JP2000243463A - Optical semiconductor electrode, photoelectric converter and photoelectric conversion method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently utilize sunlight by providing a photoelectric conversion layer of one kind or more of a tetracyanoanthraquinodimetan compound and a perylene compound on the surface of a metal oxide semiconductor. SOLUTION: This tetracyanoanthraquinodimetan compound is shown in a formula I. In the formula I, R1 and R2 are a hydrogen atom, alkyl group, aryl group, aralkyl group, alkoxyalkyl group or acyl group; n is 0 or 1. This perylene compound is shown in a formula II. In the formula II, R3 and R4 are a group represented by a formula III, etc.; when the R3 and R4 are a group represented by the formula III, 1 is 0. In the formula III, R5 and R6 are an aliphatic group, aromatic group or heterocyclic group; these may be substituted by a substituent. A1 represents a bivalent aliphatic group, aromatic group or heterocyclic group; these may be substituted by a substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optical semiconductor electrode having a specific compound adsorbed on the surface of a metal oxide semiconductor, and a photoelectric conversion device and a photoelectric conversion method using the same.

[0002]

2. Description of the Related Art In recent years, attention has been paid to the use of sunlight as an energy resource instead of fossil fuels such as oil and coal.
As a device that directly converts light energy into electric energy, a dry solar cell in which a pn junction is formed on an inorganic semiconductor such as silicon or gallium-arsenic is well known.
It has been put to practical use as a power source for remote or portable electronic devices. However, these solar cells have high conversion efficiency, but have the problem that it is difficult to use them as energy resources because the energy and cost required for production are extremely high.

On the other hand, as another method for converting light energy into electric energy, a wet solar cell utilizing a photoelectrochemical reaction occurring at an interface between a semiconductor and an electrolyte solution is known. The metal oxide semiconductors used here, such as titanium oxide, tin oxide, and zinc oxide, can be manufactured with much lower energy and cost compared to the aforementioned silicon, gallium-arsenic, etc., and future energy conversion It is expected as a material. However, since a stable metal oxide semiconductor such as titanium oxide has a wide band gap of 3 eV or more, only about 4% of ultraviolet light of sunlight can be used, and high conversion efficiency cannot be expected as it is. Therefore, organic dyes such as cyanine dyes, xanthene dyes, and coumarin dyes are used as sensitizing dyes on the surfaces of these metal oxide semiconductors.
(H.Tsubomura, et.al., Nature., 261, 402 (1976), MM
atsumura, et.al., Bull.Chem.Soc.Jpn. 50, 2533 (1
977), JP-A-10-92477, JP-A-10-93118, etc.) to adsorb and spectrally sensitize. However, when the above-mentioned cyanine dye, xanthene dye, coumarin dye or the like is used, there is a problem that the photoelectric conversion efficiency is not sufficient.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention can efficiently use sunlight, photoelectric conversion efficiency, stability, excellent durability, etc., an optical semiconductor electrode that can be easily manufactured at low cost, and using the optical semiconductor electrode, It is an object to provide a photoelectric conversion device and a photoelectric conversion method which are excellent in photoelectric conversion efficiency.

[0005]

Means for solving the above problems are as follows. That is, <1> at least one selected from a tetracyanoanthraquinodimethane compound represented by the following general formula (I) and a perylene compound represented by the following general formula (II) on the surface of the metal oxide semiconductor An optical semiconductor electrode comprising a photoelectric conversion layer according to claim 1. General formula (I)

[0006]

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In the general formula (I), R ¹ and R
² may be the same as or different from each other, and represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, or an acyl group. It may be formed.
n represents 0 or 1.

[0008]

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Formula (II)

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In the general formula (II), R ³ and R
⁴ represents a group represented by any of the following formulas (III) to (IX), which may be the same or different from each other, and at least one of which is represented by the following formula (III) ~
Represents a group represented by any of (VII) and (IX). l
Represents 0 when R ³ and R ⁴ are groups represented by any of the following general formulas (III) to (VIII), and represents a group represented by the following general formula (IX) Represents 0 to 12. General formula (III)

[0011]

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In the general formula (III), R ⁵ and R
⁶ may be the same as or different from each other, and represent an aliphatic group, an aromatic group, or a heterocyclic group, which may be substituted with a substituent. A ¹ represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. General formula (IV)

[0013]

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In the general formula (IV), A ² represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. R ⁷ and R ⁸ may be the same or different from each other, and represent a hydrogen atom,
A halogen atom, an alkyl group having 1 to 20 carbon atoms,-(CH
^{_{2) p COOR 18, - (}} CH 2) p SO 3 R 19, or -
(CH ₂ ) _p represents R ²⁰ R ²¹ . R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹
Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
p represents an integer of 0 to 20. General formula (V)

[0015]

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In the general formula (V), A ³ represents a single bond, a divalent aliphatic group, an aromatic group or a heterocyclic group, which may be substituted with a substituent. R ⁹
Represents an aliphatic group, an aromatic group or a heterocyclic group, which may be substituted with a substituent. R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,-
Represents (CH ₂ ) _p COOR ¹⁸ , — (CH ₂ ) _p SO ₃ R ¹⁹ , or — (CH ₂ ) _p NR ²⁰ R ²¹ . R ¹⁸ , R ¹⁹ , R ²⁰
And R ²¹ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p represents an integer of 0 to 20. General formula (VI)

[0017]

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In the general formula (VI), A ⁴ represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. X represents an oxygen atom, a sulfur atom or> NR ^22. R ¹¹ and R ¹² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,-(C
H ₂ ) _p COOR ¹⁸ ,-(CH ₂ ) _p SO ₃ R ¹⁹ , or-
It represents a ^{_{(CH 2) p NR 20 R}} 21. R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹
And R ²² represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p represents an integer of 0 to 20. General formula (VII)

[0019]

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In the general formula (VII), A ⁵ represents a single bond or a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. R ¹³
Represents a divalent aliphatic group, an aromatic group or a heterocyclic group, which may be substituted with a substituent. R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,-
^{_{(CH 2) p COOR 18,}} - (CH 2) p SO 3 R 19, or, - (CH ₂₎ represents a _p NR ²⁰ R ^{2 1.} R ¹⁸ , R ¹⁹ , R ²⁰
And R ²¹ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p represents an integer of 0 to 20. General formula (VIII)

[0021]

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In the general formula (VIII), A ⁶ represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. Y is -COOH, -S
OOH, or represents -NH _2. General formula (IX)

[0023]

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In the general formula (IX), X represents a hydrogen atom
2 elements, or Mg, Zn, Fe, Co, Ni, Cu,
Ru, Sn, SnO, TiO, VO, Al (OH), G
a (OH) or In (OH). R¹⁵, R¹⁶Passing
And R¹⁷Is a hydrogen atom, a halogen atom, a C1-12
Alkyl group,-(CH_Two)_mCOOH or-(C
H _Two)_mNH_TwoRepresents m and n represent an integer of 0 to 12
You. <2> Tetracyanoant represented by the general formula (I)
Laquinodimethane compound is represented by the following general formula (Ia)
Wherein the tetracyanoanthraquinodimethane compound is
An optical semiconductor electrode according to <1>. General formula (Ia)

[0025]

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In the general formula (Ia), Me represents a methyl group. n represents 0 or 1. <3> When the metal oxide semiconductor is titanium oxide, tin oxide,
<1 which is at least one selected from tungsten oxide, zinc oxide, indium oxide, niobium oxide, nickel oxide, cobalt oxide and strontium titanate
> Or <2>. <4> At least a pair of electrodes brought into contact with the electrolyte and a connecting means for connecting the pair of electrodes so as to be able to conduct electricity, and at least one of the pair of electrodes is in the range of <1> to <3>. A photoelectric conversion device characterized in that it is the optical semiconductor electrode according to any one of the above. <5> A photoelectric conversion method in which a pair of electrodes connected to each other so as to be able to conduct electricity are brought into contact with an electrolyte, and at least one of the pair of electrodes is irradiated with light to cause a photoelectric conversion reaction. Electrodes are <1> to <
3> A photoelectric conversion method characterized by being the optical semiconductor electrode according to any one of the above.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION (Optosemiconductor electrode) An optical semiconductor electrode of the present invention comprises a metal oxide semiconductor having the following general formula (I)
And a perylene compound represented by the following general formula (II).

—Metal Oxide Semiconductor— The metal oxide semiconductor is not particularly limited and can be appropriately selected depending on the intended purpose. For example, titanium oxide, tin oxide, tungsten oxide, zinc oxide, indium oxide, Examples include niobium oxide and strontium titanate. These may be used alone or may be used alone.
More than one species may be used in combination. In the present invention, among these, titanium oxide is particularly preferable for reasons such as photoelectric conversion characteristics, chemical stability, and ease of production.

The shape, structure, size and the like of the metal oxide semiconductor are not particularly limited, and can be appropriately selected according to the purpose. For example, the structure of the metal oxide semiconductor may be a structure composed of only the metal oxide semiconductor, a transparent electrode such as ITO glass, Nesa glass, a plate material such as platinum, copper, graphite, or a mesh electrode. A structure in which a thin film layer of the metal oxide semiconductor is formed on the conductive base material described above.

—Photoelectric Conversion Layer— The photoelectric conversion layer is formed on the surface of the metal oxide semiconductor by a tetracyanoanthraquinodimethane compound represented by the following general formula (I) and a general formula (II) shown below. At least one selected from perylene compounds is adsorbed. General formula (I)

[0031]

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In the general formula (I), R ¹ and R
² may be the same as or different from each other, and represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, or an acyl group. It may be formed.
n represents 0 or 1.

[0033]

Embedded image General formula (II)

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In the general formula (II), R^ThreeAnd R
^FourIs represented by any of the following general formulas (III) to (IX)
Represents a group, which may be the same or different
May be, at least one of the following general formula (III) ~
Represents a group represented by any of (VII) and (IX). l
Is R^ThreeAnd R^FourIs any of the following general formulas (III) to (VIII)
When it is a group represented by the formula, it represents 0, and has the following general formula
In the case of a group represented by (IX), 0 to Represents General formula (III)

[0035]

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In the general formula (III), R ⁵ and R
⁶ may be the same as or different from each other, and represent an aliphatic group, an aromatic group, or a heterocyclic group, which may be substituted with a substituent. A ¹ represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. General formula (IV)

[0037]

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In the general formula (IV), A ² represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. R ⁷ and R ⁸ may be the same or different from each other, and represent a hydrogen atom,
A halogen atom, an alkyl group having 1 to 20 carbon atoms,-(CH
^{_{2) p COOR 18, - (}} CH 2) p SO 3 R 19, or -
It represents a ^{_{(CH 2) p NR 20 R}} 21. R ¹⁸ , R ¹⁹ , R ²⁰ and R
²¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p represents an integer of 0 to 20. General formula (V)

[0039]

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In the general formula (V), A ³ represents a single bond, a divalent aliphatic group, an aromatic group or a heterocyclic group, which may be substituted with a substituent. R ⁹
Represents an aliphatic group, an aromatic group or a heterocyclic group, which may be substituted with a substituent. R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,-
Represents (CH ₂ ) _p COOR ¹⁸ , — (CH ₂ ) _p SO ₃ R ¹⁹ , or — (CH ₂ ) _p NR ²⁰ R ²¹ . R ¹⁸ , R ¹⁹ , R ²⁰
And R ²¹ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p represents an integer of 0 to 20. General formula (VI)

[0041]

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In the general formula (VI), A ⁴ represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. X represents an oxygen atom, a sulfur atom or> NR ^22. R ¹¹ and R ¹² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,-(C
H ₂ ) _p COOR ¹⁸ ,-(CH ₂ ) _p SO ₃ R ¹⁹ , or-
It represents a ^{_{(CH 2) p NR 20 R}} 21. R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹
And R ²² represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p represents an integer of 0 to 20. General formula (VII)

[0043]

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In the general formula (VII), A ⁵ represents a single bond, a divalent aliphatic group, an aromatic group or a heterocyclic group, which may be substituted with a substituent. R ¹³
Represents a divalent aliphatic group, an aromatic group or a heterocyclic group, which may be substituted with a substituent. R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,-
^{_{(CH 2) p COOR 18,}} - (CH 2) p SO 3 R 19, or, - (CH ₂₎ represents a _p NR ²⁰ R ^{2 1.} R ¹⁸ , R ¹⁹ , R ²⁰
And R ²¹ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p represents an integer of 0 to 20. General formula (VIII)

[0045]

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In the general formula (VIII), A ⁶ represents a divalent aliphatic group, aromatic group or heterocyclic group, which may be substituted with a substituent. Y is -COOH, -S
OOH, or represents -NH _2. General formula (IX)

[0047]

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In the general formula (IX), X represents a hydrogen atom
2 elements, or Mg, Zn, Fe, Co, Ni, Cu,
Ru, Sn, SnO, TiO, VO, Al (OH), G
a (OH) or In (OH). R¹⁵, R¹⁶Passing
And R¹⁷Is a hydrogen atom, a halogen atom, a C1-12
Alkyl group,-(CH_Two)_mCOOH or-(C
H _Two)_mNH_TwoRepresents m and n represent an integer of 0 to 12
You.

Preferred specific examples of the tetracyanoanthraquinodimethane compound represented by the general formula (I) include the following compounds (I-1 to 30). In addition,
Table 1 shows a specific example when n = 0, and Table 2 shows a specific example when n = 1.

[0050]

[Table 1]

[0051]

[Table 2]

In the present invention, among these, a tetracyanoanthraquinodimethane compound represented by the following general formula (Ia) is particularly preferred in terms of photoelectric conversion efficiency, absorption wavelength range, ease of production, and the like. Preferred (the above exemplified compound (I-1)
Compound represented by). General formula (Ia)

[0053]

Embedded image In the general formula (Ia), Me represents a methyl group. n represents 0 or 1.

The tetracyanoanthraquinodimethane compound represented by the general formula (I) is described in, for example, JP-A-63-104.
No. 062, a method of reacting an anthraquinone derivative represented by the following general formula (A) with malononitrile represented by the following general formula (B),
The compound can be synthesized by the method described in JP-A-58-55450.

[0055]

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[0056]

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The tetracyanoanthraquinodimethane compound represented by the general formula (I) has an electron-accepting portion and an electron-donating portion, and has an absorption wavelength range extending to a long wavelength range of about 700 nm. In addition, since the generated charges can be efficiently separated and moved, spectral sensitization can be performed with high efficiency.

Preferred specific examples of the perylene compound represented by the general formula (II) include the following compounds (II-1 to 1)
3).

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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In the present invention, the compound represented by the general formula (II)
The perylene compound represented by the following general formula (IX-
a). General formula (IX-a)

[0073]

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Preferred specific examples of the perylene compound represented by the general formula (IX-a) include the compounds (IX-1 to 23) shown in Table 3.

[0075]

[Table 3] In Table 3, “H2” represents two hydrogen atoms.

In the perylene compound represented by the general formula (II), those in which R ³ and R ⁴ are the same and are each a group represented by any of the general formulas (III) to (IX) are For example, it can be synthesized by reacting 3,4,9,10-perylenetetracarboxylic anhydride with compounds represented by the following general formulas (III ′) to (IX ′).

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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In the perylene compound represented by the general formula (II), those in which R ³ and R ⁴ are different from each other and are a group represented by any of the general formulas (III) to (IX) For example, by reacting 3,4,9,10-perylenetetracarboxylic anhydride and two kinds selected from the compounds represented by the general formulas (III ′) to (IX ′), or U.S. Pat.No.4,501,906, etc., 3,4,9,10-perylenetetracarboxylic monoanhydride monometal salt, and represented by the general formulas (III ') to (IX') The compound can be synthesized by sequentially reacting two kinds selected from the compounds to be prepared.

The perylene compound represented by the general formula (II) is excellent in chemical stability and durability, and excellent in retention on the surface of the metal oxide semiconductor, and is stable and highly stable for a long period of time. Efficiency can be spectrally sensitized.

—Formation of Photoelectric Conversion Layer— The photoelectric conversion layer is at least one selected from the tetracyanoanthraquinodimethane compound represented by the general formula (I) and the perylene compound represented by the above (II). By adding a seed to a solvent and immersing the metal oxide semiconductor in a solution in which the seed is dissolved, the metal oxide semiconductor can be easily formed on the surface of the metal oxide semiconductor.

The solvent is not particularly limited and can be appropriately selected from known solvents according to the purpose.
For example, methanol, alcohol solvents such as isopropyl alcohol, acetone, ketone solvents such as methyl ethyl ketone, N, N-dimethylformamide, amide solvents such as N-methylpyrrolidone, or water, or a mixed solvent thereof, and the like. Can be These may be used alone or in combination of two or more. Among these, amide solvents such as N, N-dimethylformamide are preferred. In the present invention, the solubility in at least one kind of the solvent selected from the tetracyanoanthraquinodimethane compound represented by the general formula (I) and the perylene compound represented by the above (II) is determined. For the purpose of improvement,
An acidic substance, a basic substance, and the like may be added to the solvent.

The immersion may be performed at room temperature, or at least one selected from the tetracyanoanthraquinodimethane compound represented by the general formula (I) and the perylene compound represented by the above (II). In order to promote the adsorption to the metal oxide semiconductor, heating or the like may be performed as necessary.

After the immersion, the metal oxide semiconductor is washed with an arbitrary solvent or the like and then dried, so that the surface of the metal oxide semiconductor is coated on the surface of the tetracyanoanthraquinodimethane represented by the general formula (I). An optical semiconductor electrode having a photoelectric conversion layer formed by adsorbing at least one selected from a compound and a perylene compound represented by the above (II) is obtained.

The semiconductor electrode of the present invention can be suitably used in a wide range of fields, and particularly, can be suitably used for the following photoelectric conversion device and photoelectric conversion method of the present invention.

(Photoelectric Conversion Device) The photoelectric conversion device of the present invention comprises at least a pair of electrodes brought into contact with an electrolyte, and a connecting means for connecting the pair of electrodes so as to be able to conduct electricity. And other means appropriately selected.

One of the pair of electrodes is the optical semiconductor electrode of the present invention, and the other is a counter electrode. The counter electrode is not particularly limited as long as it is stable to oxidation and reduction, and can be appropriately selected from known ones according to the purpose.For example, plate materials such as platinum, gold, and graphite, and ITO Transparent electrodes such as glass and Nesa glass.

The connection means is not particularly limited as long as it has a function of connecting the pair of electrodes so as to be able to conduct electricity, and is made of a known lead wire or a conductive material such as various metals, carbon and metal oxides. Examples include a wire, a plate, a printed film or a deposited film. The connection means is electrically connected to the pair of electrodes.

The electrolyte is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include salts such as potassium chloride, lithium chloride and tetraethylammonium perchlorate, and alkalis such as sodium hydroxide and potassium carbonate. Or an acid such as sulfuric acid or hydrochloric acid, a mixture thereof, or an aqueous solution thereof, or a non-aqueous solvent solution such as an alcohol or propylene carbonate thereof. In the present invention, for the purpose of stabilizing the photocurrent characteristics and the like, the electrolyte further contains potassium iodide, iodine,
A redox agent such as p-benzoquinone that causes a reversible redox reaction may be added. The photoelectric conversion device of the present invention can be suitably used for the following photoelectric conversion method of the present invention.

(Photoelectric Conversion Method) In the photoelectric conversion method of the present invention, the pair of electrodes connected to each other so as to be able to conduct electricity are brought into contact with the electrolyte, and at least one of the pair of electrodes is irradiated with light. Cause a conversion reaction

In the pair of electrodes, the electrode irradiated with light is the optical semiconductor electrode of the present invention, and the other is the counter electrode.

-Photoelectric Conversion Reaction- In the photoelectric conversion device and the photoelectric conversion method of the present invention, a photoelectric conversion reaction occurs as follows. That is, first, the optical semiconductor electrode and the counter electrode are connected to the electrolyte (solution).
Soak in. Next, the optical semiconductor electrode is provided with at least one absorption wavelength range selected from the tetracyanoanthraquinodimethane compound represented by the general formula (I) and the perylene compound represented by the general formula (II). Irradiation with monochromatic light, or white light or polychromatic light including any band thereof, converts these light energies into electric energy.

According to the semiconductor electrode and the photoelectric conversion device and the photoelectric conversion method using the semiconductor electrode of the present invention, good photoelectric conversion efficiency can be obtained even when irradiating visible light having a wavelength of 300 to 700 nm. In addition, it can be effectively used up to a wavelength range of visible light that cannot be used alone with a metal oxide semiconductor such as titanium oxide, and light energy such as sunlight can be efficiently converted to electric energy.

[0099]

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

Example 1 25 ml of tetraisopropyl orthotitanate was gradually added to a mixed solution of 150 ml of pure water and 1.54 g of concentrated nitric acid (specific gravity: 1.38) with vigorous stirring.
The temperature was raised to 80 ° C. while further stirring, and the stirring was continued at the same temperature for 8 hours to prepare a milky white stable colloidal titanium oxide solution. This titanium oxide colloid solution was concentrated to 30 ml at 30 ° C. under a reduced pressure of 30 mmHg. The titanium oxide colloid solution was applied to a glass substrate coated with an ITO layer (hereinafter referred to as “I”).
(Referred to as “TO glass substrate”) by spin coating and baked at 500 ° C. for 1 hour. This operation was repeated three times to form a titanium oxide layer having a thickness of about 1.0 μm on the ITO glass substrate. The crystal structure of the obtained titanium oxide film
When confirmed by X-ray diffraction, it was a mixture of an anatase type and a rutile type. Carrying the titanium oxide layer
An ITO glass substrate was used as a metal oxide semiconductor.

The metal oxide semiconductor was prepared by using the above-mentioned compound
After immersing 100 mg of (I-1) in a solution of 50 ml of N, N-dimethylformamide at about 90 ° C. for 12 hours, acetone,
Washed in order of methanol and air dried. As described above, the photoelectric conversion layer of the exemplified compound (I-1) was formed by adsorption on the surface of the metal oxide semiconductor.

Next, a lead wire was connected to the ITO layer portion coated on the glass substrate. The connection portion of the lead wire was covered with an epoxy resin and fixed. Thus, an optical semiconductor electrode was manufactured.

FIG. 1 is a schematic explanatory view for explaining the fabricated optical semiconductor electrode. The optical semiconductor electrode 1 has an ITO layer 3, a titanium oxide layer 4, and a photoelectric conversion layer 5 made of the exemplified compound (I-1) on a glass substrate 2 in this order. The connection between the ITO layer 3 and the lead wire 7 is as follows.
It is covered and fixed with an epoxy resin as a fixing agent 6, and a lead wire 7 is accommodated in a glass tube 8 at the connection portion.

FIG. 2 is a schematic diagram for explaining a photoelectric conversion method using a photoelectric conversion device provided with the optical semiconductor electrode. Here, the fabricated optical semiconductor electrode 1, the platinum electrode as the counter electrode 9, and the saturated calomel electrode as the reference electrode 10 are immersed in the transparent glass cell 13 and the electrolyte solution 11. The electrolyte solution 11 is a 0.1 M sodium sulfate / 0.02 M potassium iodide aqueous solution. Each of the electrodes is connected to a potentiostat 12 via a lead wire 7 as a connection means, so that the electrodes can be energized.

In this photoelectric conversion device, the potential of the optical semiconductor electrode 1 is maintained at 0 V with respect to the reference electrode 10 so that white light (500 W xenon lamp, illuminance 4000 Lu
x) was irradiated from the back side of the optical semiconductor electrode, and the value of the photocurrent at this time was measured with a potentiostat. Table 4 shows the measurement results.

Example 2 The procedure of Example 1 was repeated except that the example compound (I-1) was replaced by the example compound (I-3).
An optical semiconductor electrode and a photoelectric conversion device were prepared in the same manner as in 1, the photoelectric conversion method was performed, and the photocurrent was measured. Table 4 shows the measurement results.

Example 3 An optical semiconductor electrode and a photoelectric conversion device were produced in the same manner as in Example 1 except that the exemplified compound (I-1) was replaced with the exemplified compound (I-7). Then, the photoelectric conversion method was performed, and the photocurrent was measured. Table 4 shows the measurement results.

(Comparative Example 1) An optical semiconductor electrode and a photoelectric conversion device were produced in the same manner as in Example 1 except that the exemplified compound (I-1) was not used, and the photoelectric conversion method was performed. Then, the photocurrent was measured. Table 4 shows the measurement results.
It was shown to.

(Comparative Example 2) An optical semiconductor electrode and a photoelectric conversion device were prepared in the same manner as in Example 1 except that Example Compound (I-1) was replaced with 2,4,5,7-tetraiodofluorescein. A converter was manufactured, a photoelectric conversion method was performed, and a photocurrent was measured. Table 4 shows the measurement results.

Comparative Example 3 In Example 1, the exemplified compound (I-1) was replaced with (tetracarboxphthalocyaninato) copper (II)
A photo-semiconductor electrode and a photoelectric conversion device were produced in the same manner as in Example 1, except that the photo-electric conversion method was performed, and the photocurrent was measured. Table 4 shows the measurement results.

[0111]

[Table 4]

Example 4 In Example 1, the metal oxide semiconductor was immersed in a solution of 100 mg of the exemplified compound (I-1) in 50 ml of N, N-dimethylformamide at about 90 ° C. for 12 hours. Instead of Example 1 except that 50 mg of the exemplary compound (II-4) was immersed in a solution of 50% of a 2% tetra (n-butyl) ammonium hydroxide / ethanol solution at 70 to 80 ° C. for 1 hour. Similarly, an optical semiconductor electrode and a photoelectric conversion device were manufactured, a photoelectric conversion method was performed, and a photocurrent was measured. Table 5 shows the measurement results.

Example 5 An optical semiconductor electrode and a photoelectric conversion device were produced in the same manner as in Example 4, except that Example Compound (II-4) was replaced with Example Compound (II-9). Then, the photoelectric conversion method was performed, and the photocurrent was measured.
Table 5 shows the measurement results.

Example 6 In Example 4, except that the exemplified compound (II-4) was replaced by the exemplified compound (II-10),
An optical semiconductor electrode and a photoelectric conversion device were manufactured in the same manner as in Example 4, the photoelectric conversion method was performed, and the photocurrent was measured. Table 5 shows the measurement results.

(Comparative Example 4) An optical semiconductor electrode and a photoelectric conversion device were prepared in the same manner as in Example 4 except that the exemplified compound (II-4) was not used, and the photoelectric conversion method was performed. Then, the photocurrent was measured. Table 5 shows the measurement results.

Comparative Example 5 An optical semiconductor electrode and a photoelectric conversion device were prepared in the same manner as in Example 4 except that the compound (II-4) was replaced by 2,4,5,7-tetraiodofluorescein. A converter was manufactured, a photoelectric conversion method was performed, and a photocurrent was measured. Table 5 shows the measurement results.

[0117]

[Table 5]

(Example 7) In Example 1, the metal oxide semiconductor was immersed in a solution of 100 mg of the exemplified compound (I-1) in 50 ml of N, N-dimethylformamide at about 90 ° C. for 12 hours. Instead, 100 mg of Exemplified Compound (IX-4)
80 to a solution of N, N-dimethylformamide in 50 ml
Except for immersion at 100 ° C. for 1 hour, an optical semiconductor electrode and a photoelectric conversion device were prepared in the same manner as in Example 1, a photoelectric conversion method was performed, and a photocurrent was measured. Table 6 shows the measurement results.

Example 8 An optical semiconductor electrode and a photoelectric conversion device were produced in the same manner as in Example 7, except that Example Compound (IX-4) was replaced with Example Compound (IX-7). Then, the photoelectric conversion method was performed, and the photocurrent was measured.
Table 6 shows the measurement results.

Example 9 An optical semiconductor electrode and a photoelectric conversion device were fabricated in the same manner as in Example 7, except that Example Compound (IX-4) was replaced with Example Compound (IX-9). Then, the photoelectric conversion method was performed, and the photocurrent was measured.
Table 6 shows the measurement results.

(Comparative Example 6) An optical semiconductor electrode and a photoelectric conversion device were prepared in the same manner as in Example 7 except that the exemplified compound (IX-4) was not used, and the photoelectric conversion method was performed. Then, the photocurrent was measured. Table 6 shows the measurement results.

(Comparative Example 7) In Example 7, Compound (IX-4) was replaced with 2,4,5,7-tetraiodo-3 ′, 4 ′, 5 ′, 6′-tetrachlorofluorescein. In the same manner as in Example 7, an optical semiconductor electrode and a photoelectric conversion device were manufactured, a photoelectric conversion method was performed, and a photocurrent was measured. Table 6 shows the measurement results.

Comparative Example 8 In Example 7, the exemplified compound (IX-4) was replaced with (tetracarboxyphthalocyaninato) copper.
Except for replacing (II), an optical semiconductor electrode and a photoelectric conversion device were prepared in the same manner as in Example 7, the photoelectric conversion method was performed, and the photocurrent was measured. Table 6 shows the measurement results.

[0124]

[Table 6]

[0125]

According to the present invention, an optical semiconductor electrode which can efficiently utilize sunlight, is excellent in photoelectric conversion efficiency, stability, durability and the like, can be manufactured at low cost and easily, and the optical semiconductor. By using an electrode, a photoelectric conversion device and a photoelectric conversion method which are excellent in photoelectric conversion efficiency can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an optical semiconductor electrode of the present invention.

FIG. 2 is a schematic explanatory diagram for explaining a photoelectric conversion method using a photoelectric conversion device including the optical semiconductor electrode of FIG. 1;

FIG. 3 is an ultraviolet-visible absorption spectrum of the optical semiconductor electrode of Example 4.

FIG. 4 is an ultraviolet-visible absorption spectrum of the optical semiconductor electrode of Example 7.

[Explanation of symbols]

 Reference Signs List 1 optical semiconductor electrode 2 glass substrate 3 ITO layer 4 titanium oxide layer 5 photoelectric conversion layer 6 fixing agent 7 lead wire 8 glass tube 9 counter electrode 10 reference electrode 11 electrolyte solution 12 potentiostat 13 transparent glass cell

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Eiichi Hirose 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (Reference) 5F051 AA14 5H032 AA06 AS16 EE02 EE20

Claims (5)

[Claims] 1. The following general formula:
Tetracyanoanthraquinodimethane compound represented by (I)
And perylene compounds represented by the following general formula (II)
Having a photoelectric conversion layer of at least one selected from
An optical semiconductor electrode characterized by the following. General formula (I)In the general formula (I), R¹And R^TwoAre identical to each other
May be different from each other, and a hydrogen atom, a
Alkyl group, aryl group, aralkyl group, alkoxyalkyl
Represents a kill group or an acyl group.
May be formed. n represents 0 or 1
You. Embedded imageGeneral formula (II)In the general formula (II), R^ThreeAnd R^FourIs the following general formula
Represents a group represented by any of (III) to (IX),
May be the same or different from each other,
At least one of the following general formulas (III) to (VII) and (IX)
Represents a group represented by any of l is R^ThreeAnd R^FourBut below
A group represented by any of the general formulas (III) to (VIII)
In this case, it represents 0, and is a group represented by the following general formula (IX).
In this case, it represents 0 to 12. General formula (III)In the general formula (III), R^FiveAnd R⁶Are identical to each other
May be different from each other,
Represents an aromatic group or a heterocyclic group, which are substituted with a substituent.
May be. A¹Is a divalent aliphatic group, an aromatic group or
Represents a heterocyclic group, which may be substituted with a substituent.
No. General formula (IV)In the general formula (IV), A^TwoIs a divalent aliphatic group,
Represents an aromatic group or a heterocyclic group, which are substituted with a substituent.
It may be. R⁷And R⁸Are the same as each other
Good or different, hydrogen atom, halogen atom
, An alkyl group having 1 to 20 carbon atoms,-(CH_Two)_pCOO
R¹⁸,-(CH_Two)_pSO_ThreeR¹⁹Or-(CH_Two)_pN
R²⁰R^{twenty one}Represents R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is a hydrogen source
And represents an alkyl group having 1 to 20 carbon atoms. p is 0 to
Represents an integer of 20. General formula (V)In the general formula (V), A^ThreeIs a single bond or 2
Represents a divalent aliphatic, aromatic or heterocyclic group,
May be substituted with a substituent. R⁹Is aliphatic
Group, aromatic group or heterocyclic group,
May be substituted. R^TenIs a hydrogen atom, a halogen
Atom, alkyl group having 1 to 20 carbon atoms,-(CH_Two)_pCO
OR¹⁸,-(CH_Two)_pSO_ThreeR¹⁹Or-(CH_Two)_p
NR²⁰R^{twenty one}Represents R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is hydrogen
Represents an atom or an alkyl group having 1 to 20 carbon atoms. p is 0
Represents an integer of -20. General formula (VI)In the general formula (VI), A^FourIs a divalent aliphatic group,
Represents an aromatic group or a heterocyclic group, which are substituted with a substituent.
It may be. X represents an oxygen atom, a sulfur atom or> NR
^{twenty two}Represents R¹¹And R¹²Is a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms,-(CH_Two)_pCOO
R¹⁸,-(CH_Two)_pSO_ThreeR¹⁹Or-(CH_Two)_pN
R²⁰R^{twenty one}Represents R¹⁸, R¹⁹, R²⁰, R^{twenty one}And R^{twenty two}Is
Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. p
Represents an integer of 0 to 20. General formula (VII)In the general formula (VII), A^FiveIs a single bond or 2
Represents a divalent aliphatic, aromatic or heterocyclic group,
May be substituted with a substituent. R¹³Is divalent fat
Represents an aliphatic group, an aromatic group, or a heterocyclic group;
May be substituted. R¹⁴Is a hydrogen atom, a halogen
Atom, alkyl group having 1 to 20 carbon atoms,-(CH_Two)_pCO
OR¹⁸,-(CH_Two)_pSO_ThreeR¹⁹Or-(CH_Two)_p
NR²⁰R^{Two 1}Represents R¹⁸, R¹⁹, R²⁰And R^{twenty one}Is hydrogen
Represents an atom or an alkyl group having 1 to 20 carbon atoms. p is 0
Represents an integer of -20. General formula (VIII)In the general formula (VIII), A⁶Is a divalent aliphatic group,
Represents an aromatic group or a heterocyclic group, which are substituted with a substituent.
It may be. Y is -COOH, -SOOH, or
Is -NH_TwoRepresents General formula (IX)In the general formula (IX), X represents two hydrogen atoms,
Represents Mg, Zn, Fe, Co, Ni, Cu, Ru, S
n, SnO, TiO, VO, Al (OH), Ga (O
H) or In (OH). R¹⁵, R¹⁶And R¹⁷
Is a hydrogen atom, a halogen atom, an alkyl having 1 to 12 carbons.
Group,-(CH_Two)_mCOOH or-(CH _Two)_mNH
_TwoRepresents m and n represent the integer of 0-12. 2. The tetracyanoanthraquinodimethane compound represented by the general formula (I) is a tetracyanoanthraquinodimethane compound represented by the following general formula (Ia). Optical semiconductor electrodes. General formula (Ia) In the general formula (Ia), Me represents a methyl group. n represents 0 or 1. 3. The method according to claim 1, wherein the metal oxide semiconductor is titanium oxide, tin oxide, tungsten oxide, zinc oxide, indium oxide,
3. The optical semiconductor electrode according to claim 1, which is at least one selected from niobium oxide, nickel oxide, cobalt oxide, and strontium titanate. 4. The battery according to claim 1, further comprising at least a pair of electrodes brought into contact with the electrolyte, and connection means for connecting the pair of electrodes so as to be able to conduct electricity. A photoelectric conversion device, which is the optical semiconductor electrode according to any one of the above. 5. A photoelectric conversion method in which a pair of electrodes connected to each other so as to be able to conduct electricity are brought into contact with an electrolyte, and at least one of the pair of electrodes is irradiated with light to cause a photoelectric conversion reaction. A photoelectric conversion method, wherein the irradiated electrode is the optical semiconductor electrode according to claim 1.