JP2010257741A - Photoelectric conversion element and solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element and a solar cell, using a compound (dye) with high adsorbency to an oxide semiconductor and high photoelectric conversion efficiency. <P>SOLUTION: In a dye-sensitized photoelectric conversion element with a semiconductor layer and an electrolyte layer at least formed by carrying a sensitizing dye to a semiconductor between a pair of electrodes facing each other, a sensitizing dye contains a compound expressed in a general formula (1). In the formula (1), Ar denotes a substituted or unsubstituted arylene group or heterocyclic group. Each R<SB>1</SB>, R<SB>2</SB>denotes a substituted or unsubstituted alkyl group, aralkyl group, aryl group or heterocycle group, R<SB>1</SB>, R<SB>2</SB>and Ar may connect with each other to form a cyclic structure. Further, R<SB>3</SB>denotes a hydrogen atom, halogen atom, cyano group, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, amino group or heterocyclic group. R<SB>4</SB>denotes a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. R<SB>5</SB>denotes a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, seleno-alkoxy group, amino group, aryl group or heterocyclic group, substituted by X. Z denotes a sulfur atom or selenium atom, X denotes an acid group, and m denotes an integer of 1 or more. A carbon-carbon double bond may be either a cis or trans. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photoelectric conversion element and a solar cell using a novel compound (pigment).

  In recent years, the use of sunlight, which is infinite and does not generate harmful substances, has been energetically studied. What is currently put into practical use as solar energy, which is a clean energy source, includes residential single crystal silicon, polycrystalline silicon, amorphous silicon, and inorganic solar cells such as cadmium telluride and indium copper selenide. .

  However, the disadvantages of these inorganic solar cells include, for example, that silicon is required to have a very high purity, and naturally, the purification process is complicated, the number of processes is large, and the manufacturing cost is high.

  On the other hand, many solar cells using organic materials have been proposed. As an organic solar cell, a Schottky photoelectric conversion element that joins a p-type organic semiconductor and a metal having a low work function, a p-type organic semiconductor and an n-type inorganic semiconductor, or a p-type organic semiconductor and an electron-accepting organic compound are joined. There are heterojunction photoelectric conversion elements and the like, and organic semiconductors used are synthetic dyes and pigments such as chlorophyll and perylene, conductive polymer materials such as polyacetylene, or composite materials thereof. These are thinned by a vacuum deposition method, a casting method, a dipping method, or the like to form a battery material. Although organic materials have advantages such as low cost and easy area enlargement, there are many problems that the conversion efficiency is as low as 1% or less and the durability is poor.

  Under such circumstances, a solar cell exhibiting good characteristics has been reported by Dr. Gretzell of Switzerland (see Non-Patent Document 1). The proposed battery is a dye-sensitized solar cell, which is a wet solar cell using a titanium oxide porous thin film spectrally sensitized with a ruthenium complex as a working electrode. The advantage of this method is that inexpensive metal compound semiconductors such as titanium oxide do not need to be purified to high purity. Therefore, the light that is inexpensive and can be used extends over a wide visible light region, and the sun is rich in visible light components. It is that light can be effectively converted into electricity.

  On the other hand, ruthenium complexes with limited resources are used, so when this solar cell is put to practical use, the supply of ruthenium complexes is in danger. Also, this ruthenium complex is expensive and has problems with stability over time, and this problem can be solved if it can be changed to an inexpensive and stable organic dye.

  It is disclosed that when a compound having a rhodanine skeleton-containing amine structure is used as the dye, an element having high photoelectric conversion efficiency can be obtained (see, for example, Patent Document 1). However, even when these dyes are used, there is a demand for sensitizing dyes having lower conversion efficiency and higher photoelectric conversion efficiency than when using a ruthenium complex.

JP 2005-123033 A

B. O'Regan, M.M. Gratzel, Nature, 353, 737 (1991)

  The present invention has been made in view of the above problems, and has as its object the provision of a photoelectric conversion element and a solar cell using a compound (pigment) that is novel, has good adsorptivity to an oxide semiconductor, and has high photoelectric conversion efficiency. There is to do.

  The above object of the present invention is achieved by the following configurations.

  1. In a dye-sensitized photoelectric conversion element in which a semiconductor layer and an electrolyte layer in which at least a sensitizing dye is supported on a semiconductor is provided between a pair of opposing electrodes, the sensitizing dye is represented by the following general formula (1). The photoelectric conversion element characterized by containing the compound represented by these.

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ is substituted with X. Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, selenoalkoxy group, amino group, aryl group or heterocyclic group. Z represents a sulfur atom or a selenium atom, X represents an acidic group, and m represents an integer of 1 or more. The carbon-carbon double bond may be either a cis isomer or a trans isomer.)
2. 2. The photoelectric conversion element as described in 1 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₆ and R ₇ represent a hydrogen atom. , Halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or compound Represents a ring group, a linked good .n also form a cyclic structure an integer of 0 or more with each other when the _{n ≧ 2, R 6, R} 7 good be the same or different .Z sulfur atom Or, it represents a selenium atom, Y represents a sulfur atom, an oxygen atom or a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.)
3. 3. The photoelectric conversion element as described in 2 above, wherein Y of the compound represented by the general formula (2) is a sulfur atom, that is, a compound represented by the following general formula (3).

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₆ and R ₇ represent a hydrogen atom. , Halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or compound Represents a ring group, a linked good .n also form a cyclic structure an integer of 0 or more with each other when the _{n ≧ 2, R 6, R} 7 good be the same or different .Z sulfur atom Or, it represents a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.)
4). 4. The photoelectric conversion device as described in 3 above, wherein R _{4 of the} compound represented by the general formula (3) is a hydrogen atom, that is, a compound represented by the following general formula (4).

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. Represents an aryl group, an amino group or a heterocyclic group, wherein R ₆ and R ₇ are a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group or a heterocyclic group, a linked good .n also form a cyclic structure an integer of 0 or more with each other when the _{n ≧ 2, R 6, R} 7 is Flip may be different even .Z represents a sulfur atom or a selenium atom, X represents a carbon acid group - carbon double bond, cis form and a trans form)..
5). 5. The photoelectric conversion element as described in 4 above, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

(Wherein R ₈ and R ₉ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, a selenoalkoxy group, an aryl group or a heterocyclic group, n8 and n9 represent an integer of 1 to 5. When n8 and n9 are 2 or more, R ₈ and R ₉ may be the same or different, and R ₃ is a hydrogen atom, a halogen atom, a cyano group, or a substituent. Or an unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, amino group or heterocyclic group, wherein R ₆ and R ₇ are a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, substituted or Represents an unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, and may be linked to each other to form a cyclic structure; N represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different, Z represents a sulfur atom or a selenium atom, and X represents an acidic group. (The double bond may be either a cis form or a trans form.)
6). 5. The photoelectric conversion element as described in 4 above, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (6).

(Wherein R ₉ and R ₁₀ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, a selenoalkoxy group, an aryl group or a heterocyclic group, n9 and n10 each represent an integer of 1 to 5. When n9 and n10 are 2 or more, R ₉ and R ₁₀ may be the same or different, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, amino group or heterocyclic group, wherein R ₆ and R ₇ are hydrogen atom, halogen atom, hydroxyl group, thiol group, cyano group, substituted Or an unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, which are linked to each other to form a cyclic structure N represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different, Z represents a sulfur atom or a selenium atom, and X represents an acidic group. (The carbon-carbon double bond may be either a cis form or a trans form.)
7). The photoelectric conversion according to any one of 1 to 6, wherein the sensitizing dye contains a plurality of compounds selected from the compounds represented by the general formulas (1) to (6). element.

  8). 8. The photoelectric conversion element according to any one of 1 to 7, wherein the semiconductor forming the semiconductor layer is titanium oxide.

  9. A solar cell comprising the photoelectric conversion element according to any one of 1 to 8 above.

  According to the present invention, it is possible to provide a photoelectric conversion element and a solar cell using a compound (pigment) which is novel and has a good adsorptivity to an oxide semiconductor and a high photoelectric conversion efficiency.

It is sectional drawing which shows an example of the photoelectric conversion element used for this invention.

  As described above, compounds having a rhodanine skeleton-containing amine structure are conventionally known as dyes with high photoelectric conversion efficiency, but these dyes are inferior in conversion efficiency to the aforementioned ruthenium complex dyes, and further improvements are required. ing.

  When the present inventors examined the compound which has an amine structure containing thione and a seron type imidazolone skeleton, it turned out that the photoelectric conversion element using this has high photoelectric conversion efficiency. This new dye is a thiol that is an electron-withdrawing group stronger than the carbonyl group in the conjugated system following the donor part (triphenylamine structure part) to the acceptor part (imidazolone skeleton part) than the conventional compound having a rhodanine skeleton-containing amine structure. Since it has a carbonyl group or a selenocarbonyl group, it has an absorption in a long wavelength region, and light of a wide wavelength can be taken in. Therefore, it is estimated that photoelectric conversion efficiency is improved.

  Hereinafter, the present invention will be described in more detail.

[Photoelectric conversion element]
The photoelectric conversion element of the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of the photoelectric conversion element of the present invention.

  As shown in FIG. 1, it is comprised from the board | substrates 1, 1 ', the transparent conductive films 2 and 7, the semiconductor 3, the sensitizing dye 4, the charge transport layer 5, the partition 9, etc.

  The photoelectric conversion element of the present invention has a semiconductor layer having pores formed by sintering particles of a semiconductor 3 on a substrate 1 (also referred to as a conductive support) to which a transparent conductive film 2 is attached, What adsorb | sucked the pigment | dye 4 to the hole surface is used. As one electrode 6 of the pair of electrodes facing each other, a transparent conductive film 7 formed on a substrate 1 'and platinum 8 deposited thereon is used, and an electrolyte layer is used as an electrolyte layer between the electrodes. 5 is filled. A terminal is attached to the transparent conductive films 2 and 7, and a photocurrent is taken out.

  The present invention relates to a novel compound (pigment), a photoelectric conversion element using the same, and a solar cell.

<< Compound Represented by Formula (1) >>
Below, the compound represented by the said General formula (1) is demonstrated.

In the general formula (1), Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R _{2 each} represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, and R ₁ , R ₂ and Ar may be linked to each other to form a cyclic structure. R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, or a heterocyclic group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, selenoalkoxy group, amino group, aryl group or heterocyclic group substituted with X. Z represents a sulfur atom or a selenium atom, X represents an acidic group, and m represents an integer of 1 or more. The carbon-carbon double bond may be either a cis isomer or a trans isomer.

  Examples of the arylene group represented by Ar include a phenylene group and a tolylene group, and examples of the heterocyclic group include a furanyl group, a thienyl group, an imidazolyl group, a thiazolyl group, a morphonyl group, and the like.

Examples of the alkyl group represented by R ₁ and R ₂ include methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group. Group, cyclopentyl group, cyclohexyl group and the like. Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, allyl group, and the like. Examples of the alkynyl group include propargyl group, 3-pentynyl group and the like are mentioned. As the aryl group, phenyl group, naphthyl group, anthracenyl group and the like are mentioned. As the heterocyclic group, furanyl group, thienyl group, imidazolyl group, thiazolyl group, morphonyl group and the like are mentioned. It is done.

Examples of the halogen atom represented by R ₃ include a chlorine atom, a bromine atom, and a fluorine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples include an amino group, an ethylamino group, a dimethylamino group, a butylamino group, and a cyclopoentylamino group.

The alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R ₃ , R ₄ , and R _{5 have} the same definitions as those described for R ₁ and R ₂ .

Examples of the alkoxy group represented by R ₅ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and examples of the thioalkoxy group include a thiomethyl group, a thioethyl group, a thiopropyl group, a thioisopropyl group, a thiobutyl group, a thio group, and the like. -Tert-butyl group, thiohexyl group, and the like. Examples of the selenoxy group include selenomethyl group, selenoethyl group, selenopropyl group, selenobutyl group, selenohexyl group, and the like. The amino group includes amino group, ethylamino group, and the like. Dimethylamino group, butylamino group, cyclopoentylamino group and the like, and X is substituted on the alkyl of the alkoxy group, thioalkoxy group, selenoalkoxy group and amino group.

  X represents an acidic group, and examples of the acidic group include a carboxyl group, a sulfo group, a sulfino group, a sulfinyl group, a phosphoryl group, a phosphinyl group, a phosphono group, a phosphonyl group, a sulfonyl group, and salts thereof. Group and a sulfo group are preferable.

  Examples of the substituent include alkyl groups (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, cyclopentyl group, cyclohexyl group. Group), alkenyl group (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, allyl group, etc.), aryl group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), hydroxyl group, amino group Group, thiol group, cyano group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.) or heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, 2-tetrahydrofuranyl group, 2- Tetrahydrothienyl group, 2-tetrahydropyranyl group, 3-te Rahidoropiraniru group). In addition, a plurality of these substituents may be bonded to each other to form a ring.

<< Compound Represented by Formula (2) >>
Among the compounds represented by the general formula (1), the compound represented by the general formula (2) is preferable because of high photoelectric conversion efficiency.

In the general formula (2), Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R _{2 each} represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, and R ₁ , R ₂ and Ar may be linked to each other to form a cyclic structure. R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, or a heterocyclic group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. R ₆ and R ₇ represent a hydrogen atom, halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, They may be linked to form an annular structure. n represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different. Z represents a sulfur atom or a selenium atom, Y represents a sulfur atom, an oxygen atom or a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.

Examples of the halogen atom represented by R ₆ and R ₇ include a chlorine atom, a bromine atom, and a fluorine atom. The substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group or heterocyclic group has the same meaning as the aryl group, alkenyl group, alkynyl group, alkoxy group or heterocyclic group in formula (1). is there.

In the general formula (2), Ar, R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , X, Z are Ar, R ₁ , R ₂ , R ₃ , R in the general formula (1). ₄ , R ₆ , R ₇ , X, Z are synonymous.

<< Compound Represented by Formula (3) >>
The compound represented by the general formula (2) is preferably a compound in which Y is a sulfur atom, that is, the compound represented by the general formula (3) because of high photoelectric conversion efficiency.

In the general formula (3), Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R _{2 each} represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, and R ₁ , R ₂ and Ar may be linked to each other to form a cyclic structure. R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, or a heterocyclic group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. R ₆ and R ₇ represent a hydrogen atom, halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, They may be linked to form an annular structure. n represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different. Z represents a sulfur atom or a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.

In the general formula (3), Ar, R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , X, Z are Ar, R ₁ , R ₂ , R ₃ , R in the general formula (2). ₄ , R ₆ , R ₇ , X, Z are synonymous.

<< Compound Represented by Formula (4) >>
The compound represented by the general formula (3) is preferably a compound in which R ₄ is a hydrogen atom, that is, the compound represented by the general formula (4) has high photoelectric conversion efficiency.

In the general formula (4), Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R _{2 each} represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, and R ₁ , R ₂ and Ar may be linked to each other to form a cyclic structure. R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, or a heterocyclic group. R ₆ and R ₇ represent a hydrogen atom, halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, They may be linked to form an annular structure. n represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different. Z represents a sulfur atom or a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.

In General Formula (4), Ar, R ₁ , R ₂ , R ₃ , R ₆ , R ₇ , X, and Z are Ar, R ₁ , R ₂ , R ₃ , R ₆ , R in General Formula (3), respectively. ₇ Synonymous with X and Z.

<< Compound Represented by Formula (5) >>
It is preferable that the compound represented by the general formula (4) is a compound represented by the general formula (5).

In the general formula (5), R ₈ and R ₉ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, a selenoalkoxy group, an aryl group or a heterocyclic group. N8 and n9 represent an integer of 1 to 5. When n8 and n9 are 2 or more, R ₈ and R ₉ may be the same or different. R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, or a heterocyclic group. R ₆ and R ₇ represent a hydrogen atom, halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, They may be linked to form an annular structure. n represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different. Z represents a sulfur atom or a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.

As the halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group or heterocyclic group represented by R ₈ and R ₉ , the halogen atom, substituted or It is synonymous with an unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group or a heterocyclic group.

In the general formula _{(5), R 3, R} 6, R 7, X, Z has the same meaning as _{R 3, R 6, R 7} , X, Z in the general formula (4).

<< Compound Represented by Formula (6) >>
It is preferable that the compound represented by the general formula (4) is a compound represented by the general formula (6).

In the general formula (6), R ₉ and R ₁₀ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, a selenoalkoxy group, an aryl group or a heterocyclic group. N9 and n10 each represent an integer of 1 to 5. When n9 and n10 are 2 or more, R ₉ and R ₁₀ may be the same or different. R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, or a heterocyclic group. R ₆ and R ₇ represent a hydrogen atom, halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, They may be linked to form an annular structure. When n ≧ 0 and n ≧ 2, R ₆ and R ₇ may be the same or different. Z represents a sulfur atom or a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.

As the halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group or heterocyclic group represented by R ₁₀ , the halogen atom in general formula (4), substituted or unsubstituted It is synonymous with an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group or a heterocyclic group.

In the general formula _{(6), R 3, R} 6, R 7, R 9, X, Z has the same meaning as _{R 3, R 6, R 7} , R 9, X, Z in the general formula (4).

  Specific examples of the compounds represented by the general formulas (1) to (6) are shown below, but the present invention is not limited thereto. In this table, the part with the wavy line of the partial structure represents a bonded part bonded by a general formula.

  The dyes represented by the general formulas (1) to (6) (hereinafter also referred to as the dyes of the present invention) can be synthesized by a general synthesis method, among which JP-A-7-5709, It can be synthesized using the method described in JP-A-7-5706.

<Synthesis example>
Synthesis Example 1 (Synthesis of Dye 1)
Dye 1 was synthesized according to the following scheme.

  Aldehyde (Compound A) was added to 2.5 equivalents of diethyl benzoylphosphonate, 3 equivalents of K-OtBu in DMF and stirred at 120 ° C. for 1 hour. Water was added to the reaction solution, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, concentrated to dryness on a rotary evaporator, and treated with a silica column to obtain compound B.

  To a toluene solution of Compound B, 1.5 equivalents of phosphorus oxychloride and 3 equivalents of DMF were added and stirred at 60 ° C. for 1 hour. Cold water was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, concentrated to dryness on a rotary evaporator, and treated with a silica column to obtain compound C.

  An acetic acid solution in which 1.2 equivalents of Compound C, imidazolidine-2,4-dithione and 1.5 equivalents of ammonium acetate were added was stirred at 0 ° C. for 12 hours. Water was added to the reaction solution, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, concentrated to dryness on a rotary evaporator, and treated with a silica column to obtain compound D.

  To an ethanol solution of Compound D, 1.05 equivalents of bromoacetic acid and 3 equivalents of potassium hydroxide were added and stirred at room temperature for 2 hours. After concentration and drying with a rotary evaporator, water and ethyl acetate were added, and the organic layer was removed with a separatory funnel. An excess amount of 1 mol / l hydrochloric acid was added to the aqueous layer, and the mixture was stirred for 5 minutes, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, concentrated to dryness on a rotary evaporator, and treated with a silica column to obtain Dye 1. .

  The structure of the dye 1 was confirmed by a nuclear magnetic resonance spectrum and a mass spectrum.

Synthesis Example 2 (Synthesis of Dye 295)
A dye 295 was synthesized according to the following scheme.

  An acetic acid solution containing aldehyde (compound E), imidazolidine-2-selenone-4-thione 1.2 equivalents and ammonium acetate 1.5 equivalents was stirred at −20 ° C. for 48 hours. Water was added to the reaction solution, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, concentrated to dryness on a rotary evaporator, and treated with a silica column to obtain compound F.

  To an ethanol solution of Compound F, 1.05 equivalents of bromoacetic acid and 3 equivalents of potassium hydroxide were added, and the mixture was stirred at 0 ° C. for 5 hours. After concentration and drying with a rotary evaporator, water and ethyl acetate were added, and the organic layer was removed with a separatory funnel. An excess amount of 1 mol / l hydrochloric acid was added to the aqueous layer, and the mixture was stirred for 5 minutes, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, concentrated to dryness on a rotary evaporator, and treated with a silica column to obtain dye 295. .

  The structure of the dye 295 was confirmed by a nuclear magnetic resonance spectrum and a mass spectrum.

  Other compounds can be synthesized in the same manner.

  The thus obtained dye of the present invention is sensitized by supporting it on a semiconductor, and the effects described in the present invention can be achieved. Here, loading a dye on a semiconductor means various modes such as adsorption onto the surface of the semiconductor, and when the semiconductor has a porous structure such as a porous structure, the semiconductor porous structure is filled with the dye. Can be mentioned.

Further, the total supported amount of the dye of the present invention per 1 m ² of the semiconductor layer (which may be a semiconductor) is preferably in the range of 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, particularly preferably 0.8. 5-20 mmol.

  When the sensitization treatment is performed using the dye of the present invention, the dye may be used alone or in combination, and other compounds (for example, US Pat. No. 4,684,537). 4,927,721, 5,084,365, 5,350,644, 5,463,057, 5,525,440 And compounds described in JP-A-7-249790, JP-A-2000-150007, and the like.

  In particular, when the use of the photoelectric conversion element of the present invention is a solar cell to be described later, two or more types of dyes having different absorption wavelengths are used so that the wavelength range of photoelectric conversion can be made as wide as possible to effectively use sunlight. It is preferable to use a mixture.

  In order to support the dye of the present invention on a semiconductor, a method in which a semiconductor which has been dissolved in an appropriate solvent (ethanol or the like) and dried well in the solution is immersed for a long time is generally used.

  When sensitizing by combining a plurality of the dyes of the present invention or using other dyes in combination, a mixed solution of each dye may be prepared and used. It is also possible to prepare a solution and immerse in each solution in order. In the case where a separate solution is prepared for each dye and is prepared by immersing in each solution in order, the effects described in the present invention can be obtained regardless of the order in which the dye is included in the semiconductor. Alternatively, it may be produced by mixing fine particles of semiconductor adsorbing the dye alone.

  The details of the semiconductor sensitization process according to the present invention will be specifically described in the photoelectric conversion element described later.

  In the case of a semiconductor with a high porosity, it is preferable to complete the adsorption treatment of the dye or the like before water is adsorbed on the semiconductor thin film and in the voids inside the semiconductor thin film due to moisture, water vapor or the like.

  Next, the photoelectric conversion element of the present invention will be described.

[Photoelectric conversion element]
The photoelectric conversion element of the present invention has, on a conductive support, at least a semiconductor layer in which the dye of the present invention is supported on a semiconductor, an electrolyte layer, and a counter electrode. Hereinafter, the semiconductor, the electrolyte, and the counter electrode will be sequentially described.

"semiconductor"
Semiconductors used for the photoelectrode include simple substances such as silicon and germanium, compounds having elements of Group 3 to Group 5 and Group 13 to Group 15 of the periodic table (also referred to as element periodic table), metals Chalcogenides (for example, oxides, sulfides, selenides, etc.), metal nitrides, and the like can be used.

  Preferred metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxides, cadmium, zinc, lead, silver, antimony or Bismuth sulfide, cadmium or lead selenide, cadmium telluride and the like. Examples of other compound semiconductors include phosphides such as zinc, gallium, indium and cadmium, gallium-arsenic or copper-indium selenide, copper-indium sulfide, titanium nitride, and the like.

Specific examples include TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, Nb ₂ O ₅ , CdS, ZnS, PbS, Bi ₂ S ₃ , CdSe, CdTe, GaP, InP, GaAs, CuInS ₂ , CuInSe ₂ , Ti ₃ N _{4 and the} like can be mentioned, but TiO ₂ , ZnO, SnO ₂ , Fe ₂ O ₃ , WO ₃ , Nb ₂ O ₅ , CdS, and PbS are preferably used. Is TiO ₂ or Nb ₂ O ₅ , among which TiO ₂ (titanium oxide) is particularly preferably used.

As the semiconductor used for the semiconductor layer, a plurality of the above-described semiconductors may be used in combination. For example, several kinds of the metal oxides or metal sulfides described above can be used in combination, or 20% by mass of titanium nitride (Ti ₃ N ₄ ) may be mixed and used in the titanium oxide semiconductor. In addition, J.H. Chem. Soc. Chem. Commun. 15 (1999). At this time, when a component is added as a semiconductor in addition to the metal oxide or metal sulfide, the mass ratio of the additional component to the metal oxide or metal sulfide semiconductor is preferably 30% or less.

  Further, the semiconductor according to the present invention may be surface-treated using an organic base. Examples of the organic base include diarylamine, triarylamine, pyridine, 4-t-butylpyridine, polyvinylpyridine, quinoline, piperidine, and amidine, among which pyridine, 4-t-butylpyridine, and polyvinylpyridine are preferable. .

  When the organic base is a liquid, the surface treatment can be carried out by preparing a solution dissolved in an organic solvent and immersing the semiconductor according to the present invention in a liquid amine or an amine solution.

(Conductive support)
The conductive support used in the photoelectric conversion element of the present invention and the solar battery of the present invention is provided with a conductive material such as a conductive material such as a metal plate or a non-conductive material such as a glass plate or a plastic film. A structure having a different structure can be used. Examples of materials used for the conductive support include metal (for example, platinum, gold, silver, copper, aluminum, rhodium, indium) or conductive metal oxide (for example, indium-tin composite oxide, tin oxide doped with fluorine) And carbon). The thickness of the conductive support is not particularly limited, but is preferably 0.3 to 5 mm.

  Further, the conductive support is preferably substantially transparent, and substantially transparent means that the light transmittance is 10% or more, more preferably 50% or more, Most preferably, it is 80% or more. In order to obtain a transparent conductive support, it is preferable to provide a conductive layer made of a conductive metal oxide on the surface of a glass plate or a plastic film. When a transparent conductive support is used, light is preferably incident from the support side.

The surface resistance of the conductive support is preferably 50 Ω / cm ² or less, and more preferably 10 Ω / cm ² or less.

<< Fabrication of semiconductor layer >>
A method for manufacturing a semiconductor layer according to the present invention will be described.

  When the semiconductor of the semiconductor layer according to the present invention is in the form of particles, the semiconductor layer is preferably manufactured by coating or spraying the semiconductor on a conductive support. In the case where the semiconductor according to the present invention is in a film form and is not held on the conductive support, it is preferable to produce a semiconductor layer by bonding the semiconductor onto the conductive support.

  A preferred embodiment of the semiconductor layer according to the present invention includes a method of forming the semiconductor layer on the conductive support by firing using fine particles of semiconductor.

  When the semiconductor according to the present invention is produced by firing, the semiconductor sensitization (adsorption, filling in a porous layer, etc.) treatment with a dye is preferably performed after firing. It is particularly preferable to perform the compound adsorption treatment quickly after the firing and before the water is adsorbed to the semiconductor.

  Hereinafter, a method for forming a photoelectrode preferably used in the present invention by baking using semiconductor fine powder will be described in detail.

(Preparation of coating liquid containing semiconductor fine powder)
First, a coating solution containing fine semiconductor powder is prepared. The finer the primary particle diameter of the semiconductor fine powder, the better. The primary particle diameter is preferably 1 to 5000 nm, and more preferably 2 to 50 nm. The coating liquid containing the semiconductor fine powder can be prepared by dispersing the semiconductor fine powder in a solvent. The semiconductor fine powder dispersed in the solvent is dispersed in the form of primary particles. The solvent is not particularly limited as long as it can disperse the semiconductor fine powder.

  Examples of the solvent include water, an organic solvent, and a mixed solution of water and an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone, acetone and acetyl acetone, hydrocarbons such as hexane and cyclohexane, and the like are used. A surfactant and a viscosity modifier (polyhydric alcohol such as polyethylene glycol) can be added to the coating solution as necessary. The range of the semiconductor fine powder concentration in the solvent is preferably 0.1 to 70% by mass, and more preferably 0.1 to 30% by mass.

(Application of coating solution containing fine semiconductor powder and baking treatment of the formed semiconductor layer)
The semiconductor fine powder-containing coating solution obtained as described above is applied or sprayed onto a conductive support, dried, etc., and then baked in air or in an inert gas, on the conductive support. A semiconductor layer (also referred to as a semiconductor film) is formed.

  A film obtained by applying and drying a coating solution containing semiconductor fine powder on a conductive support is composed of an aggregate of semiconductor fine particles, and the particle size of the fine particles is equal to the primary particle size of the semiconductor fine powder used. Corresponding.

  Thus, the semiconductor fine particle layer formed on the conductive layer such as the conductive support is weak in bonding strength with the conductive support and fine particles, and has low mechanical strength. The semiconductor fine particle layer is baked to increase the mechanical strength and form a semiconductor layer that is strongly fixed to the substrate.

  In the present invention, the semiconductor layer may have any structure, but is preferably a porous structure film (also referred to as a porous layer having voids).

  Here, the porosity of the semiconductor layer according to the present invention is preferably 10% by volume or less, more preferably 8% by volume or less, and particularly preferably 0.01 to 5% by volume. The porosity of the semiconductor layer means a porosity that is penetrable in the thickness direction of the dielectric, and can be measured using a commercially available device such as a mercury porosimeter (Shimadzu Polarizer 9220 type).

  As for the film thickness of the semiconductor layer used as the baked material film | membrane which has a porous structure, 10 nm or more is preferable at least, More preferably, it is 500-30000 nm.

  From the viewpoint of appropriately preparing the actual surface area of the fired film during the firing treatment and obtaining a fired film having the above porosity, the firing temperature is preferably lower than 1000 ° C, more preferably in the range of 200 to 800 ° C. Especially preferably, it is the range of 300-800 degreeC.

  The ratio of the actual surface area to the apparent surface area can be controlled by the particle size, specific surface area, firing temperature, etc. of the semiconductor fine particles. In addition, after heat treatment, in order to increase the efficiency of electron injection from the dye to the semiconductor particles by increasing the surface area of the semiconductor particles or increasing the purity in the vicinity of the semiconductor particles, Plating or electrochemical plating using a titanium trichloride aqueous solution may be performed.

(Semiconductor sensitization treatment)
As described above, the semiconductor sensitization treatment is performed by dissolving the dye of the present invention in an appropriate solvent and immersing the substrate on which the semiconductor is baked in the solution. In that case, it is preferable that a substrate on which a semiconductor layer (also referred to as a semiconductor film) is formed by baking is subjected to pressure reduction treatment or heat treatment in advance to remove bubbles in the film. Such treatment allows the dye of the present invention to penetrate deep inside the semiconductor layer (semiconductor film), and is particularly preferable when the semiconductor layer (semiconductor film) is a porous structure film.

  The solvent used for dissolving the dye of the present invention is not particularly limited as long as it can dissolve the compound and does not dissolve the semiconductor or react with the semiconductor. However, in order to prevent moisture and gas dissolved in the solvent from entering the semiconductor film and hindering the sensitization treatment such as adsorption of the compound, it is preferable to perform deaeration and distillation purification in advance.

  In the dissolution of the compound, preferably used solvents are nitrile solvents such as acetonitrile, alcohol solvents such as methanol, ethanol and n-propanol, ketone solvents such as acetone and methyl ethyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran, 1, Ether solvents such as 4-dioxane, and halogenated hydrocarbon solvents such as methylene chloride and 1,1,2-trichloroethane, and a plurality of solvents may be mixed. Particularly preferred are acetonitrile, acetonitrile / methanol mixed solvent, methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran and methylene chloride.

(Tensing temperature and time)
It is preferable that the time for immersing the semiconductor-baked substrate in the solution containing the dye of the present invention deeply enters the semiconductor layer (semiconductor film) to sufficiently advance adsorption or the like and sufficiently sensitize the semiconductor. In addition, from the viewpoint of suppressing degradation of the dye produced in the solution by decomposition or the like and hindering the adsorption of the dye, it is preferably 3 to 48 hours under 25 ° C., more preferably 4 to 24 hours. is there. This effect is particularly remarkable when the semiconductor film is a porous structure film. However, the immersion time is a value under the condition of 25 ° C., and is not limited to the above when the temperature condition is changed.

  When immersed, the solution containing the dye of the present invention may be used by heating to a temperature at which it does not boil as long as the dye does not decompose. A preferable temperature range is 5 to 100 ° C., more preferably 25 to 80 ° C., but this is not the case when the solvent boils in the temperature range as described above.

<Charge transport layer>
The charge transport layer used in the present invention will be described.

  The charge transport layer is a layer having a function of rapidly reducing the oxidized oxidant and transporting holes injected at the interface with the dye to the counter electrode.

  The charge transport layer according to the present invention is mainly composed of a redox electrolyte dispersion or a p-type compound semiconductor (charge transport agent) as a hole transport material.

Examples of the redox electrolyte include I ⁻ / I ₃ ⁻ system, Br ⁻ / Br ₃ ⁻ system, and quinone / hydroquinone system. Such redox electrolyte can be obtained by a conventionally known method, for example, I ^- / I ₃ ^- system electrolyte can be obtained by mixing an ammonium salt of iodine and iodine. These dispersions are called liquid electrolytes when they are in solution, solid polymer electrolytes when dispersed in a polymer that is solid at room temperature, and gel electrolytes when dispersed in a gel-like substance. When a liquid electrolyte is used as the charge transport layer, an electrochemically inert solvent is used as the solvent, for example, acetonitrile, propylene carbonate, ethylene carbonate, or the like is used. Examples of the solid polymer electrolyte include the electrolyte described in JP-A No. 2001-160427, and examples of the gel electrolyte include the electrolyte described in “Surface Science” Vol. 21, No. 5, pages 288 to 293.

  The charge transfer agent preferably has a large band gap so as not to prevent dye absorption. The band gap of the charge transfer agent used in the present invention is preferably 2 eV or more, and more preferably 2.5 eV or more. Further, the ionization potential of the charge transport agent needs to be smaller than the dye adsorption electrode ionization potential in order to reduce the dye hole. Although the preferable range of the ionization potential of the charge transport agent used in the charge transport layer varies depending on the dye used, it is generally preferably 4.5 eV or more and 5.5 eV or less, and more preferably 4.7 eV or more and 5.3 eV or less.

  As the charge transport agent, an aromatic amine derivative having an excellent hole transport capability is preferable. For this reason, photoelectric conversion efficiency can be improved more by comprising a charge transport layer mainly with an aromatic amine derivative. As the aromatic amine derivative, it is particularly preferable to use a triphenyldiamine derivative. Triphenyldiamine derivatives are particularly excellent in the ability to transport holes among aromatic amine derivatives. Moreover, such an aromatic amine derivative may use any of a monomer, an oligomer, a prepolymer, and a polymer, and may mix and use these. Monomers, oligomers, and prepolymers have a relatively low molecular weight, and thus have high solubility in solvents such as organic solvents. For this reason, when forming a charge transport layer by the apply | coating method, there exists an advantage that preparation of charge transport layer material can be performed more easily. Among these, it is preferable to use a dimer or a trimer as the oligomer.

  Specific aromatic tertiary amine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′-bis (3- Methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di) -P-tolylaminophenyl) cyclohexane; N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl; 1,1-bis (4-di-p-tolylaminophenyl)- 4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N′-diphenyl-N, N′-di (4 -Methoxyphenyl -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N- Tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) Benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two fused aromatic rings described in US Pat. No. 5,061,569 For example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), described in JP-A-4-308688 That triphenylamine units are linked to three starburst 4,4 ', 4 "- tris [N- (3- methylphenyl) -N- phenylamino] triphenylamine (MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  Examples of charge transport agents other than aromatic amine derivatives include thiophene derivatives, pyrrole derivatives, stilbene derivatives, and the like.

  Specific examples of the charge transfer agent are shown below, but the present invention is not limited thereto.

《Counter electrode》
The counter electrode used in the present invention will be described.

  The counter electrode may be any material as long as it has conductivity, and any conductive material can be used. However, it has a catalytic ability to perform oxidation of I3- ions and other redox ions at a sufficiently high rate. Is preferred. Examples of such a material include a platinum electrode, a surface of a conductive material subjected to platinum plating or platinum deposition, rhodium metal, ruthenium metal, ruthenium oxide, and carbon.

[Solar cell]
The solar cell of the present invention will be described.

  The solar cell of the present invention has a structure in which the optimum design and circuit design for sunlight are performed as one aspect of the photoelectric conversion element of the present invention, and the optimum photoelectric conversion is performed when sunlight is used as a light source. Have That is, the semiconductor is dye-sensitized and can be irradiated with sunlight. When constituting the solar cell of the present invention, it is preferable that the photoelectrode, the electrolyte layer and the counter electrode are housed in a case and sealed, or the whole is sealed with resin.

  When the solar cell of the present invention is irradiated with sunlight or an electromagnetic wave equivalent to sunlight, the dye according to the present invention supported on the semiconductor absorbs the irradiated light or electromagnetic wave and excites it. Electrons generated by excitation move to the semiconductor, and then move to the counter electrode via the conductive support to reduce the redox electrolyte in the charge transfer layer. On the other hand, the dye according to the present invention in which electrons are transferred to a semiconductor is an oxidant, but is reduced to the original state by supplying electrons from the counter electrode via the redox electrolyte of the electrolyte layer. At the same time, the redox electrolyte of the charge transfer layer is oxidized and returned to a state where it can be reduced again by electrons supplied from the counter electrode. In this way, electrons flow, and a solar cell using the photoelectric conversion element of the present invention can be configured.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example [Production of Photoelectric Conversion Element 1]
Titanium oxide paste (anatase type, primary average particle diameter (microscope observation average) 18 nm, polyethylene glycol dispersion) is applied to fluorine-doped tin oxide (FTO) conductive glass substrate by screen printing (application area 5 × 5 mm ² ). did. Coating and drying (3 minutes at 120 ° C.) were repeated three times, and baking was carried out at 200 ° C. for 10 minutes and at 500 ° C. for 15 minutes to obtain a 15 μm thick titanium oxide thin film. On this thin film, a titanium oxide paste (anatase type, primary average particle diameter (microscope observation average) 400 nm, polyethylene glycol dispersion) was further applied and baked by the same method to form a titanium oxide thin film having a thickness of 5 μm.

The dye 1 of the present invention was dissolved in a mixed solvent of acetonitrile: t-butyl alcohol = 1: 1 to prepare a solution of 5 × 10 ⁻⁴ mol / l. The FTO glass substrate coated and sintered with titanium oxide was immersed in this solution at room temperature for 3 hours for dye adsorption treatment to obtain a semiconductor electrode.

  For the electrolyte layer (electrolytic solution), 1,2-dimethyl-3-propylimidazolium iodide 0.6 mol / l, lithium iodide 0.1 mol / l, iodine 0.05 mol / l, 4- (t-butyl) ) An acetonitrile solution containing 0.5 mol / l of pyridine was used. The photoelectric conversion element 1 was produced by assembling with the clamp cell so that the layer thickness of a charge transport layer might be set to 20 micrometers using the produced semiconductor electrode and the glass plate which vapor-deposited platinum and chromium in the counter electrode.

[Preparation of photoelectric conversion elements 2 to 34]
In the production of the photoelectric conversion element 1, photoelectric conversion elements 2 to 34 were produced in the same manner except that the dye 1 was changed to the dye of the present invention described in Table 1.

[Production of Photoelectric Conversion Element 35]
In the production of the photoelectric conversion element 1, instead of the 5 × 10 ⁻⁴ mol / l solution in which the dye 1 was dissolved in a mixed solvent of acetonitrile: t-butyl alcohol = 1: 1, the dye 1 was changed to acetonitrile: t-butyl alcohol. = 1: 5 × ¹⁰ -4 mol / l of solution and dye 362 mixture was dissolved in a solvent 1 acetonitrile: t-butyl alcohol = 1: a solution of 5 × ¹⁰ -4 mol / l dissolved in a mixed solvent of 1 A photoelectric conversion element 35 was produced in the same manner except that the dye solution was mixed in a 1: 1 ratio.

[Preparation of Photoelectric Conversion Element 36]
In the production of the photoelectric conversion element 1, instead of the 5 × 10 ⁻⁴ mol / l solution in which the dye 1 was dissolved in a mixed solvent of acetonitrile: t-butyl alcohol = 1: 1, the dye 57 was changed to acetonitrile: t-butyl alcohol. = 1: 5 × ¹⁰ -4 mol / l of solution and dye 238 mixture was dissolved in a solvent 1 acetonitrile: t-butyl alcohol = 1: a solution of 5 × ¹⁰ -4 mol / l dissolved in a mixed solvent of 1 A photoelectric conversion element 36 was produced in the same manner except that the dye solution was mixed in a 1: 1 ratio.

[Preparation of Photoelectric Conversion Element 37]
In the production of the photoelectric conversion element 1, the dye 1 is changed to the dye 501, and the charge transfer layer (electrolytic solution) is 1-methyl-3-butylimidazolium iodide 0.6 mol / l, lithium iodide 0.1 mol / l. The photoelectric conversion element 37 was prepared in the same manner as the photoelectric conversion element 1 except that a solution of 3-methoxypropionitrile containing l, iodine 0.05 mol / l, 4- (t-butyl) pyridine 0.5 mol / l was used. Obtained.

[Production of Photoelectric Conversion Element 38]
In the production of the photoelectric conversion element 37, a photoelectric conversion element 38 was produced in the same manner except that the dye 501 was changed to the dye 502.

[Preparation of Photoelectric Conversion Element 39]
The conditions until a semiconductor electrode was produced on an FTO glass substrate were produced in the same manner as the photoelectric conversion element 1 except that the dye 1 was changed to the dye 5. Then, the aromatic amine derivative 2,2 ′, 7,7′-tetrakis (N, N′-di (4-methoxyphenyl) amine) -9, which is a hole transport material, is mixed with chlorobenzene: acetonitrile = 19: 1 mixed solvent. , 9′-spirobifluorene (OMeTAD) is 0.17 mol / l, N (PhBr) ₃ SbCl ₆ is 0.33 mmol / l as a hole doping agent, and Li [(CF ₃ SO ₂ ) ₂ N] is 15 mmol / l. A hole layer forming coating solution was prepared by dissolving t-Butylpyridine so as to be 50 mmol / l. Then, the hole layer forming coating solution was applied by spin coating on the upper surface of the semiconductor layer on which the photosensitizing dye was adsorbed and bonded to form a charge transport layer. Furthermore, 90 nm of gold was vapor-deposited by a vacuum vapor deposition method, a counter electrode was produced, and the photoelectric conversion element 39 was produced. In the application by the spin coating method described above, the spin coating rotation speed was set to 1000 rpm.

[Production of Photoelectric Conversion Element 40]
In the production of the photoelectric conversion element 39, a photoelectric conversion element 40 was produced in the same manner as the photoelectric conversion element 39 except that the dye was changed to the dye 501.

[Evaluation of photoelectric conversion element]
The produced photoelectric conversion element was irradiated by irradiating 100 mW / cm ² of pseudo-sunlight from a xenon lamp through an AM filter (AM-1.5) using a solar simulator (manufactured by Eihiro Seiki). That is, for the photoelectric conversion element, current-voltage characteristics are measured at room temperature using an IV tester to determine a short circuit current (Isc), an open circuit voltage (Voc), and a form factor (FF). From this, the photoelectric conversion efficiency (η (%)) was determined.

  The evaluation results are shown in Table 1.

From Table 1, the photoelectric conversion element 11 using the dye of the present invention has improved open-circuit voltage (V _OC ), short-circuit current (I _SC ), and conversion efficiency as compared with the photoelectric conversion element 38 using the comparative dye. I understand that. Moreover, it turns out that the conversion efficiency is improving also in the photoelectric conversion elements 1-34 using the pigment | dye of this invention. Further, the conversion efficiency was improved in the photoelectric conversion elements 35 and 36 using a plurality of dyes, and the short-circuit current, the open-circuit voltage, and the conversion efficiency of the photoelectric conversion element 39 were improved as compared with the photoelectric conversion element 40. In addition, in some dyes of the present invention, the absorption wavelength of the dye adsorbed on the semiconductor layer is longer than that of the solution absorption, so that aggregation develops due to intermolecular interaction, and more wavelengths are absorbed. Absorbing light is also considered to be a factor in improving conversion efficiency.

1, 1 ′ substrate 2, 7 transparent conductive film 3 semiconductor 4 sensitizing dye 5 charge transport layer 6 counter electrode 8 platinum

Claims (9)

In a dye-sensitized photoelectric conversion element in which a semiconductor layer and an electrolyte layer in which at least a sensitizing dye is supported on a semiconductor is provided between a pair of opposing electrodes, the sensitizing dye is represented by the following general formula (1). The photoelectric conversion element characterized by containing the compound represented by these.

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ is substituted with X. Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, selenoalkoxy group, amino group, aryl group or heterocyclic group. Z represents a sulfur atom or a selenium atom, X represents an acidic group, and m represents an integer of 1 or more. The carbon-carbon double bond may be either a cis isomer or a trans isomer.) 2. The photoelectric conversion device according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₆ and R ₇ represent a hydrogen atom. , Halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or compound Represents a ring group, a linked good .n also form a cyclic structure an integer of 0 or more with each other when the _{n ≧ 2, R 6, R} 7 good be the same or different .Z sulfur atom Or, it represents a selenium atom, Y represents a sulfur atom, an oxygen atom or a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.) The photoelectric conversion element according to claim 2, wherein Y of the compound represented by the general formula (2) is a sulfur atom, that is, a compound represented by the following general formula (3).

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₆ and R ₇ represent a hydrogen atom. , Halogen atom, hydroxyl group, thiol group, cyano group, substituted or unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or compound Represents a ring group, a linked good .n also form a cyclic structure an integer of 0 or more with each other when the _{n ≧ 2, R 6, R} 7 good be the same or different .Z sulfur atom Or, it represents a selenium atom, and X represents an acidic group. The carbon-carbon double bond may be either a cis isomer or a trans isomer.) The photoelectric conversion device according to claim 3, wherein R _{4 of the} compound represented by the general formula (3) is a hydrogen atom, that is, a compound represented by the following general formula (4).

(In the formula, Ar represents a substituted or unsubstituted arylene group or heterocyclic group. R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, R ₁ , R ₂ and Ar may combine with each other to form a cyclic structure, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. Represents an aryl group, an amino group or a heterocyclic group, wherein R ₆ and R ₇ are a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group or a heterocyclic group, a linked good .n also form a cyclic structure an integer of 0 or more with each other when the _{n ≧ 2, R 6, R} 7 is Flip may be different even .Z represents a sulfur atom or a selenium atom, X represents a carbon acid group - carbon double bond, cis form and a trans form).. The photoelectric conversion element according to claim 4, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

(Wherein R ₈ and R ₉ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, a selenoalkoxy group, an aryl group or a heterocyclic group, n8 and n9 represent an integer of 1 to 5. When n8 and n9 are 2 or more, R ₈ and R ₉ may be the same or different, and R ₃ is a hydrogen atom, a halogen atom, a cyano group, or a substituent. Or an unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, amino group or heterocyclic group, wherein R ₆ and R ₇ are a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, substituted or Represents an unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, and may be linked to each other to form a cyclic structure; N represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different, Z represents a sulfur atom or a selenium atom, and X represents an acidic group. (The double bond may be either a cis form or a trans form.) 5. The photoelectric conversion element according to claim 4, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (6).

(Wherein R ₉ and R ₁₀ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, a selenoalkoxy group, an aryl group or a heterocyclic group, n9 and n10 each represent an integer of 1 to 5. When n9 and n10 are 2 or more, R ₉ and R ₁₀ may be the same or different, and R ₃ represents a hydrogen atom, a halogen atom, a cyano group, Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, amino group or heterocyclic group, wherein R ₆ and R ₇ are hydrogen atom, halogen atom, hydroxyl group, thiol group, cyano group, substituted Or an unsubstituted alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, amino group or heterocyclic group, which are linked to each other to form a cyclic structure N represents an integer of 0 or more, and when n ≧ 2, R ₆ and R ₇ may be the same or different, Z represents a sulfur atom or a selenium atom, and X represents an acidic group. (The carbon-carbon double bond may be either a cis form or a trans form.)   The photosensitizer according to any one of claims 1 to 6, wherein the sensitizing dye contains a plurality of compounds selected from the compounds represented by the general formulas (1) to (6). Conversion element.   The photoelectric conversion element according to claim 1, wherein the semiconductor forming the semiconductor layer is titanium oxide.   It has a photoelectric conversion element of any one of Claims 1-8, The solar cell characterized by the above-mentioned.

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