as the redox species.

  As the solvent for the redox species, for example, a solvent containing at least one selected from the group consisting of carbonate compounds such as propylene carbonate, nitrile compounds such as acetonitrile, alcohols such as ethanol, water, and aprotic polar substances is used. Among them, it is more preferable to use a carbonate compound or a nitrile compound alone or in combination.

<Effect>
As a result of intensive studies by the present inventor, when a thermosetting resin is used as the sealing material as described in Patent Document 2, the photosensitizer of the photoelectric conversion layer is heated by heating when the thermosetting resin is cured. It has been found that the conversion efficiency of the photoelectric conversion element decreases. As thermal degradation of the photosensitizer, for example, oxidation of the ligand, elimination and / or substitution of the ligand, or isomerization reaction and / or addition reaction of the ligand may occur.

  Then, this inventor examined using an ultraviolet curable resin instead of a thermosetting resin like patent document 3, for example. This is because when the ultraviolet curable resin is used, it is not necessary to heat the photosensitizer of the photoelectric conversion layer at the time of producing the sealing material, and it is thought that the decrease in the conversion efficiency of the photoelectric conversion element can be suppressed.

  As a result, as shown in the schematic cross-sectional view of FIG. 4, the second conductive layer 5 is in contact with the surface of the second substrate 2 so as to face the first conductive layer 3 with a space from the first conductive layer 3. When the photoelectric conversion element having the structure provided as described above is manufactured, it is necessary to cure the first sealing material precursor 7a made of the ultraviolet curable resin by irradiating the ultraviolet rays 11 from the first substrate 1 side. It was. For this reason, it has been found that the photosensitizer is deteriorated by irradiating the photosensitizer in the photoelectric conversion layer 4 with the ultraviolet rays 11, and the conversion efficiency of the photoelectric conversion element is also lowered in this case. As the deterioration of the photosensitizer due to ultraviolet irradiation, for example, oxidation of the ligand, elimination and / or substitution of the ligand, or isomerization reaction and / or addition reaction of the ligand may occur.

  Therefore, as a result of further intensive studies by the inventor, as shown in FIG. 3, the first sealing material is irradiated by irradiating the first sealing material precursor 7a with ultraviolet rays 11 from the second substrate 2 side. By adopting a structure in which the precursor 7a can be cured and the ultraviolet ray 11 incident on the photoelectric conversion layer 4 can be blocked by the second conductive layer 5, the irradiation of the ultraviolet ray 11 compared with the case of the conventional Patent Document 3. It has been found that deterioration of the photosensitizer in the photoelectric conversion layer 4 due to can be suppressed.

  Thereby, in Embodiment 1, since deterioration of a photosensitizer can be suppressed compared with the conventional patent document 2 and patent document 3, the conversion efficiency of a photoelectric conversion element can be improved.

  Furthermore, in the first embodiment, since one or more second sealing materials 8 are installed outside the first sealing material 7, leakage of the electrolyte 6 can also be suppressed.

[Embodiment 2]
FIG. 5 is a schematic cross-sectional view of the photoelectric conversion element of the second embodiment. The photoelectric conversion element of Embodiment 2 is characterized by including two second sealing materials 8. In the second embodiment, the second sealing material 8 includes an inner second sealing material 81 on the first sealing material 7 side and an outer second sealing material 82 on the outer side of the second sealing material 81a. Yes. The photoelectric conversion element of Embodiment 2 can further suppress leakage of the electrolyte 6 as compared with Embodiment 1 because the sealing material 41 is triple. Note that the number of sealing materials constituting the sealing material 41 is not particularly limited as long as it is two or more, and may be three as in the second embodiment, or may be four or more.

  Since the description other than the above in Embodiment 2 is the same as that in Embodiment 1, the description thereof will not be repeated.

[Embodiment 3]
FIG. 6 shows a schematic cross-sectional view of the photoelectric conversion element of the third embodiment. The photoelectric conversion element of Embodiment 3 includes a second substrate 21 made of acrylic glass. Since the photoelectric conversion element of Embodiment 3 uses the second substrate 21 made of acrylic glass, the photoelectric conversion element can be reduced in weight.

  Since the description other than the above in Embodiment 3 is the same as in Embodiments 1 and 2, the description thereof will not be repeated.

[Embodiment 4]
FIG. 7 is a schematic cross-sectional view of the photoelectric conversion module according to the fourth embodiment. The photoelectric conversion module of Embodiment 4 includes a plurality of photoelectric conversion cells 51a, 51b, and 51c. The photoelectric conversion cells 51 a, 51 b, 51 c are partitioned into individual cells by the first sealing material 7. The plurality of photoelectric conversion cells 51a, 51b, 51c are respectively provided on the first substrate 1 with the first conductive layer 3, the photoelectric conversion layer 4, the porous insulating layer 12, the catalyst layer 10, and the second conductive layer. 5 and an electrolyte 6 in a space surrounded by the first substrate 1, the second substrate 2 and the first sealing material 7.

  Moreover, the photoelectric conversion cell 51a and the photoelectric conversion cell 51b are electrically connected in series by electrically connecting the first conductive layer 3 of the photoelectric conversion cell 51a and the second conductive layer 5 of the photoelectric conversion cell 51b. Has been. Moreover, the photoelectric conversion cell 51b and the photoelectric conversion cell 51c are electrically connected in series by electrically connecting the first conductive layer 3 of the photoelectric conversion cell 51b and the second conductive layer 5 of the photoelectric conversion cell 51c. It is connected. Note that the photoelectric conversion cells 51a, 51b, and 51c can be electrically connected in parallel. Thereby, the photoelectric conversion cells 51a, 51b, 51c are connected in series. In addition, the outer periphery of the photoelectric conversion cells 51a, 51b, 51c that are electrically connected in series or in parallel in the region between the first substrate 1 and the second substrate 2 is the first sealing material 7 and the second substrate 2. It is surrounded by a double sealing material 41 with two sealing materials 8.

  Since the description other than the above in Embodiment 4 is the same as that in Embodiments 1 to 3, the description thereof will not be repeated.

<Example 1>
A photoelectric conversion element of Example 1 having the structure shown in FIG. 1 was produced according to the flowchart shown in FIG.

(Formation of first conductive layer)
First, a glass substrate with SnO ₂ film manufactured by Nippon Sheet Glass Co., Ltd. having a surface with a length of 120 mm × width of 420 mm is prepared, and SnO 2 is linearly formed along a direction perpendicular to the series connection direction by a laser scribing method. _Two films were removed. Thus, the dividing groove 13 is removed portion of the SnO ₂ film is formed in stripes, on a glass substrate as the first substrate 1, and the SnO ₂ film as the first conductive layer 3 is formed in a stripe shape.

(Formation of porous semiconductor layer)
Next, using a screen printing machine (LS-34TVA manufactured by Neurong Seimitsu Kogyo Co., Ltd.), a commercially available titanium oxide paste (manufactured by Solaronix, trade name: Ti-Nanoxide D / SP, average particle size: 13 nm) between the scribe lines. It was applied on SnO ₂ film located.

  Next, the coating film obtained by leveling the titanium oxide paste at room temperature for 1 hour was pre-dried at 80 ° C. for 20 minutes, and baked at 450 ° C. for 1 hour. The porous semiconductor layer 14 made of titanium oxide having a thickness of 30 μm was formed by repeating the coating process, the leveling process, the preliminary drying process, and the firing process in this order.

(Formation of porous insulation layer)
Next, a paste containing fine particles of zirconium oxide having a particle size of 100 nm (manufactured by CI Kasei Co., Ltd.) was prepared in the same manner as described above. The prepared paste was applied onto the porous semiconductor layer 14 using the screen plate used for the production of the porous semiconductor layer 14 and a screen printing machine (LS-34TVA manufactured by Neurong Seimitsu Kogyo). After leveling at room temperature for 1 hour, it was pre-dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour. By this step, the porous insulating layer 12 having a thickness of 5 μm was formed on the porous semiconductor layer 14.

(Catalyst layer formation)
Next, from a platinum film having a thickness of 5 nm on the porous insulating layer 12 by depositing platinum at an evaporation rate of 0.1 Å / S using an electron beam evaporator EVD-500A (manufactured by ANELVA). A catalyst layer 10 was formed.

(Formation of second conductive layer)
Next, using an electron beam evaporator EVD-500A (manufactured by ANELVA), titanium (Ti) is vapor-deposited at a vapor deposition rate of 0.1 Å / S to form a 2 μm thick Ti film on the catalyst layer 10. A second conductive layer 5 made of was formed.

(Installation of photosensitizer)
Next, as a sensitizing dye, Ruthenium 620-1H3TBA dye (manufactured by Solaronix) represented by the following structural formula (i) was used, and acetonitrile (manufactured by Aldrich Chemical Company) / t-butyl alcohol (manufactured by Aldrich Chemical Company) A 1: 1 solution (concentration of sensitizing dye; 4 × 10 ⁻⁴ mol / liter) was prepared. The porous semiconductor layer 14 was immersed in this solution and allowed to stand for 20 hours under a temperature condition of 40 ° C. Thereafter, the porous semiconductor layer 14 was washed with ethanol (manufactured by Aldrich Chemical Company) and then dried. In this manner, the photoelectric conversion layer 4 was formed on the first conductive layer 3 by adsorbing the sensitizing dye to the porous semiconductor layer 14. In the structural formula (i), “TBA” represents tetrabutylammonium.

(Installation of first sealing material)
Next, as the precursor 7a of the first sealing material 7, the porous semiconductor layer 14, the porous insulating layer 12, the catalyst layer 10 and the first laminated layer of the ultraviolet curable resin (TB3035B (manufactured by ThreeBond)) as described above are used. It apply | coated on the 1st conductive layer 3 so that the laminated body of 2 conductive layers 5 might be surrounded.

(Installation of second sealing material)
Next, as the precursor 8 a of the second sealing material 8, an ultraviolet curable resin (TB3118 (manufactured by ThreeBond)) is applied on the first conductive layer 3 so as to surround the precursor 7 a of the first sealing material 7. did.

(Installation of second substrate)
Next, the second substrate 2 which is a glass substrate is placed on the surfaces of the first sealing material precursor 7a and the second sealing material precursor 8a so as to face the first substrate 1, and the first substrate 1 and the 2nd board | substrate 2 were bonded together.

(UV irradiation)
Next, as shown in FIG. 3, ultraviolet rays 11 are applied to the first sealing material precursor 7 a and the second sealing material precursor 8 a that are bonded to the first substrate 1 and the second substrate 2. By irradiating from the side, the first sealing material precursor 7a and the second sealing material precursor 8a are cured, respectively, and the sealing composed of the first sealing material 7 and the second sealing material 8 A material 41 was formed. Thereby, the 1st board | substrate 1 and the 2nd board | substrate 2 were joined by the sealing material 41. FIG.

(Injection of electrolyte)
Next, as the electrolyte 6, acetonitrile is used as a solvent, and 1,2-dimethyl-3-propylimidazolium iodide (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is used therein. 0.6 mol / liter, LiI (manufactured by Aldrich Chemical Company) 0.1 mol / liter, 4-tert-butylpyridine (4-tert-butylpyridine (manufactured by Aldrich Chemical Company)) 0.5 mol / liter, I _{2 A} redox electrolyte solution in which 0.01 mol / liter (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was prepared. Then, the electrolyte 6 was injected into the space partitioned by the sealing material 41 between the first substrate 1 and the second substrate 2 from the hole for injecting the electrolyte 6 provided in advance in the second substrate 2. The photoelectric conversion element of Example 1 was produced by the above.

<Example 2>
A photoelectric conversion element of Example 2 was produced in the same manner as Example 1 except that UM (ultraviolet curable resin) manufactured by Nichiban Co., Ltd. was used as the first sealing material precursor 7a.

<Example 3>
A photoelectric conversion element of Example 3 was produced in the same manner as Example 1 except that Photolec (ultraviolet curable resin) manufactured by Sekisui Chemical Co., Ltd. was used as the second sealing material precursor 8a.

<Example 4>
A photoelectric conversion element of Example 4 having the structure shown in FIG. 5 was produced. The photoelectric conversion element of Example 4 was further coated with a hot-melt silicone resin (thermosetting resin) manufactured by Toray Dow Corning Co., which was preheated so as to surround the double-coated ultraviolet curable resin, and returned to room temperature. This was prepared in the same manner as in Example 1 except that it was cured.

<Example 5>
A photoelectric conversion element of Example 5 having the structure shown in FIG. 6 was produced. That is, the photoelectric conversion element of Example 5 was produced in the same manner as Example 1 except that the substrate 21 made of acrylic glass was used instead of the second substrate 2.

<Example 6>
A photoelectric conversion module of Example 6 in which a plurality of photoelectric conversion cells 51a, 51b, 51c having the structure shown in FIG. 7 were electrically connected in series was produced.

<Example 7>
A photoelectric conversion module of Example 7 was produced in the same manner as Example 1 except that the electrolyte 6 was injected by the ODF method. Specifically, after forming the first conductive layer 3, the photoelectric conversion layer 4, the porous insulating layer 12, and the catalyst layer 10 on the first substrate 1, the photoelectric conversion layer 4, the porous insulating layer 12, and the catalyst layer. The first sealing material precursor 7a is applied so as to surround the laminated body of the first conductive material 5 and the second conductive layer 5, and then the second sealing material precursor 8a is surrounded so as to surround the first sealing material precursor 7a. Applied. The electrolyte 6 is injected into a region surrounded by the first sealing material precursor 7a, and then the second substrate 2 is bonded and irradiated with ultraviolet rays from the second substrate 2 side, whereby the first sealing material precursor 7a. And the 2nd sealing material precursor 8a was hardened, respectively, and the sealing material 41 which consists of the 1st sealing material 7 and the 2nd sealing material 8 was formed. Thereby, the 1st board | substrate 1 and the 2nd board | substrate 2 were joined by the sealing material 41, and the photoelectric conversion element of Example 7 was produced.

<Example 8>
A photoelectric conversion module of Example 8 in which a plurality of photoelectric conversion cells 51a, 51b, 51c, 51d having the structure shown in FIG. 8 were electrically connected in parallel was produced. Specifically, the second conductive layer 5 of the adjacent photoelectric conversion cells 51a and 51b is provided as a continuous member, and the first conductive layer 3 of the adjacent photoelectric conversion cells 51b and 51c is provided as a continuous member. The second conductive layer 5 of the adjacent photoelectric conversion cells 51c and 51d is provided as a continuous member. The second conductive layers 5 of all the photoelectric conversion cells are electrically connected to the first sealing material 7 disposed between the photoelectric conversion cells 51a and 51b and between the photoelectric conversion cells 51c and 51d. Current collector electrode 9 is provided, and first conductive layer 3 of all the photoelectric conversion cells is electrically connected to first sealing material 7 disposed between photoelectric conversion cells 51b and 51c. A current collecting electrode 9 is provided.

<Comparative Example 1>
A photoelectric conversion element of Comparative Example 1 was produced in the same manner as Example 1 except that the second sealing material 9 was not formed.

<Comparative example 2>
A photoelectric conversion element of Comparative Example 2 having the structure shown in FIG. 9 was produced. In the photoelectric conversion element of Comparative Example 2, the second conductive layer 5 facing the first conductive layer 3 with a space therebetween is provided in contact with the surface of the second substrate 2, and the porous insulating layer 12 and the catalyst layer 10 are not provided. This was prepared in the same manner as in Example 1 except that. Moreover, as shown in FIG. 4, the photoelectric conversion element of the comparative example 2 irradiates the ultraviolet-ray 11 from the 1st board | substrate 1 side, respectively, and makes 1st sealing material precursor 7a and 2nd sealing material precursor 8a each. Made by curing.

<Comparative Example 3>
A photoelectric conversion element of Comparative Example 3 was produced in the same manner as Comparative Example 2 except that the second sealing material 8 was not formed.

<Evaluation>
The photoelectric conversion elements of Examples 1 to 5 and 7 and Comparative Examples 1 to 3 and the photoelectric conversion modules of Examples 6 and 8 produced as described above were 1 mW / cm ² . Conversion efficiency [%] was measured by irradiating light of energy density (AM1.5 solar simulator). The results are shown in Table 1.

  In addition, each of the photoelectric conversion elements of Examples 1 to 5 and 7 and Comparative Examples 1 to 3 and the photoelectric conversion modules of Examples 6 and 8 after the measurement of the conversion efficiency is 85 ° C. After being installed in the constant temperature bath for 1000 hours, the presence or absence of leakage of the electrolyte 6 was visually confirmed. The results are shown in Table 1.

  In the entire column of the structure in Table 1, “element” means a structure in which only one photoelectric conversion cell exists inside the sealing material 41 as shown in FIG. 1, FIG. 5, and FIG. , “Module” means a structure in which a plurality of photoelectric conversion cells exist inside the sealing material 41 as shown in FIG.

  Further, in the column of the electrode having the structure shown in Table 1, the “monolithic structure” indicates that the second conductive layer 5 is spaced apart from the second substrate 2 as shown in FIGS. 1, 5, 6, and 7. This means a structure formed on the catalyst layer 10 so as to face the two substrates 2, and the “sandwich structure” means to face the first conductive layer 3 with a gap as shown in FIG. This means a structure in which the second conductive layer 5 is provided in contact with the surface of the second substrate 2.

  In the column of electrolyte leakage in the evaluation of Table 1, “Yes” means that electrolyte leakage was confirmed, and “None” means that electrolyte leakage was not confirmed. ing.

  As shown in Table 1, the photoelectric conversion elements of Examples 1 to 5 and 7 and the photoelectric conversion modules of Examples 6 and 8 have higher conversion efficiency than the photoelectric conversion element of Comparative Example 2. confirmed. In Example 1 to Example 8, as shown in FIG. 3, the first sealing material precursor 7a and the second sealing material precursor 8a are irradiated by irradiating ultraviolet rays 11 from the second substrate 2 side. Each is cured. Thereby, in Example 1- Example 8, since the entrance to the photoelectric converting layer 4 of the ultraviolet-ray 11 was interrupted | blocked by the 2nd conductive layer 5, deterioration of the sensitizing dye in the photoelectric converting layer 4 could be suppressed. This is probably due to this. On the other hand, the reason why the conversion efficiency of the photoelectric conversion element of Comparative Example 2 is low is that ultraviolet rays 11 are irradiated from the first substrate 2 side as shown in FIG. This is considered to be because there was no member that blocks the deterioration of the sensitizing dye in the photoelectric conversion layer 4.

  Moreover, as shown in Table 1, in Examples 1 to 8, the electrolyte 6 is formed by a plurality of layers of the sealing material 41 including the first sealing material 7 and one or more second sealing materials 8. This is probably because the leakage of the electrolyte could be prevented as compared with Comparative Example 1 and Comparative Example 3 in which the electrolyte was sealed only by the single-layer sealing material.

[Appendix]
(1) An embodiment disclosed herein includes a first substrate, a second substrate facing the first substrate with a space therebetween, a first conductive layer provided on the first substrate, and a first conductive layer A photoelectric conversion layer provided on the substrate, a porous insulating layer provided on the photoelectric conversion layer, a second conductive layer provided on the porous insulating layer, and a region between the first substrate and the second substrate A sealing material provided so as to surround the substrate, and an electrolyte disposed in a region surrounded by the first substrate, the second substrate, and the sealing material, and the photoelectric conversion layer includes a porous semiconductor layer, And a photosensitizer provided on the porous semiconductor layer, and the second conductive layer is provided on the porous insulating layer so as to face the second substrate at a distance from the second substrate. The sealing material includes a first sealing material and one or more second sealing materials provided outside the first sealing material. A photoelectric conversion element comprising an ultraviolet curable resin. In the photoelectric conversion element having this configuration, the first sealing material precursor can be cured by irradiating the first sealing material precursor with ultraviolet light from the second substrate side, and the ultraviolet light incident on the photoelectric conversion layer. Can be blocked by the second conductive layer, so that deterioration of the photosensitizer in the photoelectric conversion layer due to irradiation of ultraviolet rays can be suppressed, and consequently, a decrease in conversion efficiency of the photoelectric conversion element can be suppressed. Moreover, since the 1 or more 2nd sealing material is installed in the outer side of the 1st sealing material, the leakage of electrolyte can also be suppressed.

  (2) It is preferable that the ultraviolet curable resin contained in the first sealing material contains at least one of a radical resin or a cationic resin. In this case, it becomes difficult for the first sealing material to chemically react with the electrolyte.

  (3) The second sealing material includes at least one selected from the group consisting of epoxy resins, silicone resins, fluorine resins, hot melt resins, radical resins, cationic resins, and olefin resins. It is preferable to include. In this case, the permeability of the second sealing material such as moisture or oxygen is reduced, and the adhesion between the first conductive layer and the second substrate can be increased. The bonding strength of can be increased.

  (4) The second sealing material preferably contains an ultraviolet curable resin. In this case, by irradiating the second sealing material precursor with ultraviolet light together with the first sealing material precursor, these can be cured to efficiently manufacture the photoelectric conversion element.

  (5) The ultraviolet curable resin contained in the second sealing material preferably contains at least one of a radical resin or a cationic resin. In this case, since the second sealing material is less likely to chemically react with the electrolyte, even if the electrolyte leaks from the first sealing material, the second sealing material is less likely to deteriorate due to a chemical reaction with the electrolyte. Therefore, leakage of the electrolyte can be further prevented.

  (6) It is preferable that the 2nd board | substrate contains the material which permeate | transmits an ultraviolet-ray. In this case, the first sealing material precursor can be cured by irradiating ultraviolet rays from the second substrate side.

  (7) The second conductive layer preferably includes a material that does not transmit ultraviolet light. In this case, even when the ultraviolet rays are irradiated from the second substrate side, the incidence of the ultraviolet rays to the photoelectric conversion layer can be suppressed, so that the deterioration of the photosensitizer in the photoelectric conversion layer is suppressed, and the photoelectric conversion element Conversion efficiency can be improved.

  (8) The second substrate preferably includes acrylic glass. In this case, ultraviolet rays can be irradiated from the second substrate side, and the photoelectric conversion element can be reduced in weight.

  (9) The embodiment disclosed herein includes a plurality of electrical connections between the first substrate, the second substrate facing the first substrate with a space therebetween, and the first substrate and the second substrate. A photoelectric conversion module comprising a photoelectric conversion cell, wherein the plurality of photoelectric conversion cells are respectively a first conductive layer provided on the first substrate, a photoelectric conversion layer provided on the first conductive layer, A porous insulating layer provided on the photoelectric conversion layer, a second conductive layer provided on the porous insulating layer, and an electrolyte between the first substrate and the second substrate, the photoelectric conversion layer comprising: A porous semiconductor layer and a photosensitizer provided on the porous semiconductor layer, and the second conductive layer is spaced apart from the second substrate and faces the second substrate so as to face the second substrate. The photoelectric conversion module is provided between the first substrate and the second substrate. The sealing material is provided so as to surround the replacement cell, and the sealing material includes a first sealing material and one or more second sealing materials provided outside the first sealing material. The first sealing material is a photoelectric conversion module including an ultraviolet curable resin. In the photoelectric conversion module having this configuration, the first sealing material precursor can be cured by irradiating the first sealing material precursor with the ultraviolet light from the second substrate side, and the ultraviolet light incident on the photoelectric conversion layer. Can be blocked by the second conductive layer, so that deterioration of the photosensitizer in the photoelectric conversion layer due to irradiation of ultraviolet rays can be suppressed, and consequently, a decrease in conversion efficiency of the photoelectric conversion element can be suppressed. Moreover, since the 1 or more 2nd sealing material is installed in the outer side of the 1st sealing material, the leakage of electrolyte can also be suppressed.

  (10) The ultraviolet curable resin contained in the first sealing material preferably contains at least one of a radical resin or a cationic resin. In this case, it becomes difficult for the first sealing material to chemically react with the electrolyte.

  (11) The second sealing material is at least one selected from the group consisting of epoxy resins, silicone resins, fluorine resins, hot melt resins, radical resins, cationic resins, and olefin resins. It is preferable to include. In this case, the permeability of the second sealing material such as moisture or oxygen is reduced, and the adhesion between the first conductive layer and the second substrate can be increased. The bonding strength of can be increased.

  (12) The second sealing material preferably contains an ultraviolet curable resin. In this case, by irradiating the second sealing material precursor with ultraviolet light together with the first sealing material precursor, these can be cured to efficiently manufacture the photoelectric conversion element module.

  (13) The ultraviolet curable resin contained in the second sealing material preferably contains at least one of a radical resin or a cationic resin. In this case, since the second sealing material is less likely to chemically react with the electrolyte, even if the electrolyte leaks from the first sealing material, the second sealing material is less likely to deteriorate due to a chemical reaction with the electrolyte. Therefore, leakage of the electrolyte can be further prevented.

  (14) The second substrate preferably includes a material that transmits ultraviolet light. In this case, the first sealing material precursor can be cured by irradiating ultraviolet rays from the second substrate side.

  (15) The second conductive layer preferably includes a material that does not transmit ultraviolet light. In this case, even when the ultraviolet rays are irradiated from the second substrate side, the incidence of the ultraviolet rays to the photoelectric conversion layer can be suppressed, so that the deterioration of the photosensitizer in the photoelectric conversion layer is suppressed and the photoelectric conversion module is suppressed. Conversion efficiency can be improved.

  (16) The second substrate preferably includes acrylic glass. In this case, it is possible to irradiate ultraviolet rays from the second substrate side, and it is also possible to reduce the weight of the photoelectric conversion module.

  (17) The plurality of photoelectric conversion cells include a first photoelectric conversion cell and a second photoelectric conversion cell adjacent to each other, the first conductive layer of the first photoelectric conversion cell, and the second photoelectric conversion cell. It is preferable that the second conductive layer is electrically connected. In this case, since the first photoelectric conversion cell and the second photoelectric conversion cell can be electrically connected in series, the conversion efficiency of the photoelectric conversion module can be improved. Alternatively, the first conductive layer of the first photoelectric conversion cell and the first conductive layer of the second photoelectric conversion cell are electrically connected, and the second conductive layer of the first photoelectric conversion cell and the second The second conductive layer of the photoelectric conversion cell may be electrically connected. In this case, since the first photoelectric conversion cell and the second photoelectric conversion cell can be electrically connected in parallel, the conversion efficiency of the photoelectric conversion module can be improved.

  (18) It is preferable that a first sealing material is further provided between the plurality of photoelectric conversion cells. In this case, together with the first sealing material that surrounds the entire outer periphery of the plurality of photoelectric conversion cells, the first sealing material that partitions the plurality of photoelectric conversion cells into individual cells is formed in the same process by ultraviolet irradiation. be able to.

  (19) In the embodiment disclosed herein, a step of forming a stacked body including a photoelectric conversion layer and a second conductive layer in this order on a first conductive layer on a first substrate; Installing a first encapsulant precursor containing an ultraviolet curable resin so as to surround the laminate, and at least one second encapsulant outside the first encapsulant precursor on the first substrate. A step of installing the precursor, a step of installing the second substrate on the first sealing material precursor and the second sealing material precursor so as to face the first substrate, and a state in which the second substrate is installed And a step of curing the first sealing material precursor by irradiating the first sealing material precursor with ultraviolet rays from the second substrate side. In the method for producing a photoelectric conversion element having this configuration, the first sealing material precursor can be cured by irradiating the first sealing material precursor with ultraviolet rays from the second substrate side, and the photoelectric conversion layer can be cured. Since the incident ultraviolet rays can be blocked by the second conductive layer, the deterioration of the photosensitizer in the photoelectric conversion layer due to the irradiation of ultraviolet rays can be suppressed, and thus the conversion efficiency of the photoelectric conversion element can be prevented from lowering. Moreover, since one or more 2nd sealing materials can be installed in the outer side of a 1st sealing material, the leakage of electrolyte can also be suppressed.

  (20) The ultraviolet curable resin contained in the first sealing material precursor preferably contains at least one of a radical resin or a cationic resin. In this case, it becomes difficult for the first sealing material to chemically react with the electrolyte.

  (21) The second sealing material is at least one selected from the group consisting of epoxy resins, silicone resins, fluorine resins, hot melt resins, radical resins, cationic resins, and olefin resins. It is preferable to include. In this case, the permeability of the second sealing material such as moisture or oxygen is reduced, and the adhesion between the first conductive layer and the second substrate can be increased. The bonding strength of can be increased.

  (22) The second sealing material preferably contains an ultraviolet curable resin. In this case, by irradiating the second sealing material precursor with ultraviolet light together with the first sealing material precursor, these can be cured to efficiently manufacture the photoelectric conversion element element.

  (23) The ultraviolet curable resin contained in the second sealing material preferably contains at least one of a radical resin or a cationic resin. In this case, since the second sealing material is less likely to chemically react with the electrolyte, even if the electrolyte leaks from the first sealing material, the second sealing material is less likely to deteriorate due to a chemical reaction with the electrolyte. Therefore, leakage of the electrolyte can be further prevented.

  (24) The second substrate preferably includes a material that transmits ultraviolet rays. In this case, the first sealing material precursor can be cured by irradiating ultraviolet rays from the second substrate side.

  (25) The second conductive layer preferably contains a material that does not transmit ultraviolet rays. In this case, even when the ultraviolet rays are irradiated from the second substrate side, the incidence of the ultraviolet rays to the photoelectric conversion layer can be suppressed, so that the deterioration of the photosensitizer in the photoelectric conversion layer is suppressed, and the photoelectric conversion element Conversion efficiency can be improved.

  (26) The second substrate preferably includes acrylic glass. In this case, ultraviolet rays can be irradiated from the second substrate side, and the photoelectric conversion element can be reduced in weight.

  Although the embodiments and examples have been described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  Embodiment disclosed here can be utilized for the manufacturing method of a photoelectric conversion element, a photoelectric conversion module, and a photoelectric conversion element, especially a dye-sensitized solar cell, a dye-sensitized solar cell module, and these manufacturing methods Can be suitably used.

  DESCRIPTION OF SYMBOLS 1 1st board | substrate, 2,21 2nd board | substrate, 3 1st conductive layer, 4 photoelectric conversion layer, 5 2nd conductive layer, 6 electrolyte, 7 1st sealing material, 7a 1st sealing material precursor, 8 1st 2 sealing material, 8a 2nd sealing material precursor, 10 catalyst layer, 11 ultraviolet ray, 12 porous insulating layer, 13 dividing groove, 14 porous semiconductor layer, 41 sealing material, 51a, 51b, 51c photoelectric conversion cell 81 Inside 2nd sealing material, 82 Outside 2nd sealing material.

Claims (5)

A first substrate;
A second substrate facing the first substrate at an interval;
A first conductive layer provided on the first substrate;
A photoelectric conversion layer provided on the first conductive layer;
A porous insulating layer provided on the photoelectric conversion layer;
A second conductive layer provided on the porous insulating layer;
A sealing material provided so as to surround a region between the first substrate and the second substrate;
An electrolyte disposed in the region surrounded by the first substrate, the second substrate, and the sealing material,
The photoelectric conversion layer includes a porous semiconductor layer and a photosensitizer provided in the porous semiconductor layer,
The second conductive layer is provided on the porous insulating layer so as to face the second substrate at a distance from the second substrate.
The sealing material includes a first sealing material and one or more second sealing materials provided outside the first sealing material,
Said first sealing member is seen containing an ultraviolet curable resin,
The second sealing material is a photoelectric conversion element including a thermosetting resin .   The photoelectric conversion element according to claim 1, wherein the second substrate includes a material that transmits ultraviolet light.   The photoelectric conversion element according to claim 1, wherein the second conductive layer includes a material that does not transmit ultraviolet light. A first substrate;
A second substrate facing the first substrate at an interval;
A photoelectric conversion module comprising a plurality of photoelectric conversion cells electrically connected between the first substrate and the second substrate,
Each of the plurality of photoelectric conversion cells includes a first conductive layer provided on the first substrate, a photoelectric conversion layer provided on the first conductive layer, and a porous provided on the photoelectric conversion layer. An insulating layer, a second conductive layer provided on the porous insulating layer, and an electrolyte between the first substrate and the second substrate,
The photoelectric conversion layer includes a porous semiconductor layer and a photosensitizer provided in the porous semiconductor layer,
The second conductive layer is provided on the porous insulating layer so as to face the second substrate at a distance from the second substrate.
The photoelectric conversion module includes a sealing material provided so as to surround the plurality of photoelectric conversion cells between the first substrate and the second substrate,
The sealing material includes a first sealing material and one or more second sealing materials provided outside the first sealing material,
Said first sealing member is seen containing an ultraviolet curable resin,
The second sealing material is a photoelectric conversion module including a thermosetting resin . Forming a stacked body including a photoelectric conversion layer and a second conductive layer in this order on the first conductive layer on the first substrate;
Installing a first encapsulant precursor containing an ultraviolet curable resin so as to surround the laminate on the first substrate;
Installing one or more second sealing material precursors including a thermosetting resin on the outside of the first sealing material precursor on the first substrate;
Installing a second substrate on the first sealing material precursor and the second sealing material precursor so as to face the first substrate;
Curing the first encapsulant precursor by irradiating the first encapsulant precursor in a state where the second substrate is installed from the second substrate side with ultraviolet rays. Device manufacturing method.

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