TW201211165A - Metal complex pigment, photoelectric conversion element, and photoelectrochemical cell - Google Patents

Abstract

The invention provides a metal complex pigment having high conversion efficiency and excellent durability, a photoelectric conversion element, and a phototelectrochemical cell using the metal complex pigment. The metal complex pigment has a structure represented by the following formula (1). M(LL1)m1(LL2)m2(X)m3*CI formula (1) In formula (1), M represents a metal atom. LL1 represents a specific bidentate chelate ligand or a specific tridentate chelate ligand. LL2 represents a specific bidentate chelate ligand or a specific tridentate chelate ligand. X represents a specific monodentate chelate ligand or a specific bidentate chelate ligand. m1 represents an integer of 1 to 3, m2 represents an integer of 0 to 2, and m3 represents an integer of 0 to 3. CI represents a counterion necessary to a circumstance of counterion for neutralizing the charge. Anyone of LL1, LL2, and X has at least one acid group.

Description

201211165 -----Γιτ VI. Description of the Invention: [Technical Field] The present invention relates to a metal complex pigment, a photoelectric conversion element, and a photoelectrochemistry having high conversion efficiency and excellent durability. battery. [Prior Art] The photoelectric conversion element is used in various light sensors*, copy-machines, solar batteries, and the like. The photoelectric conversion element has various methods such as a photoelectric conversion element using a metal, a photoelectric conversion element using a semiconductor, a photoelectric conversion element using an organic pigment or a dye, or a photoelectric conversion element used in combination. Among them, solar cells that use non-exhaustive solar energy do not require fuel and use inexhaustible clean energy, so they are very much expected to be practical. Among them, research and development have been carried out on the tantalum solar cells. Countries also have policy considerations and continue to gain popularity. However, 矽 is an inorganic material, which naturally has limitations in terms of throughput and molecular modification. Therefore, research on dye-sensitized solar cells is being actively carried out. In particular, Graetzel et al. of the University of EPFL in Switzerland developed a dye-sensitized solar cell in which a pigment containing a ruthenium complex is immobilized on the surface of a porous titanium oxide 4 film to realize conversion efficiency of ordinary amorphous ruthenium. Therefore, the positive battery - the researcher's _. A method of modifying the photoelectric conversion capability of a ruthenium complex pigment is disclosed in Japanese Patent Laid-Open No. 2001-291534. . 4 201211165 A 2- or 3-tooth coordination with a specific substituent on a 2,2'-bipyridine backbone is reported in U.S. Patent Application Publication No. 2001-291534. By expanding the total consumption (c〇njUgati〇n), it is possible to obtain a metal exhibiting a high molar absorption coefficient and excellent absorption capacity in a long wavelength band and excellent durability when used in a photoelectric conversion element. The complex pigment. However, in any aspect of the long-wavelength effect and durability, the metal complex dye and the photoelectric conversion element of JP-A-2001-291534 are not sufficient. [Explanation] An object of the present invention is to provide a metal complex dye which is excellent in conversion efficiency, excellent in long-lasting property, and excellent in adsorption stability on semiconductor fine particles, and a photoelectric conversion element using the metal complex dye and Photoelectrochemical cell. As a result of intensive research, the inventors of the present invention have found that a metal complex dye having a ligand which is substituted with a straight linear substituent and a straight substituent has a porous semiconductor fine particle formed by being adsorbed on the conductive support. In addition, since it is hard to be attacked by water which is a cause of pigment peeling, nucleophilic substances which decompose pigments, etc., it is possible to provide a photoelectric conversion element and a photoelectrochemical cell which have high conversion efficiency and excellent durability. The present invention has been developed based on this finding. By the present invention, the following means are provided. <1> A metal complex dye represented by the following formula (丨): 201211165^ M(LLl)ml(LL2)m2(X)m3 · Cl Formula (1) [Formula (1) In the formula, Μ represents a metal atom, LL1 represents a 2- or 3-dentate ligand represented by the following formula (2), and LL2 represents a 2- or 3-dentate coordination represented by the following formula (7). Base, X represents a group selected from the group consisting of alkyloxyxy (aCyl〇xy gr〇Up), acetylthio group, thioxyloxy, sulfur-thiol, arylaminooxy, thiouretyl 曱IS Sulfhydryl, dithiol phthalic acid g-based, thiocarbonate, dithiocarbonate, dithiocarbonate, sulfhydryl, thiocyanate, isothiocyanate, cyanate a monodentate or a 2-dentate ligand coordinated to a group consisting of an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group, and an aryloxy group, or a halogen atom or a carbonyl group, A monodentate or a 2-dentate ligand composed of a dialkyl ketone, a diketone, a carboxy oxime amino group, a thiocarbaguanyl group or a thiourea, and ml represents an integer of 1 to 3, and when mi is 2 or more, LLi Can be the same or different, m2 means 〇~2 When m2 is 2, LL2 may be the same or different, m3 represents an integer of 〇~3, and when m3 is 2 or more, X may be the same or different 'and X may be connected to each other, CI means to neutralize a counter ion in the case where the charge must be counterbalanced; 6 201211165f LL1 - LL2 > v ., [Yi η 具有 has at least one oxime group;

In the formula (2), = represents an acidic group, and a ground represents a linking group, and any formula Y=t represents a radical from the general formula (3) to the general formula (6) ==Base hydrogen atom and the obtained substituent L or L each independently represents a conjugated chain composed of an alkyne combination; the aryl group or the a? a2 of the groups independently represent an integer of 〇~3, respectively When the 'R' can be the same or different, the difference between a2 and ^ = can be different; if the same W and b2 can be independently represented by 工~3, R3 can be the same or different, or can be mutually ", think that the bamboo is the same as the case of 2 or more, and can also be phased; when / is above W", the number can be connected to the heart and the two can be independently represented by n2 and n2. The above integers, n3 and n4 are independently represented. 〖The above integer, · shot, when n3 is 2 or more, multiple Y] can be the same or different, and heart 4 is 2 or more. 201211165 Y2 can be the same or different; ζ means 〇 or 1; ] (R7)n7

General formula (3) General formula (4) General formula (5) General formula (6) In the general formula (3) to general formula (6), R5 to Ru represent a substituent, and n5 to nil each independently represent 〇~ An integer of 2, a plurality of R5 to Rii may be bonded to adjacent substituents to form a ring; the sum of n6 and n7 is 2 or less; the sum of n8 and n9 is 2 or less; and the sum of nl〇 and nil is 2 or less ; [化3]

In the formula (7), Za, Zb and Zc each independently represent a group of non-metal atoms which can form a 5-membered ring or a 6-membered ring, and may each independently have a substituent; c represents 0 or 1]. (2) The metal complex dye according to the above formula (1), wherein the LL1 is a tooth represented by the formula (2A) or a tooth of 3 8 201211165 Ligand: [Chemical 4]

(R2)a2 (R4)b2 (L2)n2—(γ2)η4_γ4 Formula (2A) [In the formula (2A), R1, r2, R4, γι, γ2, γ3 Y4, L1, L2, al , a2, bl, b2, nl, n2, n3, R1, R2, R3, R4, Y1, Y2, Y3, Y4, L1 n4 and the general formula (2), L2, ab a2, Μ, b2 ΐ ΐ, η2, η3, η4 are synonymous]. &lt;3&gt; The metal complex dye according to <1>, wherein, in the formula (2), L^'L2 represents an arylene group. &lt;4&gt; The metal complex dye according to the above formula (2A), wherein L1 and L2 represent an arylene group. &lt;5&gt; The metal complex dye according to the above formula (1), wherein LL1 is a tooth represented by the following formula (8) Or the ligand of 3 teeth: [Chemical 5]

9 201211165 General formula (8) [In the general formula (8), R1, R2, R3, R4, γ1, γ2, Υ3, γ4, al, a2, bl, b2, ηΐ, η2, η3, η4, ζ In the general formula (2), R1, R2, R3, R4, γΐ, Υ2, Υ3, Υ4, and a2, Μ, b2, w, 、, n3, π4, and z are synonymous]. &lt;6&gt; The metal complex dye according to any one of <1> to <5>, wherein 'LL1 is represented by the following formula (8Α) in the above formula (1) The base of 2 teeth or 3 teeth: [Chem. 6]

[In the general formula (8Α), R1, R2, R3, R4, γΐ, γ2, γ3, 1 'al, a2, bl, b2, nl, η2, η3, η4 and R1 in the formula (2) R2, R3, r4, γι, Υ2, γ3, γ4, and a2, M, b2, μ, η2, η3, η4 are synonymous]. The metal complex dye according to any one of the above-mentioned items (1), wherein the dish represents hydrazine. The metal complex dye according to any one of <1>, wherein the 'hydrogen atom is removed from the ring represented by the above formula (3). The linking group is represented by the following general formula (3Α): 201211165. ^yuzopif [化7]

General formula (3A) [In the general formula (3A), you, $ a / represents the upper bond = the n5 in the formula (3) is synonymous; * knot]. The bonding portion, ** represents a bond on ΥΉ4, such as the metal complex described in any one of &lt;1&gt;~<- A ^ ^ , , 8 &gt; (1) (7) [Chemical 8] R16

Formula (9) Formula (10) Formula (u) R22

General formula (12) (wherein t, R12, R13, RM, r16, r18, r19, r21, r22 represent a hydrogen atom-based group; * represents a bond on lUl2, and ** represents on Y3 or Y4 Key junction). &lt;10&gt; The metal complex dye according to <9>, wherein the substituent represented by the formula (9) to the formula (12) has a number of carbon atoms of less than 11 201211165 More than 5 aliphatic groups. &lt;11&gt; A photo-electric conversion element, which is provided with a photosensitive layer of a metal complex dye and semiconductor fine particles according to any one of &lt;1&gt; to &lt;10&gt;. The photoelectric conversion element according to the above formula (1), wherein the metal complex dye described in the above formula (1) is used in combination with another coloring matter. The photoelectric conversion element according to <12>, wherein the other coloring matter is represented by the general formula (13):

Mz(LL11)mll(LL12)ml2(X11)ml3 - CI11 Formula (13) [In the formula (13),

Mz represents a metal atom, LL represents a 2- or 3-dentate ligand represented by the following formula (14), and LLl2 represents a 2- or 3-dentate ligand represented by the following formula (15), X It is not selected from the group consisting of decyloxy, sulfonylthio, thiomethoxy, thiosulfanyl, decylaminooxy, thiamine phthalate, dithiocarbamate, thiocarbonate Base, dithiocarbonate group, trithiocarbonate group, mercapto group, thiocyanate θ group, isothiocyanate vinegar, cyanate vinegar, isocyanate vine, cyano group, sulphur group, aromatic a group of a monodentate or a 2-dentate ligand coordinated by a group consisting of a sulfur group, a county group, and an auditory group, or a dentate atom, an M group, a dialkyl ketone, a 1,3-diketone, Carboxylammonium, thiocarbamate or thiourea 12 201211165 monodentate or 2-dentate ligand, mil means 〇~3 integer 'when mii is 2 or more' LLn may or may not be. Similarly, ml2 represents an integer of 0 to 2, and when m12 is 2, LL12 may be the same or different; wherein, at least one of mil and ml2 is an integer of 1 or more; ml3 represents an integer of 0 to 3, and is 2 in ml3. Above, X11 can be the same The different 'X11' may also be linked to each other; CI11 is a counter ion in the case of the general formula (13) in which a counter ion must be counterbalanced in order to neutralize the charge; any one of LL11, LL12, and X11 has at least one acidic group] ; [化9]

In the formula (14), rIOI and r1〇2 each independently represent an acidic group, and R1Q3 and R1Q4 each independently represent a substituent, and R1{)5 and R106 each independently represent an alkyl group and an aromatic group. a group or a heterocyclic group; L11 and L12 each independently represent a conjugated chain composed of at least one selected from the group consisting of an arylene group, a heteroarylene group, an ethenylene group, and an ethynylene group; 13 201211165 all and al2 each independently represent an integer from 0 to 3. When aU is 2 or more, Ri〇i may be the same or different. When al2 is 2 or more, Hamming may be the same or different; bll and bl2 respectively Independently, an integer of 0 to 3 is represented. When bll is 2^, R(8) may be the same or different, and Ru)3 may be connected to each other to form a ring. When bl2 is 2 or more, R104 may be the same or different, rkh They may be connected to each other to form a ring; when both bll and bl2 are 1 or more, Ri〇3 and R1()4 may be joined to form a ring; ^ dll and dl2 respectively represent integers of 〇~5; dl3 represents 〇 Or 1 ; [10]

a substituent of the formula (15); f represents 0 or 1]. &lt;14&gt; As described above in <11>, in the general formula (15), Zd, Ze, and Zf each independently represent a non-metal atomic group capable of forming a 5-membered ring or a 6-membered ring, and may each independently have &lt; The photoelectric conversion 7L member according to any one of the preceding claims, which has a structure in which the photoreceptor layer, the charge transporting body and the counter electrode are sequentially formed in a contact region.

201211165t [Effects of the Invention] When the metal complex dye of the present invention is used, it is possible to provide a photoelectric conversion element and a photoelectrochemical cell which exhibit absorption in a long-wavelength region and are stably adsorbed on a semiconductor, have high conversion efficiency, and are excellent in durability. . The above and other features and advantages of the present invention will become more apparent from the written description of the appended claims. [Embodiment] When the dye of the present invention is used in a photoelectric conversion element, the ligand and the adsorption group in the metal complex dye represented by the formula (1) which functions as a sensitizing dye ( The bonding group exhibits a unique interaction to achieve both photoelectric conversion efficiency and durability. The detailed principle is presumed as follows. First, the ligand LL1 is a rigid structure in which the dipyridine ligand further has a linearity as a substituent, and two. A common system is formed together with the biting ligand. Thereby, the absorption region of the peak on the long wavelength side is further enlarged toward the long wavelength side, showing high long-wavelength absorption efficiency (molecular absorption coefficient ε). On the other hand, the adsorption group (bonding group) realizes an aligned adsorption state with the semiconductor fine particles. The ligand LL1 protects the adsorption state of the adsorbing group due to the effect of the above-mentioned straight substituent having high linearity. In other words, the rigid substituent having a high linearity is closely aligned, and it is difficult to be attacked by water which is a cause of peeling of the adsorbent or a nucleophile which decomposes the dye, and the effect of improving durability is obtained. Moreover, the reduction in conversion efficiency caused by the inefficient association of the pigment molecules with each other is also suppressed. In addition, since a sulfur-containing heterocyclic ring such as a thienyl group is provided on the terminal side of the straight structure having a high linearity, the single-electron oxidation state becomes stable, and the long-wavelength absorption effect or durability is further improved. The preferred embodiments of the present invention are described in detail below. Preferred embodiments 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 1, a photoreceptor layer 2, a charge transport layer 3, and a counter electrode 4 which are sequentially disposed on a conductive support i. The light-receiving electrode 5 is constituted by the conductive support i and the photoreceptor 2. The photoreceptor 2 has conductive fine particles 22 and a sensitizing dye 21, and the dye 21 is adsorbed on the conductive fine particles 22 in at least a part thereof (the dye is in an adsorption equilibrium state, or a part thereof may be present in the charge transporting layer). The conductive support body on which the photoreceptor 2 is formed functions as a working electrode in the photoelectric conversion element ίο. The photoelectric conversion element 1 is operated by the external circuit 6 to operate as the photoelectrochemical cell 100. In addition, the photoelectric conversion element is not particularly limited in the upper and lower directions. In the present specification, the side of the counter electrode 4 on the light receiving side is set to the upper (the sky) direction, as will be described above. The side of the support body i is set to the direction of the lower portion (bottom portion). The light-receiving electrode 5 is an electrode including a conductive support i and a photosensitive layer (semiconductor film) 2 coated with the semiconductor fine particles 22 of the dye 21 coated on the conductive support. The light incident on the photoreceptor (semiconductor film) 2 excites the color. The excitation pigment has electrons with high energy. Therefore, the electrons are transferred from the pigment 21 to the conductive strip of the semiconductor fine particles 22, and further spread to the conductive support 1 by diffusion. At this time, the molecular oxide of the pigment 21 is present. The electron side on the electrode works on the external circuit - the surface is restored to the pigment 201211165 j^uzopif oxidant, thereby functioning as a photoelectrochemical cell. At this time, the light receiving electrode 5 operates as the negative electrode of the battery. The photoelectric conversion element of the present embodiment has a photoreceptor having a layer of porous semiconductor fine particles to which a metal complex sensitizing dye to be described later is adsorbed on the conductive support. In this case, as described above, in the pigment, a part of the electrolyte may have a dissociated substance or the like. The photoreceptor may be designed as needed, and may be a single layer or a multilayer. The photoreceptor of the photoelectric conversion element of the present embodiment contains semiconductor fine particles to which a specific metal sensitizing dye is adsorbed, and has high sensitivity, and can be used as a photoelectricization battery to obtain high conversion. Efficiency, and additional durability. The present invention will be described below. (A) Pigment (A1) A metal complex dye having a structure of the formula (丨) Formula (1)

M(LLl)mi(LL2)m2(X)m3 · CI The dye having the structure of the general formula (1) is coordinated with a ligand LL2 having a coordinate titer and a specific functional group X. The It-shaped hunting is kept electrically neutral by ci. (A1·1) A metal atom of a metal atom Μ. Preferably, it is possible to carry out 4 coordination or 6 coordination. Two genera: more preferably Ru, Fe, 〇s, Cu, W cr, M 〇 Ni,

Ir Rh, Re, Mn or Zn. Particularly good is, such as, 〇 3, 17 201211165

Zn or Cu, the most preferred is RU. The (Al-2) oxime group LL1 ligand LL1 is a 2-dentate or 3-dentate ligand represented by the following formula (2), and a 2-dentate ligand is preferred. The ml indicating the number of the ligands LL1 is an integer of 1 to 3, preferably 1 to 2' is preferably 1. When ml is 2 or more, LL1 may be the same or different.丫3-(丫\广(1·%((L2)n2—(Y2)n4-Y4)z (R1>a1 General formula (2) In the general formula (2), R1 and R2 respectively Independently represents an acidic group (a substituent having a dissociative proton). The acidic group may be a carboxyl group, a sulfonic acid group, a thiol group, a hydroxamic acid group, a phosphoryl group or a phosphonyl group. Preferably, R1 or R2 is a phosphinium group or a buffer group, and more preferably a thiol group. Further, the acidic groups may be introduced to the pyridine ring via a linking group. An integer of ～3. When al is 2 or more, R1 may be the same or different. When a2 is 2 or more, R2 may be the same or different. al is preferably 〇 or 1, more preferably 0. Preferably, it is 0 or 1, more preferably 〇. 201211165t R3 and R4 each independently represent a substituent. The substituent is preferably an alkyl group (preferably an alkyl group having 1 to 2 carbon atoms, for example Anthracenyl, ethyl, isopropyl, tert-butyl, pentyl, heptyl, hydrazine-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxyindenyl, etc., and containing aralkyl The concept of a base substituted by a base) Alkenyl (preferably an alkenyl group having 2 to 2 carbon atoms, such as a vinyl group, an allyl group, an oleyl group, etc.), an alkynyl group (preferably an alkyne having 2 to 20 carbon atoms) a group such as an ethynyl group, a butadiynyl group, a phenylethynyl group or the like, a cycloalkyl group (preferably a cycloalkyl group having 3 to 2 carbon atoms, such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group). , 4-fluorenylcyclohexyl, etc., aryl (preferably an aryl group having 6 to 26 carbon atoms, such as phenyl, naphthyl, 4 methoxyphenyl, 2-phenylphenyl, 3 a -methylphenyl group or the like, a heterocyclic group (preferably a heterocyclic group having a stone anodic number of 2 to 20, for example, a 2 吼 定 group, a butyl group, a 2-imidazolyl group, a 2-benzimidazole group Alkoxy group (2, thiazolyl, 2-oxazolyl, etc.), alkoxy (preferably an alkoxy group having 1 to 2 atomic number, such as an anthraceneoxy group, an ethoxy group, an isopropoxy group, Benzyloxy or the like, an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, such as a phenoxy group, a fluorenyl-naphthyloxy group, a 3-methyloxy group, a 4-methoxybenzene group) Oxyl or the like, an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms) For example, ethoxycarbonyl, decylhexyloxycarbonyl, etc.), an amine group (preferably an amine group having a carbon number of 〇~2〇, an amine group, an N,N-dimethylamino group, N,N-diethylamino, N-ethylamino, anilino, etc.), sulfonylamino (preferably a sulfonylamino group having a carbon number of 〇~2〇) such as N,N- a fluorenyloxy group such as a dimercaptosulfonylamino group or a N-phenylsulfonylamino group (preferably, a transalkyl group having a carbon number, for example, an ethoxylated oxy group, a benzamidineoxy group, etc.), an amine group Carbam〇yl group (preferably 2〇12lll65 is an amine sulfhydryl group having 1 to 20 carbon atoms, such as n,N-dimethylamine methyl aryl, N-phenylamine fluorenyl, etc. a mercaptoamine group (preferably a mercaptoamine group having 1 to 20 carbon atoms, such as an ethylamino group, a benzoguanyl group, etc.), a cyano group or a halogen atom (for example, a fluorine atom) , a gas atom, a bromine atom, an iodine atom, etc.) are more preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a saponin-based Ik group, an amine group or a mercaptoamine group. a cyano or dentate atom, particularly preferably an alkyl group, an alkenyl group, a heterocyclic group, Group, an alkoxycarbonyl group, an amine group, acyl group or cyano group. These groups may be further substituted, and examples of the substituents include substituents of R3 and R4. The soils bl and b2 each independently represent an integer of 〇~3, preferably an integer of 〇~2. When bl is 2 or more, R3 may be the same or different, and may be interconnected to form a ring. Bl is preferably 〇~丨, especially good. When w is 2 or more, 'R4' may be the same or different, and may be bonded to each other to form a ring. = It is better that 〇~1' is particularly good... When both Μ and ... are above ,, R and R4 are expected to be (4). The ring of the ring of the r3 or r4 connecting towel shaft may be a benzene ring κ ring, a porphin ring, a ring, a cyclohexane ring, a % pentane ring or the like. Each of the sub-filaments, the sub-filaments, or the bases are independently represented. A conjugated chain. The alkynylene group is preferably a subunit having 2 to 6 carbon atoms, more preferably an alkynylene group having 2 to 4 carbon atoms. More advanced = ethyl, 1,3-butadienyl, hexamethylene, particularly preferred is arylene with 6 to 30 carbon atoms, more preferably anti-atom The number is 6 to 24 arylene groups. Into the base, naphthylene, especially good is the stupid base. The conjugated chain composed of the stellite and the oxime group 201211165 ^yuzopif is preferably a conjugated chain in which one of the ethynylene group and the phenylene group is combined. L1 or L2 is preferably an arylene group. Nl and n2 each independently represent an integer of 1 or more. Preferably, nl is 1 to 3, more preferably 1 to 2. Further, it is preferable that n2 is 1 to 3, and more preferably 1 to 2. z represents 0 or 1. z is preferably 1. When z is 1, __ LL1 is a ligand of 2 or 3 teeth represented by the following formula (2A). Y3-(Y1)n3-(L1)n1 (L2)n2-(Y2)n4-Y4

In the general formula (2A), R1, R2, R3, R4, Y1, Y2, Y3, Υ4, L1, L2, ab a2, Μ, b2, ία, η2, η3, η4 In the formula (2), R1, R2, R3, R4, Υ1, Υ2, Υ3, Υ4, L1, L2, ab, a2, bl, b2, nl, n2, n3, and n4 are synonymous. In the formula (2), Y1 and Y2 each independently represent a linking group obtained by desorbing two hydrogen atoms from the ring represented by any of the general formulae (3) to (6). [Chem. 13] 21 201211165.

General formula 〇) General formula (4) General formula (5) General formula (6) In the general formula (2), η3 and η4 each independently represent an integer of 1 or more. Η3 is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2. Further, η4 is preferably from 1 to 5, more preferably from 1 to 3, still more preferably from 1 to 2. When η3 is 2 or more, a plurality of Υ1 may be the same or different. When η4 is 2 or more, a plurality of γ2 may be the same or different. In the general formulae (3) to (6), R5 to R11 represent a substituent. Examples of the substituents include the substituents exemplified as R3 and R4. It is preferred that R5 to R11 are an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a fluorenyl group, more preferably an anthracenyl group, an alkenyl group or a fast group, and still more preferably an alkyl group or an alkynyl group. The alkyl group is preferably an alkyl group having 2 to 18 carbon atoms, more preferably 5 to 18 carbon atoms, still more preferably 6 to 18 carbon atoms, and particularly preferably a carbon atom number. 6 to 12. Examples of the alkyl group include n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, and decyl group. The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably 5 to 8 carbon atoms, still more preferably 6 to 18 carbon atoms, and particularly preferably a carbon atom number. 6 to 12. Examples of the alkenyl group include a vinyl group, an allyl group, and an oleyl group. The alkynyl group is preferably an alkynyl group having a broken atomic number of 2 to 18, more preferably a carbon number of 5 to 18, still more preferably a carbon number of 6 to 18, and particularly preferably a carbon number of 6 to 12. 22 201211165 Examples of the alkynyl group include an ethynyl group, a butadiynyl group, and a phenylethynyl group. Examples of the aryl group include a phenyl group and a triphenylamino group. These groups may be further substituted, and examples of the substituent include a substituent of R5 to R11. Y3 and Y4 represent a hydrogen atom or a substituent. Examples of the substituent represented by Y3 or Y4 are exemplified as examples of the substituent of R5 to R11. The substituent represented by the formula (3) to the formula (6) preferably has at least one (preferably 1 to 2, more preferably 1) carbon atoms of 5 or more (more preferably The aliphatic group having 6 to 18 carbon atoms and more preferably 6 to 12 carbon atoms is referred to as R5 to Ru, γ3, and γ4. The Lin group having a carbon number of 5 m can be exemplified by the above-mentioned Wei group, the base group, the base group, the (10) group, the silk, and the side is silk. Preferably, the alkynyl group is substituted with a carbon number group. The heart sinks ~ nil independently represent the integers of 〇~2. The illusion is better ~ 2, especially good 1. N6 is preferably 1 to 2, and particularly preferably, n7 is preferably 1 to 2', particularly preferably, 1118 is preferably 2, and particularly preferably is 1 to 2, The most good one is 1. NlO is preferably Bu 2, especially Bu is preferred to Bu 2, and particularly preferred is 1. (10) 盥 2 or less. N8盥n9 evening to 7? Ri τ ^ &lt;才口马 ^ The sum is 2 or less. The sum of _ and the mountain is 2 or less. When R to R are multiple, multiple r5~r1

different. Further, 'a plurality of R5 to Rn may be respectively associated with an adjacent substituent such as a ring, a face ring, a squama ring, a ring (10) ring, a ring ring ring, and when the ligand LL1 contains a burnt group or an alkenyl group, The bases may be linear keys 23 201211165 or branched, and may be substituted or unsubstituted. Further, when the ligand LL1 contains an aryl group, a heterocyclic group or the like, the groups may be a monocyclic ring or a condensed ring, and may be substituted or unsubstituted. It is preferred that the linking group obtained by desorbing the two hydrogen atoms from the ring represented by the formula (3) is bonded to a thienylene group to form a condensed ring. Preferable examples of the ring formed by bonding R5 and a thiophene group include a benzene ring, an anthracene ring, and a dioxin ring. The linking group obtained by removing the two hydrogen atoms from the ring represented by the formula (3) is preferably a linking group represented by the following formula (3A). [Chem. 14]

In the formula (3A), n5 is synonymous with n5 in the formula (3). * indicates the bonding portion on L1 or L2, and * * indicates the bonding portion on Y3 or Y4. In the above formula (2), Y1 and Y2 are preferably a linking group represented by the formula (3) or the formula (5), and more preferably a linking group represented by the formula (3). In the above formula (2), Y1 and Y2 are preferably a substituent represented by any of the following formulas (9) to (12). [Chem. 15] 24 201211165.

Formula (10) Formula (11) Formula (9)

R18 L2 is in the formula (9) to the formula (12), R12, Rl3, 'R19 &gt; p21 . r, 22 * ^ ^ _ . '

The bonding portion of Riy and R represents a hydrogen atom or a substituent R15, and Ri 氺 is represented by L1 or **, which is a bonding moiety on γ3 or Y4. In place of the substituents listed in the example of R5 to R1Q, it is preferred that the linking group represented by the formula (9) to the formula (12) preferably has a Bo: one (preferred It is one to two, more preferably one) carbon atom 曰:,,, 5 or more (more preferably, the carbon number is 6 to μ, and further preferably 16 to 12) of the aliphatic group. Let r12, r13, r15, r16, R, R22, Y3, and Y4. The aliphatic group having 5 or more carbon atoms may be a group, an alkenyl group or a fast group, preferably a decyl group or an alkynyl group, more preferably an alkynyl group. In the above formula (2), γ1 and Y2 are preferably a linking group represented by the formula (9) or the formula (11), and more preferably a linking group represented by the formula (9). The ligand LL1 in the formula (1) is preferably a ligand represented by the following formula (8). [化 16] 25 201211165

In the general formula (8), R1, R2, R3, R4, γ1, Y2, γ3, Y4, al, a2, hi, Ιλίί b2'nl, ", ", ~, three and the formula ^丨! ^, R, γ ΐ, γ2, γ3, Y4, ab a2, b b b2, n Bu n2, η, n4, z are synonymous, and the preferred range is also the same. The ligand LL1 in the formula (1) is more preferably a ligand represented by the following formula (8a). [Chem. 17]

In the general formula (8A), R1, R2, r4, γ1, γ2, γ3, Υ4' ah a2, Μ, b2, in, η2, η3, η4 and R1, R2, and R3 in the formula (2) R4, γ1, γ2, γ3, V4, , Υ, al, a2, bl, b2, nl, n2, n3, n4 are synonymous, and the preferred range is also the same. (A1-3) Ligand LL2 26 20121 In the formula (1), LL2 represents a ligand of 2 or 3 teeth represented by the following formula (7). M2 indicating the number of the ligands LL2 is an integer of 〇~2'. Preferably, 〇2 or 255 may be the same or different when m2 is 2. [Chem. 18]

The general formula (7) in the general formula (7), 'Za, Zb, and each independently represent a non-metal atomic group capable of forming a 5-membered ring or a 6-membered ring. The formed 5-membered or 6-membered ring may be substituted or unsubstituted, and may be a single ring or a condensed ring. It is preferred that Za, Zb and Zc are composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and/or a halogen atom, and it is preferred to form an aromatic ring. In the case of a 5-membered ring, it is preferred to form an imidazole ring, an oxazole ring, a snail ring or a tris(4)' in the case of a 6-membered ring, preferably a ring, a pyrimidine ring or a pyridazine ring. Or a pyridazine ring. Among them, an imidazole ring or a pyridine ring is more preferred. .

The non-metal atom group represented by Za, Zb and Zc may have a substituent, and preferably has an acidic group. The substituents may be exemplified by the examples of R3 and R4 of the formula (丨). Examples of the acidic group include a mercapto group, a thiol group, a hydroxyl group, a hydroxamic acid group, a phosphoric acid group, and a phosphonium group. In the formula (7), c represents 〇 or j. c is preferably 〇, ^ is preferably a 2-dentate ligand. 27 201211165 The ligand PL2 preferably represents an organic ligand represented by the following formula: the formula c_1〇.

[Chem. 19] C-1 HOOC C-2

POOH (Rn)e1 ~λ /=w(Rl2)e2

C-4

C-10 C-9 (R,9)e9

(^2ζ) β12 ~ '(Ra〇)e10 (^2l)e11 In the formulae C-1 to C-10, R11 to r22 represent a substituent. The substituent may, for example, be a substituted or unsubstituted alkyl group having a carbon number of 丨~12, a substituted or unsubstituted carbon number of 2 to 12, and a carbon number of 7 ~12 _ generation or unsubstituted aryl group, * liver number is (5~12 substituted silk replaced by fang 28 201211165 j^uzopif ^ 'L seven soils (these acidic groups can also form salts) The thiol moiety of the alkyl group and the aralkyl group may be linear or branched. Moreover, the aryl group and the base moiety may be monocyclic or polycyclic (condensed ring, chelating). The substituent represented by Ru to R22 may be substituted by a step, and the substituent which is substituted with a substituent which is exemplified as Ru to R22 is preferably substituted with an acidic group. R~R is 矣-, white body Is acidic or has acid 1; base 2 is preferably independent = = = Γ, :i and a respectively ~ main double ej not 〇~3, respectively, independently represent the integer edge e4 of 〇~4 And e5 and the material table bar i=, t; the integer 'e7 el〇~el2 of vrn2 respectively represent the integers of 〇~6, the integers of 4 and 4', when Rn~R22 can be respectively phased; el~el 2 is 2 independently different. Preferably, 61~(1) 1^ may be the same or different from Ru, and may be the same or different, preferably the same, and the same. Rd5 is the same, preferably the same Rl9 and R2〇 can be the same or not

(AM) Coordination group X T J In the formula (1), χ represents a single dentate group, and m3 of the number of the terminal group X represents a ligand of an integer tooth of 〇 〜3. When X is a single-dentate ligand, a preferred one is preferably (10) is a (four) ^^//2 teeth or different, and X may be linked to each other. ',, B, 'x may be the same 29 201211165 The ligand X represents a group selected from a decyloxy group (preferably a decyloxy group having 1 to 20 carbon atoms, such as an ethoxylated group or a benzamidine group). Base, salicylic acid, glycyl decyloxy, N,N-dimercaptoglycine decyloxy, ethanedioxyloxy (•oc(o)c(o)o_), etc.) Preferred are sulfhydryl groups having a carbon number of from 2 to 20, such as an ethyl sulfonylthio group, a phenyl sulfenylthio group, etc., and a thioindolyl group (preferably a thiol having a carbon number of from 1 to 20). An oxy group such as thioethenyloxy (CH3C(S)0-), etc.), thiosulfonylthio group (preferably a thiopurine thio group having 1 to 20 carbon atoms, such as thioethionylthio group ( CH3c(s)s_), thiophenylthio (PhC(S)S-), etc.), mercaptoaminooxy (preferably a mercaptoaminooxy group having 1 to 20 carbon atoms) For example, N-methylbenzyl arylaminooxy (PhC(0)N(CH3)0-), acetylaminooxy (CH3C(0)NH0.), etc.), thiamine oxime Acidic acid group (preferably, thiocarbamic acid having a carbon number of 1 to 20, such as n, N-diethylthiocarbamate, etc.), dithiocarbamate group ( Preferably, the number of carbon atoms is 1-2 thiol phthalic acid vinegar such as N-phenyldithiocarbamic acid vinegar, N,N-methyldithiocarbamic acid, N,N-diethyldithiocarbamate, N,N-dibenzyldithiocarbamate, etc., thiocarbonate group (preferably sulfur having 1 to 20 carbon atoms) a carbonate group such as a thiocarbonate group or the like, a dithiocarbonate (preferably a dithiocarbonate having a carbon number of 1 to 2 Å, such as a diethyl carbonate group (C^OC(8)S_), etc.) a sulfonium trithiocarbonate group (preferably a trithiocarbonate-branched group having a carbon number of 1 to 2 Å, such as a dithiouric acid ethyl group (C2H5SC(S)S-), etc.), a sulfhydryl group ( Preferred is a fluorenyl group having 1 to 20 carbon atoms, such as an ethyl sulfonyl group or a benzamidine group, a thiocyanate SslSb group, an isothiocyanate group, a murine acid group, and an isocyanate group. Base, cyano group, 201211165 jyuzopif alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, such as methylthio group, ethylenedisulfide group, etc.), arylthio group (preferably carbon) An arylthio group having an atomic number of 6 to 2 Å, such as a phenylthio group or a phenylene group An alkoxy group (preferably an alkoxy group having 1 to 2 carbon atoms, such as a decyloxy group) and an aryloxy group (preferably having a carbon number of 6 to 2 Å) a group of a group consisting of an oxy group such as a phenoxy group, a quinoline-8-hydroxy group, or the like, a coordinated monodentate or a 2-dentate ligand, or a halogen atom (preferably a chlorine atom, bromine Atom, iodine atom, etc.), carbonyl (...CO), dialkyl ketone (preferably a dialkyl ketone having 3 to 20 carbon atoms, such as acetone ((CH3)2C〇...), etc.), 1,3-diketone (preferably a 1,3-, diketone having a carbon number of 3 to 2 Å, such as acetamidine (CH3C (0. &quot;) CH = c(0-)ch3), three Fluoroacetone acetone (CF3C(0...)CH=C(0-)CH3), bis(trimethylethlyl) oxime (tC4H9C(0...)CH=C(0-)t- C4H9), diphenyl decyl decane (PhC(0...)CH = C(0-)Ph), 3-chloroacetoneacetone (CH3C(0...)CC1 = C(0-)CH3 Carboxylamamine group (preferably amidino group having 1 to 2 carbon atoms, such as CH3N=C(CH3)0-, -OC(=NH)-C(= ΝΗ)0 -etc.), thiocarboxyguanamine group (preferably sulfur having 1 to 2 carbon atoms) Carboxylamido group, such as CH3N=C(CH3)S-, etc., or thiourea (preferably thiourea having 1 to 20 carbon atoms, such as NH(...) = C(S-)NH2 And CH3N(...) = C(S-)NHCH3, (ch3)2n-c(s...)n(ch3)2, etc.). In addition, "..." indicates a coordinate key. The ligand X is preferably selected from the group consisting of a decyloxy group, a thioindolethio group, a mercaptoaminooxy group, a dithioamino decanoate group, a dithiocarbonate group, a trithiocarbonate group, and a thiocyanate group. Acid ester group, isothiocyanate group, cyanate group, isocyanate 31 201211165. j^u/.upif group, cyano group, sulfur group, arylthio group, alkoxy group and aryloxy group a coordinating ligand, or a fluorenyl group consisting of a halogen atom carbonyl group, an i-diketone or a sulfur group; the surface is selected from the group consisting of oxo-, decylaminooxy, dithiocarbamic acid The base of the group of thiocyanate, thiocyanate, isocyanate, cyanate, isocyanate, cyano or arylthio is used to coordinate the ligand, or (tetra) atom a ligand composed of 3 or a thiourea; particularly preferred is a composition selected from the group consisting of a diyl group, a thiocyanate, an isothiocyanate group, a cyanate group, and an isocyanic acid. a group of bases of the group, or a ligand composed of a self-atomic atom or a U-diketone; most preferably selected from the group consisting of dithiol groups, thiocyanate And the group of isothiocyanate g&quot; Group into play coordinating ligand 'or a diketone ligand constituted by a 153_. Further, in the case where the ligand X contains a silk, a silk, a silk, a thiol or the like, the groups may be linear or branched, and may be substituted or unsubstituted. Further, in the case of containing an aryl group, a heterocyclic group, a cycloalkyl group or the like, these groups may be substituted or unsubstituted, and may be monocyclic or condensed. When X is a 2-dentate ligand, X is preferably selected from the group consisting of a decyloxy group, a stilbene thioloxy group, a thioindolethio group, a mercaptoaminooxy group, a thiomethionyl group, a dithiamine. a group of groups consisting of a sulfonate group, a thiocarbonate group, a dithiocarbonate group, a dithiocarbonate group, a fluorenyl group, an alkylthio group, an arylthio group, an alkoxy group, and an aryloxy group. A ligand at the position, or a (iv) ligand composed of a 1,3-diketone, an entrained aminoguanamine group, or a thiourea. When X is a monodentate ligand, X is preferably selected from the group consisting of a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, and an alkyl sulfide 32 201211165. Arylthio group: a ligand which coordinates in the group of the group, and an atom, a county, a diterpenoid, and a sulfur riding configuration ligand. Among the #月之金属错物物s, x is particularly preferred as guanidinium isothiocyanate, "mouse ibu ester or iso-cyanate."

(A1-5) Counter ion CJ is in the formula (1) Φ, m ± T C [represents a counter ion which must be countered by the ion in order to neutralize the charge. In general, the pigment is a cation or an anion or has a pure ionic charge, depending on the metal, ligand, and substituent in the pigment. The dye of the formula (1) can also be dissociated to have a negative charge by allowing the substituent to have a dissociable group or the like. In this case, the charge of the entire dye of the formula (1) becomes electrically neutral due to CI. In the case where the counter ion CI is a positive counter ion, for example, the counter ion CI is an inorganic or organic ammonium ion (e.g., a tetraalkylammonium ion, an acridine rust ion, etc.), an alkali metal ion or a proton. In the case where the counter ion CI is a negative counter ion, for example, the counter ion CI may be an inorganic anion or an organic anion. For example, a halogen anion (for example, fluoride ion, vapor ion, bromide ion, iodide ion f, etc.), substituted arylsulfonate ion (for example, p-toluenesulfonate ion, p-benzoic acid ion, etc.) ), an aryl disulfonic acid ion (for example, anthracene, 3-phenylenedonic acid ion, 1,5-naphthalene disulfonic acid ion, 2,6-naphthalene disulfonic acid ion, etc.), alkyl sulfuric acid, a sub-such as Base sulfate ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroboric acid ion, hexafluorophosphate ion, picric acid ion, acetate ion, trifluorosulfonate ion, and the like. 33 201211165f In addition, as the charge-balancing counter ion, an ionic polymer or other pigment having an opposite charge to the pigment may be used, and a metal counter ion (for example, bis-benzene-1,2-dithiol nickel (in) may also be used). Wait). (Al_6) Binding group The dye having the structure represented by the formula (1) has one or more acidic groups (binding groups) suitable for the surface of the semiconductor fine particles. That is, at least one acidic group is present in at least one of LL1, LL2 and X. More preferably, it has one to six such binding groups in the pigment. It is particularly preferable to have one to four such binding groups. The above-mentioned bonding group preferably has a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (for example, -CONHOH, etc.), a phosphoric acid group (for example, -0Ρ(0)(0Η)2, etc.) in the dye. An acidic group (a substituent having a dissociative proton) such as a stilbene (e.g., _p(〇)(〇h)2, etc.). It is preferred to have the above acidic group on the ligand L12. Among them, it is preferred to have a phosphinium group and a rebel group on the ligand LL2. Specific examples of the metal complex dye represented by the formula (1) used in the present invention are as follows, but the present invention is not limited to these specific examples. Further, in the case where the pigment in the following specific examples contains a ligand having a proton-dissociable group, the ligand may also be dissociated to release protons as needed. * indicates the bonding moiety on the hetero ring. ** indicates the bond on the alkyl group. 34 201211165 jyyjiLKjyif [化 20]

Ra

f^N^I Ψχ co2h

Ra Rb Rc na nb X A-1 HHH 1 1 NCS A-2 c6h13 HH 1 1 NCS A-3 c6h13 cbh13 H 2 2 NCS A-4 c6h5 H CeH】7 2 2 NCO A-5 HH 1 1 NCS —05II A-6 HC, H5 c2h5 1 1 I A-7 CiaH37 HH 3 3 Br A-8 HH 1 1 NCS A-28 DNJ Lucky HH 1 1 NCS 35 201211165 jyuzopif [化21] c6h13

B A-9 A-10 ♦- - A-11 *-〇- ** A-12 A-13 * &quot;*COOTM ** A-14 A CONH— 36 201211165.

[化22]

Ra Rb Rc na nb X A-15 C9H19 H c5H” 2 2 NCS A-16 c9h19 H c5h„ 2 1 NCS A-17 C3F7 HH 1 1 NCSe A-18 HH 1 1 Cl A-19 ch3 ch3 ch3 5 5 CN A-20 HHH 1 1 NCS A-21 c2h5 HH 1 1 NCS A-22 c5h„ HH 1 1 NCS A-27 G10H21 II °w° 3 3 NCS 37 201211165 [化23] γ~ 6

Co2h

Y X fYV* Α-23 NCS Α-24 C5H11~\X^~* NCS A-25 NCO A-26 NCO 38 201211165 j^uzopif [Chem. 24]

X A-29 NCS A-30 I

[Chemistry * 25] 201211165 jyuzupif The dye represented by the formula (1) of the present invention can be prepared by using a coupling reaction prepared by various coupling reactions. Or the reference numeral 2 in the publication, and the maximum absorption wavelength of the peak of the dye having the structure of the general formula (1) on the long wavelength side in the solution is in the range of 500 nm to 1 〇〇〇 nm, more preferably 550 nm. The range of 800 nm. Further, the light absorption band of the metal complex dye represented by the formula (1) is preferably in the range of 350 nm to 1200 nm, more preferably in the range of 4 Å to 1200 nm. In addition, in the present specification, the meaning of the compound (including the complex compound and the coloring matter) is as follows: in addition to the compound itself, a salt or a complex thereof (when it is other than the complex compound), ion. Further, it is also indicated that a compound which has been modified in a predetermined form is contained within a range in which the desired effect is achieved. Further, in the specification sheet, regarding the unclear, the substituted or unsubstituted substituents indicate that the base sheet may have any yarn taken. It is also synonymous with respect to the unsubstituted and unsubstituted compounds. Examples of preferred substituents include the substituents exemplified as R3 and R4. (A2) The dye b having the structure represented by the general formula (13) is used in the photoelectric conversion element and the photoelectrochemical cell of the present invention, and the above-mentioned dye having the structure of the general formula (1) has the following formula (丨 3) The pigment of the structure indicated. 201211165. jyuzopif Μ^η)^ν2)ηη(Χ^ . CI11 General formula (13) The pigment having the structure of the general formula (13) is coordinated with a ligand LLu and/or a ligand LL on a metal atom. 2. The specific functional group X11' as the case may be electrically neutral by CI11 if necessary. (A2-1) The metal atom Mz Μ z represents a metal atom. M z is preferably 4 Or a 6-coordinate metal, more preferably Ru, Fe, 〇s, Cu, W, Mq, Ni, Pd, Pt, Co, lr, Rh, Re, Mn or Zn. Particularly preferred is Ru, 〇s, Zn or Cu' is preferably Ru. (A2-2) Coordination LL11 The ligand LL11 is a 2- or 3-dentate ligand represented by the following formula (μ), preferably It is a 2-dentate ligand. The mil indicating the number of the ligand LLn is an integer of 〇~3, preferably i~3, more preferably 丨. When it is 2 or more, LLu may be the same or different. In the meantime, at least one of ml2 indicating the number of the ligands LL12 to be described later is an integer of 丨 or more. Therefore, the ligand LL11 and/or the ligand LL12 are coordinated to the metal atom. The ligand represented by the formula (14) is not included in the ligand The ligand having the same structure as the ligand represented by the formula (2): R101 and Ri〇2 in the formula (14) each independently represent an acidic group. Examples of the acidic group include a carboxyl group, a sulfonic acid group, and a hydroxyl group. , hydrazine xamic acid group (preferably having a carbon number of 丨~ such as a hydroxamic acid group such as -CONHOH, -CONCH3〇H, etc.), a phosphate group (for example, _〇p (〇) (〇h)2, etc.) or a phosphinium group (for example, _P(0)(0H)2, etc.). Preferred is a carboxyl group, a phosphine quinone 201211165 jyu^opif group, and a more planted one is a rebel group. RQ1 and R1G2 can be substituted for any carbon atom on the *ring ring. Moreover, the acidic groups can also be introduced into the ring via the linking group.

In the formula, R R is independently a substituent. The specific example of the substituent is preferably an alkyl group (preferably an alkyl group having a carbon number such as methyl, ethyl, isopropyl, tert-butyl, pentyl, heptyl, 1- Ethylpentyl, benzyl, 2-ethoxyethyl, 1 degylmethyl, etc.), alkenyl (preferably an alkenyl group having 2 to 20 carbon atoms, such as ethylene, propyl , oleyl group, etc.), alkynyl group (preferably an alkynyl group having a carbon number of 2, such as ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl (preferably carbon) Ring number of 3~2〇, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), aryl (preferably aryl having 6~26 carbon atoms) For example, phenyl, i-naphthyl, 4-methoxyphenyl, phenyl, 3, methyl sulfenyl, heterocyclic (difficult is a heterocyclic group having 20 carbon atoms) such as 2 _ Doing base, 4_ such as fixed base millet. Sitting base, sitting base, 2 sitting base, 2_. sputum base, etc., hospital oxygen (preferably the number of sub-1 to 2G alkoxy, such as methoxy Base, ethoxy group, iso-equivalent, oxy-oxyl group, etc.), aryloxy group (preferably carbon number) 6~26 42 201211165 ^ yu^opif aryloxy group, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, towoxyphenoxy, etc.), alkoxycarbonyl (preferably An alkoxycarbonyl group having 2 to 20 carbon atoms, such as an ethoxycarbonyl group, a 2-ethylhexyloxycarbonyl group, etc., an amine group (preferably an amine group having a carbon number of 〇~2〇) , for example, an amine group, N,N-dimethylamino group, N,N-diethylamino group, N-ethylamino group, anilino group, etc.), % guanamine group (preferably having a carbon number of 〇) ~2〇 sulfonamide, such as N,N-monomethylsulfonylamino, N-phenylsulfonylamino, etc.), decyloxy (preferably carbon number is 丨~ advised 醯An oxy group such as an ethoxy group, a phenoxy group, or the like, an amine fluorenyl group (preferably an amine carbaryl group having a carbon number, such as an N,N-didecylamine fluorenyl group, a team Phenylaminocarboxamyl or the like), an alkylamino group (preferably a mercaptoamine group having a carbon number of 丨~2 (), such as an alkylamino group, a benzylamino group, etc.), a cyano group Or a _ atom (for example, a fluorine atom, a chlorine atom, a silk atom, a ruthenium atom, etc.), more preferably Affiliation, dilute, aryl, heterogeneous, green, aryloxy, silk, amine, mercaptoamine, cyano or self-priming atom, especially silk, county, heterocyclic, burning An oxy group, a silk group, an amine group, a fluorenyl group or a cyano group. The ligand LL11 contains a olefinic material which may be linear or branched. The substituent may be substituted or unsubstituted. In the case of the coordination of the L L-fff ring group or the like, the groups may be monocyclic or condensed, and may be substituted or unsubstituted. In the formula (14), R1〇:5 and 1〇6八_^ and the knives independently represent an alkyl group, a square group, or a succinyl group. In the formula (14) +, the silk, the aryl group, and the group also have a substituent. The filament is preferably a burnt group having a carbon number of -18 (preferably 6 to 18, more preferably 6 to 12): 43 201211165 For example, il': more preferably 6 to 18) Base, and preferably, the number of carbon atoms is 3 to 3. (preferably: m good reading 7^~2G) of a 5-membered ring or a 6-membered ring heterocyclic group, for example, 2-2 to B groups, 2 mils, bimivir, 4° ratio Bite base, 3_ ^ base. Further, the core and RlG6 may be a combination of two or more of the above-mentioned silk, aryl, and heterocyclic groups. R and R106 are preferably an aryl group or a heterocyclic group having a substituent. The substituent on the aryl or heterocyclic group is preferably a silk, a benzyl group, an alkynyl group, a ring-burning earth 〇3, an alkoxy group, an aryloxy group, an amine group or a decylamino group (the above preferred examples and R) It is the same as in the case of R10, or a hydroxyl group, more preferably an alkyl group, an alkoxy group, an amine group or a hydroxyl group, and particularly preferably an alkyl group. R1〇5 and Rl〇6 can be the same or different, and the car is the same. R105 and R1G6 can also be directly bonded to the pyridine ring. Ri〇5 and Rl〇6 can also be bonded via L·11 and/or B12. On the ring of pyridine. Here, L11 and L12 each independently represent a conjugated chain composed of at least one selected from the group consisting of an arylene group, a heteroarylene group, a vinylidene group and an ethynylene group. The ethyleneylene group may also have a substituent. In the case where the vinylidene group has a substituent, the substituent is preferably an alkyl group, more preferably a methyl group. The arylene group is preferably exemplified as an example of L1 or L2. Examples of the heteroarylene group include a thienylene group. L11 and L12 are each independently preferably a conjugated chain having 2 to 6 carbon atoms. More preferably, it is a vinylidene group, a butadiene group, an ethynylene group, and a 201211165 w· A butadiene, a methylvinylidene or a dimethylvinylidene group, particularly preferably a vinylidene or butadienylene group, most preferably a vinylidene group. L11 and L·12讦 may be the same or different, and are preferably the same. Further, in the case where the conjugated chain contains a broken-carbon double bond, each double bond may be a trans form or a cis form, and is also a mixture of these. The dll and dl2 independently represent integers of 〇5. The dll and dl2 are preferably 1 to 3, more preferably 1 to 2. When the dll is 2 or more, the L·11 may be the same or different. When dl2 is 2 or more, L12 may be the same or different. In the formula (14), dl3 represents 0 or 1, and is preferably 1. In the formula (14), all and al2 each independently represent an integer of 〇~3. When all is 2 or more, Rioi may be the same or different, and when al2 is 2 or more, 'Rl02 may be the same or different. All is preferably 〇 or 1, and al2 is preferably an integer of 0 to 2. Particularly when du is 〇, a preferred 疋a12 is 1 or 2'. When dl3 is 1, it is preferred that al2 is 〇 or 1. The sum of all and al2 is preferably an integer of 〇~2. Bll and bl2 each independently represent an integer of 〇3, preferably an integer of 〇2. When bll is 2 or more, R103 may be the same or different, and may be connected to each other to form a ring. When bl2 is 2 or more, r1 (j4 may be the same or different) may be connected to each other to form a ring. Further, when bll and bl2 = 1 or more, 'R 03 and r104 may be connected to each other to form a ring. Preferable examples of the enthalpy of formation include a stupid ring, a π-pyr ring, a d-cembole ring, a fluorene ring, a cyclohexane ring, a cyclopentene ring, etc. The sum of all and al2 is 丨 or more, and coordination When the group LL11 has at least one acidic group, the mil in the formula (13) is preferably 2 or 3, and more preferably 45, 201211165 jyuzopif is 2. (A2-3) the ligand LL12 is in the formula (13) Wherein, LL12 represents the number of 2 or 3 of the ligands LL12, and ml2 is an integer 1 of 0 to 2. When ml2 is 2, LL12 may be the same or different from the mil indicating the number of ligands LL11. At least an integer. The ligand of the tooth. The table is preferably ruthenium or — wherein the group 2 and the ligand of the ligand LL12 are one or more. The formula is represented by the following formula (15). 2 teeth or 3 teeth

In the formula (15), Zd, Ze and each are independently formed into a 5-membered ring or an oxime ring in a non-metal atomic group. The formed member ring / member ring may be substituted or unsubstituted, and may be a single ring or a condensed ring. Preferably, the core = and Zf are composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a scaly atom and/or a ? atom, and it is preferred to form an aromatic ring. In the case of a 5-membered ring, it is preferred to form an imidazole ring, a π oxoxime, a 'thiazole ring or a triazole ring. In the case of a 6-membered ring, it is preferred to form a pyridine ring, a pyrimidine ring, a pyridazine ring. Ring or pyrazine ring. Among them, an imidazole ring or a pyridine ring is more preferred. A 46 201211165 jyuzvpif The non-gold subgroup of the preferred silk has a substituent, and has an acidic group. The substituent may be exemplified as r: hydroxy to the formula (1). Examples of the acidic group include a county, a repeating acid group, a functional group, a phosphoric acid group, and a phosphonium group. Further, the acidic soils ' are acidic groups introduced through the linking group. The formula (15) towel 'f' denotes G or 卜 [preferably 0, LLl2 preferred 疋2 tooth ligand. with. The preferred aspect of the formula (15) is the preferred phase of the formula (7) (A2-4). The ligand χΗ is in the formula (13), and the X&quot; represents a single tooth or a 2 tooth. Bit base. In the table, ml3 of the number of the ligand X11 represents an integer of 〇~2, and the melon 13 is preferably or 2. When X11 is a monodentate ligand, ml3 is preferably 2, and when X&quot; is a 2-dentate ligand, it is preferably ^. When it is 2, X can be the same or different, and X&quot; can also be linked to each other. The ligand X11 is exemplified by the substituents exemplified as the general formula (X of the formula D), and the preferred range thereof is also the same. (Α2-5) Counterion C]: 11 CI11 in the formula (14) is represented by a counter ion in the case where the charge must be counterbalanced. In general, the pigment is a cation or an anion or has a pure ionic charge, depending on the metal, ligand, and substituent in the dye. The dissociable group or the like, the dye of the formula (14) can also be dissociated to have a negative charge. In this case, the charge of the pigment of the formula (14) 201211165 is electrically neutral due to CI11. As a counter ion Cl&quot; It is exemplified as an example of the oxime of the formula (1), and the preferred range thereof is also the same. (A2-6) The dye having the structure represented by the formula (13) having a binding group has [more than one semiconductor fine particle Suitable for the surface of the acidic group (binding group), that is, at least one acidic group in at least one of LLU, LL12 and X11. More preferably, there are one to six in the pigment. The binding group It has 1 to 4 such a bonding group. As the above-mentioned bonding group, it is preferred that the dye has a mercapto group, a sulfonic acid group, a hydroxyl group, a heterohydroxy acid group (for example, -CONHOH, etc.), and a wall acid group ( For example, -OΡ(0)(0Η)2, etc.), an acidic group such as a phosphinium group (for example, ρ(〇)(〇Η)2, etc.) (a substituent having a dissociative proton). Preferably, it is coordinated. The LLu group has the above-mentioned acidic group. Among them, it is preferred to have a phosphinium group or a carboxyl group on the ligand LLi2. Further, the acidic groups may be an acidic group introduced via a linking group. Specific examples of the dye having the structure represented by the formula (13) are as follows. However, the present invention is not limited to these specific examples. Further, the pigment in the following specific examples contains a proton-dissociable group. In the case of a bit group, the ligand can also be dissociated to release protons. 48 201211165 j^uzopif [化28] co2h

C02NBu4

^N/. : ^NCS

, 1U, CS ho2c

C02NBu4 R-2 OCgHis

C6H13n C6Hi3n

Co2h

R-3

NBu4

Co2h C104. ho2c ho2c

49 201211165 The dye represented by the formula (13) of the present invention can be synthesized by referring to the method cited in Japanese Patent Laid-Open Publication No. 2001-291534 or the publication. The maximum absorption wavelength of the dye having the structure of the general formula (13) in the solution is preferably in the range of 300 nm to 1000 nm, more preferably in the range of 35 〇 nm to 950 nm, and particularly preferably 370 nm to 900. The range of nm. Further, the light absorption band of the metal complex dye represented by the formula (13) is preferably in the range of 350 nm to 1200 nm, more preferably in the range of 4 Å nm to 900 nm. (A3) Other dyes In the photoelectric conversion element and the photoelectrochemical cell of the present invention, a usual dye may be used together with the dye having the structure of the formula (1) or the dye having the structure of the formula (13). In the photoelectric conversion element and the photoelectrochemical cell of the present invention, a metal complex dye having a structure of the formula (1) is used as an essential component. More preferably, by using a dye having a structure of the general formula (13), it is possible to utilize a wide range of wavelengths of light to ensure high conversion efficiency and to reduce the reduction rate of conversion efficiency. The ratio of the ratio of the metal complex dye having the structure of the general formula (1) to the dye having the structure of the general formula (13), if the former is R and the latter is S' in terms of the percentage of moles , r / s = 90/10 ~ 10 / 90, preferably R / S = 80 / 20 ~ 20 / 80 'More preferably R / s = 70 / 30 ~ 30 / 70, further better is R/S = 60/40 to 40/60, and the best is r/s = 55/45 to 45/55 'usually use both in a molar manner. (B) Charge-moving body 201211165, ^In the electrolyte composition used in the photoelectric conversion element of the invention, as a redox pair (her:, eGuple), for example, can be classified and an inhibitor (for example, lithium iodide, tetrabutyl) Combination of ammonium iodide, tetrapropylammonium iodide, etc., 1 base purple? (eg methyl violet essence, hexyl violet, quaternary violet, tetrafluoronium salt) and Wei original body, (4) silk (such as two hydroquinone, naphthalenediol, etc.) and its oxidant Combination, two-valent and three-valent, a combination of a substance (for example, red blood salt and yellow blood salt), etc. These groups are preferably a combination of cerium and cerium. It is a nitrogen-containing aromatic ion of 5M ring or 6 (four). Especially, the compound represented by the general formula (1) is not a moth salt, w_8456, Japanese Patent No. 543, Electrochemistry, Vol. 65, No. 11 In the pyridine 11 salt, the imidazole rust salt, and the triazole oxime described in the 923th salt year, etc., the ruthenium 3 which is preferably used in the electrotransformation of the S material has a heterocyclic quaternary salt compound and iodine. The composition as a whole is preferably 0.1% by weight to 20%, more preferably 疋0.5 wt% to 5 vv^. The electrolyte composition used in the human right in the photoelectric conversion tree can also be: electrolyte composition The solvent content in the material is preferably less than or equal to the composition. wt. The following is more preferably less than 3 wt%, and particularly preferably 10 wt%. The solvent is high, or it can be lifted to increase the effective carrier concentration, or the two materials can be used to produce the excellent ion conductivity of 51 201211165. Such a solvent can be cited as a carbonate compound (ethylene carbonate, propylene carbonate). Diesters, etc., heterocyclic compounds (3-methyl-2-oxazolidinone, etc.), ether compounds (dioxane, diethyl ether, etc.), chain ethers (ethylene glycol dialkyl ether, propylene glycol II) Alkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc., alcohols (T alcohol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkane Alkyl ether, polypropylene glycol monoalkyl ether, etc.), polyols (ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, = triol, etc.), nitrile compounds (acetonitrile, glutaronitrile, methoxyacetonitrile' Acetonitrile, benzonitrile, dicyandiethyl ether, etc.), esters (carboxylates, phosphates, phosphonates, etc.), aprotic polar solvents (dimethylammonium (Dmso), sulfolane, etc.), water, The aqueous electrolyte described in Japanese Patent Laid-Open Publication No. 2002-110262, Japanese Patent Application Laid-Open No. 2000-36332, Patent Unexamined Publication No. 0-243134, and Re-publication w〇 / thousand and Publication No. 54,361 »hexyl carrier of the electrolyte solvent and the like. These solvents may be mixed with the # Um

When the electrolyte is added by adding a polymer, the gelation of the polyelectrolyte reference-1 and 2 solution can be added and 2 (Polymer Electrolyte 52 201211165 jyyjz.Kjpif

Reviews-1 and 2) (J. R. MacCallum and C. A. Vincent co-edited, ELSEVIER APPLIED SCIENCE) compounds and the like. In this case, it is preferred to use polyacrylonitrile or polyvinylidene fluoride. In the case where the electrolyte composition is gelled by the addition of an oil gel, the oil gel can be used by the Journal of Industrial Chemistry, j Chem.

Soc. Japan, Ind. Chem. Soc. ), 46779 (1943); Journal of the American Chemical Society (J_Am. Chem. Soc.) 111, 5542 (1989); Journal of the Chemical Society's Chemical Communications (J·Chem· Soc., Chem. Commun.) 390 (1993), English in Applied Chemistry (Angew chem. Int. Ed. Engl.) 35, 1949 (1996); Chem. Lett 885, (1996); Chemistry Society Journal, Chemical Newsletter (j chem s〇c, Chem.

The compound described in Comnrnn.) 545, (1997) or the like is preferably a compound having a guanamine structure. In the case where the electrolyte composition is gelled by polymerization of a polyfunctional monomer, it is preferred to prepare a solution from a polyfunctional monomer, a polymeric yarn, an electrolyte, and a granule by washing Casting method, coating method, dipping method, impregnation method, etc., forming a molten electrolyte layer on the electrode of the coloring pigment, followed by a radical polymerization of the monomer, and a gelation method thereof. The polyg # monomer is preferably a ruthenium divinyl benzene, ethylene glycol diacetic acid vinegar or ethylene glycol dimercapto acrylate having two or more ethylenically unsaturated groups. , diethylene glycol diacrylate, diethylene glycol dimercapto acrylate, triethylene glycol diacrylate, triethylene glycol dimercapto acrylate vinegar, pentaerythritol three __ purpose, three sulfhydryl propylene Sour and so on. 53 201211165 J 〆 V The gel electrolyte may also be formed by polymerization of a mixture of monofunctional monomers in addition to the above polyfunctional monomers. As the monofunctional monomer, acrylic acid or α-alkylacrylic acid (acrylic acid, mercaptoacrylic acid, itaconic acid, etc.) or esters or guanamines of such compounds (methyl acrylate, ethyl acrylate, n-propyl acrylate, propylene) can be used. Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, _3-pentyl acrylate, third amyl acrylate, n-hexyl acrylate, acrylic acid 2, 2 _Dimethyl butyl vinegar, acrylic acid n- vinegar, acrylic acid 2-ethylhexyl, two bound acid _2 _2 propyl propyl ester, hexadecyl acrylate, acrylic acid Base vinegar, acrylic acid cyclohexene S, acrylic acid cyclopentyl vinegar, acrylic acid benzyl g, acrylic acid ethyl acetonate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, C Dilute acid-^ethoxyethoxyacetic acid, -2-hydroxyethoxyethyl acrylate, phenoxyacetic acid acrylate, 3-methoxy butyl acrylate, ethyl carbitol acrylate , 2-methyl-2-nitropropyl acrylate, 2,2,2-trifluoroethyl acrylate, octafluoropentyl acrylate, hexacylic acid, methyl methacrylate, methyl methacrylate N-butyl acrylate, isobutyl methacrylate, tert-butyl methacrylate, third amyl methacrylate, n-octadecyl methacrylate, methyl propylene dibenzyl ester, methacrylic acid hydroxyl group Ethyl ester, methacrylic acid _2_ propyl acetoacetate, methyl propyl -2- methoxy ethoxy group, methyl propyl phthalate-2-ethoxy acetoacetate, methacrylic acid-2-methyl Oxyethoxyethyl ester, dimethylaminoethyl methacrylate, 2,2,2-difluoroethyl thioglycolate, tetramethyl propyl decyl decanoate, fluorenyl Hexafluoropropyl acrylate, heptafluorophosphonium methacrylate, ethylene glycol ethyl carbonate methacrylate, -2-isobornyl methacrylate, methacrylic acid-2-norbornyl methyl ester , methacrylic acid borneol thin _2_ keel 54 201211165 α^υζ, υρίί ester, methacrylic acid-3-mercapto-2-norbornyl decyl acrylate, acrylamide, hydrazine-isopropyl acrylamide , Ν-n-butyl acrylamide, hydrazine _ tert-butyl acrylamide, hydrazine, hydrazine-dimercapto acrylamide, hydrazine- mercapto acrylamide, diacetone acrylamide, 2-propene hydrazine Amino-2-mercaptopropanesulfonic acid Propyl tridecyl gasification, mercapto acrylamide, fluorenyl fluorenyl decylamine, hydrazine-hydroxymethyl methacrylate, etc., vinyl esters (vinyl acetate, etc.), horse Or tartaric acid derived from horse acid or derived from the acid (maleic acid, monoterpene maleate, dibutyl maleate, diethyl fumarate, etc.), sodium salt of p-styrenesulfonic acid, Acrylonitrile, mercapto acrylonitrile, diene (butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compound (styrene, p-styrene, tert-butyl styrene, α·decyl styrene, sodium styrene sulfonate, etc.), fluorene-vinyl amide, Ν-vinyl-fluorene-mercaptoamine, hydrazine-vinyl acetamide, hydrazine-vinyl- Ν_mercaptoacetamide, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allylate, sodium decyl propylene sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ether (mercapto vinyl ether, etc.), ethylene, propylene, butylene, isobutylene, fluorene-phenyl maleimide, and the like. The amount of the s-energy monomer is preferably from 〇-5 wt% to 70 wt%, more preferably from 1.0 wt% to 50 wt%, based on the whole of the monomer. The above-mentioned monomers can be jointly edited by Dajin Bribe and Muxia Yayue, "The Reality of Polymer Synthesis" (Chemical Tongren) or Otsu Takayuki "Lecture Polymerization Reaction, Radicals, Free Radicals (Eggs)" The general polymer synthesis method or the sub-beam is used for radical polymerization, and the polymerization is carried out by radical polymerization. In particular, radical polymerization is carried out by heating. 55 20121m 22 ΐ ΐ 5 5 azoazobisisobutyronitrile, 2, 2 , _ azobis(2,4-dimethylvaleronitrile), 22, azobis(2-methylpropionic acid) m2, azobisisobutyric acid dioxime, etc. = ΐί=: Lauryl, benzoyl peroxide, peroxyoctanoic acid third initiator, etc. The preferred addition amount of the polymerization initiator is _wt%~2() wt% wt%~l with respect to the amount of early body u 〇wt%. The weight composition of the monomer in the gel electrolyte is preferably 〇·5 Wt% to 70 Wt%, more preferably 1.0 wt% to 50 Wt%. In the case where the cross-linking reaction is carried out to gel the electrolyte composition, f is preferably used in the composition + the addition of the polymer and the agent in the village of the reaction state. Preferably, the reactive group is a pyridine ring. Imidazole ring, thiazole ring, An azole ring, a dioxan ring, a (iv) ring K ring, a slant ring (tetra) nitrogen heterocycle, preferably a crosslinker is a functional group (electrophilic agent) having two or more nucleophilic attacks on a nitrogen atom, such as a bifunctional group. The above-mentioned toothed calcination, toothed aryl sulfonate, acid anhydride, helium gas, isocyanate, etc. 金属 Metal electrolytes (LiI, Nal, cesium, Csl, Cal2, etc.) and metal bromine may also be added to the electrolyte composition of the present invention. Compounds (LiBr, NaBr, KBr, GBr, CaBr*2, etc.), quaternary ammonium bromide salts (tetraalkylammonium bromide, brominated pyridine, etc.), metal complexes (ferrocyanide_ferricyanide) , ferrocene-ferrocene ruthenium ion, etc., sulfur compounds (polysulfuric acid (10), silk brittle silk disulfide, etc.), purple neodymium pigment, p-benzoic acid, etc. These compounds are also used in combination. In the present invention, a journal of the American Ceramic Society (J Am 56 201211165 jyuzopif) may also be added.

Ceram. Soc.), 8〇, (12), 3157-3171 (1997), a basic compound such as a second butyl pyridine or a 2-methylpyridine or a 2,6-dimercaptopyridine . The preferred concentration range for the addition of the basic compound is 0.05 Μ~2 Μ. Further, in the present invention, the electrolyte may also use a charge transfer layer containing a conductor material of a hole. The conductor material of the hole can be a 9,9'-spirodi derivative or the like. Further, the electrode layer, the photoelectric conversion layer, the hole transport layer, the conductive layer, and the counter electrode layer may be laminated in this order. A hole transporting material that functions as a p-type semiconductor can be used as the hole transport layer. A preferred hole transport layer may be, for example, an inorganic or organic hole transport material. Inorganic hole transport = material can be listed, Cu0, (four) and so on. Further, the organic hole transports the organic system hole transporting material of the molecular system and the low molecular system, and the material of the organic hole transporting material of the shovel/knife shovel is, for example, polyvinyl carbazole, and more, such as burning. Moreover, the low-molecular organic hole transports the amine derivative, the traitor, the creature, and the scale. Its towel, which is different from the stone of the previous stone, is along the main chain of Si Gongyi tomb, ϋ·» Μ #1 instead of localized σ electrons contribute to the photoelectric transmission with south hole mobility Therefore, it is better to 2818 (1987)). V ays. Rev. Β, 33, the conductive layer in the present invention is a conductive organic conductive material and a C charge of the acceptor material; := is: 57 201211165 W ^ V w ^ :, can be preferably used by The intermolecular charge transport formed by the organic donor and the acceptor is suitable for the donor body. (IV) Preferably, the donor material is electron-rich in the molecular structure. For example, the organic donor material may be exemplified by an organic donor material having a substituted or unsubstituted amine group, a woven or a sulfur atom in a π-electron system of a molecule, and specifically, a stupid amine system and a triple stupid A decane-based, carbazole-based, phenol-based, or tetrathiafulvalene-based material. Preferably, the acceptor material is a receptor 电 in the electron structure of the molecular structure. For example, there may be enumerated organic fat acceptor materials such as fullerene, such as pCBM, benzene brewing system, and naphthalene. I system is the 覼 system, _ series, four gas benzene brewing system, four desert benzene brewing system, tetracyanoquinone quinone dimethane system, Yu Bujin y y ji system. The thickness of the conductive layer is not particularly limited, and it is preferred that the porous material be completely filled. (C) Conductive support member As shown in Fig. 1, in the photoelectric conversion element of the present invention, the photoreceptor 2 in which the dye is adsorbed on the porous semiconductor fine particles 22 is formed on the conductive support 1. As described later, for example, a semiconductor liquid fine particle liquid is applied onto a conductive support and dried, and then impregnated into the dye solution of the present invention, whereby a photosensitive layer can be produced. As the conductive support, a support such as a metal having a conductive body or a glass or a high-molecular material having a conductive film layer on the surface can be used. Preferably, the electrically conductive support is substantially transparent. The term "substantially transparent" means that the transmittance of light is 10% or more, preferably 50% or more, and 58 201211165 J^vz.upif is particularly preferably 80% or more. The conductive support can be used as a support for coating a glass or a polymer material with a conductive metal oxide. The coating amount of the conductive metal oxide at this time is preferably 〇1 g to 1 〇〇 g per 1 m 2 of the support of the glass or polymer material. In the case of using a transparent conductive branch body, it is preferable to make light incident from the side of the support. Examples of the polymer material which can be preferably used include tetraethyl fluorenyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (pEN), and para-polyphenylene. Ethylene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAR), polysulfone (PSF), and quot; y (PES), polyether quinone imine (ρΕΙ) , cyclic polyolefin, brominated phenoxy group, and the like. The surface of the conductive support can also be subjected to a light management function, and for example, an alternating layer of a high refractive index and a low refractive index oxide as described in Japanese Patent Laid-Open Publication No. 2003-123859 can be cited. The light guide function described in 2002-260746 is opened. In addition to this, a metal support can also be preferably used. An example of this can be listed in j, Shao, copper, recorded, iron, and not _. The metals may also be alloys. More preferred is H copper, the special surface is titanium or Ming. The heart Ϊ 岐 makes the conductive support have the function of clear purple silk. A method in which a fluorescent material that changes ultraviolet light into visible light is present in a collecting agent. Or transparently watch the table _ method or use ultraviolet light absorption. The preferred conductive film of this patent can be exemplified by metal (such as surface, gold, silver, copper, sho, 59 201211165r, oxidized mm1 lion (indium-tin composite oxidation) The thickness of 0.03 μη^ layer is preferably 0.01哗3030, more preferably 0.050.05μιη~20μιη of the conductive branch body. The range is 50^ The lower the resistance, the better. The better surface resistance Also, it is better than 10 Ω/cm2. The lower limit is not limited. It is usually (UHW or so.) Under the cliff: the electric resistance of the electric film becomes larger, so it can be matched. A gas barrier film 3 diffusion preventing film may be disposed between the cut body and the transparent guide. The gas barrier layer may be a resin film or an inorganic film: and 'a transparent electrode and a porous semiconductor electrode photocatalyst may be provided. The electric layer can also be a structure. As a secret method, for example, FT can be laminated on the crucible. (D) The semiconductor microparticle port is shown in Fig. 1, in the photoelectric conversion element of the present invention, in the conductive branch body 1 is formed by adsorbing the pigment 21 on the porous semiconductor remainder 22 The photosensitive layer 2. As described later, for example, a dispersion of semiconductor fine particles is applied onto the conductive support, dried, and then impregnated into the dye solution of the present invention, whereby a photoreceptor can be produced. It is preferred to use a metal chalcogenide (such as an oxide, a sulfide, a selenide, etc.) or a perovskite microparticle. The metal chalcogenide is preferably titanium, tin, zinc, tungsten, rhenium, iridium, Oxide, indium, antimony, bismuth, antimony, vanadium, antimony, or niobium oxide, cadmium sulfide, cadmium selenide, etc. #51 Tai Mine is preferably listed as acid, titanium, etc. It is preferred that 201211165 ^yuzopif titanium oxide, zinc oxide, tin oxide, tungsten oxide. The semiconductor has a conductivity-related carrier, the electron is n-type and the carrier is a p-type of a hole, in the component of the present invention, It is preferable to use the n-type in terms of conversion efficiency. In addition to the intrinsic semiconductor (or intrinsic semiconductor) having the same carrier concentration of the valence band and the carrier concentration of the valence band, the n-type semiconductor has a Structure derived from impurities An n-type semiconductor having a high electron carrier concentration due to defects. The n-type inorganic semiconductor preferably used in the present invention is Ti02, TiSr03, ZnO, Nb203, Sn02, W03, Si, CdS, CdSe, V205, ZnS, ZnSe. , SnSe, KTa03, FeS2, PbS, InP, GaAs, CuInS2, CuInSe2, etc. The most preferable n-type semiconductors are TiO2, ZnO, Sn02, W03, and Nb203. Moreover, it is also preferable to use the semiconductors. A plurality of composite semiconductor materials. Large particles. In this case, the 疋+ average particle diameter of the large particles is preferably 5 〇 nm or less, preferably 2% or less. In order to maintain the viscosity of the semiconductor fine particle dispersion with the above target == as the particle diameter of the semiconductor fine particles, the average particle diameter of the primary particles is preferably 2 or more and 50 mn or less and more preferably the average particle of the secondary particles. Ultrafine particles with a diameter of 2 唧 or more and 30 nm or less. It is also possible to mix two or more kinds of fine particles having different particle diameter distributions, and in this case, a small good average size of 5 nm or less is preferable. Further, in order to scatter the incident light, the light trapping is improved:: the content is added or applied to the other layer, and the average particle diameter of the large particles of 25 Å or more, more preferably 25 Å, is preferably 1 〇〇61 201211165 nm or more. It is preferable to use a large particle for light scattering to have a haze ratio of 6 〇/° or more. The so-called haze ratio is (diffuse transmittance) + (total light transmittance). The method for producing semiconductor fine particles is preferably a 2-gel-sol method described in "The Science of Sol-Gel Method" by Agatsu-Sh〇fu Co., Ltd. (1998). Further, a method of producing an oxide by hydrolyzing at a high temperature in a gasification product developed by Deg_ Company is also preferred. In the case of semiconductor microparticles, in the case of oxidation, the high-temperature hydrolysis method of the upper gel, the gel-sol method, and the chloride in the acid hydrogen salt is preferred, and the oxidation property and application can also be learned. Technology Technology News published (4) This year, the method of sulfuric acid localization described in the towel. Correction, as a sol-gel method, Barbe et al., Journal of the American Academy of Ceramic Research (J〇urnal 〇f the

Amencan Ceramic s〇ciety), Vol. 8 pp. i2 祀 7, pp. 3171 (10) 7 years), or the material chemistry of this special person (ChemiStry〇fMaterials), Volume 1 (), The methods described in pages 2419 to 2425 are also preferred. In addition, as a method for producing semiconductor fine particles, for example, a method for producing titanium nitride nanoparticles is exemplified by a method of flame hydrolysis, a calcination method of titanium tetrahydride, a stable evening discharge, and a hydrolysis of a titanium compound. Hydrolysis of n-decanoic acid, soluble; and method of dissolving and removing soluble part after non-忒 = peroxide = granules 氧化 oxidized by core/shell structure of sol-gel method 2012 201216165 Titanium dioxide The crystal structure can be rutile type, preferably the Η Η 兄 钛 钛 、 、, brookite type, or Shi Zhu _ 疋 lack of ore type, brookite type. It is also possible to use a titanium dioxide nanotube or a titanium nitride microparticle. Α, ', 不米棒 mixed with dioxane. It is used as a binder for dioxide (-g) or as an additive for preventing reverse necking. Examples of preferred additives include: surface, whiskers, fibrous graphite, carbon rice camp, 0, Sno fiber, /, g-zinc-zinc-bonded, ,, Daweisu money green matter, Charge transfer complexes such as metal, organic ♦, and decalidane compounds, etc. In the present invention, the solid semiconductor fine particles other than the semiconductor fine particles are more than 1 G wt% or less of the entire solid semiconductor fine particle dispersion other than the semiconductor fine particles, and the slanting and densification-type dendritic polycondensation treatment, the denitrification treatment, and the ultraviolet-ozone-oxygen (Ε) semiconductor fine particle dispersion liquid. The fine particle dispersion liquid is applied onto the conductive support and heated to obtain a porous semiconductor fine particle coating layer. Further, the method of sigma=semiconductor fine particle dispersion liquid may be exemplified by a method of directly using a method of depositing fine particles when synthesizing a semiconductor, or irradiating an ultrasonic wave with a fine particle 63 2〇l2Hl65 in addition to the above-described sol-condensation method. .u ” 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎 碎Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, citronellol, and male oleyl alcohol, ketones such as acetone, and acetonitrile such as ethyl acetate. In the case of Knife, it is also possible to use a small amount of a polymer such as polyethylene glycol, ethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelate solution as a dispersing aid. (4) Preferably, the dispersing aids = before the step of forming a film on the conductive support, are removed in advance by a shouting method or a method using a separation membrane, or a separation method or the like. As the conductor fine particle dispersion, the amount of the solid matter other than the semiconductor fine particles can be 1 〇 wtOA or less of the entire chemical liquid. The concentration is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. Further preferably, it is 0.5% or less, and the most preferable one is 〇.2%. In other words, in the semiconductor fine particle dispersion, the solid matter other than the solvent and the semiconductor fine particles can be made 10% by weight or less of the entire semiconductor fine particle dispersion. Preferably, it consists essentially of only semiconductor fine particles and a dispersing solvent. When the viscosity of the semiconductor fine particle dispersion is too high, the dispersion aggregates and the film does not form a film. On the other hand, if the viscosity of the semiconductor fine particle dispersion is too low, the liquid flows and the film cannot be formed. Therefore, the viscosity of the dispersion is preferably 10 N · s/m 2 to 300 N · s/m 2 at 25 C. More preferably, it is 50 N · s/m 2 to 200 N · s/m 2 at 25 ° C. As a method of applying the semiconductor fine particle dispersion liquid, a roll method, a dipping method, or the like can be used as a method of application. Moreover, the method of the metering system can use the gas 64 201211165ir knife method, the knife method, and the like. Further, as a method of synthesizing the same portion of the application system method and the measurement system method, it is preferable that the wire rod coating method disclosed in Japanese Patent Publication No. Sho 58-4589, and the sliding material described in the specification of U.S. Patent No. 2,681,294, etc. Bucket method, extrusion method, curtain method, etc. Further, a method of applying by a spin coating method or a spray method using a general machine is also preferable. The wet printing method is preferably a gravure plate, an offset plate, a screen printing or the like which is mainly a printing method of a relief plate, a lithographic plate and a gravure. A preferred film formation method can be selected from these methods t depending on the viscosity or wet thickness of the liquid. Further, since the semiconductor fine particle dispersion of the present invention has high viscosity and is viscous, it has a strong cohesive force and does not satisfactorily fuse with the support at the time of coating. In this case, the cleaning and hydrophilization of the surface by the UV ozone treatment is performed, thereby increasing the binding force of the semiconductor residual dispersion and the surface of the conductive support, and coating the semiconductive miscible dispersion. Who is easy to become. = The thickness of the body record is G just from; ^ The thickness of the conductor particle layer is better, i is ~30哗, into -25cm. The semiconductor microparticles are supported on every 1 m2 of support ==疋〇·5 g~_g, more preferably 5 g~excited g. The electron contact between the coated semiconductor fine particle particles is enhanced by the adhesion of the two conductors (4) μ body, and the heat treatment of the +r (four) + conductor micro-sheet dispersion is performed by the heat treatment. It can form a porous semi-continuous force, and can be processed. Borrow the microparticle layer. For example, it is known that the method known in the art of forming a semiconductor, the material described in the Japanese Patent Application Laid-Open No. 2001-291534, or the greening method, and the production method are referred to in the present specification. Moreover, the energy of light can be used in addition to the heat treatment. For example, when using ^fb titanium as a semi-conducting case, it can be activated by imparting a lightly absorbable surface of a semiconductor such as ultraviolet light, or by laser light or the like The surface is activated. By irradiating the semiconductor fine particles with light which can be absorbed by the fine particles, the particles and the adsorbed impurities are decomposed by activation of the surface of the particles, and can be used in a preferred state for the above-mentioned purpose. When combined with heat treatment and ultraviolet light, it is difficult to face the semiconductor particles to ride on the particles. - Faced above the C,. Heating below C is preferably 100 C or more and 150 c or less. As described above, by photoexcitation of the semiconductor fine particles, impurities in the fine particle layer can be washed by photolysis, and physical bonding between the particles can be increased. Further, the semiconductor fine particle dispersion liquid is applied onto the conductive support, and other treatments may be performed in addition to heating or light irradiation. A preferred method is, for example, electrification, chemical treatment, or the like. The pressure may be applied after the application, and the method of applying the pressure may be exemplified in Japanese Patent Laid-Open Publication No. 2003-500857. Examples of the light irradiation include Japanese Patent Laid-Open Publication No. 2001-357896 and the like. Examples of the plasma, the microwave, and the electric current are exemplified by Japanese Laid-Open Patent Publication No. 2(8) No. 2-353453. For the chemical treatment, for example, JP-A-2001-357896 can be cited. As a method of applying the semiconductor fine particles to the conductive branch body, in addition to the method of applying the semiconductor fine particle dispersion to the conductive support 66 20121 US, the following method may be used: Japanese Patent In the method of applying a semiconductor fine particle precursor to a conductive support described in the publication of the Japanese Patent Publication No. 2664194, a method of obtaining a semiconductor fine particle film by hydrolysis of water by an air towel is used. Examples of the precursor include (NH4)2TiF6, titanium peroxide, a metal alkoxide, a metal complex, a metal organic acid salt, and the like. In addition, a slurry in which a metal organic oxide (such as an alkoxide) is coexisted, and a semiconductor is prepared by heat treatment or light treatment, and the pH of the slurry and the bulk material in which the inorganic precursor is coexisted is specified. A method of dispersing the properties of a oxidized record. These (four) towels may also be added with a small amount of a binder, and examples of the binder include cellulose, a polymer, crosslinked gum, polybutyl titanate, carboxymethyl cellulose, and the like. As a technique related to the formation of semiconductor fine particles or precursors thereof, physical methods such as corona discharge, electrophoresis, and ultraviolet rays can be cited; chemical treatment using a test or polyethylene dioxane polyphenylene bromide A bonded film such as a silk aniline. As a method of coating semiconductor fine particles on a conductive branch body, the above-mentioned (1) wet method and (7) dry method, and (3) other methods (7) dry method are preferably listed as Japanese Patent Special Publication 2_韵943 a艮 and so on. (3) Other methods are better in 2002-13. Turn (four) open method can be cited as galloping or sputtering, gas deposition method. Further, an electrophoresis method or an electrodeposition method can also be used. Further, a method of temporarily transferring a coating film on a heat-resistant substrate and transferring the film from 201201165 jyuzopif to a film of plastic or the like can be used. Preferably, after the semiconductive layer is formed on the sacrificial substrate including the inorganic salt which can be removed by the conductor sonicating agent described in the Japanese Patent Publication No. __7, which is described in the Japanese Patent Publication No. Transfer to the organic substrate to remove the sacrificial substrate: The semiconductor fine particles are preferably larger in order to adsorb more pigments, and larger semi-filaments. For example, when the semiconductor recording is applied to a large size, it is preferable that the projection area is two times when A _ 疋 (10) times or more. There is no limit to the upper limit, and = is about doubled. A preferred semiconductor micro-patent is disclosed in Japanese Laid-Open Patent Publication No. 2001-93591. #T歹歹日H兄下' The larger the H particle of the semiconductor microparticles, the higher the absorption of the dye per unit ώ of the approved carrier, the higher the absorption efficiency of light, but the increase of the electrons of the II Calling for the charge to re-knot: k into the knowledge of the consumption has also become larger. The semiconductor fine particle layer = different in the way, typically in the case of "pool", it is preferable that i μιη~50 handsome, and more 疋3 _~3〇卿. The semiconductor fine particles are applied to the support body so that the particles can be in close contact with each other, and may be from 100 to 800. (: Temperature: plus, 1G min ~ 1G hour. In the case of using glass as the branch body '' The film forming temperature is preferably 4 〇〇. 〇 ~6 〇〇. 〇. Using polymer materials as a support In the case of a building body, it is preferred to carry out film formation and post-heating in the following cases. In this case, the film forming method may be 68 201211165 A 11 (1) wet method, (2) dry method, (1) electrophoresis method (including electrodeposition) Any of the methods 'preferably' (1) wet method or (7) dry method, more preferably (1) wet method. Further, the amount of semiconductor fine particles coated on each m2 support is preferably 〇 .5 g to 500 g, more preferably 5 g to 100 g. In order to adsorb the pigment on the semiconductor fine particles, it is preferred to impregnate the sufficiently dried semiconductor fine particles for a long time in the solution containing the pigment of the present invention. In the dye solution for dye adsorption, the solution used for the dye solution for dye adsorption can be used without particular limitation as long as it is a solution which can dissolve the dye of the present invention. For example, ethanol, methanol, isopropanol, benzene, and the like can be used. Tributyl alcohol, acetonitrile, acetone, n-butanol, etc. Ethanol or benzene can be preferably used. The dye solution for dye adsorption containing the solution and the dye of the present invention can be heated to 50 as needed. (: ~100. (: The adsorption of the dye can be carried out before the application of the semiconductor fine particles. It is also possible to carry out the coating, and it is also possible to simultaneously apply the semiconductor fine particles and the dye to adsorb it. The unadsorbed pigment can be removed by washing. In the case of performing the calcination of the coated film, it is preferred. The adsorption of the pigment is carried out after the calcination. It is particularly preferable to rapidly adsorb the pigment before the water is adsorbed on the surface of the coating film after the satin is burned. The adsorbed pigment may be one of the above-mentioned pigments A1, and the pigment A2 may be further mixed. Further, other pigments may be further mixed. In order to expand the wavelength band of the photoelectric conversion as much as possible, the mixed coloring matter is selected. In the case of mixing the coloring matter, in order to dissolve all the pigments, it is preferred to prepare the pigment for adsorption. Pigment solution. The amount of the pigment used is preferably 69 201211165 ^yuzopif 〇·〇1 millimolar to 100 millimolar, and more preferably 〇·1 millimole per 1 m2 of support. ~50 millimolar, particularly preferably 0.1 millimolar to 10 millimolar. In this case, it is preferred that the pigment of the present invention is used in an amount of 5 mol% or more. The amount of adsorption of the semiconductor fine particles is preferably 0.001 millimole millimole, more preferably 0.1 millimolar to 0.5 millimole, relative to 1 g of the semiconductor fine particles. When the amount of the pigment is small, the sensitization effect is insufficient, and if the amount of the pigment is too large, the pigment that does not adhere to the semiconductor floats, and the sensitization effect is reduced. The interaction between the dyes and the dyes may also co-adsorb the colorless compounds. The co-adsorbed hydrophobic compound may be exemplified by a steroid compound (for example, cholic acid, pivalic acid (5), and the like (10). After adsorbing the pigment, the surface of the semiconductor fine particles can also be treated with an amine. Preferred amines include a third butyl group, a ratio = some of these compounds may be miscellaneous for reading materials, and may be used by dissolving in an organic solvent. The counter electrode is an electrode that operates as a positive electrode of a photoelectrochemical cell. It is synonymous with the above-mentioned conductive support, but it is not necessary to have a cut body in sufficient construction. However, those who have a support are interested in electricity. The material of the counter electrode can be listed, carbon, and conductivity. Preferred examples thereof include carbon, a conductive polymer. The structure of the day ^^=, which has a high current collecting effect, can be cited. The preferred example is J-opening + 1〇-505192 and the like. 201211165 3yU2bpif The photoreceptor electrode may be a composite electrode such as titanium oxide or tin oxide (Ti〇2/Sn〇2). Examples of the mixed electrode of the monooxygen group include JP-A-2000-113913. The mixed electrode other than titanium dioxide is exemplified by Japanese Patent Application Laid-Open No. 43-A No. Hei. No. 2003-282164. Further, as a configuration of the element, a structure in which the i-th pole layer, the first photoelectric conversion layer, the conductive layer, and the second photoelectric conversion layer 1 electrode layer are laminated in this order may be employed. In this case, the dyes in the photoelectric conversion layer of the Dijon photoelectric conversion layer may be the same or different, and the conditions may be different. In order to improve the utilization of incident light, the light receiving electrode may be shaped. Examples of the configuration of the preferred column type include the Japanese Patent Application No. 0 Γ 0 989, and the Japanese Patent Application Laid-Open No. Hei. No. 9 and the like. The reflection portion can be provided to efficiently perform light scattering and to prevent electrolysis. The counter-production caused by direct contact between the liquid and the electrode, the electric t-branched body and the porous semiconductor micro-particle layer:; a. It is better to pay a bribe to the Japanese patent _ flat G6·507999 2 ^ ^ The stop of the light-receiving electrode on the opposite electrode or the outline can be _ 日物^Γ.28= 71 201211165., Bulletin. The second resin is sealed = the second is: polyisobutylene-based thermosetting oxygen resin, ionic polymer resin (/. (meth)acrylic acid _ purpose, cyclopolymerization, laser failure method, etc. The powder glass may be mixed with propylene which is a binder. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. <Illustration of Pigment Modulation> As The metal complex dye of the present invention prepares the following pigments. In the following description, NBS represents Ν-bromobutaneimine, DMF, Ν-dimethylformamide, and pph represents triphenyl. Phosphine, dme means a scream, THF means tetrahydrofuran, dppp means ι,3-bis(diphenylphosphine)

Propane·, bpy represents bipyridine, TMS represents trimethyldecyl, and TEA represents diethylamine. (Preparation of Intermediate A-l5a) Intermediate A-15a was prepared according to the method described below. 72 201211165 jyu/opif y〇〇^B. A_15f 'c#” ^ NBS.^19^. Br 〇9Hi9 DMF DME, 75uC, 3hr 1 C5H11 A 0ςΗ^4 C9H19 A-15d CsH^ A-15e csHii ?®s ' C9Hl91i^_^C5丨

DMF

.CjH^ n-BuLi C9H19 ClSn(n-Bu)-^ THF

CsHn A-I5g'iHiCsHi1 CsH^ Sn(r&gt;-Bu)3 A-I5i A.15k OVl5j C9H19 Pd(PPl^k • Bad Burning

Modulation of A-15e

Dissolve A-15d 28 g in DMF 3〇〇 mL

g 'in the room, after riding down 5, then add water and acetic acid B NB = shrink the organic layer. It was purified by column chromatography to obtain J A-15g prepared hmft'15: 3〇g, A"5f 25 g dissolved in dimethoxyethane i 100mL) after adding catalyst The amount of Pd (PPh3) 4, 10% Na2C 〇 3 shoes ^ 75C was given 20 hours. Ethyl acetate and water were added, and the organic phase was separated and purified by liquid separation to obtain A-15g (34 g). Modulation of A-15h 73 201211165 g, _ 350 mL, add NBS 15 A /m ^ hours. Thereafter, water and ethyl acetate were added to shrink the layer of the machine. It was purified by column chromatography to obtain A-15h35g. Modulation of A-15i • 7rc^mg was dissolved in TMf i〇00 mL and cooled to ^ gas. K mL of u m n-butyl chain was added dropwise thereto to make it stand at room temperature for 1 hour. Again i;n;7?if^DC1Sn(n'Bu)325-^^ @ ] Yangshui and diethyl bond, concentrated after liquid separation extraction, and purified by column chromatography to obtain A_i5i45g . A-15k was prepared in a pot, A-151 36 g, A l5j 13 g was dissolved in 500 mL of 2° hospital. : 2: Touch: the amount of Hua h3) 4 'heated under nitrogen environment = mix for five hours. After cooling to room temperature, add ethyl acetate, potassium sulphate = liquid for 3G minutes, then carry out liquid separation, step by step with water to organic, and order m to purify it by column chromatography. 15 g. Modulation of A-I5a A-15k 15 g, Mg 0.8 g were mixed in THF 3〇〇 mL t at 5〇t for hr. At 50 t, a solution of 151·151 4 g of NlCl2 (dppp) in a catalyst was added dropwise thereto. After mixing for 5 hours, add j to water and apply the green extract to the organic phase (4). This was purified by column chromatography to obtain A_15a2Qg. 74 201211165 Preparation of the exemplified dye A-15 11.7 g of the compound A-15a obtained above and 3.2 g of Z-1 were added to 120 ml of DMF, and the mixture was stirred at 70 ° C for 4 hours under a nitrogen atmosphere. Thereafter, 4-4'-(COOH)2-2,2'· was added and the mixture was heated and stirred at 160 ° C for 3.5 hours under a nitrogen atmosphere of 2.4 g and DMF 50 m. Thereafter, 53.2 g of ammonium thiocyanate was added thereto, and the mixture was stirred at 130 ° C for 5 hours under a nitrogen atmosphere. After concentration, 5 ml of water was added and filtered, and washed with diethyl ether. The crude purified material was dissolved in a methanol solution together with TBAOH (tetrabutylphosphoric acid) and purified by a Sephadex LH-20 column. After the fraction of the main layer was collected and concentrated, cerium nitrate was added, and the precipitate was filtered, and washed with water and diethyl ether to obtain 1.5 g of tetrabutylammonium salt of hydrazine-15. The purified product was dissolved in a methanol solution, and 1% nitric acid was added thereto, and the precipitate was filtered, and washed with water and diethyl ether to obtain Α-15 1.3 g. MS-ESIm/z =1644.61 (M-H) + [Chem. 30]

75 201211165 (Preparation of the exemplified dye A-1) A-la was prepared according to the method of the following scheme, and A-1 was prepared in the same manner as in the exemplified dye A-15. MS-ESI m/z = 843.94 (M-Η) + [Chem. 31]

A-ld A-lb K2C03 MeOH A-lf YV-rTVBr A-151

TMS-^ A-lc Pd(PPh3)2Cl2, CuI, TEA, THF

Modulation of Br A-ld A-lb 16 g was dissolved in THF 500 mL, and the amount of catalyst was added.

After Pd(PPh3)2Cl2, the amount of catalyst CuI and TEA 80 mL, add A_lc 9 8 g ', stir at 80 ° C for 24 hours, add water and di-methane, and concentrate the organic layer after liquid separation. Purification by column chromatography followed by A-ld 14 g. Modulation of A-lf The lid 13 g was dissolved in Me0H 200 mL, and 25 g of carbonic acid was added and stirred at 40 c for 5 hours. Water and ethyl acetate were added, and the organic phase extracted by liquid separation was concentrated and concentrated, and purified by column chromatography to obtain 76.

II 201211165 A-lf 6.0 g 0 A-la was prepared by dissolving A-151 9 g in THF 100 mL, adding catalyst amount of Pd(PPh3)2Cl2, catalyst Cul, TEA!20 mL, Adding eight-1 [6.0 g, stirring at 80 ° C for 24 hours] then adding water and dichloromethane, and concentrating the organic layer by liquid separation, and purifying by column chromatography to obtain 12 §. (Preparation of exemplified dye A-23) A_23a was prepared according to the method of the following scheme, and was carried out in the same manner as in the exemplified dye A-15 to prepare A-23°MS-ESIm/z = 108102 (MH) + 32]

Cd&gt; A-23b

NRS , DMF , 0B A*15j 03&quot;Br 〇3^Sn(n-Bu)3 Pd(PPh3)4 , 〇J-Q-E '... 一姚 A-23e A-23c A-23d

CuI^TEAJHF A-23f A-23g

Modulation of A-23c, two tH13: 4 g was dissolved in DMF 200 Torr, and NBS 18 ̄ solution was added for 5 hours. Thereafter, water and ethyl acetate were added to carry out a knife liquid to define an organic layer. It was purified by column chromatography to obtain 77 201211165 jyu^opif A-23c 19 g 〇 A-23d Preparation A-23c 19 g was dissolved in THF 200 mL and cooled to _78 Torr. Under a nitrogen atmosphere, 6 〇 mL of a 16 hexane solution of n-butyllithium was added dropwise thereto. Allow it to stand at room temperature and stir it for a few hours. After cooling again to _78 it was added ClSn(n-Bu)3 28 g. After allowing to stand at room temperature, the mixture was stirred for 12 hours, and then water and diethyl ether were added thereto, and the mixture was subjected to liquid separation and concentrated, and purified by chromatography &amp; chromatography to obtain A-23d 26 g. Modulation of A-23e A-23d 21 g, A-15j 13 g were dissolved in dioxane 3 〇〇 ml. = Adding the amount of catalyst Pd(PPh3)4, heating it under nitrogen atmosphere, and mixing it for five hours. After cooling to room temperature, add acetic acid, vaporized aqueous solution for 3G minutes, and weaving for liquid separation. , step by step to wash the organic phase with water. It was purified by column chromatography to obtain A_23e 10 g. The preparation of A-23f dissolves A-23e 7 g in THF 1〇〇mL _, and adds a 7% 2 $ g after adding catalyst Pd(m3)2Cl2, catalyst amount of CuI, TEA2〇mL, After 24 hours, water and dioxane were added, and the surface was separated and purified by column chromatography. The preparation of A_23g dissolved 6·〇g in Me〇H just wiped the towel and added carbonic acid. g, mixing at 40C for 5 hours. Water and ethyl acetate were added to separate the liquid. The organic phase was concentrated and purified by column chromatography to obtain A-23 g of 4.0 g. A-23a was prepared by dissolving A-23h 2.3 g in THF 50 mL, adding Aq5i 1.5 g after adding catalyst amount of Pd(PPh3)2Cl2, catalyst amount of CuI, TEA 10 mL, at 80 °C After stirring for 24 hours, water and dioxane were added, and the organic layer obtained by liquid separation was concentrated, and then purified by column chromatography to obtain 2.5 g of A-23a. D (Measurement of the maximum absorption wavelength of the dye) The maximum absorption wavelength of the dye used was measured. The results are shown in Table 1. The measurement was carried out using a spectrophotometer (manufactured by U-4100 (trade name), manufactured by Toray High-Tech Co., Ltd.), and the solution was adjusted so that the concentration was 2 μΜ using THF:ethanol = 1:1. 79 201211165 [Table i] Table 1 Sample No. Pigment No. Long-wavelength side maximum absorption wavelength (nm) Long-wavelength side absorption end Preparation 1-1 A-1 546 732 The present invention 1-2 A-9 585 800 The present invention 1- 3 A-15 574 792 The present invention 1-4 A-20 548 735 The present invention 1-5 A-21 550 740 The present invention 1-6 A-22 552 740 The present invention 1-7 A-23 552 788 The present invention 1- 8 A-24 578 805 1-9 A-25 598 812 of the present invention 1-10 A-26 605 820 of the present invention 1-11 A-27 605 820 of the present invention 1-12 B-1 535 705 of the present invention Comparative Example M3 B -2 525 681 Comparative Example 1-14 B-3 518 679 Comparative Example 1-15 S-2 450 600 Comparative Example 1-16 R-1 517 680 Comparative Example 1-17 R-7 533 710 Comparative Example 1-18 R -13 540 715 Comparative Example [Experiment 1] The photoelectric conversion element 10 shown in Fig. 1 was produced in the following manner. On the glass substrate, a transparent conductive film was formed by sputtering a fluorine-doped tin oxide, and the transparent conductive film was divided into two portions by scribing the laser. Next, 32 g of anatase-type titanium oxide (P-25 (trade name) manufactured by Aimoto Aerosil Co., Ltd.) was blended in 100 ml of a mixed solvent of water and acetonitrile in a volume ratio of 4:1, and rotation/revolution was used. The semiconductor fine particle dispersion liquid was obtained by uniformly dispersing and mixing with a mixing regulator of the formula. This dispersion liquid was applied onto a transparent conductive film, and heated at 500 ° C to prepare a light-receiving electrode. 201211165 jyuzopif Thereafter, a dispersion containing cerium oxide particles and rutile-type titanium dioxide was prepared in a ratio of 4 〇:6 〇 (by weight), and the dispersion was applied to the galvanic electrode at 5 ( The insulating porous body is formed by heating under Krc. Next, a carbon electrode is formed as a counter electrode. Next, the glass substrate on which the insulating porous body is formed is immersed in an ethanol solution of the sensitizing dye described in Table 2 below. 48 hours in (3χ1〇·4 m〇1/L). The glass dyed with the sensitizing pigment was immersed in 4% tributyl hydrazine in a 10% ethanol solution for 3 minutes, and then ethanol. It was washed and allowed to dry naturally. The thickness of the photoreceptor layer thus obtained was 1 μm, and the amount of semiconductor fine particles applied was 20 g/m 2 . The electrolytic solution used dimercaptopropyl propylidene rust (0.5 mol/ L), iodine (〇.1 m〇i/L) methoxypropionitrile solution. (Measurement of conversion efficiency) By passing a 500 W gas lamp (manufactured by Ushio Inc.) through AMI.5G filter Light sheet (trade name, manufactured by 〇riei Co., Ltd.) and chopper filter (KenkoL-42, trade name) A simulated sunlight containing no ultraviolet rays. The intensity of the light is 89 mW/cm2. The light is applied to the produced photoelectric conversion element'. The photoelectricity is measured by a current-voltage measuring device (Keithley 238, trade name, manufactured by Keithley Co., Ltd.). Conversion characteristics The results of measuring the conversion efficiency of the photoelectrochemical cell are shown in the following Table 2. The case where the conversion efficiency is 6.0% or more is expressed as a, and the case where 5% or more and less than 6% is expressed as B, and 4 is The case of % or more and less than 5% is expressed as C', and the case where 3% or more and less than 4% is expressed as D, and the case where 1.5% 81 201211165 or more and less than 3% is expressed as E, and less than 1.5% is expressed. For F, the case where the conversion efficiency is D or more is regarded as acceptable. The case where the conversion efficiency is less than D is considered as the failure. Moreover, the conversion efficiency after the continuous irradiation for 4 hours at 45% RH is evaluated as the initial value of the conversion efficiency as Durability: A case where the conversion efficiency after 400 hours is 90% or more with respect to the initial value is evaluated as A 'the case where 85% or more and less than 90% is evaluated as B, and 80% or more and less than 85%. Evaluation is C, will be more than 70% The case where less than 8〇% is evaluated as D, and the case where less than 70% is evaluated as e. Moreover, the stability is that the moisture content of the electrolyte is adjusted to the conversion efficiency of the sample after continuous irradiation for 200 hours. The evaluation is performed with respect to the initial value of the conversion efficiency. The case where the reduction rate with respect to the initial value is 10% or less is ◎, the case of 2%% to 1%% is used as the 〇, and the case of 30% to 20% is taken as △, 3〇% or more is taken as X. 82 201211165 [Table 2] Table 2 Sample No. Pigment Conversion Efficiency Durability Adsorption Stability Preparation 2-1 A-1 CC ο 2-2 A-20 CB 2-3 A-21 CB of the present invention 2-4 A-22 BA of the present invention ◎ 2-5 A-15 AA of the present invention ◎ 2-6 A-9 AB of the present invention ◎ 2-7 A-23 AB of the present invention . OB 2-8 A-24 AB ◎ 2-9 A-25 AB ◎ 2-10 A-26 AA of the invention ◎ 2-11 A-27 AA of the invention ◎ 2-12 B-1 DC of the invention Δ Comparative Example 2-13 B-2 DD Δ Comparative Example 2-14 B-3 EEX Comparative Example [Chem. 33]

B-3 83 201211165 It is understood that the dye of the present invention is excellent in conversion efficiency and durability, and is hardly affected by desorption due to water and the like, and is excellent in adsorption stability. [Experiment 2] Photoelectric conversion was carried out in the same manner as in Experiment 1 except that the glass substrate was impregnated with the dye solution dissolved in ethanol at the concentrations described in Table 3; The manufacture and measurement of components. The results are shown in Table 3. The case where the conversion efficiency is 7.0% or more is evaluated as A, the case where 6.0% or more and less than 7.0% is evaluated as B, the case where 5.0% or more and less than 6.0% is evaluated as C, and the case where less than 6.5% is evaluated as D. . [Table 3] Table 3 Sample No. % 5 1 Pigment Second Pigment Conversion Efficiency Preparation Pigment No. Concentration (xio-4 mol/L) Pigment No. Concentration (xlO·4 mol/L) 3-1 A-1 0.01 Rl 3 B The present invention 3-2 A-1 0.1 Rl 3 B The present invention 3-3 A-1 3 Rl 3 A The present invention 3-4 A-21 0.01 Rl 3 B The present invention 3-5 A-21 0.1 Rl 3 B The present invention 3-6 A-21 3 Rl 3 A The present invention 3-7 A-21 0.01 R-7 3 B The present invention 3-8 A-21 0.1 R-7 3 A The present invention 3-9 A-21 3 R-7 3 A 3-10 A-21 0.01 R-7 1 A The present invention 3-11 A-21 0.1 R-7 1 A The present invention 3-12 A-21 3 R-7 1 A The present invention 3-13 A-21 0.01 R-8 1 A 3-14 A-21 0.1 R-8 1 A of the present invention 3-15 A-21 3 R-8 1 A 3-16 Bl 0.01 Rl 3 D Comparative Example 3-17 Bl 0.1 Rl 3 D Comparative Example 3-18 Bl 1 Rl 3 D Comparative Example 84 201211165 [Experiment 3] An IT conductive film was formed on a glass substrate to prepare a transparent conductive film. Thereafter, the electroporation was used to form a porous film, whereby a transparent = electroformed emulsion semi-conductive plate was obtained to produce a photoelectric conversion efficiency; and the electrodes (1) to (5) were used.八乃忐 (1) ΙΤΟ (indium tin oxide) _ raw material compound indium trioxide (m) tetrahydrate 5 58 g and chlorination, made into the original yttrium for IT ϋ film (2) FTO (fluorine doped oxidation Tin) The solution of the raw material compound vaporized tin (iv) pentahydrate 0 701 g was dissolved in ethanol 1 〇 (5), and a saturated aqueous solution of 0.592 g of ammonium fluoride was added thereto, and the mixture was placed in an ultrasonic cleaning machine. The solution was completely dissolved in about 20 minutes to prepare a raw material compound solution for the film. (3) Production of ITO/FTO transparent conductive film The surface of a heat-resistant glass plate having a thickness of 2 mm was chemically cleaned, dried, and then placed in a reactor and heated by a heater. When the heating temperature of the heater is 450 ° C, the distance from the glass plate is set to 4 mm from a nozzle having a diameter of 0.3 mm at a pressure of 0.06 MPa, and the ITO film obtained in (1) is used. The raw material solution was sprayed for 25 minutes. After spraying the raw material compound solution for the ITO film, after 2 minutes 85 201211165, the surface of the glass plate is continuously sprayed with ethanol to suppress the rise of the surface temperature of the substrate) when the heating temperature of the heater becomes 5, The FT obtained in (7) under Article 1. The membrane compound solution was sprayed for 2 minutes and 3 seconds. In this way, an FT film having a thickness of 53 〇 nm and a thickness of n 〇 nm was sequentially formed on the hot glass plate, and a transparent electric power was obtained for comparison, and was separately fabricated on a pair of hot glass plates having a thickness of 2 mm. It is only a transparent electrode plate having a film having a thickness of (10) (10), and a transparent electrode plate having a thickness of only (10) (10). The three kinds of transparent electrode plates were heated in a heating furnace at 45 Torr for 2 hours. (4) Production of photoelectrochemical cell Next, using the above three kinds of transparent electrode plates, a photoelectrochemical cell of the structure of Fig. 2 of the Japanese Patent No. 4260494 was prepared. The oxide semiconductor porous film is formed by dispersing an average particle diameter of about 23 Å (10) of titanium oxide fine particles in acetonitrile to prepare a paste, which is applied to a transparent electrode by a bar coating method. The thickness was 15 μm, and after drying, it was calcined at 450X: for 1 hour. Thereafter, the pigment described in Table 4 was carried on the oxide semiconductor porous film. The impregnation conditions in the chromate solution were the same as in Experiment 1. Further, in the counter electrode, a conductive substrate in which a ruthenium film and an FTO film are laminated on a glass plate is used, and an electrolyte solution composed of an aqueous solution of iodine/hardened material is used for the electrolyte layer. The planar size of the photoelectrochemical cell is 25 86 201211165 jyuzopif mm&gt;&lt;25 mm ° (5) Evaluation of photoelectrochemical cell The photoelectrochemical cell obtained in (4) is irradiated with simulated sunlight (AM1.5) by experiment with In the same manner, the photoelectric conversion characteristics were measured to determine the conversion efficiency. The results are shown in Table 4. A case where the conversion efficiency is 6.0% or more is expressed as A, a case where 5% or more and less than 6% is expressed as B, and a case where 4% or more and less than 5% is expressed as C, and 3% or more and less than 4% are expressed. The case is represented by D, and the case where 1.5% or more and less than 3% is expressed as E' is expressed as F in the case of less than 1.5%, and the case where the conversion efficiency is D or more is regarded as qualified. In addition, as the durability, the case where the conversion efficiency after 400 hours is 90% or more with respect to the initial value of the conversion efficiency is evaluated as A, and the case where 85% or more and less than 90% is evaluated as B, and 80% or more. In the case of less than 85%, it is evaluated as C', and 70% or more and less than 80% is evaluated as d, and less than 70% is evaluated as E. [Table 4] Table 4 Sample No. Conductive film ITO only pigment (concentration lxlC^mol/L) A-20 '2nd pigment (concentration lxl^mol/L) conversion efficiency durability

87 201211165 jyKj^KJu 4-11 FTO only A-27 - BB Not invented 4-12 ITO+FTO A-27 - AB Not invented 4-13 ITO B-3 only - ED Comparative example 4-14 FTO only B-3 - ED Comparative Example 4-15 ITO+FTO B-3 - ED Comparative Example 4-16 ITO only A-20 Rl CC Present invention 4-17 FTO only A-20 _ Rl C c 4-18 ITO+FTO A of the present invention -20 _ Rl B c Invention 4-19 ITO A-20 R-7 B c Only 4-20 of the invention FTO A-20 R-7 B c 4-21 ITO+FTO Γ A-20 _ R of the present invention -7 A c 4-22 of the invention only ITO A-20 R-8 B c 4-23 of the invention only FTO A-20 R-8 B c 4-24 ITO+FTO A-20 _ R-8 A of the invention c According to the present invention, the conversion efficiency is low in the case of a comparative dye, and the use of the exemplary dye of the present invention shows a good result. As a transparent electrode plate, in a photoelectrochemical cell using a transparent electrode plate in which an ITO film and an FT film are laminated, compared with a case where a transparent electrode plate in which only an ITO film is formed or only an FTO film is formed is used. In particular, the conversion efficiency is high, and this effect is high in the pigment of the present invention. [Experiment 4] A collector electrode was placed on the FTO film to prepare a photoelectrochemical cell, and the conversion efficiency was evaluated. The evaluation was carried out as follows, and two types of test unit (i) and test unit (iv) were used. (Test unit (i)) For heat-resistant glass of length 10〇mmx width 100mmx thickness 2mm: surface, chemically cleaned, after drying, the glass plate is heated by a heater, and the diameter is 03 mm. And the pressure of the oblique μ 06 ΜΡ &amp; 'will be set to 400 mm from the glass plate. The compound FT 〇 (doped tin oxide) film prepared in Experiment 2 is shouted for 25 minutes with the original «, ready to be attached with FTO Film glass 88 201211165 substrate. = The surface is formed by a rhyme method to form a groove having a depth of 5 μπ1 and a 电路 sub-circuit pattern. After the pattern is formed by the photolithography method, it is made rotten. In order to be able to perform electroforming, a metal conductive layer (seed layer) is formed on the / ore reduction method, and further: A metal wiring layer is formed by plating (addlt1Veplatlng). Metal, and good: The surface of the transparent substrate is formed into a convex lens shape up to a height of 3 μη. The circuit width is 60 handsome. From this, the electrode substrate (1) was fabricated by the spD method using the squat leg = dry and ^/ as a shielding layer. Another 2 04 ^ (ϊ) 2004-146425 The shape shown in Figure 2 of the towel. An oxidized fraction of 25 legs was applied to the electrode substrate (1) at an average of 450. . Heating and sintering were carried out for 1 hour. The color of the towel is not colored. The liquid towel is immersed for 4 minutes to carry the FTO Aik. The heat of the recording material is thin, and the resin is splashed. The arrangement of the resin sheet is thermally melted to fix the two plates. θ, the liquid injection port of the electricity opened from the front side of the front side of the splashing, is divided into 1=5 two dish salt and 〇.05 m hard methoxy acetonitrile solution. Further, an epoxy-based sealing resin pair was used: A test unit (1) was produced. The simulated sunlight n of the mine 5 was irradiated by the same unit (1) as the experiment 其. The results are shown in Table 5. Get rich. 89 201211165 jyuzopif (test unit (iv)) A glass substrate with an FTO film having a length of 1 mmx and a width of 100 mm was prepared by the same method as the test unit (i). A metal wiring layer (gold circuit) is formed on the FTO glass substrate by an additional plating method.嗲=属 The wiring layer (gold circuit) is formed in a lattice shape on the surface of the substrate, and the circuit width is 50 μm and the circuit thickness is 5 μm. An electrode substrate $iv) was formed by forming an FTO film having a thickness of 300 nm on the surface thereof by an SPD method as a shielding layer. The cross section of the electrode substrate (iv) was confirmed using SEM-mDX, and as a result, there was a sneak at the bottom of the wiring due to the hem of the protective layer of the electric bond, and the shadow portion was not covered with the FTO. 'Such as. Using the electrode substrate (iv), a test unit (iv) was produced in the same manner as in the test unit (i). The conversion efficiency was measured by irradiating the simulated sunlight of am15 in the same manner as in Experiment 1. The results are shown in Table 5. The results of measuring the conversion efficiency of the photoelectrochemical cell are shown in Table 5 below. The case where the conversion efficiency is 6.0% or more is expressed as a, the case where 5% or more and less than 6% is expressed as B', and the case where 4% or more and less than 5% is expressed as C' will be 3 °/. The case where the above is less than 4% is expressed as d, and the case where 1.5% or more and less than 3% is expressed as E, and the case where less than 1.5% is expressed as F 'the case where the conversion efficiency is D or more is qualified, and less than d The situation is unqualified. Further, as a long-term property, the conversion efficiency after continuous irradiation for 4 hours at 45% RH is 90% or more with respect to the initial value of the conversion efficiency, and it is evaluated as A, and 85% or more and less than 90%. The evaluation was B', and 80% or more and less than 85% were evaluated as C, 70% or more and less than 80% were evaluated as D, and less than 70% was evaluated as E. 201211165 39026pif [Table 5] Table 5

The pigment of the present invention is relatively inferior to the performance even if the unit is changed. </' [Experiment 5] This is an oxide + conductor film prepared by peroxidizing and titanium oxide fine particles. Using this oxide semiconductor film, a photoelectricized wind (photovoltaic) to a photoelectrochemical cell (D) was produced and evaluated. Preheating / (Photoelectrochemical cell (A)) (1) Adjustment of coating liquid for forming an oxide semiconductor film (A) 5 g of titanium hydride was suspended in 1 liter of pure water at a concentration of 5 wt% of % soil 400 g of hydrogen peroxide solution, followed by heating to 8 (rc 2, adding a solution of peroxotitanic acid added. From the total amount of the solution, take 9 〇 solution and add concentrated ammonia to adjust to ρΗ 9, let go to high pressure dad In::(°下201211165 jyu^opif 5 hours of hydrothermal treatment to prepare a sulphur dioxide colloid Π ray diffraction can be seen that the obtained titanium dioxide colloidal particles are,,,,,,,,,,,,,,,, Next, the dioxocene granules obtained above are mixed with the peroxygen solution, and the propylene cellulose is added as a film forming aid in the manner of the weight conversion of the titanium in the weihe solution to prepare a semiconductor. (2) Production of oxide semiconductor film (A) Next, 'the fluorine-doped tin oxide is formed as an electrode layer = the coating liquid (4)), and is naturally dried, and then: Irradiation _ 〇 1 1 ^ UV, decomposition of peroxyacid and 吏 = hardening, assigning 3G to the coating film The heating of the clock is carried out in half; and the annealing and the annealing are performed on the glass substrate (3) on the oxide semiconductor film (A). Next, the concentration of the dye of the present invention is adjusted to 3xl〇-4. Mo/L by B is a sensitizing dye. The pigment solution was applied to the metal oxide semiconductor film (A3) by a spin coater of 100 rpm to be dried. This coating and drying step was performed 5 times. (4) The electrolyte solution is prepared in a mixed solvent of acetonitrile and ethylene carbonate in a volume ratio of 1:5, = tetrapropyl fluorene is (10) mol / liter, and its secret is 0.07 mol / liter. The concentration of the electrolyte solution is adjusted. (5) Production of photoelectrochemical cell (A) 92 201211165 f (3) The oxide semiconductor produced by the film is formed as a f-:electrode's transparent glass substrate with fluorine-doped tin oxide. The resin is sealed on the side surface to form an electrolyte solution between the electrodes, and the electrodes are connected by wires to form a photoelectrode (4). (6) Evaluation of photoelectrochemical cell (A) As a photoelectrochemical cell (A), light of an intensity of 100 m was irradiated by a solar simulator to measure η (conversion efficiency), and the results are shown in Table 6. (Photoelectrochemical cell (Β)) _ Irradiation of ultraviolet peroxide to decompose peroxyacid, hardening of the film, and ion irradiation of Ar gas (Ion implantation apparatus manufactured by Nisshin Electric Co., Ltd., irradiation at 2 〇〇eV for 10 hours) Other than this, the oxide semiconductor film (B) is formed in the same manner as the oxide semiconductor film (A). The oxide semiconductor film (B) is adsorbed by the dye in the same manner as the oxide semiconductor film (A). "The photoelectrochemical cell (B) was then produced by the same method as the photoelectrochemical cell (B), and η was measured. The results are shown in Table 6. (Photoelectrochemical cell (C)) 18.3 g of the The vaporized titanium was diluted with pure water to obtain an aqueous solution containing 1·〇wt% in terms of Ti〇2, and the aqueous solution was stirred while adding a concentration of 15 wt% of ammonia water to obtain a white slurry having a pH of 9.5. The charge was filtered and washed to obtain a block of hydrated titanium oxide gel in an amount of 10.2 wt% in terms of Ti Ο 2 . The block was mixed with 5 wt% of peroxygen 93 201211165 ~J ^ \ J4~t\j \ji hydrogenation solution 400g is mixed, and then heated to 8〇&lt;=c to dissolve and prepare a solution of peroxotitanic acid. From the total amount of the solution, 9〇v〇1&lt;) / The concentrated ammonia water was added thereto to adjust the pH to 9, and it was placed in an autoclave at 25 ° C. The hydrothermal treatment was carried out for 5 hours under a saturated steam pressure to prepare titania colloidal particles (C). The peroxotitanic acid solution obtained above and the titania colloidal particles (C) are carried out in the same manner as the oxide semiconductor film (A). The oxide semiconductor film (6) is formed, and the dye of the present invention is adsorbed as a spectral sensitizing dye in the same manner as the metal oxide semiconductor (A). Thereafter, it is produced by the same method as the photoelectrochemical cell (A). Photoelectrochemical cell (C) 'Measurement of η. The results are shown in Table 6. (Photoelectrochemical cell (D)) The titanium oxide of 18·3 g was diluted with pure water to obtain a conversion of 丁1〇2. It contains 1.0 wt% of an aqueous solution, while stirring it, adding 15 wt% of ammonia water to the surface to obtain a white slurry having a pH of 9.5. The slurry is filtered and washed, and suspended in pure water. A slurry of hydrated titanium oxide gel as 耵〇2 and 0.6 wt% was added thereto, and hydrochloric acid was added thereto; after pH 2, it was placed in an autoclave, under a crucible rib and under a saturated vapor pressure. The titanium dioxide colloidal particles (d) were prepared by hydrothermal treatment for 5 hours. # Next, the titanium dioxide colloidal particles (D) were concentrated to 1% by weight, and hydroxy group was added thereto in a ratio of 3 〇% by weight in terms of Ti〇2. Preparation of a coating liquid for forming a semiconductor film by using a propyl group as a film forming aid The person applies the coating liquid on a transparent glass substrate in which fluorine-plated tin oxide is formed as an electrode layer, and performs natural drying, and then uses a low-pressure mercury lamp to irradiate 6000 mJ/cm 2 according to 94 201211165 〇yvz.Oy\f. Ultraviolet rays are used to cure the film. Further, the hydroxypropylcellulose is decomposed and annealed by heating for 30 minutes under a temperature of 3 Å to form an oxide semiconductor film (D). Next, an oxide semiconductor film (Α) The adsorption of the dye of the present invention is carried out in the same manner as a spectral sensitizing dye. Thereafter, a photoelectrochemical cell (D) was produced by the same method as the photoelectrochemical cell (Α). The photoelectrochemical cell (Α) to the photoelectrochemical cell (d) was irradiated with simulated sunlight (ΑΜ1.5). The photoelectric conversion characteristics were measured by the same method as in Experiment 1 to determine the conversion efficiency. The case where the conversion efficiency is 6.0% or more is expressed as A, the case where 5% or more and less than 6% is expressed as Β, the case where 4% or more and insufficient is expressed as C, and the case where 3% or more and less than 4% is expressed. In the case of D, 1.5% or more and less than 3% are represented as Ε, less than 1.5% is represented as f, conversion efficiency is d or more as a pass, and less than D is considered as a failure. Further, as the durability, the case where the conversion efficiency after 400 hours at 45% RH is 9% or more with respect to the initial value of the conversion efficiency is evaluated as A, and the case where 85% or more and less than 90% is evaluated as B, the case where 8〇% or more and less than 85% is evaluated as C, the case where 70% or more and less than 8〇% is evaluated as D, and the case where less than 70% is evaluated as E. 95 201211165 [Table 6] Table 6 Sample No. Photoelectrochemical Cell 1st Pigment 2nd Pigment Conversion Efficiency Durability Test 6-1 (A) A-21 - BB Present Invention 6-2 (B) A-21 - BB Invention 6-3 (C) A-21 - BB The present invention 6-4 (D) A-21 - CB The present invention 6-5 (A) A-9 - AB The present invention 6-6 (B) A-9 - AB The present invention 6-7 (C) A-9 - AB The present invention 6-8 (D) A-9 - BB The present invention 6-9 (A) A-15 - AA The present invention 6-10 (B) A- 15 - AA 6-11 (C) A-15 - AA of the present invention 6-12 (D) A-15 - BA of the present invention 6-13 (A) A-27 - AB of the present invention 6-14 (B) of the present invention A-27 - AB 6-15 (C) A-27 - AB of the present invention 6-16 (D) A-27 - BB of the present invention 6-17 (A) B-2 - DD Comparative Example 6-18 ( B) B-2 - DD Comparative Example 6-19 (C) B-2 - DD Comparative Example 6-20 (D) B-2 - DD Comparative Example 6-21 (A) A-21 Rl AB The present invention 6- 22 (B) A-21 Rl AB The present invention 6-23 (C) A-21 Rl AB The present invention 6-24 (D) A-21 Rl BB The present invention 6-25 (A) A-21 R-7 AB The present invention 6-26 (B) A-21 R-7 AB The present invention 6-27 (C) A-21 R-7 AB The present invention 6-28 (D) A-21 R-7 BB The present invention 6-29 (A) A-21 R-8 AB Invention 6-30 (B) A-21 R-8 AB The present invention 6-31 (C) A-21 R-8 AB The present invention 6-32 (D) A-21 R-8 AB The present invention is based on Table 6 In the case of the pigment of the present invention, the conversion efficiency is higher in the case of using the photoelectrochemical cell (A) to the photoelectrochemical cell (C). 96 201211165 J^uzopif [Experiment 6] Preparation of titanium oxide by changing the method The oxide semiconductor film was produced from the obtained oxidized crystal, and a photoelectrochemical cell was prepared and evaluated. (1) Preparation of titanium oxide by heat treatment method (titanium oxide 1 (brookite type), etc.) Using a commercially available anatase type titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name ST-01), it is heated to It was converted into brookite-type titanium oxide at about 900 ° C, and further heated to about 1,200 ° C to prepare rutile-type titanium oxide. These were sequentially compared to titanium oxide 1 (anatase type), titanium oxide i (brookite type), and comparative yttrium oxide 2 (rutile type). (2) Synthesis of titanium oxide by wet method (titanium oxide 2 (brookite type)) 954 ml of distilled water was placed in a reaction sample with a reflux condenser, and the temperature was raised to 95 °C. While maintaining the stirring speed at about 2 rpm and diversifying into the distilled water, 46 ml of an aqueous solution of titanium tetrachloride (Ti content of 16 3 wt%, specific gravity of 1.59, purity of 99.9%) was about 50 ml. The speed of /min was added dropwise to the reaction tank. At this time, it is noted that the temperature of the reaction liquid is not lowered. As a result, the concentration of the four mice was 0·25 mol/Ι (2 wt% in terms of oxidation). After the reaction solution was added dropwise to the reaction vessel, the reaction was continued at the beginning of the whiteness, and after the completion of the dropwise addition, it was further advanced to two points (1〇4. 〇, and kept in this state for 60 minutes to completely terminate the reaction. The sol obtained by the reaction was secondarily formed into a powder using a vacuum dryer of 60 Torr. The powder was subjected to quantitative analysis by the X-ray diffraction method. The result of the analysis of the powder was 97 201211165 (the peak intensity of the 121 surface of the brookite type) / (the peak intensity at the position where the three overlaps) The ratio of 〇38, (the main peak intensity of the rutile type) / (the peak intensity at the position where the two overlaps) is 0.05. From this, the titanium oxide is obtained as a plate. The titanate type is about 70% by weight, the rutile type is about 12% by weight, and the anatase type is about 28.8 wt%. Moreover, the fine particles are observed by a transmission electron microscope, and the result is 丨. The average particle diameter of the secondary particles is 0.015 μηη. (Titanium oxide 3 (brookite type)) An aqueous solution of titanium tri-titanate is distilled water (Ti content is 28 wt%, specific gravity is 1.5, purity is 99.9 〇/〇) _ A solution of 0.25 mol/L in terms of titanium concentration. Ice-cooling is performed so that the liquid temperature does not rise, and is kept below 50 ° C. Next, 5 〇〇 ml of the solution is poured into a reaction jet with a reflux condenser, and the surface temperature is raised to an anti-surface self-ozone gas generating device. Ozone gas having a purity of 8 〇% was bubbling at 1 L/min, and was subjected to an oxidation reaction. The reaction was completed in a state of 5 hr for 2 hours, and the reaction was completely completed. The obtained sol was filtered and vacuum dried. ^. At the end of the quantitative analysis of the powder by the X-ray diffraction method, (the peak intensity of the brookite-type 121 surface) / (the peak intensity at the position of the three overlaps) is 0.85, (rutile type The main peak intensity) / (the peak intensity at the position where the three overlaps) is 0. The titanium oxide obtained according to the above has a plate titanium expansion of about 98 Wt%, a rutile type of 〇wt%, and an anatase type. 〇wt%, about 2% is amorphous. Moreover, by observing the fine particles by penetrating f, the average particle size of the primary particles is 〇〇5. The dye-sensitized photoelectric conversion Production and evaluation of components) 98 201211165 jyuzopif conductor will make up Recording 1 ~ Oxygen 3 as a half-two == using a photoelectrochemical cell having a photo-electrochemical cell of the present invention, coating the tin oxide on the substrate of the phototransfer substrate of FIG. A transparent electric cloth method of cerium oxide particles as a raw material paste is applied to a thickness of 5 〇 〇 on the electrode surface by a bar Ϊ =, and then calcined at 5 〇 = to form a thin layer having a film thickness of about 20 μm.仃Prepare the ethanol solution of the pigment shown in Table 7 (the pigment concentration is 3x10.4 mol/L', and the ith pigment concentration is set to mol/L when two kinds of pigments are used) The glass substrate of the layer is at room temperature for four hours. As a result, the pigments are adsorbed to the titanium oxide. A photoelectric conversion element having a configuration shown in Fig. 1 of Japanese Laid-Open Patent Publication No. 2000-340269 was produced by using a solution of a salt of a tetrapropylammonium salt and a solution of a molybdenum solution as an electrolytic solution and using platinum as a counter electrode. As for the photoelectric conversion, the above-mentioned element was irradiated with light of a high-pressure mercury lamp of 160 W (the infrared portion was cut by a filter), and the conversion efficiency was measured by the same method as the experiment. The results are shown in Table 7. The case where the conversion efficiency is 6.0% or more is expressed as A, the case where 5% or more and less than 6% is expressed as B', and the case where 4% or more and less than 5% is expressed as C, and 3% or more and less than 4% The case is expressed as d, the case where 1.5% or more and less than 3% is expressed as E ' is expressed as F in the case of less than 1.5%, and the case where the conversion efficiency is D or more is regarded as qualified, and the case of 99 it 201211165 which is insufficient is regarded as not qualified. Further, as the durability, the conversion efficiency after continuous irradiation for 4 hours at 45% RH is 90% or more with respect to the initial value of the conversion efficiency, and it is evaluated that A' is 85% or more and less than 90%. In the case of B, 80% or more and less than 85% are evaluated as C, 70% or more and less than 80% are evaluated as d, and less than 70% is evaluated as E. [Table 7] Table 7 Sample Preparation Titanium 1st Pigment 2nd Pigment 0.1 mM Conversion Efficiency Durability Test 7-1 Titanium Telluride i A-27 - AB The present invention 7-2 vaporized titanium 2 A-27 - AB 7-3 titanium oxide 3 A-27 - AB of the present invention 7-4 titanium oxide 1 A-15 - AA 7-5 titanium oxide 2 A-15 - AA of the present invention 7-6 titanium oxide 3 A- of the present invention 15 - AA 7-7 titanium oxide 1 A-25 _ AA of the present invention 7-8 titanium oxide 2 Α·25 - AA of the present invention 7-9 vaporized titanium 3 Α-25 - AA 7-10 gasification of the present invention钦1 Α-1 - CC 7-11 titanium oxide 2 Α·1 - CC of the present invention 7-12 titanium telluride 3 Α-1 - B c 7-13 of the present invention Titanium 1 Bl - D c Comparative Example 7 -14 Titanium telluride 2 Bl - D c Comparative Example 7-15 Oxidation 3 Β·1 Preparation D c Comparative Example 7-16 Oxidation 1 Α-1 Rl B c The present invention 7-17 vaporized titanium 2 Α-1 Rl B c The present invention 7-18 gasification qing 3 Α-1 Rl C c The present invention 7-19 vaporized titanium 1 Α-1 R-7 A c The present invention 7-20 silver oxide 2 Α-1 R-7 A c 7-21 Oxidation 3 Α-1 R-7 B c of the present invention 7-22 Gasification 1 Α-1 R-8 A c The present invention 7-23 Oxidation: k 2 Α-1 R-8 A c 7-24 titanium oxide 3 Α- 1 R-8 A c Inventive [Experiment 7] The semiconductor fine particles were produced by using the following titanium oxide having different particle diameters. 100 201211165 = The use of the paste to prepare a photoelectrochemical cell was carried out, and the characteristics were evaluated. [Preparation of paste] (Paste 1) T-shaped particles (anatase type, average particle size is 25 nm, particles n are put into the solution, and the mixture is mixed with titanium oxide (4). Secondly, titanium dioxide. (4) Adding a thick cellulose-based binder to the machine, and mixing it with the agent (paste 2) = shape Ti02 particles 1 and other balls% Ti〇2 particles (anatase to touch ^ particle size is fine, Hereinafter, the spherical Ti〇2 particles 2) are placed in a solution to be mixed, thereby preparing the dioxins (4). Secondly, the titanium (10) is added as a cellulose binder, and the preparation is carried out. _ 2 (τκ) 2 particle weight: Weight = 30: 70). (Paste 3) The paste/11 1 and the rod-shaped Ti〇2 particles (anatase type, diameter 1 〇〇 =, lateral ratio 5 Å or less are referred to as rod-shaped Ti 〇 2 particles 〇 mixed = rod Weight of Ti〇2 particle i: weight of paste i = paste 3. (Paste 4) i and rod-shaped Ti〇2 particles! Mix and modulate the shape of rod Ή〇2 *1 1 weight: paste The weight of the agent 1 = 30: 7 糊 paste 4. (Paste 5) The paste 1 and the rod-shaped Ti 〇 2 particles j are mixed to prepare a rod-shaped chat 101 201211165 The weight of the particle 1! Weight = 50 : Paste 5. (Paste 6) Paste 1 and slab-shaped mica particles (straight 6, hereinafter referred to as slab-like primordial ^, 丄 ^ only to the weight of sub-1: _ ΓΓΓ weight Γ mixing, modulating slab-like mica (paste 7) 0: 80 paste 6. Paste 1 and rod-shaped TM2 particles (anatase type, diameter nm, aspect ratio of 6 3, 乂Only horse 3〇

Hi rod tTM2 particles 2) think together, paste 7. The weight of the paste 2, the weight of the paste 1 = 30: 7 〇 (paste 8) The paste 1 and the rod-shaped grain nm, the vertical 糌 fc Helmet, the ah and the 1 work horse 5 〇 (four) It is called a rod-shaped Tl〇2 particle 3) and it is made to see a person modulating a rod-shaped TiO 2 particle 3 夕 tongue 曰., electric gong, paste 8. The weight of child 3! The weight of the paste I = 30, (paste 9) The paste I and the rod-shaped Tl 〇 2 grains nm, the aspect ratio is 5.8, the following 谧焱怯 仫 is 75 modulation rod shape (10) particles = rod, Particle 4) Force, Paste 9. Weight of 1000%. Weight of paste I=30: 7〇(paste 10) Word paste 1 and rod-shaped Tl〇2 particles (anatase type, diameter) Surface, aspect ratio is 5.2 Modulation rod The weight of the TM2 particles 5: = 〇 2 particles 5) The weight of the paste. The weight of the paste 1 = 30: 7 〇 102 201211165. j^uzopif paste 10. (Paste 11) The TM2 particles of the nm and the longitudinal rod shape (the anatase type, the diameter of the 180-shaped rods, and the 〇2 particles are referred to as the TM2 particles 6 in 6 cases) are mixed, and the paste 11 is mixed. 'Heavy weight · Paste 1 weight = 30: 70 (paste 12) nm rod-shaped TM2 particles (anatase type, diameter, modulation rod =:: 7 under = = paste 12). Reset. Paste 1 weight = 30: 70 (paste 13) Particles (anatase type, diameter no = ^ 〇 2 particle 8 weight: paste weight one. (paste 14) The paste 1 and the rod-like particles (the sharp aspect ratio is 3.4, hereinafter referred to as the rod-shaped Ti 2 particle 9), and the weight of the rod-shaped Ti 2 particles 9 is prepared: paste 2 ^, paste 14. Liri 30 · 70 (photoelectrochemical cell 1) In the order shown below, the photo electrode 12 of the 5th article of the Japanese Patent Laid-Open No. 74 In the same manner as the photo-sensing type solar cell 20 described in FIG. 3 of Japanese Laid-Open Patent Publication No. 2002-289274, the photoelectrode is further used. A photoelectrochemical cell of a scale of 1 〇mmxl 〇 mm. A transparent electrode having a fluorine-doped Sn 〇 2 conductive film (having a film thickness of 500 nm) formed on a glass substrate is prepared, and the Sn 〇 2 conductive 臈The above-mentioned paste 2 is screen-printed and dried, and then dried in the air under conditions of 45 (rc), and the paste 4 is further used to repeatedly perform the screen printing and the baking. On the conductive film, a semiconductor electrode having the same structure as that of the semiconductor lightning pole 2 shown in FIG. 5 of the above-mentioned patent document is formed (the area of the light-receiving surface is 1 () plane _ mm, the layer thickness is 〇 、, and the semiconductor layer is The layer thickness is 6 qing, the light scattering sound is 4 _, and the rod-shaped Ti 〇 2 particles contained in the light scattering layer have a ratio of 3 to 3, and a photoelectrode containing no sensitizing dye is prepared. But adsorbed on the semiconductor electrode. The first; the pigment concentration _ 苴, in the ^ agricultural degree is L), the modulation of the pigment solution. The total amount of adsorption about the color #, t body electrode on the pole (hole _ 屌 屌 屌 屌^The same shape and size of the electrode, the thickness is 100 nm) as the opposite electrode, the nozzle system and the magnetization clock of the lanthanide redox solution as the electrolyte entanglement 104 201211165 ^yuzopif has the same size as the half (four) electrode a spacer S (trade name "Surlyn") made by DuPont As shown in FIG. 3 of Japanese Laid-Open Patent Publication No. 2002-289274, the photoelectrode 10 is completed by interposing the spacer s with the counter electrode CE, and the above-described electrolyte is filled thereinto to complete the photoelectrochemical cell 1. Battery 2) The photoelectrode shown in Fig. i described in Japanese Laid-Open Patent Publication No. 2002-289274 is produced in the same manner as in the photoelectrication of the battery 1 except that the semiconductor electrode is produced in the following manner. A photoelectrochemical cell 2 having the same configuration as that of the color-sensing type solar cell 20 described in Japanese Unexamined-Japanese-Patent No. 74-A. The paste 2 was used as a paste for forming a semiconductor layer. Then, the = electric film is _ 卩 brush _ 2, and then it is dried under +, 45 () ^ conditions to form a semiconductor layer. Further, = 丨 is used as the innermost layer forming paste of the light-scattering layer. Agent. Then, a paste scattering layer is formed with t as the outermost layer of the light-scattering layer. ^Electrochemical cell 1 is similarly formed on the semiconductor layer, and then formed on the conductive film of QA u 2002-289274 &gt; 2 with the semiconductor electrode 2 shown in Fig. 1 described in Japanese Patent Laid-Open Publication No. : semiconductor electrode (the light-receiving * _ = the thickness of the layer of the second layer is 4 (10), the layer thickness of the semiconductor layer is 3 qing, the innermost

曰", her, the innermost layer contains the rod-shaped Ti〇2 particles J 105 ~ ir 201211165, the content of Η) wt%, the outermost layer of the rod-shaped Ti 〇 particles + ^ is Called 11, the innermost is the first electrode without sensitization color. 5ΰ wt%) 'The compartment _ makes the photoelectrode and the relative electric charge: the electrolyte is completed to complete the photoelectrochemical cell 2. 1P filling (photoelectrochemical cell 3) In the production of a semiconductor electrode, a paste is used, and a paste 4 is used as the light 1 as a semiconductor layer. The paste is formed by I### and band a as the first layer, and by the other. The photoelectrode shown in Fig. 5 of the ninth publication of the first electrochemical cell i; the photoelectrochemical cell 3 having the same configuration as the subcell 20 of the (4) sub-cell No. 2__. mm, H, f In the conductor electrode, the area of the light-receiving surface is 10 mm×10, and the layer thickness of the semiconductor layer is 5 μm, and the light-scattering layer contains the impurity particles κ (photoelectrochemical cell 4) contained in the silk layer. When manufacturing a semiconductor electrode, paste 2 is used as the photoresist paste 6 as a paste for forming a plating layer, and the same chemical battery 1 is used. In the order of the photovoltaics shown in Fig. 5, the money electrode and the photovoltaic pre-cell 4 having the same configuration as that of the photo-electrical battery of the Japanese version of the Japanese Patent Laid-Open No. _289274. In the semiconductor electrode, the light-receiving surface is mm×10 mm, the layer thickness is 10 μm, and the thickness of the semiconductor layer is 6 5 , 106 201211165. The layer of the jyuzopif light-scattering layer is 3.5 μm, and the plate-like mica contained in the light scattering layer In the case of producing a semiconductor electrode, the paste 2 is used as a paste for forming a semiconductor layer, and the paste 8 is used as a paste for forming a light-scattering layer, and the paste is used as a paste for forming a light-scattering layer. The photoelectrochemical cell 5 is produced in the same manner as the photoelectrochemical cell 1. The content of the rod-shaped Ti〇2 particles 3 contained in the light-scattering layer of the semiconductor electrode is wt%. (Photoelectrochemical cell 6) In the case of producing a semiconductor electrode, the paste 2 is used as a paste for forming a semiconductor layer, and the paste 9 is used as a paste for forming a light-scattering layer, and a photoelectrochemical cell 6 is produced in the same order as the chemical battery 1 is used. . In addition, the content ratio of the rod-shaped Ti 2 particles 4 contained in the light-scattering layer of the conductor electrode is % wt%. (Photoelectric cell 7) When the semiconductor electrode is manufactured, the paste 2 is used as the semiconductor layer. In the paste, the paste 10 is used as a paste for forming a light-scattering layer, and the photoelectrochemical cell 7 is produced in the same manner as the photo-chemical cell 1. The light-scattering layer of the conductor electrode is contained in the light-scattering layer. The content of the rod-shaped Ti 2 particles 5 is 30 wt%. (Photoelectric ray battery 8) When the semiconductor electrode is manufactured, the paste 2 is used as a paste for forming a semiconductor layer, and the paste 11 is used as a light scattering layer. A photoelectrochemical cell 107 201211165 owzopif 8 was produced in the same order as the light chemical cell 1 except for the paste for formation. Further, the content of the rod-shaped TiO 2 particles 6 contained in the light-scattering layer of the conductor electrode was 30 wt%. In the production of the conductor-conducting electrode, the paste 2 is used as the paste for forming a semiconductor layer, and the paste 13 is used as the paste for forming a light-scattering layer, and the same as the photoelectrochemical cell 1 except for I. The photoelectrochemical cell 9 was fabricated in the order. Further, the content of the rod-shaped Ti 2 particles 8 containing # in the light (4) of the semiconductor electrode was 30 wt%. (Photoelectrochemical cell 10) When the semiconductor electrode is manufactured, 'paste 2 is used as a paste for forming a semiconductor layer, and paste 14 is used as a layer for forming a new layer, and the same procedure as in the case of photoelectrochemical cell is used. A photoelectrochemical cell 10 is fabricated. Further, the content of the rod-like particles 9 contained in the light-scattering layer of the '+ conductor electrode was 30 wt%. (Photoelectrochemical Cell 11) When manufacturing a semiconductor electrode, a semiconductor electrode composed of only a semiconductor layer is formed using only the paste 2 (the area of the light receiving surface is

A photoelectrochemical cell n was produced in the same order as the photoelectrochemical cell except that 10 mm x 10 mm and a layer thickness of 10 μm were used. (Electrochemical Cell 12) In the case of manufacturing a semiconductor electrode, 'paste 2 is used as a paste for forming a semiconductor layer', and paste 7 is used as a paste for forming a light-scattering layer, and the same procedure as that of photoelectrochemical cell 1 is used. A photoelectrode and a comparative photoelectrochemical cell 12 were fabricated. Further, the content of the 102 201211165 J^uzopif rod-shaped Ti 2 particles 2 contained in the light-scattering layer of the semiconductor electrode was 30 wt%. [Test and evaluation of characteristics] The photoelectrochemical cell 1 to the photoelectrochemical cell 12 were irradiated with a xenon lamp through an AM1.5 filter using a solar simulator (manufactured by WACOM, WXS-85H (trade name)).模拟W/m2 simulated sunlight. The turbulence-voltage characteristics were measured using an I-V tester to determine the conversion efficiency. The results are not shown in Table 8. The case where the conversion efficiency is 6.0% or more is expressed as A, the case where 5% or more and less than 6% is expressed as B, and the case where 4% or more and less than 5% is expressed as C 'will be 3% or more and less than 4%. The case is represented by D, the case where 1.5% or more and less than 3% is represented as E, the case where less than 1.5% is expressed as F, the case where the conversion efficiency is d or more is regarded as pass, and the case where d is less than d is regarded as unacceptable. The case where the conversion efficiency after continuous irradiation for 400 hours at RH45% is 90% or more with respect to the initial value of the conversion efficiency is evaluated as A, and the case where 85% or more and less than 90% is evaluated as B, The case where 80% or more and less than 85% was evaluated as c, the case where 70% or more and less than 80% was evaluated as D, and the case where less than 70% was evaluated as E. 109 201211165 1J.

[Table 8] Table 8 Sample No. Photoelectrochemical Cell 1st Pigment 2nd Pigment Conversion Efficiency Durability Test 8-1 Photoelectrochemical Cell 1 A-25 - BB 8-2 Photoelectrochemical Cell 2 A-25 - AB Invention 8-3 Photoelectrochemical cell 3 A-25 - AB 8-4 photoelectrochemical cell of the invention 4 A-25 - AB 8-5 photoelectrochemical cell of the invention 5 A-25 - BB 8-6 photoelectrochemical cell 6 of the invention A-25 - BB 8-7 Photoelectrochemical Cell of the Invention 7 A-25 - AB 8-8 Photoelectrochemical Cell of the Invention 8 A-25 - AB 8-9 Photoelectrochemical Cell of the Invention 9 A-25 - AB The present invention 8 -10 Photoelectrochemical Cell 10 A-25 - AB 8-11 Photoelectrochemical Cell of the Invention 1 B-3 - EE Comparative Example 8-12 Photoelectrochemical Cell 2 B-3 - EE Comparative Example 8-13 Photoelectrochemical Cell 3 B- 3 - EE Comparative Example 8-14 Photoelectrochemical cell 4 B-3 - EE Comparative Example 8-15 Photoelectrochemical cell 5 B-3 - EE Comparative Example 8-16 Photoelectrochemical cell 6 B-3 - EE Comparative Example 8-17 Photoelectrochemical cell 7 B-3 - EE Comparative Example 8-18 Photoelectrochemical cell 8 B-3 - EE Comparative Example 8-19 Photoelectrochemical cell 9 B-3 - EE Comparative Example 8-20 Photoelectrochemical cell 10 B -3 - EE Comparative Example 8-21 Photoelectrochemical Cell 11 B-3 - EE Comparative Example 8-22 Photoelectrochemical Cell 12 B-3 - EE Comparative Example 8-23 Photoelectrochemical Cell 1 A-25 R-1 AB The present invention 8-24 Photoelectrochemical Cell 1 A-25 R-7 AB 8-25 Photoelectrochemical Cell of the Invention 1 A-25 R-8 AB The present invention [Experiment 8] is prepared by adding a metal alkoxide to metal oxide fine particles. The slurry is applied onto a conductive substrate, and then subjected to UV ozone irradiation, UV irradiation, or drying to prepare an electrode. Thereafter, a photoelectrochemical cell was fabricated to measure the conversion efficiency. (Metal oxide fine particles) 110 2〇12lll65 ---- Use titanium oxide as the metal oxide fine particles. As the titanium oxide, a P25 powder (manufactured by Degussa Co., Ltd., trade name) having a 30% rutile type and a 70% anatase type average particle diameter of 25 nm was used. (Pretreatment of Metal Oxide Fine Particles) The organic matter and moisture on the surface are removed by heat-treating the metal oxide fine particles in advance. In the case of titanium oxide fine particles, it is heated in the oven at 45 (rc) for 3 minutes in the atmosphere. (Measurement of the amount of water contained in the metal oxide fine particles) Weight reduction by thermogravimetry And it is heated to 300 00. (: Karl Fisher titration of the desorbed water and titrated at a temperature of 26. (:, titanium oxide, P25 powder stored in an environment with a humidity of 72%) The amount of water contained in (manufactured by Degussa Co., Ltd., trade name) is quantified by Karl Fischer method titration. (: Dehydrated when heated under oxidized chin and P25 powder (manufactured by Degussa Co., Ltd.) The result of moisture setting contains 0 253 mg of water in 0.1033 g of titanium oxide fine powder. That is, the 'titanium oxide fine powder contains about 2.5 wt% of water. It is heat treated for 3 minutes, and stored in a desiccator after cooling. (Used as a metal alkoxide paste) As a metal alkoxide which functions to bond metal oxide fine particles, titanium tetrachloride (IV) (TTIP) is used as a titanium raw material to make tetra-n-propanol Wrong (IV) as the wrong material, use Ethanol sharp (ν) as a sharp raw material (all manufactured by Aldrich). The molar concentration ratio of the metal oxide fine particles to the metal alkoxide can be not excessively thickened by the amorphous layer produced by the hydrolysis of the metal alkoxide, and the particles are mutually 111 201211165 jyyjz^Kjyif, two lines and according to the diameter of metal oxide particles

The alkoxides are prepared by mixing al M ίίί / sub-titanium (IV) with titanium tetraisopropoxide (TTIP). For the titanium oxide microparticles 1 g, 3.55 g of ο: Μ ^ ΤΉΡ solution is mixed. At this time, the obtained titanium oxide concentration was = I2 wt%, which was reduced by the coating. Moreover, the oxygen ratio of the _ is 1:0.127:3, and the molar ratio is 1. 0.036: 5.92. Similarly, the 'mixed paste of titanium oxide fine particles and ΤΤΙρ α' was also prepared so that the concentration of the particles was 22 wt%. In the paste using zinc oxide and tin oxide fine particles, it is set to Μ wt%. In the case of zinc oxide and tin oxide, the metal alkoxide solution is mixed at a ratio of 5 25 g with respect to 1 g of the metal oxide fine particles. The metal oxide microparticles and the metal alkoxide solution were obtained in a closed container by a magnetic stirrer (4) for 2 hours to obtain a uniform paste. The (4) silk which is applied to the conductive substrate by the paste & can be made into a smear, a screen printing method, a spray coating method, etc., and a suitable paste viscosity can be appropriately selected according to the coating method. Here, a method of simply coating with a glass rod (similar to the knife-to-blade method) is used. In this case, the concentration of the metal oxide fine particles imparting a suitable paste viscosity is in the range of approximately 5 wt% to 3 wt%. The thickness of the amorphous metal oxide formed by the decomposition of the metal alkoxide is in the range of about 0.1 nm to 0.6 nm in the present test, and it can be a suitable thickness. (Coating and air drying treatment of the paste on the conductive substrate) 112 201211165t Polyethylene terephthalate (PET) film substrate with a tin-doped indium oxide (ITO) conductive film (2〇n/ Cm2) or a glass substrate (10 Ω/cm2) with a fluorine-doped tin oxide (FTO) conductive film, and 2 grazing adhesive tapes are attached in parallel at regular intervals as spacers, and uniformly coated with a glass rod. Each paste prepared by the above method. After the paste is applied, the conditions are changed depending on whether or not the ozone treatment, the UV irradiation treatment, or the drying treatment is performed before the dye adsorption, thereby producing a porous film. (Drying treatment) The crucible applied to the conductive substrate was air-dried at room temperature for about 2 minutes. In this process, the metal alkoxide in the paste is hydrolyzed by moisture in the atmosphere, and amorphous titanium oxide, zirconium oxide, and cerium oxide are formed from Ti alkoxide, Zr^ alkoxide, and canon salt, respectively. The amorphous metal oxide formed exhibits a combination of the metal oxide fine particles and (4) and the conductive substrate, and therefore, a porous film excellent in mechanical strength and adhesion is obtained only by air drying. (UV ozone treatment) 'In the uv ozone treatment, NL-UV253 UV seam cleaner manufactured by Japan Laser Electronics Co., Ltd. was used. There are 3 4 5 w mercury lamps with bright lines at 185 legs and 254 nm in the w-face, and the sample is horizontally placed at a distance of about 6.5 cm from the light source. The conductivity of the 1T tantalum film and the FTO film due to the W ozone treatment was found to be caused by the (IV) towel conducting oxygen = raw 3i in this example for 2 hours of the UV ozone treatment: Γρτ'Λ. , 113 201211165 一 / 夕, y " v ^lt (UV treatment) It is replaced by the It gas in the chamber, and the same as the above-mentioned treatment, the IT0 film and FT due to the w treatment are now performed. Low 〇 film (pigmentation) Multi-tone: 素: Using the sensitizing dye contained in the 匕 调制 调制 调制 调制 调制 调制 调制 ( ( ( ( ( ( ( ( ( The concentration f of the first dye was (U mM, and the concentration of the second dye was 0.1 mM). In the present experiment, the porous film produced by the above treatment was subjected to an oven at 10 ° C for 1 hour. After drying, it was immersed in the sensitizing dye solution and allowed to stand at a temperature of 50 minutes to adsorb the &amp; sulphate onto the surface of the titanium oxide. The sample after the dye adsorption was washed with ethanol and air-dried. Production and evaluation of battery characteristics) The conductive substrate on which the porous film was formed after the dye was adsorbed was used as a photoelectrode to align with the ΙΤο/ρΕτ film or the FTO/glass counter electrode modified by the clock face microparticles. , trial production of photoelectrochemical cells. The effective area of the above photoelectrode is 0.2 cm2. Used in an electrolyte solution containing 5-5 liters of Li, 〇.〇5 Μ I?, 〇.5 第三 of the third butyl pyridine of 3-decyloxypropionitrile, introduced by capillary action The gap between the two electrodes. The evaluation of the performance of the battery can be determined by the photocurrent action spectrum of the fixed photon number (1016 cm·2) and the Iv of the AM1.5 simulated sunlight (1〇〇mW/cm2). The measurement was carried out using a CEP-2000 spectrophotometric measuring apparatus manufactured by Spectrometer Co., Ltd. The conversion efficiency of the 114 2〇12lll65 -----rll' piece was shown in Table 9. The case of 3.5% or more is represented as A, the case of 3.0% or more and less than 3.5% is expressed as B', and the case where 2.5% or more and less than 3.0% is expressed as C, and the case where 2.0% or more and less than 2.5% is expressed as D, the case where 1.5% or more and less than 2.0% is expressed as E, and the case where less than 1.5 〇/〇 is expressed as F. Moreover, as the long-term property, the conversion efficiency after continuous irradiation for 400 hours is initial with respect to the conversion efficiency. The case where the value is 90% or more is evaluated as A', and the case where 85% or more and less than 90% is evaluated as B 80% or more and less than 85% were evaluated as C, 70% or more and less than 80% were evaluated as D, and less than 70% was evaluated as E. [Table 9] 115 201211165 Table 9 Sample No. Substrate titanium oxide pretreatment first pigment second pigment UV ozone UV drying conversion efficiency durability test 9-1 FTO/glass with A-15 - 〇X 〇AA 9-2 FTO/glass of the invention has A-15 - X 〇 〇AB 9-13 FTO/glass of the invention has A-15 - XX 〇BB 9-4 FTO/glass of the invention has A-15 - XXXBB 9-5 FTO/glass without invention A-15 XX 〇BB wood invention 9 -6 FTO/glass has A-15 - 〇X 〇AB 9-7 ITO/PET of the invention has A-15 〇X 0 AB 9-8 ITO/PET of the invention has A-15 - XX 〇BB The present invention 9- 9 FTO/glass has A-21 - 〇X 〇c A The present invention 9-10 FTO/glass has A-21 - X 〇〇c B The present invention 9-11 FTO/glass has A-21 - XX 〇DB The present invention 9-12 FTO/glass has A-21 - XXXDB 9-13 FTO/glass without A-21 - XX 〇DB 9-14 FTO/glass of the invention has A-21 - 0 X 〇c B The present invention 9- 15 ITO/PET with A-21 - 〇X 〇c B Invention 9-16 ITO/PET A-21 - XX 〇DB 9-17 FTO/glass of the invention has B-2 - 〇X 〇ED Comparative Example 9-18 FTO/glass has B-2 - X 〇〇ED comparison Example 9-19 FTO/Glass has B-2 - XX 0 ED Comparative Example 9-20 FTO/Glass has B-2 - XXXEE Comparative Example 9-21 FTO/Glass without B-2 - XX 〇ED Comparative Example 9-22 FTO/glass has B-2 - 0 X 〇ED Comparative Example 9-23 ITO/PET Available B-2 - 〇X 0 ED Comparative Example 9-24 ITO/PET Available B-2 - XX 〇ED Comparative Example 9-25 FTO/glass has A-21 R-1 〇X 〇BA The invention 9-26 FTO/glass has A-21 R-1 X 〇〇BB The invention 9-27 FTO/glass has A-21 R-1 XX 〇 AB 9-28 FTO/glass of the invention has A-21 R-1 XXXAB 9-29 FTO/glass without A-21 R-1 XX 〇AB 9-30 FTO/glass of the invention has A-21 R-1 〇X 〇BB 9-31 ITO/PET of the invention A-21 R-1 〇X 〇BB 9-32 ITO/PET of the invention A-21 R-1 XX 〇BB 9-33 FTO/glass of the invention A-21 R-7 〇X 〇BA 9-34 FTO/glass of the invention has A-21 R-7 X 〇0 BB 9-35 FTO/glass of the invention has A-21 R-7 XX 〇 AB 9-36 FTO/glass of the invention has A-21 R-7 XXXAB 9-37 FTO/glass without A-21 R-7 XX 〇AB 9-38 FTO/glass of the invention has A-21 R-7 0 X 0 BB 9-39 ITO/PET of the present invention A-21 R-7 〇X 〇BB 9-40 ITO/PET of the present invention A-21 R-7 XX 0 BB The present invention 116 201211165 is shown in Table 9, "UV Ozone" When 枋, uv uv, and 干 」 襕 、 、 、 、 、 、 UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV UV The situation in which money is spent on the New Year is recorded as "〇", and the situation that has not been processed is recorded as "Γχ". The "titanium oxide pretreatment" in Table 9 indicates the oxidation of the particles, and the presence or absence of 45 (the heat treatment in the oven under TC, such as minute). Sample 9_6, 'Sample 9_14, Sample 9_22, Sample 9_3G, Sample 9 38 is a sample which does not use a paste having a concentration of 1 TTIP (titanium oxide: TTIP molar ratio:: 0.356). Other samples (sample 9 - 〜 ~ sample 9_5, sample 9-7~sample 9-13, sample 9-15~sample 9-21, sample 9-23~sample 9-29, sample 9-31~sample 9-37, sample 9- 39. Samples 9-40) were each used as a paste of titanium oxide: TTIP = 1: 0.0356. It can be seen from Table 9 that a photoelectrochemical cell using the pigment of the present invention, after formation of a porous film, a sensitizing dye Whether there is UV ozone treatment, UV irradiation treatment, and drying treatment before adsorption. The conversion efficiency of the photoelectrochemical cell is always good, and the conversion efficiency is always acceptable. In addition, the conversion efficiency after 400 hours is 7〇% or more of the initial value. It shows excellent durability. [Experiment 9] Using acetonitrile as a solvent, it was prepared to dissolve lithium iodide, 峨0.05 mol/b diisopropyl propyl imidazolium iodide. 〇62 mol/: [electrolyte solution. The benzimidazole-based compounds of No. 1 to No. 8 shown below were added and dissolved therein so that the respective concentrations became 0.5 mol/1. [Chem. 34] 117 201211165

A conductive film is formed on the glass substrate by sputtering a fluorine-doped tin oxide as a conductive film. Applying a dispersion containing the smectite-type titanium oxide particles to the conductive film (the anatase-type titanium oxide is blended in 100 ml of a mixed solvent of water and acetonitrile in a volume ratio of 4:1 (Japan Aer〇sil) P-25 (trade name) manufactured by the company) 32 g 'Semiconductor fine particle dispersion obtained by uniformly dispersing and mixing using a mixing regulator of a rotation/revolution type, and then sintering at 500 ° C to form A photosensitive layer having a thickness of 15 μηα. Next, the photosensitive layer is an ethanol solution of a sensitizing dye described in the following table (concentration: lxl (T4 mol/L). When two types are used in combination, the concentrations of the first dye and the second dye are respectively 〇.1. Immersed in mM) for 24 hours. To the photosensitive layer, benzene was added to No. 1 to No. 8. The rice-salt compound electrolyte was placed thereon, and a frame-shaped spacer (thickness 25 μm) made of polyethylene film was placed thereon. The photoelectric conversion element was fabricated by covering it with a platinum counter electrode. The obtained photoelectric conversion element was irradiated with light having an intensity of 118 201211165 100 mW/cm 2 using a Xe lamp as a light source, and the open circuit voltage and photoelectric conversion efficiency were measured. It is shown in Table 10. (Evaluation of the results) The case where the open circuit voltage is 7.0 V or more is ◎, the case of 6 5 v or more and less than 7.0 V is taken as 〇, and the case of 6.0 V or more and less than 6 5 v is taken as Δ. The case where the value is less than 6.0 V is evaluated as X, and the evaluation is performed as 6.5 V or more. The case where the conversion efficiency is 6.0% or more is expressed as a, and the case where 5% or more and less than 6% is expressed as B, and 4% is expressed. Above and less than 5% of the situation is expressed as C, will be more than 3% and less than 4% In the case of D, the case where 丨5〇/〇 or more and less than 3% is expressed as E, the case where less than 15% is expressed as F, the case where the conversion efficiency is D or more is regarded as pass, and the case where the conversion efficiency is less than 〇 is regarded as unqualified. Moreover, as the durability, the conversion efficiency after continuous irradiation for 400 hours at RH45% is 9% or more with respect to the initial value of the conversion efficiency, and the price is A' which is 85% or more and less than 90%. The case was evaluated as B, and 80% or more and not (85% of cases evaluated as $c, 胄7〇% or more and less than 80% were evaluated as D, and less than 7〇% was evaluated as E. In addition, Table 10 also shows the results of using a photoelectric conversion element having an electrolyte solution to which a benzimidazole-based compound is not added. 119 201211165 [Table 10] Table 10 Sample No. Benzimidazole Compound Compound 1 Pigment 2nd Pigment Open Circuit Voltage Conversion Efficiency Durability test 10-1 No.l Al - ◎ Β B The present invention 10-2 No. 2 Al - ◎ Β C The present invention 10-3 No. 3 Al - ◎ Β C The present invention 10-4 No. 4 Al - ◎ Β c The present invention 10-5 No. 5 Al - ◎ Β c The present invention 10-6 No. 6 Al - ◎ Β B The present invention 10 -7 No. 7 Al - ◎ Β C The present invention 10-8 No. 8 Al - ◎ Β C The present invention 10-9 No Al - 〇 CC The present invention 10-10 No. 1 A-15 - ◎ AA The present invention 10 -11 No. 2 A-15 - ◎ AA The present invention 10-12 No. 3 A-15 - ◎ AA The present invention 10-13 No. 4 A-15 - ◎ AA The present invention 10-14 No. 5 A-15 - ◎ AA The present invention 10-15 No. 6 A-15 - ◎ AA The present invention 10-16 No. 7 A-15 - ◎ AA The present invention 10-17 No. 8 A-15 - ◎ AA The present invention 10-18 None A-15 - 〇BA The present invention 10-19 No.l B-2 - 〇DD Comparative Example 10-20 No.2 B-2 - 〇DD Comparative Example 10-21 No.3 B-2 - 〇DD Comparison Example 10-22 No.4 B-2 - 〇DD Comparative Example 10-23 No.5 B-2 - 〇DD Comparative Example 10-24 No.6 B-2 〇DD Comparative Example 10-25 No.7 B- 2 - 〇DD Comparative Example 10-26 No.8 B-2 - 〇DD Comparative Example 10-27 No B-2 - Δ ED Comparative Example 10-28 No.l Al Rl ◎ AA The present invention 10-29 No.l Al R-2 ◎ AA The present invention 10-30 No. 1 Al R-3 ◎ BA The present invention 10-31 No. 1 Al R-4 ◎ BA The present invention 10-32 No. 1 Al R-5 ◎ AA The present invention 10-33 No.l Al R-6 ◎ BA The present invention 10-34 No.l Al R-7 ◎ AA The present invention 10-35 No. 1 Al R-8 ◎ AA The present invention 10-36 No. 1 Al R-9 ◎ BA The present invention 10-37 No. 1 Al R-10 ◎ AA The present invention 10 -38 No.l Al R-ll ◎ BA 10-39 No.1 Al R-12 ◎ AA According to the present invention, it is known from Table 10 that the photoelectrochemical cell using the pigment of the present invention is opened 120 201211165

Xiao Yu’s conversion effect is less than 80% of the initial value, showing the factory and the long-term. ·", no" In addition, after 400 shows excellent resistance

?, to prevent the reduction of conversion efficiency due to the proximity of water or nucleophile, thus showing high conversion efficiency and high durability. [Experiment 10] (Photoelectrochemical cell 21) A photoelectrode having the same configuration as that of the photoelectrode 1 shown in Fig. 1 of Japanese Laid-Open Patent Publication No. 2004-152613 (the semiconductor electrode) is produced by the procedure shown below. 2 is a two-layer structure), and photoelectrochemistry having the same configuration as that of the dye-sensitized solar cell 2 shown in Fig. 1 of Japanese Patent Laid-Open Publication No. Hei. The battery (the area of the light receiving surface F2 of the semiconductor electrode 2 is 丄cm2). In the respective layers of the semiconductor electrode 2 having the two-layer structure, the layer disposed on the side close to the transparent electrode 1 is referred to as a "second layer", and the layer disposed on the side close to the opposite electrode CE is referred to as "second layer". Floor". First, a P25 powder (manufactured by Degussa Co., Ltd., trade name) having an average particle diameter of 25 nm and a titanium oxide particle having a particle diameter different from that of p25 powder (having an average particle diameter of 200 nm, manufactured by Degussa Co., Ltd., trade name) are used. , the total content of P25 and P200 is 15 wt%, and the ratio of the weight of P25 to p2 121 121 2〇l2Hl65 is P25: P200 = 30:70, and ethyl ketone, ion exchange water, The surfactant (manufactured by Tokyo Chemical Industry Co., Ltd., called "Triton-X") was kneaded to prepare a slurry for forming a second layer, which is hereinafter referred to as "slurry 1". 7 . Next, the P2 layer is used instead of P200, and the content of the second layer forming slurry is 15 wt%, which is hereinafter referred to as "slurry". 2"). On the other hand, a transparent electrode having a fluorine-doped Sn 〇 2 conductive film (having a film thickness of 7 Å) was formed on a glass substrate (transparent conductive glass) to have a U mm). Then, the slurry 2 was applied onto the Sn 2 conductive film by using a bar coater, followed by drying. Thereafter, it was calcined in the air at 450 C for 30 minutes. Thereby, the first layer of the semiconductor electrode 2 is formed on the transparent electrode. Further, using the slurry 1, the same coating and calcination as above were repeated to form a second layer on the first layer. Thereby, the semiconductor electrode 2 is formed on the Sn〇2 conductive film (the area of the light-receiving surface is ! Gem2, and the total thickness of the j-th layer and the second layer is 10 (the thickness of the first layer is 3 μηι, and the second layer is The thickness is 7 μηι)), and the photo-electrode of the dye described in Table 11 is produced in a state in which no sensitizing dye is contained. The concentration of each sensitizing dye is 3xl ().4 mGl/L. In the case of the second dye, the concentration of the first dye is lx10-4 m〇1/L, and the concentration of the second dye is ΐχΐ〇·4 m') as a dye. The light f pole 1 () is immersed in the helium liquid, and placed at a temperature of 8 ° C for 2 (H, hour. Thereby within the half (four) electrode 122 201211165 partial adsorption total about l. 〇 xl (T7mol Next, a counter electrode CE having the same shape and size as the photoelectrode is prepared. First, an isopropyl alcohol solution of chloroplatinic acid hexahydrate is added dropwise to the transparent conductive glass in the atmosphere. After drying, it was subjected to a calcination treatment for 45 minutes at a temperature of 45 Torr, thereby obtaining a platinum sintered counter electrode CE. Further, an injection hole (diameter 1 mm) of the electrolyte E was previously provided on the counter electrode CE. Secondly, dissolving zinc iodide, iodized-1,2-dimethyl-3-propylimidazolium, iodine, and 4_t-butylpyridine in a solvent-containing methoxyacetonitrile to prepare a liquid The electrolyte (the concentration of iodine is 1〇mm〇l/L, the concentration of dimethylpropylimidazolium iodide is 〇·6 m〇i/L, and the concentration of iodine is 〇〇5 m〇1/L). 4, the second butyl ratio is determined to be 1 mol/L. Next, 'prepare 〇11 P〇m_Mitsui Polychemicals co with a shape that matches the size of the semiconductor electrode. The spacer s manufactured by Ud (trade name "Himilan", ethylene/methacrylic acid random copolymer ionic polymer), as shown in Fig. i of Japanese Patent Laid-Open Publication No. Hei 4-152613, The photoelectrode is opposed to the counter electrode, and the components of the battery are obtained by laminating the respective components by hot-melting (the electrolyte is not filled) and the liquid electrolyte is injected into the casing from the hole of the opposite electrode. By plugging the hole with the material of the spacer and the material, the battery is further completed in the opposite hole + the hot coffee bottle (4). (Photoelectrochemical cell 22) The liquid electrolyte is replaced. The concentration of zinc is 5〇mmol/L, except that the 123 201211165 == learning battery 21 is prepared in the same order and conditions (photoelectrochemical cell 23). The moth clock is added instead of the liquid electrolyte. In addition, the photoelectrochemical cell 23 is fabricated by the same order and conditions as the light thousand. 4 (Electrochemical cell 24) Lithium iodide is added instead of zinc iodide in the liquid electrolyte to make the liquid electrolyte The 农化化之之之之农1〇〇mm〇l/L, except Further, a chemical battery 24 ° (test and evaluation) was produced by the same phase and conditions as those of the photoelectrochemical cell 21, and the conversion efficiency was measured for the sample using the photoelectrochemical cell 21 to the photoelectrochemical cell 24 by the following procedure. The battery characteristic evaluation test was carried out under the following measurement conditions: using a solar simulator (manufactured by WACOM ELECTRIC CO" LTD., trade name "WXS-85-H type"), and passing the AM filter (AM1. 5) The irradiation conditions of the simulated sunlight from the gas light source are set to 100 mW/cm2 (the so-called "1 Sun" irradiation condition). With respect to each photoelectrochemical cell, the current-voltage characteristics were measured at room temperature using an I-V tester, and conversion efficiency was obtained based on the above. The results obtained are not shown as "initial values" in Table 11 (illumination conditions of lSun). Moreover, the result of the conversion efficiency after 500 hours under the condition of 6 (TC, lSun irradiation, under the action of 10 Ω load, 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 In the case of a, 5% or more and less than 6% are represented as B, 4% or more and less than 5% are represented as C, and 3% or more and less than 4% are represented as D, and 1,5 The case where % or more and less than 3% is expressed as E, the case where less than 1.5% is expressed as ρ, the case where the conversion efficiency is D or more is regarded as pass, and the case where the conversion efficiency is less than 〇 is regarded as unqualified. In addition, after 50 hours The conversion efficiency was maintained at 70% or more with respect to the initial value as a pass. 125 2〇12lll65 [Table 11] Table 11 Sample No. Photoelectrochemical Cell 1st Pigment 2nd Pigment Conversion Efficiency Remarks Initial Value Reduction After 500 Hours Rate, % 11-1 Photoelectrochemical cell 21 A-21 C 15 Inventive 11-2 Photoelectrochemical cell 22 A-21 C 14 Inventive 11-3 Photoelectrochemical cell 23 A-21 - C 14 Inventive 11-4 Photoelectric Chemical battery 24 A-21 • C 15 11-5 Photoelectrochemical cell 21 A-2 of the present invention 2 B 10 Inventive 11-6 Photoelectrochemical Cell 22 A-22 B 9 11-7 Photoelectrochemical Cell of the Invention 23 A-22 • B 7 11-8 of the Invention No. 1: Chemical Battery 24 A-22 • B 8 Invention 11-9 Photoelectrochemical cell 21 A-15 • A 5 11-10 Photoelectrochemical cell of the invention 22 A-15 . A 6 11-11 Photoelectrochemical cell of the invention 23 A-15 - A 5 11-12 of the invention Chemical Battery 24 A-15 - A 5 11-13 Photoelectrochemical Cell 21 A-27 • A 9 11-14 Photoelectrochemical Cell 22 A-27 - A 9 11-15 Photoelectrochemical Cell 23 A of the Invention 27 - A 6 11-16 Photoelectrochemical Electrolysis Cell of the Invention 24 A-27 • A 8 11-17 Photoelectrochemical Cell 21-11-1 D 31 of the Invention Comparative Example 11-18 Photoelectrochemical Cell 22 Bu-1 - D 33 Comparative Example 11-19 Photoelectrochemical cell 23 B-1 - D 31 Comparative Example 11-20 Photoelectrochemical cell 24 B-1 - D 30 fch Comparative Example 11-21 Photoelectrochemical cell 21 A-21 R-1 B 20 Invention 11-22 Photoelectrochemical cell 21 A-21 R-7 B 19 Inventive 11-23 Photoelectrochemical cell 21 A-21 R-8 A 17 According to the present invention, a photoelectrochemical cell using the pigment of the present invention is known. Conversion efficiency The initial value of the standard are qualified, the conversion efficiency after the addition of 5〇〇 hours also 70% or more from the initial value, it exhibits excellent durability. On the other hand, when using a comparative pigment, there is a problem in conversion efficiency and durability. Further, a compound having a substituent having 5 or more carbon atoms on the fluorene substituent has a longer southerness and a conversion efficiency. If the stabilization due to the alignment adsorption and the amount of adsorption increase, there is a moderate non-efficiency 126 2〇l2Hl65 combined inhibitory effect. From the results of 7F in Table 11, it is understood that the dye of the present invention is excellent even in the case where zinc oxide is added to the electrolyte. [Experiment 11] ' 1. Preparation of Dioxide-Concentrating Dispersion Solution... The internal volume of the fluororesin coated on the inside is · ml. The non-recorded steel is added to the valley. The titanium oxide-breaking particles are added (manufactured by Japan Aerosil Co., Ltd.) , Degussa P-25) 15 g, water 45 g, dispersant (made by Aldrich, Triron X_100) ig, 〇5 _ oxidized granules (manufactured by Nikkato Co., Ltd.) 3 〇 g, using a sand mill (IMEXC〇 This was manufactured) and subjected to dispersion treatment at 1500 rpm for 2 hours. The cerium oxide particles were separated by filtration from the obtained dispersion. The average particle diameter of the titanium dioxide microparticles in the obtained dispersion was 2.5 μηη. Further, the particle diameter was measured by a Mastersizer manufactured by MALVERN. 2. Preparation of pigment-coated titanium oxide fine particle layer (electrode A) A 20 mm x 20 mm conductive glass plate coated with fluorine-doped tin oxide (manufactured by Asahi Glass Co., Ltd., trade name: TC〇GLASS-U) The surface resistance is about 3 〇Ω/ιη2), and the adhesive tape for the spacer is bonded to both ends of the conductive layer side (the portion having a width of 3 mm from the end portion), and the dispersion is coated with a glass rod. On the conductive layer. After the application of the dispersion, the adhesive tape was peeled off and air-dried at room temperature for 1 day. Next, the semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 type manufactured by Yamato Scientific Co., Ltd.), and calcined at 450 ° C for 30 minutes. After the semiconductor coated glass plate was taken out and cooled, the sensitized color of the sensitized color 127 201211165 shown in Table 12 (concentration: 3) &lt;1〇·4 m〇l/L. In the case of the first pigment, the concentration of the first pigment was lxl 〇 -4 m〇l / L, and the concentration of the second pigment was lxlO · 4 mol / L) for 3 hours. The semiconductive-coated glass plate to which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, and then washed with ethanol to be naturally dried. The thickness of the dye-sensitized oxidized titanium oxide particle layer thus obtained was 1 〇 μηη, and the coating amount of the titanium oxide fine particles was rib g/m2. Further, the amount of adsorption of the dye is in the range of Q i / m2 to 10 mmol / m 2 depending on the type thereof. 3. Preparation of photoelectrochemical cell a A mixture of acetonitrile and 3-methyl-2-oxazolidinone in a volume ratio of 9 Å / 1 Torr was used as a solvent. To the solvent, iodine and an iodide salt of methyl-3-hexyl imidazole rust as an electrolyte salt were added to prepare a solution containing 〇5 m〇i/Li$sulfonate and 0.05 mol/L of iodine. In the solution, 1 part by weight of the nitrogen polymer compound (α) β is added to 1 part by weight of the solvent (nitrogen-containing polymer compound + salt), and 〇1 mole is mixed with nitrogen. The electrophilic agent (ρ) of the reactive nitrogen atom of the polymer compound is prepared into a uniform reaction solution. On the other hand, on the dye-sensitized titanium oxide fine particle layer formed on the conductive glass plate, the platinum film side of the counter electrode formed of the glass plate on which platinum is deposited is placed on the spacer, and conductivity is formed. Glass plate and platinum vaporized glass plate. The open end of the assembled body was immersed in the above electrolyte solution, and the reaction solution was allowed to permeate into the dye-sensitized oxidized fine particle layer by capillary action. Next, the mixture was heated at 80 ° C for 30 minutes to carry out a crosslinking reaction. Thus 128 201211165

X is obtained on the conductive layer 12 of ===1° as shown in Fig. 2 of Japanese Patent Laid-Open Publication No. Hei. No. 2-323190, and the layer is colored; W emulsified titanium film layer 2G, electrolyte layer%, and glass plate 41 The pool a (sample number m) of the present invention comprising the (four) electrode 40. Electrochemical device, as shown in Figure 12, except for (4) Photoelectrochemical cells 12-7, 12-10, 12-13, 12._16~12_18, which are the same as the photoreceptor and/or the f-loaded mobile body. ). 4. Photoelectrochemical cell b, photoelectrochemical cell c (1) Photoelectrochemical cell b, as described above, the electrode A (2Qmmx2Gmm) composed of the oxidized crystal layer of the pigment* color-cutting sensation of the present invention is interposed. The spacers are plated on the same size scaly glass plate. Secondly, the capillary solution is used to make the electrolyte (the moth with a volume ratio of acetonitrile to 3/methyl-2 ketone ketone of 90/10 as the solvent is 〇〇5 melon), and the hindrance clock is Μ mol/L. The solution) was impregnated into the gap between the two glass plates to prepare a photoelectrochemical cell b (pattern No. 12-2). Further, as shown in Table 12, the coloring matter was changed, and the above steps were repeated, thereby obtaining a photoelectrochemical cell b-like number 12_5, sample number 12_8, sample number 12·η, sample number 12- 14). (2) Photoelectrochemical cell c (electrolyte described in Japanese Patent Laid-Open No. Hei 9/27352) The electrode A composed of the oxidized 129 201211165 titanium fine particle layer by the dye of the present invention as described above ( On the 20 mm x 20 mm), the electrolyte is applied and impregnated. In addition, the electrolytic solution is obtained by containing hexaethylene glycol methacrylate (manufactured by Nippon Oil & Fat Chemical Co., Ltd., Blemmer PE-350) lg, ethylene glycol lg, and 2-hydroxyl as a polymerization agent. -2-mercapto-1-phenyl-propane _;! ketone (Nippon Automobile Co., Ltd., OCU please 3) 2 〇mg of mixed lithium iodide 500 mg, vacuum degassing for 1 。. Next, the porous titanium oxide layer impregnated with the mixed solution is placed under reduced pressure, thereby removing bubbles in the porous titanium oxide layer, promoting the impregnation of the monomer, and then performing polymerization by irradiating ultraviolet light. Thus, the gel of the polymer compound is filled in the fine pores of the porous titanium oxide layer. The thus obtained product was exposed to an iodine atmosphere for 30 minutes to diffuse iodine into the polymer compound, and then a platinum vapor-deposited glass plate was laminated to obtain a photoelectrochemical cell c (sample No. 12-3). Further, 'the coloring matter was changed as shown in Table 12, and the above steps were repeated" to obtain a photoelectrochemical cell c (sample No. 12_6, sample No. 12-9, sample No. 12-12, sample No. 12) -15). 5. Measurement of photoelectric conversion efficiency The light of a 500 W xenon lamp (manufactured by Ushiolnc.) was passed through an AM1.5 filter (manufactured by Oriel Co., Ltd.) and a chopper filter (Kenko L-42), thereby making it Simulated sunlight containing ultraviolet light. The light intensity is 89 mW/cm2 °. The crocodile clips are respectively connected to the conductive glass plate 10 and the platinum vapor-deposited glass plate 40 of the photoelectrochemical cell, and the crocodile clips are connected to a current-voltage measuring device (Keithley SMU238 type (product) Name)). Self-conductivity 130 201211165^ The glass plate 10 is irradiated with simulated sunlight, and the generated electricity is measured by a current-voltage measuring device. The initial value of the conversion efficiency of the photoelectrochemical cell obtained by this and the rate of decrease of the conversion efficiency at the time of continuous irradiation for 500 hours are shown in Table 12. The case where the conversion efficiency is 6.0% or more is expressed as a, and the case where 5% or more and less than 6% is expressed as B, and 4 is obtained. /. The case where the above is less than 5% is expressed as C, the case where 3% or more and less than 4% is expressed as D, the case where 15 〇/〇 or more and less than 3% is expressed as E, and the case where less than 1.5% is expressed as F, the case where the conversion efficiency is D or more is regarded as a pass, and the case where the conversion efficiency is insufficient is regarded as a failure. Moreover, the reduction rate of the conversion efficiency after 500 hours has been shown in Table ^. A case where the reduction rate is 30% or less is considered as a merger, and a case where the reduction rate is more than 3 % is regarded as a failure. 131 201211165 UHif [λ 12] Table 12 Sample photoelectrochemical cell Nitrogen high electrophilic first color second conversion efficiency test number molecular sub-agent pigment initial value after 500h reduction rate (%) 12-1 photoelectrochemical cell a β β Α-1 - C 20 12-2 Photoelectrochemical Battery of the Invention b No Α-1 - C 21 The present invention 12-3 Photoelectrochemical Cell C No Α-1 - C 23 The 12-4 photoelectrochemical cell of the present invention a α β Α-15 - A 5 12-5 Photoelectrochemical cell of the invention b No Α-15 - A 5 12-6 Photoelectrochemical cell of the invention C No Α-15 - A 6 12-7 Photoelectrochemistry of the invention Battery a α β Α -27 - A 9 12-8 Photoelectrochemical Battery of the Invention b No Α-27 - A 11 12-9 Photoelectrochemical Cell C of the Invention C No Α-27 - A 13 12-10 Photoelectric of the Invention Chemical battery a α β Α-25 - A 6 12-11 Photoelectrochemical cell b of the invention b No Α-25 - A 7 12-12 Photoelectrochemical cell C of the invention C No Α-25 - A 7 12-13 of the present invention Photoelectrochemical cell a α β Β-3 - D 37 Comparative Example 12-14 Photoelectrochemical cell b No Β-3 - D 45 Comparative Example 12-15 Photoelectrochemical cell C No Β-3 - D 48 Comparative Example 12-16 Photoelectrochemical cell a α β Α-1 R-1 B 28 12-17 Photoelectrochemical cell of the invention a α β Α-1 R-7 B 25 12-18 Photoelectrochemical cell of the invention a α β Α-1 R-8 B 24 The nitrogen-containing polymer compound α and the electrophilic agent β of the present invention represent the following compounds. [化35]

132 201211165. jy\jz, vpif [Experiment 12] The porous layer of Ti〇2 was coated on ft-glass by screen printing using a suspension prepared by a sol-gel method. The calcination was carried out at 450 °C. This was impregnated with the pigment compound A_9 of the present invention and the 〇4 mol/L ethanol solution of the sensitizing dye B-1 to adsorb the dye. 100 mg of 2,2',7,7,-tetrakis(diphenylamino)-9,9'-spirobifluorene was dissolved in 5 ml of chloroform. The solution was lightly applied to the surface of the porous layer to which the pigment was adsorbed, whereby the solution was allowed to permeate into the pores of the layer. Further, one of the solutions was dropped directly onto the surface and dried at room temperature. Secondly, the coated support is mounted on the evaporation device, and further applied to the thickness of 1〇〇2, 2, 7, 7'-four (two) by thermal evaporation under a vacuum of about 10 mbar. A layer of phenylamino)_9,9'-spiro-g. Further, a gold layer having a thickness of 200 nm was coated on the coated support in the steaming device as a counter electrode. The sample thus prepared is mounted in an optical device including a high pressure lamp, a filter, a lens, and a back. The intensity can be changed by the use of the filter and the movement of the lens. A contact is attached to the gold layer and the Sn02 layer, and is mounted on the device shown in the current measuring device when the sample is irradiated. In order to carry out the measurement, light having a wavelength of less than 430 nm was blocked by using an appropriate filter. Further, the device was adjusted in such a manner that the intensity of the radiation was approximately 1000 W/m2. A joint is attached to the gold layer and the Sn02 layer, and the two contacts are connected to a potentiostat when the sample is irradiated. An electric current of about 90 nA was generated in the sample using the sensitizing dye B-1 without applying an external voltage, and flow was carried out, but the dyeing compound A_9 of the present invention produced about a branch. The affair of any sample is electric if it is not irradiated [Experiment 13] The column ^日ΓΓ寺 opens 2°. . In the same manner as in Comparative Example 1, the conversion efficiency of the dye enamel-9 of the present invention was higher than that of the comparative phthalocyanine. [Experiment 14] Iso-Titanium 125 W was added dropwise to 75 g of a W Μ· nitric acid aqueous solution (manufactured by Kishida Chemical Co., Ltd.), and the mixture was heated for 8 hours to carry out a hydrolysis reaction. The obtained solution was dissolved in a titanium high-pressure dad at 25 Gt for 15 hours to grow the particles, and then subjected to ultrasonic dispersion for 30 minutes, thereby obtaining a colloidal solution containing titanium oxide particles having an average primary particle diameter of 20 nm. . '...the obtained (four) nucleus containing titanium oxide particles is gradually concentrated in an evaporator until the titanium oxide becomes a concentration of 1Q wt%, and then added in a weight ratio of 4% by weight relative to the titanium oxide. ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The transparent conductive material of the glass substrate of the Sn 〇 2 film is obtained by the coating of the oxidized Qinxian floating liquid of the 成 成 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县The coating is applied to the pre-drying at 12°C for 30 minutes, and then subjected to an oxygen atmosphere: 134 201211165 5〇〇°C for π minutes of firing, forming a layer 1 of the second layer of multi-conversion layer. Township hole f semi-conducting county Laihou is a titanium film. P? Seven heart milk /, people will be commercially available titanium oxide particles (TayCa company created, product name TITANIX JA), particle size of about 18 〇 belly) 4 oxygen Manufactured by End (5) Hall Chemical Co., Ltd.) a4 g plus; 汕mi t, adjusted to pHy with hydrochloric acid. Further, the addition of the oxidized (tetra) granules was carried out by stirring the mixture with the coating material ||_ mixed solution. The oxidized granules were separated from the obtained dispersion. Thereafter, the addition was carried out by adding 〇工千b-small (manufactured by Kishida Chemical Co., Ltd., weight average molecule = 200,000) in an amount of 4% by weight based on the weight ratio of titanium oxide, thereby obtaining dispersion. There is a float of titanium oxide particles. . . . On the first porous semiconductor layer of the glass substrate 1 on which the titanium oxide film is formed on the first porous semiconductor layer, the prepared titanium oxide suspension is applied by a doctor blade method to obtain a coating film. The coating was pre-dried for 20 minutes, and calcined in an oxygen atmosphere for about 60 minutes to form a second layer of the porous semiconducting It layer which became the second porous photoelectric conversion layer. A titanium oxide film i of about 22 μηη. The haze ratio of the porous semiconductor layer was measured and found to be 84%. The dye (first pigment) having the maximum sensitivity absorption wavelength region in the absorption spectrum on the short-wavelength side is dissolved in ethanol by the portion of the cyanine dye S-2 represented by the following formula, and the concentration is adjusted to 3χ1〇. -4 mol / liter of the '丨' pigment adsorption pigment solution. 135 201211165t [化37]

OH The glass substrate 1 having a transparent conductive film and a porous semiconductor layer was immersed at 25 ° C to be heated to about 50 Å. (: 10 minutes in the dye solution for adsorption of the first dye) The first dye was adsorbed on the porous semiconductor layer. Thereafter, the glass substrate 1 was washed several times with absolute ethanol at about 6 Å. The glass substrate i was immersed in 0.5 N-hydrochloric acid for about 10 minutes, and then washed with ethanol to desorb the first pigment adsorbed on the second porous semiconductor layer. In addition, the glass substrate 1 is dried at about 60 ° C for about 20 minutes. Next, as a pigment (second pigment) having a maximum sensitivity absorption wavelength region in the absorption spectrum on the long wavelength side, the comparative dye B-1 is used. And the pigment (A-9, A-15, A-25 or A-27) of the present invention is dissolved in ethanol to prepare a dye solution for adsorption of a second pigment having a concentration of 3×10·4 mol/liter. The glass substrate 1 of the transparent conductive film and the porous semiconductor layer to which the first dye is adsorbed is immersed in the dye solution for adsorption of the second dye at room temperature and normal pressure for 15 minutes to adsorb the second dye to the porous semiconductor layer. Then, the glass substrate 1 is cleaned several times by absolute ethanol. It was dried at 136 201211165 and dried for about 20 minutes. Here, the haze ratio of the porous layer was measured and found to be 84% (in the case of using B), in the case of the pigment of the present invention). Next, the dimercaptopropyl-sodium iodide salt was dissolved in a 3-methoxypropionitrile solvent to a concentration of 0.5 mol/liter, and lithium iodide was dissolved to a concentration of 0.1 mol/liter to dissolve the iodine. The concentration is 〇〇5 mol/liter to prepare a redox electrolyte solution. The porous semiconductor layer side of the glass substrate i having the porous semiconductor layer to which the second pigment and the second dye are adsorbed is provided with platinum. The platinum side of the counter electrode side support body which is the ITO glass of the counter electrode layer 8 is provided in the opposite direction, and the prepared redox electrolyte solution is injected therebetween, and the epoxy resin sealing material surrounds it. The dye-sensitized photoelectrochemical cell is completed, and the second porous semiconductor layer is the same layer as the i-th porous semiconductor layer, that is, the titanium oxide suspension forming the first porous semiconductor layer is used. Forming a second layer of porous In the same manner as the titanium oxide film 1, the titanium oxide film 2 was produced in the same manner as in the case of the titanium oxide film 1. The photoelectrochemical cell was produced and evaluated in the same manner. The haze ratio of the porous photoelectric conversion layer was 15 Å/〇 (using B). -1), 16% (in the case of using the pigment of the present invention). The results of evaluating the obtained photoelectrochemical cell by the measurement condition of AM-1.5 (100 mW/cm2) are shown in Table 13. The case where the efficiency is 3.5% or more is expressed as ◎, the case where 2.5% or more and less than 3.5% is expressed as 〇, the case where 2.0% or more and less than 2.5% is expressed as Δ, and the case where less than 2.0% is expressed as x. Table 13] 137 201211165 Table 13

It is understood that the photoelectric conversion efficiency of the pigment of the present invention is also excellent in the system. [Experiment 15] Commercially available titanium oxide particles (manufactured by Tayca Co., Ltd., average particle diameter: 2 〇 nm) 4 〇g and diethylene glycol monomethyl ether 2 〇 using a hard glass bead by a paint stirrer The m丨 was dispersed for 6 hours to prepare an oxidized suspension. Next, the hard glass beads were separated by filtration from the obtained suspension, and the titanium oxide suspension was applied onto a rupture plate (electrode layer) to which a conductive layer of tin oxide was previously attached using a doctor blade to perform at 100 〇C for 30 minutes. After pre-drying, it was calcined in an electric furnace at 500 ° C for 40 minutes to form a titanium oxide film (semiconductor material) on a glass plate. Separately, the sensitizing dye and the comparative dye of the present invention shown in Table 14 were dissolved in ethanol to obtain a photosensitizing dye solution. The concentration of the photosensitizing dye solution is ΙχΙΟ·4 mol/liter (in the case where the second dye is used in combination, the concentration of the first dye is 1×1 〇 4 mol/L, 138 20121Π 65if Di 2 pigment) The degree is ixi 〇 4 m / liter). Next, the glass plate on which the film-formed titanium oxide was formed was placed in the solution, and the pigment was adsorbed for 6 minutes under 6 Torr, and then dried to form a semiconductor material and a light-increasing film on the glass plate. A photoelectric conversion layer (sample A) composed of a sensible dye. A ruthenium solution (1%) of polyethylene ruthenium (weight average molecular weight: 3,000) as a hole transport material was applied onto the photoelectric conversion layer of the sample A, and dried under reduced pressure to form a hole transport layer ( Sample B). Ethyl leaf sniffing 1.95 g as an intermolecular electro-optical movement complex and 2.03 g of 5-decylnaphthalene g-kun in 100 ml of acetone were used to repeatedly coat the resulting solution on the hole transport layer of sample b. Form a conductive layer. Next, a gold electrode (counter electrode) was vapor-deposited on the conductive layer to obtain a photoelectric conversion element (sample C). The obtained photoelectric conversion element (sample C) was irradiated with light of an intensity of 1 〇〇 w/m 2 by a solar simulator to measure the conversion ratio. The results are shown in Table 14. The case where the conversion efficiency is 1.5% or more is represented by ◎, the case where ι·〇% or more and less than 5% is expressed as 〇, and the case where 0.5% or more and less than 1.0% is expressed as Δ, and less than 0.5%. Expressed as X. 139 201211165 [Table 14] Table 14 Sample No. 1 Pigment 2nd Pigment Conversion Efficiency Reader 14-1 Α·1 - ο 太发ΒΏ 14·2 Α-20 0 14-3 Α-9 - ◎ Tai Luming 14-4 Α-25 - ◎ 木膝明 14-5 Α-27 -.. ◎ 14-6 Α-15 14-7 Β·1 — ©____ The present invention 14-8 Α-20 Rl — Δ Comparison Example 14-9 Α-20 R-7 —. ◎ The present invention shows that the dye of the present invention is excellent in photoelectric conversion efficiency and is also effective in the system. [Experiment 16] (1) The formation of the first photoelectric conversion layer was carried out using a hard glass bead, and a commercially available titanium oxide particle (manufactured by Tayca Co., Ltd., average particle diameter: 3 〇 nm) was used as a coating stirrer. A titanium oxide suspension was prepared by dispersing with 20 ml of diethylene glycol monomethyl ether for 6 hours. Next, 'the hard glass beads were separated from the titanium oxide suspension by filtration, and the titanium oxide suspension was applied onto a glass plate to which a tin oxide conductive layer was previously attached using a doctor blade, and subjected to 30 minutes at 10 ° C. After pre-drying, it was calcined in an electric furnace at 500 ° C for 40 minutes to obtain a titanium oxide film. Separately, R-1 was dissolved in ethanol to a concentration of 3χ10·4 mol/L. Next, the glass plate in which the film-formed titanium oxide was formed was placed in the solution at 60. (: The dye adsorption was performed for 720 minutes, and then dried to obtain the first photoelectric conversion layer (Sample A). (2) Formation of the second photoelectric conversion layer 140 201211165 jyu^upif The glass beads were used, and the paint lion was used. The product was made into a nickel oxide suspension by dispersing for 8 hours in the city (5) hemp chemical _, average particle size _ post) 4 ^-fermented early (four) 20 mi. Suitable: person: separating the glass beads from the nickel oxide fresh material, using a doctor blade ^ the oxidized Yifu (four) cloth on the glass with the tin oxide conductive layer pre-attached to the loot for 30 minutes pre-drying, Electric furnace, lion, lion. Calcination was carried out for 30 minutes under c to obtain a nickel oxide film. μ i The above R.1 separately dissolves the dye of the present invention shown in Table 15 and the comparative dye B-3 in a diterpene; 5 wind. The concentrations of the pigments were respectively lxl〇-4 m〇1/L. Next, the glass plate in which the film-form nickel oxide was formed was placed in the solution, and the dye was adsorbed for 60 minutes under the chuanxiong, and then dried to form the second photoelectric conversion layer of the present invention. B. (3) The photoelectric conversion element was fabricated so that the sample B was placed on the sample A. A liquid electrolyte was placed between the two electrodes, and the side surface was sealed with a resin, and a lead wire was attached to form a photoelectric conversion element (component configuration C). In addition, the lanthanum is used in a mixed solvent of acetonitrile/ethylene carbonate (volume ratio: 丨: 4) to dissolve tetrapropylammonium iodide and iodine so that the respective concentrations become 〇46 m〇i/; L, O() 6 mol/L. Further, a transparent conductive glass plate having the sample A as one of the electrodes and carrying the same as the opposite electrode was used. A liquid electrolyte was placed between the two electrodes, and the side surface was sealed with a resin, and a lead wire was attached to prepare a photoelectric conversion element (component configuration D). 141 2〇12lll65 Hunting by sunlight simulation w/ 2 ------- Too (7) (1) The intensity of the intensity of the black enamel is measured by the illumination of the fork-electrical conversion element. The results are shown in Table 15. The case where the conversion efficiency is 6.5% or more is expressed as ◎, and the case where 1 is less than 6.5% is expressed as. The case where 5 Q% or more and less than ^ is represented as Δ, and the case where less than 5·〇% is expressed as χ. ·. .

[Table 15] Table 15

The rate is excellent: the first electric conversion effect of the photoelectrochemical cell with knowledge === [Experiment 17] ^ An example of using a polymer electrolyte to produce a color-cutting type photoelectric is described. The dry electricity/coating liquid for oxidizing the immersion film is made of glass beads, and commercially available titanium oxide particles (manufactured by Tayea Co., Ltd., trade name αμτ_仪, anatase crystal, average particle size 3 Å) are used. Nm, specific surface area of 5 〇 m2 / g) = g and diethylene glycol mono (tetra) 20 ml dispersion for 7 hours to prepare the oxidation of the suspension. The glass beads are separated from the titanium oxide suspension by filtration, and used to a knife, with a film thickness of about 11 μχη, 〇 mmx 〇 right area

Sn 〇 2 is a transparent conductive film formed on a substrate on a glass substrate 1 , and the 142 201211165 titanium oxide suspension is applied to the transparent conductive film side, and pre-dried by Sun Bazhong at 1 〇〇〇 c, at 460 The crucible was calcined for 40 minutes under oxygen, and the mangosteen was made into a titanium oxide film a having a film thickness of about 8 μηη. Then, the dye of the present invention and the comparative dye B-3 were dissolved in absolute ethanol at a concentration of 3 x 1 〇 -4 mol / liter, respectively, to prepare a dye solution for adsorption. The dye solution for adsorption and the transparent substrate having the ruthenium oxide film and the conductive film obtained as described above were placed in a container and allowed to permeate for about 4 sec to adsorb the dye. Thereafter, it was dried by using anhydrous ethanol at about 60 ° C for about 20 minutes. 'Monthly, a polymer compound composed of the following monomer units is prepared: in the mercapto acrylate monomer unit represented by the following formula (105), R is a methyl group, and A is 8 poly The oxirane group and the two polypropylene oxide groups form a central core and are composed of a butane tetra group. General formula (105)

(In the formula, R is a fluorenyl group, and A is a residue in which a carbon atom is bonded to a vine group, and η is 2 to 4.) The above monomer unit is dissolved in a concentration of 20 wt% in propylene carbonate 143 201211165 In the case of PC, the 'azo' is used as a thermal polymerization initiator, and the butyronitrile (AIBN) is prepared as a monomer solution at a concentration of i wt% relative to the monomer. The monomer solution is inferior to the titanium oxide film by the method of the town. A container such as a beaker is placed in the vacuum chamber of the channel Z, and a titanium oxide film A having a transparent transparent substrate is placed therein, and a vacuum is applied by a rotary pump at about 10,000 Torr. - The surface of the vacuum vessel is kept in a vacuum state. The immersion solution is immersed for about 15 minutes (four) to make the lye solution sufficient / 12 to the titanium oxide towel. Set polyethylene separator, ΡΕτ film and pressure plate ^; Thereafter, _85 ΐ was applied for 30 minutes to thermally polymerize to form a polymer compound layer on the titanium oxide film. It is produced by redox electric charge impregnated in a polymer compound. The redox electrolyte is prepared by using Pc as _, a dissolved concentration of 0 5 and a concentration of _mole/liter. In this: the trough liquid T is impregnated with the above-mentioned oxidized __ polymer compound produced by infiltration into a redox electric (four) agent, the conductive substrate 'by epoxy sealing and 'to make the titanium oxide film Α After the adsorption of the pigment, it is not treated. 'The solution will be dissolved in PC $ solvent and 漠5 mol / liter ^ = concentration is made of G.G5 Moere / liter of redox electrolyte 匕 ^ main Between the opposing electrodes, sealing is performed to form the element B. Using A and B, the conversion efficiency was measured by irradiating _w/ = degree light with a solar simulator. The results are shown in Table 16. Strong 144 201211165 The case where the conversion efficiency is 3.5% or more is expressed as ◎, the case where 2.5% or more and less than 3.5% is expressed as 〇, and the case where 2.0% or more and less than 2.5% is expressed as Δ, which is less than 2.0%. Expressed as X. [Table 16] Table 16 Sample No. Element First Pigment Conversion Efficiency Preparation 16-1 A Al ο The present invention 16-2 B Al ο The present invention 16-3 A A-9 ◎ The present invention 16-4 B A-9 ◎ 16-6 A A-15 of the present invention ◎ 16-6 B A-15 of the present invention ◎ 16-7 A A-27 of the present invention ◎ 16-8 B A-27 of the present invention ◎ 16-9 A B-3 X of the present invention Comparative Example 16-10 B B-3 Δ The comparative example shows that the element using the dye of the present invention is excellent in photoelectric conversion efficiency and is also effective in the system. [Experiment 18] (Production of photoelectric conversion element) The photoelectric conversion element 10 shown in Fig. 1 was produced in the following manner. On the glass substrate, a fluorine-doped tin oxide is sputter-coated to form a transparent conductive film, which is scribed by a laser to divide the transparent conductive film into two portions. Next, 32 g of anatase type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) was blended in 100 ml of a mixed solvent of water and acetonitrile in a volume ratio of 4:1, and the rotation was used. /Revolving and uniformly dispersing and mixing with a mixing regulator to obtain a semiconductor fine particle dispersion. 145 201211165 This dispersion was applied onto a transparent conductive film, and heated at 500 ° C to prepare a light-receiving electrode. Thereafter, a dispersion containing cerium oxide particles and rutile-type titanium oxide in a ratio of 40:60 (weight ratio) was prepared in the same manner, and the dispersion was applied onto the light-receiving electrode, and heated at 500 ° C. An insulating porous body is formed. Next, a carbon electrode is formed as a counter electrode. Next, the glass substrate on which the insulating porous body was formed was immersed in the ethanol solution A of the sensitizing dye (mixed or separately) described in the following Table 17 for 5 hours. The glass to which the sensitizing dye was dyed was immersed in a 4-3% butyl group in a 10% ethanol solution for 30 minutes, and then naturally dried by washing with ethanol. The thickness of the photoreceptor layer thus obtained was 1 Å, and the coating amount of the semiconductor fine particles was 20 g/m2. The electrolyte was a solution of dimethyl propyl iodide (0.5 mol/L) and angstrom (0.1 mol/L) in methoxypropionitrile. (Measurement of conversion efficiency)

The light of a 500 W xenon lamp (manufactured by Ushio Inc.) was passed through an AM1.5G light-based film (trade name, manufactured by Oriel Co., Ltd.) and a chopper filter (Kenko L-42, trade name) to produce ultraviolet-free light. Simulate sunlight. The intensity of ° Haiguang is 89 m\V/cm2. The light was applied to the produced photoelectric conversion element, and the generated electricity was measured by a current-voltage measuring device (Keithley Model 238, trade name). The results of measuring the conversion efficiency of the photoelectrochemical cell obtained thereby are shown in Table 17 below. As a result, the conversion efficiency was 7.5% = the upper case was evaluated as ◎, the case where 7.3% or more and less than 7.5% was evaluated as 〇, and the case where 7.1% or more and less than 7.3% was evaluated as Δ, which was less than 7.1%. The situation was evaluated as X. 146 201211165 [Table π] Table 17 Sample No. 1st pigment (adsorption solution concentration X ΚΓ4 m〇I/L) 2nd pigment (adsorption solution concentration MO4 γποΙ/Ι^ Conversion efficiency test 17-1 R-7 1 Α 15 0.1 ◎ The present invention 17-2 R-7 1 Α-27 0.5 ◎ The present invention 17-3 R-7 1 Α·27 0.1 ◎ The present invention 17-4 R-13 1 Α·15 ' 0.1 ◎ The present invention\ n &lt; R-13 Α-27 1 0.5 ◎ The present invention 17-6 R-13 Α-27 1 0.1 ◎ The present invention 17-7 R-7 Α-1 * 1 0.1 ο The present invention 17-8 R-7 Α -9 1 0.5 ◎ The present invention 17-9 R-7 Α-9 1 0.1 ◎ The present invention 17-10 R-13 Α-1 1 0.1 ο The present invention 17-11 R-13 Α·9 1 0.5 ◎ The present invention 17 -12 R-13 Α^9-- 1 0.1 ◎ 17-13 R-7 Β·3 1 0,1 X of the present invention Comparative Example 17-14 R-13 Β·3 1 0.1 X Comparative Example 17-15 R- 7 - 1 X Comparative Example 17-16 R-13 Μ. —-----1 -1 - X Comparative Example An electrochemical cell produced by using the dye of the present invention is as shown in Table 17 (1) When the combination of the pigment of the shirt and the pigment represented by the formula (13), the conversion efficiency shows up to 75% or more. For the other cases, the conversion efficiency of the comparative example is less than 7 1% and is not sufficient. ' 147 201211165 [Experiment 19] 1. The internal volume of the titanium oxide dispersion prepared on the inside coated with the fluororesin is 2〇〇. In the non-mineral steel container of ml, titanium dioxide fine particles (manufactured by A_u Co., Ltd., Deg surface P-25) 15 g, water 45 g, dispersant (made by aldrich, WronX·) ig, diameter 〇5 legs 3 〇g of oxidized granules (manufactured by Nikkato Co., Ltd.) was subjected to a dispersion treatment at 1 rpm for 2 hours using a sand mill (manufactured by kka c〇, (5). The oxidized granules were separated from the obtained dispersion. The average particle diameter of the titanium oxide fine particles in the dispersion is 2 - 5 μηι. The particle size is measured by Mastersizei (trade name) manufactured by MALVERN. 2. The titanium oxide fine particle layer (electrode A) to which the pigment is adsorbed The conductive glass plate of 2〇mmX2〇mm coated with fluorine-doped tin oxide (manufactured by Asahi Glass Co., Ltd., trade name: TC〇GLASS-U, surface resistance of about 3〇i2/m2) is prepared. Guide Both end sides of the layer (starting from the end portion of 3 mm width) was attached with the adhesive tape spacer 'Using a glass rod coated with the above dispersion on the conductive layer. After the application of the dispersion, the adhesive tape was peeled off and air-dried at room temperature for 1 Torr. Next, the semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 type manufactured by Yamato Scientific Co., Ltd.), and calcined at 450 ° C for 30 minutes. After the semiconductor coated glass plate was taken out and cooled, it was immersed in an ethanol solution of the pigment shown in Table 18 (concentration: 3xl·4 mol/L) for 3 hours. The semiconductor-coated glass plate to which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, and then washed with ethanol to be naturally dried to obtain an adsorbed colored 148 201211165 element, a titanium oxide fine particle layer (electrode A). . The dye-sensitized oxide of the electrode A has a thickness of 1 μm ηη and a coating amount of the titanium oxide fine particles of 2 〇 g/m 2 . Further, the amount of adsorption of the pigment is in the range of 0.1 mm 〇 l / m 2 to 10 mmol / m 2 depending on the type thereof. 3. Preparation of dye-sensitized photoelectrochemical cell The dye-sensitized electrode A (2 mm plus mm) prepared as described above was superposed on a platinum vapor-deposited glass having the same size. Next, the capillary composition is used to infiltrate the electrolyte composition into the gap between the two glasses, and the electrolyte is introduced into the titanium oxide electrode. Thus, as shown in FIG. 2, a conductive support i composed of a conductive glass (a conductive layer provided on a transparent substrate of glass), a photoreceptor 2, and a charge transporting body 3 are sequentially laminated. A dye-sensitized electrochemical cell in which a counter electrode 4 made of platinum and a transparent substrate of glass (not shown) are sealed by an epoxy sealant. Among them, when the viscosity of the electrolyte composition is high and it is difficult to infiltrate the electrolyte composition by capillary action, the electrolyte composition is heated to. After applying it to the emulsified electrode, the electrode was placed under reduced pressure to sufficiently permeate the electrolyte composition, and the air in the electrode was removed, and the vapor-deposited glass (counter electrode) was laminated to produce a dye-like color. Photosensitive electrochemical cell. θ The dye was changed to perform the above procedure. A dye-sensitized electrochemical cell of sample No. 18-1 to sample No. 18-9 was produced. As the electrolyte composition used in each dye-sensitized electrochemical cell, an electrolyte composition containing 98% by weight of the above heterocyclic quaternary salt compound and 2% by weight of iodine was used. 149 201211165 [Chemical 39] H3C N^N^^^CHa 4. Measurement of photoelectric conversion efficiency The light of a 500 W xenon lamp (manufactured by ushio Inc.) was passed through an AM1.5 filter (manufactured by Oriel) and chopping The filter (KenkoL-37)' produces a simulated sunlight that does not contain ultraviolet light. The intensity of the light is 70 mW/cm2. The simulated sunlight was irradiated onto a dye-sensitized electrochemical cell under 50X:, and the generated electricity was measured by a current-voltage measuring device (Keithley SMU238 type). Further, the rate of decrease in conversion efficiency after storage for 1000 hours in a dark place at 85 ° C and the rate of decrease in conversion efficiency after continuous light irradiation for 5 hours were also measured. The results of these are shown in Table 18. [Table 18] Table 18

According to Table 18, it was found that the pigment optical cell of the present invention has improved durability as compared with the case of 150 201211165. [Experiment 20] A dye-sensitized electrochemical cell was produced and evaluated according to the method described below. The results are shown in Table 19. Ο) Preparation of a transparent conductive support as a support for a photosensitive electrode, a film coated with a conductive tin oxide uniformly coated on a single surface of a thin plate having a thickness of 0.4 mm on a surface coated with a thickness of 2 nm It has a flexible transparent conductive support. (2) A conductive sheet made of a counter electrode is coated on a single side of a Kapton (registered trademark) film made of polyimide having a thickness of 0.4 mm, and uniformly coated with a thickness of 3 Å by vacuum sputtering. Platinum film. The surface resistance is 5 Q/cm 2 . (3) Modulation of semiconductor fine particle dispersions According to C. J. Barbe et al., Journal of the American Ceramic Society (J Am)

Ceramic Soc.) The manufacturing method described in the paper of Vol. 80 and p. 3157. The titanium raw material is titanium tetraisopropoxide, and the polymerization temperature in high pressure dad will be 230C, and the concentration of titanium dioxide will be u wt. A dispersion of % anatase titanium dioxide. The primary particles of the obtained titanium oxide particles have a size of 10 nm to 30 rnn. The obtained dispersion was placed in an ultracentrifuge. The particles were separated, and the aggregate was added to the mixture, and then pulverized on a spider to obtain a semiconductor residue a of the color powder. Adding semiconductor fine particles a' in a concentration of 32 g per 〇〇 solvent in a mixture of water and B. The volume ratio of water to B is 4:1, using auto-rotation/revolution and mixing with H The obtained material is dispersed and mixed, and the obtained 151 2 〇l 2lll65 white semiconductor fine particle dispersion becomes a paste having a south viscosity of 5 〇Ν·s/m 2 to 150 Ν·s/m 2 , which is known to be suitable for direct use. Liquid properties of the coating. In sample No. 丨9-3 and sample No. 19-10, 7.7 g of a polyethylene glycol (pEG) powder having an average molecular weight of 50,000 was prepared per 1 ml of the solvent. Solid matter other than semiconductor microparticles is not added to other semiconductor fine particle dispersions. (4) Determination of the solid matter in the semiconductor fine particle dispersion solution = The applicator applies the dispersion to a thickness of 9 coffee, and then applies it to the thickness of 4〇卿~70卿. Room temperature ί ί. Thereafter, the weight change before and after heating of 0.5 small 19-3 was carried out in air and under 3 thieves. As a result, the solid content of the sample No. other than the semiconductor fine particles was 0.3. /. The solid matter other than the semiconductor fine particles outside the M type contains (5) the production and coating of the semiconductor fine particle layer (3) Gig:: The electric yoke is formed by the applicator to form a handsome ~ 70 clear The coated layer was subjected to the conditions described in 19 for 1 hour. In addition, the average film thickness of the surface of the porous semi-conductive granules by the surface sensitization is the highest (-) the fine particle layer of the conductor particles (6) the polymerization of the pigment adsorption solution is as shown in Table 19. The concentration of the dye dissolved in the dry method is (4)·4 mol/ • the second butanol: ethanol volume ratio is 152 201211165 3y〇2bpif 2 ·· 1 : 1 in a mixed solvent. In the dye solution, the structure of p-C9H19-C6H4-0-(CH2CH2-〇)3-(CH2)4-S〇3Na as an additive is dissolved in a concentration of ο 〇25 mol/liter. An organic sulfonic acid derivative is used to prepare a solution for dye adsorption. (7) Adsorption of the pigment The substrate coated with the porous semiconductor fine particle layer was immersed in the above-mentioned adsorption dye solution, and stirred under stirring. (: It is left for 3 hours. As described above, the dye is adsorbed on the semiconductor fine particle layer to prepare a dye-sensitized electrode (photosensitive electrode) used in the photosensitive layer. (8) Production of a dye-sensitized electrochemical cell is scraped off The photosensitive porous semiconductor fine particle layer was adsorbed to form a circular photosensitive electrode having a light receiving area of 1.0 cm 2 (approximately 1.1 cm in diameter). For this electrode, a thermocompression-bonded polyethylene film frame spacer (thickness 2 〇 μηι) was inserted. The platinum vapor-deposited glass substrate on which the counter electrode is laminated is heated to 120. (: The two substrates are pressure-bonded. Further, the edge portion of the cell is sealed by an epoxy resin adhesive. By using a small hole for electrolyte injection in advance at the corner of the substrate of the counter electrode, any imidazolium ion m to imidazole rust ion E4/disc - 50. 1 (weight ratio) which will be described later is used as an electrolyte solution by capillary action. The room temperature (4) formed by the composition is infiltrated into the space between the electrodes from the small holes of the substrate.

El : 1,2-dimercapto-3-propylimidazolium iodide E2 : 1-butyl-3-methyl sulphonate E3 : 1-methyl-3-propyl imidazolium rust salt E4 : 1,3-bis(2-(2_(2_曱ethoxyethoxy)ethyl)ethyl) oxime ore 153 201211165 The unit assembly step and the electrolyte injection step above the eutectic salt are all in the above It is carried out in a dry air with a dew point of -60 °C. After the injection of the molten salt, the unit was suctioned under vacuum for several hours to degas the inside of the unit including the photosensitive electrode and the molten salt, and finally the small pores were sealed with the low-melting glass. Thus, a dye-sensitized electrochemical cell in which a conductive support, a porous semiconductor fine particle electrode (photosensitive electrode) to which a dye is adsorbed, an electrolytic solution, a counter electrode, and a support are sequentially formed. (9) Evaluation of a dye-sensitized photoelectrochemical cell in a 500 W gas lamp (manufactured by Ushio Inc.), a calibration filter for solar light simulation (AM1.5direct (trade name) manufactured by Oriel Co., Ltd.), self-porous The side of the semiconductor fine particle electrode (photosensitive electrode) irradiates the above-mentioned dye-sensitized electrochemical cell with simulated sunlight having an incident light intensity of 1 μm/cm 2 . The components are closely attached to the platform of the thermostat, and the temperature of the components in the illumination is controlled to 50. (: Using a current-voltage measuring device (a type of power measuring unit 238 manufactured by Keithley Co., Ltd. (trade name, the DC current applied to the element is scanned at a constant speed of 10 mV/sec, and the photocurrent output from the element is measured, thereby The photocurrent-voltage characteristics were measured, and the energy conversion efficiency (η) of the various elements obtained above was described in Table 19 together with the contents of the constituent elements (semiconductor particles and sensitizing dye) of the unit. In the case of 6 〇% or more, it is expressed as Α, the case where the above is less than 6% is expressed as b, and the case where 4% or more and less than 5% is expressed as C', and the case where 3% or more and less than 4% is expressed as D In the case where 15% or more and less than 3% is expressed as e, it will be less than 1.5. The case indicates that 154 201211165 厶Ujjif is F, the conversion efficiency is D or more as qualified, and the case where D is less than D is regarded as unqualified. The reduction rate of conversion efficiency after continuous light irradiation for 120 hours was also measured. The results are shown in Table 19. [Table 19] Table 19 Preparation Conditions of Sample Battery Battery Performance Test No. Conductive Support 1st Pigment No. 2 pigment electricity Solid content outside the semiconductor of the liquid coating liquid Heat treatment after UV coating/UV treatment conversion efficiency (%) Conversion efficiency reduction rate after continuous light irradiation % 19-1 PEN A-27 - E3 0.3 120 °CUV treatment A 7 The present invention 19-2 PC A-27 - E3 0.3 120 ° C UV treatment A 7 19-3 PEN A-27 - E3 1 120 ° C UV treatment A 8 19-4 PC A-27 - E3 0.3 90 ° CUV treatment B 7 19-5 PEN A-27 - E3 0.3 90 °C UV treatment B 9 19-6 PEN A-27 - E3 0.3 150 ° C UV treatment A 5 19-7 PEN A-27 E3 0.3 200 ° C UV treatment B 5 19-8 PEN A-15 - E3 0.3 120 ° C UV treatment A 5 19-9 PC A-15 - E3 0.3 120 ° C UV treatment A 4 19-10 PEN A -15 - E3 1 120 ° CUV treatment A 6 19-11 PC A-15 - E3 0.3 90 ° C UV treatment B 5 19-12 PEN A-15 - E3 0.3 90 ° C UV treatment B 7 The present invention 19 -13 PEN A-15 - E3 0.3 150 °C UV treatment A 5 19-14 PEN A-15 - E3 0.3 200 ° C UV treatment B 5 19-15 PEN B-2 - E3 0.3 120 ° C UV treatment D 35 Comparative Example 19-16 PC B-2 - E3 0.3 90°C UV Treatment E 38 Comparison Example 19-17 PEN B-2 - E3 0.3 150 °C UV treatment D 39 Comparative Example 19-18 PEN B-2 - E3 0.3 200 °C UV treatment E 39 Comparative Example 19-19 PEN A-27 E2 0.3 120 °C UV treatment A 4 19-20 PEN A-27 - El 0.3 120 ° C UV treatment A 3 19-21 PEN A-27 - E4 0.3 120 ° C UV treatment A 4 19-22 PEN Al - E3 0.3 120 ° CUV treatment C 13 19-23 PC Al - E3 0.3 120 ° C UV treatment C 15 19-24 PEN Al Rl E3 0.3 120 ° C UV treatment B 18 19-25 PC Al Rl E3 0.3 120 ° C UV treatment B 20 19-26 PEN Al R-7 E3 0.3 120 ° C UV treatment B 17 19-27 PC Al R-7 E3 0.3 120 ° C UV treatment B 17 19-28 PEN Al R-8 E3 0.3 120°C UV treatment B 15 19-29 PC Al R-8 E3 0.3 120°C UV treatment B 15 The present invention 155 201211165 As shown in Table 19, it is known that adsorption is formed on the conductive support made of a conductive polymer. In the case of the porous semiconductor fine particle layer of the dye of the present invention, a dye-sensitized electrochemical cell having a practical level of photoelectric conversion efficiency is obtained. In particular, a dispersion having a solid content of 0.3% other than the semiconductor fine particles was applied onto the support at 120 ° C to 150 ° C. (When the heat treatment is performed, the ultraviolet ray is irradiated, and then the pigment of the present invention is adsorbed to form a porous semiconductor fine particle layer, the photoelectric conversion efficiency is high. Further, the dispersion having a solid content of 1.0 Wt% is obtained. It is applied to a support made of a conductive polymer and heated to form a porous semiconductor fine particle layer, and when the pigment of the present invention is adsorbed, a conversion efficiency higher than that in the case of adsorbing a comparative dye is also obtained. In the case of a dye-sensitized electrochemical cell using a comparative dye, the rate of decrease in conversion efficiency after continuous light irradiation is as high as 35% or more, whereas the present invention is used. In the case of a dye-sensitized electrochemical cell of a pigment, the conversion efficiency after continuous light irradiation is 20% or less, and the durability is excellent. [Experiment 21] Used by Epikote 828 ((trade name), Japan Epoxy Resins A resin having a diameter of 25 μm is substantially uniformly dispersed in a resin composition composed of a hardener and a plastic paste. The sealing agent paste was prepared in the same manner as the epoxy-based sealing agent of [Experiment 19], and a dye-sensitized electrochemical cell was produced to measure the photoelectric conversion efficiency. The conversion efficiency was 6.0% or more. The case is expressed as A, the case where 5% or more and less than 6% is expressed as B, and the case where 4% or more and less than 5% is 156 201211165 is expressed as C, and the case where 3% or more and less than 4% is expressed as D,丨5〇/〇 or more and less than 3% is expressed as E, less than 15% is expressed as F, conversion efficiency is D or more as qualified, and insufficient is considered as unqualified. The conversion efficiency (η) of each dye-sensitized solar cell obtained, the conversion efficiency of the conversion efficiency with respect to the initial value after storage for 1 hour at 85 c, and the conversion after continuous light irradiation The rate of decrease in efficiency with respect to the initial value is shown in Table 2. [Table 20] Table 20 Sample No. 1st Pigment Second Pigment Conversion Efficiency Conversion Efficiency Reduction Rate after Storage in Dark Places Reduced Conversion Efficiency After Continuous Light Irradiation Rate % preparation

According to Table 20, the initial values of the conversion efficiency of the dye-sensitized electrochemical cell of the present invention all showed values of up to 7 % or more. Further, after storage in the dark and after continuous light irradiation, the reduction rate was 15% or less and 2% or less, and the durability was excellent as compared with the comparative example. The present invention has been described based on the above-described embodiments, but if the invention is not in any of the details of the description of the 157 201211165 Γΐ Γΐ Γΐ ( ( 四 四 四 四 四 请 请 请 财 财 财 财 财 财 财 财A wide range of explanations. 'The application for this month's application is based on the priority of 2010-174833, which is filed in Japan on August 3, 2010. The patent application is hereby incorporated by reference. Enter one of the parts described in this manual. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A schematically shows a wearing diagram of an embodiment of a photoelectric conversion element manufactured by the present invention. [Description of main component symbols] 1: Conductive support 2. Photoreceptor layer/photoreceptor/photosensitive layer (semiconductor film) 3: Charge moving body layer 4: Counter electrode 5: Light-receiving electrode 6: Circuit/external circuit 10: Photoelectric conversion element 21: Pigment 22: Semiconductor microparticles / Conductive microparticles 100 · Photoelectrochemical cell 158

Claims (1)

201211165 j^uz-opif Seven patent application scope: l. A metal complex pigment, which is represented by the following formula (丨): General formula (1) M(LL1)ml(LL2)m2(X)m3 - CI is in the formula (1), M represents a metal atom, LL1 represents a 2-dentate or 3-dentate ligand represented by the following formula (2), and LL2 represents a 2-dental represented by the following formula (7) Or a ligand of 3 teeth, X represents a group selected from the group consisting of a decyloxy group, a sulfonylthio group, a thiomethoxy group, a thiocyanyl group, a decylamino group, a thiol phthalate group, and a dithiol group. Phthalate ester group, sulfur carbon ester group, dithiocarbonate group, trithiocarbonate group, mercapto group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group, a monodentate or a 2-dentate ligand coordinated to a group consisting of a sulfur-based i-arylthio group, an alkoxy group, and an aryloxy group, or a halogen atom, a carbonyl group, a dialkyl ketone, 1, a monodentate or a 2-dentate ligand consisting of 3-diketone, carboxyguanamine, thiocarbamamine or thiourea, and ml means an integer of 1 to 3'. When the ml is 2 or more, LL1 may be the same. Different, m2 represents an integer of 〇~2, When m2 is 2, LL2 may be the same or different, m3 represents an integer of 〇~3, and when m3 is 2 or more, X may be the same or different, and X may be connected to each other, and CI indicates that the charge is neutralized. It is necessary to counter the anti-159 201211165 balance ion; LL1, LL2, X have at least one acidic group; Η匕1] In the formula (2), R1 and R2 each independently represent an acidic group, and R3 and R4 each independently represent a substituent, and Υ1 and Υ2 each independently represent a formula (3) to a formula ( 6) a substituent obtained by desorbing two hydrogen atoms from a ring represented by any formula of the formula, wherein Υ3 and Υ4 represent a hydrogen atom or a substituent; and L1 or L2 each independently represents an alkynylene group, an arylene group or a common chain composed of a combination of bases; al and a2 each independently represent an integer of 0 to 3, and when a1 is 2 or more, R1 may be the same or different, and when a2 is 2 or more, R2 may be the same or different; Μ and b2 each independently represent an integer of 0 to 3. When bl is 2 or more, R3 may be the same or different, and may be connected to each other to form a ring. When b2 is 2 or more, R4 may be the same or different. R1 and R4 may be linked to each other to form a ring; n1 and n2 each independently represent an integer of 1 or more, and n3 and n4 respectively represent 160 or more, and 201211165 independently represents 1 or more. An integer; wherein, when n3 is 2 or more, a plurality of Y1s may be the same or different 'at n4 In the case of 2 or more, a plurality of Y2 may be the same or different; z represents 0 or 1; [Chemical 2] (R7) n7 General formula (3) general formula (4) (R8)n8 (R9)n0 (R11)n11 General formula (6) General formula (5) In the general formulae (3) to (6), R5 to R11 represent a substituent, and n5 to nil each independently represent an integer of 〇~2, and a plurality of R5 to rH are also The ring may be bonded to adjacent substituents to form a ring; the sum of n6 and n7 is 2 or less; the sum of η8 and η9 is 2 or less; and the sum of n10 and nil is 2 or less; [Chemical 3] In the formula (7), Za, Zb and Zc each independently represent a group of non-metal atoms which can form a 5-membered ring or a 6-membered ring, and may each independently have a substituent; c represents hydrazine or 1. 2. The metal complex dye according to claim 1, wherein in 161 201211165, in the formula (1), the LL1 is a 2 tooth or a 3 tooth represented by the formula (2A). Ligand: [Chemical 4] Y -(y1)n3-(L1)n1 (L2)n2—(Υ2)η4-γ4 (R3)b1·—^=N/Ni^^'(R4)b2 General formula (2A) In the formula (2A), R1, r2, R3, R4, γΐ, γ2, γ3, YL, L, 31, 82, 1)1, 62, 111, 112, 113, 114 and the formula ( 2) R1, R2, R3, R4, γ1, γ2, Υ3, γ4, L1, l2, and a2, bl, b2, nl, n2, n3, and n4 are synonymous. 3. The metal complex dye according to claim 1, wherein in the formula (2), l1 and L2 represent an arylene group. 4. The metal complex dye according to claim 2, wherein in the formula (2A), L1 and L2 represent an arylene group. The metal complex dye according to the first or third aspect of the invention, wherein in the formula (1), LLi is a tooth represented by the following formula (8) Or the ligand of 3 teeth: [Chemical 5] 2 201211165 N3, n4, and z are synonymous. , Y1, Y2, Y3, γ4, n2, n3, n4, z and Ri, nl, n2, Y3, Y4, ab, a2, b, b2, n in the general formula (2), as claimed in the patent application The complex dye according to any one of the items 1 to 5, wherein, in the formula (1), LL1 is a coordination of 2 or 3 teeth represented by the following formula (8A) Base: [Chem. 6] In the general formula (8A), EL1, R2, R3, R4, γΐ, γ2, γ3, Η2, η3, η4 are synonymous. 7. The metal complex dye according to any one of claims 1 to 6, wherein in the formula (1), Μ represents 钌. 8. The metal complex dye according to any one of claims 1 to 7, wherein the substituent obtained by desorbing 2 hydrogen atoms from the ring represented by the formula (3) Expressed by the following general formula (3Α): 163 201211165 [Chem. 7] In the formula (3A), n5 is bonded to the bond in the formula (3), and ** is represented in Shao 0. The metal complex dye according to any one of the above items, wherein the formula (1) to any of the formula (5) to the formula (5) is represented by the following formula: R12 R13 R16 General formula (9) R15 R1e, Ύ R19 Formula (ίο) Formula (η) R22 Wherein f, 〜5, r16, r18, a non-hydrogen atom or a substituent; * 丨K clothing represents a bond on the bond on L*L, which is described in item 9 of the full-time The metal complex dye, the substituent represented by any one of the formulas (9) to (10), wherein the 201211165ir group has at least one aliphatic group having 5 or more carbon atoms. A photoelectric conversion element comprising a photosensitive layer having a metal complex dye and a semiconductor microparticle according to any one of claims 1 to 10. 12. The photoelectric conversion element according to claim 5, wherein the metal complex dye described in the above formula (1) is used in combination with other dyes. 13. The photoelectric conversion element according to claim 12, wherein the other coloring matter is represented by the formula (13): ^ Mz(LL)mll(LL12)ml2(x&quot;)ml3. CI&quot; In the formula (13), Mz represents a metal atom, and the group LL11 represents a 2-dentate or 3-dentate ligand LL12 represented by the following formula (14), which is represented by the following formula (15). The coordination X11 of the tooth or tooth is selected from the group consisting of a decyloxy group, a thiol group, a thioloxy group, a thioindole = a sulfhydryl group, an aryl group, a thiomethyl group, a dithiol group. Formic acid bismuth, dithiocarbonate s, trithiocarbon-based, brewing, f =, isothiocyanate, cyanate, isocyanate, cyanarylthio, alkoxy and a group consisting of an aryloxy group, an early or a 2-dentate ligand, or a self-priming atom, a aryl group, a 165 II 201211165 dialkyl ketone, a 1,3-diketone, a carboxy oxime group, a single or two-dentate ligand composed of thiocarbalamine or thiourea, mil represents an integer of 0 to 3, and when mil is 2 or more, LL11 may be the same or different, and ml2 represents an integer of 0 to 2 , when ml2 is 2, LL12 The same may be different; wherein, at least one of mil and m12 is an integer of 1 or more; ml3 represents an integer of 0 to 3, and when ml3 is 2 or more, X11 may be the same or different, and X11 may be connected to each other; CI11 represents a counter ion in the case of neutralizing a charge in order to neutralize a charge, and any one of LL11, LL12, and X11 has at least one acidic group; [Chem. 9] 121 .-, 106' dlZ /d13 (R1〇2)a, 2 General formula (14) In the general formula (14), rKH and R1〇2 each independently represent an acidic group, and R1G3 and R1G4 each independently represent a substituent, and R1G5 and R1G6 each independently represent An alkyl group, an aryl group or a heterocyclic group; L11 and L12 each independently represent a conjugated chain composed of at least one selected from the group consisting of an arylene group, a heteroarylene group, a vinylidene group and an ethynylene group; 166 201211165f all And 12: respectively, the integers of 〇~3 are independently represented. When a 2 or more, 'R may be the same or different. When the mountain is 2 or more, (4) may be the same or different; and =12 respectively represent Q~3. In the case of b, the R(10) may be the same or different, and R~ may be connected to each other to form a sorrow. When bl2 is 2 or more, R1〇4 may be the same or different, and Ri〇4 may be connected to each other to form an integer. Ring; both M1 and bl2 are 丨, and R104 can also be joined to form a ring; f K and dll and dl2 respectively represent integers of 〇~$. dl3 represents 0 or 1; , [10] In the formula (15) = in the formula (15), Zd, Ze &amp; Zf each independently represent a group of non-metal atoms which can form a 5-membered ring or a 6-membered ring, and may have a substituent; the f represents 0 or 1. The photoelectric conversion element according to any one of the preceding claims, wherein the photoconductor layer, the charge transporting body and the counter electrode are sequentially laminated on the electroconductive support. A photoelectrochemical cell of the invention, which has the photoelectric conversion element according to any one of claims 11 to 14. 167