JP2002134178A - Photoelectric cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric cell having a high use rate of visible light, and free and from degradation of a photosensitizer, an organic electrolyte and an organic solvent for electrolyte dissolution, thereby capable of maintaining stable and high photoelectric transfer efficiency, etc., over a long period. SOLUTION: In this photoelectric cell, a substrate (P-1) having an electrode layer (1) on a surface thereof, and a metal oxide semiconductor film (2) adsorbing the photosensitizer, and formed on a surface of the electrode layer (1), and a substrate (P-2) having an electrode layer (3) on the surface thereof are arranged, so that the electrode layer (1) faces opposite the electrode layer (3), and at least one of the substrates and of electrode layers has transparency, an electrolyte layer is placed between the metallic oxide semiconductor film (2) and the electrode layer (3). On an outer surface of at least either of the substrate (P-1) and/or the substrate (P-2), a visible light antireflection film and/or an ultraviolet light shielding film are/is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photovoltaic cell for converting light energy into electric energy and extracting the same, and more particularly, has a high utilization rate of visible light, and maintains a stable high photoelectric conversion efficiency for a long period of time. To a photovoltaic cell.

[0002]

BACKGROUND OF THE INVENTION A photoelectric conversion material is a material that can continuously take out light energy as electric energy, and is a material that converts light energy into electric energy by utilizing an electrochemical reaction between electrodes. When such a photoelectric conversion material is irradiated with light, electrons are generated on one electrode side, move to the counter electrode, and the electrons moved to the counter electrode move as ions in the electrolyte and return to the one electrode. Since this conversion of photoelectric energy occurs continuously, it is used for, for example, solar cells.

In a general solar cell, first, a film of a semiconductor for a photoelectric conversion material is formed on a support such as a glass plate on which a transparent conductive film is formed to form an electrode, and then another transparent electrode is formed as a counter electrode. A support such as a glass plate on which a conductive film is formed is provided, and an electrolyte is sealed between these electrodes. When the photosensitizer adsorbed on the semiconductor for a photoelectric conversion material is irradiated with sunlight, the photosensitizer absorbs and excites light in a visible region. The electrons generated by this excitation move to the semiconductor, then to the transparent conductive glass electrode, move to the counter electrode through the conductor connecting the two electrodes, and the electrons transferred to the counter electrode are oxidized in the electrolyte. Reduce the reduction system. On the other hand, the photosensitizer in which electrons have been transferred to the semiconductor is in an oxidized state, which is reduced by a redox system in the electrolyte and returns to the original state. In this way, electrons flow continuously, and the photoelectric conversion material functions as a solar cell.

As this photoelectric conversion material, a material in which a spectral sensitizing dye having absorption in a visible light region is adsorbed on a semiconductor surface is used. For example, JP-A-1-220380 describes a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a metal oxide semiconductor layer. In addition, Japanese Patent Publication No. Hei 5-504023 describes a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a titanium oxide semiconductor layer doped with metal ions.

In such a solar cell, the electrolyte may be dissolved in a solvent to be used as an electrolyte, and an organic solvent such as alcohol may be used as the solvent at this time, and an organic electrolyte may be used as the electrolyte. May be used. However, in such a solar cell, when used for a long period of time, the electrolyte or the solvent may be deteriorated or deteriorated, or the electrolyte itself may leak out, and the photosensitizer may be desorbed or decomposed. Therefore, there is a problem that the photoelectric conversion efficiency is reduced. In addition, since the performance is not always sufficient depending on the application, it is required to further increase the utilization rate and conversion efficiency of sunlight.

Under these circumstances, the present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by forming a visible light antireflection film and / or an ultraviolet shielding film on the outer surface of the substrate. The present inventors have found that a photoelectric cell which can solve all of the above problems can be obtained, and have completed the present invention.

[0007]

An object of the present invention is to provide a photovoltaic material having a high utilization factor of visible light, without deterioration of a photosensitizer, an organic electrolyte and an organic solvent for dissolving an electrolyte. It is an object of the present invention to provide a photoelectric cell capable of maintaining the above conditions.

[0008]

SUMMARY OF THE INVENTION A photovoltaic cell according to the present invention comprises an electrode layer (1) on the surface and a metal oxide semiconductor film (2) having a photosensitizer adsorbed on the surface of the electrode layer (1). Substrate formed (P-1)
And a substrate (P-2) having an electrode layer (3) on the surface, the electrode layer
(1) and the electrode layer (3) are arranged so as to face each other, at least one of the substrate and the electrode layer has transparency, and is disposed between the metal oxide semiconductor film (2) and the electrode layer (3). A photovoltaic cell having an electrolyte layer provided thereon, wherein at least one of the transparent substrate (P-1) and / or the substrate (P-2) has an antireflection visible light film and / or an ultraviolet light shielding film on the outer surface thereof. Is formed.

A substrate in which the ultraviolet and ultraviolet shielding film has transparency.
(P-1) formed on the outer surface, a visible light antireflection film is formed on the ultraviolet light shielding film, and the refractive index of the visible light antireflection film is preferably lower than the refractive index of the ultraviolet light shielding film. . The ultraviolet shielding film is made of Ce, Fe, Ti, Sb, Zr,
It comprises oxide particles of one or more metals selected from the group consisting of Zn, or composite oxide particles of two or more metals selected from the group consisting of Ce, Fe, Ti, Sb, Zr, and Zn. Is preferred.

The visible light anti-reflection film is obtained by applying a coating solution for forming a visible light anti-reflection film, drying and heating the coating solution. Is preferably obtained by applying, drying and heating.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the photoelectric cell according to the present invention will be specifically described. [Photoelectric Cell] The photoelectric cell according to the present invention comprises an electrode layer (1) on the surface, and a metal oxide semiconductor film (2) having a photosensitizer adsorbed on the surface of the electrode layer (1). Substrate formed (P-1)
And a substrate (P-2) having an electrode layer (3) on the surface, the electrode layer
(1) and the electrode layer (3) are arranged so as to face each other, at least one of the substrate and the electrode layer has transparency, and is disposed between the metal oxide semiconductor film (2) and the electrode layer (3). A photovoltaic cell having an electrolyte layer provided thereon, wherein at least one of the transparent substrate (P-1) and / or the substrate (P-2) has an antireflection visible light film and / or an ultraviolet light shielding film on the outer surface thereof. Is formed.

FIG. 1 shows an example of such a photoelectric cell. FIG. 1 is a schematic sectional view showing one embodiment of a photoelectric cell 10 according to the present invention.
A substrate (P-1) having a transparent electrode layer 11 on the surface and a semiconductor film 12 on which a photosensitizer is adsorbed formed on the surface of the transparent electrode layer 11, and an electrode layer having a reduction catalytic ability on the surface The substrate (P-2) having the electrode layer 13 is disposed so that the electrode layers 11 and 13 face each other.

The metal oxide semiconductor film 12 and the electrode layer 13
An electrolyte 14 is sealed between the substrate and the substrate, and an ultraviolet shielding film 16 is formed on the outer surface of at least one of the transparent substrates (P-1). A film 15 is formed.

As the transparent substrate (P-1), a glass substrate, PE
A transparent and insulating substrate such as an organic polymer substrate such as T can be used. The substrate (P-2) is not particularly limited as long as it has strength enough to be used. In addition to transparent insulating substrates such as glass substrates and organic polymer substrates such as PET, metal titanium, metal aluminum, and metal copper Alternatively, a conductive substrate such as nickel metal can be used.

Further, by interposing a spacer between the metal oxide semiconductor film 12 and the electrode layer 13, a deformable substrate such as a PET film can be used as the transparent substrate (P-1) and the substrate (P-2). And a photoelectric cell having a shape other than the flat plate shape, for example, a semi-cylindrical shape. In this case, for example, it is possible to obtain a transparent or thin, flexible photoelectric cell or the like that is processed into an arbitrary shape.

As the transparent electrode layer 11 formed on the surface of the transparent substrate (P-1), tin oxide, tin oxide doped with Sb, F or P, indium oxide doped with Sn and / or F, oxide Conventionally known electrodes such as antimony, zinc oxide, and noble metals can be used. Such a transparent electrode layer 11 can be formed by a conventionally known method such as a thermal decomposition method and a CVD method.

The electrode layer 13 formed on the surface of the substrate (P-2) is not particularly limited as long as it has a reduction catalytic activity, and may be platinum, rhodium, ruthenium metal, ruthenium oxide or the like. Electrode material, tin oxide, Sb, F
Alternatively, a conventionally known electrode such as an electrode obtained by plating or depositing the electrode material on the surface of a conductive material such as tin oxide doped with P, indium oxide doped with Sn and / or F, and antimony oxide, or a carbon electrode is used. be able to.

Such an electrode layer 13 is formed by directly coating, plating or vapor-depositing the electrode on the substrate (P-2), and decomposing the conductive material by a conventionally known method such as a thermal decomposition method or a CDV method. After the formation, the electrode material can be formed on the conductive layer by a conventionally known method such as plating or vapor deposition. The substrate (P-2) may be transparent like the transparent substrate (P-1), and the electrode layer 13 may be a transparent electrode like the transparent electrode layer 11.

The visible light transmittance of the transparent substrate (P-1) and the transparent electrode layer 11 is preferably higher, specifically, 50% or more, and particularly preferably 90% or more. When the visible light transmittance is less than 50%, the photoelectric conversion efficiency may decrease. The resistance values of the transparent electrode layer 11 and the electrode layer 13 are preferably 100 Ω / cm ² or less. When the resistance value of the electrode layer exceeds 100Ω / cm ² , the photoelectric conversion efficiency may decrease.

The metal oxide semiconductor film 12 is formed on the transparent electrode layer 11 formed on the substrate (P-1). Further, the metal oxide semiconductor film 12 may be formed on the electrode layer 13 formed on the substrate (P-2). The thickness of such a metal oxide semiconductor film 12 is preferably in the range of 0.1 to 50 μm. Examples of such a metal oxide semiconductor film include at least one or two or more metal oxides selected from titanium oxide, lanthanum oxide, zirconium oxide, niobium oxide, tungsten oxide, strontium oxide, zinc oxide, tin oxide, and indium oxide. Metal oxide semiconductor film made of a material.

The metal oxide particles constituting such a metal oxide semiconductor film can be manufactured by a conventionally known method. Conventionally, for example, an acid or alkali is added to a hydrous metal oxide gel or sol obtained by a sol-gel method using an inorganic compound salt or an organic metal compound of the above-mentioned metal, followed by heating and aging. It can be manufactured by a known method.

The average particle diameter of the metal oxide particles is 5-6.
It is desirably in the range of 00 nm, preferably 10 to 300 nm. The particle size of the metal oxide particles can be measured with a laser Doppler particle size analyzer (Microtrack manufactured by Nikkiso Co., Ltd.). When the average particle diameter of the metal oxide particles is less than 5 nm, cracks are easily generated in the formed metal oxide semiconductor film, and it may be difficult to form a crack-free thick film in a small number of times, Further, the pore diameter and pore volume of the metal oxide semiconductor film may decrease, and the amount of the photosensitizer adsorbed may decrease.
Further, when the average particle diameter of the metal oxide particles exceeds 600 nm, the strength of the metal oxide semiconductor film may be insufficient.

Further, the metal oxide particles are preferably crystalline titanium oxide comprising one or more of anatase-type titanium oxide, brookite-type titanium oxide, and rutile-type titanium oxide. Such crystalline titanium oxide has a high band gap and a high dielectric constant, has a high adsorption amount of the photosensitizer as compared with other metal oxide particles, and further has stability, safety, and easy film formation. There are excellent properties such as certain.

It is preferable that the metal oxide semiconductor film 12 contains a titanium oxide binder component together with the metal oxide particles. Examples of such a titanium oxide binder component include titanium oxide composed of a hydrous titanate gel or sol obtained by a sol-gel method or the like, and a hydrous titanate gel or sol obtained by adding hydrogen peroxide to dissolve hydrous titanic acid. Decomposition products of ruoxotitanic acid and the like can be mentioned.

The term "peroxotitanic acid" refers to hydrated titanium peroxide. Such titanium peroxide has an absorption in the visible light region, and an aqueous solution of a titanium compound,
Alternatively, it is prepared by adding hydrogen peroxide to a sol or gel of hydrated titanium oxide and heating. The sol or gel of hydrated titanium oxide is obtained by adding an acid or an alkali to an aqueous solution of a titanium compound, hydrolyzing the resultant, and optionally washing, heating and aging it. The titanium compound used is not particularly limited, but titanium halide,
Titanium salts such as titanyl sulfate, titanium alkoxides such as tetraalkoxytitanium, and titanium compounds such as titanium hydride can be used.

The ratio between the titanium oxide binder component and the metal oxide particles in the metal oxide semiconductor film 12 is expressed as a weight ratio in terms of oxide (titanium oxide binder component / metal oxide particles).
Is preferably in the range of 0.05 to 0.50, preferably 0.1 to 0.3. If the weight ratio is less than 0.05, light absorption in the visible light region is insufficient, and the amount of adsorption of the photosensitizer may not increase. When the weight ratio is higher than 0.50, a porous metal oxide semiconductor film may not be obtained, and the amount of the photosensitizer adsorbed may not be increased.

The metal oxide semiconductor film 12 has a pore volume of 0.05 to 0.8 ml / g and an average pore diameter of 2 to 250 nm.
Is preferably within the range. Pore volume is 0.05ml
If it is less than / g, the amount of photosensitizer adsorbed will be low, and if it is more than 0.8 ml / g, the electron mobility in the film will be reduced and the photoelectric conversion efficiency may be reduced. When the average pore diameter is less than 2 nm, the adsorption amount of the photosensitizer decreases, and when it exceeds 250 nm, the electron mobility decreases and the photoelectric conversion efficiency may decrease.

In the present invention, an inorganic semiconductor film formed of another inorganic semiconductor material, an organic semiconductor film formed of an organic semiconductor material, an organic-inorganic hybrid semiconductor film, or the like is used as the semiconductor film instead of the metal oxide. Can be used. For example, examples of the organic semiconductor material include conventionally known compounds such as phthalocyanine, phthalocyanine-bisnaphthohalocyanine, polyphenol, polyanthracene, polysilane, polypyrrole, and polyaniline.

Next, in the present invention, the metal oxide semiconductor film 12 adsorbs the photosensitizer. The photosensitizer is not particularly limited as long as it absorbs and excites light in a visible light region and / or an infrared light region.
A metal complex or the like can be used. As organic dyes, carboxyl groups, hydroxyalkyl groups,
A conventionally known organic dye having a functional group such as a hydroxyl group, a sulfone group, and a carboxyalkyl group can be used. Specific examples include metal-free phthalocyanine, cyanine-based dyes, metalocyanine-based dyes, triphenylmethane-based dyes, and xanthene-based dyes such as uranine, eosin, rose bengal, rhodamine B, and dibromofluorescein. These organic dyes have a characteristic that the adsorption speed to the metal oxide semiconductor film is high.

Further, as the metal complex, JP-A-1-220380
No., metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine described in Japanese Patent Publication No. Hei 5-504023, chlorophyll, hemin, ruthenium-tris
(2,2'-bispyridyl-4,4'-dicarboxylate), cis-
(SCN ⁻ ) -bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium, ruthenium-cis-diaqua-bis (2,
Ruthenium-cis-diaqua-bipyridyl complex such as 2'-bipyridyl-4,4'-dicarboxylate), zinc-tetra (4-
Porphyrins such as (carboxyphenyl) porphine,
Ruthenium, osmium, such as iron-hexacyanide complex,
Complexes such as iron and zinc can be mentioned. These metal complexes are excellent in the effect of spectral sensitization and durability.

The organic dye or metal complex as the above-described photosensitizer may be used alone, or two or more kinds of organic dyes or metal complexes may be used in combination. You may use together. The method of adsorbing such a photosensitizer is not particularly limited, and a solution obtained by dissolving the photosensitizer in a solvent is absorbed by a metal oxide semiconductor film by a method such as a dipping method, a spinner method, or a spray method. Then, a general method such as drying can be adopted. Further, the absorption step may be repeated as necessary. Alternatively, the photosensitizer can be adsorbed to the metal oxide semiconductor film by bringing the photosensitizer into contact with the substrate while heating and circulating the solution.

The solvent for dissolving the photosensitizer may be any solvent capable of dissolving the photosensitizer, and specifically, water,
Alcohols, toluene, dimethylformamide, chloroform, ethyl cellosolve, N-methylpyrrolidone, tetrahydrofuran and the like can be used. The amount of the photosensitizer adsorbed on the metal oxide semiconductor film is preferably 50 μg or more per 1 cm ² of the specific surface area of the metal oxide semiconductor film. When the amount of the photosensitizer is less than 50 μg, the photoelectric conversion efficiency may be insufficient.

The photoelectric cell according to the present invention has a semiconductor film 12
And the transparent electrode layer 13 (when a semiconductor film is formed on the surface of the transparent electrode layer, the semiconductor film and the electrode layer) are arranged to face each other, the side surfaces are sealed with a resin or the like, and the electrolyte and liquid crystal are interposed between the electrodes. Formed by enclosing the electrolyte layer 14. As the electrolyte, a mixture with at least one compound forming an oxidation-reduction system together with an electrochemically active salt is used.

Examples of the electrochemically active salt include quaternary ammonium salts such as tetrapropylammonium iodide. Examples of the compound forming the redox system, quinone, hydroquinone, iodine _{^{(I - / I - 3)}} , potassium iodide, bromine _{^{(Br - / Br - 3)}} , such as potassium bromide and the like.

In the present invention, a liquid crystal is used together with the electrolyte, if necessary. The liquid crystal is not particularly limited as long as the photosensitizer adsorbed on the semiconductor film has a low solubility of the photosensitizer so as not to be desorbed and dissolved, and a conventionally known liquid crystal can be used. . As such a liquid crystal, a smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal, or the like which is conventionally known as a temperature transition type liquid crystal can be used.

Further, a concentration transition type liquid crystal, a polymer liquid crystal, a polymer dispersed liquid crystal, a disc-shaped liquid crystal and the like can be used.
Among them, when a liquid crystal compound containing a fluorine atom is used, the compound has high hydrophobicity and excellent long-term stability. Further, a solvent may be contained together with the liquid crystal. It is desirable that the solvent has low solubility of the photosensitizer so that the photosensitizer adsorbed on the metal oxide semiconductor film does not desorb and dissolve. As such a solvent, specifically, water, alcohols,
Examples thereof include oligoethers, carbonates such as propion carbonate, phosphates, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, sulfur compounds of sulfolane 66, ethylene carbonate, acetonitrile, and γ-butyrolactone.

Further, as a solvent, an organic polymerizing (gelling) agent such as a reactive monomer such as a mixture of a vinyl monomer and a divinyl monomer, an N-methylol compound, and a dicarboxylic acid can be used. Using such a reactive monomer as a solvent, after dissolving the electrolyte and forming a cell, if the monomer is cured, the electrolyte can be solidified or gelled, such as liquid leakage from the photoelectric cell. Can be suppressed.

The concentration of the electrochemically active salt in such an electrolyte layer is not particularly limited, and is usually 1 liter of a liquid crystal compound (when a solvent is contained, the sum of the liquid crystal compound and the solvent). On the other hand, 0.01 to 5 mol /
Liter, preferably in the range of 0.1 to 2 mol / l. If the concentration of the electrochemically active salt is less than 0.01 mol / liter, the concentration is too low, so that the ability to exchange electrons with the photosensitizer or the electrode is reduced and the photoelectric conversion efficiency is reduced. Sometimes. If the concentration exceeds 5 mol / liter, the electrochemically active salt may not be dissolved in the liquid crystal compound and the solvent.

The concentration of the compound forming the oxidation-reduction system is not particularly limited, and usually, the concentration of the liquid crystal compound (when a solvent is contained, the sum of the liquid crystal compound and the solvent)
It is desirably in the range of 0.01 to 5 mol / l, preferably 0.1 to 2 mol / l, based on liter. When the concentration of the compound forming the redox system is less than 0.01 mol / liter, the concentration is too low, and the ability to transfer electrons with the photosensitizer or the electrode is reduced.
The photoelectric conversion efficiency may decrease. Further, even if the concentration exceeds 5 mol / liter, the ability to transfer and receive electrons does not further increase, and the photoelectric conversion efficiency does not improve. Further, when the concentration exceeds 5 mol / liter, the long-term stability may decrease.

The molar ratio of the compound forming the redox system to the electrochemically active salt (the compound forming the redox system / the electrochemically active salt) in the electrolyte is 1/20.
It is preferably in the range of ３ to 3/10. If a solvent is included, the volume of the solvent (V _S ) and the volume of the liquid crystal (V _LC )
And the volume (V _S / V _LC ) ratio is 1.0 or less, preferably 0.1%.
It is desirably in the range of 75 or less. Volume ratio is 1.0
When the ratio exceeds the ratio of the liquid crystal, the effect of the light energy utilization rate due to the light scattering effect described above becomes insufficient,
In addition, long-term stability may not be improved.

The photovoltaic cell according to the present invention has a substrate 5 having a transparent electrode layer 11 on the surface and a semiconductor film 12 having a photosensitizer adsorbed on the surface of the electrode layer 11, and a reduction layer on the surface. The substrate 6 having the electrode layer 13 having catalytic ability is arranged so that the metal oxide semiconductor film 12 and the electrode layer 13 face each other, and the side surfaces are sealed with a resin. It is manufactured by enclosing an electrolyte, liquid crystal, and, if necessary, liquid crystal and a solvent between the layer 13 and connecting the electrodes with a lead wire.

The photoelectric cell according to the present invention as described above,
When liquid crystal is contained in the electrolyte layer, due to the light scattering effect of the liquid crystal, even if the incident angle of light increases, the amount of received light does not decrease significantly, and the light energy is stably converted to electric energy. Can be taken out. In addition, of the incident light, the light reflected by the semiconductor film without being involved in the excitation of the photosensitizer is again irradiated on the photosensitizer in the semiconductor film by the light scattering effect of the liquid crystal and converted into electric energy. Therefore, the conversion efficiency of light energy can be improved. Furthermore, when a liquid crystal having hydrophobicity is used as the liquid crystal,
Since the hygroscopic effect is reduced as compared with the case where only the electrolyte having hygroscopicity is used, the deterioration due to the decomposition of the electrolyte or the photosensitizer due to moisture absorption or the solvent is suppressed, and as a result, the effect of improving the long-term stability is obtained. can get.

In the photovoltaic cell according to the present invention, if necessary, spacer particles may be interposed between the metal oxide semiconductor film and the electrode layer. Further, the spacer particles may be embedded in the semiconductor film, and at least a part of the spacer particles may be exposed from the semiconductor film so as to be in contact with the electrode layer. Note that in the case where a metal oxide semiconductor film is formed on the surface of the electrode layer, spacer particles may be interposed between the transparent electrode layer and the metal semiconductor film that face each other.

At this time, the spacer particles are not particularly limited as long as they do not damage the metal oxide semiconductor film and the electrode layer and do not come into contact with each other, and spherical spacer particles, rod-like spacer particles and the like can be used. Conventionally known insulating particles made of a resin (plastic), an organic-inorganic composite, a metal oxide or ceramics can be used. When the spacer particles 7 are interposed, the distance between the metal oxide semiconductor film 12 and the electrode layer 13 is particularly about 1 to 5
Opto-electric cells in a small range of 0 μm can be suitably obtained.

As the resin spacer particles, JP-B-7
And resin particles disclosed in US Pat. As the spacer particles of the organic-inorganic composite, particles obtained by hydrolyzing metal alkoxides disclosed in JP-A-7-140472 and JP-B-8-25739 can be suitably used.

As spacer particles made of metal oxide or ceramics, spherical particles disclosed in JP-A-3-218915 and JP-B-7-64548 can be suitably used. Further, particles obtained by fusing a synthetic resin to the surface of each of the above-mentioned particles can also be suitably used. Such particles include, for example, those described in
The resin-coated particles disclosed in JP-A-94224 can be suitably used. In particular, particles coated with an adhesive resin are fixed by adhering to the metal oxide semiconductor film and / or the electrode layer, and can exhibit a uniform gap adjustment or a stress absorbing effect effectively without moving.

An ultraviolet shielding film 16 is formed on the outer surface of the transparent substrate (P-1), and a visible light antireflection film 15 is formed on the surface of the ultraviolet shielding film 16. In the present invention, not only the photoelectric cell shown in FIG. 1 but also any one of the antireflection film and the ultraviolet shielding film is formed on the outer surface of the transparent substrate (P-1) or the substrate (P-2). Good. Further, the antireflection film itself may be a laminated film composed of two or more antireflection films, or the ultraviolet shielding film itself may be a laminated film composed of two or more antireflection films. It may be a laminated film in which a plurality of shielding films are laminated.

More preferably, an ultraviolet shielding film is formed on the outer surface of the transparent substrate (P-1), and an antireflection film is formed on the surface of the ultraviolet shielding film. In addition, between the ultraviolet shielding film and the antireflection film, the antireflection film has a higher refractive index, and the difference in the refractive index between the ultraviolet shielding film and the antireflection film is about 0.3 or more, more preferably 0.6 or more. It is desirable. If the difference in refractive index is less than 0.3, the antireflection performance will be insufficient.

[Visible light anti-reflection film]
It is composed of an antireflection film matrix and, if necessary, inorganic compound particles. Such an antireflection film desirably has a refractive index smaller than that of the transparent substrate (P-1). A substrate with an antireflection layer that can obtain a refractive index in this manner has excellent antireflection performance.

[0050] As a matrix for an antireflection film used in the matrix present invention, an antireflection film obtained has transparency, low refractive index than the underlying substrate or ultraviolet shielding film, as long as it has a reflection preventing performance Although not particularly limited, inorganic oxides such as silica, titania, and zirconia, or composite oxides thereof, or polyester resins, acrylic resins, urethane resins, vinyl chloride resins, epoxy resins, melamine resins, fluororesins, silicone resins, and butyral Resin, phenolic resin,
Vinyl acetate resin, UV curable resin, electron beam curable resin, etc.
Coating resins such as copolymers and denatured products of these resins are exemplified. These can be selected and used in consideration of the type of the substrate and the like, adhesion, hardness, coatability and the like.

Among these, a matrix composed of silica is preferable, and in particular, silicic acid obtained by dealkalization of a partially hydrolyzed product of a hydrolyzable organosilicon compound, a hydrolyzed polycondensate, or an aqueous solution of an alkali metal silicate. A silica matrix composed of a partial hydrolyzate of the liquid and a hydrolyzed polycondensate is preferable, and a silica matrix derived from a hydrolyzed polycondensate of alkoxysilane represented by the following general formula [1] is particularly preferable.

R _a Si (OR ′) _4-a [1] (wherein R is a vinyl group, an aryl group, an acryl group, an alkyl group having 1 to 8 carbon atoms, a hydrogen atom or a halogen atom, vinyl group, an aryl group, an acrylic group, an alkyl group of carbon-based number _{1~8, -C 2 H 4 OC n} H 2n + 1 (n = 1
To 4) or a hydrogen atom, and a is an integer of 0 to 3. Examples of such alkoxylans include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane,
Examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltriisopropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and the like. The inorganic compound particle antireflection film may contain inorganic compound particles as necessary, and as such, the refractive index is 1.
60 or less, preferably 1.50 or less, having an average particle size of 5
Oxide fine particles or composite oxide fine particles having a diameter in the range of from about 300 nm to about 300 nm can be suitably used.

As such particles, Japanese Patent Application Laid-Open Nos. 5-132309 and 7-13310 by the present applicant are disclosed.
No. 5, JP-A-10-194721, JP-A-10-194721
The silica-based colloid particles disclosed in JP-A No. 0-45403 can be preferably used. In particular, among the composite oxide fine particles, it is composed of silica and an inorganic oxide other than silica, and has a thickness of 1 to 50 nm with porous core particles or cavities.
Wherein the molar ratio MO _x / SiO ₂ when the silica is represented by SiO ₂ and the inorganic oxide other than silica is represented by MO _x is in the range of 0.0001 to 0.3. The composite oxide fine particles having an average particle diameter in the range of 5 to 300 nm have a low refractive index of usually 1.40 or less,
The antireflection film containing such composite oxide fine particles has a refractive index of 1.43 or less, and has excellent antireflection performance.

When the average particle diameter of the inorganic compound particles used in the present invention is less than 5 nm, the effect of improving the adhesion to the substrate or the ultraviolet ray preventing film described later cannot be sufficiently obtained.
When the average particle size exceeds 300 nm, the transparency of the antireflection film may be reduced, or the film may be cracked.
That is, when the average particle diameter of the inorganic compound particles is in the above range, an antireflection film having excellent adhesion to a substrate or the like and excellent film strength can be obtained.

The thickness of such an antireflection film is 50 to 5
It is preferably in the range of 00 nm, preferably 80-300 nm. When the thickness of the anti-reflection film exceeds 500 nm, the anti-reflection film is too thick, so that the light transmittance is reduced and the transparency is deteriorated and the appearance is also deteriorated. Such an antireflection film is formed by using the coating liquid for forming an antireflection film described in (1) or (2) below.

(1) When the above-described resin is used as the matrix for forming the antireflection film, the inorganic compound particles and, if necessary, the inorganic compound particles are dissolved or dispersed in water and / or an organic solvent. The coating liquid (1) for forming an antireflection film is used.

The weight ratio of the inorganic compound particles to the matrix in the coating liquid (1) for forming the antireflection film was such that the ratio of the inorganic compound particles /
Matrix = 1/99 to 9/1 is desirable. When the weight ratio exceeds 9/1, the strength of the formed anti-reflection film is insufficient, resulting in lack of practicality. On the other hand, when the weight ratio is less than 1/99, it is difficult to form an anti-reflection film having excellent adhesion and strength.

(2) Coating solution for forming an antireflection film When an inorganic oxide such as silica, titania or zirconia or a composite oxide thereof is used as a matrix, silicon such as alkoxysilane, halogenated silane or silicic acid is used. Compounds, titanium compounds such as titanium alkoxide and titanium tetrachloride, and Z compounds such as zirconium alkoxide
One or more of the salts of the r and Zn compounds are hydrolyzed and polycondensed in water and / or an organic solvent in the presence of an acid or base catalyst to prepare a matrix precursor dispersion,
If necessary, the inorganic compound particles are mixed with the matrix precursor dispersion to obtain a coating liquid for forming an antireflection film.

The concentration of the matrix precursor contained in the coating solution thus obtained is 0.05 in terms of oxide.
It is preferably in the range of 10 to 10% by weight. Particularly preferably, it is in the range of 0.2 to 5.0% by weight. When the concentration of the matrix precursor contained in the coating solution is less than 0.05% by weight, the resulting film is thin, and thus may be inferior in chemical resistance and antireflection performance. A film having a sufficient film thickness may not be obtained, and a film having a uniform film thickness may not be obtained even when coating is repeatedly performed.

When the concentration of the matrix precursor exceeds 10% by weight, cracks may occur in the obtained film, or the strength of the film may be reduced. Further, the film may be too thick and the antireflection performance may be insufficient. The molecular weight of such a matrix precursor is 500 to 1 in terms of polystyrene equivalent molecular weight.
It is preferably in the range of 000, and particularly preferably in the range of 700 to 2,500.

When the molecular weight in terms of polystyrene is less than 500, unhydrolyzed products may be present in the coating solution, and the coating may not be applied uniformly. Even if applied, the adhesion to the lower layer may be poor. If the molecular weight in terms of polystyrene exceeds 10,000, the strength of the coating tends to decrease. The concentration of the inorganic compound particles used as needed in the coating solution is 0.05 to 5 in terms of oxide.
Preferably it is in the range of 3% by weight. Particularly preferably, it is in the range of 0.2 to 2% by weight.

When the concentration of the inorganic compound particles contained in the coating solution is less than 0.05% by weight, the refractive index of the obtained antireflection film is not sufficiently reduced because the amount of the inorganic compound particles is too small, and the antireflection performance is deteriorated. When the concentration of the inorganic compound particles exceeds 3% by weight, cracks may occur in the obtained film, or the strength of the film may decrease. Furthermore, the coating liquids (1) and (2) for forming an antireflection film used in the present invention include fine particles composed of a low refractive index material such as magnesium fluoride, the transparency and antireflection performance of the antireflection film. Small amounts of conductive fine particles and / or additives such as dyes or pigments to such an extent that they do not hinder the reaction.

Formation of antireflection film The method of forming the antireflection film is not particularly limited, and may be a dry thin film formation method such as a vacuum evaporation method, a sputtering method, an ion plating method, or a dipping method, a spinner method, a spray method, or the like. A wet thin film forming method in which the film is applied by a method such as a roll coater method or a flexographic printing method and then dried, can be adopted.

Among them, a wet thin film forming method is preferable because an antireflection film can be formed at low cost. The thickness of the obtained antireflection film is 50 to 500 nm, preferably 80 to 30 nm.
It is preferably in the range of 0 nm. When the thickness of the antireflection film is less than 50 nm, the strength, chemical resistance, antireflection performance, etc. of the film may be inferior.

If the thickness of the anti-reflection film exceeds 500 nm, cracks may occur in the film or the strength of the film may be reduced, and the anti-reflection performance may be insufficient because the film is too thick. When the film thickness is in the above range, the film strength and scratch resistance are excellent, and excellent antireflection performance is exhibited. For this reason, the photoelectric cell has a high utilization factor of sunlight and can obtain high photoelectric conversion efficiency.

In the present invention, a film formed by applying such a coating solution for forming an antireflection film is heated at 100 ° C. or more at the time of drying or after drying, or the uncured film is exposed to visible light. Irradiation with electromagnetic waves such as ultraviolet rays having a short wavelength, electron beams, X-rays, and γ-rays. Such heat treatment, ultraviolet irradiation,
When a treatment such as electromagnetic wave irradiation is performed, the curing of the matrix precursor is accelerated, and the hardness of the obtained antireflection film increases.

[Ultraviolet shielding film] The ultraviolet shielding film is composed of a matrix for forming an ultraviolet shielding film, Ce, Fe, Ti, Sb, Zr,
Oxide particles of one or more metals selected from the group consisting of Zn, or composite oxide particles of two or more metals selected from the group consisting of Ce, Fe, Ti, Sb, Zr, and Zn. I have.

Matrix for ultraviolet shielding film The matrix for ultraviolet shielding film used in the present invention includes:
There is no particular limitation as long as the obtained ultraviolet shielding film has transparency and adhesion to the coated surface, and examples thereof include those similar to the matrix for the antireflection film. Specifically, silica, titania, inorganic oxides such as zirconia, or composite oxides or polyester resins thereof, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin,
Coating resins such as melamine resins, fluororesins, silicone resins, butyral resins, phenol resins, vinyl acetate resins, ultraviolet curable resins, electron beam curable resins, and copolymers and modified products of these resins. These can be appropriately selected and used in consideration of the type of the substrate and the like, adhesion, hardness, coatability and the like.

Ultraviolet ray shielding particles Ultraviolet ray shielding particles include Ce, Fe, Ti, Sb, Zr,
One or more metal oxide particles selected from the group consisting of Zn, or composite oxide particles of two or more metals selected from the group consisting of Ce, Fe, Ti, Sb, Zr, and Zn are used. These particles have an ultraviolet shielding ability and a high refractive index of 1.8 or more, so that the obtained ultraviolet shielding film has a high refractive index, and thus has high antireflection performance.

As such ultraviolet shielding particles, preferably used are the colloidal particles disclosed in Japanese Patent Application Laid-Open Nos. 10-182152, 2-178219 and 62-283817 by the present applicant. be able to. Such ultraviolet shielding particles have an average particle diameter of 5
It is preferably in the range of 500 nm. A more preferred range is from 5 to 200 nm. When the average particle diameter of the ultraviolet shielding particles is less than 5 nm, the effect of improving the adhesion to the base material cannot be sufficiently obtained, and when the average particle diameter exceeds 500 nm, the transparency of the ultraviolet shielding film decreases or In some cases, cracks occur in the film. When the average particle diameter of the ultraviolet shielding particles is in the above range, an ultraviolet shielding film having excellent adhesion to a substrate or the like and excellent film strength can be obtained.

The proportion of the particles for shielding ultraviolet rays in the ultraviolet shielding film is preferably in the range of 1 to 99% by weight. A more preferred range is 30 to 80% by weight. When the proportion of the ultraviolet shielding particles in the ultraviolet shielding film is less than 1% by weight, the ultraviolet shielding effect and the effect of improving the adhesion to the substrate cannot be sufficiently obtained, and when it exceeds 99% by weight, the strength of the film is poor. May be sufficient.

Such an ultraviolet shielding film is formed by using the coating liquid for forming an ultraviolet shielding film shown in (1) or (2) below. (1) Ultraviolet shielding film forming coating liquid When the above-mentioned resin is used as the matrix, the ultraviolet shielding film forming coating liquid (1) in which the matrix and the ultraviolet shielding particles are dissolved or dispersed in water and / or an organic solvent. ) Is used.

The weight ratio of the ultraviolet shielding particles to the matrix in the ultraviolet shielding film forming coating solution (1) is preferably in the range of ultraviolet shielding particles / matrix = 1/99 to 9/1. When the weight ratio is more than 9/1, the strength of the coating film is insufficient and practicability is low. On the other hand, when the weight ratio is less than 1/99, it is difficult to form an ultraviolet shielding film having excellent adhesion to the substrate and excellent strength. (2) UV-shielding film forming coating liquid As a matrix, silica, titania, inorganic oxides such as zirconia, or when using these composite oxides, alkoxysilanes, halogenated silanes, silicon compounds such as silicic acid, titanium, etc. Alkoxides, Ti compounds such as titanium tetrachloride, Z such as zirconium alkoxides
After hydrolyzing one or more of the salts of the r and Zn compounds in water and / or an organic solvent in the presence of an acid or base catalyst, a matrix precursor dispersion is prepared.
If necessary, the particles for ultraviolet shielding are mixed with the matrix precursor dispersion to obtain a coating liquid for forming an ultraviolet shielding film.

The concentration of the matrix precursor contained in the coating solution thus obtained was 0.05 in terms of oxide.
It is preferably in the range of 10 to 10% by weight. Particularly preferably, it is in the range of 0.2 to 5.0% by weight. The concentration of the matrix precursor contained in the coating liquid thus obtained is preferably in the range of 0.05 to 10% by weight in terms of oxide. Particularly preferably, it is in the range of 0.2 to 5.0% by weight.

When the concentration of the matrix precursor contained in the coating solution is less than 0.05% by weight, a film having a sufficient film thickness may not be obtained by one coating, and even if coating is repeated, In some cases, a film having a uniform thickness cannot be obtained. If the concentration of the matrix precursor exceeds 10% by weight, cracks may occur in the obtained film or the strength of the film may be reduced. In addition, the thickness of the obtained film tends to be non-uniform and the surface tends to lack flatness.

The concentration of the ultraviolet shielding particles in the coating solution is preferably in the range of 0.05 to 30% by weight in terms of oxide. Particularly preferably, it is in the range of 1 to 10% by weight. When the concentration of the ultraviolet shielding particles contained in the coating solution is less than 1% by weight, the amount of the ultraviolet shielding particles is too small, and the ultraviolet shielding film obtained may be inferior in the ultraviolet shielding ability. If the concentration exceeds 30% by weight, cracks may occur in the obtained film, or the strength of the film may be reduced.

Further, the coating liquids (1) and (2) for forming the ultraviolet shielding film used in the present invention contain a small amount of conductive fine particles and / or a small amount so as not to impair the transparency and ultraviolet shielding effect of the ultraviolet shielding film. Alternatively, an additive such as a dye or a pigment may be included. Formation of Ultraviolet Shielding Film As a method of forming the ultraviolet shielding film, a wet thin film forming method of applying a dipping method, a spinner method, a spray method, a roll coater method, a flexographic printing method, and then drying and then drying is preferably adopted. Can be.

At this time, the thickness of the obtained ultraviolet shielding film is preferably in the range of 10 to 500 nm, more preferably 50 to 200 nm. The thickness of the ultraviolet shielding film is 10 nm
If it is less than 7, the strength of the film, the ability to block ultraviolet rays, and the like may be reduced, and the low-reflectivity of visible light may be insufficient. If the thickness of the ultraviolet shielding film exceeds 500 nm, cracks may occur in the film or the strength of the film may be reduced, and the thickness of the film may be too thick to have insufficient visible light low reflectivity.

When the film thickness is in the above range, the film strength is excellent and the excellent ultraviolet shielding ability is exhibited. For this reason, the photovoltaic cell does not deteriorate or deteriorate the electrolyte or the solvent even after long-term use, does not leak due to the deterioration of the electrolyte or the solvent, and does not desorb or deteriorate the spectral sensitizing dye. High photoelectric conversion efficiency (performance) can be maintained for a long time.

In the present invention, a film formed by applying such a coating solution for forming an ultraviolet protection film may be heated at 100 ° C. or more at the time of drying or after drying, or the uncured film may be exposed to visible light. Electromagnetic waves such as ultraviolet rays having a short wavelength, electron beams, X-rays, and γ-rays can be irradiated. By such a treatment, the curing of the matrix precursor is accelerated, and the hardness of the obtained ultraviolet protection film is increased.

The photoelectric cell according to the present invention as described above comprises:
When a visible light anti-reflection film is formed on the outer surface of the substrate, a photoelectric cell having a large amount of incident light among the irradiated visible light and a high visible light utilization rate can be obtained. In addition, when an ultraviolet shielding film is formed, the electrolyte or the solvent is not deteriorated or deteriorated even after long-term use, and is not leaked due to the deterioration, and the spectral sensitizing dye is desorbed or deteriorated. Not even. Therefore, according to the present invention, it is possible to obtain a photoelectric cell capable of maintaining high photoelectric conversion efficiency (performance) for a long period of time.

The above visible light antireflection film and / or ultraviolet light shielding film can be formed by using a coating liquid for forming an antireflection film and / or a coating liquid for forming an ultraviolet light shielding film. Such a coating is excellent in film strength, adhesion to a substrate, transparency and the like, and can be formed at low cost.

[0083]

According to the present invention, a large amount of incident light among the irradiation visible light can be obtained, so that a photovoltaic cell having high utilization of visible light can be obtained, and the electrolyte or the solvent is deteriorated even after long-term use. A photovoltaic cell capable of maintaining high photoelectric conversion efficiency (performance) for a long period of time without causing deterioration or deterioration and leaking of the spectral sensitizing dye, and without deteriorating, can be obtained.

[0084]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0085]

Example 1 Preparation of Matrix Precursor Dispersion Ethyl orthosilicate (TEOS) (SiO ₂ : 28% by weight) 50
g of ethanol, 194.6 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of pure water were stirred at room temperature for 5 hours to obtain a SiO ₂ concentration of 5%.
A weight percent matrix precursor dispersion was prepared.

Preparation of Coating Solution for Forming Ultraviolet Shielding Film Titanium oxide colloid (catalyst Chemical Industry Co., Ltd.) was added to 100 g of the above matrix precursor dispersion as ultraviolet shielding particles.
Manufacture: HPW-15R, average particle diameter 15 nm, concentration 30% by weight)
100 g of the mixture was mixed to prepare a coating solution (A) for forming an ultraviolet shielding film. Preparation of Coating Solution for Forming Visible Light Antireflection Film First, inorganic compound particles having a hollow inside were prepared as follows.

Average particle size 5 nm, SiO ₂ concentration 20% by weight
Was mixed with 190 g of pure water to prepare a reaction mother liquor, which was heated to 95 ° C. The pH of the reaction mother liquor was 10.5. To this reaction mother liquor, an aqueous solution of sodium silicate having a concentration of 1.5% by weight in terms of SiO ₂ was added.
0 g and 36,800 g of an aqueous solution of sodium aluminate having a concentration of 0.5% by weight in terms of Al ₂ O ₃ were simultaneously added. Meanwhile, the temperature of the reaction solution was kept at 95 ° C. The pH of the reaction rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate, and hardly changed thereafter.

After completion of the addition, the reaction solution was cooled to room temperature, washed with an ultrafiltration membrane, and washed with a SiO _2.
A dispersion of Al ₂ O ₃ porous material precursor particles was prepared. Next, 500 g of the dispersion liquid of the porous substance precursor particles is collected, 1,700 g of pure water is added thereto, and the mixture is heated to 98 ° C. While maintaining this temperature, the aqueous sodium silicate solution is removed with a cation exchange resin. Silicate solution (SiO 2) obtained by alkali
₍₂ concentration 3.5% by weight) was added to form a silica protective film on the surface of the porous material precursor particles. The obtained dispersion liquid of the porous substance precursor particles is washed with an ultrafiltration membrane to adjust the solid content concentration to 13% by weight. Then, 500 g of the dispersion liquid of the porous substance precursor particles is mixed with 1,125 g of pure water. In addition,
Further, concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, and after dealumination, the aluminum salt dissolved by an ultrafiltration membrane was separated while adding 10 L of a hydrochloric acid aqueous solution of pH 3 and 5 L of pure water. A particle precursor dispersion was prepared.

A mixture of 1500 g of the above particle precursor dispersion, 500 g of pure water, 1,750 g of ethanol and 626 g of 28% ammonia water was heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ : 28% by weight). Was added, and a silica outer shell layer was formed on the particle precursor surface with a hydrolyzed polycondensate of ethyl silicate, whereby particles having voids inside the outer shell layer were produced. Then, after concentrating to a solid content concentration of 5% by weight using an evaporator, ammonia water having a concentration of 15% by weight was added to adjust the pH to 10, and the mixture was heated in an autoclave at 180 ° C. for 2 hours. 20% by weight solid content
A dispersion liquid of inorganic compound particles having a hollow inside was prepared.

The cross section of the obtained particles was observed with a transmission electron microscope (TEM). As a result, particles having cavities formed inside the outer shell layer were obtained. The Al ₂ O
_{The 3} / SiO ₂ molar ratio is 0.0022 and the average particle size is 96 n.
m and the refractive index were 1.31. Next, a mixed solvent of ethanol / butanol / diacetone alcohol / isopropyl alcohol (2: 1: 1: 5 weight mixing ratio) was added to the previously prepared matrix precursor dispersion having an SiO ₂ concentration of 5% by weight. From the prepared inorganic compound particle dispersion, a coating liquid (A) for forming a visible light antireflection film having a concentration of inorganic compound particles of 0.2% by weight and a matrix precursor SiO ₂ concentration of 1% by weight was prepared.

Glass with ultraviolet shielding film and visible light antireflection film
Preparation of Substrate While a transparent glass substrate formed with fluorine-doped tin oxide as an electrode was maintained at 40 ° C., a coating solution (A) for forming an ultraviolet shielding film was applied to the surface on the opposite side of the electrode by spinner method.
Under the conditions of 90 rpm and 90 seconds, the thickness of the ultraviolet shielding film is 120
and dried.

Next, on the ultraviolet shielding film,
The spin-coating method is applied at 100 rpm for 90 seconds so that the visible light anti-reflection film has a thickness of 100 nm, dried, and heat-treated at 160 ° C. for 30 minutes to form a glass with an ultraviolet shielding film and a visible light anti-reflection film. Substrate (A) was prepared. The reflectance of the glass substrate (A) provided with an ultraviolet shielding film and a visible light antireflection film was measured using a reflectometer (MCPD-2000, manufactured by Otsuka Electronics Co., Ltd.). The reflectance at the wavelength having the lowest reflectance in the wavelength range of 400 to 700 nm was defined as the bottom reflectance, and the average reflectance in the wavelength range of 400 to 700 nm was defined as the luminous reflectance.

Table 1 shows the results. Preparation of Metal Oxide Particles for Semiconductor Film 5 g of titanium hydride was suspended in 1 L of pure water, and 400 g of a 5% hydrogen peroxide solution was added over 30 minutes.
The solution was heated to ℃ to dissolve to prepare a solution of peroxotitanic acid. The pH was adjusted to 9 by adding concentrated aqueous ammonia, and the mixture was placed in an autoclave and subjected to hydrothermal treatment at 250 ° C. for 5 hours under a saturated vapor pressure to obtain titania colloid particles (A).
Was prepared. It was anatase-type titanium oxide having high crystallinity by X-ray diffraction. The average particle size was 40 nm in Table.

Preparation of Coating Solution for Forming Semiconductor Film Next, the titania colloidal particles (A) obtained above were concentrated to a concentration of 10%, and the above peroxotitanic acid solution was mixed therewith. Hydroxypropylcellulose, which is a film-forming auxiliary, was added so as to be 30% by weight of the weight in terms of TiO ₂ to prepare a coating solution for forming a semiconductor film.

Formation of Semiconductor Film Next, the film is applied on the electrode surface of a transparent glass substrate provided with an electrode on which the above-mentioned ultraviolet shielding film and visible light antireflection film are formed, air-dried, and subsequently 6000 mJ / cm 2 using a low-pressure mercury lamp.
The semiconductor film was cured by irradiating ultraviolet rays of cm ² to decompose (hydrolyze / polycondensate) the peroxotitanic acid. Further, the substrate was heated at 300 ° C. for 30 minutes to decompose and anneal the hydroxypropylcellulose to form a titanium oxide semiconductor film (A).

Table 1 shows the thickness of the obtained titanium oxide semiconductor film (A), the pore volume and the average pore diameter determined by the nitrogen adsorption method. Adsorption of spectral sensitizing dye Concentration of ruthenium complex represented by cis- (SCN ⁻ ) -bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) as spectral sensitizing dye 3 × A 10 ^-4 mol / l ethanol solution was prepared. This spectral sensitizing dye solution was applied onto the titanium oxide semiconductor film (A) using an rpm100 spinner and dried. This coating and drying process was performed five times. The adsorption amount of the spectral sensitizing dye on the obtained titanium oxide semiconductor film is determined by the specific surface area 1c of the titanium oxide film (A).
Table 1 shows the adsorption amount per m ² . The increase in weight of the semiconductor film after coating and drying was taken as the amount of adsorption. Preparation of Photoelectric Cell First, tetrapropylammonium iodide and iodine were added to a solvent in which acetonitrile and ethylene carbonate were mixed at a volume ratio of 1: 4 as a solvent, and the respective concentrations were 0.46 mol / L and 0%. An electrolyte solution was prepared by dissolving so as to have a concentration of 0.06 mol / L.

The glass substrate (A) electrode provided with the ultraviolet shielding film and the visible light antireflection film prepared above was used as one electrode, and the other electrode was formed of fluorine-doped tin oxide as an electrode, on which platinum was supported. The transparent glass substrates thus prepared were arranged to face each other, the side surfaces were sealed with resin, the above-mentioned electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (A).

The following evaluation was performed on the obtained photoelectric cell. Performance evaluation (1) The photoelectric cell (A) was 100
By irradiating light having an intensity of W / m ² , Voc (voltage in an open circuit state), Joc (density of current flowing when a circuit is short-circuited), FF (fill factor) and η (conversion efficiency) were measured. The results are shown in the table.

Performance Evaluation (2) Eye Super UV Tester (Iwasaki Electric Co., Ltd .: 1) from a distance of 20 cm above the surface of the visible light antireflection film of the photoelectric cell (A).
(00 mW / cm ² ) for 10 hours, and Voc, Joc, FF and η were measured in the same manner as in the performance evaluation (1), and the results are shown in the table.

[0100]

[Example 2] Titanium oxide / iron oxide composite colloid (manufactured by Catalyst Kasei Kogyo Co., Ltd .;
A light emitting electric cell (B) was prepared in the same manner as in Example 1 except that 100 g of an average particle diameter of 25 nm and a concentration of 30% by weight was mixed to prepare and use a coating liquid (B) for forming an ultraviolet shielding film. , Performance evaluation (1) and performance evaluation (2).

Table 1 shows the results.

[0102]

Example 3 100 g of colloidal cerium oxide (manufactured by Kasei Kasei Kogyo Co., Ltd .: Sanver A, average particle diameter 18 nm, concentration 30% by weight) was mixed as ultraviolet shielding particles, and a coating liquid (C) for forming an ultraviolet shielding film was mixed. A photoelectric cell (C) was prepared in the same manner as in Example 1 except that
(1) and performance evaluation (2) were performed.

Table 1 shows the results.

[0104]

Example 4 Titanium oxide / zirconium oxide composite colloid (Sanvert Z, average particle diameter 20 nm, concentration 30% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.) 10 as ultraviolet shielding particles
A photovoltaic cell (D) was prepared in the same manner as in Example 1 except that 0 g was mixed to prepare and use a coating solution (D) for forming an ultraviolet shielding film, and a performance evaluation (1) and a performance evaluation (2) were performed. ).

Table 1 shows the results.

[0106]

Example 5 Preparation of Coating Solution for Forming Ultraviolet Shielding Film Titanium oxide colloid (HPW-15R, manufactured by Kasei Kagaku Kogyo KK, average particle diameter 15 nm, concentration 30) as ultraviolet shielding particles
(% By weight), passed through an ultrafiltration membrane, and the dispersion medium was replaced with ethanol. 50 g of this ethanol sol (solid content concentration 5% by weight) and acrylic resin (Hitachi Chemical
3 g of Hitaloid 1007) and a 1/1 (weight ratio) mixed solvent 47 of isopropanol and n-butanol.
g) and a coating solution for forming an ultraviolet shielding film (E)
Was prepared.

Preparation of Coating Solution for Forming Visible Light Anti-Reflection Film The dispersion liquid of inorganic compound particles having a solid content concentration of 20% by weight and having a hollow inside, which was used in Example 1, was replaced with ethanol. Was added to adjust the solid content concentration to 5% by weight, and 50 g of this was collected. 3 g of an acrylic resin (Hitaloid 1007, manufactured by Hitachi Chemical Co., Ltd.) and a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol were used. 47 g were sufficiently mixed to prepare a coating liquid (E) for forming a visible light antireflection film.

Glass with ultraviolet shielding film and visible light antireflection film
Preparation of Substrate While holding a transparent polyimide film substrate on which fluorine-doped tin oxide was formed as an electrode layer at 40 ° C., a coating solution (E) for forming an ultraviolet shielding film was applied to the opposite surface of the electrode by a bar coater method (spinner method). Under the conditions of 100 rpm and 90 seconds) so that the thickness of the ultraviolet shielding film becomes 100 nm and dried.

Next, on the ultraviolet shielding film,
The visible light antireflection film is applied by a bar coater method (100 rpm, 90 seconds by a spinner method) so as to have a thickness of 100 nm, dried, and heat-treated at 160 ° C. for 30 minutes to be subjected to ultraviolet shielding film / visible light. A glass substrate (E) with an antireflection film was prepared. The average reflectance and the luminous reflectance of the glass substrate (E) provided with an ultraviolet shielding film and a visible light antireflection film were measured.
Formation of a semiconductor film whose results are shown in Table 1. Then, the same coating liquid for forming a semiconductor film as used in Example 1 was applied onto the electrode surface of a transparent glass substrate provided with electrodes on which the above-mentioned ultraviolet shielding film and visible light antireflection film were formed. Coated, air dried and subsequently 6000 mJ / c using a low pressure mercury lamp
The semiconductor film was cured by irradiating ultraviolet rays of m ² to decompose the peroxoacid.

Further, the substrate was heated at 250 ° C. for 30 minutes to decompose and anneal hydroxypropylcellulose to form a titanium oxide semiconductor film (E). Table 1 shows the thickness of the obtained titanium oxide semiconductor film (E), the pore volume and the average pore diameter determined by the nitrogen adsorption method. Adsorption of Spectral Sensitizing Dye Next, as in Example 1, the spectral sensitizing dye (cis- (SCN)
A ruthenium complex represented by ^- )-bis (2,2'-bipyridyl-4,4'-dicarboxylate) ruthenium (II) was adsorbed. Table 1 shows the adsorption amount. Making the photovoltaic cell prepared polyimide film substrate electrode with ultraviolet shielding film and visible light anti-reflection film prepared above as one electrode, and as the other electrode formed fluorine-doped tin oxide as an electrode,
A transparent polyimide film substrate carrying platinum is placed on top of it, the sides are sealed with resin, the above-mentioned electrolyte solution is sealed between the electrodes, and the electrodes are connected with a lead wire. (E) was prepared, and performance evaluation (1) and performance evaluation (2) were performed in the same manner as in Example 1.

The results are shown in Table 1.

[0112]

Comparative Example 1 Preparation of Photoelectric Cell Example 1 was the same as Example 1 except that a transparent glass substrate formed with fluorine-doped tin oxide as an electrode without forming an ultraviolet shielding film and a visible light antireflection film was used. A photoelectric cell (F) was produced in the same manner as described above, performance evaluation (1) and performance evaluation (2) were performed, and the results are shown in the table.

[0113]

Comparative Example 2 Preparation of Photoelectric Cell In Example 5, a transparent polyimide film substrate formed with fluorine-doped tin oxide as an electrode without forming an ultraviolet shielding film and a visible light antireflection film was used as one electrode. A photoelectric cell (G) was produced in the same manner as in Example 5 except for the above, and performance evaluation (1) and performance evaluation (2) were performed.

Table 1 shows the results.

[0115]

[Table 1]

[Brief description of the drawings]

FIG. 1 shows a schematic cross-sectional view of one embodiment of the photoelectric cell of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Photoelectric cell 11 ... Transparent electrode layer 12 ... Semiconductor film 13 ... Electrode layer which has a reduction catalytic ability on the surface 14 ... Electrolyte 15 ... Visible light antireflection film 16 ... Ultraviolet shielding film P-1 , P-2 …… Substrate

Claims (4)

[Claims] An electrode layer (1) is provided on the surface, and said electrode layer (1)
A substrate (P-1) formed with a metal oxide semiconductor film (2) having a photosensitizer adsorbed on the surface, and a substrate (P-2) having an electrode layer (3) on the surface, the electrode The layer (1) and the electrode layer (3) are arranged so as to face each other, at least one of the substrate and the electrode layer has transparency, and the metal oxide semiconductor film (2) and the electrode layer (3)
And a photovoltaic cell comprising an electrolyte layer provided between at least one of a transparent substrate (P-1) and / or a substrate (P-2) and / or a visible light antireflection film on an outer surface of the substrate (P-2). An opto-electric cell, wherein an ultraviolet shielding film is formed. 2. A substrate having an ultraviolet shielding film having transparency (P-1).
2. The visible light anti-reflection film formed on the outer surface and formed on the ultraviolet light shielding film, and the visible light anti-reflection film has a refractive index lower than that of the ultraviolet light shielding film. 3. The photoelectric cell according to claim 1. 3. The method according to claim 1, wherein the ultraviolet shielding film is made of Ce, Fe, Ti, Sb,
Oxide particles of one or more metals selected from the group consisting of Zr and Zn, or composite oxide particles of two or more metals selected from the group consisting of Ce, Fe, Ti, Sb, Zr and Zn. The photoelectric cell according to claim 1 or 2, wherein: 4. The visible light anti-reflection film is obtained by applying and drying a coating solution for forming a visible light anti-reflection film, followed by heat treatment. The photovoltaic cell according to any one of claims 1 to 3, wherein the photovoltaic cell is obtained by applying a coating solution, drying and heating.