TW201004997A - Dye for dye-sensitized solar cell and dye-sensitized solar cell - Google Patents

Abstract

Disclosed is a dye for dye-sensitized solar cells, which exhibits high affinity and adhesion to porous metal oxides, while having excellent solubility in organic solvents. The dye for dye-sensitized solar cells contains a specific phosphorylthiophene compound represented by formula (1). A dye-sensitized solar cell using the dye for dye-sensitized solar cells is also disclosed.

Description

[Technical Field] The present invention relates to a dye for a dye-sensitized solar cell and a dye-sensitized solar cell using the same. [Prior Art] In order to solve the energy problems and global environmental problems faced in recent years, there have been various investigations about the energy that can replace traditional fossil fuels. Among them, solar cells using solar energy, which are not only infinite resources, but also environmentally-friendly devices, have received great attention. Among them, especially pigment-sensitized solar cells, which have cheap materials for use, There is no need to use vacuum equipment in the manufacturing process, so since the proposal of Gu Lierer et al., it has been in full swing in the direction of practical use. Φ In the dye-sensitized solar cell, a semiconductor electrode having a light absorbing effect is used in order to adsorb a dye onto a semiconductor electrode made of a porous metal oxide. The photoelectric conversion efficiency of the solar cell is proportional to the amount of electrons generated by the absorption of sunlight. Therefore, in order to improve the conversion efficiency, it is necessary to increase the amount of dye adsorption on the semiconductor electrode. Therefore, in the dye for a dye-sensitized solar cell, it is required to have high affinity or adhesion to the metal oxide. In addition, the adsorption of the dye on the semiconductor electrode is generally carried out in a solution obtained by dissolving the organic solvent of the 201004997 dye, and is carried out by impregnating the semiconductor electrode. Therefore, it is required for the organic solvent to have excellent solubility. Important nature. In the dye-sensitized solar cell dye, it has been reported that the carboxylic acid is introduced into the oligothiophene compound, and the affinity or adhesion to the porous metal oxide is improved (see Non-Patent Document 1). . However, with regard to the oligothiophene compound, there is no other method for improving the affinity and adhesion of the oligothiophene compound, and even the oligothiophene compound having a broad absorption wavelength is not carried out now. The same pigment design. Non-Patent Document 1: Tanaka K. et al., Chemistry Letters, 2006, 35(6), p. 592-593 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is, in view of the above, Further, there is provided a dye for a dye-sensitized solar cell which is excellent in solubility in an organic solvent and which has high affinity and adhesion to a porous metal oxide, and a dye-sensitized solar cell using the same. Means for Solving the Problems As a result of repeated efforts by the inventors to achieve the above object, a poly- or oligothiophene compound having a phosphate group was found, -6 - 201004997, except for a metal oxide. Since the porous semiconductor has excellent affinity and adhesion, and has good solubility in an organic solvent, it is suitably used as a dye for a dye-sensitized solar cell, and completed the present invention. In other words, the present invention provides a dye for a dye-sensitized solar cell, which comprises a phosphonylthiophene compound represented by the formula (1).

(wherein R1 to R4 and R13 to R16 each independently represent -OR5, -SR6, -NR72, or -CTN + rUMr11, and R5 to R11 each independently represent a hydrogen atom, a carbon number of 1 to 20 alkyl groups, or may be The phenyl 'Rl2 and R17 substituted by W each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amine φ group, a stanol group, a thiol group, a carboxyl group, an ester group, a thioester group, a decyl group, a cyano group, a nitro group, a monovalent hydrocarbon group, an organic oxy group, an organic amine group, an organic carbaryl group, an organic thio group, a decyl group, a sulfonic acid group, or a phenyl group which may be substituted, a halogen atom, a hydroxyl group, an amine Base, stanol, thiol, thiol, ester, thioester, decyl, cyano, nitro, monovalent, organooxy, organic amine, organomethylation, organothio a group, a fluorenyl group, or a sulfonic acid group, wherein m, 0, and P each independently represent an integer of 0 or more, and satisfy lgm + η + ο, and 2Sm + n + o + p$l〇〇〇, Z system a divalent organic group selected from the following formula (2) to (1〇), 201004997 [Chemical 2]

R18 to R4G each independently represent a hydrogen atom, a carbon number of 1 to 20 alkyl groups, a carbon number of 1 to 20 haloalkyl groups, a carbon number of 1 to 20 alkoxy groups, a carbon number of 1 to 20 alkylthio groups, and a carbon number of 1 〜20 dialkylamino group, or a phenyl group which may be substituted, R41 is a hydrogen atom, a carbon number of 1 to 20 alkyl groups, a carbon number of 1 to 20 haloalkyl groups, a carbon number of 1 to 20 alkoxy groups, or W is substituted with a phenyl group, and W is the same as defined above, except that the two ends of the phosphonylthiophene compound independently represent a hydrogen atom, a halogen atom, a carbon number of 1 to 20 monoalkylamine groups, and carbon. a 1 to 20 dialkylamino group, a phenyl group which may be substituted, a naphthyl group which may be substituted, a fluorenyl group which may be substituted, a C 1 to 10 trialkyl stannyl group, or a carbon number 1 to 10 trialkylmethanyl groups, which are the same as those described above). 2. A composition characterized by comprising a phosphonium thiophene compound 0 3- varnish, characterized by comprising a phosphonium thiophene compound of 1. 4. An organic thin film characterized by comprising 1 phosphonium Thiophene-8- 201004997 compound. 5. An organic film characterized by a varnish of 3. 6. A semiconductor electrode characterized by: a substrate having light transmittance, a transparent conductive film laminated on the substrate, and a porous semiconductor formed of a metal oxide laminated on the transparent conductive film; Further, a dye for a dye-sensitized solar cell of 1 is adsorbed on the surface of the porous semiconductor. A semiconductor electrode characterized in that a substrate having a porous semiconductor is immersed in a varnish of 3, and a dye for the dye-sensitized solar cell is adsorbed on the porous semiconductor. 8. A dye-sensitized solar cell characterized by comprising: a semiconductor electrode of six, a counter electrode, and an electrolyte interposed between the semiconductor electrode and the counter electrode. According to the present invention, it is possible to provide a dye for solar sensitization solar cell which has high affinity and adhesion to a porous metal oxide system and which has excellent solubility in an organic solvent system. And a pigment-sensitized solar cell using the same. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in further detail. In addition, 'n' in this manual refers to the positive, "i" refers to the difference, "-9- 201004997" refers to the second level "t" refers to the third level, "C" refers to the ring, "〇" refers to the neighbor "m" means "P" means "M" means methyl, r"" means ethyl, "ρΓ" means propyl, "Bu" means butyl, "Pen" "Hex" means "hexyl" "Hep" means heptyl, "Oct" means octyl' "Dec" means thiol, and "Ph" means phenyl. The dye for a dye-sensitized solar cell of the present invention is a compound containing a phosphonium thiophene compound represented by the above formula (1). In the formula (1), the carbon number is 1 to 20 alkyl groups, for example, a methyl group, an ethyl group, a η-propyl group, an i-propyl group, a c-propyl group, an n-butyl group, a fluorene-butyl group, and an s-butyl group. Base, t•butyl, c-butyl, η-pentyl, 1-methyl-n-butyl, 2-methyl-η-butyl, 3-methyl-η-butyl, l,l- Dimethyl-η·propyl, c•pentyl, 2-methyl-c-butyl, η-hexyl, 1-methyl-n-pentyl, 2-methyl-η·pentyl, U1_II Methyl _n_butyl, 1-ethyl-η-butyl, l,l,2-trimethyl-n-propyl, c-hexyl, methyl-c-pentyl, 1-ethyl-c_ Butyl, hydrazine, 2·dimethyl-e-butyl, n-heptyl, η-octyl, η-fluorenyl, n-fluorenyl, n-undecyl, n-dodecyl, η - thirteen yards, η-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, η-octadecyl 'n-nonadecyl, n_two Decylene and the like. The halogen atom 'is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The monovalent hydrocarbon group 'for example is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, a hexyl group, an octyl group or a decyl group; a cycloalkyl group such as a cyclohexyl group; a bicycloalkyl group such as a dicyclohexyl group; , 丨-propenyl, 2-propenyl, isopropanyl, 1-methyl-2-propenyl, 1- or 2- or 3-butenyl, hexenyl, etc.; phenyl, xylyl An aryl-10-201004997 group such as a tolyl group, a biphenyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group or a phenylcyclohexyl group; and the like. Further, one or all of the hydrogen atoms of the monovalent hydrocarbon group may also be a hydrocarbon group, a halogen atom, an amine group, a stanol group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphate group or an ester group. , thioester, guanamine, nitro, organooxy, organic amine, organomethylalkyl, organothio, decyl, alkyl, cycloalkyl, bicycloalkyl, alkenyl, aryl , aralkyl, etc. are substituted. The organooxy group is, for example, an alkoxy group, an alkenyloxy group or an aryloxy group. The alkyl group, the alkenyl group and the aryl group are, for example, the same as the above monovalent hydrocarbon group. An organic amine group, for example, a phenylamino group, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, An alkylamino group of a mercaptoamine group, a mercaptoamine group, a laurylamine group or the like; a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diamylamino group a di-hexylamino group, a diheptylamino group, a dioctylamino group, a fluorenylamino group, a fluorenylamino group or the like; a cyclohexylamino group; a morpholino group; Organomethylalkyl, for example, trimethylmethanyl, triethylmethyldecyl, tripropylmethyldecyl, tributylmethyldecyl, tripentylmethyl decyl, trihexylmethyl decyl, pentyl dimethyl An organic thio group such as a methyl decyl group, a hexyl dimethyl methoxyalkyl group, an octyl dimethyl methoxy decyl group or a decyl dimethyl methoxy decyl group, for example, a methylthio group or an ethylthio group; Propylthio, butylthio, pentylthio, hexylthio, heptylthio-11 - 201004997, octylthio, decylthio, decylthio An alkylthio group such as a thiol group of a laurel machine. The mercapto group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group or a benzoinyl group. The ester group is, for example, -CiCOOQ1, -OCCCOQ1. The thioester group has, for example, -C^SjOQ1, -OC^SiQ1. The amidino group has, for example, -C^CONHQ1, -NHC^COQ1, -C^CONi^Q2, -NC^CCCOQ2. Here, the above Q1 and Q2 are an alkyl group, an alkenyl group or an aryl group, and these may be, for example, the same as the above monovalent hydrocarbon group. Specific examples of the carbon number of 1 to 20 haloalkyl groups are CH2F, CHF2, CF3, CH2CH2F, CH2CHF2, CH2CF3, CH2CH2CH2F, CH2CH2CHF2, CH2CH2CF3, CH2C1, CHCh, CC13, CH2CH2C1, CH2Br, CHBr2, CBr3, CH2CH2Br, (CF2) 2CF3, (CF2)3CF3, (CF2)4CF3, (CF2)5CF3, (CF2)6CF3, (CF2)7CF3, (CF2)8CF3, (CF2)9CF3, (CH2)2CF2CF3, (CH2)2(CF2)2CF3 , (CH2)2(CF2)3CF3, (CH2)4(CF2)2CF3, (CH2)5(CF2)2CF3, (CH2)2(CF2)6CF3, (CH2)2(CF2)7CF3, (ch2)2 (cf2) 8cf3, (CH2)2(CF2)9CF3, (CH2)2CH2F, (CH2)3CH2F, (CH2)4CH2F, (CH2)5CH2F, (CH2)6CH2F, (CH2)7CH2F, (CH2)8CH2F, ( CH2)9CH2F, (CH2)2CH2C1, (CH2)3CH2C1, (CH2)4CH2C1, (ch2)5ch2ci, (CH2)6CH2C1, (CH2)7CH2C1, (CH2)8CH2C1, (CH2)9CH2C1, (CH2)2CH2Br, ( CH2) 3CH2Br, (CH2)4CH2Br, (CH2)5CH2Br 201004997, (CH2)6CH2Br, (CH2)7CH2Br, (CH2)8CH2Br, (CH2)9CH2Br. Specific examples of the carbon number of 1 to 20 alkoxy groups are OMe, OEt, OPr-n, OPr-i, OBu-n, OBu-i, OBu-s, OBu-t, OPen-n, OCHEt2, OHex-n , OCHMe(Pr-n), OCHMe(Bu-n), OCHEt(Pr-n), 0 CH 2 CH 2 C Η M e 2, ◦ H ep - η, Ο O ct - η, OD e c- n Wait.

Specific examples of the carbon number of 1 to 20 alkylthio groups are SMe, SEt, SPr-n, SPr-i, SBu-n, SBu-i, SBu-s, SBu-t, SPen-n, SCHEt2, SHex -n , SCHMe(Pr-n) , SCHMe(Bu-n), SCHEt(Pr-n), SC H2 CH 2 C Η M e 2, SH ep - n, SO ct-n, S De c - n etc. . Specific examples of the carbon number 1 to 2 0 dialkylamino group are NMe2, NEt2, N(Pr-n)2, N(Pr-i)2, N(Bu-n)2, and N(Bu-i). 2, N (Bu-s) 2, N (Bu-t) 2, N (Pen-n) 2, N (CHEt2) 2, N (Hex-n) 2, N (Hep-n) 2, N ( Oct-n)2, N(Dec-n)2, N(Me)(Bu-n), N(Me)(Pen-n), N(Me)(Hex-n), N(Me)(Hep -n) , N(Me)(〇ct-n), N(Me)(Dec-n), etc. Specific examples of the phenyl group which may be substituted include a phenyl group, a fluorene-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, a fluorenyl-trifluoromethylphenyl group, and a heart-trifluoromethyl group. Phenyl, P-trifluoromethylphenyl, p-ethylphenyl, p_i-propylphenyl, pt-butylphenyl, fluorenyl-chlorophenyl, m-chlorophenyl, p-chlorophenyl , 〇 bromophenyl, m-bromophenyl, p-bromophenyl, fluorenyl phenyl, p-fluorophenyl, 〇_methoxyphenyl, m-methoxyphenyl, p- Oxyphenyl, 0-trifluoromethoxy-13- 201004997 phenyl, p-dimethoxymethoxy, fluorenyl-nitrophenyl, m-nitrophenyl, P-nitrophenyl, hydrazine - dimethylaminophenyl, m-dimethylaminophenyl, p-dimethylaminophenyl, guanylcyanophenyl, 3,5-dimethylphenyl, 3,5-double Trifluoromethylphenyl, 3,5-dimethoxyphenyl, 3,5-bistrifluoromethoxyphenyl, 3,5-diethylphenyl, 3,5-di-i-prop Phenylphenyl, 3,5·dichlorophenyl, 3,5-dibromophenyl, 3,5-difluorophenyl, 3,5-dinitrophenyl, 3,5-dicyanophenyl , 2,4,6-dimethylphenyl, 2,4,6-tris-trimethylphenyl, 2,4,6-trimethoxyphenyl, 2, 4,6-trifluoromethoxyphenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-trifluorophenyl, fluorene-biphenyl Base, m_biphenyl, p-biphenyl, and the like. In the dye for dye-sensitized solar cells of the present invention, R5 to R11 are hydrogen in consideration of the adsorptivity of the metal oxide constituting the semiconductor electrode or the solubility of the organic solvent in the preparation of the varnish. An atom and a carbon number of 1 to 10 alkyl groups are preferred. R1 to R4 and R13 to R16 are preferably -OH or -CTN + RH^R11 for the same reason as described above. -CTN + WrWr11, then -〇-:^ + 114, _〇-:^ + \^4, -0·Ν + Εη, -〇-N + n-Pr4, -CTN + n-Bu4, etc. good. Further, R12 and R17 are preferably a hydrogen atom or a carbon number of 1 to 10 alkyl groups, and most preferably a hydrogen atom. The oxime in the formula (1) is a divalent organic group selected from at least one of the above formulas (2) to (10), and the divalent organic group represented by the formula (3) is most preferred, and R22 is preferred. And an unsubstituted thiophenyl group in which R23 is a hydrogen atom is most preferred. The above m, η, 〇, and ρ are each independently 〇 or an integer of 1 or more, and satisfy lSm + n + o, and an integer of 2Sm + n + 〇 + P$l〇〇〇 ' 201004997 only 2 m + n + o + pg 200 is preferred, and 5 S m + n + o + P $ 200 is more preferable. Among them, a compound in which m, η, yttrium and p are both ruthenium is preferable, and further, it is preferable to use a compound of n, m or yttrium. Further, the compound ' may be an oligomer satisfying 2Sm + n + o + pS20 or a polymer satisfying 20$ m + n + o + pS 1 000.

The molecular weight of the phosphonylthiophene compound is not particularly limited, and if it is a polymer, it is preferably a weight average molecular weight of from 1 to 100,000, and most preferably from 1,000 to 50,000. Further, the weight average molecular weight is converted to polystyrene by a gel filtration chromatography method. The both ends of the above phosphonylthiophene compound are independently a hydrogen atom, a halogen atom, a monoalkylamine group having 1 to 20 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, and a phenyl group which may be substituted. a naphthyl group which may be substituted, a mercapto group which may be substituted, a trialkylstannyl group having a carbon number of 1 to 10, or a trialkylcarbenyl group having a carbon number of 1 to 20, except that a hydrogen atom is used. Preferred examples of the monoalkylamine group having 1 to 20 carbon atoms are NHMe, NHEt, NHPr-n, NHPr-i, NHBu-n, NHBu-i, NHBu-s, NHBu-t, NHPen-n. , NHCHEt2, NHHex-n, NHHep-n 'NHOct-n, NHDec-n, etc. A specific example of a carbon number of l~l〇 trialkylstannyl group, there is SnMe3,

SnEt3, Sn(Pr-n)3, Sn(Pr-i)3, Sn(Bu-n)3, Sn(Bu-i)3, Sn(Bu-s)3, Sn(Bu-t)3, etc. . Specific examples of carbon number 1 to 10 trialkylcarbenyl groups are SiMe3, -15-201004997

SiEt3, Si(Pr-n)3, Si(Pr-i)3, Si(Bu-n)3, Si(Bu-i)3, Si(Bu-s)3, Si(Bu-t)3, etc. . Specific examples of the naphthyl group which may be substituted are 1-naphthyl, 2-naphthyl, 2-butyl-1-naphthyl, 3-butyl-1-naphthyl, 4-butyl-1-naphthalene , 5-butyl-1-naphthyl, 6-butyl-1-naphthyl, 7-butyl-1-naphthyl, 8-butyl-1-naphthyl, 1-butyl-2-naphthalene , 3-butyl-2-naphthyl, 4-butyl-2-naphthyl, 5-butyl-2-naphthyl, 6-butyl-2-naphthyl, 7-butyl-2-naphthalene , 8-butyl-2-naphthyl, 2-hexyl-1-naphthyl, 3-hexyl-1-naphthyl, 4-hexyl-1-naphthyl, 5-hexyl-1-naphthyl, 6- Hexyl-1-naphthyl, 7-hexyl-1-naphthyl, 8-hexyl-1-naphthyl, 1-hexyl-2-naphthyl, 3-hexyl-2-naphthyl, 4-hexyl-2-naphthalene , 5-hexyl-2-naphthyl, 6-hexyl-2-naphthyl, 7-hexyl-2-naphthyl, 8-hexyl-2-naphthyl, 2-octyl-1-naphthyl, 3- Octyl-1-naphthyl, 4-octyl-1- 1-naphthyl, 5-octyl-1-naphthyl, 6-octyl-1-naphthyl, 7-octyl-1-naphthyl, 8- Octyl-1-naphthyl, 1-octyl-2-naphthyl, 3-octyl-2-naphthyl, 4-octyl-2-naphthyl, 5-octyl-2-naphthyl, 6- Octyl-2-naphthyl, 7-octyl-2-naphthyl, 8-octyl-2-cainyl, 2-phenyl-1-indenyl, 3-phenyl-1-cainyl, 4- Phenyl-1-caiji, 5-phenyl-1-na , 6-phenyl-1-caiyl, 7-phenyl-1_cayenyl, 8-phenyl-1-caiyl, 1-phenyl-2-caiyl, 3-phenyl-2-caiyl, 4-phenyl-2-caiyl, 5-phenyl-2-cainyl, 6-phenyl-2-cainyl, 7-phenyl-2-naphthyl, 8-phenyl-2-naphthyl, 2-methoxy-1-naphthyl, 3-methoxy-1-naphthyl, 4-methoxy-1-naphthyl, 5-methoxy-1-naphthyl, 6-methoxy- 1-naphthyl, 7-methoxy-1-naphthyl, 8-methoxy-1-naphthyl, 1-methoxy-2-naphthyl, 3-methoxy-2-naphthyl, 4 -Methoxy-2-naphthyl, 5-methoxy-2-naphthyl, 6-methoxy-2-naphthyl, 7-methoxy-2-naphthyl, 8-methoxy-2 - -16- 201004997 Naphthyl, 2-ethoxy-1-naphthyl, 3-ethoxy-1-naphthyl, 4-ethoxy-1-naphthyl, 5-ethoxy-1-naphthalene 6,6-ethoxy-1-naphthyl ' 7-ethoxy-1-naphthyl, 8-ethoxy-1-naphthyl, 1-ethoxy-2-naphthyl, 3-ethoxy 2-naphthyl, 4-ethoxy-2-naphthyl, 5-ethoxy-2-naphthyl, 6-ethoxy-2-naphthyl, 7-ethoxy-2-naphthyl , 8-ethoxy-2-naphthyl, 2-butoxy-1-naphthyl, 3-butoxy-1-naphthyl, 4-butoxy-1-naphthyl, 5-butoxy 1-naphthyl, 6-butoxy-1-naphthyl, 7-butoxy 1-naphthyl, 8-butoxy-1-φnaphthyl, 1-butoxy-2-naphthyl, 3-butoxy-2-naphthyl, 4-butoxy-2-naphthalene , 5-butoxy-2-naphthyl, 6-butoxy-2-naphthyl, 7-butoxy-2-naphthyl, 8-butoxy-2-naphthyl, 2-amino- 1-naphthyl, 3-amino-1-naphthyl, 4-amino-1-naphthyl, 5-amino-1-naphthyl, 6-amino-1-naphthyl, 7-amino- 1-naphthyl, 8-amino-1-naphthyl, 1-amino-2-naphthyl, 3-amino-2-naphthyl, 4-amino-2-naphthyl, 5-amino- 2-naphthyl, 6-amino-2-naphthyl, 7-amino-2-naphthyl, 8-amino-2-naphthyl, 2-(indole, fluorenyl-dimethylamino)-1 -naphthyl, 3-(anthracene, fluorenyl-dimethylamino)-1-naphthyl, 4 (indole, fluorenyl-dimethylamino)-1-cainyl, 5-(anthracene, fluorene - one Methylamino)-1-caiyl, 6-(anthracene, dimethylamino)-1-naphthyl, 7-(anthracene, fluorenyl-dimethylamino)-1-naphthyl, 8 - (Ν,Ν-dimethylamino)-1-naphthyl, 1-(anthracene, fluorenyl-dimethylamino)-2-naphthyl, 3-(indole, fluorenyl-dimethylamino) -2-naphthyl, 4-(anthracene, fluorenyl-dimethylamino)-2-naphthyl, 5-(anthracene, fluorenyl-dimethylamino)-2-naphthyl, 6-(anthracene, fluorene -dimethylamino)-2-naphthyl, 7-(Ν,Ν- Methylamino)-2-naphthyl, 8-(anthracene, fluorenyl-dimethylamino)-2-naphthyl, 2-(indole, fluorenyl-diphenylamino)-1-naphthyl, 3 - (Ν,Ν-diphenylamino)-1-naphthyl, 4-(anthracene, fluorenyl-diphenylamino)-1-naphthyl, 5-(anthracene, fluorenyl-diphenylamino) 1-naphthyl, 6--17- 201004997 (Ν,Ν-diphenylamino)-1-naphthyl, 7-(N,N-diphenylamino)-1-naphthyl, 8- (N,N-diphenylamino)-1-naphthyl, 1-(N,N-diphenylamino)-2-naphthyl, 3-(anthracene, fluorenyl-diphenylamino)- 2-naphthyl, 4-(anthracene, fluorenyl-diphenylamino)-2-naphthyl, 5-(indole, fluorenyl-diphenylamino)-2-naphthyl, 6-(Ν,Ν- Diphenylamino)-2-naphthyl, 7-(anthracene, fluorenyl-diphenylamino)-2-naphthyl, 8-(anthracene, fluorenyl-diphenylamino)-2-naphthyl, etc. . Further, specific examples of the mercapto group which may be substituted include 1-indenyl group, 2-indenyl group, 9-fluorenyl group, 2-butyl-1-indenyl group, 3-butyl-1-indenyl group, and 4 -butyl-1-indenyl, 5-butyl-1-indenyl, 6-butyl-1-indenyl, 7-butyl-1-indenyl, 8-butyl-1-indenyl, 9 -butyl-1-indenyl, 10-butyl-1-indenyl, 1-butyl-2-indenyl, 3-butyl-2-indenyl, 4-butyl-2-indenyl, 5 -butyl-2-enyl, 6-butyl-2-onionyl, 7-butyl-2-enyl, 8-butyl-2-indenyl, 9-butyl-2-indenyl, 10 -butyl-2-indenyl, 1-butyl-9-fluorenyl, 2-butyl-9-fluorenyl, 3-butyl-9-fluorenyl, 4-butyl-9-fluorenyl, 10 -butyl-9-benzyl, 2-hexyl-1-indenyl, 3-hexyl-1-indenyl, 4-hexyl-1-indenyl, 5-hexyl-1-indenyl, 6-hexyl-1 - mercapto, 7-hexyl-1-indenyl, 8-hexyl-1-indenyl, 9-hexyl-1-onionyl, 10-hexyl-1-indenyl, 1-hexyl-2-indenyl, 3 - Hexyl-2-indenyl, 4-hexyl-2-indenyl, 5-hexyl-2-indenyl, 6-hexyl-2-indenyl, 7-hexyl-2-indenyl, 8-hexyl-2- Mercapto, 9-hexyl-2-indenyl, 10-hexyl-2-indenyl, 1-hexyl-9-fluorenyl, 2-hexyl-9-fluorenyl, 3-hexyl-9-fluorenyl 4-hexyl-9-fluorenyl, 10-hexyl-9-fluorenyl, 2-octyl-1-indenyl, 3-octyl-1-indenyl, 4-octyl-1-indenyl, 5- Octyl-1-indenyl, 6-octyl-1-indenyl, 7-octyl-1-indenyl, 8-octyl-1-inionyl, 9-ylidene-1_ onion, 10-octyl -1-onion, 1-ylidene-2-keto, 3 -octyl-2-benyl, 201004997 4 -octyl-2-indenyl, 5-octyl-2-indenyl, 6- Octyl-2 -onolinyl, 7-octyl-2-indenyl, 8-octyl-2-indenyl, 9-octyl-2-indenyl, 10-octyl-2-indenyl, 1- Octyl-9-fluorenyl, 2-octyl-9-fluorenyl, 3-octyl-9-fluorenyl, 4-octyl-9-fluorenyl, 10-octyl-9-fluorenyl, 2- Phenyl-1-fluorenyl, 3-phenyl-1-indenyl, 4-phenyl-1-indenyl, 5-phenyl-1-propenyl, 6-phenyl-1-benyl, hydrazine Benyl-1-heptyl, 8-phenyl-1-onionyl, 9-phenyl-1-benzyl, 10-phenyl-1-indolyl, 1-phenyl-2-thiol, 3- Phenyl-2-mercapto, 4-phenyl-2-propenyl, 5-phenyl-2-mercapto, 6-phenyl-2-indenyl, 7-phenyl-2-indenyl, 8- Benzene-2-Whike, 9-Benyl-2-Onion, 10-phenyl-2-onion, 1-phenyl-9-Whike, 2-phenyl-9-fluorenyl, 3- Phenyl-9-fluorenyl, 4-phenyl-9-fluorenyl 10-Phenyl-9-fluorenyl '2-methoxy-1-indenyl, 3-methoxy-1-indenyl, 4-methoxy-1-indenyl, 5-methoxy-1 - mercapto, 6-methoxy-1-indenyl, 7-methoxy-1-indenyl, 8-methoxy-1-indenyl, 9-methoxy-1-indenyl, 10- Methoxy-1-indenyl, 1-methoxy-2-indenyl, 3-methoxy-2-indenyl, 4-methoxy-2-indenyl, 5-methoxy-2- Indenyl, 6-methoxy-2-indenyl, 7-methoxy-2-yl-2-yl, 8-methoxy-2-indenyl, 9-methoxy-2-indenyl, 10- Methoxy-2-indenyl, 1-methoxy-9-indenyl, 2-methoxy-9-indenyl, 3-methoxy-9-indenyl, 4-methoxy-9- Indenyl, 10-methoxy-9-fluorenyl, 2-ethoxy-1-indenyl, 3-ethoxy-1-indenyl, 4-ethoxy-1-indenyl, 5-B Oxy-1-indenyl, 6-ethoxy-1-indenyl, 7-ethoxy-1-indenyl, 8-ethoxy-1-indenyl, 9-ethoxy-1-indolyl , 10-ethoxy-1-indenyl, 1-ethoxy-2-indenyl, 3-ethoxy-2-indenyl, 4-ethoxy-2-indenyl, 5-ethoxy 2-mercapto, 6-ethoxy-2-indenyl, 7-ethoxy-2-indenyl, 8-ethoxy-2-indenyl, 9-ethoxy-2-indenyl , 10-ethoxy-2-indenyl, 1- Oxygen-19- 201004997 -9-fluorenyl, 2-ethoxy-9-fluorenyl, 3-ethoxy-9-fluorenyl, 4-ethoxy-9-fluorenyl, 10-ethoxy -9-fluorenyl, 2-butoxy-1-indenyl, 3-butoxy-1-indenyl, 4-butoxy-1-indenyl, 5-butoxy-1-indenyl, 6-butoxy-1-indenyl, 7-butoxy-1-indenyl, 8-butoxy-1-indenyl, 9-butoxy-1-indenyl, 10-butoxy- 1-indenyl, 1-butoxy-2-indenyl, 3-butoxy-2-indenyl, 4-butoxy-2-indenyl, 5-butoxy-2-indenyl, 6- Butoxy-2-indenyl, 7-butoxy-2-indenyl, 8-butoxy-2-indenyl, 9-butoxy-2-indenyl, 10-butoxy-2- Mercapto, 1-butoxy-9-fluorenyl, 2-butoxy-9-fluorenyl, 3-butoxy-9-fluorenyl, 4-butoxy-9-fluorenyl, 10-butyl Oxy-9-fluorenyl, 2-amino-1-indenyl, 3-amino-1-indenyl, 4-amino-1-indenyl, 5-amino-1-indenyl, 6- Amino-1-indenyl, 7-amino-1indolyl, 8-amino-1-indenyl, 9-amino-1-indenyl, 10-amino-1-indenyl, 1- Amino-2-indenyl, 3-amino-2-indenyl, 4-amino-2-indenyl, 5-amino-2-indenyl, 6-amino-2-indenyl, 7- Amino-2-indenyl, 8-amino-2-indenyl, 9-amine -2 - fluorenyl, 10-amino-2-indenyl, 1-amino-9-fluorenyl, 2-amino-9-fluorenyl, 3-amino-9-fluorenyl, 4-amino -9-fluorenyl, 10-amino-9-fluorenyl, 2-(anthracene, fluorenyl-dimethylamino)-1-indenyl, 3-(N,N-dimethylamino)-1 - mercapto, 4-(N,N-dimethylamino)-1-indenyl, 5-(N,N-dimethylamino)-1-indenyl, 6·(N,N-di Methylamino)-1-indolyl, 7-(N,N-dimethylamino) onion, 8-(N,N-methylamino)-1-onion, 9_ (ice: ^-Dimethylamino)-1-indenyl, 10-(anthracene-dimethylamino)-1-indenyl, 1-(N,N-dimethylamino)-2-indenyl , 3-(N,N-dimethylamino)-2-indenyl, 4-(N,N-dimethylamino)-2-indenyl, 5-(N,N-dimethylamine 2-mercapto, 6-(N,N-dimethylamino)-2-indenyl, -20- 201004997 7- (Ν,Ν·dimethylamino)-2-indenyl, 8-(Indole, fluorenyl-dimethylamino)-2-indenyl, 9-(N,N-dimethylamino)-2-indenyl, 10-(N,N-dimethylamino -2 - mercapto, 1-(N,N-methylamino)-9-benyl, 2-(N,N-dimethylamino)-9-fluorenyl, 3-(N, N-dimethylamino)-9-fluorenyl, 4-(N,N- Methylamino)-9-fluorenyl, 10-(N,N-dimethylamino)-9-fluorenyl, 2-(N,N-diphenylamino)-1-indenyl, 3 -(N,N-diphenylamino)-didecyl, 4-(N,N-diphenylamino)-didecyl, _ 5-(N,N-diphenylamino)-1-indenyl , 6-(N,N-diphenylamino)-1-indolyl, 7·(anthracene, fluorenyl-diphenylamino)-1-indenyl, 8-(N,N-diphenylamine ))-1-indenyl, 9-(N,N-diphenylamino)-1-indenyl, 10-(N,N-diphenylamino)-1-indenyl, 1-(N ,N-diphenylamino)-2-indenyl, 3-(N,N-diphenylamino)-2-indenyl, 4-(N,N-diphenylamino)-2- Sulfhydryl, 5-(anthracene, diphenylamino)-2-indenyl, 6-(anthracene, fluorenyl-diphenylamino)-2-indenyl, 7-(anthracene, fluorene-diphenyl Amino)-2-mercapto, 8-(anthracene, fluorenyl-diphenylamino)-2-indenyl, 9-(N,N-diphenylamino)-2- fluorenyl, 10 - (N,N-diphenylamino)-2-indenyl, 1-(N,N-diphenylamino)-9-fluorenyl, 2-(indole, fluorenyl-diphenylamino) -9-fluorenyl, 3-(anthracene, fluorenyl-diphenylamino)-9-fluorenyl, 4-(anthracene, fluorenyl-diphenylamino)-9-fluorenyl, 10-(hydrazine, hydrazine -Diphenylamino)-9-fluorenyl and the like. The phosphonylthiophene compound represented by the formula (1) used for the dye for a dye-sensitized solar cell of the present invention can be obtained by the method described in the manual of International Publication No. WO 6 06/109895. The monomer compound is produced by coupling or polymerizing in an appropriate manner and, if necessary, changing its functional group. -21 - 201004997 Even if it is legal, there are no particular restrictions. For example, bisaryl coupling, Stille coupling, Suzuki coupling, uilmann coupling, Heck reaction, bacterial head coupling, Grignard reaction, etc. can be used. The polymerization method is not particularly limited as long as it can polymerize the phosphonylthiophene compound. For example, it can be selected by a conventional polymerization method such as chemical oxidation polymerization or electrolytic oxidation polymerization catalyst polymerization. In the present invention, catalyst polymerization is preferred. Catalyst polymerization is carried out by reacting a phosphonium thiophene monomer compound and, if necessary, a corresponding monomer of Z described above in the presence of a metal catalyst to form a phosphonium group represented by the formula (1). A method of thiophene oligomer or a compound of a polymer. The phosphonylthiophene monomer compound used in the polymerization of the catalyst or the monomer providing Z is preferably a phosphonylthiophene compound having a terminal (polymerizable site) substituent as a halogen atom. Among them, a bromine atom is preferred. The metal catalyst is, for example, a nickel complex or the like, and specific examples are nickel represented by bis(1,5-cyclooctadiene)nickel (0), tetrakis(triphenylphosphine)nickel (0), or the like. a complex, or nickel chloride, bis(triphenylphosphine)nickel(II) dichloride, [1,2-bis(diphenylphosphino)ethane]nickel(II) dichloride, Nickel (Π) which is represented by 1,3-bis(diphenylphosphino)propane]nickel(II) dichloride, tris(2,2'-bispyridyl)nickel(II) dibromide, etc. Combination with various ligands represented by 1,5-cyclooctadiene, 2,2'-bipyridine, and triphenylphosphine. Among them, in order to increase the degree of polymerization of the obtained polymer, a combination of bis(1,5-cyclooctadiene)nickel, 1,5-cyclooctadiene and 2,2'-bipyridine is used. It is better. -22- 201004997 The amount of the metal catalyst used is preferably 0.05 to 2.0 mole times with respect to the halogen atom of the all monomer compound of the matrix, and is preferably 0.5 to 0.8 mole times. The amount of the ligand used is preferably from 0.05 to 2.0 mol% with respect to the halogen atom of the all monomer compound of the matrix, and is preferably from 〇.5 to 0.8 moll. The reaction solvent is preferably, for example, an amide compound such as N,N-dimethylformamide, hydrazine or hydrazine-dimethylacetamide; or an aromatic hydrocarbon such as benzene, toluene or xylene; An ether compound such as tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane or diethylene glycol dimethyl ether. Among them, 1,4-dioxane is further preferred because of the high degree of polymerization of the polymer formed therefrom. The reaction temperature may be any one or less of the boiling point of the solvent, and is usually about 20 to 200 °C. There is no particular limitation on the reaction time, but it is generally about 1 to 48 hours. Further, in the phosphonylthiophene compound of the present invention, a method of solvolysis of a phosphate group with water or an alcohol is, for example, J. Chem. Soc., 959, 3950, or J. Am. Chem. S o c., 1 9 5 3 years, the method described on page 3 3 7 9 is basic. Further, a method of converting a phosphate group to a guanamine or a thioester group, for example, Organic Phosphorus Compounds, 4, Wiley-Interscience, 1972, Chapter 9, pages 155 to 253, or Organic Phosphorus Compounds, 6 rolls , Wiley-Interscience, 1 973, Chapter 14, pages 1 to 209, or Organic Phosphorus Compounds, Volume 7, -23- 201004997

The method described by Wiley-Interscience, 1976, Chapter 18, pages 1 to 486 is basic. Further, a method of converting a phosphoric acid group to -o-n+WrMr11, for example, mixing a thiophene phosphate compound with a quaternary ammonium salt in a reaction solvent. Grade 4 ammonium salts, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexylammonium hydroxide , trimethyloctyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, and the like. Among them, tetrabutylammonium hydroxide is preferred from the viewpoint that the obtained polymer has high solubility in an alcohol solvent such as methanol or ethanol. The reaction solvent is preferably water, methanol or ethanol, and among them, the solubility of the thiophenephosphoric acid of methanol is preferably high. The reaction temperature may be at most the boiling point of the solvent, and is usually about 10 to 4 (about TC. The reaction time is not particularly limited, but is usually about 5 minutes to 2 hours. Further, by changing to a tetraalkylammonium The derivative of the fourth-order ammonium salt having a hydrophobicity such as a salt can improve the solubility in various organic solvents such as methanol or ethanol. The dye-sensitized solar cell of the present invention is the above formula (1). The phosphonylthiophene compound is used as a dye, and specifically includes a semiconductor electrode, a counter electrode, and an electrolyte interposed between the electrodes; and -24-201004997 The feature has: a substrate having light transparency, a transparent conductive film laminated on the substrate, and a porous semiconductor formed of a metal oxide laminated on the transparent conductive film; and a surface of the porous semiconductor In the dye-sensitized solar cell of the present invention, the dye-sensitized solar cell of the present invention is characterized in that the phosphonylthiophene compound represented by the above formula (1) is used as the pigment. Since the pigment is used, it is not particularly limited as long as it is a solar cell component, and can be appropriately selected and used by a person skilled in the art. As an example, a substrate having light transmittance may have The substrate having the light-transmitting property and the conductive layer may be formed without any particular limitation, and a glass substrate, a transparent polymer film, or a laminate thereof may be used. The material of the above transparent polymer film may be used. Ethyl phthalocyanine (TAC), polyethylene terephthalate (PET), polyethylene naphthalate phthalate (PEN), styrene (SPS), polyphenylene sulfide (PPS), poly Carbonate (PC), polyallyl ester, polyfluorene, polyester mill (PES), polyimine (PI), polyether quinone imine (PEI), cyclic polyolefin, brominated phenoxy group, and the like. The material constituting the transparent conductive film may be, for example, lead, gold, silver, copper, zinc, titanium, aluminum, indium, a metal such as these alloys, an indium tin composite oxide, or a fluorine-doped or antimony-doped tin oxide. Metal oxides, etc., but especially doped with fluorine or antimony tin dioxide, indium tin oxide is the best The transparent conductive layer may be coated on the surface by the transparent substrate of the steaming form. -25-201004997 constituting the metal oxide semiconductor, for example, Ti〇2, Sn〇2,

Fe2〇3, W03, ZnO, Nb205, and the like. The counter electrode may be used as a positive electrode of a dye-sensitized solar cell, and is not particularly limited. For example, it may be selected from platinum, gold, silver, copper, aluminum, or the like on a glass substrate or a plastic film. And an electrode obtained by coating or vaporizing at least one metal of magnesium. The electrolyte may, for example, be an electrolyte salt containing a metal iodide such as Lil, Nal, KI, Csl or Cal2, an iodide salt of a 4-stage pyridine gun or an imidazole compound, or an iodide salt of a tetraalkylammonium compound; And then can form a redox pair of iodine: and organic solvents. An organic solvent such as a carbonate having a pendant ethyl carbonate, a propyl carbonate or the like: dioxane, diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl Ethers such as ether, polypropylene glycol dialkyl ether, methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, B Glycol, propylene glycol,

Alcohols such as polyethylene glycol, polypropylene glycol, and glycerin; nitriles such as acetonitrile, propionitrile, and benzoic acid. Further, in the dye-sensitized solar cell of the present invention, a functional layer such as a protective layer or an antireflection layer may be provided at an appropriate position. a method of adsorbing a dye for a dye-sensitized solar cell of the present invention on a surface of a porous semiconductor, a method of preparing a solution containing a dye (varnish), and immersing a substrate having a porous semiconductor therein; and containing A method of coating a pigment (varnish) on a substrate having a porous semiconductor or the like. -26- 201004997 The solvent for preparing a solution containing a pigment (varnish) is not particularly limited as long as it has a dissolving ability of a pigment, and examples thereof include methanol and ethanol. The concentration of the pigment in the solution (varnish) is not particularly limited, but it is preferably about 0.01 to 10 mmol/L. The total amount of adsorption of the pigment, for example, the unit surface area per semiconductor (1 m2), may be about 0.01 to 100 mmol. Further, in the dye-sensitized solar cell of the present invention, in addition to the color φ element of the present invention, a conventional dye such as a metal complex dye, a methine dye, a porphyrin dye or a phthalocyanine dye may be used. Among these, based on the viewpoint of high optical activity and excellent adhesion to semiconductors and durability, a bismuth-bipyridine complex is preferred, and cis-bis(thiocyano)-N is used. N'-bis(2,2'-bispyridyl.4,4.-dicarboxylic acid) ruthenium (Π) is preferred. EXAMPLES φ Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples, but the present invention is not limited to the examples described below. Further, the analysis apparatus and conditions used in the examples are as follows. [1]•H-NMR' 13C-NMR '31p-nmr Model: JNM-A500 (JEOL Ltd.) or AVANCE 400S (Brooker) [2] Gel filtration chromatography (GPC)

Model: TOSOH : HLC-8220GPC, column: SHODEX GPC -27- 201004997 KF-804L + G PC KF-805L, column temperature: 40 ° C, detector: UV detector (254 nm) and RI detector, Dissolution: THF, column flow rate: 1.0 mL/min [3] Absorption spectrum: UV-3600, Shimadzu Corporation (4) IPCE (incident-photon conversion efficiency) Spectroscopic use of spectroscope (SM-250, Spectrometer (manufactured by the spectrometer)) The 500 W Xe lamp is split in the range of 300 nm to 1100 nm, and the monochromatic light is irradiated at intervals of 10 nm, and the light emitted by the battery is detected by an ammeter (6487, manufactured by Keithley). The current is corrected by the spectral sensitivity by the spectrum of the photocurrent spectrum measured by the reference 矽 light-receiving element, and then measured. [5] Current and voltage measurement Using a solar simulator (YSS-80, manufactured by Yamashita Electric Co., Ltd.), irradiating a pseudo-like solar source (AM 1.5, 100 mW/cm2 ) 'Measure the current-voltage characteristics of the solar cell unit cell ( HSV-100, manufactured by HOKUTO DENKO) Synthesis Example 1 (Production of Polythiophene Derivative A) [Chemical 3]

2,5-Dibromo-3-diethoxyphosphonylthiophene, 2,2·-bipyridine (1.2 equivalents), 1,5 synthesized in 201004997 by the method described in the manual of International Publication No. 200 6/109895 - cyclooctadiene (1.0 equivalents), and bis(1,5-cyclooctadiene) nickel (〇) (1.2 equivalents), charged into a reaction vessel, and added 1,4-dioxane under a nitrogen atmosphere. It was heated at 60 ° C for 20 hours. After the end of the reaction, the reaction solution was filtered through a solution of fluorite, and the residue was washed with chloroform. The filtrate was washed twice with a 1% by mass aqueous hydrochloric acid solution, and further washed with 10% by mass of sodium chloride solution, and dried over anhydrous magnesium sulfate, and the solvent was evaporated. φ was depressurized and dried by a vacuum pump to obtain an orange liquid.

Mw ( GPC ) : 9,700 JH-NMR ( CDC13 ) : 1.20- 1.29 ( 6H, m ) , 4.02-4.18 (4H, m ) , 6.9 1 ( 1 H, s ) Synthesis Example 2 (Production of Polythiophene Derivative B) )

Put 2,5-dibromo-3-diethoxyphosphonylthiophene 0.75 6 g (2.00 mmol), 2,2'-double shame H to 0.937 g (6·00 mmol, 1.2 equivalent), and put into the reaction vessel. After the reaction vessel was replaced with nitrogen, 0.726 g (3 ·00 mmol) of 2,5-dibromothiophene, 0.541 g of cyclopentadiene (5.00 mmol, 1.0 equivalent), and 1 were added in a syringe. , 4-two chews 50 mL. Then, bis(1,5-cyclooctadiene)nickel (〇) 1.650 g (6.00 mmol, 1.2 equivalent) was added, and the mixture was stirred under heating at 60 ° C for 5 hours. -29- 201004997 After the reaction was completed, the reaction solution was filtered with fluorite. The residue was washed with chloroform. The filtrate was washed once with a 10% by mass aqueous solution of hydrochloric acid, and then washed three times with 10% by mass of saline. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the solvent was evaporated. Chloroform was added to the residue after the distillation to dissolve, and the mixture was dropped into η-hexane, and the precipitated solid was filtered and recovered, and then washed with η-hexane. This was vacuum-pressed and dried to give a red solid 〇. 3 5 1 g. ❹

Mw ( GPC ) : 9,232 !H-NMR ( CDC13 ) : 1.29- 1.35 ( br ) * 4.11-4.21 ( br ), 7.13 - 7.22 ( br ) » 7.50-7.83 ( br) Synthesis Example 3 (polythiophene derivative C Manufacturing) 〔化5〕

The polythiophene A produced in Synthesis Example 1 was placed in a reaction vessel, and acetonitrile was added thereto to dissolve in a nitrogen atmosphere, and trimethylsulfonium iodide (3 equivalents) was slowly dropped, and after the completion of the dropwise addition, the mixture was stirred at room temperature. hour. After the reaction, methanol was added and stirred for 1 hour, and after the excess trimethyl decane iodide was destroyed, the solvent was distilled off. Further, the crude product was dissolved in water, washed with chloroform 10 times, and passed through an ion exchange resin (IR-120B, IRA-410), and then the solvent was evaporated. The vacuum was dried to give a red solid. !H-NMR ( D2〇) : 7.14 ( 1H, s) -30- 201004997 13C-NMR ( D20 ) : 1 1 2 _ 7 ( d, J = 2 1 . 9Hz ) ' 117.9 ( s, J = 7.6Hz ), 135.1 (d, J = 13.4 Hz), 138.8 (d, 187.5 Hz) 31P-NMR (D20): 4.06 (s) Synthesis Example 4 (Production of Polythiophene Derivative D)

0.0 70 g of polythiophene derivative B produced in Synthesis Example 2 was placed in a reaction vessel, and 7 mL of dichloromethane and 5 mL of acetonitrile were added to dissolve in a nitrogen atmosphere, and trimethyl decyl iodide was slowly dropped. g, after the end of the dropwise addition, was stirred at room temperature for 1 hour. After the reaction, water was added thereto, and the mixture was stirred at room temperature for 30 minutes, and the crude product was dissolved by adding 28% by mass of aqueous ammonia, followed by washing 5 times with chloroform. The water is distilled off from the aqueous layer. After the residue was distilled, water was added to dissolve it, and it was dissolved in acetone. The precipitated solid was recovered by filtration and washed with acetone. This was vacuum-dried and dried to give a red solid of 0.055 g. 1H-NMR (CD3OD) : 1.1 4-1 ·32 ( br ) , 3.82 - 4.1 6 ( br )> 7.22-7.78 (br) The polythiophene derivatives a to D obtained in the above Synthesis Examples 1 to 4, Each of the ethanol solutions (concentration: 1 〇 - 5 m ο 1 / L) was prepared, and the absorption spectrum was measured. The results are shown in Figures 2 to 5. -31 - 201004997 Synthesis Example 5 (Production of Polythiophene Derivative E) [Chem. 7]

10 μg of the polythiophene derivative D produced in Synthesis Example 4 was added to 1 mL of ethanol, and further, tetrabutylammonium hydroxide (TBAOH ) / methanol solution (10% by mass) 〇 _ 3 mL was added, and the mixture was stirred and dissolved. The solvent was concentrated. _ A vacuum pump was used to decompress and dry to obtain a red solid. !H-NMR ( CD3OD ) : 1.00-1.05 ( t ) , 1 · 14-1.32 ( br ), 1.35-1.48 (m) , 1.61-1.71 (m) * 3.21 -3.27 ( m ), 3.82-4.16 ( br > 7.22-7.78 (br) About the polythiophene derivatives D and E obtained in Synthesis Examples 4 and 5, each was weighed 3 mg, and 0.1 mL of each of water, methanol and dimethyl sub-milling was added thereto. After stirring, the properties of the solution were observed. The results are shown in Table 1. In addition, the “completely dissolved” is marked as 〇, the color in the solution is solid residue is △, @ The color in the solution is marked as X. [Table 1] Polythiophene derivative, water methanol, dimethyl kiln, DX 〇 Δ E 〇〇〇 Example 1 (1) Production of photoelectric conversion electrode - 32 - 201004997 As shown in Fig. 1, with surface resistance 値1 On a glass substrate 11 (size: 15 mm x 25 mm) of the FTO (F: Sn02) film 12 of 〇 Ω / sq, the ceramide printing (Ti-Nanoxide T/S, manufactured by SOLARONIXS Co., Ltd.) was carried out by screen printing. After coating, it was dried at 120 ° C for 3 minutes, and then baked at 500 ° C for 30 minutes to form a chitanil semiconductor layer 13. The film thickness of the chitinal semiconductor layer 13 after the firing was measured by a stylus film thickness meter (ET4000A, manufactured by Kosaka Seisakusho Co., Ltd.), and it was 20 μm. Next, in the methanol solution (concentration: 0.1 mM) of the polythiophene derivative A obtained in Synthesis Example 1, the substrate after the baking was immersed, and the polythiophene derivative A (pigment) was omitted. The photoelectric conversion electrode 10 is fabricated by being adsorbed on the Chitanil semiconductor layer 13. The cell crystal cell electro-optical cation is made on the glass substrate 15 with the FTO Q film attached to the electrolyte injection hole of two diameters of 0.7 mm, and the ethyl-methacrylic acid copolymer ionic polymer resin film is stretched. HIMILAN (manufactured by Mitsui & Dupont Chemical Co., Ltd.) (film thickness: 30 nm) is disposed around the counter electrode 20 formed by the Pt layer 14 (film thickness: 1 nm), and the photoelectric conversion electrode 10 obtained as described above Fit together. Thereafter, the electrolyte 3 is injected from the electrolyte injection hole (the electrolyte 3 is made of iodine iodide containing 0.1 mol/L of lithium iodide, 0.025 mol/L of iodine, and 0.5 m〇l/L). Imidazole, and a 0.5 mol/L solution of t-butylpyridine in acetonitrile, and a dye-sensitized solar cell unit cell 1 was prepared. With respect to the solar cell unit obtained in Example 1, the measurement of IPCE was carried out in the range of -33 to 201004997 of 300 to 1100. The resulting IPCE spectrum is shown in Figure 6. As shown in Fig. 6, it is known that IPCE can be obtained in the corresponding region of light absorption from the ultraviolet light to the range of 500 nm. Further, the current-voltage characteristics of the obtained solar cell unit cell were measured. The results are shown in Table 2. As shown in Table 2, although the data was somewhat deviated during the measurement, it was found that there was a light conversion efficiency of 0.053%.

(Example 2) A photoelectric conversion electrode and a solar cell unit were produced in the same manner as in Example 1 except that the polypeptene derivative A was changed to the polythiophene derivative B synthesized in Synthesis Example 2. For the solar cell unit obtained in Example 2, the IPCE was measured in the range of 300 to 1 1 〇〇 nm. The resulting IPCE spectrum is shown in Figure 7. As shown in Fig. 7, it is known that IPCE can be obtained in the corresponding region of light absorption from the ultraviolet light to the range of 550 nm. Further, the current and voltage characteristics of the obtained solar cell unit cell were measured. The results are shown in Table 2. As shown in Table 2, it was found that there was 0.064% light conversion efficiency. (Example 3) A photoelectric conversion electrode and a solar cell unit were produced in the same manner as in Example 1 except that the polyparaphene derivative A was changed to the polythiophene derivative C synthesized in Synthesis Example 3. -34- 201004997 For the solar cell unit obtained in Example 3, the IPCE was measured in the range of 3 〇〇 to n 〇〇 nm. The resulting IPCE spectrum is shown in Figure 8. As shown in Fig. 8, it is known that IPCE can be obtained in the corresponding region of light absorption from the ultraviolet light to the 60 nm range. Further, the current and voltage characteristics of the obtained solar cell unit cell were measured. The results are shown in Table 2. As shown in Table 2, it was found that there was 0.469% light conversion efficiency. (Example 4) A photoelectric conversion electrode and a solar cell unit were produced in the same manner as in Example 1 except that the polythiophene derivative A was changed to the polythiophene derivative D synthesized in Synthesis Example 4. The solar cell unit obtained in Example 4 was measured for IPCE in the range of 300 to 1100 nm. The resulting IPCE spectrum is shown in Figure 9. As shown in Fig. 9, it is known that in the range from ultraviolet light to 600 nm, the light absorption is in the range of φ, and IPCE can be obtained. Further, the current and voltage characteristics of the obtained solar cell unit cell were measured. The results are shown in Table 2. As shown in Table 2, it was found that there was a light conversion efficiency of 0.568%. -35- 201004997 〔'表 2〕

Jsc (mA/cm2) Voc (V) ff V (%) Example 1 0.279 0.408 0.464 0.053 Example 2 0.273 0.461 0.506 0.064 Example 3 1.290 0.548 0.668 0.469 Example 4 2.117 0.515 0.523 0.568

Jsc : short circuit current Voc : open voltage ff : charge factor 77 : photoelectric conversion efficiency 7? = JscxVocxff

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a dye-sensitized solar cell produced in Example 1. Fig. 2 is an absorption spectrum of the polythiophene derivative A obtained in Synthesis Example 1. Fig. 3 is a schematic view showing the absorption spectrum of the polythiophene derivative B obtained in Synthesis Example 2. Fig. 4 is a schematic view showing the absorption spectrum of the polythiophene derivative C obtained in Synthesis Example 3. Fig. 5 is a schematic view showing the absorption spectrum of the polythiophene derivative D obtained in Synthesis Example 4. Fig. 6 is a schematic view showing the IPCE spectrum of the dye-sensitized solar cell unit cell produced in Example 1. Fig. 7 is a schematic view showing the IPCE spectrum of the dye-sensitized solar cell unit cell produced in Example 2. Fig. 8 is a schematic diagram of the IPCE spectrum of the dye-sensitized solar cell unit cell produced in Example 3. -36 · 201004997. Fig. 9 is a schematic view showing the IPCE spectrum of the dye-sensitized solar cell unit cell produced in Example 4. [Main component symbol] 1: Solar cell unit cell (dye sensitized solar cell) 10 : Photoelectric conversion electrode g 11: Glass substrate (substrate with light transmittance) 12 : FTO film (transparent conductive film) 13: Light Chitinir semiconductor layer (porous semiconductor) sensitized by dye adsorption 14 : Pt layer 15 : glass substrate 2 0 : counter electrode 30 : electrolyte - 37-

Claims (1)

201004997 VII. Application for patents: ◆ A dye for sensitized solar cells, characterized by containing a phosphonium thiophene compound represented by formula (1), [Chemical 1] (wherein R1 to R4 and R13 to R16 each independently represent _OR5, ·SR6, -NR72, or -CTN + rUBr11, and R5 to R11 each independently represent a hydrogen atom, a carbon number of 1 to 20 alkyl groups, or may be The phenyl group R12 and R17 substituted by W each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group 'stanol group, a thiol group, a carboxyl group, an ester group, a thioester group, a decyl group 'cyano group, a nitro group. a monovalent hydrocarbon group, an organic oxy group, an organic amine group, an organomethylalkyl group, an organic thio group, a decyl group, a sulfonic acid group, or a phenyl group which may be substituted, a halogen atom, a hydroxyl group, an amine group, Sulfhydryl, thiol, carboxyl, ester, thioester, decyl, cyano, nitro, monovalent hydrocarbyl 'organooxy, organic amine, organomethylalkyl, organothio, hydrazine a group, or a sulfonic acid group, «1, η, 〇, and p are each independently represented by 〇 or an integer of 1 or more, and satisfy 1 ^ m + n + o * and 2Sm + n + o + pSl〇〇〇, Z system A divalent organic group selected from the following formulas (2) to (10) '-38- (4) (4) 201004997 R18 to R40 each independently represent a hydrogen atom, a carbon number of 1 carbon atom: 1 to 20 haloalkyl group, a carbon number of 1 to 20 alkoxy group, a carbon number thio group, a carbon number of 1 to 20 dialkylamino group, or It may be a W phenyl group, and R41 is a hydrogen atom, a carbon number of 1 to 20 alkyl groups, a carbon number group, a carbon number of 1 to 20 alkoxy group, or may be substituted with the same meaning as described above, except that the phosphonium group The two ends of the thiophene compound are a hydrogen atom, a halogen atom, a monoalkylamino group having a carbon number of 1 to 20, a carbon alkylamino group, a phenyl group which may be substituted, a W naphthyl group, and a hydrazine group. Base, carbon number 1 to 1 decyl group, or carbon number 1 to 10 trialkylcarbenyl group, W system and meaning). 2. A composition comprising a patented phosphonium thiophene compound. 3. A varnish characterized by a patent application method; a phosphonium thiophene compound. (7) (10) -20 alkyl group, 1-20 alkyl group substituted with 1-20 molarane; phenyl group, W independently represents a number 1 to 20, and the substituted trialkyltin is previously the same E Circumference 1 I, Item 1 - 39 - 201004997 4. An organic film characterized by containing a phosphonyl thiophene compound of claim 1 of the patent application. 5. An organic film characterized by the varnish of the third application of the patent application. 6. A semiconductor electrode characterized by: a substrate having light transmittance, a transparent conductive film laminated on the substrate, and a porous semiconductor formed of a metal oxide laminated on the transparent conductive film; Further, a pigment for a dye-sensitized solar cell according to the first aspect of the patent application is adsorbed on the surface of the porous semiconductor. 7. A semiconductor electrode characterized in that a substrate having a porous semiconductor is immersed in a varnish of the third application of the patent application, and the dye for sensitizing the solar cell is adsorbed on the porous semiconductor. 〇8. A dye-sensitized solar cell characterized by having a semiconductor electrode, a counter electrode, and an electrolyte interposed between the semiconductor electrode and the counter electrode of claim 6 of the patent application. -40-