CN102027631A - Dye for dye-sensitized solar cell and dye-sensitized solar cell - Google Patents

Dye for dye-sensitized solar cell and dye-sensitized solar cell Download PDF

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CN102027631A
CN102027631A CN2009801140266A CN200980114026A CN102027631A CN 102027631 A CN102027631 A CN 102027631A CN 2009801140266 A CN2009801140266 A CN 2009801140266A CN 200980114026 A CN200980114026 A CN 200980114026A CN 102027631 A CN102027631 A CN 102027631A
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anthryl
group
naphthyl
amino
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濑川浩司
久保贵哉
中崎城太郎
大谷直树
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Nissan Chemical Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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

The dyestuff and the DSSC that are used for DSSC
Technical field
The DSSC that the present invention relates to be used for the dyestuff of DSSC and use it.
Background technology
In order to solve pressing problem, the research that substitutes conventional fossil fuel with new forms of energy is just launched in every field about the energy and global environment.
One of these researchs are about solar cell, and it relies on inexhaustible sunlight is its energy source and to the environment good conformity.
What paid close attention to especially in various solar cells is DSSC, because it can and not need vacuum equipment by the cheap material preparation in its preparation process, so since
Figure BPA00001248991500011
Since proposing, it has been studied for a long period of time with regard to its practical application.
DSSC is equipped with can light absorbing semi-conducting electrode, and this semi-conducting electrode is made of porous metal oxide and absorption dyestuff thereon.
For making solar cell have maximum conversion efficient, the amount that is adsorbed on the dyestuff on the semi-conducting electrode should be big as far as possible, and described transformation efficiency is with proportional by the amount of the electronics that absorption produced of sunlight.
Reason for this reason, the dyestuff that is used for DSSC need be to the high compatibility of metal oxide and good tack.
Its also need be in organic solvent high dissolubility, this is because it is realized by this semi-conducting electrode being immersed in the solution that dyestuff is dissolved in organic solvent usually to the absorption of semi-conducting electrode.
Reported the relevant dyestuff that is used for DSSC, this dyestuff is based on has introducing carboxyl wherein in order to improve the oligothiophene compounds to the compatibility and the tack of porous metal oxide.(referring to non-patent literature 1)
Yet, except that the improvement of containing compatibility by introducing carboxyl and tack above-mentioned not about other report of oligothiophene compounds.In addition, still do not have up to now and be prepared the polythiophene compound as having the trial of the dyestuff of wide absorbing wavelength scope.
Non-patent literature 1:Tanaka K. etc., Chemistry Letters, 2006,35 (6), the 592-593 page or leaf.
Summary of the invention
The problem to be solved in the present invention
Finished the present invention in view of aforementioned.The purpose of this invention is to provide the dyestuff that is used for DSSC and with the solar cell of its merging, this dyestuff is excellent to the compatibility of porous metal oxide and tack and the dissolubility in organic solvent.
The means that are used to address this problem
As the result with the further investigation that realizes aforementioned purpose, the poly-or oligothiophene compounds that the inventor finds to have phosphoric acid (ester) group is excellent to the compatibility of porous metal oxide and tack and the dissolubility in organic solvent and therefore it is suitable for the dyestuff that acts on DSSC.This discovery has produced the present invention.
The invention provides as follows.
1, a kind of dyestuff that is used for DSSC, contain the phosphoryl thiophene compound that following formula (1) is represented in this dyestuff:
[Chemical formula 1]
Figure BPA00001248991500021
(R wherein 1-R 4And R 13-R 16Represent any-OR independently of each other 5,-SR 6,-NR 7 2With-O -N +R 8R 9R 10R 11R 5-R 11Represent any hydrogen atom, C independently of each other 1- 20Alkyl and have a substituent phenyl that one or more optional W represent; R 12And R 17Represent any hydrogen atom, halogen atom, hydroxyl, amino, silanol group, mercapto, carboxyl, ester group, thioester substrate, amide groups, cyano group, nitro, monovalence alkyl, organic group oxygen base, organic group amino, organic group silicyl, organic group thio group (organothio group), acyl group, sulfuryl independently of each other and have the substituent phenyl that one or more optional W represent; W represents any halogen atom, hydroxyl, amino, silanol group, mercapto, carboxyl, ester group, thioester substrate, amide groups, cyano group, nitro, monovalence alkyl, organic group oxygen base, organic group amino, organic group silicyl, organic group thio group, acyl group and sulfuryl; M, n, o and p represent 0 or be not less than 1 integer and make 1≤m+n+o and 2≤m+n+o+p≤1,000 independently of each other; And Z represents to be selected from those divalent organic group of following formula [2]-[10] expression:
[Chemical formula 2]
Figure BPA00001248991500031
Wherein, R 18-R 40Represent any hydrogen atom, C independently of each other 1-20Alkyl, C 1-20Haloalkyl, C 1-20Alkoxyl, C 1-20Alkylthio group, C 1-20Dialkyl amido and have the substituent phenyl that one or more optional W represent, a R 41Represent any hydrogen atom, C 1-20Alkyl, C 1-20Haloalkyl, C 1-20Alkoxyl and have the substituent phenyl of one or more optional W (its for as mentioned above) expression, condition is that the phosphoryl thiophene compound should have end group, these end groups are any hydrogen atom, halogen atom, C independently of each other 1-20Alkyl monosubstituted amino, C 1-20Dialkyl amido, have substituent phenyl that one or more optional W represent, have substituent naphthyl that one or more optional W represent, have substituent anthryl, C that one or more optional W represent 1-10Trialkyl stannyl and C 1-20Trialkylsilkl (wherein W for as mentioned above).
2, a kind of composition, it contains the phosphoryl thiophene compound described in 1.
3, a kind of varnish, it contains the phosphoryl thiophene compound described in 1.
4, a kind of organic film, it contains the phosphoryl thiophene compound described in 1.
5, a kind of organic film is prepared by the varnish described in 4.
6, a kind of semi-conducting electrode, this electrode comprises:
Light-transmissive substrates is laminated in the nesa coating on this substrate and is laminated in metal oxide porous semi-conductor on this nesa coating, and this porous semi-conductor has the dyestuff that is used for DSSC described in 1 that is adsorbed onto its surface.
7, a kind of semi-conducting electrode, this electrode comprises the substrate with porous semi-conductor, and this substrate has been immersed in and has made described porous semi-conductor adsorb the dyestuff that is used for DSSC as described above in the varnish described in 3.
8, a kind of DSSC, this battery comprise the semi-conducting electrode described in 6, to electrode with between described semi-conducting electrode with to the electrolyte between the electrode.
The effect of invention
According to the present invention, the dyestuff that is used for DSSC is provided and has merged the solar cell of this dyestuff, this dyestuff is excellent to the compatibility of porous metal oxide and tack and the dissolubility in organic solvent.
Description of drawings
Fig. 1 is the schematic sectional view that shows the DSSC of preparation among the embodiment 1.
Fig. 2 is the coordinate diagram that shows the absorption spectrum of the polythiofuran derivative A of preparation in the synthesis example 1.
Fig. 3 is the coordinate diagram that shows the absorption spectrum of the polythiofuran derivative B of preparation in the synthesis example 2.
Fig. 4 is the coordinate diagram that shows the absorption spectrum of the polythiofuran derivative C of preparation in the synthesis example 3.
Fig. 5 is the coordinate diagram that shows the absorption spectrum of the polythiofuran derivative D of preparation in the synthesis example 4.
Fig. 6 is the coordinate diagram that shows the IPCE spectrum of the DSSC of preparation among the embodiment 1.
Fig. 7 is the coordinate diagram that shows the IPCE spectrum of the DSSC of preparation among the embodiment 2.
Fig. 8 is the coordinate diagram that shows the I PCE spectrum of the DSSC of preparation among the embodiment 3.
Fig. 9 is the coordinate diagram that shows the I PCE spectrum of the DSSC of preparation among the embodiment 4.
The explanation of reference number
1 solar battery cell (DSSC)
10 photoelectric conversion electrodes
11 glass substrate (light-transmissive substrates)
12FTO film (nesa coating)
13 have the titanium dioxide semiconductor layer of the sensitizing dyestuff that is adsorbed onto on it, and (porous is partly led
Body)
The 14Pt layer
15 glass substrate
20 pairs of electrodes
30 electrolyte
Embodiment
Be detailed description of the present invention below.List abbreviation as used in this specification below.
N represents that just, i represents different, and s represents the second month in a season, t represents uncle, the c representative ring, and o represents the ortho position, position between m represents, p represents contraposition, Me represents methyl, Et represents ethyl, and Pr represents propyl group, and Bu represents butyl, Pen represents amyl group, and Hex represents hexyl, and Hep represents heptyl, Oct represents octyl group, and Dec represents that decyl and Ph represent phenyl.
The dyestuff that is used for DSSC of the present invention contains the phosphoryl thiophene compound of above-mentioned formula (1) expression.
In the formula (1), C 1-20Alkyl comprises for example methyl, ethyl, n-propyl group, i-propyl group, the c-propyl group, n-butyl, i-butyl, s-butyl, the t-butyl, c-butyl, n-amyl group, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl group, the c-amyl group, 2-methyl-c-butyl, n-hexyl, 1-methyl-n-amyl group, 2-methyl-n-amyl group, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl group, c-hexyl, 1-methyl-c-amyl group, 1-ethyl-c-butyl, 1,2-dimethyl-c-butyl, the n-heptyl, n-octyl group, n-nonyl, n-decyl, the n-undecyl, n-dodecyl, n-tridecyl, the n-myristyl, n-pentadecyl, n-cetyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.
Halogen atom comprises for example fluorine atom, chlorine atom, bromine atoms and iodine atom.
The monovalence alkyl comprises for example alkyl (as methyl, ethyl, propyl group, butyl, t-butyl, hexyl, octyl group and decyl), cycloalkyl (as cyclopenta and cyclohexyl), bicyclic alkyl (as dicyclohexyl), thiazolinyl (as vinyl, 1-acrylic, 2-acrylic, isopropenyl, 1-methyl-2-acrylic, 1-or 2-or 3-cyclobutenyl and hexenyl), and aryl (as phenyl, xylyl, tolyl, xenyl and naphthyl), aralkyl (as benzyl, phenethyl and benzyl ring hexyl).
Incidentally, these monovalence alkyl can be chosen wantonly with any following group and replace wherein all or part of hydrogen atom: hydroxyl, halogen atom, amino, silanol group, mercapto, carboxyl, sulfo group, phosphate, phosphate-based, ester group, thioester substrate, amide groups, nitro, organic group oxygen base, organic group amino, organic group silicyl, organic group thio group, acyl group, alkyl, cycloalkyl, bicyclic alkyl, thiazolinyl, aryl and aralkyl.
Organic group oxygen base comprises for example alkoxyl, alkene oxygen base and aryloxy group, its contain with as identical monovalence alkyl such as alkyl, thiazolinyl and the aryl of above-mentioned definition.
Organic group amino comprises for example phenyl amino, alkyl amino (as methylamino, ethylamino, third amino, fourth amino, penta amino, oneself is amino, heptan is amino, suffering is amino, the ninth of the ten Heavenly Stems is amino, the last of the ten Heavenly stems is amino and bay amino), dialkyl amido (as dimethylamino, diethyl amido, dipropyl amino, dibutylamino, diamyl amino, dihexyl amino, diheptyl amino, dioctyl amino, dinonyl amino and didecyl amino), the amino and morpholino base of cyclohexyl.
The organic group silicyl comprises for example TMS, triethylsilyl, the tripropyl silicyl, the tributyl silicyl, three amyl group silicyls, three hexyl silicyls, amyl group dimetylsilyl, hexyl dimetylsilyl, octyldimethyl silicyl and decyl dimetylsilyl.
The organic group thio group comprises alkylthio group (for example methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, hot sulfenyl, the ninth of the ten Heavenly Stems sulfenyl, the last of the ten Heavenly stems sulfenyl and bay sulfenyl).
Acyl group comprises for example formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl and benzoyl.
Ester group comprises-C (O) OQ 1With-OC (O) Q 1
Thioester substrate comprises-C (S) OQ 1With-OC (S) Q 1
Amide groups comprises-C (O) NHQ 1,-NHC (O) Q 1,-C (O) NQ 1Q 2With-NQ 1C (O) Q 2
Herein, Q 1And Q 2Expression alkyl, thiazolinyl and aryl, it is illustrated as monovalence alkyl same as described above.
C 1-20Haloalkyl comprises for example CH 2F, CHF 2, CF 3, CH 2CH 2F, CH 2CHF 2, CH 2CF 3, CH 2CH 2CH 2F, CH 2CH 2CHF 2, CH 2CH 2CF 3, CH 2Cl, CHCl 2, CCl 3, CH 2CH 2Cl, CH 2Br, CHBr 2, CBr 3, CH 2CH 2Br, (CF 2) 2CF 3, (CF 2) 3CF 3, (CF 2) 4CF 3, (CF 2) 5CF 3, (CF 2) 6CF 3, (CF 2) 7CF 3, (CF 2) 8CF 3, (CF 2) 9CF 3, (CH 2) 2CF 2CF 3, (CH 2) 2(CF 2) 2CF 3, (CH 2) 2(CF 2) 3CF 3, (CH 2) 4(CF 2) 2CF 3, (CH 2) 5(CF 2) 2CF 3, (CH 2) 2(CF 2) 6CF 3, (CH 2) 2(CF 2) 7CF 3, (CH 2) 2(CF 2) 8CF 3, (CH 2) 2(CF 2) 9CF 3, (CH 2) 2CH 2F, (CH 2) 3CH 2F, (CH 2) 4CH 2F, (CH 2) 5CH 2F, (CH 2) 6CH 2F, (CH 2) 7CH 2F, (CH 2) 8CH 2F, (CH 2) 9CH 2F, (CH 2) 2CH 2Cl, (CH 2) 3CH 2Cl, (CH 2) 4CH 2Cl, (CH 2) 5CH 2Cl, (CH 2) 6CH 2Cl, (CH 2) 7CH 2Cl, (CH 2) 8CH 2Cl, (CH 2) 9CH 2Cl, (CH 2) 2CH 2Br, (CH 2) 3CH 2Br, (CH 2) 4CH 2Br, (CH 2) 5CH 2Br, (CH 2) 6CH 2Br, (CH 2) 7CH 2Br, (CH 2) 8CH2Br and (CH 2) 9CH 2Br.
C 1-20Alkoxyl comprises for example 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), OCH 2CH 2CHMe 2, OHep-n, OOct-n and ODec-n.
C 1-20Alkylthio group comprises for example 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), SCH 2CH 2CHMe 2, SHep-n, SOct-n and SDec-n.
C 1-20Dialkyl amido comprises for example NMe 2, NEt 2, N (Pr-n) 2, N (Pr-i) 2, N (Bu-n) 2, N (Bu-i) 2, N (Bu-s) 2, N (Bu-t) 2, N (Pen-n) 2, N (CHEt 2) 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) (Oct-n) and N (Me) (Dec-n).
Have the substituent phenyl that one or more optional W represent and comprise for example phenyl, the o-aminomethyl phenyl, the m-aminomethyl phenyl, the p-aminomethyl phenyl, the o-trifluoromethyl, the m-trifluoromethyl, the p-trifluoromethyl, the p-ethylphenyl, p-i-propyl group phenyl, the p-t-butyl phenyl, the o-chlorphenyl, the m-chlorphenyl, the p-chlorphenyl, the o-bromophenyl, the m-bromophenyl, the p-bromophenyl, the o-fluorophenyl, the p-fluorophenyl, the o-methoxyphenyl, the m-methoxyphenyl, the p-methoxyphenyl, the o-Trifluoromethoxyphen-l, the p-Trifluoromethoxyphen-l, the o-nitrobenzophenone, the m-nitrobenzophenone, the p-nitrobenzophenone, the o-dimethylaminophenyl, the m-dimethylaminophenyl, the p-dimethylaminophenyl, the p-cyano-phenyl, 3, the 5-3,5-dimethylphenyl, 3, the 5-bis trifluoromethyl phenyl, 3, the 5-Dimethoxyphenyl, 3, the two Trifluoromethoxyphen-ls of 5-, 3,5-diethyl phenyl, 3,5-two-i-propyl group phenyl, 3, the 5-dichlorophenyl, 3, the 5-dibromo phenyl, 3, the 5-difluorophenyl, 3, the 5-dinitrophenyl, 3,5-dicyano phenyl, 2,4, the 6-trimethylphenyl, 2,4,6-three (trifluoromethyl) phenyl, 2,4, the 6-trimethoxyphenyl, 2,4,6-three (trifluoromethoxy) phenyl, 2,4, the 6-trichlorophenyl, 2,4,6-tribromo phenyl, 2,4, the 6-trifluorophenyl, the o-xenyl, the m-xenyl, p-xenyl etc.
The dyestuff that is used for DSSC of the present invention from its adsorptivity and its deliquescent viewpoint at the organic solvent that is used for the varnish preparation to the metal oxide of formation semi-conducting electrode, should preferably have following illustrative component.R 5To R 11Preferred example be hydrogen atom and C 1-10Alkyl.R 1To R 4And R 13To R 16Preferred example be-OH and-O -N +R 8R 9R 10R 11(for example-O -N +H 4,-O -N +Me 4,-O -N +Et 4,-O -N +N-Pr 4With-O -N +N-Bu 4).
R 12And R 17Preferred example be hydrogen atom and C 1-10Alkyl (more preferred hydrogen atom).
In formula (1), Z represents to be selected from least a divalent organic group of aforementioned formula (2)-(10).Formula (3) expression divalent organic group preferably in these.Especially preferred R wherein in these 22And R 23Unsubstituted thienyl (thiophenyl) for hydrogen atom.
In aforementioned formula, m, n, o and p represent 0 or be not less than 1 integer and make 1≤m+n+o and 2≤m+n+o+p≤1,000, preferred 2≤m+n+o+p≤200, more preferably 5≤m+n+o+p≤200 independently of each other.And m, n, o and p should make that any two in them are 0, and m, n and o should make any two in them to be 0 especially.
The compound that following formula is represented can be the polymer that is defined as the oligomer of 2≤m+n+o+p≤20 or is defined as 20≤m+n+o+p≤1,000.
The phosphoryl thiophene compound be not subjected to special qualification aspect its molecular weight; Yet during for polymer form, according to the weight average molecular weight meter of the polystyrene by gel permeation chromatography, it can have 1,000-100,000, preferred 1,000-50,000 weight average molecular weight.
Aforementioned phosphoryl thiophene compound can have end group, and wherein two end groups are any hydrogen atom, halogen atom, C independently of each other 1-20Alkyl monosubstituted amino, C 1-20Dialkyl amido, have W as optional substituent phenyl, have W as optional substituent naphthyl, have W as optional substituent anthryl, C 1-10Trialkyl stannyl and C 1-20Trialkylsilkl.In these end groups, preferred hydrogen atom.
C 1-20The exemplary of alkyl monosubstituted amino comprises for example NHMe, NHEt, NHPr-n, NHPr-i, NHBu-n, NHBu-i, NHBu-s, NHBu-t, NHPen-n, NHCHEt 2, NHHex-n, NHHep-n, NHOct-n and NHDec-n.
C 1-10The exemplary of trialkyl stannyl comprises for example SnMe 3, SnEt 3, Sn (Pr-n) 3, Sn (Pr-i) 3, Sn (Bu-n) 3, Sn (Bu-i) 3, Sn (Bu-s) 3And Sn (Bu-t) 3
C 1-10The exemplary of trialkylsilkl comprises SiMe 3, SiEt 3, Si (Pr-n) 3, Si (Pr-i) 3, Si (Bu-n) 3, Si (Bu-i) 3, Si (Bu-s) 3And Si (Bu-t) 3
Having W comprises as follows as the exemplary of choosing substituent naphthyl wantonly.
The 1-naphthyl, the 2-naphthyl, 2-butyl-1-naphthyl, 3-butyl-1-naphthyl, 4-butyl-1-naphthyl, 5-butyl-1-naphthyl, 6-butyl-1-naphthyl, 7-butyl-1-naphthyl, 8-butyl-1-naphthyl, 1-butyl-2-naphthyl, 3-butyl-2-naphthyl, 4-butyl-2-naphthyl, 5-butyl-2-naphthyl, 6-butyl-2-naphthyl, 7-butyl-2-naphthyl, 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-naphthyl, 5-hexyl-2-naphthyl, 6-hexyl-2-naphthyl, 7-hexyl-2-naphthyl, 8-hexyl-2-naphthyl, 2-octyl group-1-naphthyl, 3-octyl group-1-naphthyl, 4-octyl group-1-naphthyl, 5-octyl group-1-naphthyl, 6-octyl group-1-naphthyl, 7-octyl group-1-naphthyl, 8-octyl group-1-naphthyl, 1-octyl group-2-naphthyl, 3-octyl group-2-naphthyl, 4-octyl group-2-naphthyl, 5-octyl group-2-naphthyl, 6-octyl group-2-naphthyl, 7-octyl group-2-naphthyl, 8-octyl group-2-naphthyl, 2-phenyl-1-naphthyl, 3-phenyl-1-naphthyl, 4-phenyl-1-naphthyl, 5-phenyl-1-naphthyl, 6-phenyl-1-naphthyl, 7-phenyl-1-naphthyl, 8-phenyl-1-naphthyl, 1-phenyl-2-naphthyl, 3-phenyl-2-naphthyl, 4-phenyl-2-naphthyl, 5-phenyl-2-naphthyl, 6-phenyl-2-naphthyl, 7-phenyl-2-naphthyl, 8-phenyl-2-naphthyl, 2-methoxyl group-1-naphthyl, 3-methoxyl group-1-naphthyl, 4-methoxyl group-1-naphthyl, 5-methoxyl group-1-naphthyl, 6-methoxyl group-1-naphthyl, 7-methoxyl group-1-naphthyl, 8-methoxyl group-1-naphthyl, 1-methoxyl group-2-naphthyl, 3-methoxyl group-2-naphthyl, 4-methoxyl group-2-naphthyl, 5-methoxyl group-2-naphthyl, 6-methoxyl group-2-naphthyl, 7-methoxyl group-2-naphthyl, 8-methoxyl group-2-naphthyl, 2-ethyoxyl-1-naphthyl, 3-ethyoxyl-1-naphthyl, 4-ethyoxyl-1-naphthyl, 5-ethyoxyl-1-naphthyl, 6-ethyoxyl-1-naphthyl, 7-ethyoxyl-1-naphthyl, 8-ethyoxyl-1-naphthyl, 1-ethyoxyl-2-naphthyl, 3-ethyoxyl-2-naphthyl, 4-ethyoxyl-2-naphthyl, 5-ethyoxyl-2-naphthyl, 6-ethyoxyl-2-naphthyl, 7-ethyoxyl-2-naphthyl, 8-ethyoxyl-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-naphthyl, 1-butoxy-2-naphthyl, 3-butoxy-2-naphthyl, 4-butoxy-2-naphthyl, 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-(N, the N-dimethylamino)-the 1-naphthyl, 3-(N, the N-dimethylamino)-the 1-naphthyl, 4-(N, the N-dimethylamino)-the 1-naphthyl, 5-(N, the N-dimethylamino)-the 1-naphthyl, 6-(N, the N-dimethylamino)-the 1-naphthyl, 7-(N, the N-dimethylamino)-the 1-naphthyl, 8-(N, the N-dimethylamino)-the 1-naphthyl, 1-(N, the N-dimethylamino)-the 2-naphthyl, 3-(N, the N-dimethylamino)-the 2-naphthyl, 4-(N, the N-dimethylamino)-the 2-naphthyl, 5-(N, the N-dimethylamino)-the 2-naphthyl, 6-(N, the N-dimethylamino)-the 2-naphthyl, 7-(N, the N-dimethylamino)-the 2-naphthyl, 8-(N, the N-dimethylamino)-the 2-naphthyl, 2-(N, the N-diphenyl amino)-the 1-naphthyl, 3-(N, the N-diphenyl amino)-the 1-naphthyl, 4-(N, the N-diphenyl amino)-the 1-naphthyl, 5-(N, the N-diphenyl amino)-the 1-naphthyl, 6-(N, the N-diphenyl amino)-the 1-naphthyl, 7-(N, the N-diphenyl amino)-the 1-naphthyl, 8-(N, the N-diphenyl amino)-the 1-naphthyl, 1-(N, the N-diphenyl amino)-the 2-naphthyl, 3-(N, the N-diphenyl amino)-the 2-naphthyl, 4-(N, the N-diphenyl amino)-the 2-naphthyl, 5-(N, the N-diphenyl amino)-the 2-naphthyl, 6-(N, the N-diphenyl amino)-the 2-naphthyl, 7-(N, the N-diphenyl amino)-2-naphthyl and 8-(N, N-diphenyl amino)-2-naphthyl etc.
Having W comprises as follows as the exemplary of choosing substituent anthryl wantonly: the 1-anthryl, the 2-anthryl, the 9-anthryl, 2-butyl-1-anthryl, 3-butyl-1-anthryl, 4-butyl-1-anthryl, 5-butyl-1-anthryl, 6-butyl-1-anthryl, 7-butyl-1-anthryl, 8-butyl-1-anthryl, 9-butyl-1-anthryl, 10-butyl-1-anthryl, 1-butyl-2-anthryl, 3-butyl-2-anthryl, 4-butyl-2-anthryl, 5-butyl-2-anthryl, 6-butyl-2-anthryl, 7-butyl-2-anthryl, 8-butyl-2-anthryl, 9-butyl-2-anthryl, 10-butyl-2-anthryl, 1-butyl-9-anthryl, 2-butyl-9-anthryl, 3-butyl-9-anthryl, 4-butyl-9-anthryl, 10-butyl-9-anthryl, 2-hexyl-1-anthryl, 3-hexyl-1-anthryl, 4-hexyl-1-anthryl, 5-hexyl-1-anthryl, 6-hexyl-1-anthryl, 7-hexyl-1-anthryl, 8-hexyl-1-anthryl, 9-hexyl-1-anthryl, 10-hexyl-1-anthryl, 1-hexyl-2-anthryl, 3-hexyl-2-anthryl, 4-hexyl-2-anthryl, 5-hexyl-2-anthryl, 6-hexyl-2-anthryl, 7-hexyl-2-anthryl, 8-hexyl-2-anthryl, 9-hexyl-2-anthryl, 10-hexyl-2-anthryl, 1-hexyl-9-anthryl, 2-hexyl-9-anthryl, 3-hexyl-9-anthryl, 4-hexyl-9-anthryl, 10-hexyl-9-anthryl, 2-octyl group-1-anthryl, 3-octyl group-1-anthryl, 4-octyl group-1-anthryl, 5-octyl group-1-anthryl, 6-octyl group-1-anthryl, 7-octyl group-1-anthryl, 8-octyl group-1-anthryl, 9-octyl group-1-anthryl, 10-octyl group-1-anthryl, 1-octyl group-2-anthryl, 3-octyl group-2-anthryl, 4-octyl group-2-anthryl, 5-octyl group-2-anthryl, 6-octyl group-2-anthryl, 7-octyl group-2-anthryl, 8-octyl group-2-anthryl, 9-octyl group-2-anthryl, 10-octyl group-2-anthryl, 1-octyl group-9-anthryl, 2-octyl group-9-anthryl, 3-octyl group-9-anthryl, 4-octyl group-9-anthryl, 10-octyl group-9-anthryl, 2-phenyl-1-anthryl, 3-phenyl-1-anthryl, 4-phenyl-1-anthryl, 5-phenyl-1-anthryl, 6-phenyl-1-anthryl, 7-phenyl-1-anthryl, 8-phenyl-1-anthryl, 9-phenyl-1-anthryl, 10-phenyl-1-anthryl, 1-phenyl-2-anthryl, 3-phenyl-2-anthryl, 4-phenyl-2-anthryl, 5-phenyl-2-anthryl, 6-phenyl-2-anthryl, 7-phenyl-2-anthryl, 8-phenyl-2-anthryl, 9-phenyl-2-anthryl, 10-phenyl-2-anthryl, 1-phenyl-9-anthryl, 2-phenyl-9-anthryl, 3-phenyl-9-anthryl, 4-phenyl-9-anthryl, 10-phenyl-9-anthryl, 2-methoxyl group-1-anthryl, 3-methoxyl group-1-anthryl, 4-methoxyl group-1-anthryl, 5-methoxyl group-1-anthryl, 6-methoxyl group-1-anthryl, 7-methoxyl group-1-anthryl, 8-methoxyl group-1-anthryl, 9-methoxyl group-1-anthryl, 10-methoxyl group-1-anthryl, 1-methoxyl group-2-anthryl, 3-methoxyl group-2-anthryl, 4-methoxyl group-2-anthryl, 5-methoxyl group-2-anthryl, 6-methoxyl group-2-anthryl, 7-methoxyl group-2-anthryl, 8-methoxyl group-2-anthryl, 9-methoxyl group-2-anthryl, 10-methoxyl group-2-anthryl, 1-methoxyl group-9-anthryl, 2-methoxyl group-9-anthryl, 3-methoxyl group-9-anthryl, 4-methoxyl group-9-anthryl, 10-methoxyl group-9-anthryl, 2-ethyoxyl-1-anthryl, 3-ethyoxyl-1-anthryl, 4-ethyoxyl-1-anthryl, 5-ethyoxyl-1-anthryl, 6-ethyoxyl-1-anthryl, 7-ethyoxyl-1-anthryl, 8-ethyoxyl-1-anthryl, 9-ethyoxyl-1-anthryl, 10-ethyoxyl-1-anthryl, 1-ethyoxyl-2-anthryl, 3-ethyoxyl-2-anthryl, 4-ethyoxyl-2-anthryl, 5-ethyoxyl-2-anthryl, 6-ethyoxyl-2-anthryl, 7-ethyoxyl-2-anthryl, 8-ethyoxyl-2-anthryl, 9-ethyoxyl-2-anthryl, 10-ethyoxyl-2-anthryl, 1-ethyoxyl-9-anthryl, 2-ethyoxyl-9-anthryl, 3-ethyoxyl-9-anthryl, 4-ethyoxyl-9-anthryl, 10-ethyoxyl-9-anthryl, 2-butoxy-1-anthryl, 3-butoxy-1-anthryl, 4-butoxy-1-anthryl, 5-butoxy-1-anthryl, 6-butoxy-1-anthryl, 7-butoxy-1-anthryl, 8-butoxy-1-anthryl, 9-butoxy-1-anthryl, 10-butoxy-1-anthryl, 1-butoxy-2-anthryl, 3-butoxy-2-anthryl, 4-butoxy-2-anthryl, 5-butoxy-2-anthryl, 6-butoxy-2-anthryl, 7-butoxy-2-anthryl, 8-butoxy-2-anthryl, 9-butoxy-2-anthryl, 10-butoxy-2-anthryl, 1-butoxy-9-anthryl, 2-butoxy-9-anthryl, 3-butoxy-9-anthryl, 4-butoxy-9-anthryl, 10-butoxy-9-anthryl, 2-amino-1-anthryl, 3-amino-1-anthryl, 4-amino-1-anthryl, 5-amino-1-anthryl, 6-amino-1-anthryl, 7-amino-1-anthryl, 8-amino-1-anthryl, 9-amino-1-anthryl, 10-amino-1-anthryl, 1-amino-2-anthryl, 3-amino-2-anthryl, 4-amino-2-anthryl, 5-amino-2-anthryl, 6-amino-2-anthryl, 7-amino-2-anthryl, 8-amino-2-anthryl, 9-amino-2-anthryl, 10-amino-2-anthryl, 1-amino-9-anthryl, 2-amino-9-anthryl, 3-amino-9-anthryl, 4-amino-9-anthryl, 10-amino-9-anthryl, 2-(N, the N-dimethylamino)-the 1-anthryl, 3-(N, the N-dimethylamino)-the 1-anthryl, 4-(N, the N-dimethylamino)-the 1-anthryl, 5-(N, the N-dimethylamino)-the 1-anthryl, 6-(N, the N-dimethylamino)-the 1-anthryl, 7-(N, the N-dimethylamino)-the 1-anthryl, 8-(N, the N-dimethylamino)-the 1-anthryl, 9-(N, the N-dimethylamino)-the 1-anthryl, 10-(N, the N-dimethylamino)-the 1-anthryl, 1-(N, the N-dimethylamino)-the 2-anthryl, 3-(N, the N-dimethylamino)-the 2-anthryl, 4-(N, the N-dimethylamino)-the 2-anthryl, 5-(N, the N-dimethylamino)-the 2-anthryl, 6-(N, the N-dimethylamino)-the 2-anthryl, 7-(N, the N-dimethylamino)-the 2-anthryl, 8-(N, the N-dimethylamino)-the 2-anthryl, 9-(N, the N-dimethylamino)-the 2-anthryl, 10-(N, the N-dimethylamino)-the 2-anthryl, 1-(N, the N-dimethylamino)-the 9-anthryl, 2-(N, the N-dimethylamino)-the 9-anthryl, 3-(N, the N-dimethylamino)-the 9-anthryl, 4-(N, the N-dimethylamino)-the 9-anthryl, 10-(N, the N-dimethylamino)-the 9-anthryl, 2-(N, the N-diphenyl amino)-the 1-anthryl, 3-(N, the N-diphenyl amino)-the 1-anthryl, 4-(N, the N-diphenyl amino)-the 1-anthryl, 5-(N, the N-diphenyl amino)-the 1-anthryl, 6-(N, the N-diphenyl amino)-the 1-anthryl, 7-(N, the N-diphenyl amino)-the 1-anthryl, 8-(N, the N-diphenyl amino)-the 1-anthryl, 9-(N, the N-diphenyl amino)-the 1-anthryl, 10-(N, the N-diphenyl amino)-the 1-anthryl, 1-(N, the N-diphenyl amino)-the 2-anthryl, 3-(N, the N-diphenyl amino)-the 2-anthryl, 4-(N, the N-diphenyl amino)-the 2-anthryl, 5-(N, the N-diphenyl amino)-the 2-anthryl, 6-(N, the N-diphenyl amino)-the 2-anthryl, 7-(N, the N-diphenyl amino)-the 2-anthryl, 8-(N, the N-diphenyl amino)-the 2-anthryl, 9-(N, the N-diphenyl amino)-the 2-anthryl, 10-(N, the N-diphenyl amino)-the 2-anthryl, 1-(N, the N-diphenyl amino)-the 9-anthryl, 2-(N, the N-diphenyl amino)-the 9-anthryl, 3-(N, the N-diphenyl amino)-the 9-anthryl, 4-(N, the N-diphenyl amino)-9-anthryl and 10-(N, N-diphenyl amino)-9-anthryl etc.
The phosphoryl thiophene compound of formula (1) expression (it is as the dyestuff according to DSSC of the present invention) can by phosphoryl thiophene monomer compound (it is by being disclosed in the method preparation among the PCT patent disclosure No.WO 2006/109895) by for example coupling and the polymerization of any suitable method, optionally follow the replacement of functional group to prepare.
The method of coupling is not subjected to special qualification; It is illustrated as diaryl coupling, Stille coupling, Suzuki coupling, Ullmann coupling, Heck reaction, Sonogashira coupling and Grignard reaction.
The method of polymerization is not subjected to special qualification, as long as it can make the polymerization of phosphoryl thiophene compound.It can be selected from any known method for example chemical oxidising polymerisation, electrolytic oxidation polymerization and catalytic polymerization.At last a kind of is required for the present invention wanting.
Catalytic polymerization can be finished by following: in the presence of metallic catalyst, make phosphoryl thiophene monomer (with optional monomer) reaction corresponding to the Z that above stipulates, thus the phosphoryl thiophene oligomers or the polymer compound of the expression of the formula (1) shown in more than producing.
The phosphoryl thiophene monomer compound (or monomer of generation Z) that is used for catalytic polymerization should be preferably the phosphoryl thiophene compound, and terminal substituting group in this compound (for the polymerization position) is halogen atom (a particularly bromine atoms).
Metallic catalyst can be any nickel complex, it is illustrated as nickel (0) complex compound (for example two (1, the 5-cyclo-octadiene) nickel (0) and four (triphenylphosphine) nickel (0)), nickel (II) complex compound (for example nickel chloride, two (triphenylphosphine) nickel (II) dichloride, [1, two (diphenylphosphino) ethane of 2-] nickel (II) dichloride, [1, two (diphenylphosphino) propane of 3-] nickel (II) dichloride and three (2,2 '-bipyridine) nickel (II) dibromide) and with 1,5-cyclo-octadiene, 2,2 '-bipyridine and triphenylphosphine are the combination of the various parts of representative.From the ability viewpoint of the degree of polymerization that improves resulting polymers, preferably two (1, the 5-cyclo-octadiene) nickel and 1 in these examples, 5-cyclo-octadiene and 2,2 '-combination of bipyridine.
The amount of metallic catalyst can be that every mole of halogen atom that contains in all monomeric compounds as matrix is 0.05-2.0 mole (a particularly 0.5-0.8 mole).
The amount of part can be that every mole of halogen atom that contains in all monomeric compounds as substrate is 0.05-2.0 mole (a particularly 0.5-0.8 mole).
The solvent that is used to react can be any amide compound class (for example N, dinethylformamide and N, N-dimethylacetylamide), and (oxolane (THF), 1 for example, 4-two for aromatic hydrocarbons (for example benzene, toluene and dimethylbenzene) and ether compound class
Figure BPA00001248991500141
Alkane, 1,2-dimethoxy-ethane and diethylene glycol dimethyl ether).In these examples preferably 1,4-two
Figure BPA00001248991500142
Alkane, its generation has the polymer of high polymerization degree.
Reaction temperature can be below the boiling point of solvent for use.It typically is about 20-200 ℃.Reaction time is not subjected to special qualification.It typically is about 1-48 hour.
Incidentally, phosphoryl thiophene compound according to the present invention can have it by being disclosed in J.Chem.Soc., nineteen fifty-nine, and 3950 pages or J.Am.Chem.Soc., nineteen fifty-three, it is phosphate-based that method water in 3379 pages or alcohol decompose.
In addition, phosphate-based can be by being disclosed in Organic Phosphorous Compounds, 4 volumes, Wiley-Interscience, 1972, the 9th chapter, the 155-253 page or leaf, Organic Phosphorous Compounds, 6 volumes, Wiley-Interscience, 1973, the 14th chapter, 1-209 page or leaf and Organic Phosphorous Compounds, 7 volumes, Wiley-Interscience, 1976, the 18th chapter, any one method in the 1-486 page or leaf is converted into acid amides or monothioester.
And phosphate can be converted into-O by the thiophene phosphate cpd is mixed with quaternary ammonium salt -N +R 8R 9R 10R 11
Quaternary ammonium salt comprises for example Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH, four hexyl ammonium hydroxide, trimethyl butyl ammonium hydroxide, trimethyl hexyl ammonium hydroxide, trimethyl octyl group ammonium hydroxide and trimethylphenyl ammonium hydroxide.
In these examples, make resulting polymers for example have the viewpoint of the ability of highly soluble, preferred TBAH methyl alcohol and the ethanol at alcoholic solvent from it.
Reaction dissolvent comprises water, methyl alcohol and ethanol, and wherein methyl alcohol is desired, and this is because its highly dissoluble in thiophene-sulfonic acid.
Reaction temperature can be below the boiling point of solvent for use.It typically is about 10-40 ℃.Reaction time is not subjected to special qualification.It typically is about 5 minutes-2 hours.
By the derivative that conversion obtains, for example have the tetraalkylammonium salt of hydrophobicity quaternary ammonium salt, in alcoholic solvent (for example methyl alcohol and ethanol) and various organic solvent, have the dissolubility of raising.
DSSC according to the present invention uses the phosphoryl thiophene compound of above-mentioned formula (1) expression as its dyestuff.Its by light-transmissive substrates, be laminated in nesa coating on this substrate, be laminated in semi-conducting electrode on this nesa coating, electrode and the electrolyte between these electrodes constituted with metal oxide porous semi-conductor, described porous semi-conductor has that to be adsorbed onto this porous semi-conductor lip-deep according to the dyestuff that is used for DSSC of the present invention.
According to the present invention, DSSC is characterised in that its phosphoryl thiophene compound that uses above-mentioned formula (1) expression is as dyestuff.Except that described dyestuff, do not limited aspect other component and its component can be selected from any known component.
Light-transmissive substrates can be selected from can printing opacity and play any substrate of conductive substrates effect, and it is illustrated as glass plate, transparent polymer film and their lamilated body.
Transparent polymer film comprises for example those transparent polymer films of triacetyl cellulose (TAC), PETG (PET), PEN (PEN), syndiotactic polytyrene (SPS), polyphenylene sulfide (PPS), Merlon (PC), polyarylate, polysulfones, polyester sulfone (PES), polyimides (PI), Polyetherimide (PEI), cyclic polyolefin and bromo phenoxy group.
Nesa coating can be formed by metal (for example platinum, gold, silver, copper, zinc, titanium, aluminium, indium and their alloy) and conducting metal oxide (for example tin oxide of tin indium oxide and doped with fluorine or antimony).Expectation is the tin oxide and the tin indium oxide of doped with fluorine or antimony especially.Can on the surface of aforementioned transparent substrates, form this transparency conducting layer by coating or vapour deposition.
The example that constitutes semi-conductive metal oxide comprises TiO 2, SnO 2, Fe 2O 3, WO 3, ZnO and Nb 2O 5
Electrode is not subjected to special qualification, as long as it plays the cathodic process of DSSC.It can be to have glass substrate or the plastic film that applies or deposit metal level thereon.Metal can be at least a in platinum, gold, silver, copper, aluminium and the magnesium.
Electrolyte by electrolytic salt, can constitute with iodine and the organic solvent that the I-that derives from this electrolytic salt forms redox couple.Electrolytic salt for example comprises metal iodide (for example LiI, NaI, KI, CsI and CaI 2), season pyridine " or imidazoles " salt compounded of iodine of compound and the salt compounded of iodine of tetraalkyl ammonium compound.
Organic solvent comprises for example carbonates (for example ethylene carbonate and propylene carbonate), and ethers is (as two
Figure BPA00001248991500161
Alkane, Anaesthetie Ether, ethylene glycol bisthioglycolate alkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether), alcohols (for example methyl alcohol, ethanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, polyalkylene glycol monoalkyl ether, polypropylene glycol monoalky lether, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol and glycerine), and nitrile (for example acetonitrile, propionitrile and benzonitrile).
And, can choose wantonly according to DSSC of the present invention and to have functional layer for example protective layer and anti-reflection layer.
Can adopt dipping by the solution (varnish) that preparation contains dyestuff then or apply this varnish paint had on the substrate of porous semi-conductor makes the dyestuff that is used for DSSC according to the present invention be adsorbed to the surface of porous semi-conductor thus.
The solution (varnish) that contains dyestuff can be by using any solvent (for example methyl alcohol and the ethanol) preparation that can dissolve this dyestuff.The concentration of this solution is not subjected to special qualification; It typically is about 0.01-10mmol/L.
It is about 0.01-100mmol that the amount of dyestuff to be adsorbed should be every square metre semiconductor surface.
Incidentally, can also merge with any known dyestuff (for example metal complex dyes, methine dyes, porphyrin dye and phthalocyanine dye) except that dyestuff according to the present invention according to DSSC of the present invention.
Ruthenium-bipyridyl complexes preferably in these dyestuffs, ruthenium (II) cis-two (thiocyanato)-N particularly, N '-two (2,2 '-bipyridine-4,4 '-dicarboxylate), it has high optical activity, to semi-conductive good adsorption and favorable durability.
Embodiment
To describe the present invention in more detail with reference to following synthesis example and embodiment, described embodiment is not intended to limit scope of the present invention.
Carry out embodiment by equipment and the condition of using following provisions.
[1] 1H-NMR、 13C-NMR、 31P-NMR
Model: JNM-A500 (from JEOL Ltd.) or AVANCE 400S (from Bruker)
[2] gel permeation chromatography (GPC)
Model: TOSOH:HLC-8220GPC, post: SHODEX GPC KF-804L+GPCKF-805L, column temperature: 40 ℃,
Detector: UV detector (254nm) and RI detector,
Eluent: THF, column flow rate: 1.0mL/min.
[3] absorption spectrum
Model: UV-3600 (from Shimadzu Seisakusho)
[4] IPCE (incident photon transformation efficiency) spectrum
Use by 500-W Xe lamp use spectrometer (SM-250, from Bunkou Keiki Co., the Ltd.) monochromatic light that obtains by dispersion (wavelength with the increment of 10nm from 300nm to 1100nm) irradiation solar cell.Detect photoelectric current with galvanometer (model 6487 that Keithley makes) from solar cell.Spectral sensitivity according to the spectrum of measuring with the standard silicon light receiving element is calibrated the photocurrent spectra of gained.
[5] current-voltage is measured
Utilize solar simulator (Yamashita Densou Co., the YSS-80 that Ltd. makes) by (AM 1.5,100mW/cm with simulated sunlight 2) the irradiation solar battery cell checks its I-E characteristic (HSV-100 that makes with Hokuto Denko).
[synthesis example 1]
The preparation of polythiofuran derivative A
[chemical formula 3]
Figure BPA00001248991500181
Following reactant is added in the reactor.
2,5-two bromo-3-diethoxy phosphoryl thiophene (announcing that according to being disclosed in the PCT patent method among No. 2006/109895, the WO is synthetic)
2,2 '-bipyridine (1.2 equivalent)
1,5-cyclo-octadiene (1.0 equivalent)
Two (1, the 5-cyclo-octadiene) nickel (0) (1.2 equivalent)
Then under nitrogen atmosphere with 1,4-two
Figure BPA00001248991500182
Alkane joins in this reactor.Heated this reactant 20 hours down at 60 ℃.After reaction is finished, reaction solution is filtered and with chloroform wash residual thing from Celite.Filtrate is washed 5 times with 10wt% aqueous hydrochloric acid solution washing 2 times and with the 10wt% sodium-chloride water solution.Use the anhydrous sodium sulfate drying organic layer, distillation removes and desolvates then.Dried residue under vacuum.Obtain orange liquid thus.
Mw(GPC)：9,700
1H-NMR(CDCl 3)：1.20-1.29(6H，m)，4.02-4.18(4H，m)，
6.91(1H，s)
[synthesis example 2]
The preparation of polythiofuran derivative B
[chemical formula 4]
Following reactant is added in the reactor.
2,5-two bromo-3-diethoxy phosphoryl thiophene, 0.756g (2.00mmol)
2,2 '-bipyridine, 0.937g (6.00mmol, 1.2 equivalents)
Atmosphere along with the nitrogen replacement reactor adds following reactant in this reactor.
2,5-dibromo thiophene, 0.726g (3.00mmol)
1,5-cyclo-octadiene, 0.541g (5.00mmol, 1.0 equivalents)
By using syringe with 1,4-two
Figure BPA00001248991500191
Alkane (50mL) joins in the reactor.
Following reactant is added in this reactor.
Two (1, the 5-cyclo-octadiene) nickel (0), 1.650g (6.00mmol, 1.2 equivalents)
Along with stirring reactant was heated 5 hours down at 60 ℃.
After reaction is finished, reaction solution is filtered and with chloroform wash residual thing from Celite.Filtrate is washed 3 times with 10wt% aqueous hydrochloric acid solution washing 1 time and with the 10wt% sodium-chloride water solution.Use the anhydrous sodium sulfate drying organic layer, then filter and solvent evaporation.Residue is dissolved in the chloroform, and the gained drips of solution is added in the n-hexane.By the isolated solid of filtered and recycled, then wash with the n-hexane.The solid that has washed is dry under the vacuum.Obtain red solid (0.351g) thus.
Mw(GPC)：9,232
1H-NMR(CDCl 3)：1.29-1.35(br)，4.11-4.21(br)，
7.13-7.22(br)，7.50-7.83(br)
[synthesis example 3]
The preparation of polythiofuran derivative C
[chemical formula 5]
Figure BPA00001248991500192
The polythiofuran derivative A of preparation in the synthesis example 1 is added in the reactor.Under nitrogen atmosphere, it is dissolved in the acetonitrile that adds in the reactor then.Slowly drip iodo trimethyl silane (3 equivalent), then at room temperature stirred 20 hours.Add methyl alcohol to this solution, then stirred 1 hour, make excessive iodo trimethyl silane decompose (crush) during this period, distillation removes and desolvates.The gained crude product is dissolved in water, and washs gained solution 10 times and make it pass through ion exchange resin (IR-120B, IRA-410) with chloroform.Distillation removes desolvates and residue is dry under vacuum.Obtain red solid thus.
1H-NMR(D 2O)：7.14(1H，s)
13C-NMR(D 2O)：112.7(d，J＝21.9Hz)，117.9(s，J＝7.6Hz)，
135.1(d，J＝13.4Hz)，138.8(d，J＝187.5Hz)
31P-NMR(D 2O)：4.06(s)
[synthesis example 4]
The preparation of polythiofuran derivative D
[chemical formula 6]
Figure BPA00001248991500201
The polythiofuran derivative B (0.070g) of preparation in the synthesis example 2 is added in the reactor.Under nitrogen atmosphere, it is dissolved in the carrene (7mL) and acetonitrile (5mL) that adds in the reactor then.Slowly drip iodo trimethyl silane (0.096g), then at room temperature stirred 1 hour.In this solution, add entry, then at room temperature stirred 30 minutes.The gained crude product is dissolved in the 28wt% ammoniacal liquor that joins this reactor.Wash gained solution 5 times with chloroform, and make water layer not have water by distillation.The remaining residue in distillation back is dissolved in the water of its adding.This drips of solution is added in the acetone, and by the separated solid of filtered and recycled.Solid with the acetone washing and recycling.The residue that has washed is dry under the vacuum.Obtain red solid (0.055g) thus.
1H-NMR(CD 3OD)：1.14-1.32(br)，3.82-4.16(br)，7.22-7.78(br)
Each the polythiofuran derivative A-D that obtains among the above-mentioned synthesis example 1-4 is dissolved in the ethanol.With regard to absorption spectrum to gained solution (10 -5Mol/L) detect.The results are shown among Fig. 2-5.
[synthesis example 5]
The preparation of polythiofuran derivative E
[chemical formula 7]
Figure BPA00001248991500211
The polythiofuran derivative D (10mg) of preparation adds 1mL methyl alcohol in synthesis example 4, adds the 10wt% methanol solution of 0.3mL TBAH (TBAOH) then.After by the dissolving of stirring, concentrated solvent.Residue is dry under vacuum.Obtain red solid thus.
1H-NMR(CD 3OD)：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)
Each polythiofuran derivative D that obtains in above-mentioned synthesis example 4 and 5 and E (3mg) add water, methyl alcohol and the dimethyl sulfoxide (DMSO) of 0.1mL respectively.After the stirring, gained solution is tested with regard to its state.The results are shown in the table 1.The state of solution is graded according to following standard.
Zero: sample dissolves fully.
△: sample produces colored solutions, although its part keeps not dissolving.
*: sample produces colourless solution.
Table 1
Polythiofuran derivative Water Methyl alcohol Dimethyl sulfoxide (DMSO)
D × ○ △
E ○ ○ ○
[embodiment 1]
[1] photoelectricity transforms the preparation of electrode
As shown in fig. 1, has the FTO (F=SnO that surface resistivity is 10 Ω/sq by silk screen printing with titanium dioxide thickener (Ti-Nanoxide T/S is from SOLARONIXSA) coating 2) glass substrate 11 (the size 15mm * 25mm) of film 12.Then 120 ℃ dry 3 minutes and down 500 ℃ of following roastings 30 minutes, make to form titanium dioxide semiconductor layer 13.Find by (model ET4000A from Kosaka Kenkyusho Co., Ltd.) measures (after the roasting), and titanium dioxide semiconductor layer 13 has the thickness of 20 μ m with contact pin type thickness meter.
After the roasting, substrate is immersed in the methanol solution of the polythiofuran derivative A that obtains in the 0.1mM synthesis example 1, makes polythiofuran derivative A (, not shown) be adsorbed on the titanium dioxide semiconductor layer 13 as dyestuff.Obtain photoelectricity thus and transform electrode 10.
[2] preparation of solar battery cell
To paste this on the electrode 20 as the photoelectricity conversion electrode 10 of above-mentioned preparation with the resin molding (30nm is thick) that is applied to electrode 20 peripheries.Electrode 20 is made of glass substrate 15 (being coated with the FTO film) and Pt layer 14 (1nm is thick) formed thereon.Glass substrate 15 has two holes (diameter is 0.7mm) and is used for injecting electrolyte by them.Resin is that (" Himilan " is from Mitsui Dupont Polychemicals Co., Ltd.) for the ethylene-methacrylic acid copolymer ionomer.Fill that photoelectricity transforms electrode 10 and to the space between the electrode 20 with electrolyte 30 by injecting from described hole.Electrolyte 30 " (0.5mol/L) is made up of with t-butyl-pyridinium (5mol/L) lithium iodide (0.1mol/L), iodine (0.025mol/L), dimethyl propyl iodate imidazoles.Obtain desired DSSC unit 1 thus.
At 300-1, the 100nm scope detects the solar battery cell that obtains among the embodiment 1 with regard to IPCE.The IPCE spectrum that so obtains is shown among Fig. 6.Be apparent that by Fig. 6 the light absorption wavelength scope sample from the ultra-violet (UV) band to 500nm produces high IPCE.
Also the solar battery cell that so obtains is detected with regard to I-E characteristic.The results are shown in the table 2.Be apparent that by table 2 sample is realized 0.053% electricity conversion, although there is fluctuation a little in measurement data.
[embodiment 2]
Repeat the program identical and transform electrode and solar battery cell, except with the alternative polythiofuran derivative A of the polythiofuran derivative B that obtains in the synthesis example 2 with preparation photoelectricity with embodiment 1.
At 300-1, the 100nm scope detects the solar battery cell that obtains among the embodiment 2 with regard to IPCE.The IPCE spectrum that so obtains is shown among Fig. 7.Be apparent that by Fig. 7 the light absorption wavelength scope sample from the ultra-violet (UV) band to 550nm produces high IPCE.
Also the solar battery cell that so obtains is detected with regard to I-E characteristic.The results are shown in the table 2.Be apparent that by table 2 sample is realized 0.064% electricity conversion.
[embodiment 3]
Repeat the program identical and transform electrode and solar battery cell, except with the alternative polythiofuran derivative A of the polythiofuran derivative C that obtains in the synthesis example 3 with preparation photoelectricity with embodiment 1.
At 300-1, the 100nm scope detects the solar battery cell that obtains among the embodiment 3 with regard to IPCE.The IPCE spectrum that so obtains is shown among Fig. 8.Be apparent that from Fig. 8 the light absorption wavelength scope sample from the ultra-violet (UV) band to 600nm provides high IPCE.
Also the solar battery cell that so obtains is detected with regard to I-E characteristic.The results are shown in the table 2.Be apparent that by table 2 sample is realized 0.469% electricity conversion.
[embodiment 4]
Repeat the program identical and transform electrode and solar battery cell, except with the alternative polythiofuran derivative A of the polythiofuran derivative D that obtains in the synthesis example 4 with preparation photoelectricity with embodiment 1.
At 300-1, the 100nm scope detects the solar battery cell that obtains among the embodiment 4 with regard to IPCE.The IPCE spectrum that so obtains is shown among Fig. 9.By being apparent that among Fig. 9, the light absorption wavelength scope sample from the ultra-violet (UV) band to 600nm produces high IPCE.
Also the solar battery cell that so obtains is detected with regard to I-E characteristic.The results are shown in the table 2.By being apparent that in the table 2, sample is realized 0.568% electricity conversion.
Table 2
Figure BPA00001248991500231
Jsc: short circuit current
Voc: open circuit voltage
Ff: fill factor
η: electricity conversion
η＝Jsc×Voc×ff

Claims (8)

1. dyestuff that is used for DSSC, contain the phosphoryl thiophene compound of following formula (1) expression in this dyestuff:
[Chemical formula 1]
Figure FPA00001248991400011
R wherein 1-R 4And R 13-R 16Represent any-OR independently of each other 5,-SR 6,-NR 7 2With-O -N +R 8R 9R 10R 11R 5-R 11Represent any hydrogen atom, C independently of each other 1-20Alkyl and have a substituent phenyl that one or more optional W represent; R 12And R 17Represent any hydrogen atom, halogen atom, hydroxyl, amino, silanol group, mercapto, carboxyl, ester group, thioester substrate, amide groups, cyano group, nitro, monovalence alkyl, organic group oxygen base, organic group amino, organic group silicyl, organic group thio group, acyl group, sulfuryl independently of each other and have the substituent phenyl that one or more optional W represent;
W represents any halogen atom, hydroxyl, amino, silanol group, mercapto, carboxyl, ester group, thioester substrate, amide groups, cyano group, nitro, monovalence alkyl, organic group oxygen base, organic group amino, organic group silicyl, organic group thio group, acyl group and sulfuryl;
M, n, o and p represent 0 or be not less than 1 integer and make 1≤m+n+o and 2≤m+n+o+p≤1,000 independently of each other; With
Z represents to be selected from those divalent organic group of following formula [2]-[10] expression:
[Chemical formula 2]
Wherein, R 18-R 40Represent any hydrogen atom, C independently of each other 1-20Alkyl, C 1-20Haloalkyl, C 1-20Alkoxyl, C 1-20Alkylthio group, C 1-20Dialkyl amido and have the substituent phenyl that one or more optional W represent, a R 41Represent any hydrogen atom, C 1-20Alkyl, C 1-20Haloalkyl, C 1-20Alkoxyl and have an optional substituent phenyl that one or more W represent, wherein W is for as mentioned above;
Condition is that the phosphoryl thiophene compound should have end group, and these end groups are any hydrogen atom, halogen atom, C independently of each other 1-20Alkyl monosubstituted amino, C 1-20Dialkyl amido, have substituent phenyl that one or more optional W represent, have substituent naphthyl that one or more optional W represent, have substituent anthryl, C that one or more optional W represent 1-10Trialkyl stannyl and C 1-20Trialkylsilkl, wherein W is for as mentioned above.
2. composition, it contains the phosphoryl thiophene compound described in the claim 1.
3. varnish, it contains the phosphoryl thiophene compound described in the claim 1.
4. organic film, it contains the phosphoryl thiophene compound described in the claim 1.
5. organic film, it is prepared by the varnish described in the claim 4.
6. semi-conducting electrode, this electrode comprises:
Light-transmissive substrates is laminated in the nesa coating on the described substrate and is laminated in metal oxide porous semi-conductor on the described nesa coating,
Described porous semi-conductor has the dyestuff that is used for DSSC described in claim 1 that is adsorbed onto described porous semi-conductor surface.
7. semi-conducting electrode, this electrode comprises the substrate with porous semi-conductor, and this substrate has been immersed in and has made the described porous semi-conductor absorption dyestuff that is used for DSSC as described above in the varnish described in the claim 3.
8. DSSC, this power brick contain right require the semi-conducting electrode described in 6, to electrode with between described semi-conducting electrode and described to the electrolyte between the electrode.
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