JP6534325B2 - PHOTOELECTRIC CONVERSION ELEMENT AND PHOTOELECTRIC CONVERSION MODULE - Google Patents

Description

  The present invention relates to a photoelectric conversion element and a photoelectric conversion module.

  Sunlight is attracting attention as an energy source to replace fossil fuels, and solar cells capable of converting sunlight into electricity are attracting attention. Among them, dye-sensitized solar cells are attracting attention as new-type solar cells because they have advantages such as low manufacturing cost.

  For example, Patent Document 1 discloses a monolithic dye-sensitized solar cell. The dye-sensitized solar cell of Patent Document 1 has a sealing material surrounding the outer periphery of the region between the first substrate and the second substrate in order to seal the electrolyte in the cell. However, since the sealing material is provided only in a single layer in the dye-sensitized solar cell of Patent Document 1, it is not possible to sufficiently prevent the leakage of the electrolyte.

  Therefore, for example, in Patent Document 2, a second electrolyte (submaterial (submaterial) having a viscosity higher than that of the first electrolyte (main material) is sequentially provided between the first electrolyte (main material) and the sealing portion from the first electrolyte side. The dye-sensitized solar cell which provided and the space | gap is disclosed. In Patent Document 2, the second electrolyte has a function as a bank to prevent the flow of the first electrolyte, and the void has a function to suppress the contact between the electrolyte composed of the first electrolyte and the second electrolyte and the sealing portion. As a result, it is described that the erosion of the sealing portion by the electrolyte is suppressed and the leakage of the electrolyte is thereby prevented.

JP, 2014-203539, A JP, 2014-017177, A

  However, even in the dye-sensitized solar cell described in Patent Document 2, it is difficult to completely prevent the electrolyte from leaking to the outside. Furthermore, although the electrolyte leaked to the outside will come to contact the wall surface of the sealing portion, it is actually difficult to visually check the electrolyte that crosses the wall surface. For this reason, conventionally, there has been a problem that it is not possible to detect electrolyte leakage early.

  The embodiments disclosed herein include a first substrate, a second substrate facing the first substrate at a distance, a first conductive layer positioned on the first substrate, and a photoelectric positioned on the first conductive layer. A conversion layer, a second conductive layer located on the photoelectric conversion layer, a sealing portion surrounding a first region between the first substrate and the second substrate, a first substrate, a second substrate, and a sealing material And the photoelectric conversion layer includes a porous semiconductor layer and a photosensitizer provided on the porous semiconductor layer, and the sealing portion includes: It is a photoelectric conversion element including a coloring material whose color to be changed is changed by coming into contact with an electrolyte.

  The embodiment disclosed herein includes a first substrate, a second substrate facing the first substrate at a distance, and a plurality of photoelectric conversion cells electrically connected between the first substrate and the second substrate. And a plurality of photoelectric conversion cells each having a first conductive layer located on the first substrate, a photoelectric conversion layer located on the first conductive layer, and a photoelectric conversion layer on the photoelectric conversion layer. And the electrolyte between the first substrate and the second substrate, wherein the photoelectric conversion layer comprises a porous semiconductor layer and a photosensitizer provided on the porous semiconductor layer. The photoelectric conversion module includes a sealing portion provided to surround the plurality of photoelectric conversion cells between the first substrate and the second substrate, and the sealing portion is in contact with the electrolyte. 1 is a photoelectric conversion module including a coloring material whose color changes.

  According to the embodiment disclosed herein, electrolyte leakage in the photoelectric conversion element and the photoelectric conversion module can be detected early.

FIG. 1 is a schematic cross-sectional view of a photoelectric conversion element of Embodiment 1. It is a photoelectric conversion element of Embodiment 1, and is a typical top view showing the shape of the 1st sealing material and the 2nd sealing material. It is a typical sectional view of the conventional photoelectric conversion element. 5 is a cross-sectional view conceptually showing a change in color exhibited by a color material in the photoelectric conversion element of Embodiment 1. FIG. It is a photoelectric conversion element of Embodiment 2, and is a schematic plan view which shows the shape of a 1st sealing material and a 2nd sealing material. FIG. 7 is a schematic cross-sectional view of a photoelectric conversion element of Embodiment 3. FIG. 10 is a schematic cross-sectional view of the photoelectric conversion element of Embodiment 4. FIG. 14 is a schematic cross-sectional view of a photoelectric conversion module of Embodiment 5. It is a photoelectric conversion module of Embodiment 5, and is a typical top view showing the shape of the 1st sealing material and the 2nd sealing material. It is a photoelectric conversion module of Embodiment 6, and is a typical top view showing the shape of the 1st sealing material and the 2nd sealing material. It is a photoelectric conversion module of Embodiment 7, and is a typical top view showing the shape of the 1st sealing material and the 2nd sealing material.

  Hereinafter, embodiments will be described. In the drawings used for describing the embodiments, the same reference numerals represent the same or corresponding portions. In the present specification, the notation of the form “X to Y” means the upper and lower limit (ie, X or more and Y or less) of the range, there is no description of a unit in X, and only a unit is described in Y If so, the units of X and Y are the same.

Embodiment 1
<Structure of photoelectric conversion element>
The structure of the photoelectric conversion element of Embodiment 1 will be described with reference to FIGS. 1 and 2. The photoelectric conversion element of the first embodiment includes a first substrate 1, a second substrate 2 facing the first substrate 1 with a gap, a first conductive layer 3 located on the first substrate 1, and a first conductive layer. A photoelectric conversion layer 4 located on 3 and a second conductive layer 6 located on the photoelectric conversion layer 4 are provided.

  The first substrate 1 and the second substrate 2 are bonded by a sealing portion 7. The sealing unit 7 includes a first sealing material 7 a surrounding the photoelectric conversion layer 4, a second sealing material 7 b surrounding the first sealing material 7 a, a first substrate 1, a second substrate 2, and a first sealing. A material 7a and a second region B surrounded by the second sealing material 7b.

  An electrolyte 8 is filled in a first region A surrounded by the first substrate 1, the second substrate 2 and the first sealing material 7 a, and the first substrate 1, the second substrate 2 and the first sealing material The coloring material 9 is disposed in the second region B surrounded by 7 a and the second sealing material 7 b.

(First board)
A translucent substrate having translucency can be used as the first substrate 1. However, for example, it may be made of a material that substantially transmits light of a wavelength having an effective sensitivity to a sensitizing dye described later, and it is not always necessary to have transparency to light of all wavelength ranges. Absent. Specifically, a glass substrate such as soda glass, fused quartz glass or crystalline quartz glass, or a heat-resistant resin plate such as a flexible film can be used. The thickness of the first substrate 1 is preferably 0.2 to 5 mm (0.2 mm or more and 5 mm or less).

(Second board)
The second substrate 2 is not particularly limited, and may or may not have light transmission, for example. As a translucent substrate, for example, a substrate made of ordinary glass can be used. Further, from the viewpoint of weight reduction, a substrate made of acrylic glass may be used. In addition, when the second substrate 2 has a light transmitting property, the inside of the second region can be viewed from above the second substrate 2.

(First conductive layer)
The first conductive layer 3 is provided on the surface of the first substrate 1 facing the second substrate 2. The first conductive layer 3 is not particularly limited as long as it has conductivity and translucency, and for example, indium tin complex oxide (ITO), tin oxide (SnO ₂ ), tin oxide is doped with fluorine At least one selected from the group consisting of FTO and zinc oxide (ZnO) can be used. The thickness of the first conductive layer 3 is preferably 0.02 to 5 μm. The sheet resistance of the first conductive layer 3 is preferably as low as possible, and is preferably 40 Ω / □ or less.

(Photoelectric conversion layer)
The photoelectric conversion layer 4 has a porous semiconductor layer 5 provided on the first conductive layer 3 as a base, and a photosensitizer is provided on the inside of the pores of the porous semiconductor layer 5 and the surface outside the pores. It is composed of

The porous semiconductor layer 5 is not particularly limited as long as it is generally used as a photoelectric conversion material, and, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, niobium oxide, cerium oxide, tungsten oxide, titanate Using 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 In particular, titanium oxide is preferably used in terms of high stability.

The thickness of the porous semiconductor layer 5 is not particularly limited, but can be, for example, 0.1 to 100 μm. Moreover, it is preferable that the surface area of the porous semiconductor layer 5 is 10-200 m < ² > / g.

  As the photosensitizer, for example, sensitizing dyes such as organic dyes and metal complex dyes can be used. Examples of the organic dyes include azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes, porphyrin dyes, perylenes At least one selected from the group consisting of a dye, an indigo dye and a naphthalocyanine dye can be used. The absorption coefficient of the organic dye is generally larger than the absorption coefficient of the metal complex dye in the form in which a molecule is coordinated to a transition metal.

  The metal complex dye is configured by coordination of a metal to a molecule. Examples of the molecule include porphyrin dyes, phthalocyanine dyes, naphthalocyanine dyes, and ruthenium dyes. As the metal, for example, 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, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Te and Rh And at least one selected from the above. Among them, as the metal complex dye, it is preferable to use one in which a metal is coordinated to a phthalocyanine-based dye or a ruthenium-based dye, and it is particularly preferable to use a ruthenium-based metal complex dye.

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

(Second conductive layer)
The second conductive layer 6 is provided on the surface of the second substrate 2 facing the first substrate 1. The second conductive layer 6 is not particularly limited as long as it has conductivity, and for example, the same material as the first conductive layer 3 may be used. The thickness of the second conductive layer 6 is preferably 0.02 to 5 μm. The sheet resistance of the second conductive layer 6 is preferably as low as possible, and is preferably 40 Ω / □ or less.

  A catalyst layer 10 is provided on the surface of the second conductive layer 6 facing the first substrate 1. As the catalyst layer 10, for example, at least one selected from the group consisting of platinum, carbon black, ketjen black, carbon nanotubes and fullerene can be used.

(Sealing part)
The sealing portion 7 holds the first substrate 1 and the second substrate 2 so as to face each other at an interval, and the first sealing material 7 a, the second sealing material 7 b, and the second region B. And. The first sealing material 7a surrounds the periphery of the photoelectric conversion layer 4, and the second sealing material 7b surrounds the first sealing material 7a at a distance from the first sealing material 7a.

  The first sealing material 7 a bonds the second substrate 2 and the first conductive layer 3, and bonds the first substrate 1 and the second conductive layer 6 to form the first substrate 1 and the second substrate 2. And are joined. Thereby, the first region A is sealed.

  The first sealing material 7a may be insulating, and in particular, it is preferable that the first sealing material 7a be made of an ultraviolet curable resin, a thermosetting resin, or the like from the viewpoint of easy production. Specifically, it is preferably made of silicone resin, epoxy resin, polyisobutylene resin, hot melt resin, glass frit or the like. In particular, since the first sealing material 7a is in contact with the electrolyte 8, it is preferable to use a material that does not easily react chemically with the electrolyte 8, and it is more preferable to use an ultraviolet curable resin containing an acrylic resin. The ultraviolet light is an electromagnetic wave having a wavelength of 1 to 400 nm.

  The second sealing material 7 b surrounds the first sealing material 7 a, bonds the second substrate 2 and the first conductive layer 3, and bonds the first substrate 1 and the second conductive layer 6. The first substrate 1 and the second substrate 2 are joined. Thereby, the second region B is sealed.

  The second sealing material 7 b does not necessarily have to be insulating, but is preferably insulating to suppress unnecessary short circuits. Among them, from the viewpoint of easy production, it is preferable to use an ultraviolet curable resin, a thermosetting resin, or the like, as in the case of the first sealing material 7a. In particular, since the second sealing material 7b is in contact with the air, it is preferable to use a resin having low permeability such as moisture or oxygen, and it is more preferable to use a thermosetting resin containing an epoxy resin.

(Electrolytes)
The electrolyte 8 is filled in the first region. As the electrolyte 8, an electrolyte having at least a fluidity can be used, and for example, a liquid electrolyte such as an electrolytic solution can be suitably used. The liquid electrolyte may be a liquid containing a 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, an I ⁻ / I ³⁻ system, a Br ²⁻ / Br ³⁻ system, an Fe ²⁺ / Fe ³⁺ system, a quinone / hydroquinone system and the like can be used. More specifically, as the redox species, metal iodides such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI ₂ ) and iodine (I ₂₎ The combination with (1) can be used. Also, use a combination of iodine and a tetraalkylammonium salt such as tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), tetrahexylammonium iodide (THAI), etc. You can also. Furthermore, combinations of metal bromides such as lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), calcium bromide (CaBr ₂ ) and bromine can also be used. Among them, as the redox species, it is particularly preferable to use the combination of LiI and I _2.

  As the solvent of 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 non-proton polar substance is used Among them, carbonate compounds or nitrile compounds are more preferably used alone or in combination.

  In FIG. 1, the electrolyte 8 is illustrated as being disposed only in the region between the second substrate 2 and the second conductive layer 6 in the first region A. However, since the second conductive layer 6, the catalyst layer 10 and the photoelectric conversion layer 4 each have a plurality of holes, the electrolyte 8 is a plurality of each of the second conductive layer 6, the catalyst layer 10 and the photoelectric conversion layer 4. It also exists inside the hole of.

(Coloring material)
The color material 9 is disposed in the second region B. In particular, the color material 9 is preferably filled in the second region B. In the first embodiment, the coloring material 9 has fluidity, and when it comes in contact with the electrolyte 8, the color to be presented changes.

Here, the following cases (1) and (2) can be mentioned as cases where the color to be presented changes when the coloring material 9 comes in contact with the electrolyte 8.
(1) In the case where the electrolyte 8 exhibits a specific color and the electrolyte 8 is mixed and diffused in the coloring material 9, a color change derived from the specific color is confirmed in the diffusion region.
(2) In the case where the coloring material 9 contains a compound whose color changes upon contact with the electrolyte 8.

  First, the case of the above (1) will be described. For example, when the electrolyte 8 having a specific color is mixed and diffused in the colorless and transparent color material 9, the electrolyte 8 is present in the area where the electrolyte 8 in the color material 9 is diffused. The color will be reflected. As a result, the color confirmed (visually recognized) in the diffusion area of the electrolyte 8 in the color material 9 changes from colorless and transparent to a specific color (or a color like a specific color is diluted).

The electrolyte 8 exhibiting a specific color includes, for example, a liquid electrolyte containing an I ⁻ / I ³⁻ system or a quinone / hydroquinone system redox species. Such electrolytes exhibit colors such as yellow, orange, red and the like. Examples of the colorless and transparent coloring material 9 include solvents containing at least one selected from the group consisting of carbonate compounds, nitrile compounds, alcohols, water and non-proton polar substance, and among them, acetonitrile, ethanol or water Is preferred.

Next, the case (2) will be described. For example, the electrolyte 8 contains an I ⁻ / I ^{3 −} system redox species, and the color material 9 changes its chemical structure by reaction with iodine, and the color exhibited by itself changes in solution accordingly. When the compound is contained, the color of the coloring material 9 changes in the region of the coloring material 9 in which the electrolyte 8 is diffused, along with the structural change of the compound. As a result, the color confirmed (visually recognized) in the diffusion region of the electrolyte 8 in the coloring material 9 changes from the color exhibited by the compound before structural change to the color exhibited by the compound after structural change.

  The above compounds include, for example, leuco methylene blue, glycogen, dextrin, amylopectin, amylose, and polyvinyl alcohol. When the compound contained in the coloring material 9 is one or more of the above, the solvent contained in the coloring material 9 is preferably water.

  Although leuco methylene blue is colorless and transparent in an aqueous solution, the chemical structure is changed by the redox reaction with iodine, and it changes to methylene blue exhibiting a blue color in the solution. Although glycogen, dextrin, amylopectin and amylose each show white color in aqueous solution, they react with iodine and iodine starch to convert iodine into inclusion compounds incorporated into glucose helix, whereby brown, reddish brown and purple respectively. , And bluish purple (or blue). Polyvinyl alcohol exhibits a white color in an aqueous solution, but by reacting with iodine with iodine, it turns into a clathrate compound in which iodine is incorporated in the helical structure of polyvinyl alcohol, thereby exhibiting a blue color.

<Method of manufacturing photoelectric conversion element>
The photoelectric conversion element of Embodiment 1 can be manufactured, for example, as follows.

(Formation of first conductive layer)
First, the first conductive layer 3 is formed on the first substrate 1. As a method of forming the 1st conductive layer 3, methods, such as a sputtering method, a spray method, the screen-printing method, can be used, for example. In addition, a substrate in which the first conductive layer 3 is provided in advance on the first substrate 1 may be prepared.

(Formation of photoelectric conversion layer)
Next, the porous semiconductor layer 5 is formed on the first conductive layer 3. It does not specifically limit as method to form the porous semiconductor layer 5, For example, a conventionally well-known method can be used. For example, a method of applying a suspension containing semiconductor fine particles on the first conductive layer 3 and performing at least one of drying and baking can be used.

  Next, a photosensitizer is placed on the porous semiconductor layer 5. Specifically, by causing the porous semiconductor layer 5 to adsorb a sensitizing dye that is a photosensitizer, a photoelectric conversion layer 4 in which the photosensitizer is provided on the porous semiconductor layer 5 can be formed. it can.

  As a method of adsorbing the sensitizing dye to the porous semiconductor layer 5, for example, a method of immersing the porous semiconductor layer 5 in a solution for dye adsorption in which the sensitizing dye is dissolved can be used. When immersing the porous semiconductor layer 5 in a dye-adsorbing solution in which the sensitizing dye is dissolved, the dye-adsorbing solution is impregnated in order to penetrate the interior of the pores of the porous semiconductor layer 5. It may be heated.

(Installation of a precursor of a first sealing material and a precursor of a second sealing material)
Next, a precursor of the first sealing material 7 a is applied so as to surround the periphery of the porous semiconductor layer 5 at intervals from the outer edge of the porous semiconductor layer 5. Further, the precursor of the second sealing material 7b is formed so as to surround the periphery of the precursor of the first sealing material 7a at a distance from the outer edge of the region to which the precursor of the first sealing material 7a is applied. Apply

  The application method of the precursor of the first sealing material 7 a and the precursor of the second sealing material 7 b is not particularly limited. For example, applying on the first conductive layer 3 and the first substrate 1 using a dispenser Can. In the present specification, the precursor of the first sealing material 7a and the precursor of the second sealing material 7b respectively mean a resin before curing, and the first sealing material 7a and the second sealing material 7b are used. The stoppers 7b each mean a resin after curing.

(Placement of electrolyte and coloring material)
Next, the electrolyte 8 is disposed in the area corresponding to the first area A surrounded by the first sealing material 7a, and the coloring material is formed in the area corresponding to the second area B surrounded by the second sealing material 7b. Arrange 9 The arrangement method of the electrolyte 8 and the coloring material 9 is not particularly limited. For example, a drop injection (ODF) method can be used.

(Formation of second conductive layer)
Next, the second conductive layer 6 is formed on the second substrate 2. As a method of forming the 2nd conductive layer 6, methods, such as a sputtering method, a spray method, a screen printing method, can be used, for example. In addition, a substrate in which the second conductive layer 6 is provided in advance on the second substrate 2 may be prepared.

(Formation of catalyst layer)
Next, the catalyst layer 10 is formed on the second conductive layer 6. The method of forming the catalyst layer 10 is not particularly limited, and, for example, conventionally known methods can be used.

(Bonding of the first substrate and the second substrate)
Next, the second substrate 2 including the second conductive layer 6 and the catalyst layer 10 is placed on the precursor of the first sealing material 7 a and the precursor of the second sealing material 7 b so as to face the first substrate 1. Place the two substrates together. Then, ultraviolet rays are irradiated or heat is applied to each of the precursor of the first sealing material 7 a and the precursor of the second sealing material 7 b in which the first substrate 1 and the second substrate 2 are bonded. Thereby, the precursor of the first sealing material 7 a and the precursor of the second sealing material 7 b are respectively cured to form the first sealing material 7 a and the second sealing material 7 b, and the first substrate 1 And the second substrate 2 are mutually bonded. By the above, the photoelectric conversion element of Embodiment 1 provided with the sealing part 7 can be produced.

<Function effect>
The operation and effect of the first embodiment will be described in comparison with the conventional photoelectric conversion element shown in FIG.

  As shown in FIG. 3, in the conventional photoelectric conversion element, the first region A filled with the electrolyte 8 is sealed in a single layer by the sealing portion 70. In such a structure, at the interface between the sealing portion 70 and the first substrate 1 and the interface between the sealing portion 70 and the second substrate 2, chemical bonding is caused by both members, but under a severe environment As a result, the electrolyte 8 may leak to the outside from the interface between the sealing portion 70 and the first substrate 1 (or the second substrate 2). In the case where the sealing portion 70 itself is degraded or corroded in a severe environment, the electrolyte 8 erodes the inside of the sealing portion 70 and, as a result, the electrolyte 8 leaks to the outside. There was also.

  In order to cope with the above problems, in the dye-sensitized solar cell disclosed in Patent Document 2, measures are taken to make it difficult for the sealing portion and the electrolyte to come in contact with each other. It is difficult to prevent it completely.

  Therefore, the inventors of the present invention changed the viewpoint from the conventional one and focused on the behavior when the electrolyte 8 leaks to the outside, and the electrolyte 8 is the sealing portion 70 and the first substrate 1 (or the second substrate 2). In the case where the electrolyte 8 leaks to the outside from the interface with the interface and the electrolyte 8 erodes the inside of the sealing portion 70 and leaks to the outside, the electrolyte 8 exuding to the outside is the same as that of the sealing portion 70. It was confirmed that there was a tendency to touch the surface (surface in contact with the atmosphere). Furthermore, in order to observe the exuded electrolyte 8 from the outside, for example, although it is necessary to confirm from the surface side of the first substrate 1 (downward in FIG. 3), the electrolyte passing through the surface of the sealing portion 70 It was found that it was difficult to see through and therefore early detection of leaks was difficult.

  Therefore, when the electrolyte 8 leaks to the outside of the first region A, the present invention does not bridge the surface of the sealing portion 70 but gradually makes it visible in all directions. We worked hard to build a configuration that could spread. Then, instead of the sealing portion 70, the first sealing member 7a, the second sealing member 7b, and the second region B are provided, and the color exhibited by contacting the electrolyte 8 in the second region B changes. By providing the sealing part 7 of the structure by which the coloring material 9 to be arranged is arrange | positioned, the above becomes possible, and it discovered that the leak of the electrolyte 8 could be discovered at an early stage by this.

  FIG. 4 is a cross-sectional view conceptually showing a change in color exhibited by the color material in the photoelectric conversion element of Embodiment 1. The hatching shown in the first area A and the two types of hatching shown in the second area B show the difference in the color to be viewed due to the difference in the interval of the hatching. In addition, in FIG. 4, in order to make an understanding easy, the virtual boundary line of two types of hatching shown in 2nd area | region B is shown.

  Referring to FIG. 4, when the electrolyte 8 leaks from the first region A to the second region B via the interface between the first sealing material 7 a and the second substrate 2, the electrolyte 8 is a coloring material 9. Mix in The electrolyte 8 mixed in the color material 9 is gradually diffused in all directions in the second region B as shown by the white arrow in the figure.

  The color developing material 9 changes its color as it comes in contact with the electrolyte 8. Therefore, in the second area B in which the coloring material 9 is disposed, the area (in the second area B) in which the electrolyte 8 is diffused. The difference (difference) in color is between the region shown by hatching with relatively small spacing and the region where other electrolytes 8 are not diffused (the region shown by hatching with relatively large spacing in the second region B). It occurs.

  As described above, in the photoelectric conversion element of the first embodiment, unlike the conventional photoelectric conversion element in which the leaked electrolyte 8 crosses the surface of the sealing portion 70, the leaked electrolyte 8 is entirely contained in the color material 9. It will be diffused gradually in the direction. Furthermore, as described above, in the second region B, a difference in color occurs between the region where the electrolyte 8 is diffused and the region where the electrolyte 8 is not diffused. Such a color difference is easy to view, and as a result, leakage of the electrolyte 8 to the outside can be detected early.

  In the first embodiment, the coloring material 9 is preferably filled in the second region B. In this case, the entire outer surface of the second sealing material 7b comes into contact with the coloring material 9, so even if the electrolyte 8 exudes from any position of the second sealing material 7b. , Early detection of the leak will be possible.

  Furthermore, in the first embodiment, unlike the conventional photoelectric conversion element, the photoelectric conversion layer 4 is doubly sealed by the first sealing material 7a and the second sealing material 7b. The leak of 8 can be suppressed more effectively.

The degree of difference in color (visibility) can be represented by ΔE ^* ab calculated by the color difference formula of {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2 it can. The larger the value of ΔE ^* ab, the larger the color difference, which means that visual recognition of the difference in color is easy.

In the first embodiment, the value of ΔE ^* ab is preferably 30.0 or more, more preferably 40.0 or more, and still more preferably 50.0 or more. In this case, it is possible to detect leakage of the electrolyte 8 earlier because visual recognition of the color difference is easier. L ^* , a ^* and b ^* are values represented by the CIE L ^* a ^* b ^* color system standardized in JIS Z 8701-4 (2013).

The value of ΔE ^* ab described above is, for example, the color of the coloring material 9 itself before the electrolyte is mixed using an optical spectrophotometer (model number: CM-700d, target mask: φ3 mm, Konica Minolta Co., Ltd.), and the electrolyte The difference between L ^* , a ^* and b ^* is determined by measuring the color of the color material 9 after 8 is mixed and diffused, and the difference is calculated by applying the difference to the above color difference formula.

The above-mentioned color difference is the color difference between the area where the electrolyte 8 is diffused and the area where the electrolyte 8 is not diffused in the second area B, and the color of the electrolyte 8 filled in the first area A and the second It is preferable that there is a large color difference ΔE ^* ab also with the color of the region in the region B where the electrolyte 8 is diffused.

Specifically, the color difference ΔE ^* ab between the color of the electrolyte 8 itself and the color of the coloring material 9 after contacting with the electrolyte 8 is preferably 3.0 or more, and 20.0 or more. Is more preferably 40.0 or more. In this case, visual recognition of the color difference between the first area A and the area of the second area B in which the electrolyte 8 is diffused is facilitated, and leakage of the electrolyte 8 can be detected more easily at an early stage.

  For example, when the width of the second region B (the lateral direction in FIG. 1) is sufficiently small, the color of the electrolyte 8 filled in the first region A and the region of the second region where the electrolyte 8 is diffused. Visualizing differences with color is suitable for early detection of leaks.

  In the first embodiment, the coloring material 9 is preferably the coloring material of (2) among the above (1) and (2). This is because, in the case of the above (2), the above-mentioned color difference is likely to be larger than in the case of the above (1), and the visual recognition is easier.

In particular, at least one electrolyte 8 is selected from the group consisting of leuco methylene blue, glycogen, dextrin, amylopectin, amylose, and polyvinyl alcohol, and the coloring material 9 contains a redox species of the I ⁻ / I ^3- system. It is preferred to include a compound. In order to avoid unintended difficulty in visual recognition due to mixture of hues, the color material 9 preferably contains one of the compounds described above.

  Among the compounds listed above, glycogen, dextrin, amylopectin, amylose, and polyvinyl alcohol take in iodine and become an inclusion compound, but this reduces the fluidity of electrolyte 8 that has infiltrated into second region B. Do. Therefore, the possibility that the electrolyte 8 further infiltrates into the second sealing material 7b or the possibility of infiltration into the interface between the second sealing material 7b and the substrate can be reduced, whereby the electrolyte 8 is a photoelectric conversion element. It is possible to reduce the possibility of advancing to the outside of the

  In addition, even if electrolyte 8 penetrates into second sealing member 7b and leaks to the outside of the photoelectric conversion element, the concentration of iodine in electrolyte 8 that has leaked is reduced, so that, for example, in photoelectric conversion element It is more preferable at the point which can suppress corrosion of the extraction electrode (not shown) arrange | positioned outside.

  With regard to glycogen, dextrin, amylopectin and amylose, amylose is most preferable in terms of inclusion of iodine because the property of inclusion of iodine is in the order of glycogen <dextrin <amylopectin <amylose and amylose is the highest. It is.

Second Embodiment
FIG. 5 is a schematic plan view showing the shapes of the first sealing material and the second sealing material in the photoelectric conversion element of the second embodiment. That is, in FIG. 5, only the shapes of the first sealing material 7a and the second sealing material 7b are shown in order to facilitate understanding of the difference in structure from the first embodiment.

  As shown in FIG. 5, the photoelectric conversion element of Embodiment 2 is characterized in that the second sealing material 7 b is provided only in a part of the periphery of the first sealing material 7 a. The remaining description of the second embodiment is similar to that of the first embodiment, and therefore the description thereof will not be repeated.

  Since the photoelectric conversion element of the second embodiment is improved in integration as compared with the photoelectric conversion element of the first embodiment, a photoelectric conversion module with a high integration rate can be configured.

Third Embodiment
FIG. 6 shows a schematic cross-sectional view of the photoelectric conversion element of the third embodiment. In the photoelectric conversion element of Embodiment 3, the sealing portion 7 includes the first sealing material 7 a and the second sealing material 7 c provided on the outside of the first sealing material 7 a, and the second sealing. The material 7 c is characterized in that it contains a coloring material 9 whose color to be changed changes by coming into contact with the electrolyte 8.

  The second sealing material 7c is provided to surround the first sealing material 7a and to be in contact with the first sealing material 7a. As the 2nd sealing material 7c, what mixed the compound enumerated by Embodiment 1 in the 2nd sealing material 7b of Embodiment 1 can be mentioned, for example. Such a 2nd sealing material 7c can be obtained by kneading the said compound in the precursor of the 2nd sealing material 7b, and making it harden | cure.

  The remaining description of the third embodiment is similar to that of the first and second embodiments, and thus the description thereof will not be repeated.

  In the third embodiment, compared with the photoelectric conversion element of the first embodiment, the number of manufacturing steps can be reduced. It goes without saying that the second sealing material 7c may be provided on a part of the outside of the first sealing material 7a as in the second sealing material 7b of the second embodiment.

Fourth Embodiment
FIG. 7 shows a schematic cross-sectional view of the photoelectric conversion element of the fourth embodiment. The photoelectric conversion element of the fourth embodiment is characterized in that the sealing portion 7 includes a coloring material 9 whose color to be exhibited changes by coming into contact with the electrolyte 8. That is, in the fourth embodiment, the sealing portion 7 does not have the second sealing material 7 b and the second region B, and is made only of the first sealing material 7 a, and the first sealing material 7 a is a coloring material. 9 has a configuration including The sealing part 7 of Embodiment 4 can be obtained by kneading the said compound in the precursor of the 1st sealing material 7a, and making it harden | cure.

  The remaining description of the fourth embodiment is similar to that of the first and second embodiments, and therefore the description thereof will not be repeated.

  In the fourth embodiment, as compared with the photoelectric conversion device of the first embodiment and the photoelectric conversion device of the third embodiment, the number of manufacturing steps can be reduced.

Fifth Embodiment
The structure of the photoelectric conversion module of the fifth embodiment will be described with reference to FIGS. 8 and 9.

  The photoelectric conversion module of Embodiment 5 is characterized by including a plurality of photoelectric conversion cells 100a, 100b, and 100c (100a to 100c). The photoelectric conversion cells 100a to 100c are partitioned into individual cells by the first sealing material 7a. Each of the plurality of photoelectric conversion cells 100a to 100c includes the first conductive layer 3, the photoelectric conversion layer 4, the catalyst layer 10, and the second conductive layer 6 on the first substrate 1, and The electrolyte 8 is filled in the first regions A surrounded by the first substrate 1, the second substrate 2 and the first sealing material 7 a.

  Further, the second conductive layer 6 of the photoelectric conversion cell 100a and the first conductive layer 3 of the photoelectric conversion cell 100b are electrically connected to each other through the intercell conductive portion 20, whereby the photoelectric conversion cell 100a and the photoelectric conversion are made. The cell 100 b is electrically connected in series. In addition, the second conductive layer 6 of the photoelectric conversion cell 100b and the first conductive layer 3 of the photoelectric conversion cell 100c are electrically connected to each other through the inter-cell conductive portion 20, whereby the photoelectric conversion cell 100b and the photoelectric conversion are performed. The cell 100c is electrically connected in series. Thus, the photoelectric conversion cells 100a to 100c are connected in series. The photoelectric conversion cells 100a to 100c can also be electrically connected in parallel.

  In addition, in the region between the first substrate 1 and the second substrate 2, the outer peripheries of the photoelectric conversion cells 100a to 100c electrically connected in series or in parallel are the first sealing material 7a and the second sealing material. It is surrounded by a double seal 7 with the stop 7b.

  The remaining description of the fifth embodiment is similar to that of the first embodiment, and therefore the description thereof will not be repeated.

  According to the photoelectric conversion module of the fifth embodiment, for the same reason as that of the first embodiment, leakage of the electrolyte 8 can be detected at an early stage.

Sixth Embodiment
FIG. 10 is a schematic plan view showing the shapes of the first sealing material and the second sealing material in the photoelectric conversion module according to the sixth embodiment. That is, in FIG. 10, only the shapes of the first sealing material 7a and the second sealing material 7b are shown in order to facilitate understanding of the difference in structure from the fourth embodiment.

  As shown in FIG. 10, the photoelectric conversion element module according to the sixth embodiment is different from the fifth embodiment in that the plurality of photoelectric conversion cells 100a to 100c are surrounded by the individual second sealing members 7b. Do. The remaining description of the sixth embodiment is similar to that of the fifth embodiment, and thus the description thereof will not be repeated.

Seventh Embodiment
FIG. 11 is a schematic plan view showing the shapes of the first sealing material and the second sealing material in the photoelectric conversion module according to the seventh embodiment. That is, in FIG. 11, only the shapes of the first sealing material 7a and the second sealing material 7b are shown in order to facilitate understanding of the difference in structure from the fifth embodiment.

  As shown in FIG. 11, in the photoelectric conversion module of the seventh embodiment, in each of the plurality of photoelectric conversion cells 100a to 100c, a part of the periphery of each first sealing material 7a, specifically, the lower part of FIG. The fourth embodiment is different from the fourth embodiment in that the second sealing material 7b is provided only on the outside of the first sealing material 7a on the short side located in The remaining description of the seventh embodiment is similar to that of the fifth embodiment, and therefore the description thereof will not be repeated.

Example 1
The photoelectric conversion element of Example 1 having the structure shown in FIG. 1 was produced.

(Formation of first conductive layer)
First, a glass substrate with a SnO ₂ film, manufactured by Nippon Sheet Glass Co., Ltd., having a surface with a size of 30 mm long × 120 mm wide was prepared. Thus, a member having a SnO ₂ film (length 30 mm × width 120 mm) as the first conductive layer 3 was prepared on the glass substrate as the first substrate 1. The electrical resistance of the SnO ₂ film was 12 Ω / □.

(Formation of photoelectric conversion layer)
Then, using a screen printing machine (New Long Seimitsu Kogyo Co., Ltd. LS-0.99), a commercially available titanium oxide paste (Solaronix Co., Ltd., trade name Ti-Nanoxide D / SP, average particle size 13 nm) and SnO ₂ film Applied on top.

  Next, the coating obtained by leveling the titanium oxide paste at room temperature for 1 hour was preliminarily dried at 80 ° C. for 20 minutes, and baked at 450 ° C. for 1 hour. By repeating the application process of the titanium oxide paste, the leveling process, the preliminary drying process, and the firing process in this order, a porous semiconductor layer 5 made of titanium oxide having a length of 10 mm × width 100 mm and a thickness of 5 μm was formed.

Next, Ruthenium 620-1H3TBA dye (manufactured by Solaronix) is used as a sensitizing dye, and a 1: 1 solution (acetonitrile dye) of acetonitrile (manufactured by Aldrich Chemical Company) / t-butyl alcohol (manufactured by Aldrich Chemical Company) is used. Concentration: 4 × 10 ^-4 mol / l) was prepared. The porous semiconductor layer 5 was immersed in this solution and left for 20 hours under a temperature condition of 40 ° C. Thereafter, the porous semiconductor layer 5 was washed with ethanol (manufactured by Aldrich Chemical Company) and then dried. Thus, the photoelectric conversion layer 4 was formed on the first conductive layer 3 by adsorbing the sensitizing dye to the porous semiconductor layer 5.

(Formation of second conductive layer)
A glass substrate identical to the first substrate 1 is prepared as the second substrate 2, and titanium (Ti) is formed to a thickness of 2.5 Å / S on the SnO ₂ film using an electron beam vapor deposition device EVD-500A (manufactured by ANELVA). The deposition was carried out at a deposition rate of Thereby, the second conductive layer 6 composed of the SnO ₂ film and the Ti film having a thickness of 10000 Å was formed on the second substrate 2.

(Formation of catalyst layer)
Next, platinum was vapor-deposited on the second conductive layer 6 at a vapor deposition rate of 0.1 Å / S using an electron beam vaporizer EVD-500A (manufactured by ANELVA). Thus, the catalyst layer 10 made of a platinum film having a thickness of 500 Å was formed on the second conductive layer 6.

(Installation of a precursor of a first sealing material and a precursor of a second sealing material)
Next, as a precursor of the first sealing material 7 a, an ultraviolet ray curable resin (product number: 3035 B, manufactured by Three Bond Co., Ltd.) is provided on the first conductive layer 3 and the first substrate 1 so as to surround the photoelectric conversion layer 4. It applied. Next, as a precursor of the second sealing material 7b, a thermosetting resin (product number: 3118, manufactured by ThreeBond) is placed on the first conductive layer 3 and the first conductive layer 3 so as to surround the precursor of the first sealing material 7a. 1 applied to substrate 1

  The precursor of the first sealing material 7 a is disposed at a position 8 mm inward from the outer edge of the first substrate 1, and the precursor of the second sealing material 7 b is 2 mm inwardly from the outer edge of the first substrate 1. Placed in the

(Placement of electrolyte and coloring material)
Next, as electrolyte 8, acetonitrile (purity 99.5%) is used as a solvent, in which 1,2-dimethyl-3-propylimidazole iodide (1,2-dimethyl-3-propylimidazolium iodide (Shikoku Kasei) Manufactured by Ind. Ltd.)) at 0.6 mol / l, LiI (manufactured by Aldrich Chemical Company) at 0.1 mol / l, 4-tert-butylpyridine (manufactured by Aldrich Chemical Company) at 0 A redox electrolyte in which 0.01 mol / liter of I ₂ (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was prepared. Then, the above-mentioned redox electrolytic solution was dropped in a region partitioned by the precursors of the first substrate 1 and the first sealing material 7a.

  Further, acetonitrile (purity 99.5%, manufactured by Kishida Chemical Co., Ltd.) as the coloring material 9 is partitioned by the first substrate 1, the precursor of the first sealing material 7a, and the precursor of the second sealing material 7b. It dripped to the dry area.

(Bonding of the first substrate and the second substrate)
Next, the second substrate 2 was placed on the surface of the precursor of the first sealing material 7 a and the precursor of the second sealing material 7 b so as to face the first substrate 1 in a reduced pressure atmosphere. The surface of the second substrate 2 on which the second conductive layer 6 and the catalyst layer 10 are provided is disposed so as to face the first substrate 1, and the thickness is set between the first substrate 1 and the second substrate 2. A 30 μm spacer was inserted. Then, the first substrate 1 and the second substrate 2 were pressed for 30 seconds with a force of 1.8 kN in a direction in which the first substrate 1 and the second substrate 2 approach each other. Thus, the first substrate 1 and the second substrate 2 were attached.

  Next, the precursor of the first sealing material 7a in which the first substrate 1 and the second substrate 2 are bonded is irradiated with ultraviolet light, and then the precursor of the second sealing material 7b is heated at 80 ° C. for one hour Each was cured by heating to form a sealing portion 7 composed of the first sealing material 7a and the second sealing material 7b. Thereby, the first substrate 1 and the second substrate 2 were bonded by the sealing portion 7. A UV lamp (trade name; Spot Cure, manufactured by Ushio Electric Co., Ltd.) was used for the irradiation of the ultraviolet light, and a thermostatic bath (trade name: SU-261, manufactured by ESPEC Corp.) was used for the heat treatment.

(Placement of lead-out electrode)
Next, the extraction electrode was disposed on the first conductive layer 3 exposed to the outside, and the extraction electrode was disposed on the second conductive layer 6 exposed to the outside.

  Thus, the photoelectric conversion element of Example 1 was manufactured. In addition, the area | region (namely, width | variety of 2nd area | region B) between the precursor of the 1st sealing material 7a and the precursor of the 2nd sealing material 7b was 2 mm.

Example 2
A photoelectric conversion element of Example 2 was produced in the same manner as Example 1 except that a leuco methylene blue solution was used as the coloring material 9. As the leuco methylene blue solution, a colorless and transparent aqueous solution obtained by adding an appropriate amount of glucose (product number: G0048, manufactured by Tokyo Chemical Co., Ltd.) to an aqueous solution containing 0.05% by weight of methylene blue (product number; It was.

Example 3
A photoelectric conversion element of Example 3 was produced in the same manner as Example 1 except that a glycogen solution was used as the coloring material 9. As a glycogen solution, a white aqueous solution containing 0.01% by weight of glycogen (product number: 077-05311, manufactured by Wako Pure Chemical Industries, Ltd.) was used.

Example 4
A photoelectric conversion element of Example 4 was produced in the same manner as Example 1 except that a dextrin solution was used as the coloring material 9. As the dextrin solution, a white aqueous solution containing 1% by weight of α-cyclodextrin (product number; C0766, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used.

Example 5
A photoelectric conversion element of Example 5 was produced in the same manner as Example 1 except that an amylopectin solution was used as the coloring material 9. As the amylopectin solution, a white aqueous solution containing 1% by weight of amylopectin (product number; A0456, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used.

Example 6
A photoelectric conversion element of Example 6 was produced in the same manner as Example 1 except that an amylose solution was used as the coloring material 9. As an amylose solution, a white aqueous solution containing 1% by weight of amylose (product number; A0847, manufactured by Tokyo Kasei Co., Ltd.) was used.

Example 7
A photoelectric conversion element of Example 7 was produced in the same manner as Example 1 except that a polyvinyl alcohol solution was used as the coloring material 9. As a polyvinyl alcohol solution, a white aqueous solution containing 2% by weight of polyvinyl alcohol (part number: P0469, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used.

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 7b was not formed and the coloring material 9 was not used.

<Evaluation>
In each photoelectric conversion element of Examples 1 to 7 prepared as described above, a spectrocolorimeter (model number: CM-700d, target mask: φ3 mm, manufactured by Konica Minolta, Inc.) from the side of the first substrate 1 The L ^* , a ^* and b ^* of the electrolyte 8 filled in the first region A were measured using Similarly, L ^* , a ^* and b ^* of the color material 9 filled in the second region B were measured.

Next, each photoelectric conversion element of each of Examples 1 to 7 and Comparative Example 1 is left at a temperature of 85 ° C. for 15 hours according to the method described in JIS C8938. Heat stress treatment was performed. When the photoelectric conversion elements were observed from the second substrate 2 side after the heat stress treatment, a change in color of the coloring material 9 was visually recognized. It is considered that this is because the electrolyte 8 exudes from the first region A into the second region B. Therefore, L ^* , a ^* and b ^* of the color material 9 after the color change was measured by the same method as described above.

From the measured values, ΔE ^* ab of the electrolyte 8 filled in the first region A and the color material 9 after the color change in the second region B was calculated. The results are shown in Table 1. Similarly, ΔE ^* ab of the coloring material 9 before the color change in the second region B and the coloring material 9 after the color change in the second region B was calculated. The results are shown in Table 2. The "color" in Tables 1 and 2 is the color of the color material 9 observed visually.

Referring to Table 1, in Examples 1 to 7, the color difference ΔE ^* ab between the electrolyte 8 and the coloring material 9 after contacting the electrolyte 8 was 3.0 or more. Referring to Table 2, in Examples 1 to 7, the color difference ΔE ^* ab between the color material 9 before contact with the electrolyte 8 and the color material 9 after contact with the electrolyte 8 was 30.0 or more. Moreover, although the leak confirmation of the electrolyte 8 in the photoelectric conversion element of Example 1-Example 7 by the observer was implemented, since there is sufficient color difference in any case, visual recognition of the change of the color of the coloring material 9 Was easy. That is, leakage of the electrolyte 8 could be confirmed at an early stage.

  Furthermore, in Examples 2 to 7, since the position where the color change of the color material 9 starts can be identified, it was found that even the leakage portion of the electrolyte 8 can be confirmed. This was considered to be because the color difference in Example 2 to Example 7 was larger than the color difference in Example 1.

  Moreover, regarding Example 1-Example 7, when the above-mentioned heat stress processing was performed for 150 hours, it was confirmed that the electrolyte 8 also corrodes the 2nd sealing material 7b, and leaks to the exterior of a photoelectric conversion element. It was done.

  Here, in Examples 3 to 7 among Examples 1 to 7, the corrosion of the lead-out electrode due to the leakage of electrolyte 8 is suppressed as compared with Examples 1 and 2. Was confirmed. This is because, in Examples 3 to 7, since the iodine in the electrolyte 8 forms a clathrate compound with the compound contained in the coloring material 9, the concentration of iodine in the electrolyte 8 which exudes to the extraction electrode is As a result, it was considered that the corrosiveness of the electrolyte 8 was lowered.

  On the other hand, in Comparative Example 1, although it was confirmed that the electrolyte 8 was attached to the surface (surface exposed to the atmosphere) exposed to the outside of the sealing material, much attention is required for the confirmation. there were. In addition, the location of the leak could not be identified, and the corrosion of the lead-out electrode was remarkable when the heat stress treatment was performed for 150 hours.

  In particular, when Example 1 and Comparative Example 1 were compared with respect to the degree of corrosion of the lead-out electrode, the corrosion of the lead-out electrode was more remarkable in Comparative Example 1. From this, it was found that the leakage of the electrolyte 8 to the outside can be suppressed compared with the comparative example 1 in the example 1 and, consequently, the examples 1 to 7.

  Although the embodiments and examples have been described as 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 indicated not by the above description but by the claims, and is intended to include all the modifications within the meaning and scope equivalent to the claims.

  The embodiments disclosed herein can be used for a photoelectric conversion device, a photoelectric conversion module, and a method of manufacturing the photoelectric conversion device, and in particular, a dye-sensitized solar cell, a dye-sensitized solar cell module, and a method of manufacturing them Can be suitably used. In addition, although a so-called sandwich type photoelectric conversion element is described in the present specification, the above embodiment can be applied to a so-called monolithic type photoelectric conversion element and a back contact cell type photoelectric conversion element.

  Reference Signs List 1 first substrate, 2 second substrate, 3 first conductive layer, 4 photoelectric conversion layer, 5 porous semiconductor layer, 6 second conductive layer, 7 sealing portion, 7a first sealing material, 7b, 7c second Sealing material, 8 electrolytes, 9 coloring materials, 10 catalyst layers, 20 inter-cell conductive parts, 70 sealing materials, 100a, 100b, 100c photoelectric conversion cells.

Claims (8)

A first substrate,
A second substrate facing the first substrate at an interval;
A first conductive layer located on the first substrate;
A photoelectric conversion layer located on the first conductive layer;
A second conductive layer located on the photoelectric conversion layer;
A seal surrounding a first region between the first substrate and the second substrate;
The first substrate, the second substrate, and an electrolyte filled in the first region surrounded by the sealing portion ;
The photoelectric conversion layer includes a porous semiconductor layer and a photosensitizer provided on the porous semiconductor layer,
The sealing unit includes a Teiirozai a flowable color which develops by into contact with the electrolyte is changed, the photoelectric conversion element. The photoelectric conversion device according to claim 1, wherein the coloring material is a solvent including at least one selected from the group consisting of a carbonate compound, a nitrile compound, an alcohol, water, and a non-proton polar substance. The sealing portion includes a first sealing material, a second sealing material provided on the outer side of the first sealing material, the first substrate, the second substrate, the first sealing material, and And a second region surrounded by the second sealing material,
The photoelectric conversion element according to claim 1, wherein the coloring material is disposed in the second region. The sealing portion includes a first sealing material and a second sealing material provided outside the first sealing material.
The photoelectric conversion element according to claim 1, wherein the second sealing material includes the color material. Wherein the coloring material prior to contact with the electrolyte, the color difference Delta] E ^* ab between the color former material after contact with the electrolyte, is 3.0 or more, any of claims 1 to 4 1 The photoelectric conversion element as described in a term. The electrolyte contains iodine and
The color material includes a compound whose color is changed by reacting with the iodine,
The compound is at least one selected from the group consisting of leuco methylene blue, glycogen, dextrin, amylopectin, amylose, and polyvinyl alcohol, which form the inclusion compound containing iodine by reacting with the iodine. The photoelectric conversion element according to any one of claims 1 to 5 . The electrolyte contains iodine and
The color material includes a compound whose color is changed by reacting with the iodine,
The photoelectric conversion element according to any one of claims 1 to 5 , wherein the compound reacts with the iodine to form an inclusion compound containing the iodine. 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 located on the first substrate, a photoelectric conversion layer located on the first conductive layer, and a second conductive layer located on the photoelectric conversion 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 on the porous semiconductor layer,
The photoelectric conversion module includes a sealing portion provided so as to surround the plurality of photoelectric conversion cells between the first substrate and the second substrate,
The sealing portion, the depending into contact with the electrolyte containing Teiirozai a flowable color which develops is changed, the photoelectric conversion module.

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