JP7092969B2 - Photoelectric conversion element - Google Patents

Description

The present invention relates to a photoelectric conversion element.

In recent years, the driving power in electronic circuits has become extremely small, and it has become possible to drive various electronic components such as sensors even with a weak power (μW order). In addition, when using sensors, it is expected to be applied to energy harvesting elements as an independent power source that can generate and consume power on the spot. Among these, the solar cell, which is a kind of photoelectric conversion element, is attracting attention as an element that can generate electricity anywhere as long as there is light, even if it is weak light.

Typical examples of weak light include LED (light emitting diode) lights and fluorescent lamps. These are called indoor lights because they are mainly used indoors. The illuminance of these lights is about 20 to 1,000 lux, which is very weak compared to the direct light of the sun (about 100,000 lux). In energy harvesting elements, there is a particular demand for elements that can efficiently generate electricity with indoor light such as fluorescent lamps and LED lamps.

The photoelectric conversion element is generally composed of a transparent electrode, an electron transport layer, a hole transport layer, and a counter electrode. As the material of the transparent electrode, indium tin oxide (hereinafter referred to as "ITO"), which is a material having both high transmittance and low resistance value, is used.
However, in the case of a dye-sensitized solar cell, in forming a porous layer of an electron-transporting semiconductor used as an electron-transporting layer of the photoelectric conversion element, for example, it is necessary to bake in air at 500 ° C. for 30 minutes. When ITO is used as the first transparent electrode, its resistance value is greatly increased, which deteriorates the power generation characteristics of the solar cell. As a method for avoiding this, a method of capping the surface of the ITO electrode with fluorine-doped tin oxide (hereinafter referred to as "FTO") or antimony-doped tin oxide (hereinafter referred to as "ATO") having excellent heat resistance to ITO is available. (See, for example, Patent Document 1 and Non-Patent Document 1).

Further, in the dye-sensitized solar cell, the hole blocking layer provided between the transparent electrode and the electron transport layer can be used not only as the original function of reducing electron transfer but also as a cap layer on the ITO surface. While ensuring high permeability, it is possible to suppress an increase in the resistance value of the ITO electrode in the firing temperature environment in the formation of the porous layer of the electron transfer layer (see, for example, Patent Document 2).

An object of the present invention is to provide a photoelectric conversion element capable of taking out an output having low electrical resistance without deteriorating the photoelectric conversion characteristics.

The photoelectric conversion element of the present invention as a means for solving the above-mentioned problems has a first substrate and
With the first transparent electrode arranged on the first substrate,
The hole blocking layer arranged on the first transparent electrode and
The electron transport layer arranged on the hole blocking layer and
A hole transport layer arranged on the electron transport layer and made of a hole transport material,
With a second electrode disposed on the hole transport layer,
A plurality of first micropores penetrating the hole blocking layer are formed in the first end region of the hole blocking layer where the electron transport layer, the hole transport layer and the second electrode are not arranged. The output take-out terminal portion for taking out electric power from the first transparent electrode to the outside through the plurality of first micropores.
A plurality of second micropores penetrating the hole blocking layer are formed in the second end region of the hole blocking layer where the electron transport layer and the hole transport layer are not arranged , and the plurality of second micropores are formed . Through the micropores of 2, the transparent electrode of a photoelectric conversion element adjacent to the first transparent electrode having a transparent electrode divided from the first transparent electrode, and a series cell connecting portion for connecting the second electrode are provided. death,
The opening area ratio per unit area of the first micropores when the area of a quadrangle formed by connecting the centers of any four micropores among the plurality of first micropores is taken as the unit area. And, when the area of the quadrangle formed by connecting the centers of any four micropores among the plurality of second micropores is taken as the unit area, the opening per unit area of the second micropores. The area ratio is 16.4% or more and 75.0% or less, respectively .

According to the present invention, it is possible to provide a photoelectric conversion element capable of taking out an output having low electrical resistance without deteriorating the photoelectric conversion characteristics.

FIG. 1 is a schematic view showing an example of a photoelectric conversion element of the present invention. FIG. 2 is a schematic view showing another example of the photoelectric conversion element of the present invention. FIG. 3 is a conceptual diagram of the pitch and diameter of the circular micropores machined in the output take-out terminal portion. FIG. 4 is a conceptual diagram of the pitch and width of the line-shaped fine holes machined in the output take-out terminal portion. FIG. 5 is a conceptual diagram of resistance value measurement of the output take-out terminal portion by the two-terminal method. FIG. 6 is a correlation diagram between the opening area ratio of the micropores of Production Examples 1 to 17 and the resistance value thereof.

(Photoelectric conversion element)
The photoelectric conversion element of the present invention has a first substrate and
With the first transparent electrode arranged on the first substrate,
The hole blocking layer arranged on the first transparent electrode and
An electron transport layer arranged on the hole blocking layer and made of an electron transport semiconductor having a photosensitizer adsorbed on the surface thereof.
A hole transport layer connected to the electron transport layer and made of a hole transport material,
With a second electrode disposed on the hole transport layer,
The plurality of micropores penetrating the hole blocking layer form an output take-out terminal portion for extracting electric power to the outside and a series cell connection portion connecting the second electrode and the first transparent electrode. It also has other members as needed.

In the conventional solar cell, the photoelectric conversion element of the present invention also caps the output take-out terminal portion with a hole blocking layer having a high resistance value. After the immersion, it is necessary to peel off the hole blocking layer of the output take-out terminal portion and the series cell connection portion to expose the ITO electrode. However, when the hole block layer is selectively etched only at the output take-out terminal using a photoresist or the like, the resist is applied to the porous layer of the electron-transporting semiconductor that has been fired and immersed in an acidic liquid, or the laminated photoelectric conversion element. This is based on the finding that not only the resist peeling and cleaning processes are complicated, but also the element characteristics are deteriorated and the yield is likely to be lowered.

In the present specification, the photoelectric conversion element represents an element that converts light energy into electric energy or an element that converts electric energy into light energy, and specific examples thereof include a solar cell and a photodiode.

In the photoelectric conversion element of the present invention, the output take-out terminal portion and the series cell connection portion are finely peeled off by simple laser processing or the like in the hole blocking layer having the function of suppressing the increase in resistance value of ITO, which is the first transparent electrode material. By exposing the first transparent electrode, the output take-out terminal portion and the series cell connection portion can be formed without deteriorating the photoelectric conversion characteristics.

<First board>
The first substrate is not particularly limited, and known ones can be used.
The first substrate is preferably made of a transparent material, and examples thereof include glass, a transparent plastic plate, a transparent plastic film, and an inorganic transparent crystal.

<First transparent electrode>
The first transparent electrode is not particularly limited as long as it is a conductive substance transparent to visible light, and ordinary photoelectric conversion elements, known ones used for liquid crystal panels and the like can be used. For example, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), indium-zinc oxide, niobium-titanium oxide, graphene and the like can be mentioned. These may be used alone or in combination of two or more. Among these, ITO is preferable from the viewpoint of achieving both high transmittance and low electrical resistance value.
The average thickness of the first transparent electrode is preferably 10 nm or more and 1,000 μm or less from the viewpoint of high transmittance and low efficiency.
In order to maintain a certain degree of hardness, the first transparent electrode is preferably provided on the first substrate made of a material transparent to visible light. A known one in which the first transparent electrode and the first substrate are integrated can also be used, and examples thereof include ITO-coated glass and ITO-coated transparent plastic film.
Further, for the purpose of lowering the electric resistance, a metal lead wire or the like may be used in combination. Examples of the material of the metal lead wire include metals such as aluminum, copper, silver, gold, platinum, and nickel. The metal lead wire can be formed by installing the metal lead wire on a substrate by thin film deposition, sputtering, crimping or the like, and providing ITO on the metal lead wire.

<Hole blocking layer>
The hole blocking layer is provided in order to suppress a decrease in electric power due to the electrolyte coming into contact with the electrode and the holes in the electrolyte and the electrons on the surface of the electrode being recombined (so-called reverse electron transfer). The effect of the hole blocking layer is particularly remarkable in the solid-state dye-sensitized solar cell. This is compared with the wet dye-sensitized solar cell using an electrolytic solution, and the solid dye-sensitized solar cell using an organic hole transport material or the like recombines electrons in the hole in the hole transport material and the electrode surface. (Reverse electron transfer) This is due to the high speed.
The material of the hole blocking layer is not particularly limited as long as it is transparent to visible light and is an electron transporting material, and can be appropriately selected depending on the intended purpose. For example, titanium oxide, niobium oxide, and the like. Examples thereof include magnesium oxide, aluminum oxide, zinc oxide, tungsten oxide and tin oxide. These may be used alone or in combination of two or more.

The method for forming the whole blocking layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, high internal resistance is required to suppress the loss current in the room light, and the film is formed. The method is also important. Generally, a sol-gel method in which a wet film is formed can be mentioned, but the film density is low and the loss current cannot be sufficiently suppressed. Therefore, more preferably, it is a dry-type film forming method such as a sputtering method, and the film density is sufficiently high and the loss current can be suppressed.
The average thickness of the hole blocking layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of transmittance and suppression of back electron transfer, 5 nm or more and 1,000 nm or less are preferable, and in wet film formation. It is more preferably 500 nm or more and 700 nm or less, and more preferably 10 nm or more and 30 nm or less in the dry film forming.

<Electron transport layer>
The electron transport layer is arranged on the hole blocking layer and is made of an electron transport semiconductor having a photosensitizing compound adsorbed on the surface, and the electron transport layer may be a single layer or a multilayer.
As the electron-transporting semiconductor, electron-transporting semiconductor fine particles are preferably used.
In the case of multiple layers, dispersions of semiconductor fine particles having different particle sizes can be applied in multiple layers, or different types of semiconductors, resins, and coating layers having different compositions of additives can be applied in multiple layers.
When the film thickness is insufficient by one coating, the multilayer coating is an effective means.
Generally, as the average thickness of the electron transport layer increases, the amount of the supported photosensitizer material per unit projected area also increases, so that the light capture rate increases, but the diffusion distance of the injected electrons also increases, so the charge increases. The loss due to the recombination of is also large. Therefore, the average thickness of the electron transport layer is preferably 100 nm or more and 100 μm or less.

The semiconductor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include elemental semiconductors such as silicon and germanium; compound semiconductors typified by metallic chalcogenide, and compounds having a perovskite structure. .. These may be used alone or in combination of two or more.

Examples of the chalcogenide of the metal include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, ittrium, lanthanum, vanadium, niobium, and oxides of tantalum; cadmium, zinc, lead, silver, and the like. Antimony, sulfides of bismuth; cadmium, lead selenium, cadmium tellurides, etc.
Examples of other compound semiconductors include phosphates such as zinc, gallium, indium and cadmium; gallium arsenic, copper-indium-selenium, copper-indium-sulfide and the like.

Examples of the compound having a perovskite structure include strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like.

Among the above semiconductors, oxide semiconductors are preferable, and titanium oxide, zinc oxide, tin oxide, and niobium oxide are more preferable.
The crystal type of the semiconductor is not particularly limited and may be appropriately selected depending on the intended purpose, but may be single crystal, polycrystal, or amorphous.

The size of the semiconductor fine particles is not particularly limited and may be appropriately selected depending on the intended purpose, but the average particle size of the primary particles is preferably 1 nm or more and 100 nm or less, and more preferably 5 nm or more and 50 nm or less.
It is also possible to improve efficiency by the effect of mixing or laminating semiconductor fine particles having a larger average particle size to scatter incident light. In this case, the average particle size of the semiconductor particles is preferably 50 nm or more and 500 nm or less.

The method for producing the electron transport layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of forming a thin film in a vacuum such as sputtering and a wet film forming method. Among these, the wet film forming method is preferable in consideration of the manufacturing cost and the like, and the method of preparing a paste in which semiconductor fine particles or sol are dispersed and applying the paste on the electron collecting electrode substrate is particularly preferable.
When the wet film forming method is used, the coating method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a dip method, a spray method, a wire bar method, a spin coating method, or a roller coating method can be selected. , Blade coat method, gravure coat method and the like. Further, examples of the wet printing method include letterpress, offset, gravure, intaglio, rubber plate, screen printing and the like.

When the dispersion liquid of the semiconductor fine particles is mechanically pulverized or produced by using a mill, it is formed by dispersing at least the semiconductor fine particles alone or a mixture of the semiconductor fine particles and a resin in water or an organic solvent.

The resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polymer or copolymer of a vinyl compound made of styrene, vinyl acetate, acrylic acid ester, methacrylic acid ester or the like, a silicone resin, etc. Examples thereof include phenoxy resin, polysulfone resin, polyvinyl butyral resin, polyvinylformal resin, polyester resin, cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyallylate resin, polyamide resin, and polyimide resin. .. These may be used alone or in combination of two or more.

The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alcohol-based solvents such as water, methanol, ethanol, isopropyl alcohol and α-terpineol; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketone solvent; ester solvent such as ethyl formate, ethyl acetate, n-butyl acetate; ether solvent such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolan, dioxane; N, N-dimethylformamide, N, N-dimethylacetamide , N-Methyl-2-pyrrolidone and other amide solvents; dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene. Halogenated hydrocarbon solvents such as n-pentane, n-hexane, n-octane, 1,5-hexadien, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene. , Ethylbenzene, hydrocarbon solvents such as cumene and the like. These may be used alone or in combination of two or more.

The dispersion liquid of the semiconductor fine particles or the paste of the semiconductor fine particles obtained by the solgel method or the like is an acid such as hydrochloric acid, nitric acid, acetic acid or the like; polyoxyethylene (10) octylphenyl ether or the like in order to prevent reaggregation of the semiconductor fine particles. A surfactant, a chelating agent such as acetylacetone, 2-aminoethanol, or ethylenediamine can be added.
It is also an effective means to add a thickener for the purpose of improving the film-forming property.
The thickener is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polymers such as polyethylene glycol and polyvinyl alcohol; ethyl cellulose and the like.

After the semiconductor fine particles are applied, the particles are preferably electronically contacted with each other, and firing, microwave irradiation, electron beam irradiation, and laser light irradiation are preferably performed in order to improve the film strength and the adhesion to the substrate. .. These treatments may be used alone or in combination of two or more.
In the case of firing, the firing temperature is not particularly limited and can be appropriately selected depending on the purpose. However, if the temperature is raised too high, the resistance of the substrate may increase or the substrate may melt. ° C. or higher and 700 ° C. or lower are preferable, and 100 ° C. or higher and 600 ° C. or lower are more preferable. The firing time is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 minutes or more and 10 hours or less.

The microwave irradiation may be performed from the electron transport layer forming side or from the back side. The irradiation time of the microwave is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably performed within 1 hour.

After firing, for the purpose of increasing the surface area of the semiconductor fine particles and increasing the efficiency of electron injection from the photosensitizing compound into the semiconductor fine particles, for example, chemical plating using an aqueous solution of titanium tetrachloride or a mixed solution with an organic solvent or trichloride An electrochemical plating treatment using an aqueous titanium solution may be performed.
A film obtained by laminating semiconductor fine particles having a diameter of several tens of nm by sintering or the like forms a porous state. This nanoporous structure has a very high surface area, which can be expressed using the roughness factor.
The roughness factor is a numerical value representing the actual area inside the porous medium with respect to the area of the semiconductor fine particles coated on the substrate. Therefore, the larger the roughness factor is, the more preferable it is, but it is preferably 20 or more in relation to the film thickness of the electron transport layer.

-Photosensitizer compound-
In the present invention, it is preferable to adsorb the photosensitizer on the surface of the electron transporting semiconductor of the electron transporting layer in order to further improve the conversion efficiency.
The photosensitizing compound is not particularly limited as long as it is a compound photoexcited by the excitation light used, and can be appropriately selected depending on the intended purpose. The metal complex compounds described in JP-A-233238, JP-A-2000-26487, JP-A-2000-323191, JP-A-2001-59062, etc .; JP-A-10-93118, JP-A-2002-164089. Japanese Patent Application Laid-Open No. 2004-95450, J. Mol. Phys. Chem. C, 7224, Vol. The coumarin compound described in 111 (2007) and the like; JP-A-2004-95450, Chem. Commun. , 4887 (2007) and the like; JP-A-2003-264010, JP-A-2004-63274, JP-A-2004-115636, JP-A-2004-200068, JP-A-2004-23552. , J. Am. Chem. Soc. , 12218, Vol. 126 (2004), Chem. Commun. , 3036 (2003), Angew. Chem. Int. Ed. , 1923, Vol. 47 (2008) and the like; Am. Chem. Soc. , 16701, Vol. 128 (2006), J. Mol. Am. Chem. Soc. , 14256, Vol. The thiophene compound described in 128 (2006) and the like; JP-A-11-86916, JP-A-11-214730, JP-A-2000-106224, JP-A-2001-76773, JP-A-2003-7359. Cyanine dyes described in JP-A-11-214731, JP-A-11-238905, JP-A-2001-52766, JP-A-2001-7675, JP-A-2003-7360, etc. 9-arylxanthene compounds described in JP-A-10-92477, JP-A-11-273754, JP-A-11-273755, JP-A-2003-31273, etc .; JP-A-10-93118, special publications. The triarylmethane compound described in Kai 2003-31273 and the like; JP-A-9-199744, JP-A-10-233238, JP-A-11-204821, JP-A-11-265738, J. Mol. Phys. Chem. , 2342, Vol. 91 (1987), J. Mol. Phys. Chem. B, 6272, Vol. 97 (1993), Electrical. Chem. , 31, Vol. 537 (2002), JP-A-2006-032260, J. Mol. Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed. , 373, Vol. 46 (2007), Langmuir, 5436, Vol. Examples thereof include the phthalocyanine compound and the porphyrin compound described in 24 (2008) and the like. Among these, metal complex compounds, coumarin compounds, polyene compounds, indolin compounds, and thiophene compounds are preferable, and they are represented by D131 represented by the following structural formula (1) and the following structural formula (2) manufactured by Mitsubishi Paper Co., Ltd. D102 and D358 represented by the following structural formula (3) are more preferable.

[D131]

[D102]

[D358]

Examples of the method for adsorbing the photosensitizing compound on the electron transporting semiconductor include a method of immersing an electron collecting electrode containing electron transporting semiconductor fine particles in a photosensitizing compound solution or a dispersion liquid, and photosensitization. Examples thereof include a method of applying a sensitive compound solution or a dispersion liquid to an electron transporting semiconductor and adsorbing the solution.
Examples of the method of immersing the electron collecting electrode containing the electron-transporting semiconductor fine particles in the photosensitizing compound solution or the dispersion liquid include a dipping method, a dip method, a roller method, and an air knife method.
Examples of the method of applying the photosensitizing compound solution or the dispersion liquid to the electron transporting semiconductor and adsorbing it include a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method. ..
Further, it may be adsorbed in a supercritical fluid using carbon dioxide or the like.

When adsorbing the photosensitizer, a condensing agent may be used in combination.
The condensing agent has a catalytic action such as physically or chemically binding a photosensitizing compound to the surface of an electron transporting semiconductor, and a stoichiometrically acting agent that advantageously shifts a chemical equilibrium. It may be either.
Further, a thiol or a hydroxy compound may be added as a condensation aid.

Examples of the solvent for dissolving or dispersing the photosensitizing compound include alcohol solvents such as water, methanol, ethanol and isopropyl alcohol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl formate, ethyl acetate and acetic acid. Ester solvent such as n-butyl; ether solvent such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolan, dioxane; amide such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone System solvent; Halogenated hydrocarbon solvent such as dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene; n- Hydrocarbon solvents such as pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, cumene, etc. Can be mentioned. These may be used alone or in combination of two or more.

Depending on the type of the photosensitizing compound, there is a compound that works more effectively if the aggregation between the compounds is suppressed. Therefore, an aggregation dissociating agent may be used in combination.
The coagulation dissociator is not particularly limited and may be appropriately selected depending on the dye to be used. Examples thereof include steroid compounds such as cholic acid and chenodeoxycholic acid; long-chain alkylcarboxylic acids and long-chain alkylphosphonic acids. Be done.
The amount of the coagulation dissociator added is preferably 0.01 parts by mass or more and 500 parts by mass or less, and more preferably 0.1 parts by mass or more and 100 parts by mass or less with respect to 1 part by mass of the photosensitizer.
Using these, the temperature at which the photosensitizer compound or the photosensitizer compound and the coagulation dissociator are adsorbed is preferably −50 ° C. or higher and 200 ° C. or lower.
The adsorption may be carried out by allowing it to stand still or stirring it.
The stirring method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a stirrer, a ball mill, a paint conditioner, a sand mill, an attritor, a disperser, and ultrasonic dispersion.
The time required for the adsorption is preferably 5 seconds or more and 1,000 hours or less, more preferably 10 seconds or more and 500 hours or less, and further preferably 1 minute or more and 150 hours or less.
The adsorption is preferably performed in a dark place.

<Hall transport layer>
The hole transport layer includes an electrolytic solution in which a redox pair is dissolved in an organic solvent, a gel electrolyte in which a liquid in which a redox pair is dissolved in an organic solvent is impregnated in a polymer matrix, a molten salt containing a redox pair, and a solid electrolyte. Examples include inorganic hole transport materials and organic hole transport materials. Among these, organic hole transport materials are preferable. In the following, there is a section where the organic hole transport material is described as an example, but the present invention is not limited to this.

The hole transport layer may be a single layer structure made of a single material or a laminated structure made of a plurality of compounds. In the case of the laminated structure, it is preferable to use a polymer material for the hole transport layer near the second electrode. By using a polymer material having excellent film-forming properties, the surface of the porous electron transport layer can be further smoothed, and the photoelectric conversion characteristics can be improved.
In addition, since the polymer material does not easily penetrate into the porous electron transport layer, it is excellent in covering the surface of the porous electron transport layer and is effective in preventing short circuits when providing electrodes. It is possible to obtain high performance.

Examples of the organic hole transport material used in the single-layer structure used in the single material include the oxadiazole compound shown in Japanese Patent Publication No. 34-5466; the oxadiazole compound shown in Japanese Patent Publication No. 45-555. Triphenylmethane compound, pyrazoline compound shown in Japanese Patent Publication No. 52-4188, etc .; hydrazone compound shown in Japanese Patent Publication No. 55-42380, etc .; JP-A-56-123544, etc. The oxadiazole compound shown; the tetraarylbenzidine compound shown in JP-A-54-58445; the stilbene shown in JP-A-58-65440 or JP-A-60-98437. Examples include compounds.
Among these, Adv. Mater. , 833, vol. 17, (2005) Hall transport material (2,2', 7,7'-ttrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene: may be referred to as "spiro-OMeTAD". There is) is particularly preferable.

In addition to having high hole mobility, the "spiro-OMeTAD" has two benzidine skeletal molecules twisted and bound to each other. Therefore, it forms an electron cloud that is close to a sphere, and exhibits excellent photoelectric conversion characteristics due to its good hopping conductivity between molecules. In addition, since it is highly soluble and dissolves in various organic solvents and is amorphous (amorphous substance without a crystal structure), it is easy to be densely filled in the porous electron transport layer, and it is a solid dye-sensitized solar cell. Has useful properties for. Further, since it does not have a light absorption characteristic of 450 nm or more, the photosensitizing compound can efficiently absorb light, and has a characteristic useful for a solid dye-sensitized solar cell.
The average thickness of the hole transport layer made of the "spiro-OMeTAD" is not particularly limited and may be appropriately selected depending on the intended purpose, but has a structure that penetrates into the pores of the porous electron transport layer. It is preferable, 0.01 μm or more is more preferable on the electron transport layer, and 0.1 μm or more and 10 μm or less is further preferable.

Examples of the polymer material used for the hole transport layer near the second electrode used in the laminated structure include poly (3-n-hexylthiophene), poly (3-n-octyloxythiophene), and poly (9). , 9'-dioctyl-fluoren-co-bithiophene), poly (3,3'''-zidodecyl-quarter thiophene), poly (3,6-dioctyltieno [3,2-b] thiophene), poly (2, 5-Bis (3-decylthiophene-2-yl) thieno [3,2-b] thiophene), poly (3,4-didecylthiophene-co-thiophene [3,2-b] thiophene), poly (3) , 6-Dioctyltiero [3,2-b] thiophene-co-thiophene [3,2-b] thiophene), Poly (3,6-dioctylthioeno [3,2-b] thiophene-co-thiophene), Poly Polythiophene compounds such as (3.6-dioctyltierno [3,2-b] thiophene-co-bithiophene); poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenebinylene], poly [ 2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylenebinylene], poly [(2-methoxy-5- (2-ethylphenyloxy) -1,4-phenylenebinylene) -co -(4,4'-biphenylene-vinylene)] and other polyphenylene vinylene compounds; poly (9,9'-zidodecylfluorenyl-2,7-diyl), poly [(9,9-dioctyl-2,7) -Dibinylene fluorene) -alt-co- (9,10-anthracene)], poly [(9,9-dioctyl-2,7-divinylene fluorene) -alt-co- (4,4'-biphenylene)] , Poly [(9,9-dioctyl-2,7-divinylenefluorene) -alt-co- (2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene)], poly [(9, 9-Dioctyl-2,7-diyl) -co- (1,4- (2,5-dihexyloxy) benzene)] and other polyfluorene compounds; poly [2,5-dioctyloxy-1,4-phenylene] , Poly-phenylene compounds such as poly [2,5-di (2-ethylhexyloxy-1,4-phenylene]; poly [(9,9-dioctylfluorenyl-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-phenylenebinylene-2,5-dioctyloxy-1,4-phenylenebinylene-1,4-phenylene], poly [p-triluimino-1,4-phenylene] Poly of vinylene-2,5-di (2-ethylhexyloxy) -1,4-phenylene vinylene-1,4-phenylene], poly [4- (2-ethylhexyloxy) phenylimino-1,4-biphenylene], etc. Arylamine compounds; poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (1,4-benzo (2,1', 3) thiadiazole], poly (3,4-). Examples thereof include polythiazol compounds such as didecylthiophene-co- (1,4-benzo (2,1', 3) thiaxazole). These may be used alone or in combination of two or more.
Among these, polythiophene compounds and polyarylamine compounds are particularly preferable from the viewpoint of carrier mobility and ionization potential.

Additives may be added to the organic hole transport material.
The additive is not particularly limited and may be appropriately selected depending on the intended purpose. For example, iodine, lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, copper iodide, etc. Metal iodides such as iron iodide and silver iodide; quaternary ammonium salts such as tetraalkylammonium iodide and pyridinium iodide; lithium bromide, sodium bromide, potassium bromide, cesium bromide, calcium bromide and the like Metal bromide; bromine salt of quaternary ammonium compound such as tetraalkylammonium bromide, pyridinium bromide; metal chloride such as copper chloride and silver chloride; metal acetate such as copper acetate, silver acetate and palladium acetate; copper sulfate, Metal sulfates such as zinc sulfate; metal complexes such as ferrocyanate-ferricate and ferrocene-ferricinium ions; sulfur compounds such as polysodium sulfide and alkylthiol-alkyldisulfides; viologen dyes, hydroquinones and the like, iodide 1,2-dimethyl-3-n-propylimidazolium salt, 1-methyl-3-n-hexylmidazolinium iodide, 1,2-dimethyl-3-ethylimidazolium trifluoromethanesulfonate, 1-Methyl-3-butylimidazolium nonafluorobutylsulfonate, 1-methyl-3-ethylimidazolium bis (trifluoromethyl) sulfonylimide and the like. Chem. 35 (1996) 1168. Ionic liquids; basic compounds such as pyridine, 4-t-butylpyridine, benzimidazole; lithium compounds such as lithium trifluoromethanesulfonylimide, lithium diisopropylimide and the like. These may be used alone or in combination of two or more.
Among these, an ionic liquid is preferable, and it is more preferable that the ionic liquid is an imidazolium compound.

Further, for the purpose of improving the conductivity, an oxidizing agent for converting a part of the organic hole transport material into a radical cation may be added.
Examples of the oxidizing agent include tris (4-bromophenyl) aminium hexachloroantimonate, silver hexafluoroantimonate, nitrosonium tetrafluoroborate, silver nitrate, and cobalt complex compounds.
It is not necessary that all the organic hole transport materials are oxidized by the addition of the oxidizing agent, and only a part thereof needs to be oxidized. Further, the added oxidizing agent may or may not be taken out of the system after being added.

The hole transport layer can be formed directly on the electron transport layer containing the photosensitizing compound.
The method for producing the hole transport layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of forming a thin film in vacuum such as vacuum deposition and a wet film forming method. Among these, the wet film forming method is preferable, and the method of coating on the electron transport layer is preferable in consideration of the manufacturing cost and the like.
When the wet film forming method is used, the coating method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a dip method, a spray method, a wire bar method, a spin coating method, a roller coating method, etc. Examples include the blade coating method and the gravure coating method. Further, examples of the wet printing method include letterpress, offset, gravure, intaglio, rubber plate, screen printing and the like. Further, the film may be formed in a supercritical fluid or a subcritical fluid having a temperature and pressure lower than the critical point.

The supercritical fluid exists as a non-aggregating high-density fluid in a temperature / pressure region exceeding the limit (critical point) at which a gas and a liquid can coexist, does not aggregate even when compressed, and has a critical temperature or higher and a critical pressure. The fluid is not particularly limited as long as it is in the above state, and can be appropriately selected depending on the intended purpose, but a fluid having a low critical temperature is preferable.
The supercritical fluid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an ercol solvent such as carbon monoxide, carbon dioxide, ammonia, nitrogen, water, methanol, ethanol and n-butanol can be selected. Hydrocarbon solvents such as ethane, propane, 2,3-dimethylbutane, benzene and toluene; halogen solvents such as methylene chloride and chlorotrifluoromethane; ether solvents such as dimethyl ether and the like can be mentioned. These may be used alone or in combination of two or more.
Of these, carbon dioxide is preferred. Since the critical pressure of carbon dioxide is 7.3 MPa and the critical temperature is 31 ° C., carbon dioxide is particularly preferable in that it can easily create a supercritical state and is nonflammable and easy to handle.

The subcritical fluid is not particularly limited as long as it exists as a high-pressure liquid in the temperature and pressure regions near the critical point, and can be appropriately selected depending on the intended purpose.
The compound mentioned as the supercritical fluid can also be suitably used as a subcritical fluid.
The critical temperature and critical pressure of the supercritical fluid are not particularly limited and can be appropriately selected depending on the intended purpose. However, the critical temperature is preferably -273 ° C or higher and 300 ° C or lower, and 0 ° C or higher and 200 ° C or lower. Is more preferable.
Further, in addition to the supercritical fluid and the subcritical fluid, an organic solvent or an entrainer can be used in combination. By adding the organic solvent and the entrainer, the solubility in the supercritical fluid can be adjusted more easily.

The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone; an ester such as ethyl formate, ethyl acetate and n-butyl acetate. System solvent; Ether solvent such as diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxolan, dioxane; Amido solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; dichloromethane, chloroform , Bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene and other halogenated hydrocarbon solvents; n-pentane, n-hexane, Examples thereof include hydrocarbon solvents such as n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These may be used alone or in combination of two or more.

In the present invention, the organic hole transporting material may be provided on the electron transporting layer containing the electron transporting material adsorbing the photosensitizing compound, and then pressed. It is believed that the press treatment improves the efficiency because the organic hole transport material is in close contact with the porous electrode (electron transport layer).
The press processing method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a press molding method using a flat plate as represented by an IR tablet shaper, a roll press using a roller or the like. The law etc. can be mentioned.
The pressure is preferably 10 kgf / cm ² or more, and more preferably 30 kgf / cm ² or more. The press processing time is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably performed within 1 hour. Further, heat may be applied during the pressing process.

Further, during the press process, a mold release material may be sandwiched between the press machine and the electrode.
The material used for the mold release material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoride ethylene hexafluoride propylene co-weight. Examples thereof include a coalescence, a perfluoroalkoxyfluororesin, polyvinylidene fluoride, an ethylene tetrafluoride ethylene copolymer, an ethylene chlorotrifluoroethylene copolymer, and a fluororesin such as polyvinyl fluoride. These may be used alone or in combination of two or more.

After performing the press processing step and before providing the second electrode, a metal oxide may be provided between the organic hole transport material and the second electrode. Examples of the metal oxide include molybdenum oxide, tungsten oxide, vanadium oxide, nickel oxide and the like. Among these, molybdenum oxide is preferable.
As a method of providing the metal oxide on the hole transport layer. There is no particular limitation, and it can be appropriately selected depending on the intended purpose. Examples thereof include a method of forming a thin film in vacuum such as sputtering and vacuum deposition, and a wet film forming method.
In the wet film forming method, a method in which a paste in which a metal oxide powder or a sol is dispersed is prepared and applied onto the hole transport layer is preferable.
When the wet film forming method is used, the coating method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a dip method, a spray method, a wire bar method, a spin coating method, or a roller coating method can be selected. , Blade coat method, gravure coat method and the like. Further, examples of the wet printing method include letterpress, offset, gravure, intaglio, rubber plate, screen printing and the like.
The average thickness of the hole transport layer is preferably 0.1 nm or more and 50 nm or less, and more preferably 1 nm or more and 10 nm or less.

<Second electrode>
The second electrode can be formed on the hole transport layer or on the metal oxide in the hole transport layer.
As the second electrode, the same one as the first transparent electrode can be usually used, and a support is not always necessary in a configuration in which the strength and the sealing property are sufficiently maintained.
Examples of the material of the second electrode include metals such as platinum, gold, silver, copper and aluminum; carbon-based compounds such as graphite, fullerene, carbon nanotubes and graphene; and oxidation of conductive metals such as ITO, FTO and ATO. Substances; Conductive polymers such as polythiophene and polyaniline can be mentioned.
The film thickness of the second electrode is not particularly limited, and may be used alone or in a mixture of two or more.
The coating of the second electrode can be appropriately formed on the hole transport layer by a method such as coating, laminating, vapor deposition, CVD, or bonding, depending on the type of material used and the type of hole transport layer.

In the present invention, the first transparent electrode side is transparent, and the incident light is incident from the first transparent electrode side. In this case, it is preferable to use a material that reflects light on the second electrode side, and a metal, glass, plastic, or a metal thin film deposited with a conductive oxide is preferably used. It is also an effective means to provide an antireflection layer on the incident light side.

<Output take-out terminal>
The output take-out terminal portion is formed in the hole blocking layer by a plurality of micropores extending to the first transparent electrode. The output take-out terminal portion may penetrate the first transparent electrode and reach the first transparent substrate.
Examples of the method for forming the output take-out terminal portion include a sandblasting method, a waterblasting method, abrasive paper, a chemical etching method, and a laser processing method. Among these, the laser processing method is preferable. One of the reasons for this is that fine holes can be formed without using sand, etchants, resists, etc., and processing can be performed more cleanly and with good reproducibility.

-Micropores-
The opening shape of the micropores is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a line shape, a tapered shape, and a circular shape. Of these, a circular shape is preferable. The circle in this case is a curve formed by a set of points having the same distance from the center point, but it does not necessarily have to be a perfect circle, and includes an elliptical shape that looks like a crushed perfect circle.
The minimum opening length of the micropores is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm or more and 400 μm or less, and more preferably 5 μm or more and 85 μm or less.
The minimum distance (pitch) between the adjacent micropores is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm or more and 500 μm or less, and more preferably 20 μm or more and 100 μm or less.

When the output take-out terminal portion is made into a plurality of micropores that penetrate the first transparent electrode and reach the first substrate, the total opening area of the plurality of micropores is the total area of the output take-out terminal portion. If it becomes too large, the film cross-sectional area of the first transparent electrode decreases, which increases the resistance value and causes a decrease in photoelectric conversion efficiency. Therefore, the ratio of the total opening area of the plurality of micropores to the area of the output take-out terminal portion is preferably 5% or more and 60% or less, and more preferably 15% or more and 25% or less.

The process of forming the output take-out terminal portion may be any of steps before, during, and after the element (up to the second electrode) is constructed, but in the present invention, it is preferable after the element is constructed. This is because if the output take-out terminal is formed before or during the element construction, the substrate will be contaminated with dust generated when the output take-out terminal is formed, and the board will be built on the dust. This is because the connection with the electrode or the like is hindered due to the influence of the above, and the photoelectric conversion efficiency is lowered.
In the present invention, when the output take-out terminal portion is formed by the laser processing method, at least one of the hole blocking layer, the electron transport layer, the hole transport layer, and the second electrode, and in some cases, all of them are laser processed. It can be removed by impact peeling. This is the second reason why the laser processing method is preferable in the present invention. As a result, it is not necessary to provide a mask at the time of laminating, and removal and formation of a fine output take-out terminal portion can be easily performed at the same time.

<Series cell connection>
The series cell connecting portion is a portion connecting the second electrode and the first transparent electrode.
The structure of the series cell connection portion is a structure in which a plurality of divided first transparent electrodes and second electrodes are alternately connected.
The series cell connection portion is formed by a plurality of micropores extending to the first transparent electrode in the hole blocking layer. The series cell connection portion may penetrate the first transparent electrode and reach the first substrate.
The method for forming the micropores is the same as that for the output terminal extraction unit.

In the present invention, it is preferable that the total resistance value of the output take-out terminal portion and the series cell connection portion is smaller than the series resistance Rs of the photoelectric conversion element.
The series resistance Rs of the photoelectric conversion element is preferably 1 kΩ or more and 100 kΩ or less.
The Rs are the series resistance of the photoelectric conversion element, and are calculated from the inclination between a plurality of points near the measurement point Voc where the current turns from positive to negative, but the calculation method is not particularly limited and is general. It can be calculated by the solar cell evaluation system.
The ratio of the total area of the micropores in the output take-out terminal portion and the series cell connection portion to the area of the output take-out terminal portion and the series cell connection portion is 16.4% or more and less than 82.4%. It is preferable to have.

Here, the configuration of the photoelectric conversion element of the present invention will be described with reference to FIGS. 1 and 2. 1 and 2 are schematic cross-sectional views showing an example of a photoelectric conversion element. In FIG. 1, a plurality of micropores penetrating the hole blocking layer 3 are formed in the output extraction terminal portions 8 and 9, and FIG. Then, the micropores reach the first substrate 1.
In the embodiment shown in FIGS. 1 and 2, a first substrate 1, a first transparent electrode 2 arranged on the first substrate 1, and a hole arranged on the first transparent electrode 2 are provided. The hole transporting material is connected to the blocking layer 3, the electron transporting layer 4 made of an electron transporting semiconductor arranged on the hole blocking layer 3 and having the photosensitizing compound 5 adsorbed on the surface, and the electron transporting layer 4. An example of the configuration of a photoelectric conversion element having a hole transport layer 6 composed of a hole transport layer 6 and a second electrode 7 arranged on the hole transport layer 6 is shown. Further, the first transparent electrode 2 and the second electrode 7 are conducting to the lead lines 11 and 12 via the output take-out terminal portions 8 and 9, respectively. Alternatively, when forming a series cell, the second electrode 7 is connected to the first transparent electrode of the adjacent photoelectric conversion element, and the series cell connecting portion 10 is formed.
The series cell connection portion 10 is formed by a plurality of micropores extending to the first transparent electrode 2 in the hole blocking layer 3. The series cell connecting portion 10 may penetrate the first transparent electrode 2 and reach the first substrate 1.

<Use>
The photoelectric conversion element of the present invention can be applied to a power supply device by combining with a circuit board or the like that controls the generated current. Examples of devices using such a power supply device include an electronic desk calculator and a wristwatch. In addition, a power supply device having a photoelectric conversion element of the present invention can be applied to a mobile phone, an electronic personal organizer, an electronic paper, or the like. Further, a power supply device having a photoelectric conversion element of the present invention can be used as an auxiliary power source for prolonging the continuous use time of a rechargeable or dry cell type electric appliance.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

(Manufacturing Example 1)
A dense hole blocking layer of titanium oxide was formed on an ITO (average film thickness: 300 nm) glass substrate by reactive sputtering with oxygen gas using a target made of metallic titanium to an average thickness of 100 nm.

<Formation of output take-out terminal and series cell connection by circular micropores>
Next, a glass substrate having titanium oxide formed on ITO is mounted on a stage that can be operated in the in-plane direction, and a pulse laser having a laser wavelength of λ = 349 nm is applied with an energy of 8.0 μJ per pulse and a pulse pitch of 110 μm. It was vertically incident on the glass substrate on the stage adjusted so as to be. The laser processing range was 10 mm × 10 mm. As shown in Table 1, the micropores obtained under these conditions had an average diameter of 41.1 μm and an average pitch of 110 μm.
FIG. 3 shows a conceptual diagram of the pitch and the hole diameter of the circular fine holes 20. In FIG. 3, 21 shows the pitch of the circular fine holes 20, and 22 shows the diameter of the circular fine holes 20.

<Opening area ratio>
The opening area ratio of the fine holes was determined by measuring the diameter and the average pitch of the fine holes using an optical microscope and calculating the opening area ratio of the fine holes per unit area of the output extraction terminal portion.

<Evaluation of output take-out terminal and series cell connection>
The resistance values in the obtained output take-out terminal portion and series cell connection portion were measured by the two-terminal method. A digital multimeter KU-2608 (test lead 100-50) manufactured by Kaise Co., Ltd. was used for resistance value measurement, and the test lead was installed so that the distance between the pin tips (2 terminals) was 5 mm. FIG. 5 shows a conceptual diagram of resistance value measurement of the output take-out terminal portion by the two-terminal method. In FIG. 5, 41 is the output extraction terminal (multiple microholes in the hole blocking layer), 42 is the 2-terminal test lead, 43 is the lead line connected to the digital multimeter, and 44 is the distance between the pin tips of the test lead. show. As a result of the measurement, the resistance value showed a resistance value characteristic of 6,294Ω.

(Manufacturing Examples 2 to 5)
In Production Example 1, as shown in Table 1, the output take-out terminal portions of Production Examples 2 to 5 are the same as in Production Example 1 except that the pulse pitch is changed to change the average pitch of adjacent micropores. And a series cell connection part was formed, and the resistance value was measured. The results are shown in Table 1.

(Manufacturing Example 6)
The glass substrate on which titanium oxide was formed on ITO was produced in the same manner as in Production Example 1.
Next, a glass substrate having titanium oxide formed on the ITO film is mounted on a stage that can be operated in the in-plane direction, and a pulsed laser having a laser wavelength λ = 349 nm is applied with an energy of 3.4 μJ per pulse and a line shape. The laser beam was vertically incident on the glass substrate whose scanning speed was adjusted so as to be. The line pitch was 50 μm, and the laser processing range was 10 mm × 10 mm. As shown in Table 1, the line-shaped micropores obtained under these conditions had an average width of 14.4 μm and an average pitch of 50 μm. FIG. 4 shows a conceptual diagram of the pitch and the hole diameter of the line-shaped fine holes 30. In FIG. 4, 31 indicates the pitch of the line-shaped fine holes 30, and 32 indicates the diameter of the line-shaped fine holes 30.

<Evaluation of output take-out terminal and series cell connection>
The resistance value was measured in the same manner as in Production Example 1 for the evaluation of the output take-out terminal portion. As a result, the resistance value characteristic of 81.0Ω was shown.

(Manufacturing Examples 7 to 17)
In Production Example 6, as shown in Table 1, the outputs of Production Examples 7 to 17 are taken out in the same manner as in Production Example 6 except that the energy per pulse is changed to change the average width of the line-shaped micropores. The terminal part was formed and the resistance value was measured. The results are shown in Table 1.
In Production Examples 7 to 17, the contact resistance increased as the opening area ratio decreased. On the other hand, when it becomes large, the electric resistance tends to increase due to the decrease in the membrane cross section of ITO.
Note that FIG. 6 shows a correlation diagram between the opening area ratio of the micropores of Production Examples 1 to 17 and the resistance value thereof.

(Example 1)
<Manufacturing of titanium oxide semiconductor electrode>
A dense hole blocking layer of titanium oxide was formed on an ITO (ITO film thickness: 300 nm) glass substrate by reactive sputtering with oxygen gas using a target made of metallic titanium to an average thickness of 50 nm.
Next, 3 g of titanium oxide (manufactured by Nippon Aerodil Co., Ltd., P90), 0.2 g of acetyl acetone, and 0.3 g of a surfactant (manufactured by Wako Pure Chemical Industries, Ltd., polyoxyethylene octylphenyl ether) were added to 5.5 g of water. And 1.0 g of ethanol and a bead mill treatment for 12 hours.
1.2 g of polyethylene glycol (# 20,000) was added to the obtained dispersion to prepare a paste.
This paste is applied onto the whole blocking layer so that the average thickness is 1.5 μm, dried at room temperature, calcined in air at 500 ° C. for 30 minutes, and then calcined in 100 mM aqueous solution of titanium tetrachloride at 70 ° C. at 60 ° C. It was soaked for a minute and then calcined again in air at 450 ° C. for 60 minutes to form a porous electron transport layer.

<Manufacturing of photoelectric conversion element>
The titanium oxide semiconductor electrode is immersed as a photosensitizing compound in D102 (0.5 mM, acetonitrile / t-butanol (volume ratio 1: 1) solution) manufactured by Mitsubishi Paper Co., Ltd. represented by the structural formula (2). It was allowed to stand in a dark place for 1 hour to adsorb the photosensitizing compound.
An organic hole transport material represented by the following structural formula on a titanium oxide semiconductor electrode carrying a photosensitizing compound (brand: 2,2', 7,7''-tetrakis (N, N-di-p-methoxyphenyllamino) ) -9,9'-pyrobifluorene; spiro-OMeTAD, product number: SHT-263, manufactured by Merck Co., Ltd .; CAS number 207739-72-8) 183.1 mg in 1 ml of chlorobenzene solution, lithium bis (trifluo) manufactured by Kanto Chemical Co., Ltd. A solution obtained by adding 12.83 mg of lomethanesulfonyl) imide and 21.97 mg of 4-pyrrolidinopyridine (PyP) manufactured by Tokyo Kasei Co., Ltd. was spin-coated on a semiconductor electrode carrying a photosensitizing compound to carry a hole transport layer. Was formed (average thickness 300 nm).

Next, in this state, the micropores of Production Example 5 are formed in the output take-out terminal portion and the series cell connection portion, and silver is vacuum-deposited on the output take-out terminal portion by 100 nm to prepare a second electrode for photoelectric conversion. The element was manufactured.
Next, for the obtained photoelectric conversion element, the opening area ratio (total area of micropores in the output take-out terminal portion and the series cell connection portion, the output take-out terminal portion, and the series cell connection) is the same as in Production Example 1. The ratio to the area of the part) was calculated. Further, as follows, the transmittance at 500 nm directly below the power generation layer (the transmittance of light in the hole blocking layer in the region where the micropores are not formed and the wavelength of the first transparent electrode at 500 nm), and the micropore processed portion. The total resistance value (total resistance value of the output take-out terminal part and the series cell connection part) was obtained. The results are shown in Table 2-1.

<Transmittance at 500 nm just below the power generation layer>
The transmittance was measured in the wavelength region from 300 nm to 600 nm using an ultraviolet-visible spectrophotometer V-660DS manufactured by JASCO Corporation, and the transmittance at a wavelength of 500 nm was recorded.

<Total resistance value of fine hole processing part>
The total resistance value of the fine hole machined portion was calculated as follows based on the resistance value obtained in each production example.
In Production Examples 1 to 5, the opening area ratio is 27.1%, the resistance value is 76Ω, and the number of cells in series is 1, so that the micropore forming portion is the output extraction terminal portion (+ pole, -pole). And, with one straight cell connection, there are a total of three locations. Therefore, the series resistance applied to the photoelectric conversion element by the micropore forming portion was calculated to be 76Ω × 3 locations = 228Ω.
Further, in Production Examples 6 to 17, the opening area ratio is 82.4%, the resistance value is 1,567Ω, and the number of cells in series is 6, so that the micropore forming portion is the output extraction terminal portion (+ pole). , -Pole) and 6 straight cell connections, totaling 8 locations. Therefore, the series resistance applied to the photoelectric conversion element by the micropore forming portion was calculated to be 1,567Ω × 8 locations = 12,536Ω.

<Evaluation of photoelectric conversion element>
The photoelectric conversion efficiency of the obtained photoelectric conversion element under white LED irradiation (200 lux, 10,000 lux) was measured. The white LED was measured by a desk lamp CDS-90α (study mode) manufactured by Cosmo Techno Co., Ltd., and the evaluation device was measured by a solar cell evaluation system As-510-PV03 manufactured by NF Circuit Design Block Co., Ltd. The results are shown in Tables 2-1 to 2-3.
The photoelectric conversion characteristic value Rs in Table 2-3 is the series resistance of the photoelectric conversion element, and is calculated from the inclination between a plurality of points near the measurement point Voc where the current turns from positive to negative. It is not limited, and is synonymous with Rs calculated by a general solar cell evaluation system.

(Examples 2 and 3)
In Example 1, a photoelectric conversion element was produced in the same manner as in Example 1 except that the output take-out terminal portion and the series cell connection portion were machined with the fine holes of Production Examples 3 and 12. Evaluated to. The results are shown in Tables 2-1 to 2-3.
At the aperture area ratios of 16.4% and 75.0%, the photoelectric conversion characteristics were the same as those of Example 1 in both the 200 lux environment and the 10,000 lux environment.

(Examples 4 to 7)
In Example 1, the output take-out terminal portion and the series cell connection portion are subjected to the fine hole processing of Production Examples 5, 3, 12, and 15, and the first transparent electrode and the second electrode are separated from each other. In the same manner as in Example 1 except that a photoelectric conversion element (a structure similar to that shown in FIG. 1 of JP-A-2014-143333) in which six cells on the same substrate composed of a plurality of electrodes are connected in series was manufactured. A photoelectric conversion element was manufactured and evaluated in the same manner. The results are shown in Tables 2-1 to 2-3.
In Example 4, it was found that at an opening area ratio of 27.1%, Rs was an order of magnitude larger than that in Example 1, and the inherent Rs of the photoelectric conversion element fluctuated depending on the number of series cells.
In Examples 5 to 7, since the inherent Rs of the photoelectric conversion element increased, the aperture area ratios of 16.4%, 75.0%, and 82.4% were set in a 200 lux environment and a 10,000 lux environment. Both had the same photoelectric conversion characteristics as in Example 4.

(Examples 8 and 9)
In Example 1, a photoelectric conversion element was produced in the same manner as in Example 1 except that the average thickness of the hole blocking layer was changed to 5 nm and 300 nm, and evaluated in the same manner. The results are shown in Tables 2-1 to 2-3.
When the average thickness of the hole blocking layer was 5 nm and 300 nm, good photoelectric conversion characteristics were exhibited.

(Example 10)
In Example 1, a photoelectric conversion element was produced in the same manner as in Example 1 except that the whole blocking layer was changed to niobium oxide, and evaluated in the same manner. The results are shown in Tables 2-1 to 2-3.
Even if the hole blocking layer was a metal oxide semiconductor material different from the porous electron transport layer, it showed good photoelectric conversion characteristics.

(Example 11)
In Example 1, a photoelectric conversion element was produced and evaluated in the same manner as in Example 1 except that ITO was changed to FTO. The results are shown in Tables 2-1 to 2-3.
When ITO was changed to FTO, the transmittance directly under the power generation layer was slightly reduced, and Isc was reduced, so that Pmax was slightly reduced.

(Comparative Examples 1 and 2)
In Example 1, a photoelectric conversion element was produced in the same manner as in Example 1 except that the output take-out terminal portion and the series cell connection portion were machined with the fine holes of Production Examples 15 and 16. evaluated. The results are shown in Tables 2-1 to 2-3.
In Comparative Example 1, when the opening area ratio is 82.4%, the photoelectric conversion characteristics are the same as those in Example 1 under a 200 lux environment, but Rs increases under a 10,000 lux environment, and the curve factor (FF). ) Decreased, and Pmax decreased.
The unique Rs of the photoelectric conversion element fluctuates depending on the illuminance environment, and the total resistance value of the fine hole processing part calculated by multiplying the resistance value of the fine hole processing part by the number of processing points exceeds the unique Rs of the photoelectric conversion element. It can be seen that Rs exceeds the total resistance value of the fine hole drilling portion.
Further, in Comparative Example 2, when the opening area ratio is 87.4%, the total resistance value of the micropore-machined portion exceeds the inherent Rs of the photoelectric conversion element even in a 200 lux environment, and the Rs increases. , Pmax decreased as the curve factor (FF) decreased.

(Comparative Example 3)
In Example 4, a photoelectric conversion element was produced in the same manner as in Example 4 except that the micropore processing was changed to that of Production Example 16, and the evaluation was carried out in the same manner. The results are shown in Tables 2-1 to 2-3.
Assuming that the opening area ratio is 87.4% in Comparative Example 3, the photoelectric conversion characteristics are the same as those in Example 4 under a 200 lux environment, but the total resistance value of the fine hole machined portion is increased under a 10,000 lux environment. The Pmax decreased because the Rs increased and the curve factor (FF) decreased, exceeding the inherent Rs of the photoelectric conversion element.

(Comparative Examples 4 and 5)
In Example 1, a photoelectric conversion element was produced and evaluated in the same manner as in Example 1 except that the micropore processing was changed to Production Examples 1 and 17. The results are shown in Tables 2-1 to 2-3.
When the opening area ratios of Comparative Examples 4 and 5 were 11.0% and 90.0%, the contact resistance increased and the electrical resistance increased due to the decrease in the film cross-sectional area of ITO, respectively. The total resistance value exceeded the inherent Rs of the photoelectric conversion element, Rs increased, and the curve factor (FF) decreased, so that Pmax decreased.

(Comparative Example 6)
In Example 1, a photoelectric conversion element was produced in the same manner as in Example 1 except that the hole blocking layer was not formed on the output take-out terminal portion and the series cell connection portion and the ITO glass substrate was exposed. evaluated. The results are shown in Tables 2-1 to 2-3.
When the output take-out terminal portion and the first ITO electrode of the series cell connection portion are not covered with a dense hole blocking layer as in Comparative Example 6, firing in the production of the photoelectric conversion element and the titanium tetrachloride aqueous solution. Due to the immersion, the resistance value of the first ITO electrode increased excessively, and the electric output could not be taken out from the photoelectric conversion element.

＊表２－２のＲｓに示した数値において、記号“Ｅ”は、その次に続く数値が１０を底とした“べき指数″であることを示し、その１０を底とした指数関数で表される数値が“Ｅ”の前の数値に乗算されることを示す。例えば、「１．０Ｅ＋０３」であれば、「１．０×１０^３」であることを示す。

* In the numerical values shown in Rs in Table 2-2, the symbol "E" indicates that the numerical value following it is a "power exponential" with the base of 10, and the table is an exponential function with the base of 10. Indicates that the number to be created is multiplied by the number before "E". For example, if it is "1.0E + 03", it means that it is "1.0 × 10 ³ ".

＊表２－３のＲｓに示した数値において、記号“Ｅ”は、その次に続く数値が１０を底とした“べき指数″であることを示し、その１０を底とした指数関数で表される数値が“Ｅ”の前の数値に乗算されることを示す。例えば、「１．０Ｅ＋０３」であれば、「１．０×１０^３」であることを示す。

* In the numerical values shown in Rs in Table 2-3, the symbol "E" indicates that the following numerical value is a "power exponential" with the base of 10, and the table is an exponential function with the base of 10. Indicates that the number to be created is multiplied by the number before "E". For example, if it is "1.0E + 03", it means that it is "1.0 × 10 ³ ".

As is clear above, by forming a plurality of micropores in the hole blocking layer in the present invention, it is possible to take out an excellent output having an electric resistance within a range that does not cause deterioration of the photoelectric conversion characteristics and to connect a series cell. It turned out that we could provide.

Aspects of the present invention are, for example, as follows.
<1> With the first board
With the first transparent electrode arranged on the first substrate,
The hole blocking layer arranged on the first transparent electrode and
An electron transport layer arranged on the hole blocking layer and made of an electron transport semiconductor having a photosensitizer adsorbed on the surface thereof.
A hole transport layer connected to the electron transport layer and made of a hole transport material,
With a second electrode disposed on the hole transport layer,
The plurality of micropores penetrating the hole blocking layer form an output take-out terminal portion for extracting electric power to the outside and a series cell connection portion connecting the second electrode and the first transparent electrode. It is a photoelectric conversion element characterized by being present.
<2> The photoelectric conversion element according to <1>, wherein the total resistance value of the output extraction terminal portion and the series cell connection portion is smaller than the series resistance Rs of the photoelectric conversion element.
<3> The ratio of the total area of the micropores in the output take-out terminal portion and the series cell connection portion to the area of the output take-out terminal portion and the series cell connection portion is 16.4% or more and 82.4%. The photoelectric conversion element according to any one of <1> to <2>, which is less than%.
<4> Any one of <1> to <3>, wherein the plurality of micropores formed in the hole blocking layer penetrate the first transparent electrode and reach the first substrate. The photoelectric conversion element according to the above.
<5> The photoelectric conversion element according to any one of <1> to <4>, wherein the first transparent electrode is an indium tin oxide (ITO) transparent film.
<6> The photoelectric conversion element according to any one of <1> to <5>, wherein the average thickness of the hole blocking layer is 5 nm or more and 300 nm or less.
<7> From the above <1>, wherein the whole blocking layer is a metal oxide semiconductor containing at least one selected from titanium oxide, niobium oxide, magnesium oxide, aluminum oxide, zinc oxide, tungsten oxide, and tin oxide. The photoelectric conversion element according to any one of <6>.
<8> The photoelectric conversion element according to <7>, wherein the hole blocking layer is a metal oxide semiconductor containing at least one of titanium oxide and niobium oxide.
<9> Any of the above <1> to <8>, wherein the light transmittance of the hole blocking layer in the region where the micropores are not formed and the first transparent electrode at a wavelength of 500 nm is 70.0% or more. The photoelectric conversion element according to the above.
<10> The photoelectric conversion element according to any one of <1> to <9>, which is a dye-sensitized solar cell having a metal oxide semiconductor and the metal oxide semiconductor being sensitized with a dye. Is.
<11> The photoelectric conversion element according to any one of <1> to <10>, wherein the minimum opening length of the micropores is 1 μm or more and 400 μm or less.
<12> The photoelectric conversion element according to any one of <1> to <11>, wherein the minimum distance between the micropores is 5 μm or more and 500 μm or less.
<13> A solar cell module characterized in that a plurality of photoelectric conversion elements according to any one of <1> to <12> are connected in series or in parallel.

According to the photoelectric conversion element according to any one of <1> to <12> and the solar cell module according to <13>, the conventional problems are solved and the object of the present invention is achieved. Can be done.

1 First substrate 2 First transparent electrode 3 Hole blocking layer 4 Electron transport layer 5 Photosensitizer 6 Hole transport layer 7 Second electrode 8, 9 Output take-out terminal 10 Series cell connection 11, 12 Lead line

Japanese Patent No. 4260494 Japanese Unexamined Patent Publication No. 2004-103374

Fujikura Technical Report, No. 106 (2004) 57

Claims (7)

The first board and
With the first transparent electrode arranged on the first substrate,
The hole blocking layer arranged on the first transparent electrode and
The electron transport layer arranged on the hole blocking layer and
A hole transport layer arranged on the electron transport layer and made of a hole transport material,
With a second electrode disposed on the hole transport layer,
A plurality of first micropores penetrating the hole blocking layer are formed in the first end region of the hole blocking layer where the electron transport layer, the hole transport layer and the second electrode are not arranged. The output take-out terminal portion for taking out electric power from the first transparent electrode to the outside through the plurality of first micropores.
A plurality of second micropores penetrating the hole blocking layer are formed in the second end region of the hole blocking layer where the electron transport layer and the hole transport layer are not arranged , and the plurality of second micropores are formed . Through the micropores of 2, the transparent electrode of a photoelectric conversion element adjacent to the first transparent electrode having a transparent electrode divided from the first transparent electrode, and a series cell connecting portion for connecting the second electrode are provided. death,
The opening area ratio per unit area of the first micropores when the area of a quadrangle formed by connecting the centers of any four micropores among the plurality of first micropores is taken as the unit area. And, when the area of the quadrangle formed by connecting the centers of any four micropores among the plurality of second micropores is taken as the unit area, the opening per unit area of the second micropores. A photoelectric conversion element having an area ratio of 16.4% or more and 75.0% or less, respectively . The photoelectric light beam according to claim 1, wherein the first micropores and the second micropores formed in the hole blocking layer penetrate the first transparent electrode and reach the first substrate. Conversion element. The photoelectric conversion element according to any one of claims 1 to 2, wherein the first transparent electrode is an indium tin oxide (ITO) transparent film. The photoelectric conversion element according to any one of claims 1 to 3, wherein the hole blocking layer has an average thickness of 5 nm or more and 300 nm or less. The photoelectric conversion element according to any one of claims 1 to 4, wherein the hole blocking layer contains at least one selected from titanium oxide, niobium oxide, magnesium oxide, aluminum oxide, zinc oxide, tungsten oxide, and tin oxide. .. From claim 1, the light transmittance of the hole blocking layer in the region where the first micropores and the second micropores are not formed and the first transparent electrode at a wavelength of 500 nm is 70.0% or more. 5. The photoelectric conversion element according to any one of 5. The photoelectric conversion element according to any one of claims 1 to 6, wherein the electron transport layer has a metal oxide semiconductor, and the metal oxide semiconductor is sensitized with a dye.

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