JP6009204B2 - Photoelectric conversion element, method for manufacturing photoelectric conversion element, and photoelectric conversion element module - Google Patents

Description

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

  As a photoelectric conversion element widely used in solar cells, optical sensors, etc., a pair of supports are joined using an organic polymer such as an adhesive (thermosetting resin and photocurable resin) or a thermoplastic resin (hereinafter referred to as “photoelectric conversion element”). In addition, a photoelectric conversion element having a configuration in which a photoelectric conversion unit is arranged between these supports is known.

  For example, Patent Document 1 discloses a porous structure in which peripheral portions of first and second transparent substrates are joined by an endless sealing peripheral wall made of a silicone adhesive, and a dye is adsorbed between the first and second transparent substrates. A dye-sensitized solar cell in which a material film is disposed is disclosed.

  Further, Patent Document 2 discloses an integrated thin film photovoltaic device in which the entire surfaces of a pair of substrates are joined with a close layer made of a translucent resin, and first and second thin film photovoltaic layers are disposed between the substrates. An apparatus is disclosed.

  However, it is known that the organic polymer used for the sealing portion of the photoelectric conversion element deteriorates when irradiated with light. When the organic polymer constituting the sealing portion of the photoelectric conversion element is deteriorated, the organic polymer may be cracked or the bonding between the supports may be weakened and the support may be peeled off.

  Therefore, for example, in Patent Document 3, by providing a coating layer and reducing the light transmittance in a wavelength region of 400 nm or less to 70% or less, the penetration of ultraviolet rays into the element is prevented, and the sealing material deteriorates. A dye-sensitized solar cell that has been prevented is disclosed.

  Patent Document 4 discloses a photoelectric conversion element including an ultraviolet light suppressing unit that suppresses ultraviolet light incident on the sealing portion more than ultraviolet light incident on the photoelectric conversion portion.

JP 2006-12673 A JP 2004-179560 A JP 2003-282163 A JP 2008-146922 A

  However, in the dye-sensitized solar cell described in Patent Document 3, the coating layer can reduce the amount of ultraviolet light incident on the sealing portion, but at the same time, the amount of light incident on the photoelectric conversion layer is also reduced. Therefore, there has been a problem that the photoelectric conversion efficiency is lowered.

  Moreover, in the photoelectric conversion element described in Patent Document 4, it is possible to block the vertical light that is perpendicularly incident on the sealing portion by the ultraviolet light suppression means, but the wraparound light such as scattering and the incident angle are not vertical. There was a problem of insufficient shielding against light.

  In view of the above circumstances, an object of the present invention is to provide a photoelectric conversion element and a photoelectric conversion element that can suppress deterioration of the sealing portion while suppressing a decrease in photoelectric conversion efficiency due to a reduction in the amount of light incident on the photoelectric conversion layer. And providing a photoelectric conversion element module.

The present invention includes a first conductive layer provided on a light transmissive support, a photoelectric conversion layer provided on the first conductive layer, a photoelectric conversion layer between the light transmissive support and the cover material. A porous insulating layer provided on the side surface of the photoelectric conversion layer and the light-transmitting support from the upper surface of the conversion layer, a catalyst layer provided on the upper surface of the porous insulating layer, and a light-transmitting support. A second conductive layer insulated from the first conductive layer by the porous insulating layer, a counter electrode conductive layer provided extending from the catalyst layer to the side surface of the porous insulating layer and the second conductive layer, A region partitioned by a light shielding layer provided on the counter electrode conductive layer, a sealing material provided between the light shielding layer and the cover material, and a sealing material between the light transmissive support and the cover material and a filled carrier transport material, Oh photoelectric conversion element is a sealing material is present in the recess formed by the light shielding layer .

Here, in the photoelectric conversion element of the present invention, it is preferable that the light shielding layer shields at least part of light in a wavelength region absorbed by the sealing material.

  Moreover, in the photoelectric conversion element of this invention, it is preferable that a partition part is provided on the 2nd conductive layer, and the light shielding layer is provided extending from the counter conductive layer to the side surface of the partition part. Moreover, it is preferable that the photoelectric conversion element of this invention has the side surface in which a porous insulating layer inclines, and the counter-electrode conductive layer is provided on the side surface in which a porous insulating layer inclines.

The present invention also provides a first conductive layer provided on the light transmissive support and a first photoelectric layer provided on the first conductive layer between the light transmissive support and the cover material. A conversion layer, a top surface of the first photoelectric conversion layer, a side surface of the first photoelectric conversion layer, a first porous insulating layer provided on the light-transmitting support, and a first porous insulating layer A first catalyst layer provided on the light-transmitting support, a second conductive layer provided on the light-transmitting support and insulated from the first conductive layer by the first porous insulating layer, and a second conductive layer. A second photoelectric conversion layer provided on the layer, a second porous insulating layer provided on an upper surface of the second photoelectric conversion layer and a side surface of the second photoelectric conversion layer, and a second porous insulation A second catalyst layer provided on the first layer; a side surface of the first porous insulating layer from a top surface of the first catalyst layer; and a side surface of the second conductive layer and the first porous insulating layer A second porous insulating layer counter electrode conductive layer provided extends on the side of which, a light shielding layer provided on the counter electrode conductive layer, sealing provided between the on the light-shielding layer to the cover material And a carrier transport material filled in a region partitioned by a sealing material between the light-transmitting support and the cover material, and the sealing material is present in the recess formed by the light shielding layer. This is a photoelectric conversion element module. The present invention also provides a first conductive layer provided on the light transmissive support and a first photoelectric layer provided on the first conductive layer between the light transmissive support and the cover material. A conversion layer, a top surface of the first photoelectric conversion layer, a side surface of the first photoelectric conversion layer, a first porous insulating layer provided on the light-transmitting support, and a first porous insulating layer A first catalyst layer provided on the light-transmitting support, a second conductive layer provided on the light-transmitting support and insulated from the first conductive layer by the first porous insulating layer, and a second conductive layer. A second photoelectric conversion layer provided on the layer, a second porous insulating layer provided on an upper surface of the second photoelectric conversion layer and a side surface of the second photoelectric conversion layer, and a second porous insulation A second catalyst layer provided on the layer, and a counter electrode conductive layer provided extending from the upper surface of the first catalyst layer to the side surface of the first porous insulating layer and to the second conductive layer A light shielding layer extending from above the counter electrode conductive layer to the side surface of the second porous insulating layer facing the side surfaces of the second conductive layer and the first porous insulating layer, and from above the light shielding layer A photoelectric conversion element module comprising: a sealing material provided between the cover material; and a carrier transport material filled in a region partitioned by the sealing material between the light transmissive support and the cover material. is there.

Furthermore, the present invention includes a step of forming a conductive layer on a light transmissive support, a step of separating the conductive layer to form a first conductive layer and a second conductive layer, and a first conductive layer. A step of forming a photoelectric conversion layer thereon, a step of forming a porous insulating layer so as to cover the surface of the photoelectric conversion layer, a step of forming a catalyst layer on the porous insulating layer, and a porosity from above the catalyst layer Forming a counter electrode conductive layer extending to the side surface of the porous insulating layer and the second conductive layer, forming a light shielding layer on the counter electrode conductive layer, installing a sealing material on the light shielding layer, viewed contains a step of placing the cover member on the sealing material, and filling a carrier transporting material in a region partitioned by the sealing material between the light transmissive support and the cover member, and formed by the light shielding layer This is a method for manufacturing a photoelectric conversion element in which a sealing material is present in the recessed portion .

  ADVANTAGE OF THE INVENTION According to this invention, the photoelectric conversion element which can suppress deterioration of a sealing part, suppressing the deterioration of the photoelectric conversion efficiency by reduction of the light quantity which injects into a photoelectric converting layer, the manufacturing method of a photoelectric conversion element, and a photoelectric conversion element Modules can be provided.

It is typical sectional drawing of an embodiment and the photoelectric conversion element of Example 1. FIG. It is typical sectional drawing illustrating a part of manufacturing process of an example of the manufacturing method of the photoelectric conversion element of embodiment. It is typical sectional drawing illustrating a part of manufacturing process of an example of the manufacturing method of the photoelectric conversion element of embodiment. It is typical sectional drawing illustrating a part of manufacturing process of an example of the manufacturing method of the photoelectric conversion element of embodiment. It is typical sectional drawing illustrating a part of manufacturing process of an example of the manufacturing method of the photoelectric conversion element of embodiment. It is typical sectional drawing of an embodiment and the photoelectric conversion element module of Example 4. FIG. 6 is a schematic cross-sectional view of a photoelectric conversion element of Example 2. FIG. 6 is a schematic cross-sectional view of a photoelectric conversion element of Example 3. FIG. 6 is a schematic cross-sectional view of photoelectric conversion elements of Comparative Example 1 and Comparative Example 3. FIG. 6 is a schematic cross-sectional view of a photoelectric conversion element of Comparative Example 2. FIG. 10 is a schematic cross-sectional view of a photoelectric conversion element module of Comparative Example 4. FIG.

  Embodiments of the present invention will be described below. In the drawings of the present invention, the same reference numerals represent the same or corresponding parts.

<Photoelectric conversion element>
FIG. 1 is a schematic cross-sectional view of a photoelectric conversion element according to an embodiment which is an example of the photoelectric conversion element of the present invention. 1 includes a light-transmitting support 101, a conductive layer 103 provided on the light-transmitting support 101, and a thickness direction provided on the conductive layer 103. A photoelectric conversion layer 104 having a trapezoidal cross section, a porous insulating layer 105 provided so as to cover the surface of the photoelectric conversion layer 104, a catalyst layer 106 and a light shielding layer 108 provided on the porous insulating layer 105, And a sealing material 109 provided on the light shielding layer 108, a cover material 102 provided on the sealing material 109, and a sealing material 109 between the light-transmissive support 101 and the cover material 102. And a carrier transporting material 112 filled in the region.

  The transparent electrode substrate 110 is composed of a laminate of the light transmissive support 101 and the conductive layer 103.

  Further, a partition wall portion 201 having a trapezoidal cross section in the thickness direction is provided on both sides of the photoelectric conversion layer 104, and the partition wall portion 201 is provided on the conductive layer 103. The conductive layer 103 is provided with a scribe line 111 that separates the conductive layer 103, and the catalyst layer 106 and the light shielding layer 108 are provided with scribe lines 113 that separate the catalyst layer 106 and the light shielding layer 108, respectively. ing.

  Here, the light shielding layer 108 includes, from the upper surface of the catalyst layer 106, an inclined side surface of the catalyst layer 106, an inclined side surface of the porous insulating layer 105, an upper surface of the conductive layer 103, an inclined side surface of the partition wall portion 201, and the partition wall portion 201. The conductive layer 103 is provided so as to reach the upper surface of the conductive layer 103 through the upper surface of the conductive layer 103 and the inclined side surface of the partition wall portion 201.

  In addition, the light shielding layer 108 has a recess formed by the inclined side surface of the catalyst layer 106, the upper surface of the conductive layer 103, and the portion of the light shielding layer 108 provided on the inclined side surface of the partition wall portion 201. The stopper 109 is provided so as to fill the concave portion of the light shielding layer 108.

<Light transmissive support>
The light transmissive support body 101 is a member that has a light transmissive property and can support a member formed thereon. As the light transmissive support 101, a light transmissive insulating material or the like can be used. For example, a glass substrate such as soda glass, fused quartz glass, or crystal quartz glass, or a resin substrate such as a flexible film. Etc. can be used. The light transmissive support 101 does not necessarily need to be transmissive to light in all wavelength regions.

  Examples of the flexible film that can be used for the light transmissive support 101 include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PA), Polyetherimide (PEI), phenoxy resin, Teflon (registered trademark), or the like can be used.

  The thickness of the light transmissive support 101 is preferably 0.2 mm or more and 5 mm or less. When the thickness of the light transmissive support 101 is not less than 0.2 mm and not greater than 5 mm, the light transmissive support 101 has sufficient strength to suppress the absorption of incident light and to support the photoelectric conversion element. It tends to develop.

<Conductive layer>
The conductive layer 103 is a light-transmitting conductive member. As the conductive layer 103, for example, indium tin composite oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), or the like can be used. Note that the conductive layer 103 does not necessarily have transparency to light in all wavelength regions.

  The thickness of the conductive layer 103 is preferably 0.02 μm or more and 5 μm or less. When the thickness of the conductive layer 103 is not less than 0.02 μm and not more than 5 μm, absorption of incident light by the conductive layer 103 tends to be suppressed and an increase in resistance of the conductive layer 103 tends to be suppressed.

  The resistance of the conductive layer 103 is preferably 40 Ω / sq or less. In this case, the characteristics of the photoelectric conversion element tend to be improved.

  The conductive layer 103 may be provided with a metal lead wire in order to reduce the resistance of the conductive layer 103. As the metal lead wire, for example, one containing at least one metal selected from the group consisting of platinum, gold, silver, copper, aluminum, nickel and titanium can be used. In order to avoid a reduction in the amount of incident light from the light receiving surface by providing a metal lead wire, the thickness of the metal lead wire is preferably set to 0.1 mm or more and 4 mm or less.

<Transparent electrode substrate>
As the transparent electrode substrate 110 in which the conductive layer 103 is laminated on the light transmissive support 101, for example, a transparent electrode in which the conductive layer 103 made of FTO is laminated on the light transmissive support 101 made of soda lime float glass. A substrate can be mentioned. As the transparent electrode substrate 110, for example, a commercially available transparent electrode substrate may be used.

<Photoelectric conversion layer>
The photoelectric conversion layer 104 is a layer that converts light energy into electric energy. For example, a layer in which a photosensitizer such as a dye or a quantum dot is adsorbed on a porous semiconductor layer can be used.

  The porous semiconductor layer is a semiconductor layer having a plurality of pores. As the porous semiconductor layer, for example, those having various forms such as particles or films having a large number of micropores can be used.

Examples of the material constituting the porous semiconductor layer include titanium oxide, zinc oxide, tin oxide, iron oxide, niobium oxide, cerium oxide, tungsten oxide, nickel oxide, strontium titanate, cadmium sulfide, lead sulfide, zinc sulfide, At least one selected from the group consisting of indium phosphide, copper-indium sulfide (CuInS ₂ ), CuAlO ₂ and SrCu ₂ O ₂ can be used. Especially, as a material which comprises a porous semiconductor layer, it is preferable to use at least 1 sort (s) selected from the group which consists of a titanium oxide, a zinc oxide, a tin oxide, and niobium oxide, and the photoelectric conversion efficiency of a photoelectric conversion element, stability From the viewpoint of improving safety and safety, it is particularly preferable to use titanium oxide.

  The titanium oxide that can be used for the porous semiconductor layer is selected from the group consisting of, for example, anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, and hydrous titanium oxide. At least one kind can be used. The two types of crystal systems, anatase type and rutile type, can be in any form depending on the production method and thermal history, but it is preferable to use the anatase type.

  As a form of the porous semiconductor layer, a polycrystalline sintered body formed by sintering semiconductor particles is used from the viewpoints of stability of the porous semiconductor layer, ease of crystal growth, and manufacturing cost. Is preferred.

  The average grain size of the porous semiconductor layer composed of the polycrystalline sintered body is 5 nm from the viewpoint of obtaining an effective surface area sufficiently large with respect to the projected area in order to convert incident light into electrical energy with high efficiency. The thickness is preferably less than 50 nm and more preferably 10 nm or more and 30 nm or less.

  In the present specification, the average particle diameter means a value determined by applying Scherrer's equation to a spectrum (XRD (X-ray diffraction) diffraction peak) obtained from X-ray diffraction measurement.

  The light scattering property of the photoelectric conversion layer 104 can be adjusted by the particle diameter (average particle diameter) of the semiconductor particles forming the porous semiconductor layer.

  In general, a porous semiconductor layer formed of semiconductor particles having a large average particle diameter has high light scattering properties, and can scatter incident light and improve the light capture rate. On the other hand, a porous semiconductor layer formed of semiconductor particles having a small average particle diameter has low light scattering properties, but can increase the adsorption amount of the dye and increase the adsorption amount. Moreover, you may form a porous semiconductor layer using what mixed the semiconductor particle from which these average particle diameters differ. Thus, the porous semiconductor layer in which the light scattering property is adjusted can be formed depending on the type of photosensitizer such as a dye to be used.

  Further, as the photoelectric conversion layer 104, a semiconductor particle having an average particle diameter of 50 nm or more, more preferably 50 nm or more and 600 nm or less is formed on a polycrystalline sintered body formed of semiconductor particles having an average particle diameter of less than 50 nm. The photoelectric conversion layer 104 may be formed by installing a polycrystalline sintered body formed from the above.

The specific surface area of the porous semiconductor layer used for the photoelectric conversion layer 104 is preferably 10 m ² / g or more and 200 m ² / g or less. When the specific surface area of the porous semiconductor layer used for the photoelectric conversion layer 104 is 10 m ² / g or more, a photosensitizer such as a dye described later can be adsorbed more in the porous semiconductor layer. The photoelectric conversion efficiency of the conversion element can be improved. Moreover, when the specific surface area of the porous semiconductor layer used for the photoelectric conversion layer 104 is 200 m ² / g or less, the strength necessary for holding the photoelectric conversion layer 104 tends to be ensured.

  The thickness of the photoelectric conversion layer 104 is not particularly limited, but is preferably 0.1 μm or more and 50 μm or less. When the thickness of the photoelectric conversion layer 104 is 0.1 μm or more and 50 μm or less, the photoelectric conversion efficiency of the photoelectric conversion element can be improved.

<Photosensitizer>
Examples of the photosensitizer that is adsorbed to the porous semiconductor layer of the photoelectric conversion layer 104 include one or more dyes such as organic dyes or metal complex dyes having absorption in various visible light regions and / or infrared light regions. Can be used.

  Examples of organic dyes include azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes, perylene dyes, and indigo. At least one selected from the group consisting of system dyes can be used.

  Examples of the metal complex dye include Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, From 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 A dye in which molecules are coordinated to at least one metal selected from the group can be used. Examples of such metal complex dyes include porphyrin dyes, phthalocyanine dyes, merocyanine dyes, naphthalocyanine dyes, ruthenium metal complex dyes, and the like.

  Among these, phthalocyanine dyes, merocyanine dyes or ruthenium metal complex dyes are preferably used, more preferably ruthenium metal complex dyes, and ruthenium metals represented by the following formulas (1) to (3). It is particularly preferable to use a complex dye.

  In order to firmly adsorb the dye to the porous semiconductor layer, the carboxylic acid group, carboxylic anhydride group, alkoxy group, hydroxyl group, hydroxyalkyl group, sulfonic acid group, ester group, mercapto group are contained in the dye molecule. And a dye having at least one interlock group selected from the group consisting of phosphonyl groups. As the dye having an interlock group, it is particularly preferable to use a dye having at least one of a carboxylic acid group and a carboxylic acid anhydride group.

  The interlock group provides an electrical bond that facilitates electron transfer between the excited dye and the conduction band of the porous semiconductor layer.

  Moreover, as a photosensitizer made to adsorb | suck to the porous semiconductor layer of the photoelectric converting layer 104, the at least 1 sort (s) of quantum dot selected from the group which consists of CdS, CdSe, PbS, and PbSe can also be used, for example.

<Porous insulating layer>
The porous insulating layer 105 is a porous insulating layer and is installed to ensure insulation between the photoelectric conversion layer 104, the catalyst layer 106, and the light shielding layer 108. The porous insulating layer 105 is generally provided between the photoelectric conversion layer 104 and the catalyst layer 106.

  As the porous insulating layer 105, for example, a layer made of at least one high-resistance material selected from the group consisting of glass, zirconium oxide, silicon oxide, aluminum oxide, niobium oxide, titanium oxide, and strontium titanate is used. be able to.

  The porous insulating layer 105 is preferably formed in a porous shape capable of charge transfer via an electrolyte. In this case, the average particle size of particles used for forming the porous insulating layer 105 is 5 nm or more and 500 nm or less. It is preferable that it is 10 nm or more and 300 nm or less.

<Catalyst layer>
The catalyst layer 106 is a layer that can exchange electrons with the carrier transport material 112. When the catalyst layer 106 has both high catalytic ability and conductivity, it can also serve as a counter electrode conductive layer described later.

  As the catalyst layer 106, for example, at least one of platinum and carbon is preferably used. The carbon that can be used for the catalyst layer 106 is, for example, at least one selected from the group consisting of carbon black, graphite, glass carbon, amorphous carbon, hard carbon, soft carbon, carbon whisker, carbon nanotube, and fullerene. Is preferred.

<Light shielding layer>
The light shielding layer 108 is a layer that absorbs at least a part of light in the wavelength region that the sealing material 109 absorbs. The part is surrounded in a concave shape. Note that the light-blocking layer 108 does not need to absorb all light in the wavelength region absorbed by the sealing material 109, and preferably absorbs 95% or more of light in the wavelength region absorbed by the sealing material 109.

  As a material constituting the light shielding layer 108, deterioration of the sealing material 109 can be prevented by suppressing incidence of sneak light such as vertical light and scattered light and light whose incident angle is not vertical to the sealing material 109. The material is not particularly limited as long as it can be used.

  Examples of the material constituting the light shielding layer 108 include indium tin composite oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), titanium, tungsten, gold, silver, copper, and nickel. At least one selected from the group can be used.

  Examples of the material constituting the light shielding layer 108 include an organic polymer mixed with an ultraviolet absorber such as hydroxybenzophenone, an organic polymer composed of a monomer having an ultraviolet absorbing functional group, and an inorganic material (glass, ceramic or At least one selected from the group consisting of a pigment and / or a phosphor mixed therein may be used.

  The light shielding layer 108 can also serve as a counter electrode conductive layer facing the conductive layer 103. In the case where the light shielding layer 108 also serves as a counter electrode conductive layer, the light shielding layer 108 may be formed by forming the counter electrode conductive layer up to a place where the light shielding layer 108 needs to be formed.

  The light shielding layer 108 that also serves as the counter electrode conductive layer is formed in a desired position by, for example, a patterning method using a mask or the like, or a method in which a part of the light shielding layer 108 is removed by scribe after patterning. Can be partially formed. According to the latter method, not only can the tact-up of the formation process of the light shielding layer 108 be performed, but also problems of deflection and misalignment of the patterning mask when the area is increased can be avoided.

<Encapsulant>
The sealing material 109 is a member that can confine the carrier transport material 112 inside the photoelectric conversion element, suppress volatilization of the carrier transport material 112, and suppress the intrusion of water or the like into the photoelectric conversion element. is there.

  As the sealing material 109, for example, a single layer structure made of at least one material selected from the group consisting of silicone resin, epoxy resin, polyisobutylene resin, polyamide resin, polyolefin resin, ionomer resin, and glass frit Alternatively, a stacked structure in which two or more single-layer structures are stacked, or the like can be used.

<Cover material>
The cover material 102 is a member that can suppress the volatilization of the carrier transport material 112 and also prevent water and the like from entering the photoelectric conversion element.

  As a material constituting the cover material 102, for example, at least one selected from the group consisting of soda-lime glass, lead glass, borosilicate glass, fused quartz glass, crystalline quartz glass, and a flexible film can be used. Of these, it is preferable to use soda-lime float glass.

<Carrier transport material>
The carrier transporting material 112 is a conductive material capable of transporting charges, and is sandwiched between the conductive layer 103 inside the sealing material 109 and the cover material 102. Accordingly, at least the insides of the holes of the photoelectric conversion layer 104 and the porous insulating layer 105 are filled with the carrier transport material 112.

  As the carrier transport material 112, for example, at least one electrolyte selected from the group consisting of a liquid electrolyte, a solid electrolyte, a gel electrolyte, and a molten salt gel electrolyte can be used.

  As the liquid electrolyte, for example, a liquid material containing a redox species can be used, and those that can generally be used in batteries, photoelectric conversion elements, and the like can be used without particular limitation. Specifically, it consists of a redox species and a solvent capable of dissolving it, a redox species and a molten salt capable of dissolving it, or a redox species, a solvent capable of dissolving this and a molten salt. Things can be used.

As the redox species, for example, I ⁻ / I ³⁻ type, Br ²⁻ / Br ³⁻ type, Fe 2 ⁺ / Fe ³⁺ type, quinone / hydroquinone type, or cobalt complex type can be used.

Specifically, combinations of metal iodides such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI ₂ ) and iodine (I ₂ ), tetraethylammonium Combinations of tetraalkylammonium salts such as iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), tetrahexylammonium iodide (THAI) and iodine, or lithium bromide (LiBr) ), Sodium bromide (NaBr), potassium bromide (KBr), calcium bromide (CaBr ₂ ) and other metal bromides are preferably used in combination with bromine, and in particular, a combination of LiI and I ₂ is used. It is particularly preferred.

  Further, as the solvent for the redox species, for example, 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 preferable to use at least one of a carbonate compound and a nitrile compound.

  As the solid electrolyte, for example, a non-fluid conductive material that can transport electrons, holes, or ions can be used. Specifically, a hole transport material such as polycarbazole, an electron transport material such as tetranitrofluororenone, a conductive polymer such as polyroll, a polymer electrolyte obtained by solidifying a liquid electrolyte with a polymer compound, copper iodide or thiocyanate A p-type semiconductor such as copper acid or an electrolyte obtained by solidifying a liquid electrolyte containing a molten salt with fine particles can be used.

  The gel electrolyte is usually composed of an electrolyte and a gelling agent. Examples of gel electrolytes include polymer gelation such as crosslinked polyacrylic resin derivatives, crosslinked polyacrylonitrile derivatives, polyalkylene oxide derivatives, silicone resins, or polymers having a nitrogen-containing heterocyclic quaternary compound salt structure in the side chain. An agent or the like can be used.

  The molten salt gel electrolyte is usually composed of the gel electrolyte as described above and a room temperature molten salt. Examples of the room temperature type molten salt include nitrogen-containing heterocyclic quaternary ammonium salt compounds such as pyridinium salts or imidazolium salts.

  You may add an additive to said electrolyte as needed. Examples of the additive include nitrogen-containing aromatic compounds such as t-butylpyridine (TBP), dimethylpropylimidazole iodide (DMPII), methylpropylimidazole iodide (MPII), ethylmethylimidazole iodide (EMII), Imidazole salts such as ethylimidazole iodide (EII) and hexylmethylimidazole iodide (HMII) can be used.

  The electrolyte concentration in the carrier transport material 112 is preferably 0.001 mol / liter or more and 1.5 mol / liter or less, more preferably 0.01 mol / liter or more and 0.7 mol / liter or less. .

<Scribe line>
The scribe line 111 separates the conductive layer 103 to ensure insulation between the conductive layers 103 arranged on both sides of the scribe line 111. The scribe line 113 separates the catalyst layer 106 and the light shielding layer 108 from each other to ensure insulation between the catalyst layer 106 and the light shielding layer 108 disposed on both sides of the scribe line 113.

<Counter electrode conductive layer>
The photoelectric conversion element of this embodiment mode illustrated in FIG. 1 may further include a counter electrode conductive layer between the porous insulating layer 105 and the light shielding layer 108. The counter electrode conductive layer is a layer that is electrically connected to the catalyst layer 106 and can take out the current generated by the photoelectric conversion element to the outside.

  Examples of the material constituting the counter electrode conductive layer include indium tin composite oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), titanium, tungsten, gold, silver, copper, and nickel. It is preferable to use at least one selected from the group, and it is particularly preferable to use titanium.

  In addition, the stacking order of the catalyst layer 106 and the counter electrode conductive layer is not particularly limited, and can be appropriately selected depending on the correlation with the materials used for the catalyst layer 106 and the counter electrode conductive layer.

<Extraction electrode>
An extraction electrode may be provided on the counter electrode conductive layer as necessary. By providing the extraction electrode, current generated in the photoelectric conversion element of this embodiment can be extracted from the extraction electrode to the outside of the photoelectric conversion element. The material constituting the extraction electrode is not particularly limited as long as the current generated in the photoelectric conversion element can be extracted to the outside.

<Method for producing photoelectric conversion element>
Hereinafter, an example of a method for manufacturing the photoelectric conversion element of the present embodiment shown in FIG. 1 will be described with reference to the schematic cross-sectional views of FIGS. First, as shown in FIG. 2, a conductive layer 103 is formed on one surface of the light transmissive support 101. The method for forming the conductive layer 103 is not particularly limited, and for example, a known sputtering method or spray method can be used.

  In the case where a metal lead wire (not shown) is provided on the conductive layer 103, the metal lead wire is formed by forming the metal lead wire on the light transmissive support 101 by, for example, a known sputtering method or vapor deposition method. A method of forming the conductive layer 103 on the light-transmitting support 101 or a method of forming the conductive layer 103 on the light-transmitting support 101 and forming a metal lead on the conductive layer 103. Can do.

  Next, as shown in FIG. 2, a scribe line 111 is formed in the conductive layer 103. The scribe line 111 can be formed by cutting the conductive layer 103 by, for example, a laser scribe method. Thus, the conductive layer 103 is divided into a region where the photoelectric conversion layer 104 is formed and a region where the photoelectric conversion layer 104 is not formed.

  Next, as illustrated in FIG. 3, the photoelectric conversion layer 104 is formed over the conductive layer 103. Here, the photoelectric conversion layer 104 is formed by, for example, a method of baking after applying a paste containing semiconductor particles by a screen printing method or an inkjet method, a method using a sol-gel method or an electrochemical redox reaction, or the like. Thus, the photoelectric conversion layer 104 can be formed over the region of the conductive layer 103. Among these, from the viewpoint of forming a thick porous semiconductor layer at low cost, it is preferable to use a method in which a paste containing semiconductor particles is applied onto the conductive layer 103 by screen printing and then baked.

  As a more specific example, first, 125 mL of titanium isopropoxide (manufactured by Kishida Chemical Co., Ltd.) is dropped into 750 mL of 0.1 M aqueous nitric acid (manufactured by Kishida Chemical Co., Ltd.) and hydrolyzed at 80 ° C. for 8 hours. A sol solution is prepared by heating. Thereafter, the obtained sol solution was heated in a titanium autoclave at 230 ° C. for 11 hours to grow titanium oxide particles, and then subjected to ultrasonic dispersion for 30 minutes to oxidize with an average particle size (average primary particle size) of 15 nm. A colloidal solution containing titanium particles is prepared. Subsequently, a 2-fold volume of ethanol is added to the obtained colloidal solution, and this is centrifuged at a rotational speed of 5000 rpm to obtain titanium oxide particles.

  In addition, the average particle diameter in this specification is the value calculated | required from the diffraction peak of XRD (X-ray diffraction). Specifically, the average particle diameter is determined from the half-value width of the diffraction angle in XRD θ / 2θ measurement and Scherrer's equation. For example, in the case of anatase-type titanium oxide, the half-value width of the diffraction peak (around 2θ = 25.3 °) corresponding to the (101) plane may be measured.

  Next, after washing the titanium oxide particles obtained as described above, a solution obtained by dissolving ethyl cellulose and terpineol in absolute ethanol is added and stirred to disperse the titanium oxide particles. Thereafter, the mixed solution is heated under vacuum to evaporate ethanol to obtain a titanium oxide paste. As the final composition, for example, the concentration is adjusted so that the solid concentration of titanium oxide is 20% by mass, ethyl cellulose is 10% by mass, and terpineol is 64% by mass.

  In addition to the above, the solvent used to prepare the paste containing (suspended) semiconductor particles is a glyme solvent such as ethylene glycol monomethyl ether, an alcohol solvent such as isopropyl alcohol, isopropyl alcohol / toluene, etc. Or a mixed solvent thereof or water.

  Next, a paste containing semiconductor particles is applied onto the conductive layer 103 by a method such as the above-described screen printing method or ink jet method, dried, and then fired to form a porous semiconductor layer. Drying and firing of the paste containing semiconductor particles can be performed by appropriately adjusting conditions such as temperature, time, and atmosphere depending on the type of support and semiconductor particles used.

  Firing of the above paste can be performed, for example, by heating at a temperature of about 50 to 800 ° C. for about 10 seconds to 12 hours in an air atmosphere or an inert gas atmosphere. The above-mentioned paste can be dried and fired once at a single temperature or twice or more at different temperatures.

  Then, the photoelectric conversion layer 104 is formed by making photosensitizers, such as a pigment | dye, adsorb | suck to the porous semiconductor layer formed as mentioned above. Note that adsorption of a photosensitizer such as a dye is not limited to immediately after formation of the photoelectric conversion layer 104, and may be performed after formation of the porous insulating layer 105 or formation of the light shielding layer 108, for example.

  As a method for adsorbing the dye to the porous semiconductor layer, for example, a method of immersing the porous semiconductor layer formed on the conductive layer 103 in a solution in which the dye is dissolved in a solvent (solution for dye adsorption) is used. Can do. The solvent that dissolves the dye may be any solvent that dissolves the dye. For example, alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran, nitrogen compounds such as acetonitrile, chloroform, and the like. Use of halogenated aliphatic hydrocarbons, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, esters such as ethyl acetate, and those containing at least one selected from the group consisting of water Can do.

The dye concentration in the dye adsorption solution can be appropriately adjusted depending on the kind of the dye and the solvent to be used, but is preferably 5 × 10 ⁻⁴ mol / liter or more from the viewpoint of improving the adsorption function.

  Next, as shown in FIG. 3, a porous insulating layer 105 is formed so as to cover the surface of the photoelectric conversion layer 104. The scribe line 111 formed in the conductive layer 103 is filled with the porous insulating layer 105, and insulation between the conductive layers 103 on both sides of the scribe line 111 is ensured.

  Here, the porous insulating layer 105 is not particularly limited, and for example, a method of baking after applying a paste containing semiconductor particles so as to cover the surface of the photoelectric conversion layer 104 by a screen printing method or an inkjet method. It can be formed on the surface of the photoelectric conversion layer 104 by a sol-gel method or a method using an electrochemical redox reaction. Among these, from the viewpoint of forming the thick porous insulating layer 105 at a low cost, it is preferable to use a method in which a paste containing semiconductor particles is applied onto the surface of the photoelectric conversion layer 104 by screen printing and then baked. preferable.

  In addition, in the same manner as the photoelectric conversion layer 104 and the porous insulating layer 105, the partition wall portion 201 is formed over the region of the conductive layer 103 where the photoelectric conversion layer 104 is not formed.

  Next, as shown in FIG. 3, a catalyst layer 106 is formed on the porous insulating layer 105. The catalyst layer 106 can be formed by, for example, a vapor deposition method or a printing method. For example, when the catalyst layer 106 is formed by a vapor deposition method, the catalyst layer 106 itself is porous, which is preferable in that it is not necessary to newly form a hole through which the dye adsorption solution and the electrolyte can move. Note that a counter electrode conductive layer may be formed on the catalyst layer 106 by a method similar to that for the catalyst layer 106 after the formation of the catalyst layer 106.

  Next, as shown in FIG. 3, a light shielding layer 108 having a recess is formed on the catalyst layer 106. Thereby, a recess is formed in the light shielding layer 108 by the inclined side surface of the catalyst layer 106, the upper surface of the conductive layer 103, and the portion of the light shielding layer 108 disposed on the inclined side surface of the partition wall portion 201. The light shielding layer 108 can be formed by, for example, a vapor deposition method, a printing method, a sputtering method, or the like.

  Next, as shown in FIG. 4, a part of each of the catalyst layer 106 and the light shielding layer 108 is removed by a laser scribing method or the like to form a scribe line 113.

  Next, as shown in FIG. 5, a sealing material 109 is installed so as to fill the concave portion of the light shielding layer 108. The sealing material 109 can be installed so as to fill the concave portion of the light shielding layer 108 by, for example, applying with a dispenser or installing the sealing material 109 having a hole in a predetermined shape.

  Next, as shown in FIG. 5, the cover material 102 is installed on the sealing material 109. After the cover material 102 is installed, the transparent electrode substrate 110 and the cover material 102 are bonded and fixed by curing the sealing material 109 by heating and / or ultraviolet irradiation.

  Next, as shown in FIG. 1, a carrier transporting material 112 is filled in a region partitioned by a sealing material 109 between the light transmissive support body 101 and the cover material 102. The carrier transport material 112 can be filled into the region by, for example, being injected from an electrolyte injection hole provided in the cover material 102 in advance.

<Photoelectric conversion element module>
In FIG. 6, typical sectional drawing of the photoelectric conversion element module of embodiment which is an example of the photoelectric conversion element module of this invention is shown. The photoelectric conversion element module of the embodiment shown in FIG. 6 is configured by electrically connecting two or more of the photoelectric conversion elements shown in FIG.

  In the photoelectric conversion element module of the embodiment shown in FIG. 6, the light shielding layer 108 of the photoelectric conversion element is sequentially electrically connected to the conductive layer 103 of the photoelectric conversion element arranged next to the photoelectric conversion element. It can form by comprising.

<Effect>
In the photoelectric conversion element and the photoelectric conversion element module of the embodiment, the sealing material 109 is provided so as to fill the concave portion of the light shielding layer 108. Therefore, since all of the light incident surface of the sealing material 109 is covered with the light shielding layer 108, the light incident from the light transmissive support 101 is shielded by the light shielding layer 108. Thereby, since the light irradiation amount to the sealing material 109 can be reduced more than before, the light deterioration of the sealing material 109 is suppressed.

  Further, in the photoelectric conversion element and the photoelectric conversion element module of the embodiment, the sealing material 109 is provided so as to fill only the concave portion of the light shielding layer 108. As described in Patent Document 3, the photoelectric conversion layer is provided. Since the entire surface of the light incident surface 104 is not covered with the light shielding layer 108, a decrease in photoelectric conversion efficiency due to a reduction in the amount of light incident on the photoelectric conversion layer 104 can be suppressed.

  For the reasons described above, in the photoelectric conversion element and the photoelectric conversion element module of the embodiment, deterioration of the sealing portion can be suppressed while suppressing a decrease in photoelectric conversion efficiency due to a reduction in the amount of light incident on the photoelectric conversion layer. .

<Example 1>
FIG. 1 is a schematic cross-sectional view of the photoelectric conversion element of Example 1. The photoelectric conversion element of Example 1 was produced as follows.

First, as shown in FIG. 1, a transparent electrode having a width of 10 mm, a length of 10 mm and a thickness of 1.0 mm formed by forming a conductive layer 103 made of SnO ₂ film on a light-transmitting support 101 made of glass. A substrate 110 (manufactured by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) was prepared.

  Next, as shown in FIG. 1, the scribe line 111 was formed by cutting the conductive layer 103 by a laser scribing method.

  Next, a commercially available titanium oxide paste (manufactured by Solaronix, trade name: D) using a screen plate having a pattern of a porous semiconductor layer and a screen printing machine (manufactured by Neurong Precision Industry Co., Ltd., model number: LS-150). / SP) was applied to the surface of the conductive layer 103 in a size of 5.5 mm × 5.5 mm and leveled at room temperature for 1 hour.

  Next, the obtained coating film was dried in an oven set at 80 ° C. for 20 minutes, and further, 60 minutes in the air using a baking furnace (model number: KDF P-100, manufactured by Denken Co., Ltd.) set at 500 ° C. Baked. This coating and baking process was repeated twice to form a porous semiconductor layer having a thickness of 11 μm.

  Next, a paste containing zirconia particles (average particle size of 50 nm) is applied on the porous semiconductor layer to a size of 5 mm × 5 mm using a screen printer, and then baked at 500 ° C. for 60 minutes. A porous insulating layer 105 having a distance from the surface to the flat portion of the upper surface of the porous insulating layer 105 (film thickness of the porous insulating layer 105) was 7 μm.

  Next, a glass frit was printed by a screen printing method so as to surround the laminated body of the porous semiconductor layer and the porous insulating layer 105 from four sides, and then a baking furnace (made by Denken Corporation, The partition wall part 201 was formed by baking for 60 minutes using a model number: KDF P-100).

  Next, Pt is deposited on the porous insulating layer 105 at a deposition rate of 40 nm / s using a mask on which a predetermined pattern is formed and a vapor deposition apparatus (model number: EVD500A, manufactured by Anelva Corporation), and a catalyst layer 106 was formed. The size (shape) and the position in the width direction of the catalyst layer were the same as those of the porous semiconductor layer.

  Next, a stack of a porous semiconductor layer and a porous insulating layer 105 is included at a deposition rate of 80 nm / s using a mask on which a predetermined pattern is formed and a deposition apparatus (model number: EVD500A manufactured by Anelva Corporation). A titanium film having a thickness of 400 nm was formed on the catalyst layer 106 over the entire surface. Thereafter, a light-shielding layer 108 was formed by forming a scribe line 113 at a position shown in FIG. 1 by a laser scribe method.

  Next, the laminate obtained by laminating the light shielding layer 108 in a dye adsorbing solution prepared in advance is immersed for 100 hours at room temperature, and then the laminate is washed with ethanol and about 5 at about 60 ° C. After drying for a minute, the photoelectric conversion layer 104 was formed by adsorbing the dye to the porous semiconductor layer.

Here, the dye adsorption solution is a volume ratio of 1: 1 so that the dye represented by the above formula (3) (manufactured by Solaronix, trade name: Ruthenium 620 1H3TBA) has a concentration of 4 × 10 ⁻⁴ mol / liter. And dissolved in a mixed solvent of acetonitrile and t-butanol.

  Next, the transparent electrode substrate 110 including the above laminate and the glass substrate constituting the cover material 102 are made of an ultraviolet curable resin (manufactured by Three Bond Co., model number: 31X-101) so as to surround the periphery of the laminate. Bonding was performed using the sealing material 109, and the sealing material 109 was irradiated with ultraviolet rays to cure the sealing material 109 and fix them.

  However, when the cover material 102 and the transparent electrode substrate 110 including the laminate are fixed, the sealing material 109 made of an ultraviolet curable resin is installed in the recess formed between the partition wall 201 and the laminate. The alignment was performed, and the sealing material 109 was cured by irradiating the sealing material 109 with ultraviolet rays, and these were fixed.

  Further, a carrier transport material 112 prepared in advance is injected from a carrier transport material injection hole (not shown) provided in advance on a glass substrate constituting the cover material 102, and an ultraviolet curable resin (Three Bond Co., Ltd.) is injected. Electrolyte injection hole was sealed using a product number of 31X-101. Thereby, the photoelectric conversion element of Example 1 filled with the carrier transport material 112 was completed.

In addition, the electrolytic solution which is the carrier transport material 112 uses acetonitrile as a solvent, LiI (manufactured by Aldrich) as a redox species has a concentration of 0.1 mol / liter, and I ₂ (manufactured by Kishida Chemical) has a concentration of 0.01. Further, t-butylpyridine (manufactured by Aldrich) was added at a concentration of 0.5 mol / liter and dimethylpropylimidazole iodide (manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added at a concentration of 0.6 mol / liter as additives. They were added to a liter and dissolved to form.

Ten photoelectric conversion elements of Example 1 were produced as described above. Based on the light irradiation test A-5 of JIS standard C8938, each of these ten photoelectric conversion elements of Example 1 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours. Thus, the appearance of the sealing material 109 was checked for deterioration.

  As a result, in all ten sealing materials 109 of the photoelectric conversion element of Example 1, no change such as bubbles invading was observed. Therefore, the electrolytic solution retention rate of the photoelectric conversion element of Example 1 was 100%. The results are shown in Table 1.

<Example 2>
FIG. 7 is a schematic cross-sectional view of the photoelectric conversion element of Example 2. The photoelectric conversion element of Example 2 is characterized in that a counter electrode conductive layer 107 is provided on the catalyst layer 106. The photoelectric conversion element of Example 2 was produced as follows.

  First, the layers up to the catalyst layer 106 are manufactured by the same method as in Example 1, and then ITO is formed on the catalyst layer 106 to a thickness of 500 nm using a mask and a sputtering apparatus on which a predetermined pattern is formed. The counter electrode conductive layer 107 was formed.

  Furthermore, a 400 nm-thick titanium film is formed on the counter electrode conductive layer 107 made of ITO at a deposition rate of 80 nm / s using a mask on which a predetermined pattern is formed and a deposition apparatus (model number: EVD500A manufactured by Anelva Corporation). Thus, the light shielding layer 108 was formed.

  Thereafter, ten photoelectric conversion elements of Example 2 were produced using the same method as in Example 1 from dye adsorption to injection of the carrier transport material 112 and sealing with the sealing material 109.

Ten photoelectric conversion elements of Example 2 were produced as described above. Based on the light irradiation test A-5 of JIS standard C8938, each of these ten photoelectric conversion elements of Example 2 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours. Thus, the appearance of the sealing material 109 was checked for deterioration.

  As a result, in all ten sealing materials 109 of the photoelectric conversion element of Example 2, no change such as bubbles invading was observed, so the electrolytic solution retention rate of the photoelectric conversion element of Example 2 was 100%. The results are shown in Table 1.

<Example 3>
FIG. 8 is a schematic cross-sectional view of the photoelectric conversion element of Example 3. The photoelectric conversion element of Example 3 is characterized in that a light shielding layer 108 is provided on the entire surface of the counter conductive layer 107. The photoelectric conversion element of Example 3 was produced as follows.

  The counter electrode conductive layer 107 is manufactured by the same method as in Example 2, and then the deposition rate is 80 nm / s using a mask on which a predetermined pattern is formed and a vapor deposition apparatus (model number: EVD500A, manufactured by Anelva Corporation). Thus, titanium having a thickness of 400 nm was formed on the entire surface of the counter electrode conductive layer 107. Then, the light shielding layer 108 was formed by forming the scribe line 113 in the position shown in FIG. 8 by the laser scribing method.

  Thereafter, ten photoelectric conversion elements of Example 3 were produced using the same method as in Example 1 from dye adsorption to injection of the carrier transport material 112 and sealing with the sealing material 109.

Ten photoelectric conversion elements of Example 3 were produced as described above. Based on the light irradiation test A-5 of JIS standard C8938, each of these ten photoelectric conversion elements of Example 3 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours. Thus, the appearance of the sealing material 109 was checked for deterioration.

  As a result, in all ten sealing materials 109 of the photoelectric conversion element of Example 3, no change such as bubbles invading was observed, so the electrolytic solution retention rate of the photoelectric conversion element of Example 3 was 100%. The results are shown in Table 1.

<Comparative Example 1>
FIG. 9 is a schematic cross-sectional view of the photoelectric conversion element of Comparative Example 1. The photoelectric conversion element of Comparative Example 1 is characterized in that light incident on the sealing material 109 from the light transmissive support 101 is not shielded by the light shielding layer 108. The photoelectric conversion element of Comparative Example 1 was produced as follows.

First, as shown in FIG. 9, a transparent electrode having a width of 10 mm, a length of 10 mm and a thickness of 1.0 mm, in which a conductive layer 103 made of SnO ₂ film is formed on a light transmissive support 101 made of glass. A substrate 110 (manufactured by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) was prepared.

  Next, as shown in FIG. 9, the scribe line 111 was formed by cutting the conductive layer 103 by a laser scribing method.

  Next, a commercially available titanium oxide paste (manufactured by Solaronix, trade name: D) using a screen plate having a pattern of a porous semiconductor layer and a screen printing machine (manufactured by Neurong Precision Industry Co., Ltd., model number: LS-150). / SP) was applied to the surface of the conductive layer 103 in a size of 5.5 mm × 5.5 mm and leveled at room temperature for 1 hour.

  Next, the obtained coating film was dried in an oven set at 80 ° C. for 20 minutes, and further, 60 minutes in the air using a baking furnace (model number: KDF P-100, manufactured by Denken Co., Ltd.) set at 500 ° C. Baked. This coating and baking process was repeated twice to form a porous semiconductor layer having a thickness of 11 μm.

  Next, a paste containing zirconia particles (average particle size of 50 nm) is applied on the porous semiconductor layer to a size of 5 mm × 5 mm using a screen printer, and then baked at 500 ° C. for 60 minutes. A porous insulating layer 105 having a distance from the surface to the flat portion of the upper surface of the porous insulating layer 105 (film thickness of the porous insulating layer 105) was 7 μm.

  Next, Pt is deposited on the porous insulating layer 105 at a deposition rate of 40 nm / s using a mask on which a predetermined pattern is formed and a vapor deposition apparatus (model number: EVD500A, manufactured by Anelva Corporation), and a catalyst layer 106 was formed. The size (shape) and the position in the width direction of the catalyst layer were the same as those of the porous semiconductor layer.

  Next, a 400-nm-thick titanium film is formed on the catalyst layer 106 at a deposition rate of 80 nm / s using a mask having a predetermined pattern and a vapor deposition apparatus (model number: EVD500A, manufactured by Anelva Corporation) The counter electrode conductive layer 107 was formed.

  Next, the laminate obtained by laminating the above-described counter electrode conductive layer 107 in a dye adsorption solution prepared in advance is immersed at room temperature for 100 hours, and then the laminate is washed with ethanol and about 60 ° C. After drying for 5 minutes, the dye was adsorbed on the porous semiconductor layer to form the photoelectric conversion layer 104.

Here, the dye adsorption solution is a volume ratio of 1: 1 so that the dye represented by the above formula (3) (manufactured by Solaronix, trade name: Ruthenium 620 1H3TBA) has a concentration of 4 × 10 ⁻⁴ mol / liter. And dissolved in a mixed solvent of acetonitrile and t-butanol.

  Next, the transparent electrode substrate 110 including the above laminate and the glass substrate constituting the cover material 102 are made of an ultraviolet curable resin (manufactured by Three Bond Co., model number: 31X-101) so as to surround the periphery of the laminate. Bonding was performed using the sealing material 109, and the sealing material 109 was irradiated with ultraviolet rays to cure the sealing material 109 and fix them.

  Further, a carrier transport material 112 prepared in advance is injected from a carrier transport material injection hole (not shown) provided in advance on a glass substrate constituting the cover material 102, and an ultraviolet curable resin (Three Bond Co., Ltd.) is injected. Electrolyte injection hole was sealed using a product number of 31X-101. Thereby, the photoelectric conversion element of Comparative Example 1 filled with the carrier transport material 112 was completed. Note that the same electrolyte solution as that of Example 1 was used as the carrier transport material 112.

  Then, the photoelectric conversion element of the comparative example 1 was produced by apply | coating Ag paste (Fujikura Kasei Co., Ltd. make, brand name: Dotite) as a current collection electrode part.

Ten photoelectric conversion elements of Comparative Example 1 were produced as described above. Each of these ten photoelectric conversion elements of Comparative Example 1 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours based on the light irradiation test A-5 of JIS standard C8938. Thus, the appearance of the sealing material 109 was checked for deterioration.

  As a result, it was confirmed that bubbles penetrated into the carrier transport material 112 from a part of all ten sealing materials 109 of the photoelectric conversion element of Comparative Example 1. This is considered that a part of the solvent in the carrier transporting material 112 is volatilized due to a decrease in adhesive force due to light degradation of the sealing material 109 or the occurrence of cracks. Therefore, the electrolytic solution retention rate of the photoelectric conversion element of Comparative Example 1 was 0%. The results are shown in Table 1.

<Comparative example 2>
FIG. 10 is a schematic cross-sectional view of the photoelectric conversion element of Comparative Example 2. The photoelectric conversion element of Comparative Example 2 has a configuration corresponding to the photoelectric conversion element described in Patent Document 4, and is characterized in that the sealing material 109 is not provided so as to fill the concave portion of the light shielding layer 401. . The photoelectric conversion element of Comparative Example 2 was produced as follows.

First, as shown in FIG. 10, a transparent electrode having a width of 10 mm, a length of 10 mm, and a thickness of 1.0 mm, in which a conductive layer 103 made of SnO ₂ film is formed on a light transmissive support 101 made of glass. A substrate 110 (manufactured by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) was prepared. Then, a light-shielding layer 401 was formed by forming a square aluminum thin film having an outer side of 10 mm, an inner side of 6 mm, and a thickness of 5 mm by an electron beam evaporation method on the surface on which the conductive layer 103 is formed.

  Thereafter, ten photoelectric conversion elements of Comparative Example 2 were produced using the same method as Comparative Example 1.

Ten photoelectric conversion elements of Comparative Example 2 were produced as described above. Each of these ten photoelectric conversion elements of Comparative Example 2 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours based on the light irradiation test A-5 of JIS standard C8938, and then visually observed. Thus, the appearance of the sealing material 109 was checked for deterioration.

  As a result, it was confirmed that bubbles penetrated into the carrier transport material 112 from a part of the three sealing materials 109 of the photoelectric conversion element of Comparative Example 2. This is considered that a part of the solvent in the carrier transporting material 112 is volatilized due to a decrease in adhesive force due to light degradation of the sealing material 109 or the occurrence of cracks. Therefore, the electrolytic solution retention rate of the photoelectric conversion element of Comparative Example 2 was 70%. The results are shown in Table 1.

<Comparative Example 3>
FIG. 9 is a schematic cross-sectional view of the photoelectric conversion element of Comparative Example 3. The photoelectric conversion element of Comparative Example 3 was produced in the same manner as Comparative Example 1 except that the counter electrode conductive layer 107 made of an ITO film having a thickness of 500 nm was formed by sputtering.

Ten photoelectric conversion elements of Comparative Example 3 were produced as described above. Each of these ten photoelectric conversion elements of Comparative Example 3 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours based on the light irradiation test A-5 of JIS standard C8938. Thus, the appearance of the sealing material 109 was checked for deterioration.

  As a result, it was confirmed that bubbles penetrated into the carrier transport material 112 from a part of all ten sealing materials 109 of the photoelectric conversion element of Comparative Example 3. This is considered that a part of the solvent in the carrier transporting material 112 is volatilized due to a decrease in adhesive force due to light degradation of the sealing material 109 or the occurrence of cracks. Therefore, the electrolytic solution retention rate of the photoelectric conversion element of Comparative Example 3 was 0%. The results are shown in Table 1.

<Example 4>
FIG. 6 is a schematic cross-sectional view of the photoelectric conversion element of Example 4. The photoelectric conversion module of Example 4 was produced as follows.

First, as shown in FIG. 6, a transparent electrode having a width of 50 mm, a length of 50 mm, and a thickness of 4.0 mm, in which a conductive layer 103 made of SnO ₂ film is formed on a light transmissive support 101 made of glass. A substrate 110 (manufactured by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) was prepared.

  Next, as shown in FIG. 6, the scribe line 111 was formed by cutting the conductive layer 103 by a laser scribe method.

  Next, a commercially available titanium oxide paste (manufactured by Solaronix, trade name: D) using a screen plate having a pattern of a porous semiconductor layer and a screen printing machine (manufactured by Neurong Precision Industry Co., Ltd., model number: LS-150). / SP) was applied to the surface of the conductive layer 103 in a series of 5.5 mm × 45 mm in 7 series, and leveled at room temperature for 1 hour.

  Next, the obtained coating film was dried in an oven set at 80 ° C. for 20 minutes, and further, 60 minutes in the air using a baking furnace (model number: KDF P-100, manufactured by Denken Co., Ltd.) set at 500 ° C. Baked. This coating and baking process was repeated twice to form a porous semiconductor layer having a thickness of 11 μm.

  Next, a paste containing zirconia particles (average particle size of 50 nm) is applied to the porous semiconductor layer to 5.5 mm × 45 mm using a screen printer, and then fired at 500 ° C. for 60 minutes to obtain a porous material. A porous insulating layer 105 having a distance from the surface of the semiconductor layer to the flat portion on the upper surface of the porous insulating layer 105 (film thickness of the porous insulating layer 105) was 7 μm.

  Next, Pt is deposited on the porous insulating layer 105 at a deposition rate of 40 nm / s using a mask on which a predetermined pattern is formed and a vapor deposition apparatus (model number: EVD500A, manufactured by Anelva Corporation), and a catalyst layer 106 was formed.

  Next, a stack of a porous semiconductor layer and a porous insulating layer 105 is included at a deposition rate of 80 nm / s using a mask on which a predetermined pattern is formed and a deposition apparatus (model number: EVD500A manufactured by Anelva Corporation). A titanium film having a thickness of 400 nm was formed on the catalyst layer 106 over the entire surface. Then, the light shielding layer 108 was formed by forming the scribe line 113 by the laser scribing method in the position shown in FIG.

  Next, the laminate obtained by laminating the light shielding layer 108 in a dye adsorbing solution prepared in advance is immersed for 100 hours at room temperature, and then the laminate is washed with ethanol and about 5 at about 60 ° C. After drying for a minute, the photoelectric conversion layer 104 was formed by adsorbing the dye to the porous semiconductor layer.

Here, the dye adsorption solution is a volume ratio of 1: 1 so that the dye represented by the above formula (3) (manufactured by Solaronix, trade name: Ruthenium 620 1H3TBA) has a concentration of 4 × 10 ⁻⁴ mol / liter. And dissolved in a mixed solvent of acetonitrile and t-butanol.

  Next, the transparent electrode substrate 110 including the above laminate and the glass substrate constituting the cover material 102 are made of an ultraviolet curable resin (manufactured by Three Bond Co., model number: 31X-101) so as to surround the periphery of the laminate. Bonding was performed using the sealing material 109, and the sealing material 109 was irradiated with ultraviolet rays to cure the sealing material 109 and fix them.

  However, when the cover material 102 and the transparent electrode substrate 110 including the laminate are fixed, the sealing material 109 made of an ultraviolet curable resin is installed in the recess formed between the partition wall 201 and the laminate. The alignment was performed, and the sealing material 109 was cured by irradiating the sealing material 109 with ultraviolet rays, and these were fixed.

  Further, a carrier transport material 112 prepared in advance is injected from a carrier transport material injection hole (not shown) provided in advance on a glass substrate constituting the cover material 102, and an ultraviolet curable resin (Three Bond Co., Ltd.) is injected. Electrolyte injection hole was sealed using a product number of 31X-101. Thereby, the photoelectric conversion element module of Example 4 filled with the carrier transport material 112 was completed. Note that the same electrolyte solution as that of Example 1 was used as the carrier transport material 112.

Ten photoelectric conversion element modules of Example 4 were produced as described above. Based on the light irradiation test A-5 of JIS standard C8938, each of these ten photoelectric conversion element modules of Example 4 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours. The appearance of the sealing material 109 was visually checked for deterioration.

  As a result, in all ten sealing materials 109 of the photoelectric conversion element module of Example 4, no change such as bubbles invading was observed. Therefore, the electrolytic solution holding of the photoelectric conversion element module of Example 4 The rate was 100%. The results are shown in Table 1.

<Comparative example 4>
FIG. 11 is a schematic cross-sectional view of the photoelectric conversion element module of Comparative Example 4. The photoelectric conversion element module of Comparative Example 4 is characterized in that the sealing material 109 is not provided so as to fill the concave portion of the light shielding layer 108.

First, as shown in FIG. 11, a transparent electrode having a width of 50 mm × a length of 50 mm × a thickness of 4.0 mm, in which a conductive layer 103 made of SnO ₂ film is formed on a light-transmitting support 101 made of glass. A substrate 110 (manufactured by Nippon Sheet Glass Co., Ltd., glass with SnO ₂ film) was prepared.

  Next, as shown in FIG. 11, the scribe line 111 was formed by cutting the conductive layer 103 by a laser scribing method.

  Next, a commercially available titanium oxide paste (manufactured by Solaronix, trade name: D) using a screen plate having a pattern of a porous semiconductor layer and a screen printing machine (manufactured by Neurong Precision Industry Co., Ltd., model number: LS-150). / SP) was applied to the surface of the conductive layer 103 in a series of 5.5 mm × 45 mm in 7 series, and leveled at room temperature for 1 hour.

  Next, the obtained coating film was dried in an oven set at 80 ° C. for 20 minutes, and further, 60 minutes in the air using a baking furnace (model number: KDF P-100, manufactured by Denken Co., Ltd.) set at 500 ° C. Baked. This coating and baking process was repeated twice to form a porous semiconductor layer having a thickness of 11 μm.

  Next, a paste containing zirconia particles (average particle size of 50 nm) is applied to the porous semiconductor layer to 5.5 mm × 45 mm using a screen printer, and then fired at 500 ° C. for 60 minutes to obtain a porous material. A porous insulating layer 105 having a distance from the surface of the semiconductor layer to the flat portion on the upper surface of the porous insulating layer 105 (film thickness of the porous insulating layer 105) was 7 μm.

  Next, Pt is deposited on the porous insulating layer 105 at a deposition rate of 40 nm / s using a mask on which a predetermined pattern is formed and a vapor deposition apparatus (model number: EVD500A, manufactured by Anelva Corporation), and a catalyst layer 106 was formed.

  Next, a stack of a porous semiconductor layer and a porous insulating layer 105 is included at a deposition rate of 80 nm / s using a mask on which a predetermined pattern is formed and a deposition apparatus (model number: EVD500A manufactured by Anelva Corporation). Over the entire surface, titanium having a thickness of 400 nm was formed on the catalyst layer 106 to form the light shielding layer 108.

  Next, the laminate obtained by laminating the light shielding layer 108 in a dye adsorbing solution prepared in advance is immersed for 100 hours at room temperature, and then the laminate is washed with ethanol and about 5 at about 60 ° C. After drying for a minute, the photoelectric conversion layer 104 was formed by adsorbing the dye to the porous semiconductor layer.

Here, the dye adsorption solution is a volume ratio of 1: 1 so that the dye represented by the above formula (3) (manufactured by Solaronix, trade name: Ruthenium 620 1H3TBA) has a concentration of 4 × 10 ⁻⁴ mol / liter. And dissolved in a mixed solvent of acetonitrile and t-butanol.

  Next, the transparent electrode substrate 110 including the above laminate and the glass substrate constituting the cover material 102 are made of an ultraviolet curable resin (manufactured by Three Bond Co., model number: 31X-101) so as to surround the periphery of the laminate. Bonding was performed using the sealing material 109, and the sealing material 109 was irradiated with ultraviolet rays to cure the sealing material 109 and fix them.

  Further, a carrier transport material 112 prepared in advance is injected from a carrier transport material injection hole (not shown) provided in advance on a glass substrate constituting the cover material 102, and an ultraviolet curable resin (Three Bond Co., Ltd.) is injected. Electrolyte injection hole was sealed using a product number of 31X-101. Thereby, the photoelectric conversion element module of Example 4 filled with the carrier transport material 112 was completed. Note that the same electrolyte solution as that of Example 1 was used as the carrier transport material 112.

Ten photoelectric conversion element modules of Comparative Example 4 were produced as described above. Based on the light irradiation test A-5 of JIS standard C8938, each of these ten photoelectric conversion element modules of Comparative Example 4 was continuously irradiated with light having an irradiation density of 280 mW / cm ² for 500 hours. The appearance of the sealing material 109 was visually checked for deterioration.

  As a result, it was confirmed that bubbles penetrated into the carrier transport material 112 from a part of all ten sealing materials 109 of the photoelectric conversion element module of Comparative Example 4. This is considered that a part of the solvent in the carrier transporting material 112 is volatilized due to a decrease in adhesive force due to light degradation of the sealing material 109 or the occurrence of cracks. Therefore, the electrolytic solution retention rate of the photoelectric conversion element module of Comparative Example 4 was 0%. The results are shown in Table 1.

<Result>
As shown in Table 1, the photoelectric conversion elements of Examples 1 to 3 and the photoelectric conversion of Example 4 were performed for 500 hours of continuous light irradiation of 280 mW / cm ² based on the light irradiation test A-5 of JIS standard C8938. It was confirmed that the element module has a higher electrolyte solution retention rate of the sealing material 109 than the photoelectric conversion elements of Comparative Examples 1 to 3 and the photoelectric conversion element module of Comparative Example 4. In the photoelectric conversion elements of Examples 1 to 3 and the photoelectric conversion element module of Example 4, the sealing material 109 is provided so as to fill the concave portion of the light shielding layer 108. Although all the incident surfaces are covered with the light shielding layer 108, it is considered that the photoelectric conversion elements of Comparative Examples 1 to 3 and the photoelectric conversion element module of Comparative Example 4 do not have such a configuration. .

  Further, in the photoelectric conversion elements of Examples 1 to 3 and the photoelectric conversion element module of Example 4, the light incident on the photoelectric conversion layer 104 is not shielded by the light shielding layer 108, and therefore enters the photoelectric conversion layer 104. A decrease in photoelectric conversion efficiency due to a reduction in the amount of light can also be suppressed.

  Although the embodiments and examples of the present invention 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.

  INDUSTRIAL APPLICABILITY The present invention can be used for a photoelectric conversion element, a method for manufacturing a photoelectric conversion element, and a photoelectric conversion element module, and in particular, a photoelectric conversion element such as a dye-sensitized solar cell or a quantum dot-sensitized solar cell, and a photoelectric conversion element. It can utilize for a manufacturing method and a photoelectric conversion element module.

  DESCRIPTION OF SYMBOLS 101 Light transmissive support body, 102 Cover material, 103 Conductive layer, 104 Photoelectric conversion layer, 105 Porous insulating layer, 106 Catalyst layer, 107 Counter electrode conductive layer, 108 Light shielding layer, 109 Sealing material, 110 Transparent electrode substrate, 111 , 113 scribe line, 112 carrier transport material, 201 partition wall, 401 light shielding layer.

Claims (7)

Between the light transmissive support and the cover material,
A first conductive layer provided on the light transmissive support;
A photoelectric conversion layer provided on the first conductive layer;
A porous insulating layer provided on the side surface of the photoelectric conversion layer from the upper surface of the photoelectric conversion layer and the light-transmitting support;
A catalyst layer provided on the upper surface of the porous insulating layer;
A second conductive layer provided on the light transmissive support and insulated from the first conductive layer by the porous insulating layer;
A counter electrode conductive layer provided extending from the catalyst layer to a side surface of the porous insulating layer and the second conductive layer;
A light shielding layer provided on the counter electrode conductive layer;
A sealing material provided between the light shielding layer and the cover material;
A carrier transport material filled in a region partitioned by the sealing material between the light transmissive support and the cover material ;
A photoelectric conversion element , wherein the sealing material is present in a recess formed by the light shielding layer . The photoelectric conversion element according to claim 1 , wherein the light shielding layer shields at least part of light in a wavelength region absorbed by the sealing material. Providing a partition wall on the second conductive layer;
The photoelectric conversion element of Claim 1 or Claim 2 with which the said light shielding layer is extended and provided to the side surface of the said partition part from the said counter electrode conductive layer. The porous insulating layer has an inclined side surface;
The photoelectric conversion element according to any one of claims 1 to 3 , wherein the counter electrode conductive layer is provided on an inclined side surface of the porous insulating layer. Between the light transmissive support and the cover material,
A first conductive layer provided on the light transmissive support;
A first photoelectric conversion layer provided on the first conductive layer;
An upper surface of the first photoelectric conversion layer, a side surface of the first photoelectric conversion layer, and a first porous insulating layer provided on the light-transmissive support;
A first catalyst layer provided on the first porous insulating layer;
A second conductive layer provided on the light transmissive support and insulated from the first conductive layer by the first porous insulating layer;
A second photoelectric conversion layer provided on the second conductive layer;
A second porous insulating layer provided on an upper surface of the second photoelectric conversion layer and a side surface of the second photoelectric conversion layer;
A second catalyst layer provided on the second porous insulating layer;
A second porous insulating layer facing from the upper surface of the first catalyst layer to the side surface of the first porous insulating layer and the side surfaces of the second conductive layer and the first porous insulating layer A counter electrode conductive layer provided extending to the side surface of
A light shielding layer provided on the counter electrode conductive layer;
A sealing material provided between the light shielding layer and the cover material;
A carrier transport material filled in a region partitioned by the sealing material between the light transmissive support and the cover material ;
The photoelectric conversion element module in which the said sealing material exists in the recessed part formed of the said light shielding layer . Between the light transmissive support and the cover material,
A first conductive layer provided on the light transmissive support;
A first photoelectric conversion layer provided on the first conductive layer;
An upper surface of the first photoelectric conversion layer, a side surface of the first photoelectric conversion layer, and a first porous insulating layer provided on the light-transmissive support;
A first catalyst layer provided on the first porous insulating layer;
A second conductive layer provided on the light transmissive support and insulated from the first conductive layer by the first porous insulating layer;
A second photoelectric conversion layer provided on the second conductive layer;
A second porous insulating layer provided on an upper surface of the second photoelectric conversion layer and a side surface of the second photoelectric conversion layer;
A second catalyst layer provided on the second porous insulating layer;
A counter electrode conductive layer provided extending from the upper surface of the first catalyst layer to a side surface of the first porous insulating layer and to the second conductive layer;
A light shielding layer provided extending from the counter electrode conductive layer to the side surface of the second porous insulating layer facing the side surfaces of the second conductive layer and the first porous insulating layer,
A sealing material provided between the light shielding layer and the cover material;
A photoelectric conversion element module comprising a carrier transport material filled in a region partitioned by the sealing material between the light transmissive support and the cover material. Forming a conductive layer on the light transmissive support;
Separating the conductive layer to form a first conductive layer and a second conductive layer;
Forming a photoelectric conversion layer on the first conductive layer;
Forming a porous insulating layer so as to cover the surface of the photoelectric conversion layer;
Forming a catalyst layer on the porous insulating layer;
Forming a counter electrode conductive layer extending from above the catalyst layer to a side surface of the porous insulating layer and the second conductive layer;
Forming a light shielding layer on the counter electrode conductive layer;
Installing a sealing material on the light shielding layer;
Installing a cover material on the sealing material;
See containing and a step of filling a carrier transporting material in the region partitioned by the sealing material between the cover member and the light transmissive support,
A method for manufacturing a photoelectric conversion element , wherein the sealing material is present in a recess formed by the light shielding layer .

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