CN103525116A - Organic dye and its preparing process - Google Patents

Organic dye and its preparing process Download PDF

Info

Publication number
CN103525116A
CN103525116A CN201310476298.9A CN201310476298A CN103525116A CN 103525116 A CN103525116 A CN 103525116A CN 201310476298 A CN201310476298 A CN 201310476298A CN 103525116 A CN103525116 A CN 103525116A
Authority
CN
China
Prior art keywords
chemical formula
compound
formula
manufacture
following
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310476298.9A
Other languages
Chinese (zh)
Other versions
CN103525116B (en
Inventor
安贤哲
李钟灿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongjin Semichem Co Ltd
Original Assignee
Dongjin Semichem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020100131969A external-priority patent/KR20110079514A/en
Priority claimed from KR1020100131967A external-priority patent/KR101882394B1/en
Priority claimed from KR1020100131964A external-priority patent/KR20110079512A/en
Priority claimed from KR1020100131970A external-priority patent/KR20110079515A/en
Application filed by Dongjin Semichem Co Ltd filed Critical Dongjin Semichem Co Ltd
Publication of CN103525116A publication Critical patent/CN103525116A/en
Application granted granted Critical
Publication of CN103525116B publication Critical patent/CN103525116B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

The present invention provides a novel organic dye and a method for producing the same. The organic dye of the present invention has a specific aliphatic compound as an electron donor, has a thiophene-based or dehydrothiophene-based unit at an intermediate linker (spacer), is applied to a dye-induced solar cell (DSSC), exhibits improved molar absorptivity, Jsc (short-circuit photocurrent density), and photoelectric conversion efficiency compared to conventional dyes, can greatly improve the efficiency of the solar cell, can be refined even without using expensive columns, and can dramatically reduce the cost of dye synthesis.

Description

New organic dye and manufacture method thereof
The application is to be on December 23rd, 2010 applying date, and application number is 201080059606.2, and what denomination of invention was the Chinese patent application of " new organic dye and manufacture method thereof " divides an application.
Technical field
The present invention relates to dyestuff and manufacture method thereof for dyestuff induction solar cell (dye-sensitized solar cell, DSSC).
Background technology
Within 1991, your (Michael Gratzel) research group of the ability of the Michael's lattice Lay by the federal Institute of Technology of Lausanne, SUI (EPFL) develops after dyestuff induction nanoparticle titanium oxide solar cell, is carrying out a lot of research in this field.Dyestuff induction solar cell is because being solar cell compared with existing silicon, efficiency is high, manufacturing cost is significantly low, there is the possibility that replaces existing non-crystal silicon solar cell, different from silicon solar cell, dyestuff induction solar cell is to take visible light absorbing and form the right dye molecule of electron-hole (hole) and transmit the Photoelectrochemistry that the transition metal oxide of the electronics that generated is main composition material.
As the dyestuff for dyestuff induction solar cell, the ruthenium metal complex that shows high photoelectric transformation efficiency is widely used so far, but this ruthenium metal complex has expensive shortcoming.
Recently, discovery is shifted (charge-transfer at extinction efficiency, redox reaction stability and intramolecular charge, CT) be that absorption aspect shows organic dye outstanding physical properties, that do not contain metal, the used for solar batteries dyestuff that can be used for instead expensive ruthenium metal complex, so concentrate and carry out not containing the research of the organic dye of metal.
Organic dye generally has the structure of electron donor (electron donor)-electron acceptor(EA) (electron acceptor) residue connecting by π-key unit.In most organic dye, sulfonamide derivatives is being brought into play the effect of electron donor, and 2-alpha-cyanoacrylate or rhodanine residue are being brought into play the effect of electron acceptor(EA), and these two positions connect by methyne unit or the such π-key system of thiophene chain.
General, the variation that can bring characteristic electron as the variation of the structure of the amine unit of electron donor, for example, to the extinction spectrum of cyan side displacement (shift), change π-key length and can regulate extinction spectrum and redox potential (redox potential).
But, most of organic dye so far, compared with ruthenium metal complex dyestuff, show low efficiency of conversion and low driving stability, therefore want by changing kind or the π-key length of such electron donor and acceptor, thus exploitation than existing organic dye compound there is the molar absorptivity of raising, the effort that shows the new dyestuff of high photoelectric transformation efficiency is continuing always.
Summary of the invention
The problem that invention will solve
Therefore, the object of this invention is to provide a kind of molar absorptivity, photoelectric transformation efficiency having improved that reveal than existing dye sheet, can greatly improve organic dye and the manufacture method thereof of the efficiency of solar cell.
In addition, object of the present invention provides a kind of and comprises above-mentioned dyestuff and show photoelectric transformation efficiency and Jsc (the short-circuit photocurrent density having significantly improved, and the solar cell that obviously improved of efficiency short circuit photocurrent density) and the outstanding dye-sensitized photoelectric conversion device of molar absorptivity.
For solving the means of problem
For reaching above-mentioned purpose, the invention provides the organic dye shown in the arbitrary chemical formula in following Chemical formula 1 to 4.
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
Figure BDA0000394865390000031
[chemical formula 4]
Figure BDA0000394865390000032
In above-mentioned Chemical formula 1-4, Donor group is following chemical formula D-1 to one in D-4,
[chemical formula D-1]
Figure BDA0000394865390000033
[chemical formula D-2]
Figure BDA0000394865390000034
[chemical formula D-3]
[chemical formula D-4]
Figure BDA0000394865390000041
Ar, Ar in above-mentioned formula 1, Ar 2, Ar 3be substituted or non-substituted C independently of one another 6-12aryl, * is connection portion,
A is
Figure BDA0000394865390000042
Figure BDA0000394865390000043
or their combination;
B is
Figure BDA0000394865390000044
or their combination;
C is
Figure BDA0000394865390000046
R 1to R 4be hydrogen, C independently of one another 1-12alkyl or substituted or non-substituted C 6-12aryl;
N is 1 to 5 integer.
And the invention provides the compound end obtaining after the compound shown in following chemical formula D-5 or chemical formula D-6 is reacted successively with the precursor compound of the defined A of above-mentioned Chemical formula 1 to 4, B, A and B or B and A be combined C manufacture, be expressed as Chemical formula 1 to 4 in the manufacture method of dyestuff of arbitrary chemical formula.
[chemical formula D 5]
Figure BDA0000394865390000052
[chemical formula D 6]
Figure BDA0000394865390000053
In above-mentioned formula, Donor group is with defined above identical.
And the invention provides and comprise load and have the dye-sensitized photoelectric conversion device that the oxide semiconductor particulate of the compound that is expressed as arbitrary chemical formula in above-mentioned Chemical formula 1 to 4 is feature.
And the invention provides and comprise the dyestuff induction solar cell that above-mentioned dye-sensitized photoelectric conversion device is feature.
Invention effect
Dye composition of the present invention is applied to dyestuff induction solar cell (DSSC), show the molar absorptivity, Jsc (short-circuit photocurrent density) and the photoelectric transformation efficiency that than existing dyestuff, have improved, can greatly improve the efficiency of solar cell, even if do not use the post of expensive price also can refine, can reduce the synthetic cost of dyestuff epoch-makingly.
Embodiment
The inventor is by using specific fatty compounds as electron donor, and import for increasing molar absorptivity at middle interconnecting piece (spacer (spacer)), the thiophene system or the dehydrothiophen that increase element stability are unit, make spacer that one direction exists and fixed group (anchoring group) to both direction importing etc., by this, there is new organic dye structure, what be expressed as arbitrary chemical formula in Chemical formula 1 to 4 is compound loaded while manufacturing dyestuff induction solar cell in oxide semiconductor particulate, confirmed photoelectric transformation efficiency, Jsc (short-circuit photocurrent density) and molar absorptivity are high, and show than the outstanding efficiency of existing dyestuff induction solar cell, thereby completed the present invention.
Organic dye of the present invention is characterised in that with any expression in following Chemical formula 1 to 4.
[Chemical formula 1]
Figure BDA0000394865390000061
[Chemical formula 2]
Figure BDA0000394865390000062
[chemical formula 3]
Figure BDA0000394865390000071
[chemical formula 4]
In above-mentioned Chemical formula 1-4, Donor group, Ar, Ar 1, Ar 2, Ar 3, A, B, C, R 1to R 4, and n as above-mentioned definition.The dye composition of Chemical formula 1 of the present invention is preferably with any expression in following structural formula.
Figure BDA0000394865390000073
Figure BDA0000394865390000081
Figure BDA0000394865390000091
Figure BDA0000394865390000121
Figure BDA0000394865390000131
Figure BDA0000394865390000141
Figure BDA0000394865390000151
Figure BDA0000394865390000161
Figure BDA0000394865390000171
Figure BDA0000394865390000181
Figure BDA0000394865390000201
Figure BDA0000394865390000211
Figure BDA0000394865390000221
The end of the compound that in addition, the present invention obtains after can manufacturing the compound that is expressed as chemical formula D-5 or chemical formula D-6 being reacted successively with the precursor compound of the defined A in above-mentioned Chemical formula 1-4, B, A and B or B and A is combined C and is manufactured, is expressed as the dyestuff of arbitrary chemical formula in Chemical formula 1 to 4.
[chemical formula D-5]
Figure BDA0000394865390000231
[chemical formula D-6]
Figure BDA0000394865390000232
Above-mentioned middle Donor group is as above-mentioned definition.
According to compound of the present invention, concrete example, can the compound of the compound of following chemical formula 5-1 and following chemical formula 6 be carried out to the compound that Suzuki coupled reaction is manufactured following chemical formula 7-1 by (1), (2) by the compound of chemical formula 7-1 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 1.
[chemical formula 5-1]
Figure BDA0000394865390000233
[chemical formula 6]
Figure BDA0000394865390000234
[chemical formula 7-1]
Figure BDA0000394865390000235
In above formula, B is as above-mentioned definition.
[reaction formula 1]
Figure BDA0000394865390000251
In addition, according to compound of the present invention, can the compound of the compound of following chemical formula 5-1 and following chemical formula 8 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following chemical formula 9-1, (2) compound of chemical formula 9-1 is reacted with trifluoroacetic acid in tetrahydrofuran (THF) (THF), manufacture the compound of following Chemical formula 1 0-1, (3) by the compound of Chemical formula 1 0-1 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 2.
[chemical formula 5-1]
[chemical formula 8]
Figure BDA0000394865390000262
[chemical formula 9-1]
Figure BDA0000394865390000263
[Chemical formula 1 0-1]
Figure BDA0000394865390000264
In above formula, A, B are as above-mentioned definition.
[reaction formula 2]
Figure BDA0000394865390000271
According to compound of the present invention, can the compound of the compound of following chemical formula 5-1 and following Chemical formula 11 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following Chemical formula 1 2-1, (2) compound of Chemical formula 1 2-1 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 1 3-1, (3) compound of the compound of Chemical formula 1 3-1 and chemical formula 6 is carried out to Suzuki coupled reaction, the compound of manufacturing chemistry formula 14-1, (4) by the compound of 14-1 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 3.
[chemical formula 5-1]
Figure BDA0000394865390000281
[Chemical formula 1 1]
（HO） 2B-A
[Chemical formula 1 2-1]
Figure BDA0000394865390000282
[Chemical formula 1 3-1]
Figure BDA0000394865390000283
[chemical formula 6]
[Chemical formula 1 4-1]
Figure BDA0000394865390000291
In above formula, A, B are as above-mentioned definition.
[reaction formula 3]
Figure BDA0000394865390000301
Compound according to chemical formula 4 of the present invention, can the compound of following Chemical formula 1 5-1 under existing, potassium tert.-butoxide be reacted in tetrahydrofuran (THF) (THF) with the compound of following Chemical formula 16 by (1) for instance, manufacture the compound of following Chemical formula 17, (2) compound of Chemical formula 1 7-1 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 18, (3) compound of the compound of Chemical formula 1 8-1 and chemical formula 6 is carried out to Suzuki coupled reaction, manufacture the compound of following Chemical formula 1 9-1, (4) by the compound of Chemical formula 1 9-1 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 4.
[Chemical formula 1 5-1]
Figure BDA0000394865390000311
[Chemical formula 1 6]
OHC-A
[Chemical formula 1 7-1]
Figure BDA0000394865390000312
[Chemical formula 1 8-1]
Figure BDA0000394865390000313
[chemical formula 6]
Figure BDA0000394865390000314
[Chemical formula 1 9-1]
Figure BDA0000394865390000321
In above formula, A, B are as above-mentioned definition.
[reaction formula 4]
Figure BDA0000394865390000331
In addition, according to compound of the present invention, can the compound of the compound of following chemical formula 5-2 and following chemical formula 6 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following chemical formula 7-2, (2) by the compound of chemical formula 7-2 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 5.
[chemical formula 5-2]
Figure BDA0000394865390000341
[chemical formula 6]
Figure BDA0000394865390000342
[chemical formula 7-2]
Figure BDA0000394865390000343
In above formula, B is as above-mentioned definition.
[reaction formula 5]
Figure BDA0000394865390000351
According to compound of the present invention, can the compound of the compound of following chemical formula 5-2 and following chemical formula 8 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following chemical formula 9-2, (2) by the compound of chemical formula 9-2, in tetrahydrofuran (THF) (THF), react with trifluoroacetic acid, manufacture the compound of following Chemical formula 1 0-2, (3) by the compound of Chemical formula 1 0-2 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 6.
[chemical formula 5-2]
Figure BDA0000394865390000361
[chemical formula 8]
Figure BDA0000394865390000362
[chemical formula 9-2]
Figure BDA0000394865390000363
[Chemical formula 1 0-2]
Figure BDA0000394865390000364
In above formula, A, B are as above-mentioned definition.
[reaction formula 6]
Figure BDA0000394865390000371
According to compound of the present invention, can the compound of the compound of following chemical formula 5-2 and following Chemical formula 11 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following Chemical formula 1 2-2, (2) compound of Chemical formula 1 2-2 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 1 3-2, (3) compound of the compound of Chemical formula 1 3-2 and following chemical formula 6 is carried out to Suzuki coupled reaction, manufacture the compound of following Chemical formula 1 4-2, (4) by the compound of 14-2 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 7.
[chemical formula 5-2]
Figure BDA0000394865390000381
[Chemical formula 1 1]
（HO） 2B-A
[Chemical formula 1 2-2]
Figure BDA0000394865390000382
[Chemical formula 1 3-2]
Figure BDA0000394865390000383
[chemical formula 6]
[Chemical formula 1 4-2]
Figure BDA0000394865390000392
In above formula, A, B are as above-mentioned definition.
[reaction formula 7]
Figure BDA0000394865390000391
According to compound of the present invention, can the compound of following Chemical formula 1 5-2 under existing, potassium tert.-butoxide be reacted in tetrahydrofuran (THF) (THF) with the compound of following Chemical formula 16 by (1) for instance, manufacture the compound of following Chemical formula 1 7-2, (2) compound of Chemical formula 1 7-2 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 1 8-2, (3) compound of the compound of Chemical formula 1 8-2 and following chemical formula 6 is carried out to Suzuki coupled reaction, manufacture the compound of following Chemical formula 1 9-2, (4) by the compound of 19-2 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 8.
[Chemical formula 1 5-2]
[Chemical formula 1 6]
OHC-A
[Chemical formula 1 7-2]
Figure BDA0000394865390000402
[Chemical formula 1 8-2]
Figure BDA0000394865390000403
[chemical formula 6]
Figure BDA0000394865390000404
[Chemical formula 1 9-2]
Figure BDA0000394865390000411
In above formula, A, B are as above-mentioned definition.
[reaction formula 8]
Figure BDA0000394865390000412
According to compound of the present invention, can the compound of the compound of following chemical formula 5-3 and following chemical formula 6 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following chemical formula 7-3, (2) by the compound of chemical formula 7-3 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 9.
[chemical formula 5-3]
[chemical formula 6]
[chemical formula 7-3]
Figure BDA0000394865390000423
In above formula, B is as above-mentioned definition.
[reaction formula 9]
Figure BDA0000394865390000431
According to compound of the present invention, can the compound of the compound of following chemical formula 5-3 and following chemical formula 8 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following chemical formula 9-3, (2) chemical formula 9-3 is reacted with trifluoroacetic acid in tetrahydrofuran (THF) (THF), manufacture the compound of following Chemical formula 1 0-3, (3) by the compound of Chemical formula 1 0-3 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 10.
[chemical formula 5-3]
Figure BDA0000394865390000441
[chemical formula 8]
Figure BDA0000394865390000442
[chemical formula 9-3]
Figure BDA0000394865390000443
[Chemical formula 1 0-3]
In above formula, A, B are as above-mentioned definition.
[reaction formula 10]
Figure BDA0000394865390000451
According to compound of the present invention, can the compound of the compound of following chemical formula 5-3 and following Chemical formula 11 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following Chemical formula 1 2-3, (2) compound of Chemical formula 1 2-3 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 1 3-3, (3) compound of the compound of Chemical formula 1 3-3 and following chemical formula 6 is carried out to Suzuki coupled reaction, manufacture the compound of following Chemical formula 1 4-3, (4) by the compound of 14-3 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 11.
[chemical formula 5-3]
Figure BDA0000394865390000461
[Chemical formula 1 1]
（HO） 2B-A
[Chemical formula 1 2-3]
Figure BDA0000394865390000462
[Chemical formula 1 3-3]
Figure BDA0000394865390000463
[chemical formula 6]
[Chemical formula 1 4-3]
In above formula, A, B are as above-mentioned definition.
[reaction formula 11]
Figure BDA0000394865390000481
According to compound of the present invention, can the compound of following Chemical formula 1 5-3 under existing, potassium tert.-butoxide be reacted in tetrahydrofuran (THF) (THF) with the compound of following Chemical formula 16 by (1) for instance, manufacture the compound of following Chemical formula 1 7-3, (2) compound of Chemical formula 1 7-3 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 1 8-3, (3) compound of the compound of Chemical formula 1 8-3 and following chemical formula 6 is carried out to Suzuki coupled reaction, manufacture the compound of following Chemical formula 1 9-3, (4) by the compound of Chemical formula 1 9-3 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 12.
[Chemical formula 1 5-3]
[Chemical formula 1 6]
OHC-A
[Chemical formula 1 7-3]
Figure BDA0000394865390000492
[Chemical formula 1 8-3]
[chemical formula 6]
Figure BDA0000394865390000494
[Chemical formula 1 9-3]
In above formula, A, B are as above-mentioned definition.
[reaction formula 12]
Figure BDA0000394865390000502
According to compound of the present invention, can the compound of the compound of following chemical formula 5-4 and following chemical formula 6 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following chemical formula 7-4, (2) by the compound of chemical formula 7-4 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 13.
[chemical formula 5-4]
Figure BDA0000394865390000511
[chemical formula 6]
[chemical formula 7-4]
In above formula, Ar 1, X and B be as above-mentioned definition.
[reaction formula 13]
Figure BDA0000394865390000521
According to compound of the present invention, can the compound of the compound of following chemical formula 5-4 and following chemical formula 8 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following chemical formula 9-4, (2) compound of chemical formula 9-4 is reacted with trifluoroacetic acid in tetrahydrofuran (THF) (THF), manufacture the compound of following Chemical formula 1 0-4, (3) by the compound of Chemical formula 1 0-4 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 14.
[chemical formula 5-4]
Figure BDA0000394865390000531
[chemical formula 8]
Figure BDA0000394865390000532
[chemical formula 9-4]
[Chemical formula 1 0-4]
Figure BDA0000394865390000534
In above formula, Ar1, X, A and B are as above-mentioned definition.
[reaction formula 14]
Figure BDA0000394865390000541
Figure BDA0000394865390000551
According to compound of the present invention, can the compound of the compound of following chemical formula 5-4 and following Chemical formula 11 be carried out to Suzuki coupled reaction by (1) for instance, manufacture the compound of following Chemical formula 1 2-4, (2) compound of Chemical formula 1 2-4 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 1 3-4, (3) compound of the compound of Chemical formula 1 3-4 and following chemical formula 6 is carried out to Suzuki coupled reaction, manufacture the compound of following Chemical formula 1 4-4, (4) by the compound of Chemical formula 1 4-4 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 15.
[chemical formula 5-4]
Figure BDA0000394865390000561
[Chemical formula 1 1]
（HO） 2B-A
[Chemical formula 1 2-4]
Figure BDA0000394865390000562
[Chemical formula 1 3-4]
[chemical formula 6]
Figure BDA0000394865390000564
[Chemical formula 1 4-4]
Figure BDA0000394865390000571
In above formula, Ar1, X, A and B are as above-mentioned definition.
[reaction formula 15]
Figure BDA0000394865390000572
Figure BDA0000394865390000581
According to compound of the present invention, can the compound of following Chemical formula 1 5-4 under existing, potassium tert.-butoxide be reacted in tetrahydrofuran (THF) (THF) with the compound of following Chemical formula 16 by (1) for instance, manufacture the compound of following Chemical formula 1 7-4, (2) compound of Chemical formula 1 7-4 is reacted with N-bromo-succinimide, manufacture the compound of following Chemical formula 1 8-4, (3) compound of the compound of Chemical formula 1 8-4 and following chemical formula 6 is carried out to Suzuki coupled reaction, manufacture the compound of following Chemical formula 1 9-4, (4) by the compound of Chemical formula 1 9-4 in CH3CN under piperidines exists, react with cyanoacetic acid and manufacture.Its concrete example can be represented by following reaction formula 16.
[Chemical formula 1 5-4]
Figure BDA0000394865390000582
[Chemical formula 1 6]
OHC–A
[Chemical formula 1 7-4]
Figure BDA0000394865390000591
[Chemical formula 1 8-4]
Figure BDA0000394865390000592
[chemical formula 6]
Figure BDA0000394865390000593
[Chemical formula 1 9-4]
Figure BDA0000394865390000594
In above formula, Ar1, X, A and B are as above-mentioned definition.
[reaction formula 16]
Figure BDA0000394865390000601
In addition, the invention provides dye-sensitized photoelectric conversion device, it is feature that above-mentioned dye-sensitized photoelectric conversion device be take on oxide semiconductor particulate dyestuff shown in arbitrary chemical formula in the above-mentioned Chemical formula 1 to 4 of load.The present invention is also applicable following methods certainly, be that dye-sensitized photoelectric conversion device removes dyestuff shown in arbitrary chemical formula in the above-mentioned Chemical formula 1 to 4 of use, also the dyestuff that can apply is in the past manufactured used for solar batteries dye-sensitized photoelectric conversion device, a concrete example is, the method that No. 10-2009-38377th, applicable Korea S publication communique (application Ren Wei Dong Jin Shi-Mei Ken Co., Ltd) is recorded, be preferably dye-sensitized photoelectric conversion device application oxide semiconductor particulate of the present invention, on substrate, manufacture oxide semiconductor thin-film, follow load dyestuff of the present invention on above-mentioned film.
Below, according to embodiment, more specifically describe the present invention.But these embodiment are only illustration the present invention, the present invention is not limited thereto.
Embodiment 1
1-1) intermediate (la) is synthetic
By the bromo-9-phenylacridine of 2,7-bis-and (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, tetrakis triphenylphosphine palladium and 2M K 2cO 3the aqueous solution, refluxes 12 hour after mixing in dimethyl formamide (DMF).The reaction soln as a result of obtaining is cooling, add water (30ml) and salt solution, separated also the refining of organic layer obtained having to the intermediate of following chemical formula.
[intermediate la]
Figure BDA0000394865390000611
1-2) compound 1 is synthetic
Mix above-described embodiment 1-1) intermediate (la) manufactured and cyanoacetic acid by after the mixture vacuum-drying of manufacture, mix with second cyanogen and piperidines, reflux 6 hours.After the reaction soln as a result of obtaining is cooling, under vacuum, remove organic layer.The solid substance as a result of obtaining is refining with silica gel chromatography, obtain following compound 1.Gained compound is carried out to the result of FD-MS (Field desorption mass spectrum, field desorption(FD) mass spectrum), confirmed for C 35h 19n 3o 4s 2=610, m/z (measured value)=610.
[compound 1]
Figure BDA0000394865390000621
Embodiment 2
Except in above-described embodiment 1, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, use (E)-(5-oxo thieno-[3,2-b] thiophene-2 (5H)-subunit) beyond methyl-boron-dihydroxide, the method for implementing similarly to Example 1 successively obtains and following compound 2.Above-claimed cpd is carried out to the result of FD-MS, confirmed for C 39h 19n 3o 4s 4=722, m/z (measured value)=721.
[compound 2]
Figure BDA0000394865390000622
Embodiment 3
Except in above-described embodiment 1, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, (E)-(7-oxo-2,3-dihydro-thiophene is [3,4-b] [Isosorbide-5-Nitrae] two also in use english-5 (7H)-subunit), beyond methyl-boron-dihydroxide, the method for implementing similarly to Example 1 successively obtains following compound 3.Above-claimed cpd is carried out to the result of FD-MS, confirmed for C 39h 23n 8o 3s 2=726, m/z (measured value)=725.
[compound 3]
Figure BDA0000394865390000631
Embodiment 4
By the bromo-N of 3,6-bis-, two (4-the methoxyphenyl)-10-phenylanthracene-9-amine of N-, (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, tetrakis triphenylphosphine palladium and 2M K 2cO 3the aqueous solution, refluxes 12 hour after mixing in dimethyl formamide (DMF).The reaction soln as a result of obtaining is cooling, add water (30ml) and salt solution, separated also the refining of organic layer obtained to intermediate.
Mix the intermediate of above-mentioned manufacture and cyanoacetic acid and by after the mixture vacuum-drying of manufacturing, mix with acetonitrile and piperidines, refluxing 6 hours.After the bearing reaction solution of gained is cooling, under vacuum, remove organic layer.The solid substance as a result of obtaining is refining and obtain compound 4 with silica gel chromatography.Gained compound 4 is carried out to the result of FD-MS, confirmed for C 50h 33n 3o 6s 2=836, m/z (measured value)=835.
[compound 4]
Figure BDA0000394865390000632
Embodiment 5
Except in above-described embodiment 4, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, use (E)-(5-oxo thieno-[3,2-b] thiophene-2 (5H)-subunit) beyond methyl-boron-dihydroxide, implement method similarly to Example 4 successively and obtain following compound 5.Above-claimed cpd 5 is carried out to the result of FD-MS, confirmed for C 54h 33n 3o 6s 4=948, m/z (measured value)=947.
[compound 5]
Figure BDA0000394865390000641
Embodiment 6
Except in above-described embodiment 4, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, (E)-(7-oxo-2,3-dihydro-thiophene is [3,4-b] [Isosorbide-5-Nitrae] two also in use
Figure BDA0000394865390000642
english-5 (7H)-subunit), beyond methyl-boron-dihydroxide, implement successively method similarly to Example 4 and obtain compound 6.Above-claimed cpd is carried out to the result of FD-MS, confirmed for C 54h 37n 3o 10s 2=952, m/z (measured value)=951.
[compound 6]
Figure BDA0000394865390000643
Embodiment 7
By the bromo-9-(4-methoxyphenyl of 3,6-bis-)-9H-carbazole, (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, tetrakis triphenylphosphine palladium and 2M K 2cO 3the aqueous solution, refluxes 12 hour after mixing in dimethyl formamide (DMF).The reaction soln as a result of obtaining is cooling, add water (30ml) and salt solution, separated also the refining of organic layer obtained to intermediate.
Mix the intermediate of above-mentioned manufacture and cyanoacetic acid and by after the mixture vacuum-drying of manufacturing, mix with second cyanogen and piperidines, refluxing 6 hours.After the reaction soln as a result of obtaining is cooling, under vacuum, remove organic layer.The solid substance as a result of obtaining is refining and obtain compound 7 with silica gel chromatography.The compound 7 obtaining is carried out to the result of FD-MS, confirmed for C 35h 21n 3o 5s 2=628, m/z (measured value)=627.
[compound 7]
Figure BDA0000394865390000651
Embodiment 8
Except in above-described embodiment 7, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, use (E)-(5-oxo thieno-[3,2-b] beyond the methyl-boron-dihydroxide of thiophene-2 (5H) – subunit), implement method similarly to Example 7 successively and obtain compound 8.Above-claimed cpd 8 is carried out to the result of FD-MS, confirmed for C 39h 21n 3o 5s 4=740, m/z (measured value)=739.
[compound 8]
Figure BDA0000394865390000652
Embodiment 9
Except in above-described embodiment 7, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, (E)-(7-oxo-2,3-dihydro-thiophene is [3,4-b] [Isosorbide-5-Nitrae] two also in use
Figure BDA0000394865390000653
beyond English (5 (7H)-subunit) methyl-boron-dihydroxide, the method for implementing similarly to Example 7 successively obtains compound 9.Above-claimed cpd is carried out to the result of FD-MS, confirmed for C 39h 25n 3o 9s 2=744, m/z (measured value)=743.
[compound 9]
Figure BDA0000394865390000661
Embodiment 10
By the bromo-10-(4-methoxyphenyl of 3,7-bis-)-10H-thiodiphenylamine and (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, tetrakis triphenylphosphine palladium and 2M K 2cO 3the aqueous solution, refluxes 12 hour after mixing in dimethyl formamide (DMF).The reaction soln as a result of obtaining is cooling, add water (30ml) and salt solution, separated also the refining of organic layer obtained to intermediate.
After the mixture vacuum-drying that the intermediate of above-mentioned manufacture and cyanoacetic acid is mixed and manufacture, mix with acetonitrile and piperidines, reflux 6 hours.After the reaction soln as a result of obtaining is cooling, under vacuum, remove organic layer.The solid substance as a result of obtaining is refining and obtain compound 10 with silica gel chromatography.The compound 10 obtaining is carried out to the result of FD-MS, confirmed for C 35h 21n 3o 5s 3=660, m/z (measured value)=659.
[compound 10]
Figure BDA0000394865390000662
Embodiment 11
Except in above-described embodiment 10, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, use (E)-(5-oxo thieno-[3,2-b] thiophene-2 (5H)-subunit) beyond methyl-boron-dihydroxide, implement method similarly to Example 10 successively and obtain following compound 2.Above-claimed cpd 11 is carried out to the result of FD-MS, confirmed for C 39h 21n 3o 5s 5=772, m/z (measured value)=771.
[compound 11]
Embodiment 12
Except in above-described embodiment 10, replace (E)-(5-oxo thiophene-2 (5H)-subunit) methyl-boron-dihydroxide, (E)-(7-oxo-2,3-dihydro-thiophene is [3,4-b] [Isosorbide-5-Nitrae] two also in use english-2 (7H)-subunit), beyond methyl-boron-dihydroxide, implement successively method similarly to Example 10 and obtain following compound 12.Above-claimed cpd is carried out to the result of FD-MS, confirmed for C 39h 25n 3o 9s 3=776, m/z (measured value)=775.
[compound 12]
Figure BDA0000394865390000673
The manufacture of dyestuff induction solar cell
For evaluating the I-E characteristic according to dyestuff of the present invention, utilize 13+10 μ mTiO2 transparent layer to manufacture dyestuff induction solar cell.
Specifically, washed FTO (Pilkington8 Ω sq-1) glass substrate is contained and is immersed in the 40mMTiCl4 aqueous solution.By TiO 2slurry (Switzerland Solaronix company, 13nm anatase octahedrite) carries out silk screen printing, manufactures a TiO of 13 μ m thickness 2layer, for the 2nd TiO of 10 μ m thickness is manufactured in scattering of light with other slurry (CCIC, HWP-400) 2scattering layer.By the TiO manufacturing 2electrode, containing being immersed according to dye solution of the present invention (containing the 3a of 10mM, in the ethanol of 7a-dihydroxyl-5b-cholic acid, the compound 1-12 that above-described embodiment 1-12 is manufactured is dissolved into 0.3mM separately), is placed 18 hours in room temperature.On FTO substrate, apply H 2ptCl 6solution (containing 2mg Pt in ethanol 1mL) is manufactured electrode.Then, the ionogen that has dissolved 0.6M3-hexyl-1,2 dimethylimidazole iodine, 0.04M I2,0.025M LiI, 0.05M guanidine thiocyanate and 0.28M tert .-butylpyridine in acetonitrile is injected into battery, manufactures dyestuff induction solar cell.Use 1000W xenon light source to measure the photocell performance of dyestuff induction solar cell, the results are shown in following table 1.
Table 1
? Efficiency (η) (%)
Compound 1 4.4
Compound 2 4.6
Compound 3 4.6
Compound 4 5.2
Compound 5 5.5
Compound 6 5.4
Compound 7 3.8
Compound 8 3.9
Compound 9 4.0
Compound 10 4.8
Compound 11 5.2
Compound 12 4.9
As shown in Table 1, new dye of the present invention shows outstanding photoelectric transformation efficiency.Thus, new dye compound of the present invention can improve solar battery efficiency greatly, even if do not use the post of expensive price also can refine, can reduce the synthetic cost of dyestuff epoch-makingly.
Industry is utilized possibility
Dye composition of the present invention is for dyestuff induction solar cell (DSSC), show the molar absorptivity, Jsc (short-circuit photocurrent density) and the photoelectric transformation efficiency that than dyestuff in the past, have improved, can greatly improve the efficiency of solar cell, even if do not use the post of expensive price also can refine, can reduce the synthetic cost of dyestuff epoch-makingly.

Claims (5)

1. an organic dye, is represented by following Chemical formula 1:
[Chemical formula 1]
Figure FDA0000394865380000011
In above-mentioned Chemical formula 1, Donor group is following chemical formula D-2,
[chemical formula D-2]
Figure FDA0000394865380000012
In above-mentioned formula, Ar 1, Ar 2, Ar 3be substituted or non-substituted C independently of one another 6-12aryl, * is connection portion,
B is or their combination, C is
Figure FDA0000394865380000014
or
Figure FDA0000394865380000015
R 1to R 4be hydrogen, C independently of one another 1-12alkyl or substituted or non-substituted C 6-12aryl,
N is 1 to 5 integer.
2. organic dye claimed in claim 1, is characterized in that, described dyestuff is any in following structural formula:
Figure FDA0000394865380000021
Figure FDA0000394865380000031
In above-mentioned formula, R is hydrogen, C 1-12alkyl or substituted or non-substituted C 6-12aryl.
3. the manufacture method of the dyestuff shown in the defined Chemical formula 1 of claim 1, is to be combined C and to manufacture described dyestuff for the end of the compound that makes to obtain after the precursor compound reaction of the compound shown in following chemical formula D-5 and the defined B of claim 1,
[chemical formula D 5]
Figure FDA0000394865380000041
In above-mentioned formula, Donor group is the same with claim 1 definition.
4. a dye-sensitized photoelectric conversion device, is characterized in that, comprises the have the right oxide semiconductor particulate of organic dye of requirement 1 of load.
5. a dyestuff induction solar cell, is characterized in that the dye-sensitized photoelectric conversion device that comprises claim 4.
CN201310476298.9A 2009-12-30 2010-12-23 Organic dye and its preparing process Expired - Fee Related CN103525116B (en)

Applications Claiming Priority (17)

Application Number Priority Date Filing Date Title
KR10-2009-0134315 2009-12-30
KR20090134315 2009-12-30
KR10-2009-0135531 2009-12-31
KR10-2009-0135538 2009-12-31
KR20090135541 2009-12-31
KR10-2009-0135541 2009-12-31
KR20090135538 2009-12-31
KR20090135531 2009-12-31
KR10-2010-0131969 2010-12-21
KR1020100131969A KR20110079514A (en) 2009-12-31 2010-12-21 Novel organic dye and preparation thereof
KR10-2010-0131967 2010-12-21
KR10-2010-0131970 2010-12-21
KR1020100131967A KR101882394B1 (en) 2009-12-31 2010-12-21 Novel organic dye and preparation thereof
KR1020100131964A KR20110079512A (en) 2009-12-31 2010-12-21 Novel organic dye and preparation thereof
KR1020100131970A KR20110079515A (en) 2009-12-30 2010-12-21 Novel organic dye and preparation thereof
KR10-2010-0131964 2010-12-21
CN2010800596062A CN102695759A (en) 2009-12-30 2010-12-23 Organic dye and its preparing process

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN2010800596062A Division CN102695759A (en) 2009-12-30 2010-12-23 Organic dye and its preparing process

Publications (2)

Publication Number Publication Date
CN103525116A true CN103525116A (en) 2014-01-22
CN103525116B CN103525116B (en) 2015-09-09

Family

ID=46750886

Family Applications (2)

Application Number Title Priority Date Filing Date
CN2010800596062A Pending CN102695759A (en) 2009-12-30 2010-12-23 Organic dye and its preparing process
CN201310476298.9A Expired - Fee Related CN103525116B (en) 2009-12-30 2010-12-23 Organic dye and its preparing process

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN2010800596062A Pending CN102695759A (en) 2009-12-30 2010-12-23 Organic dye and its preparing process

Country Status (3)

Country Link
JP (1) JP5875988B2 (en)
CN (2) CN102695759A (en)
TW (1) TWI529221B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108456435A (en) * 2018-03-07 2018-08-28 南京正春电子科技有限公司 A kind of new dye photosensitizer and preparation method thereof
WO2021261447A1 (en) * 2020-06-22 2021-12-30 富士フイルム株式会社 Photoelectric conversion element, imaging element, optical sensor, and compound

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002100419A (en) * 2000-09-25 2002-04-05 Mitsubishi Chemicals Corp Photoelectric transfer element
US20060130249A1 (en) * 2003-03-14 2006-06-22 Masaaki Ikeda Dye-sensitized photoelectric conversion device
WO2007119525A1 (en) * 2006-03-31 2007-10-25 National Institute Of Advanced Industrial Science And Technology Organic compound, semiconductor thin film electrode using the same, photoelectric transducer, and photoelectrochemical solar cell
US20080115826A1 (en) * 2006-11-20 2008-05-22 Konica Minolta Business Technologies, Inc. Photoelectric conversion element, method of manufacturing the same and solar cell
JP2008147122A (en) * 2006-12-13 2008-06-26 Konica Minolta Business Technologies Inc Dye-sensitized photoelectric conversion element, and dye-sensitized solar cell
WO2008146975A1 (en) * 2007-05-25 2008-12-04 Dongjin Semichem Co., Ltd Novel organic dye containing n-arylcarbazole moiety and preparation thereof
KR20090055302A (en) * 2007-11-28 2009-06-02 삼성에스디아이 주식회사 Photosensitizer for photovoltaic cell, and photovoltaic cell including same
TW200936702A (en) * 2008-01-30 2009-09-01 Dongjin Semichem Co Ltd Novel organic sensitizers and method for preparing the same
WO2009109499A1 (en) * 2008-03-07 2009-09-11 Basf Se Dye sensitised solar cell

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI297038B (en) * 2000-11-22 2008-05-21 Academia Sinica 3,6,9-trisubstituted carbazoles for light emitting diodes
CA2608934A1 (en) * 2005-05-24 2006-11-30 Nippon Kayaku Kabushiki Kaisha Dye-sensitized photoelectric conversion device
US20080146816A1 (en) * 2006-12-18 2008-06-19 Commissariat A L'energie Atomique Monomer of the "push-pull" type and photochromic electroconducting polymer material obtained from this monomer
JP5239262B2 (en) * 2007-09-05 2013-07-17 コニカミノルタビジネステクノロジーズ株式会社 Solar cell
JP5266714B2 (en) * 2007-10-25 2013-08-21 コニカミノルタビジネステクノロジーズ株式会社 Photoelectric conversion element and solar cell
KR20100136929A (en) * 2009-06-19 2010-12-29 주식회사 동진쎄미켐 Novel organic dye and preparation thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002100419A (en) * 2000-09-25 2002-04-05 Mitsubishi Chemicals Corp Photoelectric transfer element
US20060130249A1 (en) * 2003-03-14 2006-06-22 Masaaki Ikeda Dye-sensitized photoelectric conversion device
WO2007119525A1 (en) * 2006-03-31 2007-10-25 National Institute Of Advanced Industrial Science And Technology Organic compound, semiconductor thin film electrode using the same, photoelectric transducer, and photoelectrochemical solar cell
US20080115826A1 (en) * 2006-11-20 2008-05-22 Konica Minolta Business Technologies, Inc. Photoelectric conversion element, method of manufacturing the same and solar cell
JP2008147122A (en) * 2006-12-13 2008-06-26 Konica Minolta Business Technologies Inc Dye-sensitized photoelectric conversion element, and dye-sensitized solar cell
WO2008146975A1 (en) * 2007-05-25 2008-12-04 Dongjin Semichem Co., Ltd Novel organic dye containing n-arylcarbazole moiety and preparation thereof
KR20090055302A (en) * 2007-11-28 2009-06-02 삼성에스디아이 주식회사 Photosensitizer for photovoltaic cell, and photovoltaic cell including same
TW200936702A (en) * 2008-01-30 2009-09-01 Dongjin Semichem Co Ltd Novel organic sensitizers and method for preparing the same
WO2009109499A1 (en) * 2008-03-07 2009-09-11 Basf Se Dye sensitised solar cell

Also Published As

Publication number Publication date
TWI529221B (en) 2016-04-11
TW201132709A (en) 2011-10-01
CN103525116B (en) 2015-09-09
JP5875988B2 (en) 2016-03-02
JP2013516510A (en) 2013-05-13
CN102695759A (en) 2012-09-26

Similar Documents

Publication Publication Date Title
CN103254658B (en) Thiophene dye and preparation method thereof
US11056287B2 (en) Isodiketopyrrolopyrrole dye and use thereof
Farre et al. Synthesis and properties of new benzothiadiazole-based push-pull dyes for p-type dye sensitized solar cells
CN104073017B (en) Organic dye sensitized dose, preparation method and the application in photoelectric conversion
Marszalek et al. Structural variations of D–π–A dyes influence on the photovoltaic performance of dye-sensitized solar cells
CN105238092A (en) Novel 2,6-site-substituted BODIPY organic dye sensitizer and preparation method therefor
CN102618066A (en) Organic dye containing calixarene derivative and preparation method and application thereof
Tamilavan et al. Synthesis of triphenylamine-based thiophene-(N-aryl) pyrrole-thiophene dyes for dye-sensitized solar cell applications
Guo et al. Structure-property relationship of different electron donors: new organic sensitizers based on bithiazole moiety for high efficiency dye-sensitized solar cells
TWI662085B (en) Photoelectric conversion elements, pigment-sensitized solar cells, metal complex pigments, pigment solutions, and terpyridine compounds or its esters
CN103525116B (en) Organic dye and its preparing process
WO2013008951A1 (en) Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell
JP5498355B2 (en) Organic and inorganic sensitizing dyes
Houarner-Rassin et al. Improved efficiency of a thiophene linked ruthenium polypyridine complex for dry dye-sensitized solar cells
KR20140082569A (en) Novel organic dye and method for preparing thereof
CN104487522B (en) Organic dyestuff for DSSC
Panicker et al. Thiophene-bithiazole based metal-free dye as DSSC sensitizer: Effect of co-adsorbents on photovoltaic efficiency
CN106810898A (en) Organic dye sensitized dose of the triphen amine of pyrroles's dithione modification and its application
KR101109548B1 (en) Novel compounds containing fused-triarylamine, methods of preparing the compounds and dye-sensitized solar cells using dyes comprising the compounds
Xu et al. Synthesis of triarylamine dyes containing secondary electron-donating groups and application in the dye-sensitized solar cells
CN111534125B (en) Triphenyldihydroacridine dye, preparation method thereof and application thereof in dye-sensitized solar cell
KR101882394B1 (en) Novel organic dye and preparation thereof
KR101339707B1 (en) Thieno-Quinoxaline Based Compound, Organic Dye Containing the Same, and Dye-Sensitized Solar Cells Comprising the Organic Dye
KR20110079515A (en) Novel organic dye and preparation thereof
KR20110079512A (en) Novel organic dye and preparation thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150909

Termination date: 20191223