JP2014229747A - Photoelectric conversion element using perovskite compound and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid junction solar cell replaceable for a dye-sensitized solar cell inferior in durability and an organic thin film solar cell inferior in light resistance and humidity resistance.SOLUTION: A solid junction photoelectric conversion element is a photoelectric conversion element which includes a photoelectric conversion layer between a pair of transparent electrode substrates each comprising a transparent substrate and a transparent electrode layer formed on the transparent substrate. The photoelectric conversion layer is formed by embedding a first semiconductor layer into a second semiconductor layer, the first semiconductor layer being formed by the film formation or adsorption of a polymer amine-containing organic inorganic hybrid perovskite compound on a surface of a porous semiconductor fine particle layer formed on the electrode substrates, and the second semiconductor layer comprising an inorganic perovskite compound and/or an organic inorganic hybrid perovskite compound.

Description

  The present invention relates to a solid junction photoelectric conversion element using an organic-inorganic hybrid perovskite compound and an inorganic perovskite compound in a photoelectric conversion layer.

  In recent years, pn junction solar cells have been actively studied as photoelectric conversion elements that convert solar energy into electric power. In this pn junction type 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 are disadvantages that the cost of the plant is high and the energy payback time is long.

  As a next-generation solar cell that replaces these conventional solar cells, development of an organic solar cell that can be manufactured at a lower temperature and at a lower cost is expected. One of them is a dye-sensitized solar cell that can be mass-produced at low cost in the air, and a highly efficient photoelectric conversion method using a porous semiconductor fine particle layer carrying a sensitizing dye has been proposed (Patent Document 1). ). The dye-sensitized solar cell is a wet solar cell that employs an electrolytic solution.

  The dye-sensitized solar cell is a photoactive electrode substrate in which a sensitizing dye is supported on a porous semiconductor fine particle layer made of metal oxide semiconductor nanoparticles represented by titanium dioxide nanoparticles formed on a transparent conductive substrate ( A photoelectrode) and a counter electrode substrate (opposite electrode) in which a platinum or carbon counter electrode layer is formed on a conductive substrate are placed facing each other, and the electrolyte solution is filled between the substrates, and the electrolyte solution is sealed. It consists of the structure. This dye-sensitized solar cell has a merit that the manufacturing process is simple and can be manufactured at a low cost, but there is a problem that sufficient durability cannot be obtained because a liquid is used as the electrolytic solution.

Non-Patent Document 1 discloses a dye-sensitized solar cell in which a sensitizing dye is adsorbed on a porous semiconductor fine particle (titanium oxide) layer and a hole-moving inorganic perovskite compound (CsSnI ₃ ) is used instead of the electrolytic solution ( DSC). However, since the ruthenium dye, which is a sensitizing dye, is an organometallic compound, there is a problem in the durability of the solar cell due to desorption and decomposition of the dye. Non-Patent Document 2 discloses that an organic-inorganic hybrid perovskite compound is used instead of a sensitizing dye. However, there is a problem that sufficient durability cannot be obtained for using the electrolytic solution.

  On the other hand, organic thin-film solar cells that do not use a sensitizing dye are generally widely known. However, the photoelectric conversion efficiency is lower than that of the dye-sensitized solar cell, and there is a concern about the durability of the solar cell because an organic material is used. Moreover, many processes are required for manufacturing these solar cell module units, and simplification of the manufacturing process is desired for cost reduction.

US Pat. No. 4,927,721

Nature 2012, 485, 486 Journal of the American Chemical Society 2009, 131, 6050

  In the present invention, by using a solid photoelectric conversion element having a high energy conversion efficiency composed of an organic-inorganic hybrid perovskite compound and an inorganic perovskite compound in the photoelectric conversion layer, durability due to deterioration of the sensitizing dye or leakage of the electrolytic solution is achieved. It has been found that the above-mentioned problems of a dye-sensitized solar cell having a problem or an organic thin-film solar cell having a problem with light resistance and moisture resistance are solved.

The present invention can be implemented in the following aspects (1) to (5).
(Aspect 1) A photoelectric conversion element having a photoelectric conversion layer between a transparent substrate and a pair of transparent electrode substrates formed of a transparent substrate and a transparent electrode layer formed on the transparent substrate, the photoelectric conversion layer on the transparent electrode substrate The first semiconductor layer in which the organic / inorganic hybrid perovskite compound A represented by the following general formula (1) is formed or adsorbed on the surface of the porous semiconductor fine particle layer formed on the inorganic perovskite compound B represented by the following general formula (2): And / or a solid junction photoelectric conversion element characterized by being embedded in a second semiconductor layer made of an organic-inorganic hybrid perovskite compound C represented by the following general formula (3) or (4). The porous semiconductor fine particle layer used in the present invention is necessary for increasing the surface area of the photoelectric conversion layer composed of the first semiconductor layer and the second semiconductor layer, and contributes to the improvement of the characteristics of the solar cell. Moreover, the stability (preservability) of a solid junction photoelectric conversion element can be improved by using the organic-inorganic hybrid perovskite compound A as an amine polymer salt.
R ¹ (M ¹ X ₃ ) _n (1)
In formula (1), n is a positive integer, R ¹ is at least one amine polymer selected from the following general formulas (1a) to (1c), and M ¹ is a divalent metal ion. , X is F, Cl, Br, I or a combination thereof.
(1a)
(1b)

(1c)
In the formulas (1a) to (1c), n is a positive integer, x is 0 or an integer of 1 to 4 (preferably 0 or 1), and each R is independently H or An alkyl group having 1 or more carbon atoms, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or an aromatic heterocyclic group;
CsM ² X ₃ (2)
In formula (2), M ² is a divalent metal ion, and X is F, Cl, Br, or I.
CH ₃ NH ₃ SnX ₃ (3)
In formula (3), X is F, Cl, Br, I.
(R ² NH ₃ ) ₂ SnX ₄ (4)
In the formula (4), R ² is an alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group or aromatic heterocyclic group having 2 or more carbon atoms, and X is F, Cl, Br, or I. .

(Aspect 2) The film or adsorbent comprising the organic-inorganic hybrid perovskite compound A constituting the first semiconductor layer is formed using a solution containing a precursor that can constitute the organic-inorganic hybrid perovskite compound A. The solid junction photoelectric conversion element described in (Aspect 1). By using the solution, a coating or adsorbent of the organic / inorganic hybrid perovskite compound A can be uniformly formed inside the porous semiconductor fine particle layer having fine pores.

(Aspect 3) The second semiconductor layer is formed by impregnating the first semiconductor layer with a solution containing a precursor that can constitute the inorganic perovskite compound B and / or the organic-inorganic hybrid perovskite compound C. A solid junction photoelectric conversion element as described in (Aspect 1) or (Aspect 2). This facilitates embedding the pores of the porous semiconductor fine particle layer covered or adsorbed by the first semiconductor layer with the second semiconductor layer.

(Aspect 4) The above (Aspect 1) to (Aspect 3) are characterized in that the organic-inorganic hybrid perovskite compounds A and C are organic-inorganic hybrid perovskite compounds represented by general formula (1) and general formula (3), respectively. ) Is a solid junction photoelectric conversion element.

(Aspect 5) The (Aspect 1) to (Aspect 4), wherein a buffer layer is formed between the electrode substrate and the first semiconductor layer and / or between the electrode substrate and the second semiconductor layer. It is the solid junction type photoelectric conversion element described in 1.

  The present invention does not require an electrolyte layer required for a photoelectric conversion layer of a wet solar cell typified by a dye-sensitized solar cell. For this reason, durability is not spoiled by electrolyte solution leakage, an electrolyte solution injection process is unnecessary, and the manufacturing process is greatly simplified. Moreover, the solid junction type photoelectric conversion element which is excellent in photoelectric conversion efficiency can be provided compared with the existing organic thin film solar cell.

It is a schematic diagram which shows an example of the structure of the solid junction type photoelectric conversion element of this invention. It is a schematic diagram which shows another example of the structure of the solid junction type photoelectric conversion element of this invention. It is a schematic diagram which shows another example of the structure of the solid junction type photoelectric conversion element of this invention. It is a schematic diagram which shows another example of the structure of the solid junction type photoelectric conversion element of this invention. It is sectional drawing which shows an example of the cell structure of the solid junction type photoelectric conversion element of this invention. It is the top view (upper stage) and sectional drawing (lower stage) which show one example which bonded the mask film to the transparent conductive substrate in order to form the photoelectric converting layer of the solid junction type photoelectric conversion element of this invention.

  Hereinafter, the structure of the solid junction photoelectric conversion element of the present invention will be described.

1. Structure of Solid Junction Photoelectric Conversion Device FIG. 1 is a schematic diagram showing an example of the structure of a solid junction photoelectric conversion device of the present invention. The solid junction photoelectric conversion element 1 includes a photoelectric conversion layer 3 between a pair of transparent electrode substrates 2 in which a transparent conductive layer 22 is formed on a transparent substrate 21. The photoelectric conversion layer 3 includes a first semiconductor layer 4 and a second semiconductor layer 5. In the first semiconductor layer 4, an organic / inorganic hybrid perovskite compound 42 is formed as a film on the surface of the porous semiconductor fine particle layer 41. The second semiconductor layer 5 is made of an organic / inorganic hybrid perovskite compound and / or an inorganic perovskite compound, and embeds the first semiconductor layer 4. FIG. 2 is a schematic diagram showing an example of the structure of the solid junction photoelectric conversion element of the present invention when the buffer layer 6 is provided between the electrode substrate 2 and the photoelectric conversion layer 3. FIG. 3 is a schematic diagram showing an example of the structure of the solid junction photoelectric conversion element of the present invention when the width of the second semiconductor layer is thicker than that of the first semiconductor layer 4. FIG. 4 shows an example of the structure of the solid junction photoelectric conversion element of the present invention when the first semiconductor layer 4 is formed with the adsorbent 43 of the organic / inorganic hybrid perovskite compound 42 on the surface of the porous semiconductor fine particle layer 41. It is a schematic diagram which shows.
Hereinafter, the transparent electrode substrate 2, the photoelectric conversion layer 3, and the buffer layer 6 will be described in this order.

[1] Transparent electrode substrate The transparent electrode substrate of the present invention is obtained by forming a transparent conductive layer on a transparent substrate.
(1) Transparent substrate The transparent substrate used in the present invention is preferably a glass or plastic substrate. As the plastic substrate material, an uncolored material having high transparency, high heat resistance, excellent chemical resistance and gas barrier properties, and low cost is preferable. 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 of these plastic substrates, or its composition, If it deserves to comprise the solid junction type photoelectric conversion element of this invention, it can utilize. The glass substrate material may be any material that has a visible light transmittance exceeding 80%, such as an inorganic substrate made of white plate glass, soda glass, borosilicate glass, or the like.

  The heat resistance of the plastic substrate preferably satisfies at least one of the physical properties of a glass transition temperature (Tg) of 100 ° C. or higher and a linear thermal expansion coefficient of 40 ppm / ° C. or lower. The Tg and linear expansion coefficient of the plastic substrate are measured by the plastic transition temperature measurement method described in JIS K 7121 and the linear expansion coefficient test method based on the thermomechanical analysis of plastic described in JIS K 7197. The Tg and linear expansion coefficient of the plastic film can be adjusted by additives. Examples of such a thermoplastic resin having excellent heat resistance include polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.). , Polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound of JP 2001-150584 A, 162 ° C.), fluorene ring Modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A: 205 ° C.), acryloyl compound (JP 2002) Compound of No.-80616 300 ° C. or higher), polyimide and the like (in parentheses indicate the Tg), they are suitable as substrates in the present invention. Especially, it is preferable to use an alicyclic polyolefin for the use for which transparency is particularly required.

(2) Transparent conductive layer The material of the transparent conductive layer of the present invention includes conductive metals (eg, platinum, gold, silver, copper, aluminum, indium, titanium), conductive carbon (carbon black, carbon nanofiber, Carbon nanotubes), conductive metal oxides (eg, tin oxide, zinc oxide) or conductive composite metal oxides (eg, indium-tin oxide, indium-zinc oxide). 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: 500 nm) of the electrode substrate provided with the transparent electrode layer on the transparent substrate is preferably 60% or more, more preferably 75% or more, most preferably 80% or more, and particularly 85. % Or more is preferable. The conductivity and transparency of the transparent electrode substrate can be achieved by optimizing the formation method of the transparent conductive layer, for example, by optimizing the deposition time, the amount of dispersion applied, and the like. In the present invention, either one of the pair of electrode substrates may not be a transparent electrode substrate.

  In the present invention, a metal can be used 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.

[2] Photoelectric conversion layer The photoelectric conversion layer of the present invention is formed between a pair of transparent electrode substrates, and contributes to charge separation of the solid junction photoelectric conversion element of the present invention. It has a function of transporting holes toward electrodes in opposite directions. The photoelectric conversion layer of the present invention is composed of a first semiconductor layer and a second semiconductor layer.

(A) First Semiconductor Layer The first semiconductor layer of the present invention has a function close to n-type semiconductor characteristics, and an organic / inorganic hybrid perovskite compound A is formed on the surface of the porous semiconductor fine particle layer formed on the transparent electrode substrate. Is formed or adsorbed.

(1) Porous semiconductor fine particle layer The porous semiconductor fine particle layer of the present invention comprises a so-called mesoporous semiconductor layer in which nano-sized pores are formed in a network. As the semiconductor fine particles forming the porous semiconductor fine particle layer, metal oxides and metal chalcogenides can be used. Examples of the metal element constituting the metal oxide and the metal chalcogenide include titanium, tin, zinc, iron, tungsten, zirconium, strontium, aluminum, indium, cerium, vanadium, niobium, tantalum, cadmium, zinc, lead, antimony, Bismuth, cadmium, lead and the like can be mentioned. This will be described below.

(2) Semiconductor fine particles The semiconductor fine particles of the present invention can be produced using a known method. As the production method, for example, the sol-gel method described in “Science of Sol-Gel Method”, Agne Jofu Co., Ltd. (1998), or metal chloride is converted to an oxide by high-temperature hydrolysis in an inorganic hydrogen salt. It can be prepared by a production method, a vapor-phase spray pyrolysis method in which a metal compound is thermally decomposed at a high temperature in a gas phase to form ultrafine particles. The ultrafine particles and nanoparticles of titanium dioxide (TiO2) produced by these methods are explained in “Particle Engineering System Vol. 2 (Applied Technology)” supervised by Hiroaki Yanagida (2002). Examples of the metal oxide semiconductor material include oxides of titanium, tin, zinc, iron, tungsten, zirconium, strontium, aluminum, indium, cerium, vanadium, niobium, tantalum, cadmium, lead, antimony, and bismuth. As the semiconductor material, there is an n-type inorganic semiconductor material. _{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.

As a method for producing titanium dioxide, there are a liquid phase method in which titanium tetrachloride and titanyl sulfate are hydrolyzed and a gas phase method in which titanium tetrachloride and oxygen or an oxygen-containing gas are mixed and burned. In the liquid phase method, anatase can be obtained as the main phase, but it becomes a sol or slurry, and drying is necessary to use it as a powder, but there is a problem that aggregation (secondary particle formation) proceeds by drying. . On the other hand, the vapor phase method is characterized by excellent dispersibility, high temperature during synthesis, and excellent crystallinity compared to the liquid phase method because no solvent is used.
By the way, there are anatase type, brookite type and rutile type in the crystal form of titanium dioxide nanoparticles. When titanium oxide is produced by a vapor phase method, titanium oxide that is stable at the lowest temperature is anatase type, and is converted into a brookite type or a rutile type as heat treatment is applied. The crystal structure can be determined by measuring a diffraction pattern by an X-ray diffraction method or detecting a crystal lattice image by observation with a transmission electron microscope. Moreover, the average particle diameter of the titanium dioxide nanoparticles can be calculated from a particle size distribution measurement by a light correlation method using a laser light scattering method or a scanning electron microscope observation method.

  Crystalline titanium dioxide nanoparticles having an average primary particle diameter of 40 to 70 nm used in the present invention are obtained by a gas phase method, and are a mixture of rutile type crystals and anatase type crystals. The form of the titanium dioxide nanoparticles may be various forms such as amorphous, spherical, polyhedral, fibrous, and nanotube-like, but a polyhedral or nanotube-like form is preferable, and a polyhedral form is more preferable. From the viewpoint of dispersion stability, the solid content concentration contained in the semiconductor fine particle dispersion is 0.1 to 25 wt%, preferably 0.5 to 20 wt%, and more preferably 0.5 to 15 wt%.

  On the other hand, metal oxide semiconductor nanoparticles having an average primary particle size of 10 to 30 nm used in the present invention are prepared as an aqueous solution of acidic sol in which titanium dioxide nanoparticles containing brookite crystals obtained by a liquid phase method are dispersed. Yes. This is because brookite-type titanium oxide is excellent in binding property to a dye and can provide higher photoelectric conversion efficiency than rutile or anatase-type titanium oxide. Brookite-type titanium oxide produced by a liquid phase method, particularly brookite-type titanium oxide produced by hydrolysis of titanium tetrachloride or titanium trichloride is preferred. This is because there is no problem in the state of the dispersed sol because it is used as a semiconductor nanoparticle dispersion for forming a porous semiconductor fine particle layer, the dispersion state is stable, and the coating properties are excellent. In order to enhance dispersibility, the aqueous medium is adjusted to be acidic, and the pH is 1 to 6, preferably 3 to 5. From the viewpoint of dispersion stability, the solid content concentration contained in the semiconductor fine particle dispersion is 1 to 15 wt%, preferably 2 to 12 wt%, and more preferably 2 to 10 wt%.

(3) Semiconductor Fine Particle Dispersion In the present invention, a semiconductor fine particle dispersion is applied on a transparent electrode substrate, and is heated to form a porous semiconductor fine particle layer. In the case of using a plastic substrate in the present invention, a low temperature film forming method is adopted, so that the dispersion composition does not contain a binder material such as resin or latex added for the purpose of improving the film forming property and leveling property of the dispersion. Is preferred. The semiconductor fine particle dispersion of the present invention is a viscous milky white liquid in which semiconductor fine particles are dispersed in a solvent comprising a mixture of water and an alcohol having 5 or less carbon atoms.

  The solvent used for the semiconductor fine particle dispersion of the present invention is a mixed solvent of a hydrophilic organic solvent mainly containing ethanol and water. As the hydrophilic solvent, other alcohols having 3 to 5 carbon atoms can be selected, and t-butanol, 2-butanol and the like can be added. In the semiconductor fine particle dispersion of the present invention, water is used as a dispersion solvent in addition to the alcohol. This is added for the purpose of maintaining the dispersion stability of the semiconductor fine particles and maintaining the viscosity of the dispersion at an appropriate level.

  In the present invention, the dispersion may contain both semiconductor fine particles having an average primary particle diameter of 10 to 30 nm and semiconductor fine particles having an average primary particle diameter of 40 to 70 nm. By simply mixing semiconductor fine particles whose primary particle size ranges do not overlap, a porous semiconductor fine particle layer having a large specific surface area and a porous structure can be easily produced. Therefore, a metal oxide semiconductor nanoparticle dispersion liquid containing metal oxide semiconductor nanoparticles and a solvent as essential components as proposed in Japanese Patent Application Laid-Open No. 2002-324591 can be changed continuously or discontinuously. There is no need to spray. Moreover, the volume shrinkage distortion at the time of drying can be relieve | moderated by mixing the particle | grains from which an average particle diameter differs greatly. Furthermore, the structure of the porous semiconductor fine particle layer formed after drying is solidified by dehydration condensation of the semiconductor fine particles having an average primary particle size of 10 to 30 nm.

  A paint conditioner, a homogenizer, an ultrasonic stirrer, or the like is used as a method for dispersing semiconductor fine particles having an average primary particle size of 40 to 70 nm in a solvent in the present invention, and a rotating / revolving combined mixing conditioner is preferable. Used. After dispersing semiconductor fine particles having an average primary particle size of 40 to 70 nm in a solvent, an acidic sol aqueous solution in which semiconductor fine particles having an average primary particle size of 10 to 30 nm are dispersed is added to obtain a semiconductor fine particle dispersion. Prepare. From the viewpoint of dispersion stability and coating film formability, the solid content concentration of the entire semiconductor fine particles contained in the dispersion is 5 to 30 wt%, preferably 8 to 25 wt%, and more preferably 8 to 20 wt%.

  As a coating method of the metal oxide semiconductor nanoparticle dispersion liquid, a known method such as a screen printing method, a drop casting method, a spin coating method, an air spray method, or the like can be used. From the viewpoint of the uniformity of the formed porous semiconductor fine particle layer, an air spray method using a spray device is preferred.

  The spraying apparatus used for spraying the metal oxide semiconductor nanoparticle dispersion of the present invention can form the metal oxide semiconductor nanoparticle dispersion in a mist of 200 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. Use the device. For example, there are an air spray device, an inkjet device, and an ultrasonic spray device. Here, the air spray device refers to a device that scatters liquid in a certain direction using a pressure difference generated by expansion of compressed air. From the viewpoint of uniformly forming a coating film having a certain width, it is preferable to use a two-fluid slit nozzle. An ink jet device refers to a device that discharges liquid as fine particles by volume shrinking or increasing the temperature of a fine nozzle filled with a liquid to be sprayed. The ultrasonic spray device refers to a device that scatters liquid in a mist form by irradiating the liquid with ultrasonic waves. These apparatuses can be arbitrarily selected depending on the size of the porous semiconductor fine particle layer to be produced, in other words, the size of the photoelectrode or the solid content concentration of the dispersion.

  The thickness of the porous semiconductor fine particle layer formed by spraying the metal oxide semiconductor nanoparticle dispersion on the transparent electrode substrate is preferably less than 30 μm, more preferably less than 20 μm in consideration of absorption loss of transmitted light. The porosity of the formed porous semiconductor fine particle layer (ratio of the volume occupied by the vacancies in the film) is preferably 50 to 85%, more preferably 65 to 85%. The heat treatment temperature is within the range of heat resistance of the conductive substrate. For example, when the transparent conductive substrate is a plastic substrate, the porous semiconductor is formed by a low temperature film formation method (eg, 200 ° C. or lower, preferably 150 ° C. or lower). A fine particle layer can be formed.

(4) Organic-inorganic hybrid perovskite compound A
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 ABX ₃ structure, which has a three-dimensional network of vertex sharing BX ₆ octahedrons. The B component of the ABX ₃ structure is a metal cation that can take octahedral coordination of the X anion. A cations are located in 12 coordination holes between BX ₆ octahedra and are generally inorganic cations. By substituting A from an inorganic cation to an organic cation, an organic-inorganic hybrid perovskite compound is formed.

The organic-inorganic hybrid perovskite compound A of the present invention is a compound represented by the following general formula (1).
R ¹ (M ¹ X ₃ ) _n (1)
In formula (1), n is a positive integer, R ¹ is at least one amine polymer selected from the following general formulas (1a) to (1c), and M ¹ is a divalent metal ion. , X is F, Cl, Br, I or a combination thereof.
(1a)
(1b)

(1c)
In the formulas (1a) to (1c), n is a positive integer, x is 0 or an integer of 1 to 4 (preferably 0 or 1), and each R is independently H or An alkyl group having 1 or more carbon atoms, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or an aromatic heterocyclic group;

The inorganic framework in the organic-inorganic hybrid perovskite compound A of the present invention has a metal halide octahedron layer sharing a vertex. Anionic metal halide layers (eg, M ¹ X ₃ ²⁻ , M ¹ X ₄ ²⁻ ) are generally divalent metals in order to balance the positive charge from the cationic organic layer. The metal constituting the anionic metal halide layer of the organic / inorganic hybrid perovskite compound A of the present invention is specifically M ¹ (eg, Cu ²⁺ , Ni ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ ). ²⁺ , Pd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ , Eu ²⁺ ).

  The halide constituting the anionic metal halide layer of the organic / inorganic hybrid perovskite compound A of the present invention is fluoride, chloride, bromide, iodide, or a combination thereof. This halide is preferably bromide or iodide.

  R in the above general formulas (1a) to (1c) of the present invention is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a linear, branched or cyclic alkyl chain (preferably having 2 to 30 carbon atoms). Yes, more preferably 2-20 carbon atoms, most preferably 2-18 carbon atoms). Specifically, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, isooctyl group, nonyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group Group, icosanyl group, docosanyl group, triacontanyl group, tetraacontanyl group, cyclopentyl group, cyclohexyl group and the like.

  The substituted or unsubstituted aralkyl group having 1 to 40 carbon atoms means a lower alkyl group substituted with an aryl group, the alkyl portion is linear or branched, and preferably 1 to 5 carbon atoms. More preferably, it is 1, and the aryl part preferably has 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

  The alkenyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and most preferably 3 to 12 carbon atoms. For example, a vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, oleyl group, allyl group and the like can be mentioned. Examples of the alkynyl group include acetylenyl, propargyl group, 3-pentynyl group, 2-hexynyl, and 2-decanyl.

  The aryl group is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl etc.), more preferably a phenyl group having 6 to 20 carbon atoms or 10 carbon atoms. A naphthyl group having 24 to 24, more preferably a phenyl group having 6 to 12 carbon atoms or a naphthyl group having 10 to 16 carbon atoms. For example, a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, xylyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like can be mentioned. These groups may further have a substituent. In the general formula (1), examples of the heterocyclic group include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group. These groups may further have a substituent.

  Examples of the aromatic heterocyclic group include furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, carbazolyl, carbolinyl, diaza Examples thereof include a carbazolyl group (in which one of carbon atoms constituting the carboline ring of the carbolinyl group is replaced with a nitrogen atom), a phthalazinyl group, and the like. These groups may further have a substituent.

  The at least one amine polymer selected from the above general formulas (1a) to (1c) constituting the organic / inorganic hybrid perovskite compound A of the present invention includes R is H or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. Is an aliphatic amine polymer. Specific examples include poly (allylamine), alkylated poly (allylamine), poly (vinylamine), poly (diallylamine), and poly (ethyleneimine). The weight average molecular weight of the amine polymer is preferably 500 to 500,000, more preferably 1000 to 50,000, and particularly preferably 2000 to 50,000.

  The organic / inorganic hybrid perovskite compound A of the present invention can be synthesized by a self-assembly reaction using a precursor solution. The film or adsorbent of the organic / inorganic hybrid perovskite compound A of the present invention is obtained by dissolving the perovskite compound A in an organic solvent, and then gravure coating method, bar coating method, printing method, spraying method, spin coating method, dip method, die coating method. It can be formed by a coating method such as.

(5) Solution of organic / inorganic hybrid perovskite A The solvent for preparing the solution of organic / inorganic hybrid perovskite A used in the present invention is not particularly limited as long as it can dissolve the organic / inorganic hybrid perovskite A. 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, chloroform, 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).

(B) Second Semiconductor Layer The second semiconductor layer of the present invention has a function close to p-type semiconductor characteristics, and is composed of an inorganic perovskite compound B and / or an organic-inorganic hybrid perovskite compound C. The first semiconductor layer is formed so as to enclose the first semiconductor layer.

(1) Inorganic pebrotite compound B
The inorganic perovskite compound B of the present invention is represented by the following general formula (2).
CsM ² X ₃ (2)
In formula (2), M ² is a divalent metal ion, and X is F, Cl, Br, or I.

Specifically, the metal constituting the anionic metal halide layer of the inorganic perovskite compound B of the present invention is M ² (eg, Cu 2+, Ni 2+, Mn 2+, Fe 2+, Co 2+, Pd 2+, Ge 2+, Sn 2+, Pb 2+, Eu 2+). ).

  The halide constituting the anionic metal halide layer of the inorganic perovskite compound B of the present invention is fluoride, chloride, bromide, iodide, or a combination thereof. This halide is preferably bromide or iodide.

Specific examples of the inorganic perovskite compound B of the present invention include CsSnI ₃ and CsSnBr ₃ .

  The inorganic perovskite compound B of the present invention can be synthesized by a self-organization reaction using a precursor solution. The second semiconductor layer of the present invention can be formed by dissolving a perovskite compound B in an organic solvent and then applying a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, a die coating method, or the like. . As the organic solvent, it is necessary to select a solvent that dissolves, decomposes, or does not swell the first semiconductor layer.

(2) Organic-inorganic hybrid perovskite compound C
The organic-inorganic hybrid perovskite compound C of the present invention is represented by the following general formula (4) and / or general formula (5).
CH ₃ NH ₃ SnX ₃ (3)
In formula (3), X is F, Cl, Br, I.
(R ² NH ₃ ) ₂ SnX ₄ (4)
In the formula (4), R ² is an alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group or aromatic heterocyclic group having 2 or more carbon atoms, and X is F, Cl, Br, or I. .

The inorganic framework in the organic-inorganic hybrid perovskite compound C of the present invention has a metal halide octahedron layer sharing a vertex. In order to balance the positive charge from the cationic organic layer, the anionic metal halide layer (eg M ¹ X ₃ ²⁻ , M ¹ X ₄ ²⁻ ) is a divalent metal (Sn ²⁺ ). It is.

  The halide constituting the anionic metal halide layer of the organic / inorganic hybrid perovskite compound C of the present invention is fluoride, chloride, bromide, iodide, or a combination thereof. This halide is preferably bromide or iodide.

R ^{2 in} the above general formula (4) of the present invention is a substituted or unsubstituted alkyl group having 2 to 40 carbon atoms, a linear, branched or cyclic alkyl chain (preferably having 2 to 30 carbon atoms, more Preferably it is C2-C20, and C2-C18 is the most preferable). Specifically, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, isooctyl group, nonyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, icosanyl Group, docosanyl group, triacontanyl group, tetraacontanyl group, cyclopentyl group, cyclohexyl group and the like.

  The substituted or unsubstituted aralkyl group having 2 to 40 carbon atoms means a lower alkyl group substituted with an aryl group, the alkyl portion is linear or branched, and preferably has 1 to 5 carbon atoms, More preferably, it is 1, and the aryl part preferably has 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

  The alkenyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and most preferably 3 to 12 carbon atoms. For example, a vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, oleyl group, allyl group and the like can be mentioned. Examples of the alkynyl group include acetylenyl, propargyl group, 3-pentynyl group, 2-hexynyl, and 2-decanyl.

  The aryl group is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl etc.), more preferably a phenyl group having 6 to 20 carbon atoms or 10 carbon atoms. A naphthyl group having 24 to 24, more preferably a phenyl group having 6 to 12 carbon atoms or a naphthyl group having 10 to 16 carbon atoms. For example, a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, xylyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like can be mentioned. These groups may further have a substituent. In the general formula (1), examples of the heterocyclic group include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group. These groups may further have a substituent.

  Examples of the aromatic heterocyclic group include furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, carbazolyl, carbolinyl, diaza Examples thereof include a carbazolyl group (in which one of carbon atoms constituting the carboline ring of the carbolinyl group is replaced with a nitrogen atom), a phthalazinyl group, and the like. These groups may further have a substituent.

A specific example of the organic / inorganic hybrid perovskite compound C of the present invention is CH ₃ NH ₃ SnI ₃ .

  The organic-inorganic hybrid perovskite compound C of the present invention can be synthesized by a self-assembly reaction using a precursor solution. The second semiconductor layer of the present invention can be formed by dissolving the perovskite compound C in an organic solvent and then applying a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, a die coating method, or the like. . As the organic solvent, it is necessary to select a solvent that dissolves, decomposes, or does not swell the first semiconductor layer.

(5) Solution of organic / inorganic hybrid perovskite C As a solvent for preparing a solution of organic / inorganic hybrid perovskite C used in the present invention, an organic / inorganic hybrid perovskite C can be dissolved, and the first semiconductor layer is dissolved, The solvent is not particularly limited as long as it does not decompose or swell. 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, -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), amide solvents (eg, N, N-dimethylformamide, acetamide, N, N-dimethylacetamide, etc.), nitrile solvents (eg, acetonitrile, isobutyronitrile, propylene, etc.) Pionitrile, methoxyacetonitrile, etc.), carboat agents (eg, ethylene carbonate, propylene carbonate, etc.), halogenated hydrocarbons (eg, methylene chloride, dichloromethane, chloroform, 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).

[3] Buffer layer The buffer layer has a role of preventing a short circuit between the transparent electrode substrate and the photoelectric conversion layer. Moreover, it also has a role which improves the adhesiveness of a transparent electrode substrate and a photoelectric converting layer.

  The material of the buffer layer is not particularly limited as long as it is a high resistance semiconductor and insulating material. Examples include titanium oxide, niobium oxide, tungsten oxide, tin oxide, and zinc oxide. As a method for forming the buffer layer, a method of directly sputtering the above-mentioned material onto a transparent conductive layer, Electrochim. There is a spray pyrolysis method described in Acta 40, 643-652 (1995). Or the solution which melt | dissolved the said raw material in the solvent, the solution which melt | dissolved the metal hydroxide which is a precursor of a metal oxide, or the solution containing the metal hydroxide which melt | dissolved the organometallic compound in the mixed solvent containing water, There is a method of applying and drying on a conductive substrate composed of a substrate and a conductive layer, and sintering as necessary. The preferable film thickness of the buffer layer is 5 to 100 nm. Examples of the coating method include a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, and a die coating method.

2. FIG. 5 is a cross-sectional view showing an example of the cell structure of the solid junction photoelectric conversion element of the present invention. Based on FIG. 5, the cell structure of the solid junction photoelectric conversion element of the present invention will be described. A cell 10 of a solid junction photoelectric conversion element has a photoelectric conversion layer 3 between a pair of transparent electrode substrates 2 in which a transparent conductive layer 22 is formed on a transparent substrate 21. The photoelectric conversion layer 3 includes a first semiconductor layer 4 and a second semiconductor layer 5. In the first semiconductor layer 4, an organic / inorganic hybrid perovskite compound 42 is formed as a film on the surface of the porous semiconductor fine particle layer 41. The second semiconductor layer 5 is made of an organic / inorganic hybrid perovskite compound and / or an inorganic perovskite compound, and embeds the first semiconductor layer 4. A buffer layer 6 is provided between the transparent electrode substrate 2 and the photoelectric conversion layer 3. The side surface of the photoelectric conversion layer 3 is sealed with a sealing layer 7. The pair of transparent electrode substrates are provided with current collecting 9 and extraction electrode 8, respectively.

  The upper part of FIG. 6 is a plan view of the transparent conductive substrate 2 to which the mask film of the present invention is bonded, and the lower part of FIG. 6 is a cross-sectional view of the transparent conductive substrate 2 to which the mask film of the present invention is bonded. In addition, FIG. 6 is an aspect in the case where 6 rows of cells of the solid junction photoelectric conversion element of the present invention are arranged to form a battery module. As shown in FIG. 6, in the cell of the solid junction photoelectric conversion element of the present invention, first, a mask film 11 is bonded onto the transparent conductive substrate 2 on which the buffer layer 6 is formed, and the bonded mask film. After the metal oxide semiconductor nanoparticle dispersion is applied and dried on the open portion 12 to form a porous semiconductor fine particle layer, the organic / inorganic hybrid perovskite compound A is coated or adsorbed to form a first semiconductor layer. Thereafter, the formed first semiconductor layer is manufactured by impregnating the second semiconductor layer made of the inorganic perovskite compound B and / or the organic / inorganic hybrid perovskite compound C. The open part of the mask film serves as a cell model of the solid junction photoelectric conversion element of the present invention. The planar shape of the open portion 23 of the mask film is a rectangle having four rounded corners, and its size is determined by the planar shape of the porous semiconductor fine particle layer to be formed. Hereinafter, it demonstrates in order of a mask film, a sealing layer, a current collection line, and an extraction electrode.

[1] Mask film The mask film of the present invention has an open portion serving as a model of the photoelectric conversion layer of the present invention, and at the same time, is easily attached to a transparent conductive substrate or a transparent conductive substrate on which a buffer layer is formed. The adhesive film is not particularly limited as long as it is an adhesive film having an adhesive layer that can be easily peeled off after applying a metal oxide semiconductor nanoparticle dispersion or a perovskite compound solution. Specifically, it is a laminated film in which a slightly adhesive layer and a release film are provided on one side of a base film, and an antistatic layer and an antifouling layer are provided on the other side. It is a laminated adhesive film used for a surface protective film of a phase difference film. 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 of the present invention 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 solid junction photoelectric conversion element is a rectangle, and the area (S) of the rectangle is 300 mm 2 to 600 mm 2. This is because by setting the planar shape within such a range, the internal resistance per unit area of the solid junction photoelectric conversion element can be minimized and the conversion efficiency can be maximized.

[2] 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 includes a spacer for forming a photoelectric conversion layer by adjusting a necessary gap between a sealing material for bonding a pair of transparent electrode substrates and the pair of transparent electrode substrates. Has been.

(1) Sealing material The sealing material of the present invention is not particularly limited as long as it can bond a pair of transparent electrode substrates and seal the photoelectric conversion layer. 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 sealing material 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.

(2) Spacer The spacer of the present invention is not particularly limited as long as the necessary gap between the pair of transparent 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.

  It is preferable that the thickness of the sealing layer of the present invention is 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. Further, the width of the sealing layer of the present invention is not particularly limited, but for example, it is preferably in the range of 0.5 mm to 5 mm, particularly in the range of 0.8 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 that contributes to power generation in the photoelectric conversion element is large. This is because the effective area is reduced with respect to the module area and the effective power generation efficiency may be reduced.

[3] Electric current collector In the present invention, the surface resistivity of the transparent transparent electrode made of a transparent conductive film is lowered by arranging a current collector made of a metal (good conductor) on the transparent conductive film. The current collector is preferably provided outside the photoelectric conversion layer separated 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 0.5 mm to 5 mm, more preferably 0.7 mm to 3 mm, and the thickness of the current collector is 5 μm to 50 μm, more preferably 6 μm to 20 μm. In addition to ensuring sufficient electrical conductivity per line cross-sectional area, it is necessary to have appropriate width and thickness in order to secure the necessary gap between the pair of transparent electrode substrates in combination with conductive fine particles described later. Because.

[4] Extraction Electrode In the present invention, the photoelectric conversion element 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.

[5] Exterior and barrier package In the present invention, the substrate is designed to reduce its permeability to water vapor and gas, but there is a possibility that output degradation may be seen due to severe environmental conditions. In particular, it is important to provide durability under high temperature and high humidity environmental conditions. These improvement methods can be achieved by making the substrate a substrate having a barrier property against gas or water vapor, or by enclosing the solid junction photoelectric conversion element of the present invention in a packaging body having a barrier property. Hereinafter, the barrier film preferably used in the present invention, particularly the water vapor barrier property will be described below.

  As described above, the solid junction photoelectric conversion element of the present invention also preferably has a layer having a barrier property against gas and water vapor outside the substrate. Furthermore, it is preferable that it is packaged or wrapped with a packaging material having a water vapor barrier property. At that time, there may be a space between the solid junction photoelectric conversion element of the present invention and the high barrier packaging material, or the solid junction photoelectric conversion element of the present invention may be adhered with an adhesive. Furthermore, the solid junction photoelectric conversion element of the present invention is used as a packaging material by 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.). It may be packaged.

  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 solid junction photoelectric conversion element of the present invention, the amount of light necessary for the solid junction photoelectric conversion element of the present invention is obtained. A substrate or packaging material that is permeable and has a barrier property because it needs to be unhindered, and its transmittance is preferably 50% or more, more preferably 70% or more, and still more preferably 85%. Above, particularly preferably 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 and material, If it has this characteristic, it will not specifically limit.

A preferred substrate or packaging material having a 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 Laid-Open Publication No. 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 features) 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. 2004-46497).

Next, an embodiment that exhibits the effect of the present invention will be shown as an example.
[1] Example 1
(1-1) Synthesis of organic-inorganic hybrid perovskite compound A1 In a three-necked flask, 1 g of polyallylamine (weight average molecular weight: 15,000) and 100 ml of methanol were added, and hydrobromic acid was added while nitrogen bubbling to adjust the pH. After adjusting to about 3-4, it stirred with the 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 were mixed and dissolved in dimethylformaldehyde at a molar ratio of 1: 1 of amine and Pb to a concentration of 15% by weight, and an organic-inorganic hybrid perovskite was dissolved. A dimethylformaldehyde solution of Compound A1 was prepared.

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

(1-3) Synthesis of organic-inorganic perovskite compound C In a three-necked flask, 1 g of methylamine and 100 ml of methanol were added, and after adjusting the pH to about 3 to 4 by adding hydroiodic acid while carrying out nitrogen bubbling, magnetite was added. Stir with a tic stirrer for 1 hour. This solution was distilled by an evaporator, dried at 40 ° C., and repurified to synthesize methylamine iodide. Next, the synthesized methylamine iodide and tin iodide were dissolved at a molar ratio of 1: 1 in acetonitrile to a concentration of 10% by weight, and the organic / inorganic hybrid perovskite compound C [CH ₃ NH ₃ SnI ₃ ] was dissolved. An acetonitrile solution was prepared.

(1-4) Production of first semiconductor layer Transparent conductive substrate (sheet resistance 13 ohm / mm) coated on transparent substrate (polyethylene naphthalate film, thickness 200 μm) with transparent conductive layer [indium-tin composite oxide (ITO)] On the sq), conductive silver paste (K3105, manufactured by Pernox Co., Ltd.) is printed and applied at intervals according to the photoelectrode cell width by screen printing, and then heated and dried in a hot air circulation oven at 150 degrees for 15 minutes. The current collector was formed. 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.
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 having an adhesive layer coated on a polyester film is stacked is an opening for forming a porous semiconductor fine particle layer. A part (length: 60 mm, width 5 mm) was punched out. The punched mask film was bonded so that air bubbles would not enter the current collecting 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 is 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.) is peeled and removed, and further heated and dried in a hot air circulation oven at 150 degrees for 5 minutes. A fine particle layer (length: 60 mm, width 5 mm) was formed. A predetermined amount of a dimethylformaldehyde solution of an organic / inorganic hybrid perovskite compound A1 is dropped on a transparent conductive substrate on which a porous semiconductor layer is formed with a syringe with a 0.2 μm filter, and heated in a 60 ° C. hot air circulating oven for 10 minutes. It dried and the 1st semiconductor layer was produced.

(1-5) Production of Second Semiconductor Layer An acetonitrile solution of inorganic perovskite compound B [CsSnI ₃ ] was removed in advance in a vacuum chamber with a syringe with a 0.2 μm filter on the first semiconductor layer produced as described above. A predetermined amount of the solution was dropped into the first semiconductor layer subjected to the gas treatment, and the dripped solution was sufficiently permeated. Then, 60-degree heat dried in a hot air circulating oven for 10 minutes to prepare a second semiconductor layer made of an inorganic perovskite compound B [CsSnI _3].

(1-6) Production of photoelectric conversion element The surface of the first semiconductor layer embedded in the second semiconductor layer is used as the upper surface, and is fixed on an aluminum adsorption plate using a vacuum pump. A curable sealant (manufactured by Three Bond Co., Ltd.) was applied to the outer peripheral portion of the coating film pattern by an automatic application robot. Using an automatic laminating apparatus, a transparent conductive substrate (sheet resistance 13 ohm / sq) coated with a transparent conductive layer [indium-tin composite oxide (ITO)] on a transparent substrate (polyethylene naphthalate film, thickness 200 μm) They were laminated and pasted in a reduced pressure environment. Light irradiation was performed from the transparent substrate side with a metal halide lamp, and the sealing agent was solidified to form a sealing layer. A solid-junction photoelectric conversion element was produced by pasting a conductive copper anchor tape (CU7636D, manufactured by Sony Chemical & Information Device Co., Ltd.) to the extraction electrode portion.

(1-7) Evaluation of Solid Junction Type Photoelectric Conversion Element A pseudo solar light source (PEC-L11 type, manufactured by Pexel Technologies Co., Ltd.) in which an AM1.5G filter was mounted on a 150 W xenon lamp light source device was used as a light source. 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 solid junction type photoelectric conversion element 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 0.8 V in units of 0.01 V under 1 sun light irradiation. Similarly, measurement was performed by stepping the bias voltage from 0.8 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 conversion efficiency of the solid junction photoelectric conversion element was 4.0%. The obtained conversion efficiency is equivalent to that of conventionally known dye-sensitized solar cells, and it can be seen that the solid junction photoelectric conversion element of the present invention has a good photoelectric conversion ability.
Furthermore, the conversion efficiency after the solid junction photoelectric conversion element of the present invention was stored for 30 hours in an atmosphere of 30 ° C. and a relative humidity of 80% was 3.8%. It turns out that it is excellent.

[2] Example 2
Example 2 was carried out in the same manner as in Example 1 except that the organic / inorganic hybrid perovskite compound A1 was changed to the organic / inorganic hybrid perovskite compound A2 as the perovskite compound forming the first semiconductor layer in Example 1.
(2-1) Synthesis of organic-inorganic hybrid perovskite compound A2 In a three-necked flask, 1 g of polyallylamine (weight average molecular weight: 8,000) and 100 ml of methanol were added, and hydroiodic acid was added while performing nitrogen bubbling to adjust the pH. After adjusting to about 3-4, it stirred with the 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 purified again to synthesize polyallylamine iodide. Next, the synthesized polyallylamine iodide and tin iodide are dissolved in acetonitrile at a molar ratio of 1: 1 of amine and Sn so as to have a concentration of 10% by weight, and an organic / inorganic hybrid perovskite compound A2 in acetonitrile solution Was prepared.

(2-2) Production of first semiconductor layer Transparent conductive substrate (sheet resistance 13 ohm / mm) coated on transparent substrate (polyethylene naphthalate film, thickness 200 μm) with transparent conductive layer [indium-tin composite oxide (ITO)] On the sq), conductive silver paste (K3105, manufactured by Pernox Co., Ltd.) is printed and applied at intervals according to the photoelectrode cell width by screen printing, and then heated and dried in a hot air circulation oven at 150 degrees for 15 minutes. The current collector was formed. 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.
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 having an adhesive layer coated on a polyester film is stacked is an opening for forming a porous semiconductor fine particle layer. A part (length: 60 mm, width 5 mm) was punched out. The punched mask film was bonded so that air bubbles would not enter the current collecting 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 is 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.) is peeled and removed, and further heated and dried in a hot air circulation oven at 150 degrees for 5 minutes. A fine particle layer (length: 60 mm, width 5 mm) was formed. A predetermined amount of acetonitrile solution of organic-inorganic hybrid perovskite compound A2 is dropped on a transparent conductive substrate on which a porous semiconductor layer is formed with a syringe with a 0.2 μm filter, and heated in a 60 ° C. hot air circulating oven for 10 minutes. It dried and the 1st semiconductor layer was produced.

(2-3) Preparation of Second Semiconductor Layer An acetonitrile solution of inorganic perovskite compound B [CsSnI ₃ ] was removed in advance in a vacuum chamber using a syringe with a 0.2 μm filter on the first semiconductor layer prepared as described above. A predetermined amount of the solution was dropped into the first semiconductor layer subjected to the gas treatment, and the dripped solution was sufficiently permeated. Then, 60-degree heat dried in a hot air circulating oven for 10 minutes to prepare a second semiconductor layer made of an inorganic perovskite compound B [CsSnI _3].

(2-4) Fabrication of photoelectric conversion element The surface of the first semiconductor layer embedded in the second semiconductor layer is used as the upper surface, and is fixed on an aluminum adsorption plate using a vacuum pump to obtain liquid light. A curable sealant (manufactured by Three Bond Co., Ltd.) was applied to the outer peripheral portion of the coating film pattern by an automatic application robot. Using an automatic laminating apparatus, a transparent conductive substrate (sheet resistance 13 ohm / sq) coated with a transparent conductive layer [indium-tin composite oxide (ITO)] on a transparent substrate (polyethylene naphthalate film, thickness 200 μm) They were laminated and pasted in a reduced pressure environment. Light irradiation was performed from the transparent substrate side with a metal halide lamp, and the sealing agent was solidified to form a sealing layer. A solid-junction photoelectric conversion element was produced by pasting a conductive copper anchor tape (CU7636D, manufactured by Sony Chemical & Information Device Co., Ltd.) to the extraction electrode portion.

(2-5) Evaluation of Solid Junction Type 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 solid junction type photoelectric conversion element 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 0.8 V in units of 0.01 V under 1 sun light irradiation. Similarly, measurement was performed by stepping the bias voltage from 0.8 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 conversion efficiency of the solid junction photoelectric conversion element was 3.8%. The obtained conversion efficiency is equivalent to that of conventionally known dye-sensitized solar cells, and it can be seen that the solid junction photoelectric conversion element of the present invention has a good photoelectric conversion ability.
Furthermore, the conversion efficiency after storage of the solid junction photoelectric conversion element of the present invention for 300 hours in an atmosphere of 30 ° C. and 80% relative humidity is 3.6%, and the storage stability over time under high humidity conditions is improved. It turns out that it is excellent.

[3] Example 3
Example 2 was carried out in the same manner as in Example 1 except that the organic / inorganic hybrid perovskite compound A1 was changed to the organic / inorganic hybrid perovskite compound A3 as the perovskite compound forming the first semiconductor layer in Example 1.

(3-1) Synthesis of organic-inorganic hybrid perovskite compound A3 In a three-necked flask, 1 g of polyallylamine (weight average molecular weight: 8,000) and 100 ml of methanol were placed, and hydrobromic acid and hydroiodic acid were added while performing nitrogen bubbling. (Molar ratio 1: 1) was added, 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 bromoiodinated polyallylamine. Next, the synthesized bromoiodinated polyallylamine and tin iodide are dissolved in acetonitrile at a molar ratio of 1: 1 of amine and Sn so as to have a concentration of 10% by weight, and an organic-inorganic hybrid perovskite compound A3 Acetonitrile solution was prepared.

(3-2) Production of first semiconductor layer Transparent conductive substrate (sheet resistance 13 ohm / mm) coated on transparent substrate (polyethylene naphthalate film, thickness 200 μm) with transparent conductive layer [indium-tin composite oxide (ITO)] On the sq), conductive silver paste (K3105, manufactured by Pernox Co., Ltd.) is printed and applied at intervals according to the photoelectrode cell width by screen printing, and then heated and dried in a hot air circulation oven at 150 degrees for 15 minutes. The current collector was formed. 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.
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 having an adhesive layer coated on a polyester film is stacked is an opening for forming a porous semiconductor fine particle layer. A part (length: 60 mm, width 5 mm) was punched out. The punched mask film was bonded so that air bubbles would not enter the current collecting 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 is 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.) is peeled and removed, and further heated and dried in a hot air circulation oven at 150 degrees for 5 minutes. A fine particle layer (length: 60 mm, width 5 mm) was formed. A predetermined amount of acetonitrile solution of organic-inorganic hybrid perovskite compound A3 is dropped on a transparent conductive substrate on which a porous semiconductor layer has been formed with a syringe with a 0.2 μm filter, and dried by heating in a 60 ° hot air circulation oven for 10 minutes. Thus, a first semiconductor layer was produced.

(3-3) Preparation of Second Semiconductor Layer An acetonitrile solution of inorganic perovskite compound B [CsSnI ₃ ] was removed in advance in a vacuum chamber using a syringe with a 0.2 μm filter on the first semiconductor layer prepared as described above. A predetermined amount of the solution was dropped into the first semiconductor layer subjected to the gas treatment, and the dripped solution was sufficiently permeated. Then, 60-degree heat dried in a hot air circulating oven for 10 minutes to prepare a second semiconductor layer made of an inorganic perovskite compound B [CsSnI _3].

(3-4) Production of photoelectric conversion element The surface of the first semiconductor layer embedded in the second semiconductor layer is used as the upper surface, and fixed on an aluminum adsorption plate using a vacuum pump. A curable sealant (manufactured by Three Bond Co., Ltd.) was applied to the outer peripheral portion of the coating film pattern by an automatic application robot. Using an automatic laminating apparatus, a transparent conductive substrate (sheet resistance 13 ohm / sq) coated with a transparent conductive layer [indium-tin composite oxide (ITO)] on a transparent substrate (polyethylene naphthalate film, thickness 200 μm) They were laminated and pasted in a reduced pressure environment. Light irradiation was performed from the transparent substrate side with a metal halide lamp, and the sealing agent was solidified to form a sealing layer. A solid-junction photoelectric conversion element was produced by pasting a conductive copper anchor tape (CU7636D, manufactured by Sony Chemical & Information Device Co., Ltd.) to the extraction electrode portion.

(3-5) Evaluation of Solid Junction Type Photoelectric Conversion Element A pseudo solar light source (PEC-L11 type, manufactured by Pexel Technologies Co., Ltd.) in which an AM1.5G filter is attached to a 150 W xenon lamp light source device was used as a light source. 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 solid junction type photoelectric conversion element 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 0.8 V in units of 0.01 V under 1 sun light irradiation. Similarly, measurement was performed by stepping the bias voltage from 0.8 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 conversion efficiency of the solid junction photoelectric conversion element was 4.1%. The obtained conversion efficiency is equivalent to that of conventionally known dye-sensitized solar cells, and it can be seen that the solid junction photoelectric conversion element of the present invention has a good photoelectric conversion ability.
Furthermore, the conversion efficiency after the solid junction photoelectric conversion element of the present invention is stored for 30 hours in an atmosphere of 30 ° C. and a relative humidity of 80% is 3.7%. It turns out that it is excellent.

The solid junction photoelectric conversion element of the present invention can provide a solar cell excellent in durability, light resistance and moisture resistance.

DESCRIPTION OF SYMBOLS 1 Photoelectric conversion element 2 Transparent electrode substrate 21 Transparent substrate 22 Transparent conductive layer 3 Photoelectric conversion layer 4 1st semiconductor layer 41 Porous semiconductor fine particle layer 42 Organic-inorganic hybrid perovskite compound A
5 Second semiconductor layer (inorganic perovskite compound B / organic / inorganic hybrid perovskite compound C)
6 Buffer layer 7 Sealing layer 8 Extraction electrode 9 Current collector 10 Cell 20 of solid junction photoelectric conversion element Transparent conductive substrate 11 with mask film bonded Mask film 12 Open portion of mask film

Claims (5)

A photoelectric conversion element having a photoelectric conversion layer between a transparent substrate and a pair of transparent electrode substrates formed of a transparent electrode layer formed on the transparent substrate, wherein the photoelectric conversion layer is formed on the transparent electrode substrate. The first semiconductor layer in which the organic / inorganic hybrid perovskite compound A represented by the following general formula (1) is formed or adsorbed on the surface of the porous semiconductor fine particle layer is coated with the inorganic perovskite compound B represented by the following general formula (2) and / or A solid junction photoelectric conversion element characterized by being embedded in a second semiconductor layer comprising an organic-inorganic hybrid perovskite compound C represented by the general formula (3) or (4).
R ¹ (M ¹ X ₃ ) _n (1)
In formula (1), n is a positive integer, R ¹ is at least one amine polymer selected from the following general formulas (1a) to (1c), and M ¹ is a divalent metal ion. , X is F, Cl, Br, I or a combination thereof.
(1a)
(1b)

(1c)
In the formulas (1a) to (1c), n is a positive integer, x is 0 or an integer of 1 to 4 (preferably 0 or 1), and each R is independently H or An alkyl group having 1 or more carbon atoms, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or an aromatic heterocyclic group;
CsM ² X ₃ (2)
In formula (2), M ² is a divalent metal ion, and X is F, Cl, Br, or I.
CH ₃ NH ₃ SnX ₃ (3)
In formula (3), X is F, Cl, Br, I.
(R ² NH ₃ ) ₂ SnX ₄ (4)
In the formula (4), R ² is an alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group or aromatic heterocyclic group having 2 or more carbon atoms, and X is F, Cl, Br, or I. .   The film or adsorbent comprising the organic / inorganic hybrid perovskite compound A constituting the first semiconductor layer is formed using a solution containing a precursor capable of constituting the organic / inorganic hybrid perovskite compound A. The solid junction photoelectric conversion element according to claim 1.   The second semiconductor layer is formed by impregnating the first semiconductor layer with a solution containing a precursor that can constitute the inorganic perovskite compound B and / or the organic-inorganic hybrid perovskite compound C. The solid junction photoelectric conversion element according to claim 1 or 2.   4. The solid junction type according to claim 1, wherein the organic-inorganic hybrid perovskite compounds A and C are organic-inorganic hybrid perovskite compounds represented by general formulas (1) and (3), respectively. Photoelectric conversion element.   5. The solid junction photoelectric device according to claim 1, wherein a buffer layer is formed between the electrode substrate and the first semiconductor layer and / or between the electrode substrate and the second semiconductor layer. Conversion element.