JP2002111019A - Solid-state photoelectric converter, its manufacturing method, solar cell using solid state photoelectric converter and power source - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid-state photoelectric converter having a high energy conversion efficiency even in the case of a low light quantity, excellent long term stability, small restriction in element design, excellent in productivity, and suitable for reduction in size and weight, a method for manufacturing the same, a solar cell using the solid-state photoelectric converter and a power source. SOLUTION: The solid-state photoelectric converter comprises a transparent conductive electrode 5, an anatase-type titanium oxide 6, a photosensitizing compound 7, a hole transport layer, and a solid substance 8 used also as a hole collecting electrode.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid-state photoelectric conversion element containing a solid substance as a component, a solar cell using the element, a method for manufacturing the same, and an apparatus using the same.

[0002]

2. Description of the Related Art In recent years, there has been concern about the depletion of fossil fuel resources such as coal, oil, and natural gas, and global environmental problems such as global warming due to an increase in carbon dioxide and the like caused by their use have become apparent. I have. Solar power generation using a solar cell, which is a clean energy source, is one of the leading methods for solving these problems, and research and development of solar cells are being vigorously conducted.

[0003] Above all, a solar cell using silicon has a maximum energy conversion efficiency of about 20% in a single crystal silicon solar cell, a maximum energy conversion efficiency of 12 to 17% in a polycrystalline silicon solar cell, and an amorphous silicon solar cell. Energy conversion efficiency: 10-1
2.5% has been attained, and research and development for application to high power applications has become even more active.

[0004] However, in the current silicon-based solar cell, a large amount of energy is required to produce metal silicon as a raw material, so that the production cost is high.
Further, there is a problem that a period (energy payback time) required to recover energy required for manufacturing is long. Further, in silicon for solar cells, since the residual material from the process of manufacturing silicon for semiconductor is generally used, the absolute amount is limited and is influenced by demand trends in the semiconductor industry. In addition, it has been pointed out that an amorphous silicon solar cell has a shortage of silane gas supply required in the manufacturing process. In order to solve these problems, researches on compound semiconductors such as cadmium telluride and copper indium selenide have been actively conducted.

On the other hand, an organic solar cell using an organic substance,
Organic-inorganic hybrid solar cells combining organic and inorganic substances are expected to be cheaper and have a larger area, and research and development are being actively conducted. In recent years, a 100 mW / cm ² simulated solar cell has been developed for a wet photochemical cell comprising a photosensitized electrode having a ruthenium complex supported on an electrode surface having a pore structure formed by sintering titanium oxide fine particles, an electrolyte solution, and a counter electrode. Energy conversion efficiency of about 10% is achieved under light (JOURNAL OF
AMERICA CHEMICALSOCIETY
Vol. 115, No. 14, pp. 6382-6390, 199
3 years. NATURE Volume 353, 737-740
1991. ), This type of organic-inorganic hybrid solar cell is of interest.

However, since this type of solar cell is a wet type solar cell, there is a problem in long-term stable performance in terms of liquid leakage and the like. To solve this problem, a quasi-solid dye-sensitized solar cell in which the electrolyte solution is replaced with a gel electrolyte solution in which the electrolyte and the solvent are held by a small amount of a polymer component has been developed (S. Mikoshiba et al.). al., Th
e 16 ^th European photovolta
ic solar energy conference
e and exhibition, (2000-
5), Glasgow, Scotland. ), A solvent that dissolves the electrolyte is required, and there is a problem in terms of long-term stability. Attempts have been made to replace the electrolyte solution with a solid polymer electrolyte having ion conductivity or a π-conjugated polymer having electron conductivity as a solid electrolyte. As an example of a π-conjugated polymer, an attempt has been made to use doped polypyrrole as a solid electrolyte (CHEMISTRY LETTERS 4).
71-472, 1997).

However, when these polymers are used as a solid electrolyte, it is necessary to perform electrochemical polymerization under light irradiation and to electrochemically optimize the doping amount of a counter anion (dopant) in order to improve hole transportability. In addition, a complicated process is required in the manufacturing process of forming an electrode by depositing gold or the like as a counter electrode. In addition, the electrical connection of the doped π-conjugated polymer formed in the electrochemical polymerization in the solid and the electrical connection between the doped π-conjugated polymer solid and the gold counter electrode are insufficient. Exists.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high energy conversion efficiency even under a low light quantity, excellent long-term stability, less restrictions on element design, excellent productivity, and
An object of the present invention is to provide a solid-state photoelectric conversion element suitable for reduction in size and weight. Another object of the present invention is to provide a method for manufacturing a solid-state photoelectric conversion device that can easily manufacture the above-described solid-state photoelectric conversion device.

Another object of the present invention is to provide a solar cell and a power supply using the solid-state photoelectric conversion element.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the electrical connection in the solid electrolyte is good, the hole transport ability is sufficient, and the layer of the solid electrolyte itself is photosensitized. This layer can be used as a counter electrode by forming up to the upper part of the surface of the mold electrode, and the present invention has been completed by finding that an element having such a configuration is useful as a photoelectric conversion element such as a solar cell.

That is, a first gist of the present invention resides in a solid-state photoelectric conversion element having a solid substance which also functions as a hole transport layer and a hole current collecting electrode. A second gist of the present invention is that a solid material containing a metal oxide, a photosensitizing compound and a π-conjugated compound has a surface resistance of 10 ³ Ω / □ or less on the outermost surface of the solid material. A solid-state photoelectric conversion element. A third aspect of the present invention is characterized in that the single cell element is formed from one or more single cell elements, and the light transmittance when the light having a wavelength of 500 nm is applied to the single cell element is 5% or more. The solid-state photoelectric conversion element. According to a fourth aspect of the present invention, there is provided a solid-state photoelectric conversion device comprising a single cell or a plurality of single-cell elements, the single-cell element having flexibility with respect to at least two axes on an electrode plane. Exists in the element. Another gist of the present invention is that after impregnating a solution containing a π-conjugated compound and / or a complex compound composed of a conjugated compound and a metal element into pores of a metal oxide having a photosensitizing compound on its surface. There is provided a method for manufacturing a photoelectric conversion element, which comprises removing a solvent to form a solid substance layer containing a π-conjugated compound and / or a complex compound composed of a conjugated compound and a metal element up to the outermost surface. Another gist of the present invention is that a solution containing a monomer that forms a π-conjugated polymer, a polymerization catalyst, and a compound that reduces the polymerization rate is impregnated into pores of a metal oxide having a photosensitizing compound on its surface. There is provided a method for producing a photoelectric conversion element, characterized by forming a solid substance layer containing a π-conjugated polymer up to the outermost surface after polymerization.

Another aspect of the present invention resides in a solar cell using the solid-state photoelectric conversion element and a power supply using the solar cell.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A photoelectric conversion element is typically constructed as shown in FIG.
As shown in FIG. 1, an electron collecting electrode 1, an electron acceptor / electron transporting layer 2, an electron donor / hole transporting layer 3, a hole collecting electrode 4
Consists of In the photoelectric conversion device of the present invention, the electron donor / hole transport layer and the hole current collecting electrode are the same solid substance, and the electron donor / hole transport layer (hereinafter, simply referred to as hole transport layer) and the hole current collecting electrode are combined. The feature is that they can also be used. FIG. 2 is a schematic view of one embodiment of the solid-state photoelectric conversion element of the present invention. In FIG. 2, a solid substance 8 which is also used as a hole transport layer and a hole current collecting electrode is indicated by reference numeral 8.

As the electron collecting electrode used in the present invention, any known conductive material which is transparent to visible light can be used. For example, indium tin oxide, fluorine-doped Tin oxide and the like can be mentioned, and among them, fluorine-doped tin oxide is preferable. The thickness of the electron collecting electrode is preferably from 0.005 to 1 μm, more preferably from 0.01 to 0.1 μm.

The electron collecting electrode is preferably provided on a substrate made of a material transparent to visible light in order to maintain hardness, and the thickness of the substrate is preferably 0.01 to 20 m.
m, more preferably 0.1 to 5 mm. As a substrate transparent to visible light, for example, glass or a transparent polymer is used. As the electron acceptor / electron transport layer used in the present invention (hereinafter simply referred to as an electron transport layer), an electron transport layer formed by sintering oxide fine particles is preferably used. The oxide used for the electron transport layer is not particularly limited as long as it is an oxide that transmits visible light and has an electron transport ability.
Preferably titanium oxide, zirconium oxide, zinc oxide,
Metal oxides such as tin oxide and barium titanate are used, and more preferably, anatase type titanium oxide is used. The size of the fine particles is preferably from 5 nm to 100 nm, more preferably from 15 nm to 50 nm. When these oxide particles are sintered, a pore diameter of usually 2 to 20 nm is formed.

The thickness of the electron transport layer is 0.0
It is preferably from 1 to 5 μm, more preferably from 0.1 to 3 μm. The photoelectric conversion element of the present invention is provided with a dense electron transporting layer between the electron collecting electrode and the electron transporting layer, if necessary, to avoid direct contact between the electron collecting electrode and the hole transporting layer. You may. The dense electron transporting layer refers to an electron transporting layer having substantially no pores, and particularly if it has the same composition and crystal type as an electron transporting layer formed by sintering oxide fine particles. Not restricted.

As a preferred specific example, for example, a dense anatase-type titanium oxide film is provided between an electron collecting electrode and an electron transport layer having a pore structure formed by sintering anatase-type titanium oxide fine particles. When preparing the dense anatase type titanium oxide, using an ethanol solution of diisopropoxytitanium bisacetylacetonate,
A method of forming by a spray drying method is exemplified.

In the present invention, a charge separation layer is formed by adhering or fixing a photosensitizing compound on the surface of the electron transport layer obtained by sintering various oxide fine particles. The photosensitizing compound used as the charge separation layer is not particularly limited as long as it is a compound that is photoexcited by the excitation light used. Specifically, (cis-di (thiocyanic acid) -N, N′-bis (2 , 2 '
-Bipyridyl-4,4'-dicarboxylic acid) ruthenium complex dyes such as ruthenium (II), metal complexes of porphyrins and phthalocyanines, and organic dyes such as perylene dyes and eosin dyes. It is not something to be done. In addition, the mode of adhesion or fixation is as follows:
It is sufficient that the photosensitizing compound is present on the surface of the electron transporting layer, but it is preferable that the compound is chemically adsorbed.

Next, as the solid substance which also serves as an electron donor and hole transport layer (hereinafter simply referred to as a hole transport layer) and a hole current collecting electrode in the present invention, a substance having good hole transport ability is used. As such a substance, a π-conjugated compound is preferable from the viewpoint of hole transporting ability, and the π-conjugated compound has at least 4 or more, preferably 6 or more, more preferably 8 or more carbon atoms constituting conjugate. I just need. Of these, π-conjugated oligomers such as oligothiophene derivatives, oligoparaphenylene derivatives, oligopyrrole derivatives, oligoparaphenylene vinylene derivatives, and π such as polythiophene derivatives, polyparaphenylene derivatives, polypyrrole derivatives, and polyparaphenylene vinylene derivatives Conjugated polymers are preferred, but not limited thereto.

Among these, compounds having a thiophene skeleton as a structural unit are preferable from the viewpoint of hole transporting ability and production, and among them, an oligomer or a polymer having the following atomic group (1) is more preferable.

[0021]

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(In the formula (1), R ¹ and R ² are each independently
Hydrogen atom, halogen atom, alkyl group, alkoxy group,
Represents an alkylthio group, an alkylamino group, or a dialkylamino group, and these substituents may be bonded to each other to form a cyclic structure) Of the substituents represented by R ¹ and R ² , an alkoxy group is preferable, and among them, More preferably, the two alkoxy groups of R ¹ and R ² are bonded to form a cyclic structure.

As represented by the following general formula (2), the above-mentioned π-conjugated oligomer or π-conjugated polymer may be, for example, iron (III) chloride, iodine, iron (III) tris-p-toluenesulfonate. And the like.

[0024]

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(In the general formula (2), A ⁻ represents a counter anion derived from a dopant.) When a doped π-conjugated polymer is used, there is no particular limitation on the doping concentration, and the photosensitized electrode is fine. The doping concentration may be different between the π-conjugated polymer in the pore and the π-conjugated polymer in the upper part of the surface of the photosensitizing electrode. However, the π-conjugated polymer on the upper surface of the photosensitizing electrode is preferably in a highly doped state in order to function as a hole current collecting electrode. Specifically, when the concentration of the dopant is represented by the molar ratio of the dopant to the repeating unit of the π-conjugated polymer,
The concentration is preferably higher than 10: 1, and more preferably higher than 5: 1. Here, the doped π-conjugated polymer means a polymer having a cation site in a part of the main chain of the π-conjugated polymer due to the action of a dopant.

Further, the compound represented by the following formula (3) is an example of a structural unit forming a complex compound comprising a π-conjugated compound and a metal element used in the present invention.

[0027]

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The method for producing the photoelectric conversion element of the present invention will be described below. In manufacturing the photoelectric conversion element of the present invention,
In the pores of the electron transport layer and on the back side of the electron transport layer, as a method of introducing the above-described solid hole transport layer and hole collecting electrode, impregnated with a solution containing a π-conjugated compound or complex compound, or a monomer forming a π-conjugated polymer,
A method of impregnating a mixed solution containing a polymerization catalyst and, if necessary, a compound for reducing the polymerization rate, followed by polymerization, and removing the solvent to form a solid substance layer up to the outermost surface can be used.

In order to form a solid material layer up to the outermost surface, the operations of impregnation, polymerization and solvent removal may be repeated a plurality of times. Here, to form up to the outermost surface means that the oxide and the sensitizing compound that are the electron transport layer are
This means that the solid substance is formed until it is completely covered with the solid substance layer which is also a hole transport layer and a hole current collecting electrode. The solvent is a π-conjugated compound or complex compound, or π
There is no particular limitation as long as it dissolves the monomer that forms the conjugated polymer, the polymerization catalyst, and the compound that controls the polymerization rate. Preferred solvents include butanol, ethanol, acetonitrile and the like.

When impregnating the pores with the solution or the mixed solution under reduced pressure, the pressure is reduced while the photosensitizing electrode is immersed in the solution or the mixed solution, or the solution or the mixed solution is placed on the photosensitized electrode. The pressure may be reduced after the mixed solution is developed. The degree of vacuum at the time of pressure reduction may be at most atmospheric pressure, depending on the viscosity of the solution or the mixed solution, but is preferably 16,000 Pa or less, more preferably 1600 Pa or less. Although there is no particular lower limit for the degree of vacuum, it is preferably 100 Pa or more in view of the simplicity in production.

The compound that reduces the polymerization rate of the π-conjugated polymer is not particularly limited as long as it does not directly react with the monomer forming the π-conjugated polymer and reduces the polymerization rate. Specifically, a Lewis basic compound is used, and among them, a compound having a Lewis basic nitrogen atom or a Lewis basic sulfur atom is preferable, and a cyclic compound having a Lewis basic nitrogen atom such as imidazole is more preferable.

Further, when polymerizing a π-conjugated polymer, the polymer may be left at room temperature under reduced pressure or may be subjected to a heat treatment.
In order to form a solid layer up to the outermost surface of the electron transport layer, the above treatment may be repeated. In the present invention, a solution containing a π-conjugated compound or a complex compound, or a mixture containing a monomer that forms a π-conjugated polymer, a polymerization catalyst, and a compound that reduces the polymerization rate are contained in the pores of the oxide that is the electron transport layer. When the solution is impregnated with ultrasonic waves in the pores of the oxide, the oxide may be immersed in the solution or the mixed solution and ultrasonic waves may be applied. For the production, a thiophene compound as described below, preferably in an alcoholic solvent, in the presence of a Lewis basic compound such as imidazole, with a metal compound of a strong acid such as anhydrous tris-p-toluenesulfonate (III). It can be produced by reacting.

[0033]

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One embodiment of the solid-state photoelectric conversion device of the present invention will be described with reference to FIG. In this embodiment, the photoelectric conversion device of the present invention is formed from a solid material containing a metal oxide, a photosensitizing compound and a π-conjugated compound, and particularly has a photosensitizing compound on the surface of the metal oxide, It is preferable that the oxide has pores and at least a part of the pores has a π-conjugated compound. In the example of FIG. 2, a transparent conductive electrode (electron current collecting electrode) coated on a substrate such as glass is used.
5, an electron acceptor / electron transport layer 6 made of a metal oxide such as titanium oxide is provided, and a photosensitizing compound 7 is chemisorbed on a part of the electron transport layer. Then, a solid substance (π-conjugated compound) 8, which is a hole transport layer and a hole current collecting electrode, is provided so as to come into contact with the photosensitizing compound 7 and partially enter the pores of the titanium oxide 6. .

Therefore, the solid substance containing the metal oxide, the photosensitizing compound and the π-conjugated compound constituting the photoelectric conversion element of the present invention has a surface resistance of the outermost surface of the solid substance of 10 ³ Ω. / □ or less. The surface resistance is preferably 100Ω / □ or less, more preferably 50Ω / □ or less. The smaller the surface resistance is, the better.
Often Ω / □ or more.

Further, the photoelectric conversion element of the present invention can be formed transparent, though solid, by selecting a material as described in Examples. When the single-cell device is irradiated with light having a wavelength of 500 nm, which is high in sunlight, the device of the present invention has a transmittance of 5% of 500 nm light.
The above can be considered. In particular, when transparency is required,
The transmittance is preferably 10% or more, more preferably 20% or more. The transmittance is preferably higher, but it is necessary to absorb a substantial amount of light for photoelectric conversion. Therefore, the transmittance is preferably 95% or less, particularly preferably 80% or less. In the present invention, the term "single cell element" refers to an element having a photoelectric conversion function in which each electrode has one electron collecting electrode and one hole collecting electrode, and these electrodes are not connected in series. Say. Furthermore, since the photoelectric conversion element of the present invention has the above-described configuration, by selecting a material,
It is also possible for a single cell element to be flexible for at least two axes on the electrode surface. In the present invention, the term "flexible" means that a single cell element can be bent without breaking at least 5 degrees, particularly at least 10 degrees around a desired axis.

The present invention relates to a solid-state photoelectric conversion element comprising a solid substance which also functions as a hole transport layer and a hole current collecting electrode, and which is used as a hole transport layer and a hole current collecting electrode. Good electrical connection at the interface between the hole current collecting electrode and the hole current collecting electrode, such as forming a hole transport layer as conventionally performed, and then depositing gold or the like under high vacuum to form a hole current collecting electrode Simple and efficient manufacturing can be achieved, such as avoiding the manufacturing process. Further, since the present invention is an all-solid-state element in which the hole transport layer and the hole current collecting electrode are also used, restrictions on element design are reduced, and a photoelectric conversion element having a free shape can be manufactured. The present invention can be applied to a portable solar cell and a power supply device using the solar cell.

Further, since the light conversion efficiency is high even in a place with a small amount of light, such as under cloudy weather or under a fluorescent lamp, the present invention is also excellently applied to an area where the sunshine time is short or a device which is not always used outdoors. . As an application example, any device that conventionally uses a solar cell or a power supply device using the same can be used. For example, an electronic desk calculator,
Although it may be used for a solar cell for a wristwatch, examples of advantageous use of the features of the above-described photoelectric conversion element of the present invention include, for example, mobile phones, portable radios and other portable audio devices, car accessories, and sunshine hours. Examples include road signs used in short areas. Further, it can be used as an auxiliary power supply for extending the continuous use time of a rechargeable or dry battery type electric appliance, and it is particularly effective to use it as a power supply device for charging a secondary battery.

[0039]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. [Example 1] Titanium oxide fine particles (crystal anatase 80%, particle diameter about 20 nm) on 1 mm thick transparent conductive glass
Is applied and sintered, and then used as a sensitizing dye (cis-
Di (thiocyanic acid) -N, N'-bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium (II) was chemically adsorbed on a photosensitizing electrode of 3,4-ethylenedioxythiophene. 0.070 g, anhydrous iron (III) tris-para-toluenesulfonate 0.547 g, imidazole 0.0
50 g was immersed in a mixed solution of 2.000 g of methanol for 15 minutes, and then heated at 110 ° C. for 5 minutes, and poly (3,4-ethylenedioxy) doped with tris-para-toluenesulfonic acid anion in the pores. Thiophene) was polymerized and filled.

After cooling to room temperature, the product was washed with methanol and dried naturally. By this operation, a film having a total thickness of about 1 μm and about 2 μm was formed on the transparent conductive glass. When the sheet resistance of the surface was measured by the four-end needle method, it was 20.
Tris-para-toluenesulfonate anion-doped poly (3,4-
Ethylenedioxythiophene) was confirmed to work as a hole current collecting electrode. Also, poly (3,4) doped with tris-para-toluenesulfonic acid anion in the pores
-Ethylenedioxythiophene) is polymerized and filled, and the electrical conductivity in the thickness direction is filled with poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonic acid anion in the pores. The electrical conductivity in the direction of the film thickness in the case of not being carried out is increased by about 9 orders of magnitude, and in the sample prepared by this operation, the transparent conductive glass and the poly (3) doped with the tris-para-toluenesulfonic acid anion were used. , 4-ethylenedioxythiophene) were found to be conducting.

A film having a total thickness of about 1 μm has a thickness of 1 μm.
mm including transparent conductive glass with a wavelength of 500 n
m was 44% for irradiation light and 74% for irradiation light having a wavelength of 650 nm. On the other hand, the transmittance of a film having a total thickness of about 2 μm, including a transparent conductive glass having a thickness of 1 mm, is 44% with respect to irradiation light having a wavelength of 500 nm and 65%.
It was 51% with respect to the irradiation light of 0 nm.

Example 2 A suspension of titanium oxide fine particles (crystal anatase 80%, particle diameter of about 20 nm) was applied to a transparent conductive glass having a thickness of 1 mm, and the suspension was sintered. 3,4-di (thiocyanic acid) -N, N'-bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) on a photosensitized electrode on which ruthenium (II) is chemically adsorbed.
0.069 g of ethylenedioxythiophene, 0.546 g of anhydrous iron (III) tris-para-toluenesulfonate,
0.050 g of imidazole was added to normal butanol 2.0
The mixed solution dissolved in 00 g was dropped and developed.
After standing at 0 Pa for 5 minutes, the mixture was heated at 110 ° C. under atmospheric pressure for 5 minutes, and poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonic acid anion was polymerized and filled in the pores.

After cooling to room temperature, the product was washed with normal butanol and dried naturally. A series of processes of drop development of the mixed solution, standing under reduced pressure, heating, washing, and natural drying was repeated five times, and the poly (3,4) was doped with tris-para-toluenesulfonate anion on the surface of the photosensitized electrode. -Ethylenedioxythiophene). The photoelectric conversion of the present invention by attaching a lead wire to a layer of poly (3,4-ethylenedioxythiophene) doped with a tris-para-toluenesulfonic acid anion formed on the surface of a transparent conductive glass and a photosensitizing electrode. An element was obtained. Also in this case, as in Example 1, the transparent conductive glass and the poly (3,4-ethylenedioxythiophene) doped with the tris-para-toluenesulfonic acid anion were conductive. 400 nm or less and 10
When a short-circuit current was measured by irradiating light of 1.34 mW / cm ² with a xenon lamp that cuts light of a wavelength of 00 nm or more as a light source, the transparent conductive glass and the tris-para-toluenesulfonic acid anion were doped. Although the poly (3,4-ethylenedioxythiophene) was conducting, a photocurrent was observed as shown in FIG. From the above, in the photoelectric conversion element of the present invention, the solid substance filled in the pores of the photosensitizing electrode functions as a hole transporting layer and has good electrical connection with the solid layer on the photosensitizing electrode surface and has a good hole. It turned out to be working as a collecting electrode.

[0044]

According to the present invention, a solid-state photoelectric conversion element having high energy conversion efficiency even under a low light quantity, excellent long-term stability, less restrictions on element design, excellent productivity, and suitable for miniaturization and weight reduction. And a solar cell and a power supply device using the same.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a typical photoelectric conversion element.

FIG. 2 is a schematic view of the solid-state photoelectric conversion element of the present invention.

FIG. 3 is a graph showing a photocurrent by a photoelectric conversion element manufactured in Example 1.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 electron collecting electrode 2 electron acceptor and electron transporting layer 3 electron donor and hole transporting layer 4 hole collecting electrode 5 transparent conductive electrode (electron collecting electrode) coated on glass substrate 6 anatase-type titanium oxide (electron (Acceptor and electron transport layer) 7 Photosensitizing compound (charge separation layer) 8 Solid substance which is both hole transport layer and hole current collecting electrode

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yuki Tanaka 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Corporation (72) Inventor Shuichi Maeda 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation F-term (reference) 5F051 AA14

Claims (15)

[Claims] 1. A solid-state photoelectric conversion device having a solid substance which also serves as a hole transport layer and a hole current collecting electrode. 2. The photoelectric conversion device according to claim 1, wherein the solid substance contains a π-conjugated compound. 3. The photoelectric conversion device according to claim 1, further comprising an electron transport layer in which oxide fine particles are sintered, and a charge separation layer in which a photosensitizing compound is adsorbed on the electron transport layer. 4. A solid material containing a metal oxide, a photosensitizing compound and a π-conjugated compound, wherein the surface resistance of the outermost surface of the solid material is 10 ³ Ω / □ or less. Solid-state photoelectric conversion element. 5. The surface resistance of the outermost surface of the solid substance is 10
The photoelectric conversion device according to claim 4, wherein the value is 0 Ω / □ or less. 6. The metal oxide has a photosensitizing compound on its surface, the metal oxide has pores, and at least a part of the pores has a π-conjugated compound. Item 6. The photoelectric conversion element according to item 4 or 5. 7. The method according to claim 2, wherein the π-conjugated compound is a π-conjugated oligomer or a π-conjugated polymer.
7. The photoelectric conversion element according to 4, 5, or 6. 8. The photosensitizing compound is one or more selected from the group consisting of a ruthenium complex dye, a porphyrin compound, a phthalocyanine compound, a perylene dye, and an eosin dye. 7. The photoelectric conversion element according to any one of 3 to 6. 9. A solid-state photoelectric conversion device comprising a single cell or a plurality of single-cell devices, wherein the single-cell device has a light transmittance of 5% or more when the single-cell device is irradiated with light having a wavelength of 500 nm. element. 10. A solid-state photoelectric conversion element formed of one or more single-cell elements, wherein the single-cell element has flexibility in at least two axes on an electrode plane. 11. The photoelectric conversion device according to claim 9, wherein the photoelectric conversion device is formed of a solid material containing a metal oxide, a photosensitizing compound, and a π-conjugated compound. 12. The solvent is removed after impregnating a solution containing a π-conjugated compound and / or a complex compound composed of a conjugated compound and a metal element into pores of a metal oxide having a photosensitizing compound on the surface. And forming a solid substance layer containing a π-conjugated compound and / or a complex compound composed of a conjugated compound and a metal element up to the outermost surface. 13. A monomer forming a π-conjugated polymer,
A solid substance containing a π-conjugated polymer up to the outermost surface, after being impregnated with a solution containing a polymerization catalyst and a compound that reduces the polymerization rate into pores of a metal oxide having a photosensitizing compound on its surface. A method for manufacturing a photoelectric conversion element, comprising forming a layer. 14. The method according to claim 12, wherein the pores are impregnated with the solution under reduced pressure. 15. A solar cell using the photoelectric conversion element according to claim 1. Description: