TW201210835A - Photoelectric converting device, photoelectrochemical cell, plgment for photoelectric converting device and pigment solution for photoeletric converting device - Google Patents

Abstract

A photoelectric converting device includes a photoreceptor layer having a pigment represented by the following formula (1) and having semiconductor micron particles. The pigment is a compound which is represented by the following formula (1) and has an aliphatic group having 5 to 18 carbons. In the formula (1), Q represents a four-valent aromatic group; X1 and X2 independently represent a sulfur atom, an oxygen atom, or CR1R2, wherein R1 and R2 independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group bonded by carbon atoms, respectively; R and R' independently represent an aliphatic group, an aromatic group, a heterocyclic group bonded by carbon atoms, respectively; P1 and P2 independently represent a pigment residue, respectively; W1 represents a counter ion necessary for charge neutralization.

Description

201210835 38254pif VI. Description of the invention: This application is based on the Japanese Patent Application No. 2〇1〇_124〇2〇, filed in the application for the Intellectual Property Office of Sakamoto on May 31, 2010. Patent application No. 2010-287040 filed on December 24th with the Sakamoto Intellectual Property Office, and the application for the patent application of the Japanese Intellectual Property Office on March 17, 2011. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; [Technical Field] The present invention relates to a photoelectric conversion element and a photoelectrochemical cell which are excellent in conversion efficiency and excellent in durability, and also relates to a coloring element for a photoelectric conversion element and a dye solution for a photoelectric conversion element. [Prior Art] The photoelectric conversion element can be used in various photo sensors, copying machines, solar cells, and the like. The photoelectric conversion element can be put into practical use by using various forms such as a metal, a semiconductor, an organic pigment or a dye, or a combination of these. In particular, solar cells using non-drying solar energy sources do not require fuel and can utilize endless clean energy, so their practical utility is greatly expected. Among them, tantalum solar cells have been researched and developed since the past, and have been widely developed due to the consideration of national policies. However, silicon is an inorganic material with natural limits for both throughput and molecular modification (m〇iecuiar m〇dificatj〇n). So 'dye sensitized solar cells (Dye_Sensitized Solar 201210835 38254pif

The research of Cells was actively carried out. In particular, Graetzel et al. of the University of Technology in Lausanne, Switzerland, have developed a dye-sensitized solar cell in which a pigment formed of a ruthenium complex is fixed on the surface of a porous titanium oxide film to achieve a common amorphous state.转换 conversion efficiency. Therefore, the dye-sensitized solar cell has attracted the attention of researchers all over the world. Patent Document 1 describes a dye-sensitized photoelectric conversion element in which the above-described technique is applied and semiconductor fine particles sensitized with a ruthenium complex dye are used. However, the conventional erbium complex dye is capable of photoelectric conversion using visible light, but it is almost impossible to absorb infrared light having a long wavelength of more than 700 nm or longer, and thus the photoelectric conversion energy in the infrared region is low. In a proposal, a photoelectric conversion element having a high conversion efficiency by using a polymethine dye having a specific structure and having a high wavelength of 700 nm or more is provided (for example, refer to Patent Document 2). Further, the photoelectric conversion element must have high conversion efficiency in the initial stage in the wide wavelength region, and the reduction in conversion efficiency after use is less excellent in durability. However, the portion of the durability is not sufficiently described in the photoelectric conversion element described in Patent Document 2. Therefore, a photoelectric conversion element having high conversion efficiency and excellent durability and a photoelectrochemical cell are necessary. Further, a dye for a photoelectric conversion element and a dye solution for a photoelectric conversion element are also necessary. [Prior Technical Literature] [Patent Literature]

In the present invention, an object of the present invention is to provide a photoelectric conversion element and a photoelectrochemical cell which have high conversion efficiency and excellent durability, and are disclosed in Japanese Patent No. 4, 427, 720. . Another object of the present invention is to provide a dye for a photoelectric conversion element and a dye solution for a photoelectric conversion element. As a result of intensive studies, the inventors of the present invention have found that a photoreceptor including a porous semiconductor fine particle layer having a polymethine dye (pigment compound) having a specific structure adsorbed on a conductive support, a charge transporting body, and The photoelectric conversion element having a multi-layered structure and a photoelectrochemical cell using a ruthenium have high conversion efficiency in a wide wavelength region and excellent durability. The present invention has been implemented based on the above knowledge. The object of the present invention is achieved in the following manner. _ &lt;1&gt; - a photoelectric conversion element comprising a body layer having a dye of a general formula (1) and a semiconductor body, and a compound represented by the formula (1) of the aliphatic group of the above color 5 to 18 Pigment t

X1 In the above general formula (1), 'Q is represented as a tetravalent aromatic group 201210835 38254pif

Xj is independently represented by a sulfur atom, an oxygen atom or CR1r\, wherein R1 and R2 are each independently represented as a hydrogen atom, an aliphatic group, or a heterocyclic group in which an aromatic group is bonded by a carbon atom, and may be substituted. R and R are each independently represented by an aliphatic group, an aromatic group, a heterocyclic group bonded with a carbon atom, and may be substituted. P1 and p2 are each independently represented as a pigment residue. W1 represents the relative ions necessary to neutralize the charge. The photoelectric conversion element according to <1>, wherein the aliphatic group having 5 to 18 carbon atoms is a branched alkyl group. The photoelectric conversion element according to the above formula (1), wherein Q in the above general formula (1) is represented by a benzene ring or a naphthalene ring. &lt;3&gt; The photoelectric conversion element according to any one of the above-mentioned general formula (1), wherein P1 and P2 in the above general formula (1) are each independently a general formula (2) or a general formula (3). ) said. [Chemical 2]

General formula (2)

S 201210835 38254pif [化3] z O'

The above general formula (2) or the general formula (3) towel 'is a hydrogen atom or a substituent. η is an integer of 〇~4, and when n is 2 or more, vl may be the same or different, and may be bonded to each other to form a ring.匕I is expressed as S, NR9 or CRY. Among them, Han 9 is represented by a gas atom, a ruthenium, an aromatic group or a heterocyclic group bonded by a carbon atom. R1(), 尺" = is a ^, a fatty filament, an aromatic group or a carbon-bonded clothing group which may be the same or different and may be bonded to each other to form a ring.

Zf is a pigment, a group or a carbon atom-bonding group, and it may have a substituent. The clothes R to R6 and R8 are each independently represented by a gas atom, an aliphatic aryl group or a heterocyclic group, and may have a substituent. R7 is an oxygen atom or a carbon atom having two substituents, and the sum of the substitution constants (σρ) of the two substituents 'Hammett' rule is a positive number. 201210835 38254pif [化4]

[化5] ο

In the above general formula (4) or general formula (5), V1 is represented by a hydrogen atom or a substituent. η represents an integer of 0 to 4, and when η is 2 or more, V1 may be the same or different, and may be bonded to each other to form a ring. Υ is expressed as S, NR9 or CR1GRU. Wherein R9 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. R1Q and R11 are represented by a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, which may be the same or different, or may be bonded to each other to form a ring. Z represents an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and may have a substituent. &lt;6&gt; The photoelectric conversion element according to <4> or <5>, wherein the above V1 has an acidic group. The photoelectric conversion element according to any one of <4>, wherein the above V1 is a hydrogen atom, a 5-carboxy group, a 5-sulfonic acid group, a 5-fluorenyl group or a 4, 5 - Benzene ring 201210835 38254pif condensation. The photoelectric conversion element according to <6>, wherein the above Z and V1 are an acidic group or a group having an acidic group. The photoelectric conversion element according to any one of <4>, wherein the general formula (2) is represented by the general formula (6), and the above general formula ( 3) is expressed by the general formula (7). [6] E11

[Chemistry 7]

In the above general formula (6) or general formula (7), Y, Z, and R3 to R8 are the same as defined in the general formula (2) or the general formula (3), Y, Z, and R3 to R8. V12 is represented as an acidic group. At least one of E11 to E13 is represented as a pull electron group. p is an integer of 2 or more. <10> The photoelectric conversion element according to <4>, wherein the general formula (2) is represented by a general formula (8), and the general formula (3) is represented by a general formula (9). 11 201210835 38254pif [化8]

General formula (8) [Chemical 9]

Rb Formula A Formula B Formula C Formula D In the above general formula (8) or general formula (9), Υ, Z, R3 to R8 are Y, Z, R3 of the general formula (2) or the general formula (3). R8 is defined the same. L is represented by the above formulas A to D, and m is an integer of 0, 1, or 1 or more. When m is 2 or more, L may be different. In the above formula A, Xa represents NRe, Ο, S, and Re represents a hydrogen atom or a substituent. In the above formulas A and C, Ra to Rd are represented by an acidic group. In the above general formula (8), p represents an integer of 2 or more, and Rx represents an acidic group. The photoelectric conversion element according to any one of <4> to <10>, wherein

12 S 201210835 38254pif The above Y is represented by S, NCH3 or C(CH3)2, and Z is represented by an aliphatic group having 5 to 18 carbon atoms. The photoelectric conversion element according to any one of the above-mentioned formulas, wherein the formula R7 is represented by any one of the formulas (10) to (13). [化11]

)^=S | π II

〇 ^COORf NC C00Rf RfOOC Person COORf NC Human CN General Formula (10) General Formula (1) General Formula (10) General Formula (10) In the above formula (10) to formula (13), Rf is represented by a hydrogen atom or a substituent. The photoelectric conversion element according to any one of <4>, wherein the above formula R7 is represented by the formula (14) or the formula (15). [化 12]

HOOC (14) General formula (15) <14> The photoelectric conversion element of any one of <1> to <13>, wherein the above-mentioned general formula (1) towel is not a benzene ring Χ1 and χ2 are each independently represented by a sulfur atom, a ruthenium atom or C(CH3)2, and R and R are represented by an aliphatic group having a carbon number of 5 to 18. The photoelectric conversion element according to any one of <1>, wherein the semiconductor fine particles are titanium oxide fine particles. &lt;16&gt; A photoelectrochemical cell, comprising the photoelectric conversion element according to any one of &lt;1&gt; to &lt;15&gt;. &lt;17&gt; A dye for a photoelectric conversion element comprising a compound represented by the general formula (1) having an aliphatic group having 5 to 18 carbon atoms. V1 γ2 Ρ1=&lt; X Ρ2 R R' General formula (1) In the above general formula (1), Q represents a tetravalent aromatic group. X1 and X2 are each independently represented by a sulfur atom, an oxygen atom or CWr2. Here, Ri and R are each independently represented by a hydrogen atom, an aliphatic group, an aromatic group, a hetero group bonded with a carbon atom, and may be substituted. r and 尺' are each independently represented by an aliphatic group, an aromatic group, a heterocyclic group bonded by a carbon atom, and may be substituted. P1 and P2 are each independently represented as a pigment residue. Wl denotes the relative ions necessary to neutralize the charge. &lt;18&gt; A dye solution for a photoelectric conversion element, which comprises a dye for a photoelectric conversion element according to &lt;17&gt; which is contained in an organic solvent. The present invention can provide an electro-optical device and a photoelectrochemical cell which are excellent in conversion efficiency and excellent in durability. Further, the present invention can provide a dye solution for a photoelectric conversion element 201210835 38254pif and a photoelectric conversion element. The above-described features and advantages of the present invention will become more apparent from the following description. [Embodiment] The inventors of the present invention have repeatedly conducted intensive studies and found that a photoelectric conversion element including a photoreceptor layer having a specific dye and semiconductor fine particles, and a photoelectric conversion battery using the same have high photoelectric conversion efficiency, durability, and particularly The reduction in photoelectric conversion efficiency is small. The present invention has been made based on the above findings. - Next, a preferred example of the photoelectric conversion element of the present invention will be described with reference to the drawings. As shown in Fig. 1, the photoelectric conversion element 10 includes a conductive support p and a photoreceptor layer 2, a charge transporting layer 3 and a counter electrode 4, which are arranged in this order on the conductive support 1. The conductive support 1 and the photoreceptor layer 2 constitute the light-receiving electrode 5. The photoreceptor layer 2 has the semiconductor fine particles 22 and the sensitizing dye 21, and at least a part of the dye 21 is adsorbed to the semiconductor fine particles 22 (the pigment may be present in a part of the charge transporting layer when it is in an adsorption equilibrium state). . The conductive support 1 on which the photoreceptor layer 2 is formed functions as a working electrode in the photoelectric conversion element 10. This photoelectric conversion element 1 is operated by an external circuit 6, and can also be operated as a photoelectrochemical cell. The light receiving electrode 5 is an electrode including a conductive support i and a photoreceptor layer (semiconductor film) 2, and the photoreceptor layer (semiconductor film) 2 contains semiconductor fine particles 22 which adsorb the dye 21 coated on the conductive support. The light incident on the photosensitive layer (semiconductor film) 2 excites the dye, and the excitation pigment has an electron of 15 201210835 38254pif high energy. Therefore, the above electrons can be transported from the dye 21 to the conduction band of the semiconductor fine particles 22, and further diffuse to the conductive support 1' and the molecules of the dye 21 form an oxidized body. The electrons on the electrodes are outside. When the 卩 circuit operates, it returns to the dye oxidant and acts as a photochemical battery. In this case, the light receiving electrode 5 operates as a negative electrode of the battery. The photoelectric conversion element of the present invention has a photosensitive layer </ RTI> on the conductive support, and the photoreceptor layer has a porous semiconductor fine particle layer in which a specific dye described later is adsorbed. The photoreceptor layer may be designed as a single layer structure for the purpose of 'or a multilayer structure'. Further, the dye in the photoreceptor layer may be a mixture of a plurality of types of dyes, but at least a dye described later is used. When a photoreceptor layer containing the semiconductor fine particles to which the above dye is adsorbed is used as the photoelectric conversion device of the present invention, a photoelectric conversion element having high sensitivity to light in a wide wavelength region can be obtained. When the above-mentioned photoelectric conversion element is used as the photoelectrochemical cell, a photoelectric conversion element which can obtain high conversion efficiency, has a small reduction in conversion efficiency, and is excellent in durability can be obtained. (A) Pigment (A1) The dye of the formula (1) In the photoelectric conversion element of the present invention, a dye of a compound represented by the following general formula (丄) is used. The above dye can be used as a photoelectric conversion element and has an aliphatic group having 5 to 18 carbon atoms. The aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group, more preferably an alkyl group or an alkenyl group. Most preferred is an alkyl group, which may, for example, be pentyl, hexyl, heptyl, octyl, nonyl, decyl or eleven And, 201210835. j〇z, ^*+pif dodecyl, octadecy!, cycl〇hexyl, 2-ethylhexyl, and the like. The alkyl group is preferably a branched alkyl group, which is, for example, 2-ethylhexyl, 2-methylhexyl (2-meth hexyl), 2-methylpentyl, 3,5,5-triazine Cyclohexyl (3,5,5-trimethylhexyI), 2-cyclopentaneethyl (2-CyCl〇pentaneethyl), 2-cyclohexylethyl (2 cycl〇hexyIethyl), and the like. Since it has an alkyl group having a carbon number of 5 to 18, it can suppress decomposition of a pigment caused by water and a nucleophile, and can suppress the durability of water caused by the chromatic nucleophilic particles. reduce. Further, since the aggregation or excessive adsorption of the dyes can be suppressed, the inefficient axis ' can be suppressed and the photovoltaic efficiency can be improved. Further, since the burning base is branched, the effect of improving the durability particularly in the above effects can be obtained more remarkably. [Chem. 14] p X1 ... X2

IT I R N I R, W] - (1) In the general formula U), Q is an aromatic group having at least four or more functional groups. Examples of the aromatic compound include aromatic hydrocarbons and aromatic heterocyclic rings. Among them, the aromatic hydrocarbon is, for example, stupid, naphthene, anthraene, phenanthrene, etc., and the aromatic heterocyclic ring is, for example, anthraquinium (inhalaq Uin〇ne), carbazole (carbazole) Pyridine), 啥琳17 201210835 38254pif (quinoline), thiophene, furan (furan), xanthene, thianthrene, etc., in addition to having a substituent other than the linking moiety. The aromatic group represented by Q is preferably an aromatic furnace, more preferably benzene or naphthalene. Here, the bond of ## to N(R,) of Q is also included in the formula of Fig. (R') The position X2 is bonded and the bond is bonded at the χ2 position r'. Further, X1 and X2 are each independently represented by a sulfur atom, an oxygen atom or CRi2. χΐ and X2 are preferably a sulfur atom or cr1r2, More preferably, it is cr1r2: wherein R1 and R2 are each independently represented by a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. The heterocyclic group bonded with a carbon atom may, for example, be exemplified. (pyrrole), furan, thiophene, imidaz〇le, oxazole, thiaz〇le Pyrazol, isoxazole, iso-plug. Isothiaz〇le &quot;bite, pyridazine, pyrimidine, pyran, etc. Ri R2 is preferably an aliphatic group or an aromatic group. The aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group, more preferably an alkyl group or an alkenyl group. The alkyl group may be a linear or branched alkyl group. More preferably, it is an alkyl group having a carbon number of 5 to 18 (for example, pentyl, hexyl, heptyl, octyl, decyl, decyl, eleven, decyl, octadecylcyclohexyl, 2_ Ethylhexyl or the like. Among the alkyl groups, a branched alkyl group is preferred, and is, for example, 2-ethylhexyl, 2-decylhexyl, 2-methylpentyl, 3,5, 5-tridecylhexyl , 2-cyclopentanylethyl, 2-cyclohexylethyl, etc. Since it has a carbon number of 5 to 18, it can inhibit the decomposition of pigments caused by water and nucleophiles, and can prevent water from approaching the adsorption point. The durability of the pigment is removed from the semiconductor fine particles, and the aggregation or excessive adsorption of the dyes can be suppressed. In 201210835, inefficient electron movement can be suppressed and In addition to the improvement of the photoelectric conversion efficiency, since the burning base is branched, the effect of improving the above-mentioned effects, particularly the long-term reliability, can be more remarkably obtained. (4) Silk is preferred as silk, naphthalene, and the like. The sub-bonded filament is an aliphatic group, An aromatic group or a ring group of the original t, and which may also be substituted. The heterocyclic group bonded by a carbon bond is, for example, a scale, a bite, a sputum, a sputum, a sputum, and a sputum. Seymour and 吼t are different. Sputum, σ than bite, β荅肼, σ close bite, fox murmur, etc. R and R are preferably an aliphatic group or an aromatic group, and the aromatic filaments preferably have a carbon number of 5 〜', more preferably 5 or 61, and the substituted aromatic group is preferably a phenyl group or a phenyl group. The sclerosing filament is preferably a silk, a county or a silk, more preferably an alkyl group or an alkenyl group, more preferably an alkyl group having a carbon number of 5 to 18 (for example, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an anthracene group). Base, undecyl, dodecyl, octadecylcyclohexyl, 2-ethylhexyl, etc.). In the alkyl group, a branched alkyl group is preferred, which is, for example, 2-ethylhexyl, 2-methylhexyl, 2-decylpentyl, 3,5,5-tridecylhexyl, 2-cyclopentane. Ethyl, 2-cyclohexylethyl and the like. By having a carbon number of 5 to 18, it is possible to suppress the decomposition of the pigment by water and a nucleary phile, and to prevent the water from approaching the adsorption point and to prevent the dye from being peeled off from the semiconductor fine particles. reduce. Further, since aggregation or excessive adsorption of the pigments can be suppressed, inefficient electron movement can be suppressed and the photoelectric conversion efficiency can be improved. Further, since the alkyl group is branched, the effect of improving the durability particularly in the above effects can be more remarkably obtained. 1 2 卜 p, p is expressed as a pigment residue. The term "pigment residue" refers to a group of atoms necessary for forming a pigment compound as a whole, in addition to the structures other than P and P of the general formula (1). P1 and P2 are direct bonds or a bond of 201210835. JOZJHpif bond to form a pigment of the general formula (1). The pigment (pigment compound) formed by pi and P2 is, for example, Cyanine, melocyanine, rh〇dacyanine, 3 nucleus anthocyanins, allopolar, half flower Polymethine pigments such as hemicyanine, styryl, oxonol, cyanine, etc., containing acridine, dibenzopyran, sulfur Diarylmethine, triarylmethine, coumarin, indoaniline, indophenol, pyrazine (thioxanthene) Diazine), oxazine, thiazine, 0 pirazine and ° ratio (Diketopyrrolopyrrole), indigo, indigo, perylene, quinacridone ), naphthoquinone, bipyridyl, terpyridyl, tetrapyridyl, phenanthroline, and the like. Preferably, it is a cyanine, anthocyanin, anthocyanin, a trinuclear anthocyanin, an allopolar, a hemi-cyanine, a cinnamon, and the like. At this time, a substituent on the methine bond forming a dye in the cyanine is also included to form a dye of a squarylium ring and a croconium ring. The above-mentioned pigments are described in detail in F, Μ, Harmer, JOHN WILEY & SONS Publishing House, "Heterocyclic Compounds - Cyanine Dyes and Related Compounds" published in New York and London in 1964. The general formula of cyanine, merocyanine, and safflower anthocyanin is preferably represented by (XI), (XII), (XIII) of U.S. Patent No. 5,340,694. another

Further, it is preferable that at least one of the pigment residues formed by p1 and p has a sulfhydryl ring and a ketone acid ring, more preferably two ratios. Among the pigments having the above-described structure (U), P1 and P2 are preferably independently represented by the following general formula (2) or general formula (3).

Z General (2) [Chem. 16]

In the above general formula (3), in the general formula (3), vl represents a hydrogen atom or a substituent 'n represents an integer of 0 to 4, and when n is 2 or more, v is different'. Bonded to each other to form j裒. n car Jiaojia is 〇~3, better ~2 〇 Q Y is expressed as sulfur atom, service 9 or CRl〇R&quot;. A heterocyclic group in which a hydrogen atom, an aliphatic group, an aromatic group or a bond is a ruthenium, for example, a sputum "salvation", a saliva, a singularity, a singularity, a ridge 21 201210835, and the like. A preferred example of R9 is an aliphatic group, and it is preferably an alkyl group, an alkenyl group or an alkynyl group, more preferably an alkyl group or an alkenyl group. Further, it is more preferably an alkyl group having 5 to 18 carbon atoms (e.g., pentyl, hexyl, heptyl, octyl, decyl, decyl, eleven, decyl, octadecyl, cyclohexyl, 2 _Ethylhexyl, etc.). The aromatic group is preferably benzene, naphthalene, anthracene or the like. R11 is represented by a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and Ri and Ru may be the same or different and may be bonded to each other to form a ring. The heterocyclic group bonded to a carbon atom is, for example, pyrrole, furan, cel. Ηη sit, 嗟π sit, α pyridine, 嗒肼, pyrimidine, 呱 等 and so on. A preferred example of R1 吡 pyrazole, isoxazole, isothiazole, pyridine 0 and R11 is an aliphatic earth, and it is preferably an alkyl group, an alkenyl group or an alkynyl group, more preferably an alkyl group or an alkenyl group. Further, an alkyl group having a carbon number of 5 to 18 is more preferable (for example, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a decyl group, a dodecyl group, a decyl group, a cyclohexyl group, or a 2- Ethylhexyl, etc.). The aromatic group is preferably benzene, naphthalene, anthracene or the like. Z is represented by an aliphatic group, a group group or a heterocyclic group bonded by a carbon atom and may also have a wire. A preferred complement of the substituent is an acidic group, more preferably a group having a carboxyl group, eR3 to 6 8 . Heterogeneous aids bonded by carbon atoms, 丨l a"-

a gas atom, an aliphatic group, an aromatic group or a heterocyclic group, and R and

S 22 201210835 38254pif base, 2_ ethane hexyl group, etc.). R3 to R6 and R8 are more preferably a hydrogen atom. R7 represents a divalent carbon atom in which the sum of the substitution constants (σρ) of the two substituents of the oxygen atom or the bond is positive in Hammett's law. In general, the general formula (1) preferably has at least one of R, R, pl &amp; Ρ2 having an acidic group. The acid group refers to a substituent having a dissociated proton (pr melt), such as a carboxyl group (carbo(3xyl gr〇up), a phosphinyl group (ph〇sph〇nyl group), and a suifonyl gr〇). Up), boric acid group (b〇ric, 叩 叩), etc. or have the silk base, which is more than the base of the New Zealand. In addition, the acidic group may also be in the form of dissociation by releasing protons. In (1), W1 represents a relative ion when a relative ion is required to neutralize the charge. Usually, whether the pigment is a cation, an anion, or a net ionic charge is based on an auxochrome in the pigment. And a substituent. When the dye having the structure of the general formula (1) has a dissociable substituent, it can be dissociated and has a negative charge. The charge of the entire molecule can be neutralized by W1. It is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, pyridiniumi〇n), or an alkali metal ion. In addition, when W1 is an anion, it may be an inorganic anion or an organic anion. Any For example, a halogen ani〇n (for example, fluoride ion, vapor ion, bromide ion, iodide ion), substituted arylsulfonic acid ion (for example, P'toluenesulfonic acid ion, p-chl〇r〇benzenesulfonic acid ion, aryl bis-acid acid 23 201210835 38254pif (aryldisulfonic acid ion) (for example, 1,3_ 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalene diacid acid ion, alkyl sulphate ion Alkyl sulfate ion (for example, sulfhydryl sulfate ion), sulfate ion, thiocyanic acid ion, perchloric acid ion, tetrafluoroboric acid ion , picric acid ion, acetic acid ion, trifluoromethane sulfonic acid ion, and the like. Moreover, as the charge equalization counter ion, an ionic polymer or other pigment having a pigment and a reverse charge may be used, and a metal counter ion (for example, bisbenzene-1) may also be used. , 2-dithiolato nickel (III)). In the above general formula (1), P1 and P1 are each independently represented by the following general formula (4) or general formula (5), and accordingly, a dye having a high molar absorptivity can be obtained. [Chem. 17]

24 S 1 - General (4) 201210835 38254pif [Chem. 18]

(V 〇

2 Ο The general formula (5 ^^ and 丫 is the same as defined in the above general formula (2) and the general formula. In the above general formula (4) or general formula (5), V is represented by a nitrogen atom substituent, η It is expressed as an integer of 〇~4, and when η is 2 or more, ν1 may be phased or different, or may be bonded to each other to form a ring. Y is represented by S, NR9 or CRY, wherein it is represented by a gas atom, an aliphatic group, An aromatic group or a heterocyclic group bonded with a carbon atom. Han 1 () Han &quot; expressed as a hydrogen atom, a secret wire, an aromatic county such as a carbon-bonded R1 ring group, which may be the same or different, or may be mutually Bonding to form a ring." Z is represented by a lanthanyl group, a fragrant group or a rhyme-bonding group, and may also have a substituent. "In the case of a private formula (4) or a general formula (5), '¥ is preferably expressed as Sulfurogen a = JiCH3)2, and 2 is preferably represented as fat 3 having a carbon number of 5-18. . = group base is silk, dilute base, more preferably burnt or I soil U is more preferably a stone of 5 to 18 (for example, pentyl,

Base, heptyl, octyl, sulfhydryl, Christine 1_ ^ U pp, 9_gan, earth, eleven, eleven, eighteen, two earth/hexyl, etc.) by using 2 as The amount of carbon having a carbon number of 5 to 18 can be increased. Further, the aliphatic group is also 25 201210835 . r^ilt In the above general formulas (2) to (5), v1 is preferably an acidic group. The acidic group is a substituent having a dissociated proton. The νι may have an acidic group, or may have an acidic group bonded through a linking group. The acidic group is not particularly limited, and examples thereof include a thiol group, a phosphonic acid group, a sulfo group, a suif0nate group, a hydroxyl radical, and a hydroxamic acid group. Xamic gr〇up), phosphoryl group, phosphinium group, sumn〇gr〇up, sulfinyl group, ph〇sphinyl gr〇up , a phosphono group, a thi〇l group and a sulfonyl group, and salts thereof. The above salts are not particularly limited, and may be any of an organic salt and an inorganic salt. Representative examples include, for example, metal ions (Clock (Li) 'Sodium (Na), Potassium (K), etc.), Alkaline earth metal ions (Mg, Ca, etc.), Ammonium, Alkyl Ammonium (alkylamm〇nium) (eg, 'diethylammonium, tetrabutylammonium, etc.), pyridinium (pyridinium), alkylpyridinium (eg, methylpyridinium) ), guanidinium, tetraalkylphosphonium and other salts. In the general formula (1), when the number of acidic groups is plural, they may be the same or different. The above acidic group of the present invention is preferably a carboxyl group, a phosphoric acid group or a phosphonium group, more preferably a fluorenyl group. V1 preferably has a hydrogen atom, a 5-carboxyl group, a 5-sulfonic acid group, a 5-fluorenyl group or a 4,5-C()ndensed benzene-ring. Here, the position number is rotated counterclockwise with N+ as 1

S 26 201210835 Note. According to this, an effect of improving the molar absorption coefficient or improving the electron injection efficiency can be obtained. Further, in the general formula (2) to the general formula (5), in addition to V1, z is preferably a group having an acidic group. Z is an acid group which can be set to be the same as V1. The acidic group has an action of adsorbing semiconductor fine particles in the dye of the present invention. The number of acidic groups in the dye is preferably one or more and more preferably from j to 2. Further, by setting both of V1 and Z to an acidic group, durability can be improved by an increase in the adhesion force. The above general formula (2) can be represented by the general formula (6), and the above general formula (3) can be represented by the general formula (7). [Chem. 19]

[Chem. 20]

EU~E13. In addition, at least one of the above general formula (6) or general formula (7) is represented by an electron withdrawing group, and examples of the acidic group include an acidic group which is represented by an integer of 2 or more in the furnace. The same 27 201210835 J»ZD4pif acidic base. The electron withdrawing group is preferably a cyano group, a nitro group, a sulfonyl group, a sulfoxi group, a brewing group (30丫1§1&gt;0叩), a hospital Oxygen group (311 &lt;;0\&gt;^1*1) 01^1§1*0叩), carbamoyl group 'better than cyano, nitro, sulfonyl, more Good for cyano. In the above general formula (6), p is an integer of 2 or more, and p is preferably 2 to 5, more preferably 2 to 3. In the above general formula (8) and general formula (7), at least one of the v!2 acidic groups '#~ is represented as an electron-withdrawing group, and the vicinity of the adsorption point of the conductor particle layer

In El3, it is better to achieve the photoelectric conversion efficiency for E it: ": The input can be efficiently performed, and E12 is the electron-based basis. E ' The above general formula (2) is preferably - (3) Preferably, it is represented by the formula (8) represented by the general formula (9), and the above-mentioned [21]

S 28 201210835 38254pif [Chem. 22] RX-(L)m

General formula (9) [Chem. 23]

Rb type A

NIC γ^/

COOH Formula 、, in the above general formula (8) or in the general formula (9), Y, Z, R3 to R8 are the same as defined in the general formula (2) or the general formula (3), Y, Z, R3 to R8. In the case where 'm is represented by the above formulas A to D, it is represented by 〇 or an integer of 1 or more, and when m is 2 or more, L may be different. In the above formula, xa is represented by NRe, 〇, s, Re, and is represented by a hydrogen atom or a substituent. In the above formula A and formula C, Ra to Rd represent a substituent. The substituent represented by the following substituent is exemplified as a specific example in the case of Ra to Re. The hydrazine is a substituent, and is represented, for example, as an aliphatic group, an aromatic group, or a carbon-bond-bonded ring group, and it may be substituted. a heterocyclic group bonded by a carbon atom, for example, a sputum, a snail, a sputum, a oxazole, a oxazole, a carbazole, a squat, a heart, a scorpion, a sigma, a scorpion, a scorpion Biting, licking melon and so on. r, r, preferably a lipid group or a group group, the rhyme of the group group, more preferably ～16 ′ or 5 or unsubstituted aromatic group is preferably a phenyl group or a phenyl group. The aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group, more preferably a silk or a dilute 29 201210835 J»ZD4pif group 'more preferably an alkyl group having a carbon number of 5 to 18 (for example, a pentyl group, a hexyl group, a heptyl group) , octyl, fluorenyl, fluorenyl, undecyl, dodecyl, octadecyl, cyclohexyl 1, 2-ethylhexyl, etc.). In the alkyl group, a branched alkyl group is preferred, which is, for example, 2-ethylhexyl, 2-decylhexyl, 2-decylpentyl, 3,5,5-tridecylhexyl, 2-cyclopentane. Ethyl, 2-cyclohexylethyl and the like. The hospital base having a carbon number of 5:18 can suppress the decomposition of the pigment by water and a nucleophile, and can suppress the decrease in durability of the pigment from the semiconductor fine particles when the water approaches the adsorption point. Further, since aggregation or excessive adsorption of the dyes can be suppressed, inefficient electron movement can be suppressed and the photoelectric conversion efficiency can be improved. Further, since the alkyl group is branched, the effect of improving the durability particularly in the above effects can be more remarkably obtained. In the above general formula (8), p represents an integer of 2 or more, and Rx represents an acidic group. Among them, the acidic group may be the same acidic group as the above-exemplified acidic groups. Rx is preferably a group represented by formula E. Since the above general formula (2) is represented by the general formula (8), the above general formula (3) is represented by the general formula (9), so that an effect of an absorption region enlargement or an increase in an absorption coefficient can be obtained, and photoelectric conversion efficiency can be produced. Improve the effect. In the above general formula (3), general formula (5), and general formula (9), the ruler is preferably expressed by any one of formulas (10) to (13). [Chem. 24] NC^C〇〇Rf General formula (11) wCOORf General formula (10)

X

RfOOC Eight COORf General (12) NC and CN General (13)

S 30 201210835 38254pif In the above formula, Rf is a hydrogen atom or a substituent. The substituent may, for example, be an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and these substituents may be substituted. Among them, the substituent is preferably an aliphatic group or an aromatic group. Thereby, the absorption on the short wavelength side can be enhanced. In the above general formula (3), general formula (5) and general formula (9), r7 is preferably represented by formula (14) or formula (15). [Chem. 25]

Thereby, the effect of improving the electron injection efficiency can be obtained. The dye of the present invention represented by the melon formula (1) has a maximum absorption wavelength of preferably from 67 〇 nm to 11 〇〇 nm in a solution of tetrahydroethylene: ethanol-1:1, more preferably 7 〇〇11111~9〇〇11111 range. The following is a preferred embodiment of the compound represented by the general formula (丨) in the present invention, but the present invention is not limited thereto. 31 201210835" [Chem. 26]

V

i CH =CH CH

=CH CH ΧΓ

Z

V Compound XY z R V2 V3 W1 sl ss CbHh C5H11 HHI* S-2 ss C10H21 C10H21 5-COOH 5-COOH 1- S-3 C(CH3)2 C(CH3)2 C18II37 C18H37 Ancient-COOH 5-COOH Γ S-4 C(CH3)2 C(CH3&gt;2 CH2CH2COOH CsHn H 5-COOH ci· S.5 0 C(CH3)2 C10H21 C2H5 H 4,5-benzo Γ

Compound XY z1 Z2 R V2 V3 S-6 s C(CH3)2 CsHit CsHn CsHit HH S-7 s C(CHa)2 CHa CHs C10H21 4,5*benzo 5-C00H S-8 C(CH3)2 s CsHn CaHn CaHs H 5-COOH S-9 C(CbHii)2 C(C5Hu)2 CHa CsHn CHa 4,5*benzo 5-COOH s-io C(CHs)a NCHs CHa CeHis 0βΗΐ3 5-CHa 5-COOH 7 2 dagger

V

CH CHN.RXYN.R CH&gt;

2 3 s 201210835 38254pif [化 28] v of 1 o R Ο of 2

Compound XY Z1 Z2 R V2 V3 S.11 SC(CH3)j C3H7 CsHt C10H21 HH S-12 SC(CH3)2 C2H5 C2H5 C10H21 H 5-SO3H S-13 C(CH3)3 c(ch3)2 CsHl7 CsHe CaHs H 5-C00H S-14 c(ch3)2 c(ch3)3 Cl〇H21 CH3 C10H21 4,5*benzo 5-COOH S-15 C(CH3)2 C(CH3)2 Cl〇H21 CsHn CioHai 4, 5-benzo 5COOH S-16 C(C5Hu)2 C(C5Hh)2 Cl〇H21 C10H21 C10H21 4,5-benzo 5-COOH S17 C(CH3&gt;2 NCsHn CeHn CHs C2H6 5-CH3 5-COOH

[化29]

Further, the following is a preferred specific example of the dye having the structure of the general formula (6)-formula (9) in the present invention, but the present invention is not limited thereto.

Pigment basic frame? 虏A Part B Part C Part R3 ~R5, R6 ' R8 R, Y z V1Z T-1 A-1 B-3 C-2 All Me - s Z-3 COOH T-2 A-6 B-1 C-3 All Η 0 s Zl COOH T-3 A-7 B-2 C-1 All Η NC^COOH C(CH3)2 Z-3 COOH T-4 A-8 B-5 C -1 All Η NC^COOH C(CH3)2 Z-4 H Pigment basic structure Α Part B Part C R6 R8 R7 YZ Vw L m Rx E丨丨E12 E13 T-5 A-2 B-3 C- 1 All Ht 〇C(CH3)2 Z-2 COOH H CN H T-6 A-2 B-3 C-3 All Et 〇C(CH3)2 Z-4 COOH Τ-7 A-2 B- 3 C_4 All are Et 0 C(CH3)2 Z-2 — L-12 1 COO H Τ-8 A-2 B-3 C-4 All Ht 0 C(CH3)2 Z-2 — L-3 1 COO H Τ-9 A-2 B-6 C-4 All Ht 0 C(CH3)2 Z-5 — L-2 2 COO H Τ-1 A-2 B-3 C-3 All Et NC^ OOH C(CH3)2 Z-3 — 201210835 38254pif [Specific Example 1] [Chemical Example 31] (Specific example 2)

S 201210835 38254pif [Chem. 32] (Specific example 3)

Basic structure of pigment Part A Part B Part C R6 R8 R7 Υ z V12 L m Rx E&quot; E12 E13 T-11 A-3 B-3 C-1 All Η 0 c(ch3)2 Z-2 COOH FHH T- 12 A-3 B-3 CI All Η 0 C(CH3)2 Z-2 COOH HFH T-13 A-3 B-3 C-1 All Η 0 C(CH3)2 Z-2 so3h FFH T- 14 A-3 B-3 C-1 All Η 0 C(C5Hm)2 Z-2 po3h H CN H T-15 A-3 B-3 C-3 All Η 0 C(CH3)2 Z-2 COOH T-16 A-3 B-3 C-3 All Η 0 C(C5Hu)( ch3) Z-2 COOH T-17 A-3 B-3 C-3 All Η 0 C(CH3)2 Z -4 COOH T-18 A-3 B-3 C-3 All Η ΝΟ, ^ΟΟΗ C(CH3)2 Me H T-19 A-3 B-3 C-4 All Η 0 C(CH3)2 Z-2 L-2 2 COO H T-20 A-3 B-3 C-4 All Η 0 C(CH3)2 Z-2 L-3 3 COO H T-21 A-3 B-3 C- 4 All Η 0 C(CH3)2 Z-2 Ll 1 COO H T-22 A-3 B-4 CI All Η 0 C(CH3)2 Z-2 COOH FHH 35 201210835 38254pif

Τ-23 Α-3 Β·4 C-1 All Η 〇c(ch3)2 Z-2 COOH HFF T-24 Α-3 Β-4 C-3 All Η 0 c(ch3)2 Z-2 COOH Τ-25 Α-3 Β-4 C-3 All Η 0 C(C5Hu)( ch3) Z-2 COOH Τ-26 Α-3 Β-4 C-3 All Η 0 c(ch3)2 Z -4 COOH Τ-27 Α-3 Β-4 C-3 All Η NC^COOH c(ch3)2 Me H Τ-28 Α-3 Β-4 C-4 All Η Ο c(ch3)2 Z -2 L-2 2 COO H Τ-29 Α-3 Β-4 C-4 All Η 0 c(ch3)2 Z-2 L-3 3 COO H Τ-30 Α-3 Β-4 C-4 All Η 0 C(CH3)2 Z-2 Ll 1 COO H Τ-31 Α-3 Β-6 C-3 All Η 0 C(CH3)2 Z-4 COOH 36 201210835 38254pif [化33] Example 4) Basic structure of pigment Part A Part B Part C R6, R8 R' Y z V·2 L m Rx E11 En E13 T-32 A-4 B-2 Cl All Me 0 C(CH3)2 Z-5 COOH H CN Η T-33 A-4 B-5 C-3 All Me 〇C(CH3)2 Z-3 COOH T-34 A-4 B-4 C-3 All Me 〇C(CH3)2 Z-2 COOH T-35 A-5 B-8 C-3 All Η 0 C(CH3)2 Z-2 so3h One — — — — — T-36 A-6 B-7 C-3 All Η 〇C(CH3)2 Zl COOH — one — — one — T-37 A-7 B-4 C-4 All Η NC^COOCsH" C(CH3)2 Z-2 - L-2 1 COOH — — — T-38 A-8 B-4 C-3 All Η NC^COOH C(CH3)2 Z-2 H — — — 一 — — T-39 A-9 B-9 C-3 All Η ο C(CH3)2 Z-4 COOH — — — — 一 — T-40 A-9 B-9 Cl All ο ο C(CH3)2 ch3 COOH — — — H Η F T-41 A-9 Bl 0 C-3 All Η NCs^COOWIe C(CH3)2 ch3 COOH — — — — — — T-42 A- 9 Bl 0 C-3 All Η NC^CN C(CH3)2 Cl〇h2, COOH — — — — — One T-43 Α·1 0 Bl 0 C-3 All Η CiHtiOOC^COOCjHn C(CH3) 2 CH, COOH One - one - one T-44 Α-1 1 Bl 0 C-3 All Η NC^COOCsH,, C(CH3)2 ch3 COOH — — — — One — T-45 A-9 Bl C-3 All Η WteOOC^CN C(CH3)2 ch3 COOH — — — — — One T-46 A-9 B-9 C-3 All Η oc(ch3)2 Z-4 COOH — — — One — A T-47 A-9 B-9 Cl is all Η o C(CH3)2 Z-4 COOH — — one Η CO OH Η T-48 A-9 B-9 Cl all oc(ch3)2 Z- 4 COOH - — - COO Η Η 37 201210835 38254pif

In the description of _, the basic structure A is expressed as Α·1 to A_12 described below, and the basic structure B is expressed as any of b-b u described below.

The structure c is expressed as any of the following C1 to c types. Further, Z is represented by the following Z_1 to Z_5, and the linking group L is represented by any of L-1 to l_12 τ described below. * In the specific examples 1 to 4, the basic structure A and the basic structure B are in the carbon atom-carbon double bond bonding of each other, and the basic structure B and the basic structure c are in the carbon atoms of each other using carbon-carbon double Key bond.

38 S 201210835 38254pif [Chem. 34]

39 201210835 38254pif [化35]

A-10

A-12 s 201210835 38254pif [化36]

[化37]

ο Β-1 B- 41 201210835 [Chem. 38]

C-3 C-4

Z-1 Z-2

L-12, for example, in the above specific examples, it can be expressed as T-2, T-6, T-9, T-10, T-12, T-16, T-17, T-18, T- as below. 24, T-30, T-37, T-40

S 42 201210835 38254pif ~ T-50 structural formula. [化39]

Τ-10 43 201210835 38254pif [化 40]

44 s 201210835 [化41]

Τ-37 45 201210835 38254pif [化42]

[化43]

46 s 201210835 x-ir [化 44]

Moreover, the following pigments are also mentioned. 47 201210835 38254pif [化45]

The synthesis of the dye having the above structure can be carried out by referring to Ukrainskii Khimicheskii Zhurnal, Vol. 40, No. 3, pp. 253 to 258, Dyes and Pigments, Vol. 21, pp. 227 to 234, and the contents of the documents cited therein. (B) Conductive support member As shown in Fig. 1, in the photoelectric conversion element of the present invention, the photoconductor layer 2 in which the dye 21 is adsorbed to the porous semiconductor fine particles 22 is formed on the conductive support 1 . As described later, for example, after the dispersion of the semiconductor fine particles is applied and dried in the conductive branch body, the photoreceptor can be produced by being immersed in the dye solution of the present invention. As the conductive support, a support which is electrically conductive like a metal or a glass or a polymer material having a conductive film layer on its surface can be used. The electrically conductive support is preferably substantially transparent. The fact that it is substantially transparent means that the transmittance of light is 10% or more, preferably 5% or more, more preferably more. In addition, it is possible to use a conductive metal coated on a glass or polymer material.

S 48 201210835 . Oxide as a conductive support. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the glass or polymer support. When a transparent conductive support is used, light is preferably incident from the support side. An example of the polymer material to be used is preferably tetraacetyl cellulose (TAC), polyethylene terephthalate (PET) or polyethylene terephthalate (polyethylene terephthalate). Polyethylene Naphthalate ' PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide ' PPS, polycarbonate, PC, polyarylate ' PAR , polygypsy (polysulfone, PSF), polyether sulfone (PES), polyetherimide (PEI), cyclic polyolefin, brominated phenoxy, and the like. In the present invention, a preferred conductive support is a metal support. As the conductive metal support, a conductive metal support composed of any one of Group 4 to Group 13 can be used as the conductive support. Here, the 4 red to 13 group refers to an element in the long period type periodic table. The thickness of the conductive metal branch body of the present invention is preferably 10 or more and 2000 μm or less, more preferably 1 Torr or more, or less, more preferably 50 μm or more and 500 μm or less. If the thickness of the conductive metal substrate is too thick, the flexibility is insufficient, so that failure occurs when used as a photoelectric conversion element. Further, if the thickness is too thin, the photoelectric conversion element may be damaged during use and thus is not preferable. The surface resistance of the conductive metal support used in the present invention is preferably lower than that of 49 201210835 38254pif. The surface resistance is preferably in the range of 1 to 2 or less, more preferably 1 Ω/m or less, and more preferably 〇 i Ω / ηι 2 or less. The value of the surface resistance is too large for the temple to change, and it is difficult to apply electricity to the photoelectric conversion element. The conductive metal branch body preferably uses at least one selected from the group consisting of titanium, samarium, copper, ferrous, iron, stainless steel, zinc, molybdenum, niobium, tantalum and niobium. These metals may also be alloys. Among them, titanium, aluminum, copper, nickel, iron, stainless steel and zinc are preferred, and titanium, aluminum and copper are more preferred, and titanium and aluminum are preferred. When aluminum is used, it is preferable to use an aluminum alloy stretch material, a lanthanide-7000 series (Light Metal Association: Aluminum Handbook, Light Metal Association (1978) 26), etc., because the surface resistance of the conductive metal support is small, so that The internal resistance of the photoelectrochemical cell is lowered, and a high output battery can be obtained. In addition, when the conductive metal support is used, the support is not softened even if the conductive metal support to which the semiconductor fine particle dispersion described later is applied is heated and dried to be baked. . Therefore, by appropriately selecting the heating conditions, a porous semiconductor microparticle layer having a large specific surface area can be formed. According to the above, the amount of dye adsorption can be increased, and a photoelectric conversion element having high conversion efficiency at a high output can be provided. Further, while continuously feeding the wound metal piece, the semiconductor fine particle dispersion liquid is applied onto the metal piece and then heated to obtain a porous conductive support. Thereafter, the dye of the present invention is continuously applied to form a photosensitive layer on the conductive support. Through the above process, it is possible to inexpensively manufacture a photoelectric conversion element or a photoelectrochemical cell.

S 50 201210835 38254pif The conductive metal support of the present invention is preferably a substrate provided with a conductive layer on a polymer material or a layer. The polymer material layer is not particularly limited, but the material which retains the shape when the semi-conductive liquid dispersion is applied to the conductor layer and heated. The conductive layer is a layer of a molecular material used for forming a layer on a polymer material layer by a conventional method such as extrusion coating, for example, tetraacetic acid cellulose (tac) or polyparaphenylene f. Acid Ethylene (PET), polyethylene terephthalate (Cong), polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (pc), polyaryl vinegar (PAR) ), polyphenolite (PSF), poly, wind (PES), poly-imine (PEI), cyclic polyolefin, brominated phenoxy, and the like. The conductive material layer is provided on the polymer material layer to be used as the conductive metal support of the present invention, and the polymer material layer functions as a protective layer of the photoelectric conversion element or the photoelectrochemical cell. When an electrically insulating material is used as the polymer material, the polymer material layer can function not only as a protective layer but also as an insulating layer. According to the above, the insulation of the photoelectric conversion element itself can be ensured. When the polymer material layer is used as an insulating layer, it is preferable that the bulk resistivity is 1 〇 10 〜 1 〇 22 Ω cm, and the bulk resistivity is 1011 〜 1 〇 19 q. cm. When the above materials are used, if a conductive material is not particularly mixed, a conductive metal support having an insulating layer having a volume resistivity within the above range can be obtained. The electrically conductive metal support is preferably substantially transparent. The transmittance of the light of 400 nm to 1200 nm is substantially 1% or more, preferably 50% or more, more preferably 8 % by weight or more. 201210835 The outer pif can also be provided with a light management function on the surface of the conductive metal support. For example, an antireflection film or a lightguide function can be provided with a high refractive film and a low refractive index oxide film interleaved. It is preferable to have a function of blocking ultraviolet light on the conductive support. For example, there is a method in which a fluorescent material capable of converting ultraviolet light into visible light is present inside or on the surface of the polymer material layer. Further, other preferred methods are exemplified by a method using an ultraviolet absorber. The function described in Japanese Laid-Open Patent Publication No. Hei-250-944, and the like can also be applied to the conductive support. When the battery area becomes large, the resistance value of the conductive film becomes large, so that the collector electrode can also be disposed. The shape and material of the current collector electrode are preferably those described in Japanese Laid-Open Patent Publication No. Hei 11-266028. Further, a gas barrier film and/or an ion diffusion preventing film may be disposed between the polymer material layer and the conductive layer. The gas barrier film may be either a resin film or an inorganic film. (C) Semiconductor fine particles As shown in Fig. 1, the photoelectric conversion element of the present invention has the photoconductor layer 2 in which the dye 21 is adsorbed to the porous semiconductor fine particles 22 on the conductive support 1 . For example, after the above-described conductive support is applied and dried, the dispersion of the semiconductor fine particles is dried, and then the photoreceptor can be produced by being immersed in the coloring matter solution of the present invention. The semiconductor fine particles are preferably fine particles of a metal chalcogenide (e.g., oxide, sulfide, seienide, etc.) or perovskites. Metal chalcogenide is preferred

S 52 201210835 38254pif is titanium, tin, zinc, tungsten, tantalum, hafnium, strontium, indium, cerium, yttrium, lanthanum , vanadium (vanadium), yttrium or button oxide, cadmium sulfide, cadmium selenide. The mother titanium ore is preferably strontium titanate or caicium titanate. More preferably, it is a titanium oxide, a zinc oxide, a tin oxide, a oxidized crane, a semiconductor t, a type 22 in which a carrier is an electron, and a P type in which a carrier is a hole, but the conversion is performed using the 〇 type in the element of the present invention. The efficiency is better. In an n-type semiconductor, in addition to an intrinsic semiconductor (or intrinsic semiconductor) having a concentration of a conduction band electron having no impurity level and a carrier of a valence electron charged hole, a structural defect due to impurities may exist. An 11-type semiconductor having a high electron carrier concentration. The n-type inorganic semiconductor preferably used in the present invention is D1, TiSr〇3, Zn〇,

Nb203, Sn02, W03, Si, CdS, CdSe, V2〇5, ZnS, ZnSe, SnSe, KTa03, FeS2, PbS, InP, GaAs, CuInS2, CuInSe2, and the like. Among them, the most preferable n-type semiconductors are Ti〇2, ZnO, Sn02, W03 and NbA3. Further, a semiconductor material obtained by laminating a plurality of these semiconductors can be preferably used. The particle diameter of the conductor fine particles is preferably such that the average particle diameter of the primary particles is 2 nm or more and 50 nm or less for the purpose of maintaining high viscosity of the semiconductor fine particle dispersion. Further, the ultrafine particles having an average particle diameter of primary particles of 2 nm or more and 30 nm or less are more preferable. It is also possible to mix two or more kinds of fine particles having different particle diameter distributions, and in this case, the average size of the small particles is preferably 5 nm or less. In addition to the purpose of scattering incident light to increase the light trapping rate, a large particle having a low content ratio of an average particle diameter of more than 5 Å may be added to the above ultrafine particles. In this case, the content of the large particles is preferably 5 Å under the mass of the particles of the average granule side (10), and more preferably the following. The average particle diameter of the large particles to be mixed for the above purpose is preferably (10) (10) or more and more than the legs. The method for producing the semiconductor fine particles is preferably a gluten-gel method (s〇l_gelmeth〇d) method described in "The Science of Sol-Gel Method" by AGNE Chengfeng Press (10) 8 years). . Further, a method of producing an oxide by subjecting a chloride developed by the company of the company to an oxyhydrogen salt and hydrolyzing it by water is preferred. When the semiconductor fine particles are titanium oxide, it is preferably one of the above-mentioned sol-gel method, gel/sol method, and high-temperature hydrolysis method in the oxyhydroxide of the vapor, and more preferably "Titanium Dioxide Properties and Application Technology" published in the Technical Report Hall (1997), the sulfuric acid method and the gas method. Further, the sol-gel method is preferably a method described by c, J, Barbe et al. in J0urnai 0f American Ceramic Society, Vol. 80, No. 12, pp. 3157~3171, or s, D, Burnside et al., in Chemistry of Materials. The method described in Vol. 10, No. 9 on pages 2419 to 2425. Further, the method for producing a semiconductor fine particle is preferably, for example, a method for producing titanium oxide nanoparticles, a method of decomposing a flame by four-titanium titanium, a method of burning titanium tetra-titanium, and a stable chalcogenide. Hydrolysis of matter, hydrolysis of orthotropic acid, formation of semiconductor microparticles from soluble and insoluble fractions, dissolution and removal of soluble fractions

54 S 201210835 Method of 38254pif, hydrothermal synthesis of aqueous peroxide solution, or production of titanium oxide having a core/shell structure by a sol-gel method. The crystal structure of titanium oxide is, for example, anatase type. (anatase), brookite type or rutile type (printed (1)^, preferably anatase type, brookite type. In addition, titanium oxide nanotubes may also be mixed in the titanium oxide fine particles. · Nano wire • Nano column. Titanium oxide can also be doped by non-metallic elements, etc., in addition to the dopant (d〇pant) as an additive for titanium oxide, in order to improve necking (necking) Adhesive and anti-electron movement can be used, additives can be used on the surface. The additive is preferably 'Indium, Tin Oxide (ITO), Tin Oxide (Sn〇) particles, whiskers, fibrous graphite, carbon Fibrous substances such as graphite carbon nanotubes, zinc oxide neck bonds, and cellulose, metal, organic 矽rgan〇silic〇n, eleven-based phthalic acid (dodecyl) Benzene sulfonic acid) A charge-shifting molecule such as silane), and a dendrimer such as a potential tilting type. For the purpose of removing surface defects such as oxidation, it is also possible to perform acid-base or redox on titanium oxide before the pigment is adsorbed. Further, processing such as etching, oxidation treatment, hydrogen peroxide treatment, dehydrogenation treatment, UV_ozone, oxygen plasma, etc. may be performed. (D) Semiconductor fine particle dispersion in the present invention, The semiconductor fine particle dispersion liquid is applied onto the conductive support, and by heating appropriately, a porous half 55 201210835 38254pif conductive fine particle coating layer can be obtained. The semiconductor fine particle separation ship can be manufactured by the above sol gel. In addition, a method of directly using fine particles in a solvent when synthesizing a semiconductor, a method of pulverizing ultrafine particles by irradiating ultrasonic waves or the like, or a method of mechanically pulverizing and crushing using a stone mill or a spider is used. Etc. The dispersing solvent may use water and/or various organic solvents, and organic solvents such as methanol, ethanol, Alcohols such as is〇pr〇pyl alcohol, dtronelloi, terpine alcohol (1), ketones such as acetone, ethyl acetate, etc. Dichloromethane, acetonitriie, etc. When dispersing, a small amount of, for example, polyethylene glycol, hydrethyl alcohol cellulose, carboxy fluorenyl cellulose (carb 〇) may be used as needed. The polymer, surfactant, acid or chelating agent of xymethyi ceuui〇se) is regarded as a dispersing aid. However, it is preferred to remove most of these dispersing aids in advance by a filtration method or a separation membrane method, or a telecentric separation method, before the film formation process is carried out on the electroconductive support. If the viscosity of the semiconductor fine particle dispersion is too high, the dispersion will aggregate and the film cannot be formed. Conversely, if the viscosity of the semiconductor fine particle dispersion is too low, the solution will flow out and the film cannot be formed. Therefore, the viscosity of the dispersion is preferably 25. (: ION, S/m2 to 300 N, S/m2, more preferably 25. (: 50N, S/m2 to 200 N, S/m2. Application method of semiconductor fine particle dispersion, application type) The method of the wheel method 0〇 is 1'11^11(^), dip-dip method ((^11^11〇(1), etc.

56 S 201210835 J82!&gt;4pif, you can also use the air knife method (air knife meth〇d), the blade method, etc.. Further, the method of using the application method and the adjustment method in the same portion is preferably described in the wire bar method disclosed in Japanese Patent Publication No. Sho 58-4589, the specification of U.S. Patent No. 2,681,294, and the like. The sHde h〇pper method, the extrusion method (extrusi〇n meth〇d), the curtain method ((3) and the method). Further, it is preferred to apply the coating by a spin method or a spraying method using a general machine. The wet printing method is mainly three printing methods of relief printing, stencil and gravure, and preferably gravure (intagH〇, rubber sheet (pool 1^1) 1攸), net Version printing (like from 11 deduction 11 such as §) and so on. Therefore, in the above method, a preferred film forming method can be selected depending on the liquid viscosity and the wet thickness. Since the semiconductor fine particle dispersion of the present invention has high viscosity and is viscous, it has a strong cohesive force, and thus it may not easily fuse with the support at the time of coating. In the above case, the surface is cleaned and hydrophilized by the oral ozone treatment to increase the adhesion force of the surface of the semiconductor fine particle dispersion after coating and the surface of the conductive support, so that the semiconductor fine particles of the semiconductor fine particle dispersion The thickness of the layer as a whole is preferably 〇. 丨μιη~1 〇〇 ' 'the thickness of the semiconductor fine particle layer is more preferably i μηη~3〇μιη, more preferably $μπι~25 μιη. The age of each 丨y support of the semiconductor fine particles is preferably 5 g to 400 g 'more preferably 5 g to 1 〇〇 g ^ for the layer of the coated semiconductor fine particles, for the contact of the electrons of the semiconductor fine particles Strengthening, and adhesion to the support, also increased; 57 201210835 38254pif has dried the coated semiconductor fine dispersion, and applied heat treatment. By the above-described heat treatment, the porous semiconductor fine particles can be formed. In addition to the heat treatment, an energy source of light can be used. When titanium oxide is used as the semiconductor fine particles, it is also possible to give a surface such as an ultraviolet conductor. It is activated and can be used to hybridize the surface of the semiconductor age. It is fine for the semiconductor - this can absorb (4)' whereby the impurity f adsorbed on the surface of the particle can be decomposed by activation of the particle table, and can be favored for the above purpose. In the case of combining heat treatment with ultraviolet light, it is preferable to heat the light of the semi-conductor = by the particle-side riding, and the heating is performed by the upper side, the lower side, and more preferably the trace c or more, 15 Gt. Add the following... As described above, by photo-decomposing the semiconductor filaments, the photo-decomposition = impurities in the micro-particle layer can enhance the physical division between the micro-particles. The semiconductor micro-particles are coated on the above-mentioned conductive branch (4) and heated or Other treatments can be performed other than irradiation. Preferred methods include, for example, energization, chemical treatment, and the like. Japanese may also be Yang pressure, and Yang pressure (4) may be listed as Japanese ίίΓ3,857. Examples of the light irradiation include, for example, Japanese Patent Application Laid-Open No. Hei No. 3, No. H, for example, Japanese Patent Publication No. 357896

S 58 201210835 38254pif The above method for coating semiconductor fine particles on a conductive support can be applied to a conductive support by applying a method of coating a semiconductor fine particle dispersion on a conductive support. The method of obtaining a semiconductor fine particle film by hydrolyzing water in the air by the precursor of the semiconductor fine particles described in the publication No. 2664194. The above-mentioned ruthenium precursor is, for example, (NH4)2TiF6, titanium peroxide, a metal oxide compound, a metal complex, a metal organic acid salt or the like. Further, a method of forming a semiconductor film by heat treatment, light treatment, or the like with a slurry which is coexisted with a metal organic oxide (alkoxy compound or the like), and a slurry which coexists with the inorganic precursor are used. The properties of the slurry and the dispersed titanium particles are a specific method. A binder may also be added in a small amount to these slurries, such as cellulose, fluoropolymer, cross-linked mbber, polybutyltitanate, carboxymethyl fiber. Prime. The technique for forming a semiconductor fine particle or a precursor layer thereof, for example, a method of hydrophilizing by a physical method such as corona discharge, plasma, or UV, by means of a test or polyethylation Chemical treatment such as polyethylened10Xythiophene and polystyrenesulfonic acid (p〇1), formation of an intermediate film for bonding of polyaniline or the like, and the like. The method of coating the semiconductor fine particles on the conductive branch body may be combined with the above-mentioned (1) method to make the Xiao (2) dry method, and (3) the other method (2) the dry method is preferably Japanese Patent No. 2__231943 Wait. (3) Other methods can be listed as Japanese patent calendar _13娜号59 201210835 38254pif newspaper. The dry method is, for example, vapor deposition or sputtering, aer〇s1 deposition method, or the like, and electrophoresis or electrolysis can also be used. Further, a method of transferring the film onto a heat-resistant substrate and transferring it to a film such as a plastic may be used. Preferably, the method of transferring by ethylene vinyl acetate (EVA) is described in JP-A-2002-184475, or the ultraviolet light described in Japanese Laid-Open Patent Publication No. 2003-98977 A method in which a semiconductor layer and a conductive layer are formed on a sacrificial substrate of an aqueous salt-removed inorganic salt, and then transferred onto an organic substrate, and then the sacrificial substrate is removed. In order to adsorb a large amount of pigment, it is preferred that the semiconductor fine particles have a large surface area. For example, in the state in which the semiconductor fine particles are coated on the support, the surface area thereof is preferably 1 〇 or more, more preferably 丨〇〇 or more, with respect to the projected area. However, the above upper limit is not particularly limited and is usually about 5 times. The structure of the preferred semiconductor fine particles is exemplified by Japanese Laid-Open Patent Publication No. 2001-93591. In general, although the thickness of the layer of the semiconductor fine particles is larger, the amount of the pigment which can be carried by the bit area is increased, and the light absorption efficiency is changed, but the diffusion distance of the generated electrons is increased, so the charge is re The loss of the combination will also increase. The preferred thickness of the semiconductor fine particle layer may vary depending on the use of the element 'typically at 〇丨μιη~(10)μιη. Further, in the case of being used as a photoelectrochemical cell, the thickness of the semiconductor fine particle layer is preferably from 1 μm to 50 μm, more preferably from 3 μm to 30 μm. In order to make the semiconductor microparticles adhere to each other after being applied to the support, it may be heated at a temperature of 〇1010t 201210835 38254pif 280 ° C for 10 minutes to 1 hour. When glass is used as the support body, the film forming temperature is preferably 400 〇C to 600. (: - When using a surface molecular material as a support, it is preferred to heat the film after 25 〇〇c or less. The film forming method in the above case may be (1) wet method (2) dry method, (3) Any one of electrophoresis (including electrolysis), preferably (1) wet method or (2) dry method, more preferably (1) wet method. Further, each of semiconductor fine particles The coating amount of the m2 support is 〇. 5 g to 500 g, preferably 5 g to 1 〇〇 g. In order to adsorb the dye to the semiconductor fine particles, it is preferred to dip the body electrode after the film formation. In the dye which is formed by the solution and the dye of the present invention, the solution is used in the dye solution. The solution used for the pigment dye solution is not particularly limited as long as it is a color which can dissolve the photoelectric conversion element of the present invention. For example, an organic solvent such as ethanol, decyl alcohol, isopropanol, toluene, third: alcohol, acetonitrile, acetone, n-butanol or the like can be used. Among them, ethanol and toluene are preferably used, and the organic solvent can be used alone. It can also be used in a few times. In order to make the pigment evenly spread to the semiconductor microparticles, the above pigment The concentration is preferably 0.01 mm〇ie / L~1. 0 mmc) ie / L 'is more preferably 0 · 1 mmole / L~1. Square mm〇le / L. The pigment dye solution formed by the solution and the pigment of the present invention can be heated to 5 〇c to 1 视 depending on the suspension. Hey. The adsorption of the pigment can be carried out before the coating of the semiconductor particles or after the coating. Alternatively, the particles may be simultaneously coated with the fine particles and the dye to adsorb the dye. Unadsorbed pigments can be removed by washing. In the coating film secret, it is preferred to adsorb the pigment after baking, and it is more preferable to rapidly adsorb the pigment before the 201210835 38254 pif water is adsorbed on the surface of the coating film after the baking. Pigments having other structures may also be mixed within the scope of not impairing the gist of the present invention. When the coloring matter is mixed, in order to dissolve all the pigments, it is necessary to use a dye solution for dye adsorption. Preferably, the amount of the dye used is from 1 mmole to 100 mmole, more preferably from 1 mm〇ie to 5〇mmole, more preferably from 0.1 mmole to 1〇mm〇ie. . In this case, the amount of the coloring matter of the present invention is preferably 5 mol% or more. In addition, the amount of the pigment to the semiconductor microparticles is preferably 〇1 e1 mmole~1 mmole, more preferably 〇1 mmole~0. 5 mmole. According to the amount of the dye as described above, the sensitizing effect in the semiconductor can be sufficiently obtained. According to this, when the amount of the pigment is small, the sensitizing effect is insufficient, and when the amount of the pigment is too large, the dye which is not attached to the semiconductor is suspended and the sensitizing effect is lowered. In addition, the interaction between the dyes such as aggregation is lowered. For the purpose, it is also possible to co-adsorb a colorless compound. The co-adsorbed hydrophobic compound may, for example, be a steroid compound having a slow group (e.g., ch〇iic acid, pivaloyl acid) or the like. An amine can also be used to treat the surface of the semiconducting microparticles after the pigment is adsorbed. Preferred amines are, for example, 4-tert-butylpyridine, polyvinylpyridine and the like. The above amines may be used as they are in the case of a liquid, or may be dissolved in an organic solvent. The counter electrode can function as a positive electrode of a photoelectrochemical cell. Correct

S 62 201210835 38254pif ^ The electrode is synonymous with the above-mentioned conductive support, but if it is a mold capable of retaining the strength, the support is not necessarily required. However, those having a T-body are advantageous from the viewpoint of airtightness. The material of the counter electrode is, for example, iridium platinum, carbon or a conductive polymer, and preferably platinum, carbon or a conductive polymer. The structure of the counter electrode is preferably a structure having a high current collecting effect, and a preferred example is Japanese Laid-Open Patent Publication No. Hei 10-505192. Further, a human &lt;RTIgt; The mixed electrode other than the ruthenium is exemplified by Japanese Patent Publication No. 185243, and Japanese Patent Laid-Open No. 2003-282164. In order to improve the utilization of incident light, etc., the light-receiving electrode may be of a tandem type, and an example of a preferred tandem type structure is exemplified in Japanese Patent Laid-Open Publication No. Hei. It is also possible to efficiently perform light scattering inside the light-receiving electrode layer: the reflected light is a function of the light, and it is preferable to be described in Japanese Patent No. 2_-93 peach. It is preferable to form a short-circuited Z-stop layer between the conductive support and the porous semiconductor fine particle layer in order to prevent a reverse current which is directly contacted between the electrolytic solution and the electrode. It is better to be solved, and the Japanese patent publication (4) Cong No.物二 63 201210835 38254pif The one described in the publication No. 2001-283941. (E) Representative redox couples of electrolytes such as iodine and iodide (for example, lithium iodide, tetrabutylammonium tetrachloride, tetrapr0pyiammonium i〇 (jide), combination-based viologen (alkyl viologen) (eg, methyl viologen chloride, hexyl vi〇1〇gen bromide, &gt; benzyi vi〇l〇gen tetrafluoroborate) a combination of polyhydroxybenzenes (eg, hydroquinone, naphthhydroquinone, etc.) with its oxides, both valence and trivalent An iron complex (for example, a combination of red (jprUssiate) and yellow blood salt (yellow prussiate), etc., wherein a combination of iodine and iodide is preferred. The organic solvent of the above redox couple is dissolved. A non-protic polar solvent (eg, 'acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, Sulfolane ), 1,3-dimethylimidazolinone, 3-methyl oxazolidinone, etc.) a polymer used in a matrix of a gel electrolyte For example, polyacrylonitrile, p〇ly Vinylidene fluoride, etc. The molten salt is, for example, by lithium iodide and at least one other type of lithium salt (for example, 'lithium acetate, a polyperoxide in a lithium perchlorate or the like, and a molten salt having a fluidity at room temperature. Addition of the polymer in the above case

64 S 201210835 38254pif The amount is 1% by mass to 50% by mass. Further, γ-butyrolactone may be contained in the electrolyte, whereby the diffusion efficiency of the adduct ions may be increased and the conversion efficiency may be improved. The addition of the electrolyte_, in addition to the above-mentioned 4-t-butyl acridine, may be added to an amine pyridine aminopyridine compound, a benzimiazole compound, or an aminotriazole system. Compounds and amines, aminothiazole compounds, glutinous rice compounds, amino triazine compounds, urea derivatives, amide compounds, pyrimidine compounds, and Nitrogen-containing heterocycle. Further, in order to improve the efficiency, a method of controlling the moisture of the electrolyte may be employed. A preferred method for controlling moisture includes a method of controlling the concentration and a method of coexisting with the dehydrating agent. In order to reduce the toxicity of the filling, a cyclodextrin-containing dathrate compound may be used, and in contrast, a method of frequently replenishing water may be used. Further, an anti-oxidation inhibitor, a hydrolysis inhibitor, a decomposition inhibitor, and zinc telluride may be added as a cyclic amidine. Further, a molten salt may be used as the electrolyte, and a preferred molten salt such as an ionic liquid containing an imidazolium or a triazolium type cation, an oxazolium system, a pyridine system, an anthraquinone system, and combinations thereof . These cations may be combined with a specific anion, and an additive may be added to the above-mentioned molten salt, and a liquid crystal substituent may also be added. Further, a molten salt of a quaternary ammonium salt system can also be used. 65 201210835 38254pif A molten salt other than the above is, for example, mixed with a polyethylene oxide in a decomposing clock and at least other lithium salts (for example, lithium acetate, lithium percarbonate, etc.), and has a room temperature Liquidity, etc. Alternatively, it may be gelated by adding a gelling agent to an electrolytic solution including an electrolyte and a solvent to pseudo-solidify the electrolyte. The gelling agent is, for example, an organic compound having a molecular weight of 1,000 or less, an Si-containing compound having a molecular weight of 500 to 5,000, an organic salt formed of a specific acidic compound and a basic compound, or a sorbitol derivative (sorbit〇1 derivative). Polyethylene-based "Bite" In addition, a method of limiting a matrix polymer, a cross-linking polymer compound or a monomer, a crosslinking agent, an electrolyte, and a solvent to a polymer can also be used. The matrix polymer is preferably a polymer having a nitrogen-containing heterocyclic ring in a repeating unit of a main chain or a side chain, a crosslinking agent which reacts with an electrophilic compound, a polymer having a triazine structure, and a mercapto urea. (ureide) polymer, liquid crystal compound-containing polymer, ether linkage polymer, polyfluorinated vinylene, decyl acrylate, acrylic, thermosetting resin, crosslinked polyfluorene Oxygen alkane, polyvinyl alcohol (p〇lyvinyl alcoho PVA), water y 7 儿 丰 〆 一 a small crystal cage compound such as dextrin, addition of oxygen or sulfur polymer system, natural polymer, and the like. In the above, a base swelling polymer, a polymer having a compound capable of forming a cation moiety and a charge shifting property of iodine in one polymer may be added. The matrix may also be a component having two or more functional isocyanates (jS〇Cyanate) as a part, and it may also be used with a hydroxyl group, an amine group, a carboxyl group, or the like.

S 66 201210835 38254pif The type of crosslinked polymer of the functional group reaction. Further, a crosslinked polymer such as a hydrosilyl group and a double bond compound, a polysulfone acid or a polycarboxylic acid, and a metal ion having a valence of 2 or more may be used. The crosslinking method of the compound reaction. A solvent which can be preferably used in combination with the electrolyte of the above-mentioned pseudo solids can be exemplified by a specific mixed acid containing a specific acid ester, an ethylene carbonate-containing ethylene carbonate, and a specific dielectric constant. (dielectric constant) solvent. Further, the solid electrolyte membrane may be held or the liquid electrolyte solution may be held in the pores. The method is preferably a cloth-like solid such as a conductive polymer membrane, a fibrous solid or a filter. Further, a solid charge transport layer such as a p-type semiconductor or a hole transport material may be used instead of the above liquid electrolyte and solidified body electrolyte. The electroconductive material and the transport material are preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole or polydecane, and a spiro compound having two tetrahedral structures such as C and Si as a medium-halogen. An aromatic amine derivative such as triarylamine, a triphenylene derivative, a nitrogen-containing heterocyclic derivative, or a liquid crystalline cyanide derivative. a mole/L, more preferably 〇·3, because a redox pair can be a carrier for electrons, so a certain concentration is necessary, and the total wave length is preferably 〇, more preferably 0.1 mole/L, more preferably 〇·3 M〇ie/L or more. The upper limit of the above-mentioned concentrated production is not particularly limited, and is usually about 5 toes. The present invention will be described in more detail based on the examples, and the present invention is not limited thereto. 67 201210835 38254pif [Preparation of Pigment] The following (SA-1) 0. 45 g and the following (sb-i) 〇 26 g are mixed in a solvent mixture of 1 to butanol 10 ml and toluene 10 ml. Mix and then stir while stirring for 4 hours under 丨(9)^. Thereafter, the obtained crystal was subjected to filtration under reduced pressure, and purified by silica gel c〇lumn chromatography to prepare the above-mentioned dye S14 〇 26 g. [Chem. 46]

+

HOOC

SB-1 [Experiment 1] (Production of photoelectric conversion element) The following methods are used to produce the photoelectric conversion element as shown in Fig. 1. On the glass substrate, fluorine-doped tin oxide is formed by sputtering to have d as a transparent conductive film, and then the transparent conductive film is divided into portions by laser cutting. Thereafter, an anatase-type oxidation d is sintered on one of the conductive films to fabricate a light-receiving electrode. Next, a dispersion containing 4:60 (mass ratio) of cerium 4 and rhodopsin-type titanium oxide was applied to the light-receiving electrode, and then baked to form an insulating porous body. The coating amount of the semiconductor fine particles is ^ g / m 2 ' followed by formation of a carbon electrode as a counter electrode. Then, it was smashed in an ethanol solution of the dye described in Table 1 below for 48 hours. Then, the glass dyed with the sensitizing pigment is immersed in 4_third.

After 6 minutes of 6S S 201210835 38254pif acridine in 10% ethanol, it was washed with ethanol and allowed to dry naturally. The thickness of the obtained photoreceptor was 10 μm. The amount of the pigment is, in view of the kind of the visible pigment, suitably selected from the range of 0.1 mmole/m2 to 10 rnmole/m2. As the electrolytic solution, a methoxypropionitrile solution of dimercaptopropylimidazolium iodide (0.5 mole/L) and iodine (0.1 mole/L) can be used. (Measurement of the maximum absorption wavelength of the dye) The maximum absorption wavelength of the dye used was measured, and the results are shown in Table 1. The measurement of the maximum absorption wavelength can be carried out by using a spectrophotometer (U-4100 (trade name), manufactured by Hitachi High-Technology Co., Ltd.), and the solution can be adjusted to 2 μM by using THF:ethanol = 1:1. (Measurement of photoelectric conversion efficiency) By using a 500W xenon lamp (manufactured by ushi Co., Ltd.), it passes AM1.5G filter, light sheet (manufactured by Oriel), sharp wave filter, and light sheet (Kenko L-42, trade name). ), producing a simulated sunlight that does not contain ultraviolet light. The above light intensity is 89 mW/cm2. The above-described light was irradiated onto the produced photoelectric conversion element. The photoelectric conversion characteristics were measured by a current-voltage measuring device (Keithley Model 238, trade name). The measurement results of the initial values of the conversion efficiency of the photoelectrochemical cell are shown as conversion efficiency in Table 1 below. When the conversion efficiency is 2.5% or more, it is represented by ◎, and when it is 1% or more and less than 2.5%, it is represented by ,, and when it is 0.3% or more, less than 1% is represented by Δ, and less than 0. 3% is represented by X. The conversion efficiency is 〇. The above is qualified, and less than 0.3% is unqualified. In addition, the initial value of the relative conversion efficiency was evaluated as the durability after the reduction of the conversion efficiency after 500 hours 69 201210835 . 90% or more of the above results were evaluated as ◎, 60% or more, less than 90% were evaluated as 〇' 40% or more, less than 60% were evaluated as △, and less than 40% were evaluated as X' and relative conversion The initial value of efficiency is acceptable if the conversion efficiency after 5 hours is 60% or more, and less than 60% is unqualified. Table 1 Sample number Pigment pigments Maximum absorption wavelength (nm) Conversion efficiency Durability Remarks 1-1 si 741 Δ 〇 The present invention 1-2 S-2 739 〇〇 The present invention 1-3 S-3 735 〇〇 The present invention 1 -4 S-4 - - 727 〇〇 1-5 S-5 727 of the present invention 〇〇 1-6 S-6 746 of the present invention 〇〇 not invented 1-7 S-7 782 ◎ ◎ 1-8 S- of the present invention 8 769 〇〇 1-9 S-9 752 of the present invention ◎ 1-10 S-10 745 of the present invention 1 1-11 S-11 788 of the present invention △ 〇 1-12 S-12 786 of the present invention 1-13 S-13 765 〇〇 1-14 S-14 772 of the present invention ◎ ◎ 1-15 S-15 772 of the present invention ◎ ◎ 1-16 S-16 773 of the present invention ◎ ◎ 1-17 S-17 of the present invention 761 〇〇Not invented 1-18 S-18 791 ◎ ◎ 1-19 T-2 790 〇 ◎ ◎ 1-20 T-6 785 ◎ ◎ The present invention 1-21 T-9 800 ◎ ◎ The present invention 1 -22 T-10 810 ◎ ◎ i invention 1-23 T-12 800 ◎ ◎ 1-24 T-16 770 of the present invention ◎ ◎ 1-25 T-17 770 of the present invention ◎ ◎ 1-26 T-18 770 of the present invention ◎ ◎ 1-27 T-24 770 of the present invention ◎ ◎ 1-28 T-30 800 of the present invention ◎ ◎ 70 of the present invention

S 201210835 38254pif 1-29 T-37 820 ◎ ◎ The present invention 1-30 T-41 795 〇 ◎ The present hair 1-31 T-42 810 ◎ ◎ The present invention f 1-32 T-43 810 ◎ ◎ The present invention 1- 33 A-1 731 〇X is more than 1-34 A-2 770 〇X. In the experiments 1 to 10, 'the following Al and Al are used as the comparative pigments. Comparative compound

As is clear from Table 1, the photoelectrochemical cell using the dye of the present invention has an initial value of conversion efficiency as an acceptable standard, and the conversion efficiency after 500 hours has passed is 60% or more of the initial value, and shows excellent durability. In the case where the above comparative dye is used, the initial value of the conversion efficiency is an acceptable standard, but there is a problem in durability. [Experiment 2; | A transparent conductive film was produced by forming an ITO film on a glass substrate and then laminating an FTO film thereon. Thereafter, a transparent electrode plate is obtained by forming an oxide semiconductor porous film on the transparent conductive film. Next, a photoelectrochemical cell was fabricated using this transparent electrode plate, and the conversion efficiency was measured. The above methods are as follows (1) to (5). (1) Preparation of a solution of a raw material compound for ITO (oxidized sulphate) film. Indium (m) chl〇ride tetrahydrate 5. 58 g and tin (II) vapor dihydrate (tin(II) cW〇ride dihydrate) 23. 23 g was dissolved in 1 〇〇ml of ethanol to serve as a raw material compound solution for IT ruthenium film. (2) Preparation of FTO (fluorine-doped tin oxide) film with a raw material compound solution. Dissolve tin (IV) pentahydrate 〇. 701 g in ethanol, and then add 1 to 0. 592 a saturated aqueous solution of g, and then the above mixture is placed in an ultrasonic cleaner for about 20 minutes to completely dissolve, as a raw material compound solution for ft〇 film (3) ITO/FTO transparent conductive film, heat-resistant glass having a thickness of 2 mm. After the surface of the board was chemically cleaned and dried, the glass plate was placed in a reactor and heated by a heater. When the heating temperature of the heater becomes 45 (TC), the raw material compound solution for the IT film obtained in (1) is passed from a nozzle having a diameter of 33:11111 at a pressure of ]6]^1^, from the glass plate. Spraying at a distance of 400 mm for 25 minutes. After spraying the raw material compound solution for the ITO film described above, it took 2 minutes (in the meantime, the ethanol was continuously sprayed on the surface of the glass substrate to suppress the rise of the substrate surface temperature). When the heating temperature of the heater is changed to 53 Torr, the raw material compound solution for the F Τ Ο film obtained in (2) is subjected to the mist under the same conditions for 2 minutes and 30 seconds. According to the above, the heat-resistant glass can be obtained. The ITO film with a thickness of 530 nm and the thickness of the film with a thickness of m ^ are sequentially formed on the plate.

S 72 201210835 38254pif electrode plate. In order to compare 'on a heat-resistant glass plate having a thickness of 2 mm, a transparent electrode having an ITO film having a film thickness of 53 G nm and a transparent electrode having an FTO 成 having a thickness of 180 nm were formed in the same manner. The above three kinds of transparent electrodes were heated in a heating furnace at 45 Torr for 2 hours. (4) Preparation of a photoelectrochemical cell Next, the use of the above-mentioned three types of pervaporated electrode plates was carried out to prepare Japanese Patent No. 426_4. _2Qing's photoelectrochemical cell is formed, and the porous film of the compound semiconductor is formed by dispersing an average particle size of the titanium oxide fine particles in an acetonitrile towel and then using a bar coating method. d) The coating was applied to the transparent electrode n at a degree of 15 μm, followed by drying and baking at 4503⁄4 for 1 hour. Next, the dye described in Table 2 was carried on the oxide semiconductor porous film. Further, an electrolyte substrate which is formed by laminating a ruthenium film and an FTO film on a glass plate is used extremely, and an electrolyte containing a non-aqueous solution of ruthenium/deuterium is used for the electrolyte t. The planar size of the photoelectrochemical cell is 25 mm x 25. (5) Evaluation of photoelectrochemical cell The photoelectrochemical cell produced by (4) was measured for photoelectric conversion characteristics by the same method as that of Experiment 1, and the conversion efficiency was measured. The knots are shown in Table 2. Regarding the job efficiency, it means = the relative value when the sample number 2_9 is regarded as 丨. Regarding the stagnation, the initial value of the relative conversion efficiency, after 500 hours of conversion efficiency, the above is ◎, 60% or more, less than 90% are 〇, 4〇% or more, less than 6%% 73 201210835 38254pif is △, less than 40% is χ, and the initial value of relative conversion efficiency, the conversion efficiency after 500 hours is 60% or more, and less than 60% is unqualified. Table 2 Sample No. Conductive Film Pigment Conversion Efficiency Durability Remarks 2-1 Only ΠΌ S-2 0.55 〇 Inventive 2-2 FTO S-2 only 0.59 〇 2-3 ITO+FTO S-2 0.89 〇1 of the present invention 2-4 ITO S-8 0.61 only 〇 2-5 of the invention only FTO S-8 0.63 〇 2-6 of the invention ITO+FTO S-8 0.91 〇 the invention 2-7 only ITO S-13 0.65 〇 the invention 2 -8 FTO S-13 0.76 only 〇 2-9 ITO+FTO S-13 1.00 〇 〇 2-10 ITO T-16 0.99 ◎ ◎ 2-11 only FTO T-16 0.97 ◎ The present invention 2- 12 ITO+FTO T-16 1.10 ◎ 2-13 of the present invention only ITO T-24 0.97 ◎ - 2-14 of the present invention only FTO T-24 0.93 ◎ 2-15 of the present invention ITO+FTO T-24 1.07 ◎ The present invention 2 -16 ITO T-12 1.00 only ◎ 2-17 of the present invention only FTO T-12 1.05 ◎ ^ 2-18 ITO+FTO T-12 1.30 of the invention ◎ 2-19 of the invention only ITO A-2 0.62 X Comparative Example 2 -20 FTO only A-2 0.68 X Comparative Example 2-21 ITO+FTO A-2 0.82 X Comparative Example It can be seen from Table 2 that even if the conductive layer is only an ITO film or only an FTO film, In the photoelectrochemical cell of the invention, the conversion efficiency is also lowered, and the conductive layer is When the ITO film formation ft〇 film, showing conversion efficiency tends to become high. The above tendency is also similar in the case of the photovoltaic cell of the comparative example. Despite this, the photoelectrochemical cell of the present invention is subjected to 74

S 201210835. The conversion efficiency after 500 hours is 6 % or more, and exhibits excellent durability. The photoelectrochemical cell of the comparative example has a conversion efficiency of less than 40% after 5 hours, and is known to have durability. The problem. [Experiment 3] A collector electrode was placed on the FTO film to fabricate a photoelectrochemical cell, and the conversion efficiency was evaluated. The evaluation was as follows, and two types of test battery (i) and test battery (iv) were used. (Test cell (1)) After chemically cleaning and drying the surface of a heat-resistant glass plate of 100 mm x 100 mm x 2 mm, 'put the glass plate in a reactor and heat it with a heater'. The FTO used in the above experiment 2 ( Fluorine-d〇pedtin oxide's solution of the raw material compound for the film, sprayed by a nozzle having a diameter of 3 mm at a pressure of 0.06 MPa at a distance of 4 mm from the glass plate for 25 minutes. To prepare a glass substrate with an FTO film. On the surface of the substrate described above, a groove having a depth of 5 μm is formed on the lattice circuit pattern by an etching method. Then, after patterning by photolithography, etching is performed using hydrofluoric acid. In order to form metal plating, a metal conductive layer (seed layer) is formed by sputtering, and a metal wiring layer can be formed by using an additional plating layer. The metal wiring layer is formed at a height of 3 μm from the surface of the transparent substrate to the convex lens. The circuit is 60 μηη wide. From the above, the shielding layer 5 is an FTO film having a thickness of 400 nm formed by the SpD method as the electrode substrate (1). The cross-sectional shape of the electrode substrate (1) is changed to 75 201210835 as shown in Fig. 2 of Japanese Patent Laid-Open No. Hei. No. 4,464,425. On the electrode substrate (i), the coating and drying of titanium oxide having an average particle diameter of 25 nm are dispersed. After the solution, the mixture was heated and sintered at 450 ° C for 1 hour. Then, it was immersed in an ethanol solution of the pigment shown in Table 3 t for 4 minutes to carry the pigment. Further, it is preliminary to investigate the solubility of the dye used in the present invention for various organic solvents. The above results show that it can be dissolved in toluene, so as shown in Table 3, it is also prepared to be impregnated in a toluene solution for 4 minutes. The platinum sputter substrate is disposed opposite to the substrate by a 50 μη thick thermoplastic sheet, and the resin sheet is thermally melted to fix the two plates. However, 'the liquid injection port of the electrolyte which is pre-opened on the side of the splatter plating, the main component t contains 0.5 Μ of iodized salt and methoxy acetonitrile of 碘. 5 Μ iodine, And filled between the electrodes. Further, the peripheral portion and the electrolyte injection port were sealed with an epoxy-based encapsulating resin, and a silver paint was applied to the collector terminal portion to serve as a test cell (1). Next, similar sunlight of AM15 was irradiated on the test cell (i) in the same manner as in Experiment 1 to measure the conversion efficiency, and the results are shown in Table 3. (Test Battery (iv)) A glass substrate having an FTO film of 1 mm × 10 mm was prepared in the same manner as in the test battery (i). On the above-mentioned 1:1 glass substrate, a metal wiring layer (gold circuit) was formed by an additional plating method. The metal wiring layer (gold circuit) described above is formed in a lattice shape on the surface of the substrate, and has a circuit width of 5 μm and a circuit thickness of 5 (four). Then, on the surface thereof, an FTO film having a thickness of 300 nm was formed by using the spD method as a shielding layer to serve as an electrode substrate (iv. When the cross section of the electrode substrate (iv) was confirmed by SEM-EDX, it was found that the bottom of the wiring was 201210835 38254pif It is considered that the immersion of the skirt-shaped bottom portion due to the plating resist layer is partially covered with FTO. Using the electrode substrate (iv), the battery (4) was tested in the same manner as the test battery (1). The test was carried out in the same manner as in Experiment 1. The battery (iv) i radiant AMI. 5 is similar to sunlight to measure the conversion efficiency. The results of the initial values of the above conversion efficiency are shown as conversion efficiency in Table 3. The conversion efficiency is 2.5% or more, expressed as ◎, 1 % or more, =〇 means '0·grass above, less than 1% is represented by △, less than 〇3% f is represented by x, and the conversion efficiency is 〇. 3% or more are qualified, less than 〇. 3% In addition, the initial value of the relative conversion efficiency, the conversion effect after 5 hours, the above is evaluated as ◎, 6〇% or more, less than 9〇% is evaluated as 〇苴40% or more, Less than 6〇% are evaluated as △, and less than 4% are evaluated as X', which is expressed in Table 3 as Durability relative value of the initial conversion efficiency, the conversion efficiency after 500 hours was 60% or more are qualified, less than 60% were unacceptable. 77 2012108351. .pit Table 3

Sample number &quot;&quot;&quot;3^i ~Γ2 3^3 3^4 ~3^5 ~Γ6 3^7 ~~3^8 ~3^9 ~3^10 3-11 3-12~~ 3 -13 3-14 3-15~ 3-16~ 3-17~~ 3-18~~ 3-19~ 3-20~~ Table U吏: The conversion efficiency of the test cell of the pigment of the present invention is l/ ό Above, and the table does not show a high value. In addition, the solvent used in the dye solution can improve the conversion efficiency (&amp; ^ test = 3-3, 3-4 comparison). In the case of using a comparative pigment, the initial value of the conversion efficiency is higher than that of the present invention, but the efficiency is greater than the 500-hour system (four), and the durability reduction in the case of using the pigment of the gamma is significantly less, and the display is Excellent characteristics. [Experiment 4] Peroxytitanic acid and titanium oxide fine particles were produced and used to prepare an oxide 78 201210835 38254 pif semiconductor film. New's used an oxide semi-conductive bribe to make a photoelectrochemical cell and evaluated it. (Production of photoelectrochemical cell (A)) (1) Preparation of a coating liquid (A1) for forming an oxide semiconductor film 5 g of hydrogenation was suspended in 1 l of pure water, and then added to 5 masses in 3 minutes. A percentage (%) of hydrogen peroxide solution was 4 g, followed by twisting to 8 Torr and dissolution to prepare a solution of peroxotitanic acid. Fractional 90% by volume (ν〇ι%) from the full amount of the above solution, then add concentrated ammonia to adjust the pH to pH9, and put it into the still kettle, and perform 25-hour hydrothermal treatment at 25 °C under saturated steam pressure. The titanium oxide colloidal particles (A2) are prepared, and the obtained oxidized &amp; colloidal particles are diffracted by X-rays to form an anatase-type titanium oxide having high crystallinity. Next, the obtained titanium oxide colloidal particles are obtained. (A2) Concentrated to 1 〇 mass. /. 'The above-mentioned peroxotitanic acid solution was mixed, and Ti 2 in the above-mentioned mixed liquid was converted into Ti 〇 2 to add hydroxypropyl acrylate in an amount of 3 〇 mass% of Τι〇2 mass. The hydroxypropyl cellulose is used as a film forming aid to adjust the coating liquid (A1) for forming a semiconductor film. (2) Preparation of an oxide semiconductor film (A3) Next, fluorine-doped tin oxide is used. On the transparent glass substrate formed as the electrode layer, the above coating liquid (A1) was applied and naturally dried, and then ultraviolet rays of 6 〇〇〇mJ/cm 2 were irradiated with a low pressure mercury lamp to decompose peroxo acid. And the coating film is hardened. The coating film is heated by 3 〇〇. The hydroxypropylcellulose is decomposed and annealed (anneaHng) to form an oxide semiconductor film (A3) on a glass substrate. (3) Adsorption of a pigment in an oxide semiconductor film (A3) 79 201210835 38254pif Next An ethanol solution having a concentration of the dye of the present invention of 3χ1〇-4 m〇le/L is prepared as a spectral sensitizing dye. The dye solution is applied to a metal oxide semiconductor film (A3) by being rotated at (10) rpm. On, and dry. Then '5 times of coating and drying process. (4) Preparation of electrolyte solution in the mixed solvent of acetonitrile and ethylene carbonate acetonitrile volume W: 5, dissolved worming four secrets 0 · 46 The mole/L makes the fineness of the Q7 mGk/L in order to modulate the electrolyte solution. (5) The fabrication of the photoelectrochemical cell (A), the formation of the oxide semiconductor film (A3) of the adsorbent: ίί 'Formation of doping_tin oxide as ΐ 2 ί is # ° Then 'on the electrode, the oppositely placed carrier electrolyte solution. Then, between the electrodes, the electric 曰 1 is enclosed (4) to learn the battery (Α). (4) For photoelectricization (production of photoelectrochemical cell (Β)) In addition to ultraviolet irradiation The line is decomposed by ion permeation (five) ion irradiation (manufactured by Fuxin Electric Co., Ltd.: after: = after 'argon irradiation Η) hour), with the oxide semi-injection device, 2 〇〇... into the oxide semiconductor chat 3 ). 11 Difficult 3) The same procedure as in the case of the oxide semiconductor film (B3) The chemical cell (A) is adsorbed in the same manner as the oxide semiconductor film (A3). Then, a photoelectrochemical cell (B) was produced by an electrophoto method. (Production of Photoelectrochemical Cell (C)) 201210835 38254pif 18.3 g of titanium tetrahydrate was diluted with pure water to obtain an aqueous solution containing 1.0% by mass in terms of Ti〇2. While stirring the above aqueous solution, 15% aqueous ammonia was added to obtain a white slurry of pH 9.5. The slurry was filtered and washed to obtain a filter cake of water and titanium oxide gel in an amount of 1.0% by mass in terms of Ti〇2. Then, the above filter cake and 4 mass% hydrogen peroxide 4 g were mixed, followed by heating to 80 ° C and dissolved to prepare a solution of peroxotitanic acid. The full amount of the above solution was fractionated by 90 vol%', then concentrated ammonia was added to adjust the pH to pH 9, and placed in a pressure dad, and hydrothermally treated at 250 C under a saturated vapor pressure for 5 hours to prepare titanium oxide colloidal particles ( C2). Next, the peroxotitanic acid solution obtained above and the titanium oxide colloidal particles (C2) are used in the same manner as the oxide semiconductor film (A3) to form an oxide semiconductor film (C3), followed by an oxide semiconductor film (A3). In the same manner, the adsorption of the dye of the present invention is carried out as a spectral sensitizing dye. Then, a photoelectrochemical cell (Q. (Production of photoelectrochemical cell (D)) was prepared in the same manner as in the photoelectrochemical cell (A), and 13.3 g of titanium tetrahydrate was diluted with pure water to obtain a Ti-containing titanium oxide. 2: An aqueous solution of 1.% by mass is added. While stirring the above aqueous solution, 15% of ammonia water is added to obtain a white slurry having a pH of 9 to 5. After washing the slurry, 0.6% of water is suspended in pure water. The slurry of titanium oxide gel was added as hydrochloric acid to pH 2 as Τι〇2', and then placed in an autoclave at 18 Torr. The hydrazine was hydrothermally treated under a saturated vapor pressure for 5 hours to prepare titanium oxide colloidal particles (D2). Then, hydroxypropylcellulose was added as a 201210835, ----ρπ film forming aid, by concentrating the titanium oxide colloidal particles (D2) to 10% by mass and adding 30% by mass in terms of Ti〇2. The coating liquid for forming a semiconductor film is prepared. Next, on the transparent glass substrate formed by pushing the discolored tin oxide as an electrode layer, a coating liquid is applied and naturally dried, and then irradiated with a low-pressure mercury lamp. ^111 UV rays, make coating After hardening, the coating film is heated at 3 ° C for 30 minutes to carry out decomposition and annealing of propyl cellulose to form an oxide semiconductor film (D3). Next, with an oxide semiconductor film ( A3) The same method is used to carry out the adsorption of the pigment in the present month as a spectral sensitizing dye. Then, a photoelectrochemical cell (D) is produced in the same manner as in the photoelectrochemical cell (A). About the photoelectrochemical cell (A) ~ ( D) Irradiation-like sunlight (AM1.5) 'The photoelectric conversion efficiency was measured by the same method as the experiment to obtain the conversion efficiency. The results of the initial values of the above-described conversion ratios are expressed by conversion efficiency in Table 4. The efficiency is 2.5% or more, expressed as ◎, 1% or more, and less than 2.5% is expressed by 〇, 舰. Ship, less than 1% is represented by △, less than 0. 3% is represented by X The conversion efficiency is 3% or more, and the pass is not acceptable. J. 3% is unqualified. In addition, the initial conversion value of the conversion efficiency, the conversion efficiency after $(10) hours, the above is evaluated as ◎, 6〇% or more, no To 9〇%, the price is 〇', the % of the touch is evaluated as △, and the less than the shed is evaluated as X, the above Values shown in Table 4 in durability relative to the initial value of the conversion efficiency, the conversion efficiency 5GG hours or more qualified persons who fail.

S 82 201210835 38254pif

As is clear from Table 4, in the photoelectrochemical cell using the dye of the present invention, the initial value of the conversion efficiency is an acceptable standard, and the conversion efficiency after 500 hours has passed is 60% or more of the initial value' and shows excellent durability. In contrast to the above, it is known that when a comparative dye is used, the initial value of the conversion efficiency is an acceptable standard, but there is a problem in durability. [Experiment 5] The titanium oxide was prepared by changing the method, and an oxide semiconductor film and a photoelectrochemical cell were prepared from the obtained titanium oxide 83 201210835 38254pif and evaluated. (1) Preparation of titanium oxide (titanium oxide 1 (brookite type), etc.) by a heat treatment method Using a commercially available anatase type titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name ST-01) 'heat it to about 9 〇〇〇c was converted into brookite-type titanium oxide, and further heated to about 丨, 2001 as a gold-red type titanium oxide. Then, titanium oxide 1 (anatase type), comparative titanium oxide brookite type, and titanium oxide 1 (gold red ore type) were compared in order. (2) Synthesis of titanium oxide by wet method (titanium oxide 2 (brookite type), etc.) 954 ml of distilled water was placed in a reaction vessel equipped with a reflux condenser, and the mixture was heated to 95 °C. While maintaining the stirring speed at 2 rpm, the amount of gas (10): 16, '% specific gravity W, purity was dropped into the distilled water in the reaction tank at a rate of about 5.0 ml/min. At this time, care should be taken not to let the reaction (4) temperature be the above result, and the concentration of titanium tetra-titanate is 0.25 m〇le/L (2 mass% in terms of titanium oxide). In the reaction tank, the reaction liquid starts to turbid from the start of the human body, and the temperature of the scaly female continues until the end of the instillation, and then the temperature is raised and heated (four) points (〇, to maintain the reaction for 60 minutes until the reaction is completely completed. Filtering the sol obtained by the reaction Then, using 6 (a powder made of rc. The quantitative analysis of the powder by the 1XX sputum method, the peak intensity of the 121-plate surface of the samarium ore type) / (in the case of three weights of 4 positions ^ (4)) is G.38 The ratio of 'the main peak intensity of the gold-red mineral type' / (the peak intensity at the three weights) is Q·Q5. The yttrium oxide obtained by the above is ^70 84 201210835 ore type about 70· o mass% 'The gold red ore type is about 2% by mass, and the anatase type is about 28.8% by mass of crystallinity. In addition, the above-mentioned fine particles are observed by a transmission electron microscope, and the average particle diameter of the primary particles is 〇〇. 15 μπ! (titanium oxide 3 (brookite type), etc.) Diluted the aluminum trititanate aqueous solution (titanium content: 28%, specific gravity 1.5, purity 99·9%) with distilled water, and the concentration of titanium The solution was converted to 25. 25 m〇1/L. At this time, in order to prevent the liquid temperature from rising, ice cooling was performed and kept below. 5 〇〇mi of the above solution was placed in a reaction tank equipped with a reflux condenser, and the ozone gas generated by the ozone gas generating device was bubbled at a rate of j L/min while heating to 85 ° C. The oxidation reaction was carried out for 2 hours in the above state until the reaction was completely completed. The obtained sol was filtered and vacuum dried to obtain a powder. The result of quantitative analysis of the powder by X-ray diffraction was , (the peak intensity of the brookite-type 丨21 surface) / (the peak intensity at the three overlapping positions) is 〇85, (the main peak intensity of the gold-red mineral type) / (the peak intensity at the three overlapping positions) The ratio is 0. The titania obtained by the above is about 98% by mass of the brookite type, about 0% by mass of the gold ore type, about 0% by mass of the anatase type, and about 2% of amorphous. The above-mentioned fine particles were observed by a transmission electron microscope, and the average particle diameter of the i-th particle was 0.05 μπ! (Production and evaluation of photoelectrochemical cell) Titanium oxide 丨3 prepared by the above method was used as a semiconductor, and was produced by the following method. Make A photoelectrochemical cell of a photoelectric conversion element having the structure shown in Fig. 1 described in JP-A-2000-340269. A fluorine-doped tin oxide is applied onto a glass substrate to serve as a conductive electrode 85 201210835 38254pif a bright electrode. The surface is made of individual titanium oxide particles as a raw material, and the thickness is applied to the electrode by a bar coating method, and baking is performed at 5 Å to form a thin layer having a film thickness of about 2 μm. As a result of investigation, it was found that the dye used in the present invention has high solubility in various organic solvents. Therefore, ethanol was used as a solvent, and the concentration of the dye=liquid was changed and evaluated. The dye used in the present invention is a standard dye solution of 3 x 10 Å and 6 χ 1 〇 4 μ. The comparative dye had low solubility in a solvent, and since it was impossible to prepare a 6χ1〇·4Μ solution, it was evaluated using only a dye solution of 3χ1〇-4 。. An ethanol solution having a concentration of the dye as shown in Table 5 was prepared, and a thin glass substrate on which the above titanium oxide was formed was immersed therein and kept under a chamber for 12 hours. As a result of the above, the above-mentioned dye was adsorbed on a thin layer of titanium oxide. An iodine salt of tetrapropylammonium and an acetonitrile solution of lithium iodide were used as an electrolyte, and platinum was a counter electrode to prepare a photoelectric conversion element having no structure as disclosed in Japanese Patent Laid-Open No. 69-No. The photoelectric conversion was carried out by irradiating the light of a high-pressure mercury lamp of 16 G W in the above-mentioned element (the cut-off infrared ray of the calender: the 'initial value of the conversion efficiency was measured by the same method as the experiment 1). The above is shown in Table 5. The conversion efficiency is 2.5% or more, expressed as ◎, 1% or more, less than 2.5%, the 〇 table is not '0.3% or more, the undone is △, less than 〇. 3% t is not 'the conversion efficiency is Q · 3% or more are qualified, less than G. 3% are not ^ ° other 'relative conversion efficiency of the initial value, after the closing of the conversion effect 90 /. The above β parity is ◎ , 6〇% or more, less than 9(10)◦

S 86 201210835 〇' 40% or more, less than 6〇% was evaluated as Δ, and less than 4% was evaluated as 乂, and the above values are shown in Table 5. The initial value of the relative conversion efficiency, the conversion efficiency after 500 hours is more than 6〇%, and the less than 6〇% are unqualified. Table 5 Sample No. Titanium Pigment Pigment Solution Concentration (χ10-4Μ) Conversion Efficiency言 主 5-1 Titanium oxide 1 S-2 3 〇〇 The present invention 5-2 Titanium oxide 2 S-2 3 〇〇 The present invention 5-3 Titanium oxide 3 S-2 3 ◎ 〇 The present invention 5-4 5-5 Titanium oxide 1 Titanium oxide 2 S-2 6 ◎ 〇 S-2 6 ◎ 〇 〇 5-0 5-7 Titanium oxide 3 S-2 6 ◎ 氧化 氧化 氧化 氧化 氧化 1 1 1 1 1 1 1 B-month 5 - 〇c η titanium oxide 2 S-8 3 ◎ ◎ 5-10 5-11 of the present invention Titanium 3 S-8 3 ◎ ◎ The present invention I: I: 3⁄4 1 S-8 6 ◎ ◎ The present invention Gasified Titanium 2 S-8 6 ◎ 1 ◎ J-\ Δ of the present invention Titanium 3 3-8-8 ◎ ◎ 5-13 Titanium oxide 1 T-10 3 〇 ◎ ◎ 5-14 Titanium oxide of the present invention 2 T-10 3 〇 ◎ — 5-15 C 1 f. __^ 匕 Titanium 3 T-10 — ' 3 ◎ ◎ D- 1 Ο 5-17 ~ ^ Titanium 1 匕 Titanium 2 T-10 T-10 6 6 ◎ (Q) ◎ (0) The present invention 5-18 __^ Titanium 3 T-10 6 ◎ ◎ The present invention 5-19 ^化钦1 Α·1 5-20 __ g titanium 2 Α-1 ό 3 〇X Comparative Example 5-21 5-22 5-23 匕Titanium 3 ～ Titanium 1 Α-1 Α-2 3 3 ◎ 〇AX Δ Comparative Example Comparative Example Bud 5-24 匕Titanium 2 1__^匕Titanium 3 Α-2 Α-2 3 3 ◎ ◎ ^ *l〇C Ί7'1 Comparative Example Comparative Example It is understood from Table 5 that the use of the dye of the present invention is improved by 87 201210835 38254pif The concentration of the dye solution, and the initial value of the conversion efficiency is known to be high. This is considered to be because the adsorption of the pigment of titanium oxide is also increased by increasing the concentration of the dye solution. When using a comparative pigment, the initial value of the conversion efficiency is also an acceptable standard. However, when the durability is used, the dye is used in the case of using the comparative dye, and the dye of the present invention exhibits excellent characteristics. [Experiment 6] A coating material of dispersed semiconductor fine particles was prepared using titanium oxide having different particle diameters. Then, a photoelectrochemical cell was fabricated and evaluated for characteristics 〇 [modulation of the coating] (coating 1) and spherical Ti〇2 The particles (anatase type, average particle diameter: 25 nm, hereinafter referred to as spherical Ti〇2 particles 1) were placed in a js bromic acid solution, and the titanium slurry was prepared by scramble. Next, a cellulose-based binder was added to the titanium paste as a tackifier, and kneading was carried out to prepare a coating. (Coating 2) Spherical Ti〇2 particles 1 and spherical Ti〇2 particles (anatase type, average particle diameter: 200 nm, hereinafter referred to as spherical Ti〇2 particles 2) were placed in a nitric acid solution by mixing To prepare the titanium slurry. Next, a cellulose-based binder was added as a tackifier to the titanium mass, and kneading was carried out to prepare a coating (spherical Ti〇2 particle 1: spherical butyrene 2 particle 2 = 30:70). 2 (paint 3)

S 88 201210835 38254pif In the coating 1 'mixed rod-shaped TiO 2 particles (anatase type, diameter: lOOnm, aspect ratio: 5, hereinafter referred to as rod-shaped TiO 2 particles 1) to prepare rod-shaped Ti 〇 2 particles 1 Quality: Paint 1 quality = 1 〇: 90 paint. (Coating 4) In the coating material 1, the rod-shaped TiO 2 particles 1 were mixed to prepare a coating of the mass of the rod-shaped Ti 2 particles 1 : the mass of the coating material 1 = 30:70. (Coating material 5) In the coating material 1, the rod-shaped TiO 2 particles 1 ' were mixed to prepare a coating of the mass of the rod-shaped Ti 2 particles 1 and the mass of the coating material 1 = 50:50. (Coating material 6) In the coating material 1, 'the plate-shaped mica particles (straight particle diameter··10Q nm, aspect ratio: 6, or hereinafter referred to as plate-like mica particles 1) are mixed to modulate the mass of the plate-shaped mica particles 1: Paint 1 quality = 20: 80 paint. (Coating material 7) In the coating material 1, rod-shaped TiO 2 particles (anatase type, diameter: 30 nm, aspect ratio: 6.3, hereinafter referred to as rod-shaped Ti 〇 2 particles 2) were mixed to prepare a rod shape. Quality of Ti〇2 particle 2: Coating 1 mass = 30: 70 coating. (Coating 8) In the coating material 1, rod-shaped Ti〇2 particles (anatase type 'diameter: 50 nm, aspect ratio: 6.1, hereinafter referred to as rod-shaped Ti〇2 particles 3) were mixed to prepare The mass of the rod-shaped Ti〇2 particle 3: the mass of the coating 1 = 30: 70 coating. (Coating 9) In the coating material 1, rod-shaped Ti〇2 particles (anatase type, diameter: 75 nm, aspect ratio: 5.8, hereinafter referred to as rod-shaped Ti〇2 particles 4) were mixed to prepare 89 201210835 38254pif Quality of rod-shaped Ti〇2 particles 4: Coating 1 quality = 30: 70 coating. (Coating 10) In the coating 1, 'mixed rod-shaped Ti〇2 particles (anatase type, straight: 130 nm, aspect ratio: 5.2, hereinafter referred to as rod-shaped Ti〇2 particles 5), The mass of the rod-shaped Ti〇2 particles 5 was adjusted: the mass of the coating material = 30: 70 of the coating °. (Coating material 11) In the coating material 1, rod-shaped Ti〇2 particles (anatase type, diameter: 180 nm, aspect ratio: 5, hereinafter referred to as rod-shaped Ti〇2 particles 6) were mixed to prepare a rod-shaped Ti. 〇 2 The quality of the particle 6: the quality of the coating 1 = 3 〇: 70 coating. (Coating material 12) In the coating material 1, rod-shaped Ti〇2 particles (anatase type, diameter: 240 nm, aspect ratio: 5, hereinafter referred to as rod-shaped Ti〇2 particles 7) were mixed to prepare a rod shape. The mass of the Ti〇2 particle 7: the mass of the coating 1 = 3 〇: 70 coating. (Coating material 13) In the coating material 1, a rod-shaped Ti〇2 particle (rear type, diameter: llOnm, aspect ratio: 4.1, hereinafter referred to as rod-shaped Ti〇2 particle 8) was mixed to prepare a rod The quality of the Τι〇2 particle 8: the quality of the coating 1 = 3 〇: 7 〇 of the coating. (Coating material 14) In the coating material 1, rod-shaped Ti〇2 particles (anatase type, diameter: 105 nm, aspect ratio: 3.4, hereinafter referred to as rod-shaped Ti〇2 particles 9) were mixed to prepare a rod-shaped Τι 〇 2 particle 〇 quality: paint 丨 quality = 3 〇: 7 〇 paint. (Photoelectrochemical Cell 1) An electrophotovoltaic 201210835 38254 pif electrode having the same structure as that of the photoelectrode 12 described in FIG. 5 of Japanese Laid-Open Patent Publication No. 2002-289274, and then using a photoelectrode, was fabricated in accordance with the procedure described below. A photoelectrochemical cell 1 having the same structure as the dye-sensitized solar cell 20 is provided in addition to the photoelectrode. A transparent electrode having a fluorine-doped Sn 〇 2 conductive film (film thickness: 500 nm) was prepared on a glass substrate. On the Sn〇2 conductive film, the above coating was screen printed and then dried. Thereafter, baking is performed in the air at 45 (rc conditions. Then, using the coating 4', the screen printing and baking are repeated, and the above-mentioned patent document is formed on the SnC^f: film. The semiconductor electrode of the same structure as the half electrode 2 shown (area of the light-receiving surface: mm, layer thickness: 1 () μιη, layer thickness of the semiconductor layer: 6 Å, layer thickness of the light-scattering layer: 4 μm, in the light-scattering layer It contains two 30% by mass of bar-like particles, and it is used as a photoelectrode that does not contain a pigment.

Mol/L Next, in the semiconductor electrode, the dye was adsorbed as follows. First, the absolute concentration of the pigment described in Table 6 was dissolved in an anhydrous ethanol solvent dehydrated with magnesium eth〇xide to become 3 secrets. Then, the semiconductor electrode was immersed in the above Ίγ minus the total amount of the adsorbed dye in the semiconductor electrode, and 7 mol/cm' was drawn to complete the photoelectrode j〇. (Lan = PCT: a material having a platinum electrode of the same shape and size as the above-mentioned photoelectrode) (10) is used as a counter electrode to prepare an emulsification solution containing iodine and a bismuth clock as electrolysis fs (:r:Ais: r&quot;^(Dup〇NT)-^-α ryn"), as shown in Fig. 3 of Japanese Patent Laid-Open Publication No. 2002-289274, No. 2012-201283835, 38254 pif, the photo electrode i 〇 and the counter electrode CE are paired by the spacer S In the same manner as in the photoelectrochemical cell 1, the photoelectrochemical cell (photoelectrochemical cell 2) is fabricated in the same manner as in the photoelectrochemical cell 1 as described in Japanese Laid-Open Patent Publication No. 2002-289274. The photoelectrode cell 2 of the same configuration as the dye-sensitized solar cell 20 shown in Fig. 3 described in Japanese Laid-Open Patent Publication No. 2002-289274 is produced. The coating material 2 is used as a coating material for forming a semiconductor layer. Then, the above-mentioned coating 2 was screen-printed on a Sn02 conductive film, followed by drying. Thereafter, baking was carried out in the air at 45 ° C to form a semiconductor layer. The coating material 3 was used as the innermost layer forming coating material for the light-scattering layer, and the coating material 5 was used as the outermost layer-forming coating material for the light-scattering layer. Then, a light scattering layer is formed on the semiconductor layer in the same manner as the photoelectrochemical cell. Then, a semiconductor electrode having the same structure as the semiconductor electrode 2 shown in the figure shown in Japanese Patent Laid-Open Publication No. 2002-289274 (the area of the light-receiving surface: 1 〇 mm x l 〇 mm, layer thickness) is formed on the Sn02 conductive film. ΙΟμπι, layer thickness of the semiconductor layer: 3 μm, layer thickness of the innermost layer: 4 μm, content of the rod-shaped Ti〇2 particles contained in the innermost layer: 1% by mass, the outermost layer Layer thickness: 3 μm, content of rod-shaped Ti〇2 particles 1 contained in the innermost layer: 50% by mass), and then produced without containing a sensitizing color

S 201210835. Thereafter, in the same manner as in the photoelectrochemical cell 1, the precursor electrode and the _CE are placed in a lie, and the above-mentioned electrolyte is filled in (4) to complete the photoelectrochemical cell 2. (Photoelectrochemical cell 3) In the production of a semiconductor electrode, except that the coating material is used as a coating for forming a semiconductor layer, and the material 4 is used as a light-scattering layer, it is used in the same order as in the photoelectrochemical cell. The photoelectrochemical cell 3 having the same structure as that of the photoelectrochemical cell 20 shown in Fig. S described in Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. 2-289274 is described in Japanese Laid-Open Patent Publication No. 2002-28-A. . Wherein the 'semiconductor electrode is: the area of the light-receiving surface: 1 〇 mm x l 〇 mm layer thickness. 10 μιη, the thickness of the semiconductor layer: 5, the layer thickness of the light-scattering layer: 5 μm, and the rod-shaped damming particles contained in the light-scattering layer The content of bismuth: 3 〇 mass%. (Photoelectrochemical cell 4) In the production of the semiconductor electrode, the coating material 2 is used as a coating material for forming a semiconductor layer, and the coating material 6 is used as a coating material for forming a light-scattering layer. The photoelectrode 10' shown in Fig. 5 and the photoelectrochemical cell 4 having the same structure as the photoelectrochemical cell 20 shown in Fig. 3 described in Japanese Patent Laid-Open Publication No. 2002-289274. Wherein the area of the semiconductor electrode is the light-receiving surface: 10 mm×l〇mm, the layer thickness: 10 μm, the layer thickness of the semiconductor layer: 6.5 μm, and the layer thickness of the light-scattering layer: 3. 5 μm, and the light-scattering layer contains The content of the plate-like mica particles 1 is 20% by mass. 93 201210835 38254pif (photoelectrochemical cell 5) In the production of the semiconductor electrode, the coating material 2 is used as a coating for forming a semiconductor layer, and the coating material 8 is used as a coating for forming a layer. The photoelectrochemical cell 5 is fabricated in sequence. The content ratio of the rod-shaped Ti〇2 particles 3 contained in the light-scattering layer of the semiconductor electrode was 30% by mass. (Photoelectrochemical cell 6) In the production of the semiconductor electrode, the coating material 2 is used as a coating material for forming a semiconductor layer, and the coating material 9 is used as a coating material for forming a light-scattering layer, and is produced in the same order as the photoelectrochemical cell 1. Photoelectrochemical cell 6. The content ratio of the rod-shaped Ti〇2 particles 4 contained in the light-scattering layer of the semiconductor electrode was 30% by mass. (Photoelectrochemical cell 7) In the production of a semiconductor electrode, the coating material 2 is used as a coating material for forming a semiconductor layer, and the coating material 1 is used as a coating material for forming a light-scattering layer. A photoelectrochemical cell 7 was fabricated. The content ratio of the rod-shaped Ti〇2 particles 5 contained in the light-scattering layer of the semiconductor electrode was 30% by mass. (Photoelectrochemical cell 8) In the production of a semiconductor electrode, the coating material 2 is used as a coating material for forming a semiconductor layer, and the coating material 11 is used as a coating material for forming a light-scattering layer, and is produced in the same order as the photoelectrochemical cell. Photoelectrochemical cell 8. The content of the rod-shaped Ti〇2 particles 6 contained in the light-scattering layer of the semiconductor electrode: 30% by mass ^

94 S 201210835 38254pif (photoelectrochemical cell 9) In the production of a semiconductor electrode, the coating material 13 is used as a coating material for forming a semiconductor layer, and the coating material 13 is used as a coating material for forming a light-scattering layer, and the photoelectrochemical cell 1 is used. The photoelectrochemical cell 9 was fabricated in the same order. The content ratio of the rod-shaped TiO 2 particles 8 contained in the light-scattering layer of the semiconductor electrode was 30% by mass. (Photoelectrochemical cell 10) In the production of the semiconductor electrode, the coating material 2 is used as a coating material for forming a semiconductor layer, and the coating material 14 is used as a coating material for forming a light-scattering layer, and is produced in the same order as the photoelectrochemical cell 1. Photoelectrochemical cell 10. The content ratio of the rod-shaped Ti〇2 particles 9 contained in the light-scattering layer of the semiconductor electrode was 30% by mass. (Photoelectrochemical Cell 11) In the production of a semiconductor electrode, except for the use of the coating material 2, a semiconductor electrode formed of only a semiconductor layer (area of the light-receiving surface: 10 mm×10 mm, layer thickness: 10 μm) was used. The battery 1 is fabricated in the same order as the photoelectrochemical cell 11. (Photoelectrochemical cell 12) In the production of the semiconductor electrode, the coating material 2 is used as a coating for forming a semiconductor layer, and the coating material 7 is used as a coating for forming a light-scattering layer. A photoelectrochemical cell 12 is fabricated. The content ratio of the rod-like particles 2 contained in the light-scattering layer of the semiconductor electrode was 30% by mass. [Test and evaluation of characteristics] 95 201210835 38254pif For the photoelectrochemical cells 1 to 12, a solar simulator (manufactured by WACOM, WXS-85H (trade name)) was used, and the illumination was passed through an AM 1.5 filter. 1 〇〇〇W/m2 of sunlight similar to the xenon lamp. The current-voltage characteristics were measured using an I-V test to obtain an initial value of the conversion efficiency. The above results are shown in Table 6. The conversion efficiency is 2.5% or more, expressed as ◎, 1% or more, less than 2.5%, expressed as ,, 0.3% or more, less than 1%, expressed as △, less than 〇. It is indicated that the conversion efficiency is 〇·3% or more, and less than 〇·3% is unqualified. In addition, the initial conversion value of the conversion efficiency is 90% or more, and the evaluation is ◎, and 6% or more and less than 9% are evaluated as 〇, 40% or more, and less than 60%. The evaluation was Δ, and less than 4% was evaluated as the parent, and the above results are shown in Table 6. The initial value of the relative conversion efficiency is 500 hrs. The conversion efficiency is fine, and less than _ is unqualified.

S 201210835 38254pif Table 6 Sample No. Photoelectrochemical Cell Pigment Conversion Efficiency Durability Remarks 6-1 Photoelectrochemical Cell 1 S-15 〇〇Inventive 6-2 Photoelectrochemical Cell 2 S-15 ◎ 〇Inventive 6-3 Photoelectrochemical Cell 3 S-15 ◎ 〇 6-4 photoelectrochemical cell of the invention 4 S-15 ◎ ◎ 6-5 photoelectrochemical cell of the invention 5 S-15 〇 ◎ 6-6 photoelectrochemical cell of the invention 6 S-15 〇〇 the invention 6-7 Photoelectrochemical cell 7 S-15 ◎ 〇 6-8 photoelectrochemical cell of the invention 8 S-15 ◎ ◎ 6-9 photoelectrochemical cell of the invention 9 S-15 ◎ 〇 6-10 photoelectrochemical cell of the invention 10 S -15 ◎ ◎ 6-11 Photoelectrochemical cell of the invention 1 T-6 〇 ◎ 6-12 photoelectrochemical cell 2-6 of the invention ◎ ◎ 6-13 photoelectrochemical cell 3-6 of the invention ◎ ◎ 6- 14 Photoelectrochemical cell 4 T-6 ◎ ◎ 6-15 photoelectrochemical cell of the invention 5 T-6 〇 ◎ 6-16 photoelectrochemical cell of the invention 6 T-6 〇 ◎ 6-17 photoelectrochemical cell of the invention 7 T-6 ◎ ◎ 6-18 photoelectrochemical cell of the invention 8 T-6 ◎ ◎ 6-19 photoelectrochemical cell of the invention 9 T-6 ◎ ◎ Invention 6-20 Photoelectrochemical cell 10 T-6 ◎ ◎ 6-21 Photoelectrochemical cell of the invention 1 A-1 〇 Δ Comparative Example 6-22 Photoelectrochemical cell 2 A-1 〇 △ Comparative Example 6-23 Photoelectrochemical cell 3 A-1 ◎ △ Comparative Example 6-24 Photoelectrochemical cell 4 A-1 ◎ Δ Comparative Example 6-25 Photoelectrochemical cell 5 A-1 〇Δ Comparative Example 6-26 Photoelectrochemical cell 6 A-1 〇Δ Comparative Example 6 -27 Photoelectrochemical cell 7 A-1 ◎ X Comparative Example 6-28 Photoelectrochemical cell 8 A-1 ◎ Δ Comparative Example 6-29 Photoelectrochemical cell 9 A-1 ◎ Δ Comparative Example 6-30 Photoelectrochemical cell 10 A- 1 ◎ Δ Comparative Example 6-31 Photoelectrochemical cell 11 A-1 Δ X Comparative Example 6-32 Photoelectrochemical cell 12 A-1 Δ X Comparative Example From Table 6, it is understood that the photoelectrochemical cell using the pigment of the present invention has conversion efficiency. The initial value of the initial value is 1% or more, and the conversion efficiency after the passage of 500 hours is 201210835 38254pif, which is 60% or more of the initial value, and shows excellent durability. As described above, when the comparative coloring matter is used, the initial value of the conversion efficiency is an acceptable standard, but there is a problem in durability. [Experiment 7] A slurry of a metal alkoxide was added to a metal oxide fine particle coated on a conductive substrate, followed by UV ozone irradiation, uv irradiation or drying to prepare an electrode. Next, a photoelectrochemical cell was fabricated and the conversion efficiency was measured. '(Metal oxide fine particles) oxidized chin as a metal oxide fine particle, and oxidized chin is a p25 powder (manufactured by Deguss Co., Ltd.) having a mass ratio of 30% gold red ore and 70% anatase type and an average particle diameter of 25 nm. name). (Pretreatment of Metal Oxide Fine Particles) The metal oxide fine particles are heat-treated in advance to remove organic substances and moisture on the surface. In the case of titanium oxide fine particles, it was heated in an oven at a temperature of 303⁄4 for 30 minutes. (Measurement of the amount of water contained in the metal oxide fine particles) The amount of water contained in the titanium oxide and P25 powder (manufactured by Deguss Co., Ltd.) stored in an environment having a temperature of 26 C and a humidity of 72% can be measured by thermogravimetry. The weight was reduced, and the Karl Fischer titration of the amount of water removed at 300 ° C was used for quantification. When the amount of water removed by heating the titanium oxide or P25 powder (manufactured by Deguss Co., Ltd., trade name) at 3 ° C is quantified by Karl Fischer titration, 氧化钛·〇33 g of titanium oxide micro The powder contains 0.253

S 201210835 38254pif mg of water. 5质量百分比的含水。 The titanium oxide micropowder containing about 2. 5 mass% of water. After heat treatment and cooling for 30 minutes, it was stored in a desiccator for use. (Preparation of metal alkoxide coating) The metal alkoxide which binds the action of the metal oxide microparticles uses titanium (IV) tetraisopropoxide (TTIP) as a titanium raw material and tetra-n-propoxygenation ( IV) (zirc〇nium (IV) tetra n-propoxide) is used as a raw material for bismuth, and nibium (v) pentaethoxide is used as a raw material for bismuth (all manufactured by a丨dr丨ch). The molar concentration ratio of the metal oxide fine particles to the metal alkoxide is based on the metal oxide fine particles in such a manner that the amorphous layer produced by the hydrolysis of the metal alkoxide is not excessively thick and the bonding of the particles is sufficiently performed. Make appropriate adjustments to the path. Further, the metal alkoxide is used as a solution of 〇. i M in ethanol. In the case of mixing oxide titanium fine particles with titanium tetraisopropylate (ινχττιρ), 3.55 g of a 0.1 Μ TTIP solution was mixed with respect to the oxide titanium fine particles 丨g. At this time, the concentration of the titanium oxide in the obtained coating material was about 22% by mass, and the viscosity was appropriately applied to the coating. Further, the mass ratio of titanium oxide to ττιρ to ethanol at this time is 〇·127:3 42, and the molar ratio is 1 : 〇. 036 : 5. 92. Similarly, the mixed coating of the titanium oxide fine particles and the alkoxide other than TTIP was also prepared so that the fine particle concentration was 22% by mass, and the coating using zinc oxide and tin oxide was 16% by mass. In the case of zinc oxide and tin oxide, it is mixed at a ratio of 5 Å of the metal oxide oxide solution to the metal oxide fine particles. Next, the metal oxide microparticles and the metal oxide oxide solution were placed in a 99 201210835 38254pif closed grain oven, and the magnetic stirrer was used to scramble for 2 hours to obtain a uniform coating. The coating method of the coating material on the conductive substrate: a doctor blade method, a screen printing method, a nozzle coating method, or the like can be used. The appropriate coating viscosity is appropriately selected according to the coating method. Here, it is a simple glass rod coating method (similar to the blade forming method). In this case, the concentration of the metal oxide fine particles to which the appropriate coating viscosity is applied is approximately in the range of 5 mass% to 30 mass%. The thickness of the amorphous metal oxide formed by decomposing the metal alkoxide is in the range of about 1 nm to about 6 nm in the present invention, and it can be used as an inversely suitable thickness. '(Coating and air drying treatment of the coating on the conductive substrate) A polyethylene terephthalate (PET) film substrate (20 Ω/cm 2 ) in which an indium tin oxide (ITO) conductive film is disposed, or On a glass substrate (1〇Q/crn2) equipped with a fluorine-doped oxygen-tin (FTO) conductive film, the adhesive tape 2 is affixed in parallel at regular intervals to serve as a spacer, and then the glass rod is used to prepare according to the above method. The coating is evenly coated. The conditions for the &amp;uv ozone treatment, the UV irradiation treatment or the drying treatment are changed after the application of the coating material and before the dye adsorption to prepare a porous membrane. (Drying treatment) ' The film applied to the conductive substrate was air-dried at room temperature for about two minutes. In this process, the metal alkoxide in the coating is hydrolyzed by the water in the gas, and the amorphous oxide, oxidized dream is formed from the Ti alkoxide, the Zr alkoxide, and the Nb alkoxide. , yttrium oxide. β 201210835. (uv ozone treatment) The ozone treatment is an NL_UV253 UV ozone cleaning device manufactured by Laser Electronics, Japan. The uv light source is provided with three 4·5 W mercury lamps having 185 nm and 254 nm glow lines, and the sample is horizontally disposed at a distance of about 6.5 cm from the light source. Then, an oxygen gas flow is introduced in the chamber to generate ozone. In this example, uv ozone treatment was carried out for 2 hours. However, the decrease in the electrical conductivity of the IT film &amp; FT film treated with the above uv ozone was not observed. (UV treatment) The treatment was carried out for 2 hours in the same manner as in the above-described UV ozone treatment except that the treatment was carried out by substituting nitrogen gas in the chamber. The decrease in the electrical conductivity of the IVO film and the FT0 film treated by the above uv was not observed. (Pigment adsorption) The dyes were prepared by using the dyes described in Table 7 and preparing a 5 mM ethanol solution of each pigment. In this experiment, the porous film prepared by the above process was dried in a 100 C oven for 1 hour, then immersed in a solution of the sensitizing dye, and then left at room temperature for 5 minutes to be on the surface of the titanium oxide. Adsorption of pigments. Thereafter, the sample after the dye adsorption was washed with ethanol and air-dried. (Production of Photoelectrochemical Cell and Evaluation of Battery Characteristics) A conductive substrate on which a porous film after dye adsorption was formed was used as a photoelectrode', and a ΙΤο/ρΕτ film or an FT0/glass pair modified with a squirting clock. Extremely opposite configuration to try out photoelectrochemical cells. The effective area of the above photoelectrode is about 0.2 cm2. The electrolyte solution is 3 曱 methoxy 101 using 10 Μ 5 Μ Lil, 〇. 〇 5 Μ I and 5 5 M butyl acridine 101 201210835 38254pif C Nitrile (3-11161:11 (^口1*(^〇11如16), and is introduced into the gap between the two electrodes by capillary phenomenon. According to the current action spectrum measurement under a certain number of photons (1〇16 cm2) And the battery performance was evaluated by IV measurement under irradiation of AM 1.5 (100 mW/cm 2 ). The above measurement was performed using a CEP-2000 spectrophotometric measuring device manufactured by Spectrometer Co., Ltd. The conversion efficiency is shown in Table 7. The conversion efficiency is 2.0% or more, which is represented by ◎, 〇·8% or more, less than 2.0%, which is represented by ,, 0.3% or more, less than 8%.8%, which is represented by Δ, To 0.3%, it is represented by X, and the conversion efficiency is 3% or more, and less than 1 = unqualified. In addition, the initial value of relative conversion efficiency, _, and later 评价 评价 is evaluated as ◎, coffee, less than · The subject is 〇, the above is less than _, the evaluation is X, and the above values are expressed as durability after hours. The conversion efficiency is _ or more: ί 102 201210835f Ί Sample No. Substrate Oxidation Pretreatment Color UV Ozone UV Drying Conversion Efficiency Durability Remarks 7-1 FTO/Glass has S-16 〇X 〇◎ ◎ 7-2 FTO of the present invention /glass has S-16 X 〇〇◎ 〇7-3 FTO/glass has S-16 XX 〇〇〇7-4 FTO/glass has S-16 XXX 〇〇7-5 FTO/glass of the invention No S-16 XX 〇〇〇This invention 7-6 FTO/glass has S-16 〇X 〇〇〇This invention 7-7 ITO/PET has S-16 〇X 〇◎ 〇This invention 7-8 ITO/PET There are S-16 XX 〇〇〇 The present invention 7-9 FTO/glass has T-24 〇X 〇 ◎ ◎ The present invention 7-10 FTO/glass has T-24 X 〇〇 ◎ ◎ 7-11 FTO/glass of the present invention There are T-24 XX 〇〇 ◎ The invention 7-12 FTO / glass has T-24 XXX 〇〇 The invention 7-13 FTO / glass without T-24 XX 〇〇〇 The invention 7-14 FTO / glass has T- 24 〇X 〇〇〇The present invention 7-15 ITO/PET has T-24 〇X 〇◎ 〇7-16 ITO/PET has T-24 XX 〇〇〇This invention 7-17 FTO/glass has A -2 〇X 〇◎ △ Comparative Example 7-18 FTO/glass has A-2 X 〇〇〇X Comparative Example 7-19 FTO/glass has A-2 XX 〇〇X Comparative Example 7-20 FTO/glass has A -2 XXX 〇X Comparative Example 7-21 FTO/Glass without A-2 XX 〇〇X Comparative Example 7-22 FTO/Glass has A-2 〇X 〇〇X t匕Comparative Example 7-23 ITO/PET A -2 〇X 〇◎ Δ Comparative Example 7-24 ITO/PET A-2 XX 〇〇X Comparative Example In Table 7, the fields of "UV ozone", "UV", and "dry" are indicated as After the formation of the porous membrane and before the adsorption of the sensitizing dye, there is no UV ozone treatment, UV irradiation treatment, or drying treatment. The processed person is "〇" and the unprocessed person is "X". The "pretreatment of Ti〇2" in Table 7 is indicated by the presence or absence of pretreatment of titanium oxide 103 201210835 38254pif microparticles (heat treatment in an oven at 450 ° C for 30 minutes). Samples 6, 14, and 22 are shown as samples using a coating having a high TTIP concentration (titanium oxide: TTIP molar ratio of 1:0·356), and other samples (samples 1 to 5, 7 to 13, 23, 24) All are coatings using titanium oxide: ΤΤΙΡ = 1: 〇. 0356. As is clear from Table 7, in the photoelectrochemical cell using the dye of the present invention, the presence or absence of υν ozone treatment, UV irradiation treatment, and drying treatment after the formation of the porous membrane and before the adsorption of the sensitizing dye is compared with the use of the above-mentioned pigment alone. In the case, the conversion efficiency of the photoelectrochemical cell is generally high, and the conversion efficiency of an acceptable standard can be obtained. Further, the conversion efficiency after 500 hours passed was 60% or more of the initial value, and showed excellent durability. As described above, when the comparative coloring matter is used, the initial value of the conversion efficiency is an acceptable standard, but there is a problem in durability. [Experiment 8] Using acetonitrile as a solvent, lithium iodide 〇. lm 〇 1 / L, iodonium 〇 5 mol / L, dimethyl propyl methacrylate, 62 mol / L ' was dissolved to prepare an electrolyte solution. Here, the polybenzimidazole-based compound of No. 1 to n〇.8 shown below was separately added and dissolved so as to have a concentration of 0.5 m〇l/L.

104 S 201210835 38254pif [化 48] N〇·1

No.2

OH OH No. 3 ίΡ^

OH

No.4

PH

No. 5

No.6

No. 7

No.8 OC^CHo On the conductive glass, the porous titanium semiconductor film (thickness 15 (four)) of the pigment described in Table 8 was dropped on the Nq1 to the 8th version of the miso compound electrolysis f. New Zealand, New Zealand A frame type spacer (thickness 25 (four), followed by covering the scale electrode to fabricate a photoelectric conversion element. On the obtained photoelectric conversion element, the light of the immediately read W is irradiated, and the obtained open voltage and photoelectricity are shown in the table. 8. In the middle, the dry (the evaluation of the result) W open voltage is 7.0 V#. The above is not indicated by 0 in ◎, 6.GV or more, less than _: ^ is not i6. 0 V is represented by x, and 6 5 v or more are qualified. (8) Conversion efficiency is 2. 〇% or more to 2.0%, ^, ^, L uw or more, y U is not ' 〇 · 3% or more, not 8% △ indicates 105 201210835 . Less than 3% · 3% are represented by X, and conversion 钕 Λ 尤 尤 μ μ μ μ μ μ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 . . . . . 3 3 3 3 3 3 3 3 3 In addition, the initial value of the relative conversion efficiency, the conversion efficiency after _ hours, the above is evaluated as ◎, _ or more, less than the evaluation of Ο, above, not %% The evaluation is △, * is the evaluation of X, and the above values are shown in Table 8. The initial value of the relative conversion efficiency is less than 6〇% after the conversion efficiency of 500% or more. Failed. ° ° 'No additional, in Table 8, the results of using a photoelectric conversion element of an electrolyte without a polybenzimidazole-based compound are also shown. 106 201210835 38254pif Table 8 Sample number polystyrene and oxime compound Pigment open voltage/V conversion efficiency and long-term remarks 8-1 No.l S-9 ◎ ◎ ◎ The present invention 8-2 No. 2 S-9 ◎ ◎ 〇 The present invention 8-3 No. 3 S-9 ◎ ◎ 〇 发明 8 -4 8-4 No. 4 S-9 ◎ ◎ 〇 发明 8 8 8-5 No. 5 S-9 ◎ ◎ 〇 The present invention 8-6 No. 6 S-9 ◎ ◎ ◎ The present invention 8-7 No .7 S-9 〇◎ 〇8-8 No.8 S-9 of the present invention 88-9 without S-9 〇〇〇The present invention 8-10 No.l T-24 ◎ ◎ ◎ The present invention 8-11 No. 2 T-24 ◎ ◎ ◎ The present invention 8-12 No. 3 T-24 ◎ ◎ ◎ The present invention 8-13 No. 4 T-24 ◎ ◎ ◎ The present invention 8-14 No. 5 T- 24 ◎ ◎ ◎ The present invention 8-15 No. 6 T-24 ◎ ◎ ◎ The present invention 8-16 No. 7 T-24 〇 ◎ ◎ The present invention 8-17 No. 8 T-24 〇〇 ◎ The present invention 8-18 No T-24 〇〇 ◎ The present invention 8-19 No. l T- 9 ◎ ◎ ◎ The present invention 8-20 No. 2 T-9 ◎ ◎ ◎ The present invention 8-21 No. 3 T-9 ◎ ◎ ◎ The present invention 8-22 No. 4 T-9 ◎ ◎ ◎ The present invention 8- 23 No. 5 T-9 ◎ ◎ ◎ The present invention 8-24 No. 6 T-9 ◎ ◎ ◎ The present invention 8-25 No. 7 T-9 〇 ◎ ◎ The present invention 8-26 No. 8 T-9 〇 ◎ ◎ The present invention 8-27 No T-9 〇 ◎ ◎ The present invention 8-28 No. 1 Al ◎ ◎ Δ Comparative Example 8-29 No. 2 Al ◎ ◎ X Comparative Example 8-30 No. 3 Al ◎ ◎ X Comparative Example 8-31 No. 4 Al ◎ ◎ X Comparative Example 8-32 No. 5 Al ◎ ◎ X Comparative Example 8-33 No. 6 Al ◎ ◎ Δ Comparative Example 8-34 No. 7 Al 〇 ◎ Δ Comparative Example 8-35 No.8 Al 〇〇X Comparative Example 8-36 No Al 〇〇X Comparative Example 107 201210835 . ----»11 It can be seen from Table 8 that the photoelectrochemical cell using the dye of the present invention is open voltage and The initial values of the conversion efficiency are all eligibility criteria, and the conversion efficiency after 500 hours is 6〇% or more than the initial value. It also shows excellent durability. In the case where the comparative dye is used as described above, the initial values of the open voltage and the conversion efficiency are acceptable standards, but there is a problem in durability. [Experiment 9] (Photoelectrochemical cell 1) A photoelectrode having the same structure as that of the photoelectrode 1 shown in Fig. 1 of Japanese Laid-Open Patent Publication No. 2004-152613 was produced in the following order, and then the light was used. A photoelectrochemical cell (area of the light-receiving surface F2 of the semiconductor electrode 2: 1 cm 2 ) having the same configuration as that of the dye-sensitized solar cell 20 shown in Fig. 1 of the Japanese Patent Publication No. 2004-152613 is prepared. In the respective layers of the semiconductor electrode 2 having the two-layer structure, a layer disposed on the side close to the transparent electrode 1 is referred to as a "first layer", and a layer disposed on a side close to the porous layer PS is referred to as a "second layer". Floor". First, P25 powder (manufactured by Deguss Co., Ltd., trade name) having an average particle diameter of 25 nm, titanium oxide particles having a different particle diameter, and P2 powder (having an average particle diameter of 200 nm, manufactured by Deguss Co., Ltd.) are used. The total content of P25 and P200 is 15%, and the mass ratio of P25 to P200 is P25: P200-30.70, in which acetyiacetone, ion exchange water, and surfactant are added (Tokyo Chemical Co., Ltd.) Manufacturing, trade name: "Triton-X"), and kneading to prepare a slurry for forming a second layer (hereinafter referred to as "slurry 1"). 108 201210835 38254pif Next, the slurry for forming the second layer is prepared by the same modulation sequence as that of the above-described slurry 1 except that P2 is not used, and P25 is used (the content of P1 is 15%, hereinafter referred to as "Polymer 2"). - Aspects A transparent electrode in which a fluorine-doped Sn 〇 2 conductive film (film thickness: 7 〇〇 nm) was formed on a glass substrate (transparent conductive glass) was prepared. Next, the above slurry 2 was applied by a bar coating method on 'on the Sn 2 conductive film', and then dried. Thereafter, baking was carried out for 3 minutes in air at 45 ° C. As described above, the first layer of the semiconductor electrode 2 is formed on the transparent electrode. Then, using the slurry 1, the second layer was formed on the first layer by repeating the same coating and baking as described above. As described above, the semiconductor electrode 2 is formed on the Sn〇2 conductive film (area of the light-receiving surface: 1·〇cm2, total thickness of the first layer and the second layer: ίο μιη (thickness of the first layer: 3 μm, second) The thickness of the layer is 7 μηη)) ' Then a photoelectrode 1 不 containing no sensitizing dye is prepared. Thereafter, an ethanol solution of the dye described in Table 9 (degree of each sensitizing dye: 3Χ10-4 m〇l/L) was prepared as a dye. Then, the photoelectrode 1 is smashed in the above solution and left at a temperature of 8 ° C for 2 Torr, thereby absorbing the sensitizing dye in the inside of the semiconductor electrode. /cm2. Next, a counter electrode CE having the same shape and size as the above-described photoelectrode was produced. First, a solution of chloroplatinic add hexahydrate in isopropyl alcohol was dropped on a transparent conductive glass, dried in air, and then baked at 450X: for 30 minutes. Sintered to the pole CE. Further, a hole (1 mm in diameter) for injection of the mass E is previously provided in the counter electrode CE. 109 201210835. Next, prepare a liquid solution of zinc telluride, deuterated-1,2-dimethyl-3-propylimidazolium, hydrazine, and 4_t-butylhydrazine using f-oxyacetonitrile as a solvent. Electrolyte (concentration of magnetization: 10 mmol/L, concentration of dimethylpropylimidazolium iodide · 0.6 mol/L, concentration of iodine: 〇· 〇 5 mo〗/L, 4_t-butyl Acridine concentration: 1 mol/L). Then, a spacer S manufactured by DU PONT-MITSUI POLYCHEMICALS, which has a shape conforming to the size of the semiconductor electrode, is prepared (trade name: "Hi-milan", ethylene/methacrylic acid random copolymerization polyionic polymerization As shown in Fig. 1 of the Japanese Patent Laid-Open Publication No. 2 ι 4_ι 526 ΐ 3, the photoelectrode and the pair are disposed opposite each other by a spacer, and the housing of the battery is joined by heat fusion, respectively. Unfilled electrolyte). Then, after injecting the liquid electrolyte into the casing from the hole of the counter electrode, the hole is plugged with a member of the same material as the spacer, and then the hole is sealed in the hole of the counter electrode to seal the hole to complete the photoelectric Chemical battery 1. (Photoelectrochemical Cell 2) The photoelectrochemical cell 2 was produced in the same manner as in the photoelectrochemical cell 1 except that the amount of molybdenum in the liquid electrolyte was 5 Å. (Photoelectrochemical cell 3) In the liquid electrolyte, the addition of the gorging clock to the zinc oxide is carried out, and the concentration of the bismuth clock in the liquid electrolyte is 2 〇mm〇i/L, in the same order as the photoelectrochemical cell 1. And strip #, to make a comparative photoelectrochemical battery (comparative photoelectrochemical battery 4)

S 110 201210835 38254pif In addition to lithium iodide instead of zinc iodide in the liquid electrolyte, the concentration of lithium iodide in the liquid electrolyte is 1 〇〇 mmol/L, and the order and conditions are the same as those of the photoelectrochemical cell 1 . To make a comparative photoelectrochemical cell 4. (Test and Evaluation) According to the following procedure, the conversion efficiency was measured for the sample used in the photoelectrochemical cell [~4]. The battery characteristic evaluation test was performed using a solar light simulator (*in (:〇1^, trade name: "WXS-85H type"), similar to the light source from the xenon lamp passing through the AM filter (AM1. 5). The irradiation conditions of the sunlight are measured under the measurement conditions of 1 (9) mW/cm 2 (so-called "1 Sun" irradiation conditions). For each photoelectrochemical cell, the current-voltage characteristics were measured at room temperature using a Ι-ν test. The conversion efficiency was determined as follows. The results obtained above are not shown in the "initial value" of Table 9A (irradiation conditions of 1 Sun). In addition, under the irradiation of _ lSun, the operating conditions of the (10) (four) charge, the transition efficiency 〇J The results of the subsequent conversion efficiency are also shown in Table 9a. The conversion efficiency = the period value is 2. The round is qualified, and less than 24% is unqualified. In addition, the phase value is 'elapsed period, after the conversion efficiency The reduction rate was 2% or less, and the case was more than 2%%. The evaluation was performed in the same manner except for the conversion efficiency =, ,, and σ after the measurement of the conversion efficiency for 5 {) (). The above results indicate that the crime is 0 丨Ε _ 111 201210835 38254pif

Table 9A Sample No. Γ . η 1 a — No 1: Chemical Cell Pigment _ Turn S Initial Help t Efficiency Note yi a 9-2A~~~ 9-3A ~~~93⁄4 Photoelectrochemical Cell 1 Photoelectrochemical Cell 2 Photoelectric Chemical Battery 3 S-18 S-18 S-18 3.1 3.0 2.9 JUD Small B Guard 2.9 2.7 2.5 The present invention The present invention is ~~~9^5A^ 9-6A 9-7A y\jiu ^ 4 Γ Photoelectrochemistry Battery 1 Photoelectrochemical Turbine Pool 2 Photoelectrochemistry - Battery 3 S-18 A-2 A-2 Α-Γ~ 2.9 2.9 3.0 2.4 1.3 1.1 Comparative Example of the Invention Comparative Example 2.8 1.2 Comparative Example ------1 Chemical Battery 4 A-2 2.8 0.9 Comparative Example It is understood from Tables 9A and 9B that the photoelectrochemical cell using the dye of the present invention has an initial value of conversion efficiency as an acceptable standard, and the reduction rate of conversion efficiency after 300 hours has passed to 20% or less. 'And shows excellent durability. With respect to the above, it is known that the conversion efficiency is 112 in the case of using a comparative pigment.

S 201210835 38254pif The initial value is an acceptable standard, but there is a problem with durability. [Experiment 10] 1. Preparation of titanium dioxide dispersion liquid A titanium oxide fine particle (manufactured by Aer〇sil Co., Ltd., Japan) was placed in a 200 ml stainless steel container with a fluororesin inside.

Degussa P-25) 15 g, water 45 g, dispersant (made by Aldrich, Japan, Triron X_l〇〇) lg, diameter 〇 5 mm of cerium oxide beads (see Sigma) 30 g, then sand grinder (manufactured by Aimex Corporation) Dispersion treatment was carried out for 2 hours under Moo® 111. The oxidized hammer beads were filtered from the obtained dispersion. 5 μιη。 The average particle size of the titanium dioxide particles having a particle size of 2. 5 μιη. Among them, the particle size was measured by a Mastersizer (trade name) manufactured by MALVERN &amp; 2. Preparation of titanium oxide fine particle layer (electrode A) for adsorbing pigment Preparation of a 20 mm x 20 mm conductive glass plate covered with fluorine-doped tin oxide (manufactured by AGC Co., Ltd., TC0 glass, surface resistance: about 30 Ω/ m) 'After the two sides of the conductive layer side (a portion wider than 3 mm from the end portion), the spacer adhesive tape was attached, and the dispersion liquid was applied on the conductive layer using a glass rod. After the dispersion was applied, the adhesive tape was peeled off and air-dried at room temperature for one day. Next, the above-mentioned semiconductor coated glass plate was placed in an electric furnace (muffle furnace type FP-32 manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C for 30 minutes. The semiconductor coated glass plate was taken out, and after cooling, it was immersed in an ethanol solution (concentration: 3 x 1 CT 4 mol/L) of the pigment shown in Table 1 for 3 hours. The semiconductor coated glass plate on which the dye was adsorbed was immersed in 4-tert-butyl acridine for 15 minutes, and then washed with ethanol at 113 201210835 38254 pif and naturally dried to obtain a titanium oxide fine particle layer (electrode A) which adsorbed the dye. The thickness of the dye-sensitized titanium oxide fine particle layer of the electrode A was 1 〇 111, and the amount of the titanium oxide fine particles applied was 2 〇 g/m 2 . Further, the amount of adsorption of the dye depends on the type of the pigment in the range of 〇·1 mm〇l/m2 to 1〇mm〇1/m2. 3. Preparation of photoelectrochemical cell a The bath was a mixture of 90/10 by volume ratio of acetonitrile to 3-mercapto-2-oxo salin. To the above solvent, iodine and an iodide salt of 1-mercapto-3-hexylimidazole as an electrolyte salt were added to prepare a solution containing 〇 5 m〇1/L of the electrolyte and 0.05 mol/L of moth. In the above solution, 1 part by mass of a nitrogen-containing polymer compound (〇〇. Further, reactivity with a nitrogen-containing polymer compound) is added to 1 part by mass of (solvent + nitrogen-containing polymer compound + salt). A nitrogen atom is mixed with an electrophilic agent (β) 〇·1 m〇le to form a uniform reaction solution. On the other hand, a glass including a platinum-evaporating layer by a spacer is provided on the dye-sensitized titanium oxide fine particle layer of the electrode A. The platinum film side of the opposite pole of the plate is fixed with a conductive glass plate and a platinum vapor-deposited glass plate. The open end of the obtained assembly is immersed in the above electrolyte solution, and the reaction solution is impregnated into the pigment by capillary action. In the titanium oxide fine particle layer, it is heated at 80 ° C for 3 minutes to carry out a crosslinking reaction. In the above manner, the conductive glass plate shown in Fig. 2 of Japanese Patent Laid-Open Publication No. 2000-323190 The conductive layer 12 of 10 includes a dye-sensitized titanium oxide fine particle layer 20, an electrolyte layer 30, and a photoelectrochemical cell dip of the present invention in which the platinum film 42 and the counter electrode 40 of the glass plate 41 are sequentially laminated (sample number 丨04)

114 S 201210835. Further, in addition to changing the combination of the composition of the pigment and the electrolyte composition as shown in Table ', by repeating the above process, a photoelectrochemical cell a having different photoreceptors and/or charge carriers is obtained. 2 (sample number 1 〇-4). 4. Production of photoelectrochemical cells b and c (1) Photoelectrochemical cell b In the above-described manner, an electrode A (2 〇 mm x 2 〇 mm) including a titanium oxide fine particle layer sensitized with the dye of the present invention was used. Overlap on the same size platinum-deposited glass plate by spacers. Then, using the capillary phenomenon, the mixture of the electrolyte (the mixture of acetonitrile and 3-mercapto-2- oxalate _ 90/10 by volume) as a solvent between the gaps of the two glass plates is used as a solvent. /L, Aihuajing. 5 mol/L solution) soaked to make photoelectrochemical cell b-Ι. Further, the photoelectrochemical cell b-2 (sample No. 10-5) was obtained by repeating the above process except that the dye shown in Table 1 is changed. (2) Photoelectrochemical cell c (electrolyte described in Japanese Patent Laid-Open Publication No. Hei 9-27352) In the above-described manner, on the electrode A (20 mm x 20 mm) including the titanium oxide fine particle layer sensitized with the dye of the present invention. , coating the electrolyte 'and impregnating it. In the above, the electrolyte is contained in Hexaethylene glycol methacrylate ester (manufactured by Sakamoto Oil & Chemical Co., Ltd., BLEMMERPE-350), 1 g of ethylene glycol, and 1 g of ethylene glycol. 2-hydroxy-2-indolyl-1_phenyl-propan-1-one-ketone (2-11}^1: 〇\7-2-11^11丫1-1-卩11611丫1131^11 -1-〇116) (Japan (^3-layer 61§&gt;^ Co., Ltd., DAROCUR 1173) in a mixture of 20 mg 'dissolved 5 〇〇mg of lithium iodide and removed by vacuum for 10 minutes Get it with gas.

115 S 201210835 38254pif, the porous titanium oxide layer impregnated with the above mixed solution is placed under reduced waste to remove bubbles in the porous titanium oxide layer to promote the impregnation of the monomer, and the fine layer of the porous titanium oxide layer The pores are filled with a uniform sol of a polymer compound polymerized by irradiation with ultraviolet light. The article obtained in the above manner was exposed to an iodine atmosphere for 30 minutes to diffuse iodine into the polymer compound, and then the platinum vapor-deposited glass plate was laminated to obtain a photoelectrochemical cell c_1. Further, the photoelectrochemical cell C_2 (sample No. 10-6) was obtained by repeating the above process except that the pigment shown in Table 10 was changed. 5. Measurement of photoelectric conversion efficiency By using a 500 W xenon lamp (manufactured by ushio Co., Ltd.), it is passed through an AM 1.5 filter (manufactured by Oriel) and a sharp wave filter (Kenk 〇 L_42) as ultraviolet-free. Simulated sunlight. The light intensity was 89 mW/cm2. An alligator clip is attached to each of the conductive glass plate 1 of the above photoelectrochemical cell and the platinum vapor deposition glass plate 40, and each of the alligator clips is connected to a current-voltage measuring device (Keithley SMU238 type (trade name)). Here, the simulated sunlight is irradiated from the side of the conductive glass plate 10, and the generated electric current is measured by a current-voltage measuring device. The initial value of the conversion efficiency of the photoelectrochemical cell thus obtained and the rate of decrease in the conversion efficiency at the time of continuous irradiation for 300 hours are shown in Table 10. The initial value of the conversion efficiency is 2.7% or more, and less than 27% is unqualified. In addition, the rate of decrease in conversion efficiency after 300 hours has passed, and the rate of reduction of 2% or less has passed, and more than 20% has failed.

S 116 201210835 Table 10 Sample number Photoelectrochemical cell Nitrogen-containing molecular electrophilic dye conversion efficiency Remarks Reduction rate after initial value 300h 10% Photoelectrochemical cell a-1 α β S-13 3.1 7 10 of the present invention -2 Photoelectrochemical cell b-1 No S-13 2.9 10 The present invention 10-3 Photoelectrochemical cell c-1 No S-13 3.0 15 The present invention 10-4 photoelectrochemical cell a-2 α β Α-1 2.9 55 Comparative Example 10-5 Photoelectrochemical cell b-2 No Α-1 2.9 77 Comparative Example 10-6 Photoelectrochemical cell c-2 No Α-1 3.0 63 Comparative Example (Remarks) (1) The symbol of the pigment is as follows As described in this article. (2) The nitrogen-containing polymer α and the electrophilic agent β are represented by the following compounds. [化49]

As is clear from Table 10, in the photoelectrochemical cell using the dye of the present invention, the initial value of the conversion efficiency is an acceptable standard, and the reduction rate of the conversion efficiency after 300 hours has passed is 15% or less, and it is excellent. Long-term financial. 117 201210835 38254pif In the early stage, the conversion efficiency was better than in the case of pigmentation, but there was a problem in durability. The invention is disclosed by way of example, but it is not intended to limit the brief description of the present invention. The spirit and scope of the schematic invention of one example of the photoelectric conversion element according to the present invention has the general knowledge 'without departing from the scope of protection. n彳 can be used for some changes and retouching, so this hair [Figure ΐ ΐ Γ Γ Γ Γ Γ Γ Γ Γ 专利 专利 专利 专利 专利 专利 专利 【 【 【 【 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: 1: Body layer 4: Counter electrode 5: Light-receiving electrode 6: Circuit 10: Photoelectric conversion element 21: Pigment 22: Semiconductor particle 10 (1: Photoelectrochemical cell

Claims (1)

201210835 38254pif VII. Patent application range: 1. A photoelectric conversion element comprising a photoreceptor layer having a dye and semiconductor fine particles represented by the following general formula (1), wherein the dye includes an aliphatic group having a carbon number of 5 to 18. The dye of the compound represented by the following general formula (1), [Chemical Formula 1] p1 = &lt; X1 N II IR .X2 , Q (produces p NIR' W1 General Formula (1) In the above general formula (1), Q It is represented by a tetravalent aromatic group; X1 and X2 are each independently represented by a sulfur atom, an oxygen atom or CR1!^, wherein Ri and R are each independently represented by a hydrogen atom, an aliphatic group, an aromatic group, and bonded by a carbon atom. a heterocyclic group, and R1 and R2 may be substituted; r and R are each independently represented by an aliphatic group, an aromatic group, a heterocyclic group bonded with a carbon atom, and R and R' may be substituted; P1, P2 are each independently represented as a pigment residue; wi is a relative ion when necessary to neutralize the charge. 2. The photoelectric conversion element according to the above-mentioned claim, wherein the carbon having a carbon number of 5 to 18 The group base is a branched alkyl group. 3. As described in the scope of claim a photoelectric conversion element, wherein Q in the above general formula (1) is represented by a benzene ring or a naphthalene ring. 4. The photoelectric conversion element according to the above claim 119, 201210835 38254pif in the above general formula (1) P1 and P2 are respectively represented by the following general formula (3), and [C2] Z c=c I c FT General (2) [Chemical 3] Z - General formula (3) In the above general formula (2) or general formula (3), 'V1 is represented by a hydrogen atom or a substituent, and η is an integer of 0 to 4'. When η is 2 or more, νι may be the same or different. , may also be bonded to each other to form a ring; ~ Y is represented by S, NR9 or CR10Rii, wherein R9 is represented by a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and R10, ^ is shown as ^Sub, lanthanyl, aromatic or heteroatom group 'R^R11 bonded with a carbon atom may be the same or different, or may be bonded to each other to form a ring; $ is an aliphatic group, an aromatic group or a carbon atom-bonded group, and 2: may have a substituent; the lengths R and R are independently represented by a hydrogen atom, an aliphatic group, and an aromatic group; 201210835 38254pif ring group ' and R3 to R6 and R8 may have a substituent; # u A is a gas atom or a carbon atom having two substituents, and two of the seven quinones of the thiol group are σρ_. The photoelectric conversion element according to claim 1, wherein ^ and ρ2 in the general formula (1) are independently represented by the general formula (5), [v4] (vt0^ts =^= 2 - General (4) [5] c= Η (5), in the above general formula (4) or in the general formula (5), V1 represents a hydrogen atom or a substituent, η represents an integer of 〇~4, and when η is 2 or more, yl may be the same or Different, they may be bonded to each other to form a ring; a Y is represented by S, NR9 or CI^R11, wherein R9 is represented by a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, R1 ( And Rll is represented by an atom, an aliphatic group, an aromatic group or a heterocyclic group bonded by a carbon atom, and R and HU may be the same or different, or may be bonded to each other to form a ring; t 121 201210835 38254pif Z is represented by An aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and Z may have a substituent. 6. The photoelectric conversion element according to claim 4, wherein the above V1 has an acidic group. 7. The photoelectric conversion element according to Item 4 or 5, wherein the above V1 is a hydrogen atom, a 5-carboxy group, a 5-supply acid group, a 5-methyl group or a 4-benzene ring condensation. 8. The photoelectric conversion element according to Item 4 or 5, wherein the above z and v are an acidic group or a group having an acidic group. 9. The photoelectric conversion element according to item 4 of the patent application, wherein the general formula (2) is represented by the following general formula (6), and the above general formula (3) is described as the general formula (7). Said, [/fb6] E11 General formula (6) &gt; In the general formula (6) and the general formula (7), γ, Z, R3 to R8 and 122 S 201210835 38254pif are the same as Y, Z, R3 to R8 of the general formula (2) or the general formula (3); V12 is represented by an acidic group; at least one of E11 to E13 is represented by a pull electron group; and p is an integer of 2 or more. 10. The photoelectric conversion element according to claim 4, wherein the general formula (2) is represented by the following general formula (8), and the general formula (3) is represented by the following general formula (9), [ 8] [化10] Rb Formula A Formula B Formula C Formula D In the above general formula (8) or general formula (9), Y, Z, R3 to R8 and Y, Z, R3 to R8 of the general formula (2) or the general formula (3) The definition is the same; L is 123 201210835 38254pif expressed by the above formula A to formula D, m is 〇 or an integer of 1 or more, and when m is 2 or more, L may be different from each other; in the above formula A, Xa is represented by NRe 〇, S, and Re are represented by a hydrogen atom or a substituent; in the above formulas a and C, Ra to Rd are represented by an acidic group; in the above general formula (8), p is an integer of 2 or more, and Rx is acidic. base. The photoelectric conversion element according to Item 4 or Item 5, wherein the Y is represented by S, NCH3 or C(CH3)2, and z is an aliphatic group having 5 to 18 carbon atoms. 12. The photoelectric conversion element according to Item 4, wherein the above formula R is represented by any one of the following formulas (1〇) to (13), [Chem. 11] General formula (10) NC Eight COORf General formula (1)) Meaning 1 RfOOC Eight COORf NC Human CN General formula 〇 2) General formula (13) In the above formula (10) to formula (13), Rf is represented by a hydrogen atom or a substituent. . 13. The photoelectric conversion element according to claim 4, wherein the above formula R7 is represented by the formula (14) or the formula (15), ^ 124 S 201210835 38254pif [Chem. 12] General formula (14) The optical conversion element according to the above-mentioned general formula (1), wherein Q is represented by a benzene ring, and X1 and X2 are independently represented as a sulfur atom or an oxygen atom. Or C(CH3)2, R and R each independently represent an aliphatic group having an A number of 5 to 18. The photoelectric conversion element according to claim 1, wherein the semiconductor fine particles are titanium oxide fine particles. 16. A photoelectrochemical cell comprising the photoelectric conversion element according to claim 1 of the patent application. 17. A dye for a photoelectric conversion element comprising a compound represented by the following general formula (1) having an aliphatic group having a carbon number of 5 to a, wherein X X χ 2 9 ρ = &lt; X ρ 2 RR· General formula (1) In the above general formula (1), 'Q represents a tetravalent aromatic group; χΐ and X2 are each independently represented as a sulfur atom, an oxygen atom or CWr2, wherein ri, 125 201210835 38254pif sub-bonds are Hydrogen, sub-, aliphatic, aromatic, dry carbon AA and R, W can also be substituted; R, R, respectively, independent of April, aliphatic, aromatic, carbon atom bond A heterocyclic group of the knot, and R, R' may also be substituted; p1, p2 are turned upside down to represent a pigment residue; and wl is a relative ion when necessary to neutralize charge. 18. A dye solution for a photoelectric conversion S-piece, comprising: a dye for a photoelectric conversion element according to claim 17 which is contained in an organic solvent and which has been dissolved. 126