JP2018085497A - Photoelectric conversion element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, by a simple method, a perovskite-type photoelectric conversion element composed of a halide organic-inorganic hybrid perovskite compound layer.SOLUTION: The perovskite-type photoelectric conversion element is provided that includes: a photoelectrode substrate 1 having opposing conductive layers 2 at least one of which is transparent; a counter electrode substrate 1 having the conductive layer 2; and a photoelectric conversion layer 4 disposed between the photoelectrode substrate and the counter electrode substrate and having a halide organic-inorganic hybrid perovskite compound as a component. The perovskite-type photoelectric conversion element has at least one adhesion layer 5. The halide organic-inorganic hybrid perovskite compound has perovskite structure which is represented by a general formula: R-M-Xn (here, R is an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom, and n is an integer.)SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photoelectric conversion element using an organic-inorganic hybrid perovskite compound for a photoelectric conversion layer.

  At present, pn junction type solar cells, which are solid type solar cells, are commercialized and widely used in the market. In this pn junction solar cell, a silicon crystal, an amorphous silicon thin film, or a non-silicon compound semiconductor multilayer thin film is used. However, since these solar cells are manufactured at a high temperature or under vacuum, there is a limit in reducing the manufacturing cost, and there is a drawback that it takes time to recover the investment. For this reason, it is desired to develop a solar cell that can be manufactured at a lower temperature at a lower temperature. One of them is a dye-sensitized solar cell that can be mass-produced at low cost in the atmosphere. The dye-sensitized solar cell is a photoactive electrode in which a sensitizing dye is supported on a porous semiconductor fine particle layer made of metal oxide semiconductor nanoparticles typified by titanium dioxide nanoparticles formed on a transparent conductive substrate. A substrate (photoelectrode) and a counter electrode substrate (counter electrode) in which a counter electrode layer such as platinum is formed on a conductive substrate are arranged to face each other, the electrolyte solution is filled between the substrates, and the electrolyte solution is sealed It consists of a structure. The dye-sensitized solar cell has a simple manufacturing process and can be manufactured at low cost, but uses a liquid as an electrolyte and uses a ruthenium dye that is an organic dye or an organometallic compound as a sensitizing dye. For this reason, there is a problem that sufficient durability cannot be obtained particularly in a severe environment (Patent Document 1).

  On the other hand, organic thin-film solar cells that do not use an electrolytic solution and a sensitizing dye are generally widely known. However, the photoelectric conversion efficiency is lower than that of the dye-sensitized solar cell, and there are concerns about the durability of the solar cell. Moreover, many processes are required for manufacturing these solar cell module units, and simplification of the manufacturing process is desired for cost reduction. In recent years, solar cells using organic / inorganic perovskite compounds and / or inorganic perovskite compounds have been actively studied as next-generation solar cells. Non-Patent Document 1 discloses a dye-sensitized solar cell using a hole transfer type inorganic perovskite compound (CsSnI3) instead of an electrolytic solution. However, the same ruthenium dye as the dye-sensitized solar cell is used as the light absorbing material by adsorbing it to the porous semiconductor fine particle (titanium oxide) layer, so there is a problem in the durability of the solar cell due to the desorption and decomposition of the dye. is there. Non-Patent Document 2 discloses the use of an organic / inorganic perovskite compound instead of a sensitizing dye. However, there is a problem that sufficient durability cannot be obtained because an electrolytic solution is used as in the dye-sensitized solar cell.

  Patent Document 2 discloses a solid-state photoelectric conversion element in which an organic inorganic perovskite compound is adsorbed on a porous semiconductor fine particle layer and neither an electrolytic solution nor an organic dye is used. This is considered to be a solar cell in which the porous semiconductor fine particle layer is n-type and the organic / inorganic perovskite compound is p-type, and has the potential as a solar cell that can be manufactured at low cost and has good durability. However, it is necessary to further simplify the configuration of the photoelectric conversion element layer in order to produce a low-cost and commercially advantageous solar cell in place of the current silicon type solar cell.

  Patent Document 3 discloses a solid-state photoelectric conversion element in which an organic / inorganic perovskite compound is bonded as n-type and an inorganic perovskite compound is bonded as p-type without using a porous semiconductor fine particle layer. However, the bonding between the photoelectrode and the counter electrode is only physically bonded, and an improvement in the durability of the solar cell is desired.

  Non-Patent Documents 3 and 4 disclose solar cells having a single-layer structure using a perovskite oxide typified by lead zirconate titanate, which is a ferroelectric material, between a pair of transparent electrode substrates. . Although this solar cell has a single-layer structure and is a preferred form, these perovskite oxides exhibiting ferroelectricity do not absorb in the visible light region, and therefore have low photocurrent and very high photoconversion efficiency as a solar cell. There is a problem that it is low. Moreover, although the structure of a solar cell is very simple, since it cannot manufacture at normal temperature and needs to manufacture by vacuuming, there exists a problem that manufacturing cost becomes high.

  Non-Patent Document 5 discloses that an organic / inorganic perovskite compound having a specific crystal structure exhibits dielectric properties at room temperature. Furthermore, according to the method described in Patent Document 4, a high-efficiency photoelectric conversion element composed of a specific organic-inorganic hybrid semiconductor layer is required by defining the arithmetic average roughness of the electrode. However, in Patent Document 4, a gold film by vacuum deposition is formed as an anode, and in Patent Document 5, since silver is deposited as an anode, a volatile component such as an organic-inorganic perovskite layer reaches a necessary vacuum state. However, it takes time to manufacture a large-area module, and it has a problem that it is difficult to form a desired anode without reaching a predetermined degree of vacuum.

   Conventional photoelectric conversion elements using organic / inorganic perovskites are related to improvement in conversion efficiency and durability, and although improvement in the effect is recognized, cost considerations in commercialization of products are greatly lacking. . As for the assembly of the perovskite photoelectric conversion element, the counter electrode such as gold or silver is finally applied by vapor deposition or the photoelectrode and the counter electrode are physically overlapped. There was a problem with sex.

  The present invention has found a method for producing a photoelectric conversion element in consideration of its cost and characteristic stability in commercialization of these near future photoelectric conversion elements, and it is durable without reducing power generation efficiency by a simple method. Improved.

US Pat. No. 4,927,721 EP2693503 JP 2014-049596 A JP 2006-119468 A JP-T-2006-513077

Nature 2012, 485, 486 Journal of the American Chemical Society 2009, 131, 6050 Journal of Materials Chemistry A 2014, 2, 6027-6041 Journal of the American Chemical Society 2012, 12, 2803 The Journal of Physical Chemistry Letters 2014, 5, 3335

  In the present invention, by using a perovskite photoelectric conversion element having a high energy conversion efficiency made of a halide organic-inorganic hybrid perovskite compound in the photoelectric conversion layer, there is a problem in durability due to deterioration of the sensitizing dye or leakage of the electrolytic solution. An object of the present invention is to solve the above-mentioned problems of a certain dye-sensitized solar cell or an organic thin-film solar cell having problems in light resistance and moisture resistance. Furthermore, when a photoelectrode having a photoelectric conversion layer made of the halide organic-inorganic hybrid perovskite compound and a counter electrode are produced in combination, the configuration is achieved by a very simple method. Another object of the present invention is to provide a highly efficient perovskite photoelectric conversion element, module, and solar cell by an inexpensive method.

  The present invention can be implemented in the following (Aspect 1) to (Aspect 8).

(Aspect 1) A photoelectrode substrate having conductive layers facing each other, at least one of which is transparent, a counter electrode substrate having a conductive layer, and a halide-based organic-inorganic hybrid perovskite compound or a halide-based organic-inorganic hybrid perovskite compound and a halide-based material The perovskite photoelectric conversion element having a photoelectric conversion layer made of an inorganic perovskite compound, wherein the perovskite photoelectric conversion element has at least one adhesive layer.

(Aspect 2) The aspect 1 is characterized in that the adhesive layer is an adhesive layer containing an adhesive selected from at least one polymer, a polymerizable monomer and / or a polymerizable oligomer compound, and a mixture thereof. The perovskite photoelectric conversion element described.

(Aspect 3) The perovskite type according to aspect 1 or 2, wherein the adhesive layer is an adhesive layer containing at least one type of halide-based organic / inorganic hybrid perovskite compound, inorganic perovskite compound, or hole transport compound. It is a photoelectric conversion element.

(Aspect 4) The halide organic-inorganic hybrid perovskite compound is represented by the general formula RM-Xn (where R is an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom, and n is an integer). 4. The perovskite photoelectric conversion element according to any one of aspects 1 to 3, which has a perovskite structure.

(Aspect 5) The perovskite photoelectric conversion element according to any one of aspects 1 to 4, wherein the perovskite photoelectric conversion element has at least one conductive layer, and / or a buffer layer and / or an electron transport layer.

(Aspect 6) The perovskite photoelectric conversion element according to any one of aspects 1 to 5, wherein the perovskite photoelectric conversion element has at least one conductive layer and / or a hole transport layer and / or a buffer layer. .

(Aspect 7) The perovskite type according to any one of aspects 1 to 6, wherein the conductive material of the perovskite photoelectric conversion element is a conductive material selected from a metal compound, a metal oxide, and an organic conductive compound. It is a photoelectric conversion element.

(Aspect 8) The perovskite photoelectric conversion element includes a photoelectrode substrate, a conductive layer, a buffer layer, an electron transport layer, a fine particle semiconductor layer, a photoelectric conversion layer having at least one halide organic-inorganic hybrid perovskite compound, and a hole transport layer. A perovskite photoelectric conversion element according to any one of claims 1 to 7, wherein the perovskite photoelectric conversion element is formed by sequentially laminating a conductive layer and a counter electrode substrate, and the perovskite photoelectric conversion element has at least one adhesive layer. It is an element.

  According to the present invention, it is possible to manufacture a photoelectric conversion element that is structurally simple and inexpensive to manufacture. Moreover, it becomes possible to produce a photoelectric conversion element having excellent photoelectric conversion efficiency and excellent durability. Furthermore, according to the present invention, it is possible to manufacture a large-area cell, module or solar battery.

It is a schematic diagram which shows the 1st embodiment of the layer structure of the perovskite type photoelectric conversion element of this invention. It is a schematic diagram which shows the 2nd embodiment of the layer structure of the perovskite type photoelectric conversion element of this invention. It is a schematic diagram which shows the 3rd embodiment of the layer structure of the perovskite type photoelectric conversion element of this invention.

  1 to 3 are schematic views showing an embodiment of the layer structure of the perovskite photoelectric conversion element of the present invention. Examples 1 (FIG. 1), Examples 12, 13 (FIG. 2), and Example 20 described later are used. This corresponds to (FIG. 3). However, the present invention is not limited to these embodiments.

  Hereinafter, the perovskite photoelectric conversion element of the present invention will be described. Here, the coating method of each layer described below is not particularly limited as long as a desired layer can be installed. The coating method of the solution or dispersion forming each preferred layer is not particularly limited, and spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, A known coating method such as an inkjet printing method or a dipping method can be used. Of these, spin coating, bar coating, screen printing, spray coating, dip coating, ink jet printing, dipping, and the like are preferable.

Hereinafter, although each basic layer which comprises this invention is demonstrated, it is not limited to this.
The basic configuration of the present invention is that a photoelectrode (hereinafter referred to as “conductive photoelectrode”) having a photoelectric conversion layer made of a halide organic-inorganic hybrid perovskite compound and a counter electrode (hereinafter referred to as “conductive photoelectrode”) having a conductive layer. It is a perovskite photoelectric conversion element in which a conductive counter electrode is referred to) and has at least one adhesive layer. Furthermore, the conductive photoelectrode comprises a photoelectrode substrate and a conductive layer, optionally a buffer layer, an electron transport layer, a fine particle layer, and a photoelectric conversion layer containing a halide organic-inorganic hybrid perovskite compound. It is a perovskite photoelectric conversion element having a counter electrode substrate, a conductive layer, and optionally a hole transport layer, and further having at least one adhesive layer between these substrates and each layer. The conductive photoelectrode and the conductive counter electrode may be a conductive photoelectrode substrate or a conductive counter electrode substrate composed of a conductive substrate and a conductive layer, or at least one substrate may also serve as a conductive layer. For example, a substrate in which a metal compound or a conductive compound is incorporated in the substrate may be used. The basic configuration may be changed depending on the manufacturing form, and is not fixed to this. For example, the configuration as a conductive photoelectrode can include a photoelectrode substrate / conductive layer / buffer layer / electron transport layer / fine particle layer / perovskite layer. The conductive counter electrode can be a counter electrode substrate / conductive layer. Mention may be made of layer / hole transport. A photoelectric conversion element obtained by laminating a conductive photoelectrode and a conductive counter electrode is characterized in that it further has at least one adhesive layer in one place of each layer.

First, the adhesive layer used in the present invention will be described.
[Adhesive layer]
In the present invention, the perovskite photoelectric conversion layer element is provided with an adhesive layer in at least one layer to produce a perovskite type photoelectric conversion element, and thereby, between the layers of the constituent layers of the perovskite type solar cell. Adhesiveness can be greatly increased, and photoelectric conversion efficiency can be greatly improved. Conventionally, a vacuum deposition process or the like is required when manufacturing the counter electrode. However, this process is not necessary, and the cost can be greatly reduced. The adhesive layer is a layer that adheres without gaps between the constituent layers of the perovskite photoelectric conversion element, and preferred materials include the following. For example, an organic compound (low molecular compound, oligomer or polymer) as a binder, a material for forming a hole transport layer, a material for forming a perovskite layer, an inorganic material (particularly a fine particle material), or a mixture thereof can be used.

  Among these, the material preferably used is an organic substance, and the material and the usage method are not limited as long as the power generation between the conductive photoelectrode and the conductive counter electrode is not hindered. The material that can be preferably used is a material having adhesiveness with various materials, and preferably includes a polymer and a reactive adhesive layer material (reactive monomer, reactive oligomer, reactive polymer, etc.). The reactive monomer, the reactive oligomer, and the reactive polymer are not particularly limited as long as they are used for at least one adhesive layer and become a raw material having adhesiveness with an adjacent layer. In the case of a reactive adhesive layer material, the adhesive layer applied to the photoelectric conversion element can be cured by applying light irradiation, electron beam irradiation, heat, etc. from the outside after bonding, to strengthen the adhesion Is preferred. For example, a curable acrylic monomer or oligomer that is representative of a cured acrylic resin layer can be mentioned, and after applying to the outermost layer of the counter electrode and bonding it to the photoelectrode, it is also possible to cure by irradiating light. preferable. By these, it becomes possible to produce the perovskite photoelectric conversion element, module and solar cell of the present invention.

(polymer)
First, a preferable material for the adhesive layer includes a polymer, and the material is not particularly limited. For example, an acrylic polymer, a rubber polymer, a vinyl alkyl ether polymer, a silicone polymer, a polyester polymer, a polyamide polymer, and a urethane. Polymer, fluorine polymer, epoxy polymer, ethylene / vinyl acetate copolymer resin, α-olefin (isobutene-maleic anhydride polymer, α-olefin (isobutene-maleic anhydride) polymer, vinyl chloride resin, chloroprene rubber , Nitrile rubber, urethane polymer, etc. These polymers can be used alone or in combination of two or more, and other materials (for example, monomers, oligomers, inorganic compounds, etc.) can be used. Use together You can also.

  The adhesive layer having the polymer of the present invention is not particularly limited. However, material selection of the adhesive layer and the like can be easily performed by forming a polymer by selecting a monomer as necessary. The polymer preferably contains an acrylic polymer. The acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth) acryloyl group in the molecule) as a constituent monomer component. Acrylic polymers can be used alone or in combination of two or more.

  Here, an acrylic polymer is one of the materials preferably used as the adhesive layer provided between the constituent layers in the present invention, and will be described below. It is preferable that a (meth) acrylic acid alkyl ester is included as a monomer component constituting the acrylic polymer. Examples of the (meth) acrylic acid alkyl ester include ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) ) Acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) ) And (meth) acrylic acid alkyl esters having an alkyl group having 1 to 14 carbon atoms such as acrylate and n-tetradecyl (meth) acrylate. Among these, (meth) acrylic acid alkyl ester having an alkyl group having 3 to 13 carbon atoms is preferable, and isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meta) is more preferable. ) Acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) ) Acrylate, n-tridecyl (meth) acrylate. Acrylic monomers can be used alone or in combination of two or more.

  The monomer component constituting the acrylic polymer preferably further contains a hydroxyl group-containing monomer. Although it does not specifically limit as said hydroxyl group containing monomer, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate , 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol , Allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. The hydroxyl group-containing monomers can be used alone or in combination of two or more.

   Furthermore, a polyfunctional monomer may be contained in the monomer component constituting the acrylic polymer from the viewpoint that a crosslinked structure can be introduced into the acrylic polymer and necessary cohesive force can be obtained. Although it does not specifically limit as said polyfunctional monomer, For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, N, N'-methylenebisacrylamide, etc. . The said polyfunctional monomer can be used individually or in combination of 2 or more types.

  The ratio of the polyfunctional monomer to the total monomer component (100% by weight) constituting the acrylic polymer is not particularly limited, but is preferably 0.1 to 30% by weight, and more preferably 0.1 to 10% by weight. %. When the ratio of the polyfunctional monomer is 0.1% by weight or more, the flexibility and adhesiveness are excellent. When the ratio of the polyfunctional monomer is 30% by weight or less, the cohesive force does not become too high, and an appropriate adhesive strength can be obtained. Although the monomer component which comprises the said acrylic polymer is not specifically limited, It is preferable that the alkylene oxide group containing reactive monomer is further included.

  Examples of the monomer component constituting the (meth) acrylic polymer include (meth) acrylic acid alkylene oxide adducts, and specific examples thereof include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene. Glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (Meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauroxypolyethylene Glycol (meth) acrylate, stearoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octoxypolyethylene glycol - polypropylene glycol (meth) acrylate.

(Reactive monomer, reactive oligomer, reactive polymer)
In addition, the adhesive layer of the present invention can be preferably used as an adhesive layer made of a reactive monomer or reactive oligomer, and is not particularly limited as long as it can achieve adhesion between the constituent layers of the photoelectric conversion element. When using reactive monomers and reactive oligomers, coat them on either side of the photoelectric conversion element, bond them with the counter electrode, and then cure it by some means. Can be used by strengthening the bonding. The reactive monomers and reactive oligomers that can be preferably used are described below. The reactive monomer and reactive oligomer composition may contain a polymerization initiator. Examples of reactive monomers and reactive oligomers include reactive monomers and reactive oligomers having a radical reactive bond and / or a cationic reactive bond in the molecule. The reactive monomer, reactive oligomer, and reactive polymer may include a non-reactive polymer, an active energy ray sol-gel reactive composition.

Examples of the reactive monomer having a radical reactive bond include a monofunctional monomer and a polyfunctional monomer.
Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl ( )) (Meth) acrylate derivatives such as acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate; (meth) acrylic acid, (meth) acrylonitrile; styrene, α -Styrene derivatives such as methylstyrene; (meth) acrylamide derivatives such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and the like. These may be used alone or in combination of two or more.

  Polyfunctional monomers include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (3- ( Ta) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) ) Butane, dimethylol tricyclodecane di (meth) acrylate, ethylene oxide adduct di (meth) acrylate of bisphenol A, propylene oxide adduct di (meth) acrylate of bisphenol A, neopentyl glycol di (meth) hydroxypivalate Bifunctional monomers such as acrylate, divinylbenzene, and methylenebisacrylamide; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide Functional tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate and other trifunctional monomers; succinic acid / trimethylolethane / acrylic acid 4 or more functional monomers such as dipentaerystol hexa (meth) acrylate, dipentaerystol penta (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethanetetra (meth) acrylate; bifunctional or more Urethane acrylates, bifunctional or higher functional polyester acrylates, and the like. These may be used alone or in combination of two or more.

  Examples of the reactive monomer having a cationic reactive bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable. In the present invention, a reactive alkoxysilane compound can be used. For example, as an alkoxysilane compound, tetramethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, methyltriethoxysilane Methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, and trimethylbutoxysilane. Fluorine-containing silane coupling agents include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethoxysilane, Examples include decafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane.

  Examples of the reactive oligomer or reactive polymer include unsaturated polyesters such as a condensation product of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy ( Examples thereof include a meth) acrylate, a urethane (meth) acrylate, a cationic polymerization type epoxy compound, and a single or copolymer of the above-described monomer having a radical reactive bond in the side chain.

  Examples of the photopolymerization initiator in the case of using a photocuring reaction when a reactive monomer, reactive oligomer or reactive polymer is used include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethyl) Carbonyl compounds such as amino) benzophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Examples include 6-trimethylbenzoyldiphenylphosphine oxide and benzoyldiethoxyphosphine oxide. These may be used alone or in combination of two or more. The active energy ray-curable resin composition may contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving the antifouling property, fine particles, and a small amount of a solvent, if necessary.

  A urethane-based adhesive layer can also be used, and refers to a resin obtained by reacting polyisocyanate and polyol, and is formed by applying a polyurethane adhesive to a thin film. In order to obtain a uniform thickness and good appearance, a method of laminating the base layer B as a solvent solution or an aqueous dispersion by coating is preferable. Examples of the polyol include polytetramethylene glycol, polyester polyol, polyether polyol, polycarbonate polyol, polyacetal polyol, polyacrylate polyol, polyesteramide polyol, and polythioether polyol. Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4′-diphenylmethane. Diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4 '-Biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene dii Cyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4 ' -Polyisocyanate monomers such as dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, dimers, trimers, burettes, allophanates, polyols derived from the above polyisocyanate monomers Examples thereof include adduct-type multi-tubular polyisocyanates. The polyisocyanate can be used in combination of two or more. When the polyol and the polyisocyanate are reacted, the ratio of the OH group in the polyol to the NCO group in the polyisocyanate is preferably reacted under the condition of NCO group: OH group = 2: 1 to 100: 1. Other additives include, for example, coupling agents such as silane coupling agents and titanium coupling agents, tackifiers such as terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins, UV absorbers, and oxidation agents. You may use stabilizers, such as an inhibitor, a heat-resistant stabilizer, a heat-resistant hydrolysis stabilizer, etc. as needed.

  In the present invention, it suffices to provide at least one adhesive layer between the layers of the photoelectric conversion element constituting layer. However, the adhesive layer is preferably a thin film. A method is preferred in which the composition is dissolved to form a coating solution for the adhesive layer, and this coating solution is applied to one of the constituent layers to which the adhesive layer is applied. Alternatively, a method (transfer method) may be used in which the adhesive is dissolved in a solvent or the like, and the adhesive layer coating solution is once applied to the peelable sheet and then transferred to the constituent layer to be bonded. The latter transfer method is preferably used when any of the constituent layers does not have solvent resistance when the adhesive layer is provided in the constituent layers, or when the constituent layers do not have heat resistance against heat during solvent drying. Examples of the coating method that can be used include a bar coating method, a screen printing method, a spray method, a spin coating method, a dip method, a die coating method, and a gravure coating method. Although the film thickness and the coating surface shape of the adhesive layer of the present invention are not particularly limited, the film thickness is preferably 1 to 500 nm, more preferably 2 to 200 nm, and particularly preferably 3 to 100 nm.

(Conductive electrode substrate)
The present invention is characterized in that at least one of the conductive photoelectrode and the conductive counter electrode is a transparent conductive electrode. Here, the transparent conductive electrode is an electrode substrate having a conductive layer composed of a transparent electrode substrate and a transparent conductive layer. The material for the transparent electrode substrate and the transparent conductive layer used for the transparent electrode used at that time is not particularly limited as long as it is transparent. In addition, functional layers can be appropriately added to or reduced from the constituent layers of the photoelectric conversion element according to the purpose. The transparent electrode substrate or opaque electrode substrate in which the photoelectrode and the counter electrode are used will be described below.

(Transparent electrode substrate)
One of the pair of photoelectrode side and counter electrode side electrode substrates used in the present invention is a transparent electrode substrate, and specifically, a glass electrode substrate or a transparent plastic electrode substrate is a preferred substrate. As the transparent plastic substrate material, a material that is not colored and has high transparency, high heat resistance, excellent chemical resistance and gas barrier properties, and low cost is suitable. Suitable materials include, for example, polyesters (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), styrenes (eg, syndiotactic polystyrene (SPS), etc.), polyphenylene sulfide (PPS), polycarbonate, etc. (PC), polyarylate (PAr), polysulfone (PSF), polyestersulfone (PES), polyetherimide (PEI), transparent polyimide (PI), cycloolefin copolymer (trade name Arton, etc.) and alicyclic polyolefin (product) Name such as ZEONOR). Of these, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and alicyclic polyolefin are particularly preferable in terms of chemical stability and cost. In addition, it does not specifically limit in the structure and composition of these plastic substrates, If it deserves to comprise the photoelectric conversion element of this invention, it can utilize.

  The heat resistance of the plastic substrate preferably satisfies at least one of the physical properties of a glass transition temperature (Tg) of 80 ° C. or higher and a linear thermal expansion coefficient of 60 ppm / ° C. or lower. Examples of the glass substrate material include inorganic substrates made of white plate glass, soda glass, borosilicate glass, and the like. The transparency of these substrates is preferably high in the transmittance of visible light, which is the absorption region of the perovskite compound, and preferably has a visible light transmittance of more than 50% (550 nm), more preferably a visible light transmittance of 70%. Those exceeding (550 nm) are preferable, and those exceeding visible light transmittance of 80% (550 nm) are particularly preferable. The thickness of the substrate is not particularly limited and can be used as long as the strength of the substrate is maintained, but is preferably 10 to 500 μm, more preferably 30 to 300 μm, and still more preferably 80 to 250 μm. .

(Transparent conductive layer)
As a material for the transparent conductive layer of the present invention, conductive metals (eg, platinum, gold, silver, copper, aluminum, indium, titanium), conductive organic materials represented by conductive carbon and conductive polymers, Specifically, examples of the conductive polymer include polyacetylene, PEDOT (poly (3,4-ethylenedioxythiophene)), oligothiophene, polypyrrole, polyaniline, polyparaphenylene, and polyparaphenylene vinylene. There are conductive metal oxides (eg, tin oxide, zinc oxide) or conductive composite metal oxides (eg, indium-tin oxide, indium-zinc oxide), Ag nanowires.

  In terms of having high optical transparency, conductive metal oxides and conductive composite metal oxides are preferred, and in terms of heat resistance and chemical stability, indium-tin composite oxide (ITO) and indium- Zinc oxide (IZO) is particularly preferred. In the material, the composition may be mixed with other materials, and the form is not limited. In addition, the method for forming the conductive layer is not limited, and a sputtering method, a vapor deposition method, a method of applying a dispersion, and the like can be selected. The light transmittance (measurement wavelength: 550 nm) of the electrode substrate having a transparent conductive layer provided with a transparent electrode layer on the transparent electrode substrate is preferably 40% or more, more preferably 60% or more, and 75% or more. Is most preferable, and 80% or more is particularly preferable. The conductivity and transparency of the electrode substrate having a transparent conductive layer can be made compatible by optimizing the method for forming the transparent conductive layer (for example, vapor deposition time, dispersion coating amount, etc.).

  In the present invention, it is also preferable to use a metal for the conductive layer in order to achieve a low surface resistance value. High transparency can also be achieved by forming a transparent conductive layer having a metal mesh structure. It is preferable to form a transparent conductive layer having a metal mesh structure using a low-resistance metal material (eg, copper, silver, aluminum, platinum, gold, titanium, nickel, etc.). In this case, auxiliary leads for collecting current can be disposed on the conductive layer by patterning or the like. The auxiliary lead is also formed of a low-resistance metal material (eg, copper, silver, aluminum, platinum, gold, titanium, nickel, etc.) in the same manner as the conductive layer. The resistance value of the surface including the auxiliary lead is not particularly limited as long as it has the object of the present invention. Here, the auxiliary lead pattern is preferably formed on the transparent substrate by vapor deposition, sputtering, or the like, and a transparent conductive layer made of tin oxide, ITO film, IZO film or the like is further provided thereon. The conductivity of the transparent conductive layer of the present invention is not a problem as long as the generated electrons can flow. However, it is preferably 1000Ω or less, more preferably 100Ω or less, still more preferably 30Ω or less, and particularly preferably. It is 15Ω or less.

(Opaque conductive layer)
Although the present invention includes a pair of electrodes, at least one may be transparent and the other may be opaque. In the opaque electrode used in this case, either the substrates or the conductive layer is opaque or both are opaque. That is, in the present invention, either one of the pair of conductive electrode substrates can be an opaque conductive electrode substrate. Even in this case, the material used for the transparent conductive layer can be used, and in this case, the substrate is opaque. In particular, the metal conductive layer is a material having both a conductive layer and an electrode substrate, and its application is also preferable. The opaque conductive layer has a light transmittance (measurement wavelength: 550 nm) of 10% or less. The conductivity of the opaque conductive layer of the present invention is not a problem as long as the generated electrons can flow, but the surface resistance is preferably 1000Ω or less, more preferably 100Ω or less, and further preferably 30Ω or less. There is a particularly preferred value of 15Ω or less.

[Photoelectric conversion layer]
The photoelectric conversion layer constituting the photoelectrode of the present invention is formed between a pair of conductive photoelectrode substrate and conductive counter electrode substrate, contributing to charge separation of the photoelectric conversion element of the present invention, It has a function of transporting the generated electrons and holes toward the electrodes in opposite directions. The photoelectric conversion layer of the present invention forms at least one halide organic / inorganic hybrid perovskite compound film, but may be a photoelectric conversion layer composed of two or more multilayer films. The layer of the halide-based organic / inorganic hybrid perovskite compound functions as a light absorber and self-dielectrically acts as a ferroelectric substance to cause charge separation. Therefore, a single layer can be used as a solar cell. The halide organic / inorganic hybrid perovskite compound of the present invention will be described below. In addition to the pair of conductive electrode substrates, the organic / inorganic perovskite solar cell of the present invention has a general formula RMXn (where R is an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom, and n is an integer). A halide-based organic-inorganic hybrid perovskite compound layer having a perovskite structure represented by:

(Halide organic / inorganic hybrid perovskite compounds)
The organic / inorganic hybrid perovskite compound refers to a perovskite compound (organic / inorganic hybrid) in which desirable physical properties characteristic of both organic and inorganic components are combined in a single molecular scale composite. The basic structural form of perovskite is the RMX3 structure, which has a three-dimensional network of vertex sharing MX6 octahedrons. The M component of the RMXn structure is a metal cation that can take octahedral coordination of the X anion. These organic-inorganic hybrid perovskites are not particularly limited. The halide organic / inorganic hybrid perovskite compound, which is an organic / inorganic perovskite compound preferably used, will be described below.

  The halide organic-inorganic hybrid perovskite compound is represented by, for example, a general formula RMXn (where R is an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom, and n is an integer). By using the organic / inorganic perovskite compound, the solar cell obtained by the method for producing a solar cell of the present invention can be made excellent in photoelectric conversion efficiency because of its very high charge separation efficiency. Further, since the halide organic-inorganic hybrid perovskite compound having both the flexibility and impact resistance of the organic material and the durability and heat resistance of the inorganic material is excellent in durability, the method for producing a solar cell of the present invention is used. The obtained solar cell is also excellent in durability.

R is an organic molecule and is preferably represented by ClNmHp (l, m, and p are all positive integers).
Specifically, R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl. Amine, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, pyrrole, aziridine, azirine, Azetidine, azeto, azole, imidazoline, carbazole and their ions (eg, methylammonium (CH ₃ NH ₃ )) and fluorine And enethylammonium. Of these, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their ions and phenethylammonium are preferred, and methylamine, ethylamine, propylamine and these ions are more preferred.

  Said M is a metal atom, for example, lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, Europium etc. are mentioned. These metal atoms may be used independently and 2 or more types may be used together. X is a halogen atom or a chalcogen atom, and examples thereof include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms or chalcogen atoms may be used alone or in combination of two or more. Among these, halide organic-inorganic hybrid perovskite compounds containing halogen in the structure are soluble in organic solvents and can be applied to inexpensive printing methods and the like. Furthermore, iodine is more preferable as the halogen atom because the energy band gap of the halide organic-inorganic hybrid perovskite compound becomes narrow.

The organic-inorganic hybrid perovskite compound preferably has a cubic structure in which a metal atom M is disposed at the body center, an organic molecule R is disposed at each vertex, and a halogen atom or a chalcogen atom X is disposed at the face center. Further, n is not particularly limited as long as it forms a perovskite structure, but is preferably 3 or 4, particularly 3 is a preferable number.
The organic / inorganic hybrid perovskite compound is preferably a crystalline semiconductor. The crystalline semiconductor means a semiconductor capable of measuring the X-ray scattering intensity distribution and detecting a scattering peak. When the organic-inorganic hybrid perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic-inorganic hybrid perovskite compound is increased, and the photoelectric conversion efficiency of the solar cell is improved. Examples of a method for increasing the crystallinity of the organic-inorganic hybrid perovskite compound include thermal annealing, irradiation with intense light such as laser, and plasma irradiation.

Specific examples of the halide organic-inorganic hybrid perovskite compound of the present invention are described below. Preferred halide-based organic / inorganic hybrid perovskite compounds used in the present invention are, for example, CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbF ₃ , CH ₃ NH ₃ PbBrI _{2. , CH 3 NH 3 PbBrCl 2,} CH 3 NH 3 PbIBr 2, CH 3 NH 3 PbICl 2, CH 3 NH 3 PbClBr 2, CH 3 NH 3 PbI 2 Cl, CH 3 NH 3 SnBr 3, CH 3 NH 3 SnBrI 2 CH ₃ NH ₃ SnBrCl ₂ , CH ₃ NH ₃ SnI ₃ , CH (═NH) NH ₃ PbI ₃ , CH ₃ NH ₃ SnF ₂ Br, CH ₃ NH ₃ SnIBr ₂ , CH ₃ NH ₃ SnICl ₂ , CH ₃ NH ₃ SnICl _{2 3} SnF ₂ I, CH ₃ NH ₃ SnClBr ₂ , _CH 3 _NH 3 _SnI 2 Cl and _{CH 3 NH 3 SnF 2 Cl,} (C 6 H 5 C 2 H 4 NH 3) 2 PbBr 4, (C 2 H 5 NH 3) 2 PbI 4, (CH 2 = CHNH ₃ ) ₂ PbI ₄ , (CH≡CNH ₃ ) ₂ PbI ₄ , (n-C ₃ H ₇ NH ₃ ) ₂ PbI ₄ , (n-C ₄ H ₉ NH ₃ ) ₂ PbI ₄ , (C ₆ H ₅ NH _{3) 2 PbI 4, (C} 6 H 3 F 2 NH 3) 2 PbI 4, (C 6 F 5 NH 3) 2 PbI 4, (C4H 3 SNH 3) 2 PbI 4, (CH 3 (CH 2) nCHCH ₃ NH ₃ ) ₂ PbI ₄ [n = 5 to 8]. _{Here, C} 4 _{H 3} SNH 3 in _{(C 4 H 3 SNH 3)} 2 PbI 4 is aminothiophene.

In the present invention, among these, a more preferred halide-based organic-inorganic hybrid perovskite _{compound, CH 3 NH 3 PbBrI 2,} CH 3 NH 3 PbBrCl 2, CH 3 NH3PbIBr 2, CH 3 NH 3 PbCl 2 I, CH 3 NH 3 PbClBr ₂ , CH ₃ NH ₃ PbI ₂ Cl, CH ₃ NH ₃ SnBrI ₂ , CH ₃ NH ₃ SnBrCl ₂ , CH ₃ NH ₃ SnF ₂ Br, CH ₃ NH ₃ SnIBr ₂ , CH ₃ NH ₃ Sn ₃ Cl ₂ , CH ₃ NH ₃ SnBr ₂ , CH ₃ NH ₃ Sn ₃ Cl ₂ It is preferred to select from SnF ₂ I, CH ₃ NH ₃ SnClBr ₂ , CH ₃ NH ₃ SnI ₂ Cl and CH ₃ NH ₃ SnF ₂ Cl.

Further, as a halide-based organic / inorganic hybrid perovskite compound, CH ₃ NH ₃ PbBrI ₂ , CH ₃ NH ₃ PbBrCl ₂ , CH ₃ NH ₃ PbIBr ₂ , CH ₃ NH ₃ PbICl ₂ , CH ₃ NH ₃ PbClBr ₂ , CH ₃ NH ₃ P _{2 Cl, CH 3 NH 3 SnF} 2 Br, CH 3 NH 3 SnICl 2, CH 3 NH 3 SnF 2 I, CH 3 NH 3 SnI 2 Cl and _CH is preferably selected from 3 _NH 3 _SnF 2 Cl. More preferably, the halide-based organic-inorganic hybrid perovskite compound is CH ₃ NH ₃ PbBrI ₂ , CH ₃ NH ₃ PbBrCl ₂ , CH ₃ NH ₃ PbIBr ₂ , CH ₃ NH ₃ PbCl ₂ I, CH ₃ NH ₃ PbClBr ₂ , CH ₃ NH ₃ PbI ₂ Cl, CH ₃ NH ₃ SnF ₂ Br, CH ₃ NH ₃ SnF ₂ I and CH ₃ NH ₃ SnF ₂ Cl may be mentioned. Particularly preferably, as the halide-based inorganic organic hybrid perovskite, CH ₃ NH ₃ PbBrI ₂ , CH ₃ NH ₃ PbBrCl ₂ , CH ₃ NH ₃ PbIBr ₂ , CH ₃ NH ₃ PbCl ₂ I, CH ₃ NH ₃ SnF ₂ Br and CH ₃ NH ₃ SnF ₂ I may be mentioned.

Other preferred halide organic-inorganic hybrid perovskite compound has the formula _{(H 2 N = CH-NH} 2) PbI 3z Br 3 (1-z) and the like (the z is less than 1 greater than 0). Specifically, (H ₂ N═CH—NH ₂ ) PbI ₃ or (H ₂ N═CH—NH ₂ ) PbBr ₃ can be used. In the present invention, it is also effective to use two or more halide-based inorganic / organic hybrid perovskites. For example, combinations thereof include, for example, CH ₃ NH ₃ PbICl ₂ and CH ₃ NH ₃ PbIBr ₂ , CH ₃ NH ₃ PbICl _2. And combinations of CH ₃ NH ₃ PbBrI ₂ , CH ₃ NH ₃ PbBrCl ₂ and CH ₃ NH ₃ PbIBr ₂ , or CH ₃ NH ₃ PbBrCl ₂ and CH ₃ NH ₃ PbIBr ₂ are recommended.

Furthermore, in the present invention, it is also preferable to introduce a fluorine atom into a part of the organic functional group in order to improve the coating surface shape of the halide-based organic / inorganic hybrid perovskite compound layer and the bonding property with the adjacent layer. For example, as specific examples of the compounds and examples thereof, for example _{CF 3 NH3PbCl 3, CF 3 NH} 3 PbBr 3, CF 3 NH 3 PbI 3, CF 3 NH 3 PbBrI 2, CF 3 NH 3 PbBr 2 I, CF 3 NH _{3 SnBr 3, CF 3 NH 3} SnI 3, CHF 2 NH 3 PbCl 3, CHF 2 NH 3 PbBr 3, CHF 2 NH 3 PbI 3, CHF 2 NH 3 PbBrI 2, CHF 2 NH 3 PbBr 2 I, CHF 2 NH _{3 SnBr 3, CHF 2 NH 3} SnI 3, CH 2 FNH 3 PbCl 3, CH 2 FNH 3 PbBr 3, CH 2 FNH 3 PbI 3, CH 2 FNH 3 PbBrI 2, CH 2 FNH 3 PbBr 2 I, CH 2 FNH _{3 SnBr 3, CH 2 FNH 3} SnI 3, ( _{6 H 3 F 2 NH 3)} 2 PbI 4, (C 6 F 5 NH 3) 2 PbI 4, (CF 3 CH 2 NH 3) 2 PbI 4, (CHF 2 CH 2 NH 3) 2 PbI 4, (CH ₂ FCH ₂ NH ₃ ) 2PbI ₄ , (CF ₃ CF ₂ CH ₂ NH ₃ ) ₂ PbI ₄ , ((CF ₃ ) ₂ CHNH ₃ ) ₂ PbI ₄ , (CH ₃ (CF ₂ ) ₅ CH ₂ NH ₃ ) ₂ PbI ₄ , (CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ NH ₃ ) ₂ PbI ₄ , ((CF ₃ ) ₃ CNH ₃ ) ₂ PbI ₄ may be mentioned.

Furthermore, in the halide-based organic / inorganic hybrid perovskite compounds used in the present invention, compounds composed of organic amine polymers described in Published Patent Application No. 2014-229747 may be used. For example, polyethylene polyamine, polyallylamine and lead bromide Can be synthesized from
The halide organic-inorganic hybrid perovskite compound of the present invention can be synthesized from metal halogens and organic amines. For example, a perovskite compound can be synthesized with reference to Patent Document 1. Also, Akihiro Kojima, Kenjiro Teshima, Yasuo Shirai, and Tsutomu Miyasaka, “Organometric Halide Perovskites as Visible Slightly.” Am. Chem. Soc. , 2009, 131 (17), 6050-6051 as appropriate, a perovskite compound can be synthesized.

(Inorganic perovskite compounds)
In the present invention, a halide-based inorganic perovskite compound may be used in combination. For example, CsSnI ₃ , CsSnBr _{3 and the} like can be given as specific examples.

(Halide-based organic / inorganic hybrid perovskite film formation)
The halide organic-inorganic hybrid perovskite compound of the present invention can be synthesized by a self-assembly reaction using a precursor solution. The thin film of the organic / inorganic perovskite compound of the present invention is prepared by dissolving the organic / inorganic perovskite compound in an organic solvent, and then applying a bar coating method, a screen printing method, a spray method, a spin coating method, a dip method, a die coating method, a gravure coating method, etc. It can be formed by a coating method. Moreover, a film can be formed by a vacuum evaporation method. The film thickness of the halide-based organic / inorganic hybrid perovskite layer of the present invention is preferably 1 to 500 nm, more preferably 2 to 200 nm, and still more preferably 3 to 150 nm.

(Halide organic / inorganic hybrid perovskite solution)
The solvent for preparing the solution of the halide organic / inorganic hybrid perovskite compound used in the present invention is not particularly limited as long as it can dissolve the halide organic / inorganic hybrid perovskite compound. Esters (eg, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc.), ketones (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, Dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.), ethers (eg, diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3- Dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, etc.), alcohols (eg, methanol, ethanol, 1-propanol, 2-propanol, 1 Butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2, 2,3,3-tetrafluoro-1-propanol, etc.), glycol ethers (cellosolves) (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol) Dimethyl ether, etc.), amide solvents (eg, N, N-dimethylformamide, acetamide, N, N-dimethylacetamide, etc.), nitrile solvents (eg, acetonitrile, isobutyronitrile, pro Pionitrile, methoxyacetonitrile, etc.), carboat agents (eg, ethylene carbonate, propylene carbonate, etc.), halogenated hydrocarbons (eg, methylene chloride, dichloromethane, chloroholeme, etc.), hydrocarbons (eg, n-pentane, cyclohexane) , N-hexane, benzene, toluene, xylene, etc.) and dimethyl sulfoxide. These may have a branched structure or a cyclic structure. Two or more functional groups of esters, ketones, ethers, and alcohols (that is, —O—, —CO—, —COO—, —OH) may be contained. The hydrogen atom in the hydrocarbon moiety of the esters, ketones, ethers and alcohols may be substituted with a halogen atom (particularly a fluorine atom).

(Buffer layer)
In the present invention, it is preferable to provide a buffer layer between the surface of the transparent conductive layer of the photoelectrode and the electron transport layer, the fine particle layer, or the halide-based organic / inorganic hybrid perovskite compound layer, thereby preventing reverse current, which is a problem in the photoelectric conversion element. It fulfills the function to do. The buffer layer material is not particularly limited, but is preferably a transparent and insulating substance. For example, titanium oxide, tin oxide, niobium oxide, tungsten oxide, silicon oxide, magnesium oxide, aluminum oxide, calcium carbonate, and further as an organic material Examples thereof include polyvinyl alcohol and polyurethane. Of these, titanium oxide, tin oxide, magnesium oxide, aluminum oxide and the like are preferable. In particular, it is preferable to convert titanium oxide into titanium oxide by forming an oligomer solution. The thickness of the buffer layer is preferably 1 to 1000 nm, more preferably 2 to 500 nm, still more preferably 3 to 200 nm, and particularly preferably 3 to 100 nm.

(Electron transport layer)
Furthermore, in the present invention, an electron transport material can be included in the constituent layer of the photoelectrode as the electron transport layer. Preferred electron transport layer materials include fullerene or fullerene derivatives, electrolytes, or organic electron transport materials, preferably perylene or derivatives thereof, or poly {[N, N-bis (2-octyldodecyl) -naphthalene-1 , 4,5,8-bis (dicarboximido) -2,6-diyl] -alt-5,50- (2,20-bithiophene)} (P (NDI2OD-T2)). In general, it is preferable to provide an electron transport layer between the photoelectrode conductive layer and the organic / inorganic perovskite layer and, when a buffer layer is present, between the buffer layer and the halide organic / inorganic hybrid perovskite compound layer. The film thickness of the electron transport layer is preferably 1 to 1000 nm, more preferably 2 to 500 nm, more preferably 3 to 200 nm, and particularly preferably 3 to 100 nm.

(Fine particle layer)
In the present invention, the photoelectrode layer may contain a fine particle layer, and is preferably a porous layer having pores in which fine particles are deposited or adhered. The fine particle layer may be a fine particle layer in which two or more kinds of multi-fine particles are deposited. The average particle diameter of the fine particles forming the fine particle layer is preferably 1 nm to 500 nm as the primary particles. More preferably, it is 2 nm-300 nm, and 4 nm-250 nm are mentioned especially. The material forming the fine particle layer may be an insulator (insulating material), a conductive material, or a semiconductor (semiconductive material). As a material for forming the porous layer, for example, perovskite compounds obtained from metal chalcogenides (for example, oxides, sulfides, selenides, etc.) are excluded. ), Silicon oxide (eg, silicon dioxide, zeolite) can be used. The metal chalcogenide is not particularly limited. Examples thereof include cadmium selenide. Examples of the crystal structure of the metal chalcogenide include an anatase type, brookite type and rutile type, and anatase type and brookite type are preferable.

In addition, the inorganic perovskite compound can form a fine particle layer, and is not particularly limited, and examples thereof include transition metal oxides. For example, strontium titanate, calcium titanate, barium titanate, lead titanate, barium zirconate, barium stannate, lead zirconate, strontium zirconate, strontium tantalate, potassium niobate, bismuth ferrate, strontium barium titanate , Barium lanthanum titanate, calcium titanate, sodium titanate, bismuth titanate. Of these, strontium titanate, calcium titanate and the like are preferable.

  The material for forming the fine particle layer is preferably an oxide of titanium, tin, zinc, zirconium, aluminum or silicon, and more preferably titanium oxide or aluminum oxide. Furthermore, the fine particle layer may be formed of at least one of the aforementioned metal chalcogenides, perovskite compounds, and silicon oxides, and may be formed of a plurality of types. Although the film thickness of a fine particle layer is not specifically limited, Usually, it is the range of 0.1-100 micrometers, and when using as a solar cell, 0.1-50 micrometers is preferable and 0.3-30 micrometers is more preferable. Among these, the fine particle layer used as a preferable example will be described below.

(Semiconductor fine particles)
In the present invention, semiconductor fine particles can be preferably used as the fine particles of the fine particle layer, and can be produced using a known method. Preferred semiconductor fine particles include oxides of titanium, tin, zinc, iron, tungsten, zirconium, strontium, aluminum, indium, cerium, vanadium, niobium, tantalum, cadmium, lead, antimony, and bismuth. _{Specifically, TiO 2, ZnO, Nb 2} O 3, SnO 2, WO 3, Al 2 O 3, Si, CdS, CdSe, V 2 O 5, ZnS, ZnSe, etc. KTaO _3, FeS _2, PbS is Preferably, TiO ₂ , ZnO, Nb ₂ O ₃ , SnO ₂ , WO ₃ , and Al ₂ O ₃ are more preferable, and titanium dioxide (TiO ₂ ) is particularly preferable. From the viewpoint of dispersion stability, the solid content concentration contained in the fine particle dispersion is 0.1 to 25 wt%, preferably 0.5 to 20 wt%, and more preferably 0.5 to 15 wt%.

(Fine particle dispersion)
In the present invention, a fine particle dispersion is applied on a transparent electrode substrate, and heat treatment is performed to form a fine particle layer. When a plastic substrate is used in the present invention, it is preferable to employ a low-temperature film forming method, and a dispersion composition that does not contain a binder material is preferable. The fine particle dispersion of the present invention is preferably one in which fine particles are dispersed in a solvent composed of a mixture of water and an alcohol having 5 or less carbon atoms. Examples of the alcohol include t-butanol and 2-butanol. In the method for dispersing fine particles of the present invention, a paint conditioner, a homogenizer, an ultrasonic stirring device, or the like is used, and a rotating / revolving combined type mixing conditioner is also preferably used, but is not limited thereto. As the concentration of the fine particles, the solid content concentration of the whole fine particles contained in the dispersion is 5 to 60 wt%, preferably 8 to 40 wt%, and more preferably 8 to 30 wt%. As a method for applying the fine particle dispersion, a known method such as a screen printing method, a drop cast method, a spin coating method, an air spray method or the like can be used. From the viewpoint of the uniformity of the fine particle layer to be formed, an air spray method using a spray device may be preferable. The thickness of the fine particle layer is preferably less than 20 μm, more preferably less than 1 μm, preferably 1 μm or less, and more preferably 0.5 μm or less. The porosity of the fine particle layer to be formed (the ratio of the volume occupied by the vacancies in the film) is preferably 50 to 200%, more preferably 65 to 150%. The heat treatment temperature is within the heat resistance range of the conductive substrate. For example, when the transparent conductive substrate is a plastic substrate, the fine particle porous layer is formed by a low temperature film formation method (eg, 200 ° C. or lower, preferably 150 ° C. or lower). Can be formed.

(Hole transport layer)
Next, in the present invention, the photoelectric conversion element is more preferably provided with a hole transport layer on the conductive photoelectrode side in addition to the above-described layers. The hole transport layer is preferably provided between the organic-inorganic hybrid semiconductor layer and a counter electrode described later. The material of the hole transport layer is not particularly limited. Surfactants such as organic conductive materials having any of the benzoporphyrin skeletons, fluoro group-containing phosphonic acids, and carbonyl group-containing phosphonic acids can be used.

  The hole transport layer material can be a single or a mixture of two or more hole transport materials, which may or may not be doped with one or more dopant elements. The material of the hole transport layer can be selected from a polymer or a molecular hole transport layer material as the organic compound. The hole transport layer material of the present invention is, for example, spiro-OMeTAD (2,2 ′, 7,7′-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9′-spirobifluorene. )), P3HT (poly (3-hexylthiophene)), PCPDTBT (poly [2,1,3-benzothiadiazole-4,7-diyl [4,4-bis (2-ethylhexyl) -4H-cyclopenta [2, 1-b: 3,4-b ′] dithiophene-2,6-diyl]]), PVK (poly (N-vinylcarbazole)), HTM-TFSI (1-hexyl-3-methylimidazolium bis (trifluoro) Methylsulfonyl) imide), Li-TFSI (lithium bis (trifluoromethanesulfonyl) imide), or tBP (tertiary butylpyridine), PEDOT: PSS can be mentioned. The hole transport layer material is preferably spiro-OMeTAD, P3HT, PCPDTBT and PVK, PEDOT: PSS, more preferably spiro-OMeTAD, PEDOT: PSS.

  Furthermore, the following hole transport layer can also be used. They are m-MTDATA (4,4 ′, 4 ″ -tris (methylphenylphenylamino) triphenylamine), MeOTPD (N, N, N ′, N′-tetrakis (4-methoxyphenyl) -benzidine. ), BP2T (5,5′-di (biphenyl-4-yl) -2,2′-bithiophene), di-NPB (N, N′-di-[(1-naphthyl) -N, N′-diphenyl) ] -1,1′-biphenyl) -4,4′-diamine), α-NPB (N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine), TNATA (4 4 ′, 4 ″ -tris- (N- (naphthylene-2-yl) -N-phenylamine) triphenylamine), BPAPF (9,9-bis [4- (N, N-bis-biphenyl-4) -Yl-amino) phenyl]- H-fluorene), spiro-NPB (N2, N7-di-1-naphthalenyl-N2, N7-diphenyl-9,9′-spirobi [9H-fluorene] -2,7-diamine), 4P-TPD (4 4'-bis- (N, N-diphenylamino) -tetraphenyl) and the like.

In addition, as an inorganic hole transport layer material, nickel, vanadium, copper or molybdenum oxide; CuI, CuBr, CuSCN, Cu2O, CuO or CIS, amorphous Si, p-type group IV semiconductor, p-type III-V Group semiconductors, p-type II-VI semiconductors, p-type I-VII semiconductors, p-type IV-VI semiconductors, p-type V-VI semiconductors, and p-type II-V semiconductors. Preferably, an inorganic hole transporter selected from CuI, CuBr, CuSCN, Cu2O, CuO or CIS can be used. In the present invention, when the hole transport layer is provided, it is preferable that the photoelectrode has a semiconductor fine particle layer. For example, if Spiro-OMeTAD is used as the hole transport layer material, TiO ₂ that forms the semiconductor fine particle layer is used. A dense layer is preferred. The film thickness of the hole transport layer is preferably 1 to 1000 nm, more preferably 2 to 500 nm, more preferably 3 to 200 nm, and particularly preferably 3 to 100 nm.

  Further, there is no problem in using a polymer for the hole transport layer, and a known hole transport polymer material is used. Specific examples thereof include poly (3-n-hexylthiophene), poly (3-n-octyl). Oxythiophene), poly (9,9′-dioctyl-fluorene-co-bithiophene), poly (3,3 ′ ″-didodecyl-quarterthiophene), poly (3,6-dioctylthieno [3,2-b] Thiophene), poly (2,5-bis (3-decylthiophen-2-yl) thieno [3,2-b] thiophene), poly (3,4-didecylthiophene-co-thieno [3,2-b Thiophene), poly (3,6-dioctylthieno [3,2-b] thiophene-co-thieno [3,2-b] thiophene), poly (3,6-dioctylthieno [3,2-b] thiophene − -Thiophene), polythiophene compounds such as poly (3.6-dioctylthieno [3,2-b] thiophene-co-bithiophene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene Vinylene], poly [2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylenevinylene], poly [(2-methoxy-5- (2-ethylhexyloxy) -1,4 -Phenylene vinylene) -co- (4,4′-biphenylene-vinylene)] and other polyphenylene vinylene compounds, poly (9,9′-didodecylfluorenyl-2,7-diyl), poly [(9,9 -Dioctyl-2,7-divinylenefluorene) -alt-co- (9,10-anthracene)], poly [(9,9-dioctyl-2,7-divinylenefull) Len) -alt-co- (4,4′-biphenylene)], poly [(9,9-dioctyl-2,7-divinylenefluorene) -alt-co- (2-methoxy-5- (2-ethylhexyl) Oxy) -1,4-phenylene)], poly [(9,9-dioctyl-2,7-diyl) -co- (1,4- (2,5-dihexyloxy) benzene)] and the like , Poly [2,5-dioctyloxy-1,4-phenylene], polyphenylene compounds such as poly [2,5-di (2-ethylhexyloxy-1,4-phenylene], poly [(9,9-dioctylful) Olenyl-2,7-diyl) -alt-co- (N, N′-diphenyl) -N, N′-di (p-hexylphenyl) -1,4-diaminobenzene], poly [(9,9 -Dioctylfluorenyl -2,7-diyl) -alt-co- (N, N'-bis (4-octyloxyphenyl) benzidine-N, N '-(1,4-diphenylene)], poly [(N, N'- Bis (4-octyloxyphenyl) benzidine-N, N ′-(1,4-diphenylene)], poly [(N, N′-bis (4- (2-ethylhexyloxy) phenyl) benzidine-N, N ′ -(1,4-diphenylene)], poly [phenylimino-1,4-phenylenevinylene-2,5-dioctyloxy-1,4-phenylenevinylene-1,4-phenylene], poly [p-tolylimino-1 , 4-phenylene vinylene-2,5-di (2-ethylhexyloxy) -1,4-phenylene vinylene-1,4-phenylene], poly [4- (2-ethylhexyloxy) phenylimino 1,4-biphenylene] and other polyarylamine compounds, poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (1,4-benzo (2,1 ′, 3) And polythiadiazole compounds such as poly (3,4-didecylthiophene-co- (1,4-benzo (2,1 ′, 3) thiadiazole)). Particularly preferred are polythiophene compounds and polyarylamine compounds, which can be used alone or as a mixture of two or more.

  Moreover, in the solar cell of this invention, you may add various additives to the hole transport compound shown above. Additives include iodine, lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, copper iodide, iron iodide, silver iodide and other metal iodides, tetraalkylammonium iodide, Quaternary ammonium salts such as pyridinium iodide, metal bromides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide and calcium bromide, quaternary ammonium compounds such as tetraalkylammonium bromide and pyridinium bromide Metal chlorides such as bromine salts, copper chloride and silver chloride, metal acetates such as copper acetate, silver acetate and palladium acetate, metal sulfates such as copper sulfate and zinc sulfate, ferrocyanate-ferricyanate, ferrocene -Sulfur compounds such as metal complexes such as ferricinium ions, sodium polysulfide, alkylthiol-alkyl disulfides Viologen dye, hydroquinone, 1,2-dimethyl-3-n-propylimidazolinium iodide, 1-methyl-3-n-hexylimidazolinium iodide, 1,2-dimethyl-3-ethylimidazo 1-methyl-3-butylimidazolium nonafluorobutylsulfonate, 1-methyl-3-ethylimidazolium bis (trifluoromethyl) sulfonylimide, 1-methyl-3-n- Ionic liquids such as hexylimidazolium bis (trifluoromethyl) sulfonylimide, 1-methyl-3-n-hexylimidazolium dicyanamide, basic compounds such as pyridine, 4-t-butylpyridine and benzimidazole, lithium trifluoromethane Sulfonylimide, lithium diisopropylimi Lithium compounds such can be mentioned. Of these, an imidazolinium compound as the cation and an additive having a bis (trifluoromethyl) sulfonylimide anion as the anion are preferable. These additives can be used alone or as a mixture of two or more.

  In the photoelectric conversion element of the present invention, an acceptor material may be further added as necessary in addition to the hole transport compound and various additives described above. Acceptor materials include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5 , 7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-trinitrodibenzo Examples include thiophene-5,5-dioxide and diphenoquinone derivatives. These acceptor materials can be used alone or as a mixture of two or more.

  Moreover, you may add the oxidizing agent for making a part of hole transport compound into a radical cation for the purpose of improving electroconductivity. Examples of the oxidizing agent include tris (4-bromophenyl) aminium hexachloroantimonate, silver hexafluoroantimonate, nitrosonium tetrafluorate, and silver nitrate. It is not necessary for all hole transport materials to be oxidized by the addition of the oxidizing agent, and only a part of the hole transporting material needs to be oxidized. The added oxidizing agent may be taken out of the system after the addition or may not be taken out.

  In the photoelectric conversion element of the present invention, it is also important to provide various functional layers in addition to the above-described functional layers. However, the present invention is not limited to these. In particular, in a cell or module consisting of multiple layers, or a solar cell that combines these, it is necessary to fully exhibit its performance and obtain commercial utility. These are described below.

(Mask film)
In the present invention, when a photoelectric conversion element cell or a photoelectric conversion element module, or even a solar battery is manufactured, a mask film is used for dividing and dividing each cell in order to prevent a short circuit between the shapes and adjacent cells. It is preferable to use it. The mask film used can be easily attached to a transparent conductive substrate or a transparent conductive substrate on which a buffer layer is formed at the same time that the open part serves as a model of the photoelectric conversion layer of the present invention, After the fine particle dispersion or the perovskite compound solution is provided, there is no particular limitation as long as it is an adhesive film having an adhesive layer that can be easily peeled off.

  Specifically, it is a laminated film in which a slight adhesive layer and a release film are provided on one surface of a substrate of a photoelectric conversion element, and an antistatic layer and an antifouling layer are provided on the other surface. The laminated adhesive film used for the surface protection film of a film or retardation film can be used. At the time of use, a peeling film is peeled and a mask film is bonded to a transparent conductive substrate or a transparent conductive substrate on which a buffer layer is formed. However, since it is necessary to heat and dry the metal oxide semiconductor nanoparticle dispersion applied to form the semiconductor fine particle layer and the perovskite compound solution applied to form the photoelectric conversion layer, the base film is It is necessary that the thermal contraction rate is the same as that of the transparent conductive substrate on which the buffer layer is formed. Specifically, the thermal contraction rate (MD · TD) under heating conditions (150 ° C., 30 min) is 0.5% or less, more preferably 0.2% or less.

The mask film can be used by laminating a plurality of mask films having different adhesive forces. This is because the uppermost layer is peeled off after forming the porous semiconductor fine particle layer, and the mask film can be peeled off after protecting the transparent conductive substrate or the transparent conductive substrate on which the buffer layer is formed at the time of applying the perovskite compound solution. The planar shape of the cell of the photoelectric conversion element is a rectangular, the rectangular area (S) is 300mm ² ~600mm ^2. This is because by setting the planar shape within such a range, the internal resistance per unit area of the photoelectric conversion element can be minimized and the conversion efficiency can be maximized.

(Sealing layer)
The sealing layer of the present invention is provided around the photoelectric conversion layer and has a function of sealing the photoelectric conversion layer. The sealing layer basically adjusts a necessary gap between the sealing agent for bonding a pair of transparent electrode substrates and the pair of transparent electrode substrates, and in some cases for forming a photoelectric conversion layer It is composed of spacers. The thickness of the sealing layer of the present invention is preferably substantially the same as the thickness of the photoelectric conversion layer. This is because the gap between the pair of transparent electrode substrates is kept uniform to show stable power generation efficiency. The width of the sealing layer of the present invention is not particularly limited, but is preferably in the range of, for example, 0.2 mm to 5 mm, and more preferably in the range of 0.5 mm to 3 mm. If the width of the sealing layer is too narrow, the protective function of the photoelectric conversion layer may not be sufficiently exhibited. If the width of the sealing layer is too wide, the element area contributing to power generation in the photoelectric conversion element is reduced. This is because the effective area with respect to the module area decreases, and the effective power generation efficiency may decrease.

(Sealing agent)
The sealing agent of this invention will not be specifically limited if a pair of transparent electrode substrate can be adhere | attached and a photoelectric converting layer can be sealed. It is preferable that it is excellent in the adhesiveness between board | substrates, light resistance, and high temperature, high humidity durability (moisture heat resistance). This is because, in order to make the photoelectric conversion layer function continuously, it is necessary to have excellent light resistance and moisture and heat resistance in addition to adhesiveness.
Examples of the sealant excellent in adhesiveness, chemical resistance, and wet heat resistance include thermoplastic resins, thermosetting resins, and active radiation (light, electron beam) curable resins. Examples of the material include acrylic resin, fluorine resin, silicon resin, olefin resin, and polyamide resin. From the viewpoint of excellent handleability, a photocurable acrylic resin is preferred.

(spacer)
The spacer of the present invention is not particularly limited as long as a necessary gap between a pair of electrode substrates can be adjusted to a desired range. Usually, spherical resin particles, inorganic particles, glass beads and the like can be appropriately selected. In the present invention, it is preferable to use perfect circle resin particles. As a particle size, 1 micrometer-100 micrometers are preferable, 1 micrometer-50 micrometers are more preferable, and 1 micrometer-20 micrometers are especially preferable. This is because the pair of transparent electrode substrates are not in contact with each other and the photoelectric conversion efficiency is improved by keeping the shorter gap uniform.

(Collector)
In the present invention, the surface resistivity of both the conductive layer of the photoelectrode and the counter electrode is lowered by arranging a current collector made of metal (good conductor) on the transparent conductive film. It is preferable that the current collector is provided outside the photoelectric conversion element divided by the sealing layer. The material of the current collector is not particularly limited as long as it has conductivity, but at least one selected from metal materials having a relatively low resistivity, for example, silver, copper, aluminum, tungsten, nickel, and chromium. It is preferably made of the above metals or alloys thereof, and silver is more preferable from the viewpoint of low resistivity and easy formation as a line. The current collector may be formed in a lattice shape on the transparent conductive layer. As a method for forming the current collector, sputtering, vapor deposition, plating, screen printing, or the like is used. The width of the current collector is 0.1 mm to 5 mm, more preferably 0.2 mm to 3 mm, and the thickness of the current collector is 3 μm to 50 μm, more preferably 4 μm to 20 μm. In addition to ensuring sufficient electrical conductivity per line cross-sectional area, it is necessary to have the appropriate width and thickness to ensure the necessary gap between the pair of transparent electrode substrates when using conductive particles described later. And a desired current collecting line may be used.

(Extraction electrode)
In the present invention, the photoelectric conversion element preferably includes a pair of extraction electrodes. When the photoelectric conversion element is covered with an exterior or barrier package described later, a lead material can be attached to the extraction electrode. The material of the extraction electrode is not particularly limited as long as it has conductivity. It is preferably made of a metal material having a relatively low resistivity, for example, at least one metal selected from gold, platinum, silver, copper, aluminum, nickel, zinc, titanium, and chromium, or an alloy thereof. The thickness of the extraction electrode is preferably 50 nm to 100 μm. This is because it is necessary that the thickness of the extraction electrode is not too thin so that the yield of the photoelectric conversion element does not decrease due to disconnection, and it is not necessary to increase the thickness excessively from the viewpoint of cost. The shape of the extraction electrode is not particularly limited. For example, any of metal foil, a metal tape, plate shape, and string shape may be sufficient. A metal tape is preferable from the viewpoint of workability.

(Exterior and barrier packaging)
In the present invention, a material having low permeability to water vapor or gas is used as the substrate when both electrodes are made of plastic, but it is not sufficient particularly under severe environmental conditions at high temperature and high humidity. There is a possibility that deterioration of electric output is observed. These improvement methods can be achieved by making the substrate have a barrier property against gas or water vapor, or by wrapping the photoelectric conversion element of the present invention in a package having a barrier property against water vapor or gas. . At that time, there may be a space between the photoelectric conversion element of the present invention and the high barrier packaging material, or the photoelectric conversion element of the present invention may be bonded with an adhesive. Further, the photoelectric conversion element of the present invention is packaged in a packaging material using a liquid or solid that is difficult to pass water vapor or gas (for example, liquid or gel paraffin, silicon, phosphate ester, aliphatic ester, etc.). Also good. Hereinafter, the barrier film preferably used in the present invention, particularly the water vapor barrier property will be described below.

The preferable water vapor permeability of the substrate or packaging material having a barrier property preferably used in the present invention is 0.1 g / m 2 / day or less in an environment of 40 ° C. and a relative humidity of 90% (90% RH), more preferably. Is 0.01 g / m 2 / day or less, more preferably 0.0005 g / m 2 / day or less, and particularly preferably 0.00001 g / m 2 / day or less. Further, even when the environmental temperature is 60 ° C. and 90% RH, the water vapor permeability of the substrate or packaging material having a barrier property is more preferably 0.01 g / m 2 / day or less, and still more preferably. 0.0005 g / m 2 / day or less, particularly preferably 0.00001 g / m 2 / day or less. The oxygen permeability of the substrate or packaging material having a barrier property is preferably about 0.001 g / m 2 / day or less, more preferably 0.00001 g / m 2 / day in an environment of 25 ° C. and 0% RH. preferable.

  Although there is no particular limitation on imparting via properties to water vapor or gas to the barrier substrate or packaging material for the photoelectric conversion element of the present invention, it is necessary that the amount of light necessary for the photoelectric conversion element of the present invention is not hindered. Therefore, it is a substrate or packaging material that is permeable and has a barrier property, and its transmittance is preferably 50% or more, more preferably 70% or more, still more preferably 85% or more, particularly preferably. Is 90% or more. The board | substrate or packaging material which has the said characteristic with a barrier property is not specifically limited in the structure or material, and if it has this characteristic, it will not specifically limit.

  A substrate or packaging material having a preferable barrier film of the present invention is preferably a film in which a barrier layer having low water vapor and gas permeability is provided on a plastic support. Examples of the gas barrier film include those obtained by vapor-depositing silicon oxide and aluminum oxide (Japanese Patent Publication No. Sho 53-12953, Japanese Patent Laid-Open Publication No. 58-217344), and those having an organic-inorganic hybrid coating layer (Japanese Patent Laid-Open No. 2000-323273, Japanese Patent Application Laid-Open No. 2004-2004). 25732), those having an inorganic layered compound (Japanese Patent Laid-Open No. 2001-205743), those obtained by laminating inorganic materials (Japanese Patent Laid-Open No. 2003-206361, Japanese Patent Laid-Open No. 2006-263389), those obtained by alternately laminating organic layers and inorganic layers (special No. 2007-30387, US Pat. No. 6413645, Affinito et al., Thin Solid Films 1996, pages 290-291), and organic layers and inorganic layers laminated continuously (US Pat. No. 2004-4s6497). When the barrier film packaging material is bonded to both sides of the photoelectric conversion element, it is recommended that the barrier film packaging material be adhered with an adhesive. Moreover, it is also preferable to fill a polymer, a reactive monomer, or an oligomer between the packaging material for the barrier film and the photoelectric conversion element and adhere them.

(Module, photoelectric conversion element form)
In the present invention, the form is not particularly limited when actually used. The module form may be a single cell, a module in which a large number of cells are connected, or a solar battery in a commercial form. In connecting a large number of cells, the connection method is not particularly limited, and a serial method or a parallel method can be arbitrarily selected, and further, a desired module or solar cell can be produced by combining them. Here, in order to avoid problems even if some cells in the solar cell become malfunctioning, module groups in which a large number of cells are connected in series are further connected in series in a group relationship so that power generation can be maintained. Is also recommended.

  Embodiments that exhibit the effects of the present invention will be described below as examples. Table 1 shows the summary. However, the present invention is not limited to these.

(P1) Synthesis of halide organic-inorganic hybrid perovskite compound (P1-1) Synthesis of halide organic-inorganic hybrid perovskite compound-A [CH ₃ NH ₃ PbI ₃ ] In a three-necked flask, a methylamine [CH ₃ NH ₂ ] solution 1 g and 100 ml of methanol were added, and hydroiodic acid was added while nitrogen bubbling to adjust the pH to about 3 to 4, followed by stirring with a magnetic stirrer for 1 hour. This solution was distilled with an evaporator, dried at 40 ° C., and purified again to synthesize methylamine iodide. Next, the synthesized methylamine [CH ₃ NH ₄ I] and lead iodide are mixed and dissolved in dimethylformaldehyde so as to have a concentration of 15% by weight in a molar ratio of 1: 1. An inorganic hybrid perovskite compound-A [CH ₃ NH ₃ PbI ₃ ] solution was prepared.

(P1-2) Synthesis of Halide-based Organic-Inorganic Hybrid Perovskite Compound-B [C ₂ H ₅ NH ₃ PbI ₃ ] In a three-necked flask, 1 g of an ethylamine [C ₂ H ₅ NH ₂ ] solution and 100 ml of methanol are placed, and nitrogen bubbling is performed. Hydrochloric acid [HI] was added while adjusting the pH to about 3 to 4, and the mixture was stirred with a magnetic stirrer for 1 hour. This solution was distilled with an evaporator, dried at 40 ° C., and repurified to synthesize ethyl iodide [C ₂ H ₅ NH ₄ I]. Next, the synthesized ethylamine [C ₂ H ₅ NH ₄ I] and lead iodide [PbI ₂ ] are mixed and dissolved in dimethylformaldehyde at a molar ratio of 1: 1 to a concentration of 15% by weight. Then, a halide-based organic / inorganic hybrid perovskite compound-B [C ₂ H ₅ NH ₃ PbI ₃ ] solution was prepared.

(P1-3) Synthesis of Halide-Based Organic-Inorganic Hybrid Perovskite Compound-C [CH ₃ NH ₃ SnI ₃ ] Into a _three- necked flask, 1 g of a methylamine [CH ₃ NH ₂ ] solution and 100 ml of methanol are placed, and nitrogen bubbling is performed. Hydroiodic acid [HI] was added to adjust the pH to about 3 to 4, followed by stirring with a magnetic stirrer for 1 hour. This solution was distilled by an evaporator, dried at 40 ° C., and purified again to synthesize methylamine iodide [CH ₃ NH ₄ I]. Next, the synthesized methylamine [CH ₃ NH ₄ I] and tin iodide [SnI ₂ ] are dissolved at a molar ratio of 1: 1 in acetonitrile so as to have a concentration of 10% by weight. A mixed perovskite compound-C [CH ₃ NH ₃ SnI ₃ ] solution was prepared.

(P1-4) Synthesis of Halide-based Organic-Inorganic Hybrid Perovskite Compound-D [C ₂ H ₅ NH ₃ SnI ₃ ] In a three-necked flask, 1 g of an ethylamine [C ₂ H ₅ NH ₂ ] solution and 100 ml of methanol are placed, and nitrogen bubbling is performed. The pH was adjusted to about 3 to 4 by adding hydroiodic acid while carrying out the above, and then stirred for 1 hour with a magnetic stirrer. This solution was distilled with an evaporator, dried at 40 ° C., and repurified to synthesize ethyl iodide [C ₂ H ₅ NH ₄ I]. Next, the synthesized ethylamine [C ₂ H ₅ NH ₄ I] and tin iodide [SnI ₂ ] are dissolved at a molar ratio of 1: 1 in acetonitrile so as to have a concentration of 10% by weight. An inorganic hybrid perovskite compound-D [C ₂ H ₅ NH ₃ SnI ₃ ] solution was prepared.

(P1-5) halide organic-inorganic hybrid perovskite compound -E _{[(C 2 H 5 -) (} C 4 H 9 -) CH-CH 2 -NH 3) 2 PbI 4 ] 40% of the synthetic 2-ethylhexyl amine A methanol solution (27.86 mL) and an aqueous solution of 57% by mass hydrogen iodide (hydroiodic acid, 30 mL) were stirred in a flask at 0 ° C. for 2 hours. Then, it concentrated and obtained the ammonium compound. The obtained ammonium compound was dissolved in ethanol, added with diethyl ether and recrystallized. The crystal was collected by filtration, dried under reduced pressure at 60 ° C. for 24 hours, and purified ammonium compound [(C ₂ H ₅ −) ( C ₄ H ₉ -) was obtained _CH-CH 2 -NH ₃ I]. Subsequently, the ammonium compound [(C ₂ H ₅ −) (C ₄ H ₉ −) CH—CH ₂ —NH ₃ I] and lead iodide [PbI ₂ ] are adjusted to a molar ratio of 2: 1, and the t-butanol solvent is used. The mixture was stirred at 60 ° C. for 12 hours, mixed, then filtered through a polytetrafluoroethylene (PTFE) syringe filter, and a halide-based organic-inorganic hybrid perovskite compound-E [(C ₂ H _5- ) (C ₄ H _{9 -) CH-CH 2 -NH 3} ) was prepared 2 PbI _4].

(P1-6) Synthesis of Halide-Based Inorganic Perovskite Compound-F [CsSnI ₃ ] Cesium iodide [CsI] and tin iodide [SnI ₂ ] in a molar ratio of 1: 1 to 10% by weight in acetonitrile Thus, a halide-based inorganic perovskite compound-F [CsSnI ₃ ] solution was prepared.

<Example 1>
(1-1) Production of photoelectrode (1-1-1) Production of buffer layer Organic set on a coating coater on the conductive surface side of an FTO transparent conductive glass substrate (sheet resistance 11Ω) and diluted to 1.6% A PC-600 solution (manufactured by Matsumoto Fine Chemical) was applied with a wire bar at a sweep rate (10 mm / second), dried at room temperature for 10 minutes, and further heated and dried at 150 ° C. for 10 minutes to form a buffer layer (6 nm). .

(1-1-2) Production of photoelectric conversion layer Syringe with 0.2 μm filter of N, N-dimethylformaldehyde solution of halide organic inorganic perovskite compound-A on FTO transparent conductive glass substrate provided with the buffer layer A predetermined amount was dropped and spin-coated at a rotational speed of 3000 rpm, and then heat-dried in a hot air circulation oven at 60 ° C. for 10 minutes to prepare a conductive photoelectrode-01 having a photoelectric conversion layer.

(1-1-3) Application of adhesion layer (1-1-3-1) Synthesis of acrylic polymer syrup-01 2-ethylhexyl acrylate (2EHA) (65 parts by weight), butyl acrylate (BA) as monomers (30 parts by weight), acrylic acid (AA) (5 parts by weight), and 0.1 parts by weight of a trade name “Irgacure 651” (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator were mixed, and then nitrogen gas was added The dissolved oxygen was removed by blowing, and then ultraviolet rays were irradiated until the viscosity (BH viscometer, No. 5 rotor, 10 rpm, measurement temperature: 30 ° C.) reached about 15 Pa · s, and a part of the monomer was polymerized. Acrylic polymer syrup-01 was prepared.

(1-1-3-2) Synthesis of acrylic oligomer-01 After compounding cyclohexyl methacrylate (CHMA) (100 parts by weight) and thioglycolic acid (3.5 parts by weight), nitrogen gas was blown to dissolve dissolved oxygen. Removed. Next, when the temperature was raised to 90 ° C., perhexyl O (manufactured by NOF Corporation) (0.005 parts by weight) and perhexyl D (manufactured by NOF Corporation) (0.01 parts by weight) were mixed. Furthermore, after stirring at 90 ° C. for 1 hour, the temperature was raised to 130 ° C. over 1 hour. Then, after stirring at 130 ° C. for 1 hour, the temperature was raised to 170 ° C. over 30 minutes and stirred at 170 ° C. for 60 minutes. Next, the pressure was reduced at 170 ° C., and the mixture was stirred for 1 hour to remove the residual monomer, to obtain acrylic oligomer-01. In addition, the weight average molecular weight of the obtained oligomer was 4500.

(1-1-3-3) Preparation of acrylic adhesive composition For acrylic polymer syrup-01 (100 parts by weight) obtained by the above method, hexanediol diacrylate (0.1 parts by weight), the above The acrylic oligomer 01 (20 parts by weight) obtained in 1 was blended to obtain an acrylic pressure-sensitive adhesive composition-01. 1 part by weight of this mixture was diluted to 999 parts by weight of ethyl acetate to obtain an acrylic adhesive composition-01 solution.

(1-1-3-4) Application of acrylic adhesive layer On the conductive photoelectrode-01 having the photoelectric conversion layer prepared in (1-1-2) above, the acrylic adhesive composition-01 liquid Was coated with a bar coater so that the film thickness was about 6 nm, and a conductive photoelectrode-01 having an adhesive applied to the outermost layer was produced.

(1-2) Production of counter electrode Spiro-OMeTAD (180 mg) as a hole transport material was dissolved in chlorobenzene (1 mL) on the conductive surface side of the FTO transparent conductive glass substrate (sheet resistance 11Ω). To this chlorobenzene solution, an acetonitrile solution (37.5 μL) in which lithium-bis (trifluoromethanesulfonyl) imide (170 mg) was dissolved in acetonitrile (1 mL) and t-butylpyridine (TBP, 17.5 μL) were added. A hole transport material solution was prepared by mixing. Next, the prepared hole transport material solution was applied onto an FTO substrate by spin coating and dried to form a hole transport layer-01 (film thickness 100 nm), and a conductive counter electrode-01 was produced. .

(1-3) Production of photoelectric conversion element (1-1) Conductive photoelectrode-01 provided with an adhesive on the outermost layer obtained by production of the photoelectrode and conductivity produced in the above (1-2) The functional layer surfaces of the counter electrode-01 were opposed to each other and applied with a load. After bonding, the sample of the present invention in which the adhesion was strengthened by heating at 70 ° C. for 60 seconds was designated as a photoelectric conversion element-01. Note that in the production of the photoelectric conversion element, all the steps were performed in a dry nitrogen atmosphere.

(1-4) Evaluation of photoelectric conversion element As a light source, a pseudo solar light source (PEC-L11 type, manufactured by Pexel Technologies Co., Ltd.) in which an AM1.5G filter was attached to a 150 W xenon lamp light source device was used. The amount of light was adjusted to 1 sun (about 100,000 lux AM1.5G, 100 mWcm-2 (JIS C 8912 class A)). The produced photoelectric conversion element-01 was connected to a source meter (2400 type source meter, manufactured by Keithley). For the current-voltage characteristics, the output current was measured while changing the bias voltage from 0 V to 1.8 V in units of 0.01 V under 1 sun light irradiation. Similarly, measurement was performed by stepping the bias voltage from 1.8 V to 0 V in the reverse direction, and the conversion efficiency was obtained using the average value of the measurement in the forward direction and the reverse direction as photocurrent data. The obtained conversion efficiency was 5.5%. The conversion efficiency is equivalent to that of a conventionally known solar cell using an oxide having ferroelectricity, and it can be seen that the photoelectric conversion element-01 of the present invention has a good photoelectric conversion ability.

<Comparative Example 1>
Photoelectric conversion element having no adhesive layer obtained by omitting the step of applying the acrylic adhesive layer described in (1-1-3-4) in the production of (1-2) counter electrode described in Example 1 Except for changing to −02, a comparative photoelectric conversion element-02 consisting of pressing a conductive photoelectrode having no adhesive layer and a conductive counter electrode was produced in the same manner as in Example 1. When the photoelectric conversion element-02 was evaluated in the same manner as in Example 1, the conversion efficiency was 1.9%, and the performance as a solar cell was extremely inferior.

<Comparative example 2>
In Example 1, a gold layer is formed by sputtering on the surface of the photoelectric conversion layer made of the perovskite compound of the outermost layer in the conductive photoelectrode-01 having no adhesive layer without producing the conductive counter electrode-01. Thus, a photoelectric conversion element-03 was prepared and evaluated in the same manner as in Example 1 except that the photoelectric conversion element was manufactured.
The photoelectrode and the counter electrode (in this case, the gold layer acts as a conductive layer) are integrated, and the photoelectric conversion element-03 was evaluated in the same manner as in Example 1. Was 3.2%, and the performance as a photovoltaic cell was insufficient. This is because a sufficient photoelectric conversion rate could not be obtained by applying the counter electrode directly to the photoelectrode by sputtering.

<Example 2>
In Example 1, the photoelectric conversion element-04 was evaluated in the same manner as in Example 1 except that an N, N-dimethylformaldehyde solution of a halide organic-inorganic hybrid perovskite compound-B was used as the perovskite compound. The conversion efficiency was 6.3% and it had sufficient performance.

<Example 3>
In Example 1, the photoelectric conversion element-05 was evaluated in the same manner as in Example 1 except that an acetonitrile solution of the halide organic-inorganic hybrid perovskite compound-C was used as the perovskite compound. The conversion efficiency was 5.7% and had sufficient performance.

<Example 4>
In Example 1, the photoelectric conversion element-06 was evaluated in the same manner as in Example 1 except that the perovskite compound was used as the perovskite compound and an acetonitrile solution of the mixed organic / inorganic hybrid perovskite compound-D was used. The conversion efficiency was 5.4% and had sufficient performance.

<Example 5>
In Example 1, the photoelectric conversion element-07 was evaluated in the same manner as in Example 1 except that a t-butanol solution of the halide organic-inorganic hybrid perovskite compound-E was used as the perovskite compound. The conversion efficiency was 5.6% and had sufficient performance.

<Example 6>
In Example 1, as the perovskite compound, a solution in which an N, N-dimethylformaldehyde solution of halide organic / inorganic hybrid perovskite compound-A and an acetonitrile solution of inorganic perovskite compound F were mixed at a ratio of 1: 1 was used. The photoelectric conversion element-08 was evaluated in the same manner as in Example 1. The conversion efficiency is 5.5%, and it can be seen that good photoelectric conversion efficiency can be obtained.

<Example 7>
In Example 6, except that the substrate of the photoelectrode was ITO / PEN (film thickness 125 μm, sheet resistance 13Ω) ITO surface was washed with an acetone solution and irradiated with a low-pressure mercury lamp for 20 minutes to form a photoelectrode substrate. In exactly the same manner as in Example 6, a photoelectric conversion element-09 of the present invention was produced and evaluated. The conversion efficiency was 5.4% and had sufficient performance.

<Example 8>
In Example 1, the photoelectric conversion element-10 was evaluated in the same manner as in Example 1 except that the film formation of the halide organic-inorganic hybrid perovskite compound-A as the perovskite compound was performed by a co-evaporation method. The conversion efficiency was 5.7% and had sufficient performance.

<Example 9>
In Photoelectrode-01 in which an adhesive was applied to the outermost layer described in (1-1-3-4) Acrylic adhesive layer application in Examples, except that the adhesive was changed to the adhesive prepared in (9-1) below. In exactly the same manner as in Example 1, a photoelectric conversion element-11 composed of a photoelectrode-11 having a photoelectrode and an adhesive layer was produced. When the evaluation was performed in the same manner as in Example 1, the conversion efficiency was 5.4%, and the solar cell performance was excellent.

(9-1) Preparation of adhesive In a reactor, dimethylolpropionic acid (2,2-di (hydroxymethyl) propionic acid) 13 4 parts, triethylamine 10 1 parts, and ε-caprolactone 4 6 5. 5 parts were charged and stannous octoate was used as a catalyst at a rate of 50 ppm and heated with stirring under a nitrogen stream to dissolve each component uniformly. And it was made to react at 120 degreeC for 6 hours, and after confirming that content of (epsilon) -caprolactone was 1% or less, the temperature of the reaction system was cooled. The obtained carboxylate amine group-containing polyester polyol is liquid at room temperature and contains dimethylolpropionic acid. 0% and a number average molecular weight of 7 0 0.

<Example 10>
In Photoelectrode-01 in which an adhesive was applied to the outermost layer described in (1-1-3-4) Acrylic adhesive layer application in Example 1, the adhesive prepared in (10-1) below was applied. Except for changing to photoelectrode-12, a photoelectric conversion element-12 consisting of a counterelectrode having a photoelectrode and an adhesive layer was produced in exactly the same manner as in Example 1. When the photoelectric conversion element-12 was evaluated in the same manner as in Example 1, the conversion efficiency was 5.5% and the solar cell performance was excellent.

(10-1) Preparation of adhesive In a reaction vessel equipped with a cooling pipe, a nitrogen gas introduction pipe, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 2, 2 as a polymerization initiator After charging 0.1 parts of '-azobisisobutyronitrile with 200 parts of ethyl acetate and introducing nitrogen gas with gentle stirring to replace the nitrogen, the liquid temperature in the flask was kept at around 60 ° C. for 6 hours. A polymerization reaction was performed to prepare an acrylic polymer solution. The acrylic polymer had a weight average molecular weight of 2.1 million and was used as an adhesive.

<Example 11>
In the conductive photoelectrode-01 having an adhesive applied to the outermost layer described in (1-1-3-4) Acrylic adhesive layer application in Example 1, the urethane polymer prepared in (11-1) below. A photoelectric conversion element-13 was produced in the same manner as in Example 1 except that the conductive photoelectrode was changed to a conductive photoelectrode provided with an adhesive. The conversion efficiency was 5.2%, and the solar cell performance was excellent.

(11-1) Preparation of Adhesive 49 parts of PCDLT5650J (polycarbonate polyol, manufactured by Asahi Kasei Chemicals Co., Ltd.) and 0.5 part of Denacol DA850 (manufactured by Nagase ChemteX Corporation) were used as polyols. 0.05 parts of dilaurate and 60 parts of toluene were blended and heated to 50 ° C. in a flask. Subsequently, 10.7 parts of xylylene diisocyanate was added dropwise to the flask to initiate the reaction. After reacting for 2 hours as it was, 3 parts of ethylenediamine was added as a chain extender to obtain a urethane polymer having a weight average molecular weight of 110,000 to obtain an adhesive.

<Example 12>
(12-1) Production of photoelectrode (12-1-1) Production of conductive support A fluorine-doped SnO ₂ conductive film (surface resistance value 14Ω) is formed on a glass substrate (thickness 2.2 mm). And the electroconductive support body-14 of the glass plate with FTO was produced.

(12-1-2) Preparation of Buffer Layer Titanium diisopropoxide Bis (acetylacetonate) in a 15% by mass isopropanol solution (Aldrich) was diluted with 1-butanol to give a 0.02M buffer layer solution. Was prepared. A buffer layer-14 (thickness 8 nm) made of titanium oxide was formed on the SnO 2 conductive film at 450 ° C. by spray pyrolysis using the prepared 0.02M blocking layer solution.

(12-1-3) Formation of Fine Particle Layer Ethyl cellulose, lauric acid and terpineol were added to an ethanol dispersion of titanium oxide (anatase, average particle size 20 nm) to prepare a titanium oxide paste. The prepared titanium oxide paste was applied onto the buffer layer-14 by screen printing and baked. The titanium oxide paste was applied and fired twice. As the firing temperature, the first firing was performed at 130 ° C., and the second firing was performed at 500 ° C. for 1 hour. The obtained titanium oxide fired body was immersed in a 40 mM TiCl 4 aqueous solution, heated at 60 ° C. for 1 hour, and subsequently heated at 500 ° C. for 30 minutes to form a fine particle layer-14 composed of TiO 2 (film thickness 200 nm). Formed.

(12-1-4) Formation of Photoelectric Conversion Layer On the fine particle layer-14, a halide-based organic / inorganic hybrid perovskite compound-A is used by spin coating method (2000 rpm for 60 seconds, followed by 3000 rpm for 60 seconds). After coating, the film was dried at 100 ° C. for 40 minutes under normal pressure in a nitrogen atmosphere by a hot plate to form a photoelectric conversion layer-14 having a perovskite compound (thickness 200 nm: including fine particle layer thickness 200 nm). .

(12-1-5) Preparation of adhesive layer On the photoelectric conversion layer-14, in the same manner as the application of the (1-2-2-4) acrylic adhesive layer in Example 1, the adhesive layer was Conductive photoelectrode-14 having an outer layer and an adhesive layer applied to the outer layer was obtained.

(12-2) Preparation of counter electrode (12-2-1) Preparation of hole transport layer for conductive counter electrode The following hole transport layer is formed on the conductive layer surface side of the FTO transparent conductive glass substrate (sheet resistance 11Ω). Was granted. Spiro-OMeTAD (180 mg) as a hole transport material was dissolved in chlorobenzene (1 mL). To this chlorobenzene solution, an acetonitrile solution (37.5 μL) in which lithium-bis (trifluoromethanesulfonyl) imide (170 mg) was dissolved in acetonitrile (1 mL) and t-butylpyridine (TBP, 17.5 μL) were added. A hole transport material solution was prepared by mixing. Next, the prepared hole transporting material solution was applied onto the FTO glass by a spin coating method and dried to form a hole transporting layer (film thickness: 100 nm). The counter electrode thus obtained was named counter electrode-14.

(12-3) Production of photoelectric conversion element (12-1) Conductive photoelectrode-14 having an adhesive layer obtained by production of photoelectrode, and counter electrode-14 obtained in (12-2) The functional layer surfaces were opposed to each other and applied with a load. After pasting, photoelectric conversion element-14 which heated at 70 degreeC for 60 second and strengthened adhesion was obtained. Note that in the production of the photoelectric conversion element, all steps were performed under a dry nitrogen atmosphere.

(12-4) Evaluation of Photoelectric Conversion Element Evaluation of photoelectric conversion element-14 was carried out in the same manner as the evaluation of (1-4) photoelectric conversion element in Example 1. The obtained conversion efficiency is 5.8%, and it turns out that the photoelectric conversion element of this invention has a favorable photoelectric conversion ability.

<Comparative Example 3>
In the production of the (12-1) photoelectrode of Example 12, (12-1-5) Except for changing to the photoelectric conversion element-15 obtained without carrying out the production of the adhesive layer, exactly the same as in Example 12, A comparative photoelectric conversion element-15 consisting of pressing a photoelectrode having no adhesive layer and a counter electrode was produced. When the photoelectric conversion element-15 was evaluated in the same manner as in Example 14, the conversion efficiency was 2.6%, and the performance as a solar cell was extremely inferior.

<Example 13>
A photoelectric conversion element-16 was produced in the same manner as in Example 12 except that the following layers of Example 12 were changed.
(13-1) Production of conductive photoelectrode (13-1-1) Production of conductive support-16 (12-1-1) Instead of production of conductive support, the following conductive substrate was used. It was. That is, the ITO surface of ITO / PEN (film thickness 125 μm) (sheet resistance 13Ω) was washed with an acetone solution and irradiated with a low-pressure mercury lamp for 20 minutes to obtain a counter electrode substrate.
(13-1-2) Formation of Fine Particle Layer (12-1-3) Instead of forming the fine particle layer, the following fine particle layer was formed. That is, a binder-free titanium oxide paste (PECC-C01-06, manufactured by Pexel Technologies Co., Ltd.) that does not contain a polymer component was applied by a Baker type applicator. After the paste was dried at room temperature for 10 minutes, the protective film on the upper side of the mask film (NBO-0424 manufactured by Fujimori Kogyo Co., Ltd.) was peeled off and dried in a hot air circulation oven at 150 ° C. for another 5 minutes, A film thickness of 200 nm) was formed. The photoelectrode thus obtained was designated as conductive photoelectrode-16.

(13-2) Preparation of counter electrode (13-2-1) Preparation of hole transport layer for counter electrode (12-2-1) ITO / PEN instead of preparation of hole transport layer for counter electrode The following hole transport layer was provided on the conductive surface side of a transparent conductive plastic substrate (sheet resistance 13Ω, transmittance 83%). Spiro-OMeTAD (180 mg) as a hole transport material was dissolved in chlorobenzene (1 mL). To this chlorobenzene solution, an acetonitrile solution (37.5 μL) in which lithium-bis (trifluoromethanesulfonyl) imide (170 mg) was dissolved in acetonitrile (1 mL) and t-butylpyridine (TBP, 17.5 μL) were added. A hole transport material solution was prepared by mixing. Next, the prepared hole transport material solution was applied onto an ITO / PEN substrate by spin coating and dried to form a hole transport layer-16 (film thickness 100 nm). Produced.

(13-3) Production of Photoelectric Conversion Element The conductive photoelectrode-16 and the counter electrode-16 were bonded together with a load applied with the functional layer surfaces facing each other. After pasting, the sample which heated at 70 degreeC for 60 second and strengthened adhesion was used as photoelectric conversion element-16. Note that in the production of the photoelectric conversion element, all steps were performed under a dry nitrogen atmosphere.

(13-4) Evaluation of photoelectric conversion element The characteristics of the photoelectric conversion element-16 of the present invention were examined in exactly the same manner as in Example 12. The obtained conversion efficiency is 6.1%, and it can be seen that the photoelectric conversion element of the present invention has a good photoelectric conversion ability.

<Example 14>
(14-1) Preparation of conductive photoelectrode (14-1-1) Synthesis of halide organic-inorganic hybrid perovskite compound-G In a three-necked flask, 1 g of polyallylamine (weight average molecular weight: 15,000) and 100 ml of methanol were added. Then, hydrobromic acid was added while nitrogen bubbling was performed to adjust the pH to about 3 to 4, followed by stirring with a magnetic stirrer for 1 hour. The solvent was removed from the solution with an evaporator at 60 ° C. under reduced pressure. Further, 100 ml of a hexane solution was added and stirred, and then the supernatant was removed. The residue was removed with an evaporator under reduced pressure at 60 ° C. and repurified to synthesize polyallylamine bromide. Next, the synthesized polyallylamine and lead bromide are mixed and dissolved in dimethylformaldehyde at a molar ratio of 1: 1 of amine and Pb to a concentration of 15% by weight, and a halide organic inorganic A dimethylformaldehyde solution of hybrid perovskite compound-G was prepared.

(14-1-2) Synthesis of Inorganic Perovskite Compound-H [CsSnI ₃ ] Cesium iodide and tin iodide were dissolved in acetonitrile at a molar ratio of 1: 1 to a concentration of 10% by weight, and inorganic perovskite An acetonitrile solution of compound-H [CsSnI ₃ ] was prepared.

(14-1-3) Production of First Fine Particle Layer Transparent Conductive Substrate (Sheet Resistance) Coated with Transparent Conductive Layer [Indium-Tin Composite Oxide (ITO)] on Transparent Substrate (Polyethylene Naphthalate Film, Thickness 200 μm) 13 ohm / sq) is printed and coated with conductive silver paste (K3105, manufactured by Pernox Co., Ltd.) at intervals according to the photoelectrode cell width by screen printing, and heated in a 150 degree hot air circulation oven for 15 minutes. Dried to form a current collector. The buffer layer was set on a coating coater with the current collecting surface of the transparent conductive substrate facing up, and an organic PC-600 solution (manufactured by Matsumoto Fine Chemical) diluted to 1.6% was swept with a wire bar (10 mm). / Second), dried at room temperature for 10 minutes, and further dried by heating at 150 ° C. for 10 minutes. On the buffer layer forming surface of the transparent conductive substrate on which the buffer layer was formed, laser treatment was performed at intervals according to the photoelectrode cell width to form insulating lines.
An opening for forming a porous fine particle layer on a mask film (bottom: PC-542PA manufactured by Fujimori Kogyo Co., Ltd., upper: NBO-0424 manufactured by Fujimori Kogyo Co., Ltd.) in which a protective film coated with an adhesive layer is coated on a polyester film. (Length: 60 mm, width 5 mm) was punched out. The punched mask film was bonded so that air bubbles would not enter the surface of the transparent conductive substrate on which the buffer layer was formed. A high-pressure mercury lamp (rated lamp power 400 W) is placed at a distance of 10 cm from the mask bonding surface, and immediately after irradiation with electromagnetic waves for 1 minute, a binder-free titanium oxide paste that does not contain polymer components (PECC-C01-06, Pexel Technologies) Co., Ltd.) was applied with a Baker type applicator. After the paste was dried at room temperature for 10 minutes, the protective film on the upper side of the mask film (NBO-0424 manufactured by Fujimori Kogyo Co., Ltd.) was peeled off and dried in a hot air circulation oven at 150 ° C. for another 5 minutes, and the fine particle layer ( (Length: 60 mm, width 5 mm). A predetermined amount of a dimethylformaldehyde solution of a halide-based organic / inorganic hybrid perovskite compound-G is dropped on a transparent conductive substrate on which a fine particle layer is formed with a syringe with a 0.2 μm filter, and is placed in a hot air circulation oven for 10 minutes. The first fine particle layer was produced by heating and drying.

(14-1-4) Production of second fine particle layer Acetonitrile solution of inorganic perovskite compound-H [CsSnI ₃ ] was previously vacuum chambered with a syringe having a 0.2 μm filter on the first fine particle layer produced as described above. A predetermined amount was dropped into the first fine particle layer that had been deaerated inside, and sufficient permeation of the dropped solution was achieved. Thereafter, it is heated and dried in a hot air circulation oven at 60 ° C. for 10 minutes to give a second fine particle layer made of an inorganic perovskite compound-H [CsSnI ₃ ], and an electrically conductive light to which no adhesive is applied to the outermost layer. Electrode-17 was obtained.

(14-1-5) Application of adhesion layer (1-1-3-1) Synthesis of acrylic polymer syrup-01 described in Example 1, (1-1-3-2) Synthesis of acrylic oligomer 01 (1-1-3-3) Preparation of acrylic adhesive composition, and (1-1-3-4) Application of acrylic adhesive layer are the same as in Example 1, and are adhered to the outermost layer. A conductive conductive photoelectrode-17 provided with an agent was prepared.

(14-2) Production of counter electrode The following hole transport layer was provided on the conductive surface side of the ITO / PEN transparent conductive plastic substrate (sheet resistance 13Ω, transmittance 83%). Spiro-OMeTAD (180 mg) as a hole transport material was dissolved in chlorobenzene (1 mL). To this chlorobenzene solution, an acetonitrile solution (37.5 μL) in which lithium-bis (trifluoromethanesulfonyl) imide (170 mg) was dissolved in acetonitrile (1 mL) and t-butylpyridine (TBP, 17.5 μL) were added. A hole transport material solution was prepared by mixing. Next, the prepared hole transport material solution is applied onto an ITO / PEN substrate by spin coating and dried to form a hole transport layer-17 (film thickness: 100 nm). Made

(14-3) Production of photoelectric conversion element layer Conductive photoelectrode-17 provided with an adhesive on the outermost layer is fixed on an aluminum suction plate using a vacuum pump, and is liquid photocurable sealing The agent (manufactured by Three Bond Co., Ltd.) was applied to the outer peripheral portion of the coating film pattern by an automatic application robot. The counter electrode-17 was laminated and bonded in a reduced pressure environment using an automatic bonding apparatus. Light irradiation was performed with a metal halide lamp from the transparent substrate side to solidify the sealing agent, thereby forming a sealing layer. A photoelectric conversion element-17 was produced by sticking a conductive copper-clad tape (CU7636D, manufactured by Sony Chemical & Information Device Co., Ltd.) to the extraction electrode portion.

(14-4) Evaluation of photoelectric conversion element The photoelectric conversion element-17 of the present invention was evaluated in the same manner as (1-4) Evaluation of photoelectric conversion element described in Example 1, and the conversion efficiency was 6 2%. It turns out that the obtained conversion efficiency has the outstanding photoelectric conversion ability. Furthermore, it can be seen that the photoelectric conversion element of the present invention has a conversion efficiency of 5.7% after being stored for 500 hours in an atmosphere at 60 ° C., and is excellent in storage stability under high temperature conditions.

<Comparative Example 4>
The conductive photoelectrode-18 for comparison which does not have an adhesive layer without implementing (14-1-5) adhesive layer of Example 14 was produced. Using this conductive photoelectrode-18 and the counter electrode-18 produced in exactly the same manner as the counter electrode-17 of Example 14, a comparative photoelectric conversion element-18 was produced in the same manner as in Example-14. The conversion efficiency was examined. The conversion efficiency was 2.9%, the conversion efficiency after storage for 500 hours in an atmosphere at 60 ° C. was 1.5%, and the storage stability with time under high temperature conditions was poor. On the other hand, compared with the photoelectric conversion element-17 of the present invention formed using the photoelectrode having the adhesive layer as the outermost layer in Example 14, the comparative photoelectric conversion element having no adhesive layer has the characteristics. It turns out that it is inferior.

<Example 15>
A photoelectric conversion device-19 of the present invention was produced in exactly the same manner as in Example 12 except that the production of the (12-3) photoelectric conversion device of Example 12 was changed to the production of the following photoelectrode.
(15-1) Production of photoelectrode Except for changing the production of the adhesive layer of (12-1-5) adhesive layer of Example 12 to the application of the following (15-1-5) adhesive layer, exactly the same as Example 12. Thus, the photoelectrode-19 of the present invention was produced.

(15-1-5) Application of adhesive layer (15-1-5-1) Synthesis of acrylic polymer syrup-19 As a monomer, 2-ethylhexyl acrylate (2EHA) (65 parts by weight), butyl acrylate (BA) (30 parts by weight), acrylic acid (AA) (5 parts by weight), a trade name “Irgacure 651” (manufactured by Ciba Specialty Chemicals) (0.1 part by weight) as a photopolymerization initiator, and nitrogen Gas is blown to remove dissolved oxygen, and then ultraviolet rays are irradiated until the viscosity (BH viscometer, No. 5 rotor, 10 rpm, measurement temperature: 30 ° C.) reaches about 15 Pa · s, and a part of the monomer is polymerized. Acrylic polymer syrup-19 was prepared.

(15-1-5-2) Synthesis of acrylic oligomer 19 After compounding 8100 parts by weight of cyclohexyl methacrylate (CHMA) 9 and 83.5 parts by weight 9 of thioglycolic acid, nitrogen gas was blown to remove dissolved oxygen. Next, when the temperature was raised to 90 ° C., perhexyl O (manufactured by NOF Corporation) (0.005 parts by weight) and perhexyl D (manufactured by NOF Corporation) (0.01 parts by weight) were mixed. Furthermore, after stirring at 90 ° C. for 1 hour, the temperature was raised to 130 ° C. over 1 hour. Then, after stirring at 130 ° C. for 1 hour, the temperature was raised to 170 ° C. over 30 minutes and stirred at 170 ° C. for 60 minutes. Next, the pressure was reduced at 170 ° C., and the mixture was stirred for 1 hour to remove residual monomers, whereby an acrylic oligomer 19 was obtained. In addition, the weight average molecular weight of the obtained oligomer was 4000. The glass transition temperature (Tg) was 55 ° C.

(15-1-5-3) Preparation of Adhesive (Acrylic Adhesive Composition) To acrylic polymer syrup-19 (100 parts by weight) obtained by the above method, hexanediol diacrylate (0.1 wt. Part) and the acrylic oligomer 19 (20 parts by weight) obtained above were blended to obtain an acrylic pressure-sensitive adhesive composition-19. Furthermore, the hole transport layer solution-19 (6 parts by weight) in the preparation of the following (15-1-5-4) hole transport layer solution-19 was diluted with acetonitrile (994 parts by weight), and the acrylic adhesive 1 part by weight was mixed with the agent composition-19 (1 part by weight) to obtain an acrylic adhesive composition-19 liquid.

(15-1-5-4) Preparation of hole transport layer solution-19 Spiro-OMeTAD (180 mg) as a hole transport material was dissolved in chlorobenzene (1 mL), and lithium-bis (trifluoromethanesulfonyl) imide (170 mg). ) In acetonitrile (1 mL) and acetonitrile solution (37.5 μL) and t-butylpyridine (TBP, 17.5 μL) were added and mixed to prepare a hole transport layer solution-19. .

(15-1-5-5) Application of acrylic adhesive layer (12-1-4) Adhesion of (15-1-5-3) to a photoelectrode without an adhesive layer obtained by forming a photoelectric conversion layer. The acrylic adhesive composition-19 produced in the preparation of the agent was applied and dried with a bar coater so that the film thickness was about 4 nm, to produce a conductive photoelectrode-19 having an adhesive applied to the outermost layer.

(15-2) Production of Photoelectric Conversion Element The conductive photoelectrode-19 and the conductive counterelectrode-19 were bonded to each other with a load with the functional layer surfaces facing each other. After pasting, a sample which was heated at 70 ° C. for 60 seconds to strengthen the adhesion was designated as a photoelectric conversion element-19. Note that in the production of the photoelectric conversion element, all steps were performed under a dry nitrogen atmosphere.

(15-3) Evaluation of photoelectric conversion element When the characteristic evaluation of the obtained photoelectric conversion element-19 was carried out in the same manner as in Example 1, the conversion efficiency was 6.4% and it was 500 hours in an atmosphere of 60 ° C. It can be seen that the conversion efficiency after storage over time is 6.2%, and the storage over time under high temperature conditions is also excellent.

<Example 16>
The photoelectric conversion of the present invention was carried out in the same manner as in Example 15 except that the application of (15-1-5) adhesive layer in Example 15 was changed to the application of (16-1-5) adhesive layer described below. Element-20 was produced.
(16-1-5) Application of Adhesive Layer The following adhesive layer was applied to the outermost layer of the photoelectric conversion layer that had no adhesive layer in the outermost layer obtained in the same manner as in Example 15.

(16-1-5-1) Synthesis of acrylic polymer syrup-20 (15-2-2-1) Acrylic polymer syrup-20 was prepared in the same manner as the synthesis of acrylic polymer syrup-19.
(16-1-5-2) Synthesis of acrylic oligomer 1 Acrylic oligomer 20 was prepared in exactly the same manner as (15-2-2) Synthesis of acrylic oligomer 19.
(16-1-5-3) Preparation of Acrylic Adhesive Composition For acrylic polymer syrup-20 (100 parts by weight) obtained by the above method, hexanediol diacrylate (0.1 wt), The obtained acrylic oligomer-20 (20 parts by weight) was blended to obtain an acrylic pressure-sensitive adhesive composition-20. Further, the acrylic pressure-sensitive adhesive composition-20 (1 part by weight) and the halide organic-inorganic hybrid perovskite compound-A (1 part by weight) were diluted in acetonitrile (998 parts by weight) to obtain an adhesive composition-20 solution. Obtained.
(16-1-5-4) Application of Acrylic Adhesive Layer The adhesive composition-20 solution was applied with a bar coater to a thickness of about 9 nm, and the outermost layer of the present invention was applied in the same manner as in Example 19. A conductive photoelectrode-20 having an adhesive layer was prepared.

(16-2) Production of Photoelectric Conversion Element The conductive photoelectrode-20 and the conductive counterelectrode-20 having an adhesive layer as the outermost layer were bonded to each other with a load applied with the functional layer surfaces facing each other. After bonding, the sample of the present invention in which the adhesion was strengthened by heating at 70 ° C. for 60 seconds was designated as a photoelectric conversion element-20. Note that in the production of the photoelectric conversion element, all steps were performed under a dry nitrogen atmosphere.

(16-3) Evaluation of photoelectric conversion element The characteristics of the obtained photoelectric conversion element-20 were evaluated in the same manner as in Example 1. As a result, the conversion efficiency was 6.8%, and the atmosphere was at 60 ° C for 500 hours. It can be seen that the conversion efficiency after storage over time is 6.3%, and the storage over time under high temperature conditions is also excellent.

<Example 17>
In (16-1-5-3) Preparation of acrylic adhesive composition of Example 16, except that the halide organic-inorganic hybrid perovskite compound-A was changed to the halide organic-inorganic hybrid perovskite compound-C. In exactly the same manner as in Example 16, a photoelectric conversion element-21 of the present invention was produced. When the characteristic evaluation of the obtained photoelectric conversion element-21 was carried out, the conversion efficiency was 7.1%, the conversion efficiency after being stored over time for 500 hours in an atmosphere at 60 ° C. was 6.8%, and high It was excellent in durability at temperature.

<Example 18>
In Example 17, except that the counter electrode substrate and the conductive layer of the conductive counter electrode are changed to the PEN substrate provided with the following carbon nanotube conductive layer, the photoelectric conversion element of the present invention- 22 was produced.
(18-2-1) Production of counter electrode substrate The following conductive PEN substrate was used as a counter electrode substrate. That is, the ITO surface of ITO / PEN (film thickness 125 μm) (sheet resistance 13Ω) was washed with an acetone solution and irradiated with a low-pressure mercury lamp for 20 minutes. The following PEDOT / PSS (poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid) layer was coated on the ITO surface.
(18-2-1-1) Preparation and Application of PEDOTSS Dispersion Aqueous solution of PEDOT / PSS (R-iCP500; manufactured by Rigaku Corporation) in an amount of 1.0 wt% and sodium carboxymethyl cellulose 0.05 wt% Adjusted. This liquid was applied to a film thickness of 0.1 μm to obtain a conductive PEN support provided with a PEDOT / PSS layer having a sheet resistance of 15Ω.

(18-3) Production of photoelectric conversion element Except for changing the conductive counter electrode of Example 17 to the conductive counter electrode obtained in the above (18-2), (1) of Example 1 is further formed thereon. 1-3) A photoelectric conversion element-22 of the present invention was obtained in exactly the same manner as in Example 17 of the acrylic adhesive group obtained by applying the adhesive layer. Note that in the production of the photoelectric conversion element, all the steps were performed under a dry nitrogen atmosphere.

(18-4) Evaluation of photoelectric conversion element Photoelectric conversion element-22 was evaluated in the same manner as in Example 1. The obtained conversion efficiency was 6.6%, the conversion efficiency after aging for 500 hours in an atmosphere at 60 ° C. was 6.4%, and the photoelectric conversion element-22 of the present invention had good photoelectric conversion. It can be seen that it has the ability.

<Example 19>
(19-1) Production of photoelectrode (19-1-1) Production of buffer layer Organic placed on a coating coater on the conductive surface side of an FTO transparent conductive glass substrate (sheet resistance 11Ω) and diluted to 1.6% A PC-600 solution (manufactured by Matsumoto Fine Chemical) was applied with a wire bar at a sweep rate (10 mm / second), dried at room temperature for 10 minutes, and further heated and dried at 150 ° C. for 10 minutes to form a buffer layer.
(19-1-2) Production of Photoelectric Conversion Layer An N, N-dimethylformaldehyde solution of halide organic-inorganic hybrid perovskite compound-A is attached to the FTO transparent conductive glass substrate provided with the buffer layer with a 0.2 μm filter. A predetermined amount was dropped with a syringe, spin-coated at a rotation speed of 3000 rpm, and then heated and dried in a hot air circulation oven at 60 ° C. for 10 minutes to prepare a conductive photoelectrode-23 having a photoelectric conversion layer.

(19-2) Production of counter electrode (19-2-1) Production of hole transport layer Conductivity of FTO transparent conductive glass substrate (sheet resistance 11Ω) on the conductive surface side of FTO transparent conductive glass substrate (sheet resistance 11Ω) On the surface side, Spiro-OMeTAD (180 mg) as a hole transport material was dissolved in chlorobenzene (1 mL). To this chlorobenzene solution, an acetonitrile solution (37.5 μL) in which lithium-bis (trifluoromethanesulfonyl) imide (170 mg) was dissolved in acetonitrile (1 mL) and t-butylpyridine (TBP, 17.5 μL) were added. A hole transport material solution was prepared by mixing. Next, the prepared hole transport material solution is applied onto an FTO substrate by spin coating and dried to form a hole transport layer-01 (thickness 200 nm) to produce a counter electrode substrate, and a conductive counter electrode -23.
(19-2-2) Application of adhesive layer (19-2) Obtained by applying (1-1-3) adhesive layer of Example 1 to the obtained conductive counter electrode-23. The acrylic adhesive composition-01 liquid adhesive layer was applied to obtain a conductive counter electrode-23 having an adhesive layer.

(19-3) Production of Photoelectric Conversion Element The functional layer surface of the conductive photoelectrode-23 and the conductive counter electrode-23 having the adhesive layer was opposed to each other with a load applied thereto. After bonding, the sample of the present invention in which the adhesion was strengthened by heating at 70 ° C. for 60 seconds was designated as a photoelectric conversion element-23. Note that in the production of the photoelectric conversion element, all the steps were performed under a dry nitrogen atmosphere.

(19-4) Evaluation of photoelectric conversion element Photoelectric conversion element-23 was evaluated in the same manner as in Example 1. The conversion efficiency obtained was 6.8%. The conversion efficiency is equivalent to that of a conventionally known solar cell using an oxide having ferroelectricity, and it can be seen that the photoelectric conversion element-23 of the present invention has a good photoelectric conversion ability.

<Example 20>
(20-1) Preparation of buffer layer Wire is made of an organic PC-600 solution (manufactured by Matsumoto Fine Chemical Co., Ltd.) which is set on a coating coater on the conductive surface side of an FTO transparent conductive glass substrate (sheet resistance 11Ω) and diluted to 1.6%. After applying at a sweep rate (10 mm / second) with a bar and drying at room temperature for 10 minutes, it was further heated and dried at 150 ° C. for 10 minutes to form a buffer layer (8 nm).

(20-2) Production of photoelectric conversion layer N, N-dimethylformaldehyde solution of halide organic-inorganic hybrid perovskite compound-A was applied to the FTO transparent conductive glass substrate provided with the buffer layer with a syringe with a 0.2 μm filter. A predetermined amount was dropped, spin-coated at a rotation speed of 3000 rpm, and then heat-dried in a hot air circulation oven at 60 ° C. for 10 minutes to produce a conductive photoelectrode-24 having a photoelectric conversion layer.

(20-3) Preparation of hole transport layer The following hole transport layer is applied to the outermost layer of the conductive photoelectrode-24 having a photoelectric conversion layer in (20-2) to form a hole transport layer. The precursor of the photoelectric conversion element which has was obtained. That is, Spiro-OMeTAD (180 mg) as a hole transport material was dissolved in chlorobenzene (1 mL). To this chlorobenzene solution, an acetonitrile solution (37.5 μL) in which lithium-bis (trifluoromethanesulfonyl) imide (170 mg) was dissolved in acetonitrile (1 mL) and t-butylpyridine (TBP, 17.5 μL) were added. A hole transport material solution was prepared by mixing. Next, the prepared hole transporting material solution is applied onto an ITO / PEN substrate by a spin coating method and dried to form a hole transporting layer-24 (film thickness 100 nm). A conversion element precursor-24 was prepared.

(20-4) Production of conductive counter electrode having adhesive layer The ITO surface of ITO / PEN (thickness 125 μm) (sheet resistance 13Ω) was washed with an acetone solution and irradiated with a low-pressure mercury lamp for 20 minutes to counter electrode The acrylic adhesive composition-01 solution obtained in (01-1-3-3) <Preparation of acrylic adhesive composition> in Example 01 was used to form a substrate for the coating, and the film thickness was about A conductive counter electrode substrate -24 having a thickness of 10 nm and an adhesive applied to the outermost layer was produced.

(20-5) Production of Photoelectric Conversion Element Photoelectric Conversion Element Precursor-24 having a hole transport layer produced in (20-3) and (20-4) Production of a conductive counter electrode having an adhesive layer. The functional layer surface of the conductive counter electrode substrate-24, to which an adhesive was applied, was applied to the outermost layer obtained in the above while applying a load. After bonding, the sample of the present invention, which was heated at 70 ° C. for 60 seconds to strengthen the adhesion, was designated as a photoelectric conversion element-24. Note that in the production of the photoelectric conversion element, all the steps were performed under a dry nitrogen atmosphere.

(20-6) Evaluation of photoelectric conversion element Photoelectric conversion element-24 was evaluated in the same manner as in Example 1. The obtained conversion efficiency was 6.2%. The conversion efficiency is equivalent to that of a conventionally known solar cell using an oxide having ferroelectricity, and it can be seen that the photoelectric conversion element-24 of the present invention has a good photoelectric conversion ability.

  The photoelectric conversion element of the present invention can provide a photoelectric conversion element having high efficiency and excellent durability, and can be manufactured by a simpler method than the conventional method, and can provide an inexpensive solar cell.

DESCRIPTION OF SYMBOLS 1 Electrode substrate 2 Conductive layer 3 Buffer layer 4 Photoelectric conversion layer 5 Adhesive layer 6 Hole transport layer 7 Fine particle layer 8 Conductive photoelectrode 9 Conductive counter electrode

Claims (8)

A photoelectrode substrate having an opposing conductive layer, at least one of which is transparent, a counter electrode substrate having a conductive layer, and a halide organic-inorganic hybrid perovskite compound or a halide organic-inorganic hybrid perovskite compound and a halide inorganic perovskite compound A perovskite photoelectric conversion element having a photoelectric conversion layer, wherein the perovskite photoelectric conversion element has at least one adhesive layer. The perovskite according to claim 1, wherein the adhesive layer is an adhesive layer containing an adhesive selected from at least one polymer, a polymerizable monomer and / or a polymerizable oligomer compound, and a mixture thereof. Type photoelectric conversion element 3. The perovskite photoelectric conversion element according to claim 1, wherein the adhesive layer is an adhesive layer containing at least one halide-based organic / inorganic hybrid perovskite compound, inorganic perovskite compound, or hole transport compound. . The halide organic / inorganic hybrid perovskite compound is represented by the general formula R-M-Xn (where R is an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom, and n is an integer). The perovskite photoelectric conversion element according to claim 1, wherein: The perovskite photoelectric conversion element according to claim 1, wherein the perovskite photoelectric conversion element has at least one conductive layer and / or a buffer layer and / or an electron transport layer. The perovskite photoelectric conversion element according to claim 1, wherein the perovskite photoelectric conversion element has at least one conductive layer and / or a hole transport layer and / or a buffer layer. The perovskite photoelectric conversion element according to claim 1, wherein the conductive material of the perovskite photoelectric conversion element is a conductive material selected from a metal compound, a metal oxide, and an organic conductive compound. . The perovskite photoelectric conversion element is a photoelectrode substrate, a conductive layer, a buffer layer, an electron transport layer, a fine particle semiconductor layer, a photoelectric conversion layer having at least one halide-based organic-inorganic hybrid perovskite compound, a hole transport layer, a conductive layer, The perovskite photoelectric conversion element according to any one of aspects 1 to 7, which is a perovskite photoelectric conversion element in which counter electrode substrates are sequentially stacked, and the perovskite photoelectric conversion element has at least one adhesive layer.