JP2005108807A - Solid type dye-sensitized element and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that enegry conversion efficiency is low since there is a leakage current between a P-type layer and a negative layer because of bad denseness of a short circuit prevention film formed of a solid type dye-sensitized element, and plastic material with low thermal resistance is not usable for board material since rapid thermal anealing is required to form the short circuit prevention film. <P>SOLUTION: Energy conversion efficiency is improved by forming a short circuit prevention film of a solid type dye-sensitized element with N-type conductive polymer having preciseness and flexibility, fullerene, endocyst fullerene, or N-type conductive polymer in which fullerene and endocyst fullerene are scattered. The short circuit prevention film is formed using a pressurization process, an electrostatic electrodeposition process or laser irradiation process in order to carry out the process in low temperature, thereby enabling to use a plastic board so that the solid type dye-sensitized element has a broader applicable field. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a solid-type dye-sensitized element and a method for producing the same.

Functional Materials June 2003 Vol.23 No.6 p.26-33 All-solid-state dye-sensitized solar cells using CuI Dye-sensitized solar cells are expected to be inexpensive and high-performance next-generation solar cells Yes. Wet solar cells that use iodine-based electrolytes have an energy conversion efficiency of around 10%, the highest energy conversion efficiency among dye-sensitized solar cells, but they are safe because they use electrolytes and corrosive iodine. Problems with durability have been pointed out. In order to solve this problem, research on solidification of the electrolytic solution portion is underway, but sufficient energy conversion efficiency has not been obtained as compared with wet processing.

FIG. 5 is a cross-sectional view of a conventional solid dye-sensitized solar cell. In the conventional solid dye-sensitized solar cell, a negative electrode 102 and a short-circuit prevention layer 103 made of TiO ₂ are laminated on a support substrate 101, and a porous material in which a Ru-based dye 105 is adsorbed on the short-circuit prevention layer 103. A TiO ₂ layer 104 is deposited, a CuI layer 106 is deposited so as to fill the pores of the porous TiO ₂ film 104, and a positive electrode 107 is stacked. The light entering through the transparent support substrate 101 is absorbed by the dye 105 and becomes excited. Electrons are injected from the dye into the porous TiO ₂ layer 104, which is an N-type semiconductor, and electrons flow from the negative electrode 102 to the positive electrode 107 via an external circuit. The dye that has released the electrons is in an oxidized state, but is reduced again by electrons flowing from the positive electrode 107 to CuI, which is a P-type semiconductor, and the power generation process is repeated. Since the porous TiO ₂ layer is used, the surface area of the dye to absorb light is large, and the energy conversion efficiency is increased. Part of the pores of the porous TiO ₂ layer 104 penetrates to the negative electrode 102, and when there is no short-circuit prevention layer 103, the CuI layer 106 and the negative electrode 102 which are P-type semiconductors are short-circuited, It will not function as a solar cell. Therefore, conventionally, a TiO ₂ thin film, which is an N-type semiconductor, is formed between the negative electrode 102 and the porous TiO ₂ layer 104 to prevent a short circuit (Non-Patent Document 1).

FIGS. 6 (a) to 6 (f) are cross-sectional views showing a conventional method for producing a solid dye-sensitized solar cell. A transparent negative electrode 102 made of ITO or the like is deposited on a support substrate 101 made of glass (FIG. 6 (a)). Next, a short-circuit prevention layer 103 made of a TiO ₂ film is deposited on the negative electrode 102 by spray pyrolysis from an ethanol solution of Ti (OPr) ₄ and acetylacetone (FIG. 6 (b)). Next, a gel-like liquid containing Ti (OPr) ₄ added with TiO ₂ fine particles is dropped on the short-circuit prevention layer 103 to grow a scab-like TiO ₂ lump, and further baked at 450 ° C. A TiO ₂ layer 104 is formed (FIG. 6 (c)). Next, the porous TiO ₂ layer 104 is immersed in a solution containing the Ru-based dye 105, and the dye 105 is adsorbed on the porous TiO ₂ layer 104 (FIG. 6 (d)). A CuI solution is dropped on the heated porous TiO ₂ layer 104 of the supporting substrate 101 until the porous TiO ₂ layer 104 is sufficiently covered with the CuI layer 106 (FIG. 6 (e)). A solar cell is completed by sandwiching a multilayer film consisting of a short-circuit prevention layer, porous TiO ₂ layer, dye, and CuI layer formed on the support substrate between the positive electrodes (Fig. 6 (f)).

Conventional solid-state dye-sensitized solar cells, due to the use of short-circuit preventing layer composed of TiO _2, to form an electrical conduction path between TiO ₂ particles are required heat treatment above 400 ° C.. For this reason, the film quality is fragile, and a sufficiently dense film cannot be formed. CuI permeated into the fine holes formed in the short-circuit prevention layer, and a minute current flowed between the CuI layer and the negative electrode, which hindered improvement in energy conversion efficiency.

  In addition, if the short-circuit prevention layer is made thick so that there is no hole in the short-circuit prevention layer, the short-circuit prevention layer functions as an internal resistance of the solar cell, which also causes a reduction in energy conversion efficiency.

  Further, since a heat treatment at 400 ° C. or higher is necessary, a solar cell could not be manufactured on a support substrate having low heat resistance such as plastic. Since the solar cell has to be manufactured on a substrate such as glass having no flexibility and weight, its use has been limited.

  A solid-type dye-sensitized element according to the present invention includes a support substrate, a first electrode layer disposed on the support substrate, an N-type conductive polymer, fullerene, or inclusion included on the first electrode layer. A short-circuit prevention layer made of fullerene, an N-type semiconductor layer made of a porous metal oxide layer disposed on the short-circuit prevention layer, a dye adsorbed on the surface of the N-type semiconductor layer, and the N-type semiconductor layer A P-type semiconductor layer disposed on the N-type semiconductor layer and a second electrode layer disposed on the P-type semiconductor layer.

(Function)
Short-circuit between the P-type semiconductor layer and the negative electrode can be prevented and the internal resistance of the solar cell can be reduced at the same time by using an N-type conductive polymer film with low resistivity and dense film quality as the material for the short-circuit prevention layer Therefore, energy conversion efficiency is improved.

  In addition, as a material for the short-circuit prevention layer, it is also possible to use a thin film in which fullerene and encapsulated fullerene are vapor-deposited instead of the N-type conductive polymer film. Fullerene or endohedral fullerene functions as an N-type semiconductor, has a dense film quality similar to the conductive polymer film, and has a lower resistivity, thereby further improving energy conversion efficiency.

According to the solid dye-sensitized solar cell of the present invention, the following effects can be obtained.
(1) Since it is a solid type, it is superior in terms of safety and durability as compared with wet solar cells.
(2) Since a short-circuit prevention layer having a small and dense resistivity can be formed even if it is thin, the short-circuit current of the solar cell is increased by 1.5 to 3 times compared to the conventional solid-type dye-sensitized solar cell, and the energy conversion of the solar cell Efficiency is improved.
(3) Since a solar cell can be produced at room temperature or at a low temperature of 100 ° C. or lower, a substrate having low heat resistance such as plastic can be used. Light and thin film-type solar cells can be manufactured, enabling applications in residential windows and mobile phones. Further, since a roll-to-roll manufacturing process can be used, the manufacturing cost can be greatly reduced.
(4) The use of polyethylene terephthalate, polyetherimide, or polyethersulfone widely used for plastic bottles or the like as a material for the plastic substrate is effective in reducing raw material costs.
(5) By using a flexible material for the short-circuit prevention layer, a fibrous solid-type dye-sensitized solar cell can be produced.

If a fibrous solid dye-sensitized solar cell is produced according to the present invention, the following effects can be further obtained.
(6) Since light from any angle can be received and converted into electrical energy, energy conversion efficiency is high.
(7) Since a fabric-like solar cell can be produced by processing a fibrous solar cell, a large-area solar cell can be produced regardless of the scale of the production facility.
(8) Since fiber or cloth solar cells are flexible, they have various uses such as tents, umbrellas and clothes having the functions of solar cells.

  As a material for the short-circuit prevention layer, an N-type conductive polymer in which fullerene or encapsulated fullerene is dispersed can be used instead of the N-type conductive polymer film. The resistivity of the N-type conductive polymer can be lowered by doping fullerene or endohedral fullerene.

FIG. 1 is a cross-sectional view of a solid dye-sensitized solar cell according to a first embodiment of the present invention. In the solid dye-sensitized solar cell according to the first embodiment of the present invention, a short-circuit preventing layer 3 made of an N-type conductive polymer in which a negative electrode 2 and an inclusion fullerene are dispersed is laminated on a support substrate 1. The porous TiO ₂ layer 4 adsorbing the Ru-based dye 5 is deposited on the short-circuit prevention layer 3, the CuI layer 6 is deposited so as to fill the pores of the porous TiO ₂ layer 4, and the positive electrode 7 is formed. It has a stacked structure.

2 (a) to 2 (f) are cross-sectional views showing a method for producing a solid dye-sensitized solar cell according to the first embodiment of the present invention. As the support substrate 1 and the negative electrode 2, a glass substrate on which an FTO (fluorine-doped tin oxide) thin film to be a transparent electrode is deposited is used. In addition, ITO (indium oxide-tin oxide) and ATO (tin oxide-antimony oxide) can be used as the transparent electrode (FIG. 2 (a)). Next, the short-circuit prevention layer 3 made of an N-type conductive polymer in which the endohedral fullerene is dispersed is coated by dipping, vapor deposition, plating, etc. (FIG. 2 (b)). For example, as an N-type conductive polymer, any one of polyparaphenylene, polythiophene, and poly (3-methylthiophene) dopants of Na, K, Ca, AsF ₅ / AsF ₃ , or ClO ₄ ⁻ is used. use. Next, a porous TiO ₂ layer is formed on the short-circuit prevention layer 3 by press-pressing TiO ₂ nanoparticles at a pressure of about 1 × 10 ⁵ Pa to 1 × 10 ⁶ Pa (FIG. 2 (c)). ). Next, the porous TiO ₂ layer 4 is immersed in a solution containing the Ru-based dye 5 and the dye 105 is adsorbed on the porous TiO ₂ layer 4 (FIG. 2 (d)). As the dye 5, a coumarin dye can be used instead of an expensive Ru dye. A CuI solution is dropped on the porous TiO ₂ layer 4 of the heated support substrate 1 until the porous TiO ₂ layer 4 is sufficiently covered with the CuI layer 6 (FIG. 2 (e)). A solar cell is completed by sandwiching a multilayer film composed of a negative electrode 2, a short-circuit prevention layer 3, a porous TiO ₂ layer 4, a dye 5 and a CuI layer 6 formed on the support substrate 1 between the positive electrodes 7 (FIG. 2). (F)).

As a method for depositing the porous TiO ₂ layer 4 at room temperature or at a low temperature of 100 ° C. or lower, an electrostatic electrodeposition method or a laser irradiation method can be used in addition to the pressure press method. In the case of using the electrostatic electrodeposition method, immersing the film substrate in the TiO ₂ nanoparticle suspension of TiO ₂ nanoparticles is deposited on the film substrate by applying an electric field to the film substrate. In the case of using the laser irradiation method, the TiO ₂ nanoparticle suspension is applied on the coated substrate, and then the laser is irradiated to densify the TiO ₂ thin film.

As the short-circuit prevention layer, it is also possible to use a thin film in which fullerene or encapsulated fullerene is deposited. Fullerenes or endohedral fullerenes have the property of depriving electrons when absorbing light, resulting in excessive electrons, and transporting electrons by hopping, and function as N-type semiconductors. For example, an endohedral fullerene composed of C ₆₀ encapsulating Na is heated to 500 to 600 ° C. in a vacuum chamber to be sublimated and deposited on a coated substrate. Since the coated substrate itself does not exceed 100 ° C., it can be deposited on a substrate having low heat resistance. The vapor deposition film of the endohedral fullerene is suitable for the short-circuit prevention layer of the dye-sensitized solar cell because it is dense and flexible, and has a low resistivity, like the conductive polymer film.

  In addition, as the short-circuit prevention layer, a thin film made of an N-type conductive polymer in which fullerene or endohedral fullerene is dispersed can be used. The resistivity of the N-type conductive polymer can be lowered by doping fullerene or endohedral fullerene.

  In addition, the thickness of the short-circuit prevention layer is preferably 10 nm or more and 200 nm or less. When the thickness of the short-circuit prevention layer is less than 10 nm, the short-circuit prevention layer itself becomes brittle, so that a leak current easily flows between the P-type semiconductor layer and the negative electrode, and the energy conversion efficiency is drastically reduced. A problem occurs. Further, when the thickness of the short-circuit prevention layer is greater than 200 nm, the short-circuit prevention layer functions as a filter. Even in this case, the energy conversion efficiency of the dye-sensitized element is greatly reduced because the proportion of incident light absorbed by the short-circuit prevention layer increases and the amount of light absorbed by the dye-sensitized element decreases. The problem occurs. By setting the thickness of the short-circuit prevention layer to 10 nm or more and 200 nm or less, the film quality of the short-circuit prevention layer can be made dense, and absorption of incident light by the short-circuit prevention layer can be minimized. Compared with a solid-state dye-sensitized element, the energy conversion efficiency can be greatly improved.

According to the present invention, a plastic substrate having low heat resistance is used as the support substrate 1 because a low-temperature process such as pressure pressing, electrostatic electrodeposition, or laser irradiation is used to form the porous TiO ₂ film 4. Can be used. The use of polyethylene terephthalate (PET), polyetherimide (PEI), polyethersulfone (PES), etc., which are widely used for plastic bottles and the like as a plastic substrate, is effective in reducing raw material costs.

FIG. 3 is a perspective view of a solid dye-sensitized solar cell according to the second embodiment of the present invention. The solid-type dye-sensitized solar cell according to the second embodiment of the present invention has a negative electrode wire 8 made of a conductive polymer and a short-circuit prevention film 9 made of an N-type conductive polymer in which encapsulated fullerene is dispersed. Then, the porous TiO ₂ film 10 adsorbing the Ru-based dye 11 is coated on the short-circuit prevention film 9, and the CuI film 12 is coated so as to fill the pores of the porous TiO ₂ film 10. The positive electrode film 13 made of a conductive polymer is coated thereon.

For example, the material of the negative electrode line 8 or the positive electrode film 13 is any one of polyacetylene, polyacene, oligoacene, polythiazyl, polythiophene, poly (3-alkylthiophene), oligothiophene, polypyrrole, polyaniline, and polyphenylene. Use materials. The N-type conductive polymer material for the short-circuit prevention film 9 includes any one of Na, K, Ca, AsF ₅ / AsF ₃ , or polyparaphenylene doped with ClO ₄ ⁻ , polythiophene, or poly (3-methylthiophene). Use one material.

  In the embodiment, a conductive polymer is used as the material of the negative electrode wire 8, but it is also possible to use a conductive fiber such as a highly conductive graphite fiber, a copper wire, a silver wire, or an aluminum wire. Moreover, it is also possible to use a fiber having a hollow region as the conductive fiber that becomes the negative electrode wire 8. When a fiber having a hollow region is used, the linear solar cell can be made lighter. Furthermore, it is also possible to use fibers coated with a conductive film. For example, PET fiber, polyester fiber, acrylic fiber, or nylon fiber is used as the fiber material coated with the conductive film. The fiber material is not limited to an insulator material, and a semiconductor material or a conductor material can also be used. As the conductive film for coating the fibers, a thin film made of a metal, an alloy, or a metal compound is used. Further, when a polymer organic material is used as the material of the conductive fiber that becomes the center of the linear solar cell, it is preferable to mix fullerene or encapsulated fullerene in the conductor region. As the fullerene, Cn (n = 60 to 80) is preferable. The endohedral atoms of the endohedral fullerene are preferably Na, Li, H, N, and F.

In addition, as a method of coating the conductive film on the fiber, any one of the following methods is used.
1) Cu, Ni, or an alloy of Cu and Ni is coated on the fiber by an electroless plating method.
2) Al or Ag is vapor-deposited on the fiber.
3) Copper sulfide is chemically bonded onto the fiber.

4 (a) to 4 (f) are perspective views showing a method for manufacturing a solid dye-sensitized solar cell according to the second embodiment of the present invention. Using the negative electrode wire 8 as a supporting material (FIG. 4 (a)), a short-circuit prevention film 9 made of an N-type conductive polymer in which the endohedral fullerene is dispersed is dipped, vapor-deposited and plated on the negative electrode wire 8 (Fig. 4 (b)). Next, TiO ₂ nanoparticles are electrodeposited on the short-circuit prevention film 9 by an electrostatic electrodeposition method to form a porous TiO ₂ film 10 (FIG. 4 (c)). Next, the support material is immersed in a solution containing the Ru-based dye 5, and the dye 11 is adsorbed to the porous TiO ₂ film 10 (FIG. 4 (d)). Further, the CuI film is coated by dipping, vapor deposition, plating, or the like until the porous TiO ₂ film 10 is sufficiently covered with the CuI film 12 (FIG. 4 (e)). Next, the positive electrode film 13 is coated on the CuI film 12 by dipping, vapor deposition, plating or the like to complete the solar cell (FIG. 4 (f)).

(Measurement Example 1)
FIG. 7 shows data obtained by measuring photoelectric conversion characteristics of a conventional dye-sensitized solar cell and the dye-sensitized solar cell of the present invention. The solar cell used for the measurement of photoelectric conversion characteristics was prepared by the method described below.

Conventional Solar Cell Manufacturing Method (1) Preparation of Substrate, Formation of Negative Electrode: A transparent quartz glass substrate (30 mm × 30 mm) having a thickness of 0.5 mm was prepared. Further, an ITO film having a thickness of 340 mm was formed on the prepared glass substrate by sputtering. The ITO film on the glass substrate was used as the negative electrode of the solar cell. The transparent glass substrate side was used as a light receiving part of the solar cell.
(2) Formation of a short-circuit prevention layer: A titanium oxide film serving as a short-circuit prevention layer was deposited on the ITO film by a thickness of 0.5 mm from an ethanol solution of Ti (OPr) ₄ and acetylacetone by spray pyrolysis.
(3) Formation of N-type semiconductor layer: Titanium conversion titanium oxide powder (average particle size 30 nm) was prepared, and titanium powder was dissolved in a gel-like liquid containing Ti (OPr) ₄ . Next, a gel-like liquid in which titanium oxide powder was dissolved was dropped on the titanium oxide film on the substrate to grow a scab-like titanium oxide lump, and an N-type semiconductor layer was deposited. Further, in order to make the film quality of the short-circuit prevention layer made of titanium oxide dense, heat treatment was performed in a heating oven at 450 ° C. for 30 minutes.
(4) Dye adsorption: A Sigma Ru complex was dissolved in chloroform at a concentration of 2.8 × 10 ⁻⁴ mol / l to prepare a Ru complex solution. The substrate on which the N-type semiconductor layer was formed was immersed in a prepared Ru complex solution for 30 hours and then dried to adsorb the Ru complex on titanium oxide.
(5) Formation of P-type semiconductor layer: A CuI solution was dropped onto a substrate adsorbing a dye (Ru-based dye) composed of a Ru complex to form a P-type semiconductor layer.
(6) Formation of positive electrode: An ITO electrode (30 mm × 30 mm) serving as the positive electrode of the solar cell was placed on the substrate to complete a solid dye-sensitized solar cell.

Manufacturing method of solar cell of the present invention (1) Preparation of substrate and formation of negative electrode: A PET film substrate (30 mm × 30 mm) with ITO having a thickness of 125 μm and made by Oji Tobi was prepared. The ITO film on the PET film substrate functions as the negative electrode of the solar cell. The PET film substrate and the ITO film are transparent, and the negative electrode side is the light receiving part of the solar cell.
(2) Formation of short-circuit prevention layer: A PET film substrate was placed in a vacuum chamber of a resistance heating type vapor deposition apparatus, and the inside of the chamber was depressurized to a vacuum degree of 2 × 10 ⁻⁶ Torr. As an evaporation source, 50 mg of powdered Na-encapsulated fullerene (Na @ C ₆₀ ) was prepared. The evaporation source was heated to about 600 ° C., and an inclusion fullerene film functioning as a short-circuit prevention layer of the solar cell was deposited on the PET film substrate. An endohedral fullerene film having a thickness of about 50 nm was deposited by vapor deposition for 30 seconds. During the vapor deposition process, the temperature of the PET film substrate is maintained at a temperature from 20 ° C. to 50 ° C., and the PET film substrate is not altered or deformed.
(3) Formation of N-type semiconductor layer: Titanium conversion titanium oxide powder (average particle size 30 nm) was prepared, and titanium powder was dissolved in a gel-like liquid containing Ti (OPr) ₄ . Next, a gel-like liquid in which the titanium oxide powder was dissolved was dropped onto the titanium oxide film on the substrate to grow a scab-like titanium oxide lump. In addition, two pressure plates were prepared by laminating a Teflon sheet (registered trademark), silicon rubber, and a metal plate (made of brass). A PET film substrate on which titanium oxide and a short-circuit prevention layer were placed was sandwiched between two pressure plates, and the pressure was increased to 4.9 × 10 ⁵ Pa by screwing. In a pressurized state, the substrate was heated in an oven at about 90 ° C. in a nitrogen atmosphere for 60 hours to adhere titanium oxide powder onto the substrate to form an N-type semiconductor layer made of titanium oxide. According to the manufacturing method of the present invention, since a heat treatment at 400 ° C. or higher including a heat treatment for densifying the short-circuit prevention layer is unnecessary, it is possible to use a substrate having low heat resistance.
(4) Dye adsorption: A Sigma Ru complex was dissolved in chloroform at a concentration of 2.8 × 10 ⁻⁴ mol / l to prepare a Ru complex solution. The substrate on which the N-type semiconductor layer was formed was immersed in a prepared Ru complex solution for 30 hours and then dried to adsorb the Ru complex on titanium oxide.
(5) Formation of P-type semiconductor layer: A CuI solution was dropped onto a substrate adsorbing a dye (Ru-based dye) composed of a Ru complex to form a P-type semiconductor layer.
(6) Formation of positive electrode: An ITO electrode (30 mm × 30 mm) serving as the positive electrode of the solar cell was placed on the substrate to complete a solid dye-sensitized solar cell.

  The solar cell created by the above method is irradiated with light with a central wavelength of 700 nm and light intensity of 3 mW from the negative electrode side by a halogen lamp, and the IV characteristics between the positive electrode and the negative electrode of the solar cell are measured by semiconductor parameters. Measured with an instrument (Agilent 4155). A black drawing paper having a square hole with a side of 1 cm was pasted on the surface of the substrate so that the irradiation area irradiated with light was the same in both the conventional solar cell and the solar cell of the present invention.

As shown in the measurement data in FIG. 7, regarding the electromotive force, both the conventional solar cell and the solar cell of the present invention are about 0.6 V, but when comparing the short-circuit current, the conventional solar cell is − 0.4 mA / cm ^2, to the light irradiation of the same intensity towards the solar cell of the solar cell of the present invention present invention as -0.65mA / cm ^2, it can be about 1.6 times the current flow.

  As a result of measuring the short-circuit current for a plurality of cells and comparing it with the measurement data of the conventional solar cell, the solar cell of the present invention according to measurement example 1 is 1.5 times to 3.0 times the conventional solar cell. It was found that a short-circuit current of.

(Measurement Example 2)
As a short-circuit prevention layer, a photovoltaic cell was prepared using a coating film in which an endohedral fullerene was dispersed in an N-type conductive polymer instead of a vapor deposition film of the endohedral fullerene, and was subjected to photoelectric conversion characteristics by the same measurement method as in Measurement Example 1. Was measured. Regarding the preparation of the substrate, the formation of the negative electrode, the formation of the N-type semiconductor layer, the adsorption of the dye, the formation of the P-type semiconductor layer, and the formation of the positive electrode, the manufacturing method of the solar cell of the present invention described in Measurement Example 1 Created by the same method.

The method for creating the short-circuit prevention layer in Measurement Example 2 is as follows.
Formation of short-circuit preventing layer: Aldrich polypyrrole (product number 53,057-3) was prepared as an N-type conductive polymer. Powdered Na-encapsulated fullerene (Na @ C60) was dispersed in a conductive polymer composed of polypyrrole at a weight ratio of 10 wt%, and a short-circuit prevention layer having a thickness of 100 nm was formed on the ITO film by a coating method.

  Further, an N-type semiconductor layer, dye adsorption, a P-type semiconductor layer, and a positive electrode were formed on the short-circuit prevention layer to complete a solar battery cell according to Measurement Example 2 of the present invention.

  In Measurement Example 2, the short-circuit current of the solar cell was measured by the same measurement method as in Measurement Example 1, and as compared with the conventional solar cell, 1.5 times to 3.0 times as in Measurement Example 1. It was found that a short-circuit current can flow.

It is sectional drawing of the solid-type dye-sensitized solar cell which concerns on the 1st Example of this invention. (a) thru | or (f) is sectional drawing which shows the manufacturing method of the solid-type dye-sensitized solar cell which concerns on the 1st Example of this invention. It is a perspective view of the solid-type dye-sensitized solar cell which concerns on the 2nd Example of this invention. (a) thru | or (f) is a perspective view which shows the manufacturing method of the solid-type dye-sensitized solar cell which concerns on the 2nd Example of this invention. It is sectional drawing of the conventional solid type dye-sensitized solar cell. (a) thru | or (f) is sectional drawing which shows the manufacturing method of the conventional solid type dye-sensitized solar cell. It is measurement data of the photoelectric conversion characteristic of a solid dye-sensitized solar cell.

Explanation of symbols

1, 101 Support substrate
2, 102 Negative electrode 3, 103 Short-circuit prevention layer 4, 104 Porous TiO ₂ layer 5, 105 Ru-based dye 6, 106 CuI layer 7, 107 Positive electrode 8 Negative electrode wire
9 Short-circuit prevention film 10 Porous TiO ₂ film 11 Ru-based dye 12 CuI film 13 Positive electrode film

Claims (15)

A support substrate, a first electrode layer disposed on the support substrate, an N-type conductive polymer, fullerene, or an endohedral fullerene disposed on the first electrode layer; and the short-circuit prevention layer. An N-type semiconductor layer composed of a porous metal oxide layer disposed on the surface, a dye adsorbed on the surface of the N-type semiconductor layer, and a hole portion of the N-type semiconductor layer embedded in the N-type semiconductor layer A solid-state dye-sensitized element comprising a P-type semiconductor layer disposed on the P-type semiconductor layer and a second electrode layer disposed on the P-type semiconductor layer. The solid-state dye-sensitized element according to claim 1, wherein the short-circuit preventing layer is made of an N-type conductive polymer in which fullerene or encapsulated fullerene is dispersed. 3. The solid-state dye-sensitized element according to claim 1, wherein the N-type semiconductor layer is made of TiO ₂ and the P-type semiconductor layer is made of CuI. 4. The solid dye sensitizing element according to claim 1, wherein the supporting substrate is made of a plastic material. 5. The solid dye-sensitized element according to claim 4, wherein the support substrate is made of polyethylene terephthalate, polyetherimide, or polyethersulfone. The solid-state dye-sensitized element according to any one of claims 1 to 5, wherein the short-circuit preventing layer has a thickness of 10 nm or more and 200 nm or less. A step of depositing a short-circuit prevention layer on the support substrate on which the first electrode layer is deposited by vapor deposition, coating, dipping, spin coating, or plating; A step of depositing an N-type semiconductor layer by an electrodeposition method or a laser irradiation method, a step of adsorbing the dye on the N-type semiconductor layer, and a step of depositing the P-type semiconductor layer on the N-type semiconductor layer And by placing a second electrode film on the P-type semiconductor layer, a multilayer structure comprising the first electrode layer, the short-circuit prevention layer, the N-type semiconductor layer, and the P-type semiconductor layer is formed on the support substrate and the P-type semiconductor layer. A method for producing a solid-state dye-sensitized element comprising a step of sandwiching by a second electrode film. A first electrode wire, a short-circuit prevention film made of an N-type conductive polymer, fullerene, or an inclusion fullerene disposed around the first electrode wire, and a porous metal oxide disposed around the short-circuit prevention film An N-type semiconductor film composed of a film, a dye adsorbed on the surface of the N-type semiconductor film, a P-type semiconductor film disposed on the N-type semiconductor film by filling a hole in the N-type semiconductor film, A solid-state dye-sensitized element comprising a second electrode film disposed around the P-type semiconductor film. The solid dye-sensitized element according to claim 8, wherein the first electrode wire is a fiber coated with a conductive film or a conductive fiber. The solid dye-sensitized element according to claim 9, wherein the first electrode wire is a conductive fiber having a hollow region. The solid-state dye-sensitized element according to claim 9, wherein the fiber coated with a conductive film is a fiber made of a conductor material, a semiconductor material, or an insulator material. The solid-state dye-sensitized element according to any one of claims 8 to 11, wherein the short-circuit prevention film is made of an N-type conductive polymer in which fullerene or endohedral fullerene is dispersed. 13. The solid type dye sensitizing element according to claim 8, wherein the N-type semiconductor film is made of TiO ₂ and the P-type semiconductor film is made of CuI. The solid-state dye-sensitized element according to any one of claims 8 to 13, wherein the short-circuit prevention layer has a thickness of 10 nm or more and 200 nm or less. Using the first electrode wire as a support material, a step of coating a short-circuit prevention film around the first electrode line by vapor deposition, coating, dipping, spin coating, or plating, and a pressure press on the short-circuit prevention film A step of coating an N-type semiconductor film by a method, an electrostatic electrodeposition method, or a laser irradiation method, a step of adsorbing the dye on the N-type semiconductor film, and a P-type semiconductor film on the N-type semiconductor film A method for producing a solid-state dye-sensitized element, which comprises a step of depositing and a step of coating a second electrode film on the P-type semiconductor film.

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