JP5655591B2 - Photoelectric conversion element - Google Patents

Description

  The present invention relates to a photoelectric conversion element for a dye-sensitized solar cell.

  As a next-generation solar cell, development of an organic solar cell that can be manufactured at a low temperature and at a lower cost is expected. Among organic solar cells, dye-sensitized solar cells have the potential to significantly reduce manufacturing costs, have the same performance as amorphous silicon solar cells, and can produce colored transparent solar cells. It has attracted particular attention because of its attractiveness not found in batteries.

  In general, a dye-sensitized solar cell includes a semiconductor electrode having a photoelectric conversion layer made of a semiconductor having a dye adsorbed on a conductive substrate, and a counter electrode having a catalyst layer provided on a conductive substrate provided oppositely. The electrolyte layer is held between the semiconductor electrode and the counter electrode. As the electrolyte layer, an iodine-based redox couple dissolved in an organic solvent is generally used. Iodine-based redox couples have excellent performance, such as high ion conductivity and a high rate of reducing oxidized dyes, while low reactivity on the conductive glass surface and titanium oxide surface of the working electrode. ing.

However, iodine-based electrolytes can obtain high conversion efficiency, but have the following problems.
-It is very difficult to seal because of its high volatility.
-Since it has high corrosivity, the material which can be used as an electrode is limited.
・ Iodine-based redox couples have a very large absorbance coefficient in the visible light region, impeding the light absorption of the dye, causing performance degradation, and when emphasizing the design of solar cells, the iodine color This prevents the vividness of the pigment from being fully utilized.

Thus, although the iodine-based redox couple has high performance as a redox couple, it also has drawbacks, so a redox couple that replaces the iodine-based one is required. For example, bromine-based, sulfur-based, selenium-based, Redox couples such as iron complex system, cobalt complex system, benzoquinone / hydroquinone system, (SCN) ⁻ / (SCN) ₂ , (SeCN) ⁻ / (SeCN) ₂ system have been proposed. However, it is difficult to say that the practicality is high because the change efficiency is low and there are problems in stability and safety.

  On the other hand, nitrile solvents such as acetonitrile and carbonate solvents such as propylene carbonate are usually used when preparing charge transport materials, but there are problems with long-term stability and low reliability due to volatilization and liquid leakage. In order to improve durability and reliability, the charge transport liquid is made non-volatile or pseudo-solid. For example, Patent Document 1 proposes that the electrolyte layer be a nanocomposite gel composed of an electrolytic solution and fine particles having substantially the same refractive index as the electrolytic solution.

JP 2007-200808 A

  However, in Patent Document 1, an iodine-based redox pair is used as the redox pair, and there is a problem in color. Therefore, an object of the present invention is to provide a photoelectric conversion element suitable for a solar cell, which suppresses light absorption of a dye, does not impair color, and has high efficiency and excellent design properties and high stability.

In order to solve the above problems, the present invention provides the following photoelectric conversion element.
(1) A photoelectric conversion element comprising a semiconductor electrode, a counter electrode, and an electrolyte layer held between the two electrodes,
Wherein the electrolyte layer is a compound represented by the following general redox pairs 2,5-di -t- butyl Benzokino down及 beauty 2,5-di -t- butyl Hidorokino down both respectively 1.0MM～1.0M, as additives A photoelectric conversion element comprising 1.0 mM to 2.0 M of an ammonium salt having a basic skeleton represented by the formula (A) and being pseudo-solidified with a metal oxide.
_{^{NH 4 + X - ···· (A}} )
(Wherein, X ^- is a carboxylate ion)
(2) the metal _{oxide, SiO 2, TiO 2, SnO} 2, WO 2, ZnO 2, ITO, BaTiO 3, Nb 2 O 5, In 2 O 3, ZrO 2, Ta 2 O 5, La 2 O _{3, SrTiO 3, Y 2 O} 3, Ho 2 O 3, Bi 2 O 3, above, wherein at least one Tanedea Rukoto selected from the group consisting of CeO ₂ and _Al 2 _{O 3} (1) according Photoelectric conversion element.

  In the present invention, a hydroquinone / benzoquinone-based redox pair is used. However, compared with an iodine charge transport material, although coloring can be suppressed, there is a problem that power generation efficiency is inferior. Therefore, by adding a specific ammonium salt, it is possible to achieve high performance and stability as a charge transport material, and furthermore, it is possible to achieve a redox couple in which coloring is suppressed as compared with iodine. Moreover, durability is further increased by making the electrolyte layer pseudo-solid (nanocomposite gelation) with a metal oxide.

According to the present invention, 2,5-di -t- butyl Hidorokino on / 2,5-di -t- butyl Benzokino emissions contained in the electrolyte layer, the specific ammonium salt mixture charge transporting material, a high redox pairs In addition to performance and stability, it is lighter in color than iodine-based charge transport materials, so it does not impair the color of the photoelectric conversion element, is highly efficient and excellent in design, and the electrolyte layer is made of metal oxide. Due to the quasi-solidification, a photoelectric conversion element with higher durability can be provided.

It is sectional drawing which shows a photoelectric conversion element.

  Hereinafter, the photoelectric conversion element of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view showing a photoelectric conversion element A. A semiconductor electrode 8 in which a transparent conductive film 2 is formed on one surface of a transparent substrate 1 and a semiconductor layer 3 is further integrated on the surface, and an electrode substrate A counter electrode 9 having a catalyst layer 6 formed on one surface of the material 7 is arranged so as to be separated so that the transparent electrode film 2 and the catalyst layer 6 face each other, and between the semiconductor electrode 8 and the counter electrode 9. The electrolyte layer 5 is interposed. Further, the sensitizing dye 4 is adsorbed on the semiconductor layer 3. Below, each component is explained in detail.

[Transparent substrate 1]
As the transparent substrate 1, one that transmits visible light can be used, and transparent glass can be preferably used. Moreover, incident light can be utilized with high efficiency by processing the surface on the side where the transparent conductive film 2 is formed and scattering incident light. Moreover, not only glass but a plastic plate, a plastic film, etc. can be used if it transmits light.

  The thickness of the transparent substrate 1 is not particularly limited because it varies depending on the shape and usage conditions of the photoelectric conversion element A. For example, when glass or plastic is used, 1 mm to 1 cm in consideration of durability during actual use. The degree is preferable, flexibility is required, and when a plastic film or the like is used, about 1 μm to 1 mm is preferable.

[Transparent conductive film 2]
The transparent conductive film 2 can be made of a material that transmits visible light and has conductivity. An example of such a material is a metal oxide. Although not particularly limited, for example, tin oxide doped with fluorine (hereinafter abbreviated as “FTO”), indium oxide, a mixture of tin oxide and indium oxide (hereinafter abbreviated as “ITO”), antimony, and the like. Oxide-doped tin oxide, zinc oxide, and the like can be suitably used.

  In addition, an opaque conductive material can be used as long as visible light is transmitted through a treatment such as dispersion. Such materials include carbon materials and metals. Although it does not specifically limit as a carbon material, For example, graphite (graphite), carbon black, glassy carbon, a carbon nanotube, fullerene, etc. are mentioned. Further, the metal is not particularly limited, and examples thereof include platinum, gold, silver, ruthenium, copper, aluminum, nickel, cobalt, chromium, iron, molybdenum, titanium, tantalum, and alloys thereof.

  The thickness of the transparent conductive film 2 is not particularly limited because the conductivity varies depending on the material to be used, but is generally 0.01 μm to 5 μm, preferably 0.1 μm to 1 μm in the FTO coated glass generally used. It is. Further, the required conductivity varies depending on the area of the electrode to be used, and it is required that the wider the electrode, the lower the resistance. In general, the sheet resistance (surface resistivity) is 100Ω / □ or less, preferably 10Ω. / □ or less, more preferably 5Ω / □ or less. This sheet resistance is an electrical resistance value of a thin film or film-like substance, and its unit is Ω, but is conventionally described as “Ω / □ (ohm / square)” to indicate that it is a sheet. Since the thickness of the laminated body of the transparent substrate 1 and the transparent conductive film 2 or the thickness obtained by integrating the transparent substrate 1 and the transparent conductive film 2 varies depending on the shape and use conditions of the photoelectric conversion element A as described above. Although not particularly limited, it is generally about 1 μm to 1 cm.

[Semiconductor layer 3]
The semiconductor layer 3 is composed of a porous metal oxide semiconductor so that the sensitizing dye 4 can be adsorbed, but is not particularly limited, and examples thereof include titanium oxide, zinc oxide, tin oxide, and particularly titanium dioxide, Anatase type titanium dioxide is preferred. Further, it is desirable that the metal oxide has few grain boundaries in order to reduce the electric resistance value. Further, in order to adsorb more sensitizing dye 4, the semiconductor layer 3 preferably has a large specific surface area, specifically 10 to 200 m ² / g.

  Such a semiconductor layer 3 can be provided on the transparent conductive film 2 by a known method, and examples thereof include a sol-gel method, application of a dispersion paste, electrodeposition and electrodeposition. The thickness of the semiconductor layer 3 is not particularly limited because the optimum value varies depending on the oxide used, but is 0.1 μm to 50 μm, preferably 3 to 30 μm, and more preferably 5 to 15 μm.

[Sensitizing dye 4]
As the sensitizing dye 4, any dye that can be excited by sunlight and can inject electrons into the semiconductor layer 3 can be used, and dyes generally used in photoelectric conversion elements can be used, but the conversion efficiency is improved. For this purpose, it is desirable that the absorption spectrum overlaps with the sunlight spectrum in a wide wavelength range and has high light resistance. Examples of the sensitizing dye 4 include metal complex dyes such as ruthenium complexes, iron complexes, and copper complexes. Further examples include cyan dyes, porphyrin dyes, polyene dyes, coumarin dyes, cyanine dyes, squaric acid dyes, methine dyes, xanthene dyes, indoline dyes, and the like.

[Electrolyte layer 5]
The electrolyte layer 5, a 2,5-di -t- butyl Hidorokino in as redox couple in the present invention, a 2,5-di -t- butyl Benzokino emissions, ammonium salt represented by the following general formula (A) The composition is mixed.
_{^{NH 4 + X - ···· (A}} )
Wherein, X ^-, considering the solubility in organic solvents, acid dissociation constant is rather large, NH ₄ ⁺ acetate ions can exist stably, propionate ion, a carboxylic acid typified benzoate the ion.

  The concentration of the ammonium salt in the redox composition is in the range of 1.0 mM to 2.0 M with respect to the solvent. When the concentration is smaller than 1.0 mM, the effect of adding an ammonium salt is hardly obtained, and the conversion efficiency is hardly improved. On the other hand, even if the concentration is higher than 2.0M, the conversion efficiency is hardly improved, and ammonium salts may be precipitated in the solution due to solubility problems. A preferred concentration is 20 mM to 2.0 M.

The concentration of 2,5-di -t- butyl Hidorokino emissions of oxidized ring original composition in the range of 1.0mM~1.0M the solvent. When the concentration is smaller than 1.0 mM, the addition effect is hardly obtained, and the conversion efficiency is hardly improved. On the other hand, increasing the concentration from 1.0 M, the improvement of the conversion efficiency not only hardly observed, from 2,5-di -t- butyl Hidorokino down solubility problems, 2,5-di -t - there is a possibility that the butyl Hidorokino down will be precipitated in the solution. A preferred concentration is 10 mM to 1.0 M.

The concentration of 2,5-di -t- butyl Benzokino emissions of oxidized ring original composition in the range of 1.0mM~1.0M the solvent. When the concentration is smaller than 1.0 mM, the addition effect is hardly obtained, and the conversion efficiency is hardly improved. On the other hand, increasing the concentration from 1.0 M, the improvement of the conversion efficiency not only hardly observed, from 2,5-di -t- butyl Benzokino down solubility problems, 2,5-di -t - there is a possibility that the butyl Benzokino down will be precipitated in the solution. A preferred concentration is 10 mM to 1.0 M.

Further, 2,5-di -t- butyl Hidorokino emissions, 2,5-di -t- butyl Benzokino down, the mixing ratio of the ammonium salt is not particularly limited, 2,5-di -t- butyl Hidorokino Nmo Le Concentration the x, the molar concentration of 2,5-di -t- butyl Benzokino down y, when the molar concentration of ammonium salt is z, it is preferable to satisfy the following expression.
0.05 ≦ x / y ≦ 20, 0.5 ≦ (x + y) /z≦2.0

  The solvent for dissolving the redox couple is not particularly limited as long as it is a compound capable of dissolving the redox couple, and can be arbitrarily selected from a non-aqueous organic solvent, a room temperature molten salt, a protic organic solvent, and the like. In addition, the ammonium salt may be hardly soluble in an organic solvent. In that case, the ammonium salt can be dissolved by adding a carboxylic acid to the solvent.

  Examples of organic solvents include nitrile compounds such as acetonitrile, methoxyacetonitrile, parelonitrile, and 3-methoxypropionitrile, lactone compounds such as γ-butyllactone and parerolactone, carbonate compounds such as ethylene carbonate and propylene carbonate, dioxane, diethyl ether, and ethylene. Examples include glycol dialkyl ethers, ethers such as low-polymerization polyethylene glycol, alcohols such as methanol and ethanol, and dimethylformamide and imidazoles. Among them, acetonitrile, pareronitrile, 3-methoxypropionitrile, propylene carbonate, low Polymerization degree polyethylene glycol etc. can be used conveniently.

  As carboxylic acid, saturated carboxylic acid represented by formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, unsaturated carboxylic acid represented by acrylic acid, methacrylic acid, 2-ethylpropenoic acid, benzoic acid, Examples include aromatic carboxylic acids such as phthalic acid, hydroxy acids such as lactic acid, malic acid, and citric acid.

  The composition of the solvent only needs to dissolve the ammonium salt, but the conversion efficiency tends to decrease as the amount of the carboxylic acid component added increases. Therefore, the amount of the carboxylic acid component added is preferably as small as possible. When the ammonium salt is dissolved in the organic solvent used, it is not necessary to add a carboxylic acid component.

In addition, the electrolyte layer 5 is quasi-solidified to enhance durability and reliability. In the present invention, a nanocomposite gel is formed by dispersing metal oxide nanoparticles to form crosslinking points. The metal oxide is not limited as long as the charge transport liquid containing the redox _couple and the solvent can be gelled, and is SiO ₂ , TiO ₂ , SnO ₂ , WO ₂ , ZnO ₂ , ITO, BaTiO ₃ , Nb ₂ O. ₅ , metal oxides such as In ₂ O ₃ , ZrO ₂ , Ta ₂ O ₅ , La ₂ O ₃ , SrTiO ₃ , Y ₂ O ₃ , Ho ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ and Al ₂ O ₃ Is preferably used. These may be used alone or as a mixture of two or more. Although nano-particles can be made into microcomposite gels using polymer nanoparticles such as polymethyl methacrylate and polymethyl acrylate, and carbon-based materials such as carbon fibers and carbon nanotubes, the nanoparticles are used for reducing the color of the electrolyte layer 5. Since carbon must be colorless or white, a carbon-based material is not preferable. In addition, polymer nanoparticles are not preferred because of concerns about solubility in organic solvents.

  The smaller the particle size of the nanoparticles, the better, and 1 to 1000 nm is preferred. If the particle size is less than 1 nm, the production becomes difficult and the cost becomes high.

  The addition amount of the nanoparticles is an amount capable of gelling the charge transport liquid, but is preferably 5 to 70% by mass with respect to the weight of the charge transport liquid. If the addition amount is 5% by mass, the charge transport liquid cannot be sufficiently retained, and the electrolyte layer 5 cannot be quasi-solidified. On the other hand, if it exceeds 70 mass%, the charge transport liquid is completely solidified, and the transfer of electrons between the semiconductor electrode 8 and the counter electrode 9 does not proceed smoothly, and the change efficiency may be reduced.

  Furthermore, a lithium salt, an imidazolium salt, a quaternary ammonium salt, a room temperature molten salt, or the like can be added to the electrolyte layer 5 as a supporting electrolyte. These additives can be added to such an extent that the characteristics of the electrolyte layer are not impaired.

[Catalyst layer 6]
The catalyst layer 6 is not particularly limited as long as it has electrode characteristics capable of promptly proceeding with a reduction reaction for reducing the oxidized form of the redox couple in the electrolyte to a reduced form. , Heat treated materials, platinum catalyst electrodes deposited with platinum, carbon materials such as activated carbon, glassy carbon and carbon nanotubes, inorganic sulfur compounds such as cobalt sulfide, conductive polymers such as polythiophene, polypyrrole and polyaniline, etc. However, among them, a platinum catalyst electrode can be preferably used. The thickness of the catalyst layer 6 is suitably 5 nm to 5 μm, particularly preferably 50 nm to 2 μm.

[Electrode substrate 7]
Since the electrode substrate 7 is used as a support and a current collector of the catalyst layer 6, it is preferable that the surface portion has conductivity, for example, platinum, gold, silver, ruthenium, copper, aluminum as a metal, Nickel, cobalt, chromium, iron, molybdenum, titanium, tantalum, and alloys thereof, and carbon materials such as graphite, carbon black, glassy carbon, carbon nanotube, fullerene, etc., metal oxides such as FTO, ITO Indium oxide, zinc oxide, antimony oxide, or the like can be used. In addition, an insulator such as glass or plastic can be used if the surface is treated so as to have conductivity.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further, this invention is not restrict | limited at all by this.

(Preparation of photoelectric conversion element)
A photoelectric conversion element having the structure shown in FIG. 1 was produced as follows.

[Production of semiconductor electrode]
Cut the glass with ITO film (sputtered product) manufactured by Geomat Co., Ltd. into the required size, wash with glass cleaner, rinse the cleaner with pure water, then acetone, hexane, acetone, pure water, pure water in this order Then, ultrasonic cleaning was performed for 5 minutes each. After drying, finish cleaning was performed for 10 minutes using a UV ozone cleaner, and then immersed in an aqueous TiCl ₄ solution at 70 ° C. for 30 minutes. After immersion, the substrate was washed with pure water and dried well, and a TiO ₂ paste (Ti-Nanoxide D) was applied to the surface of the ITO film to a thickness of about 50 μm with a K control coater (manufactured by Matsuo Seisakusho). After standing and drying for about 30 minutes, firing was performed in the air in the order of 30 minutes at 80 ° C. and 30 minutes at 450 ° C. to obtain a semiconductor electrode having 10 μm thick porous titanium oxide.

[Adsorption of sensitizing dye]
As a sensitizing dye, cis-bis (isothiocyanato) bis (2,2′-pybilidyl-4,4′-dicarboxylate) ruthenium (II) (manufactured by Wako Pure Chemical Industries, Ltd.) called N3 was used. The dye solution was a 0.3 mM ethanol solution. And said semiconductor electrode was immersed in the pigment | dye solution, and it left still at about 40 degreeC under light-shielding for 3 hours. Thereafter, the excess pigment was washed with ethanol and air-dried.

[Preparation of counter electrode]
The counter electrode used was a platinum thin film layer deposited on a glass substrate. The thickness of the platinum thin film was about 200 nm.

(Electrolyte layer)
Ammonium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), ammonium benzoate (manufactured by Wako Pure Chemical Industries, Ltd.), 2,5-di-t-butylhydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.), 2, 5-di-t-butylbenzoquinone (manufactured by Wako Pure Chemical Industries, Ltd.), acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), benzoic acid (Wako Pure Chemical Industries, Ltd.) (Made by Co., Ltd.) and silicon dioxide (“silica gel # 200 (particle size: 12 nm)” manufactured by Nippon Aerosil Co., Ltd.) or titanium dioxide (“Ti-Nanoxide D (particle size: 13 nm) manufactured by SOLARONIX)” as a nanoparticle, The acetic acid and acetonitrile were frozen and degassed, and the benzoic acid was stored in a dry container purged with argon as it was.

  Specifically, ammonium acetate or ammonium benzoate was placed in a glass container that had been dried and purged with argon, acetic acid or 3-propiomethoxynitrile (3-MPN) was added, and the mixture was shaken until the solid was completely dissolved. Thereafter, 2,5-di-t-butylbenzoquinone and 2,5-di-t-butylhydroquinone were added to prepare a charge transport liquid. Next, nanoparticles were added to the charge transport liquid, and the mixture was sufficiently stirred and dehydrated using a planetary agitation / desorption apparatus to form a nanocomposite gel.

  In Comparative Examples 1 and 5, the nanoparticles were not added and the electrolyte layer was not gelled. The charge transport liquid in Comparative Example 6 is as shown in Table 2.

[Assembly of photoelectric conversion element]
An electrolyte layer was interposed between the semiconductor electrode and the counter electrode, and the side surfaces were sealed with an epoxy adhesive. This operation was performed in a glove box substituted with argon.

[Evaluation of photoelectric conversion element]
The photoelectric conversion element was evaluated using (1) a solar simulator. Pseudo sunlight used light of 100 mW / cm ² under AM1.5 conditions, and calculated photoelectric conversion characteristics by calculating conversion efficiency from open circuit voltage, short circuit current, and fill factor. (2) The conversion efficiency was measured again after 1000 hours of light irradiation, and the durability was evaluated from the relative ratio with the conversion efficiency immediately after assembly. Further, (3) the appearance of the electrolyte layer and the element was visually observed. The results are shown in Table 1.

  In each of Examples 1 to 7, since the electrolyte layer contains 2,5-di-t-butylbenzoquinone, 2,5-di-t-butylhydroquinone, and an ammonium salt, and is further nanocomposite gelled, 60 Even after light irradiation at 1000 ° C. for 1000 hours, no significant change appears in the photoelectric conversion specification, indicating excellent durability.

  Moreover, as shown in Examples 1-3 and Comparative Examples 1-3, sufficient durability cannot be obtained when the amount of silicon dioxide nanoparticles added is small (Comparative Example 2), but the addition of silicon dioxide nanoparticles. Durability improves as the amount increases (Examples 1 to 3). The conversion efficiency immediately after assembly is slightly improved as compared with the case where the silicon dioxide nanoparticles are not added (Comparative Example 1), which is considered to be an effect of promoting the charge transfer rate by the addition of the silicon dioxide nanoparticles. (Refer to “Fujikura Technique No. 107, October 2004, pp 73-78,“ Dye-enhanced Solar Cell Using Nanocomposite Ion Gel ”). However, if the amount of silicon dioxide nanoparticles added is excessive (Comparative Example 3), the charge transport liquid is not completely retained by the silicon dioxide nanoparticles, and the semiconductor electrode 3 and the counter electrode 9 are not Since the exchange of electrons with the counter electrode 9 is hindered, the conversion efficiency is greatly reduced.

  As shown in Examples 2, 4, and 5, the conversion efficiency increases as the concentration of each compound increases. However, when the concentration is too low as shown in Comparative Example 4, almost no improvement in conversion efficiency is seen, and when the concentration of each compound is too high as shown in Comparative Example 5, each compound is completely dissolved. The charge transport liquid cannot be prepared.

  As shown in Example 6, even when the type of nanoparticles is changed, the conversion efficiency and durability are improved.

  As shown in Example 7, when 3-methoxypropionitrile having a boiling point higher than that of acetonitrile is used as a solvent, the conversion efficiency is slightly reduced, but the durability is further improved.

  In Comparative Example 6 using a conventional iodine-based electrolyte, the conversion efficiency is higher than that of the present invention, but the dark brown of the iodine-based redox couple is mixed with the vivid color of the pigment, and the appearance of the photoelectric conversion element is dark brown The design has been greatly impaired. Moreover, even if it becomes nanocomposite gel, it turns out that there exists a problem also in durability.

  As described above, in the photoelectric conversion element of the present invention, the electrolyte layer has a conventional iodine-based redox couple, and is superior in durability and design (discoloration) than the electrolyte layer or non-gelled one. It can be seen that it is highly practical with excellent performance, durability, cost, and design.

A Photoelectric conversion element 1 Transparent substrate 2 Transparent conductive film 3 Semiconductor layer 4 Sensitizing dye 6 Catalyst layer 7 Electrode substrate 8 Semiconductor electrode 9 Counter electrode

Claims (2)

A photoelectric conversion element comprising a semiconductor electrode, a counter electrode, and an electrolyte layer held between the two electrodes,
Wherein the electrolyte layer is a compound represented by the following general redox pairs 2,5-di -t- butyl Benzokino down及 beauty 2,5-di -t- butyl Hidorokino down both respectively 1.0MM～1.0M, as additives A photoelectric conversion element comprising 1.0 mM to 2.0 M of an ammonium salt having a basic skeleton represented by the formula (A) and being pseudo-solidified with a metal oxide.
_{^{NH 4 + X - ···· (A}} )
(Wherein, X ^- is a carboxylate ion) The metal oxide is SiO ₂ , TiO ₂ , SnO ₂ , WO ₂ , ZnO ₂ , ITO, BaTiO ₃ , Nb ₂ O ₅ , In ₂ O ₃ , ZrO ₂ , Ta ₂ O ₅ , La ₂ O ₃ , SrTiO ₃ . _{3, Y 2 O 3, Ho} 2 O 3, Bi 2 O 3, the photoelectric conversion element according to claim 1 wherein at least one Tanedea wherein Rukoto selected from the group consisting of CeO ₂ and _Al 2 _{O 3.}

Images