TWI529221B - Novel organic dye and preparation thereof - Google Patents

Description

Novel organic dye and preparation method thereof Field of invention

The invention relates to a dye used in a dye-sensitized solar cell (DSSC) and a preparation method thereof.

Background of the invention

After the development of dye-sensitized nanoparticle titanium oxide solar cells by the research team of Michael Gratzel of the Swiss National Institute of Technology in Lausanne (EPFL) in 1991, much research has been done in this field. Dye-sensitized solar cells are more efficient than existing tantalum solar cells and have significantly lower manufacturing unit prices, which may replace existing amorphous tantalum solar cells. Unlike tantalum solar cells, dye-sensitized solar cells use dye molecules and A photoelectrochemical solar cell having a transition metal as a main structural material, the dye molecule can absorb visible light to form an electron-hole pair, and the transition metal oxide transfers the generated electron.

Although the dye used in the dye-sensitized solar cell is widely used as a base metal complex exhibiting high photoelectric conversion efficiency, the base metal complex has a disadvantage of being too expensive.

Recently, it has been found that an organic dye is used as a dye-sensitized solar cell dye which can replace high-priced ruthenium metal complexes in light absorption efficiency, redox reaction stability, and intramolecular charge-transfer (charge-transfer, CT) shows excellent physical properties and does not contain metals, and research on organic dyes containing no metal is being carried out with emphasis.

The organic dye generally has a structure of an electron donor-electron acceptor residue linked by a π-bonding unit. In most organic dyes, the amine derivative functions as an electron acceptor, and the 2-cyanoacrylic acid or rhodanine residue acts as an electron acceptor, which utilizes a methyne unit or A π-bonding system such as a thiophene chain is linked.

In general, structural changes in the amine unit of the electron donor can alter the electronic properties, such as shifting the absorbance spectrum to the blue side, changing the length of the π-bond, and adjusting the absorbance spectrum and the redox potential ( Redox potential).

However, the actual situation is that most of the organic dyes known to date exhibit low conversion efficiency and low drive stability compared to the ruthenium metal complex dyes, and thus the use of changing such electron donors and acceptor species or π-bonding The length of the method has been developed to develop a novel dye which is higher than the existing organic dye compound and exhibits a high photoelectric conversion efficiency.

Accordingly, it is an object of the present invention to provide an organic dye which exhibits higher molar absorption coefficient and photoelectric conversion efficiency than conventional dyes and which can greatly improve the efficiency of solar cells.

Further, an object of the present invention is to provide a dye up-and-down photoelectric conversion element and a solar cell comprising the aforementioned dye, which exhibits a markedly improved photoelectric conversion efficiency, and J _SC (short-circuit photocurrent density, short) The circuit photocurrent density is excellent with the Mohr absorption coefficient, and the efficiency of the solar cell is remarkably improved.

In order to achieve the above object, the present invention provides an organic dye represented by any one of Chemical Formulas 1 to 4 below.

In the above Chemical Formulas 1-4, the Donor group is one of the following Chemical Formulas D-1 to D-4,

In the above formula, Ar, Ar ₁ , Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-12 aryl group, * is a linking moiety, and A is a system. Or a combination of these; B series Or a combination of these; C series

R ₁ to R ₄ are each independently hydrogen, a C _1-12 alkyl group or a substituted or unsubstituted C _6-21 aryl group; n is an integer of 1 to 5.

Further, the present invention provides the dyeing of any one of Chemical Formulas 1 to 4.

A method for preparing a material, which is a compound represented by the following chemical formula D-5 or formula D-6 and a precursor compound of A, B, A and B or B and A as defined in the above chemical formulas 1 to 4. It is prepared by sequentially bonding C to the terminal of the compound obtained by the reaction.

In the foregoing, the donor group is as defined above.

Further, the present invention provides a dye-increasing/decreasing photoelectric conversion element characterized by comprising oxide semiconductor fine particles loaded with a compound represented by any one of the above Chemical Formulas 1 to 4.

Further, the present invention provides a dye-sensitized solar cell characterized by comprising the aforementioned dye up-and-down photoelectric conversion element.

The dye compound of the present invention is used in a dye-sensitized solar cell (DSSC), exhibits higher molar absorption coefficient than conventional dyes, J _SC (short-circuit photocurrent density), and photoelectric conversion efficiency, and can greatly improve the efficiency of solar cells even if It can also be refined without using expensive columns, which can reduce the unit price of dye synthesis as never before.

Form for implementing the invention

The present inventors used a specific aliphatic compound as an electron donor, and in order to increase the molar absorption coefficient and increase the stability of the element, a thiophene-based or dihydrothiophene-based unit was introduced at an intermediate linking portion (spacer), in two The spacers present in a single direction and the anchoring group are introduced in the direction, and the compound represented by any one of Chemical Formulas 1 to 4 having a novel organic dye structure is supported on the oxide semiconductor. Microparticles, in the case of dye-sensitized solar cells, photoelectric conversion efficiency, J _SC (short-circuit photocurrent density), and high molar absorption coefficient, showing superior efficiency to conventional dye-sensitized solar cells, confirming the above facts, and completing this invention.

The organic dye of the present invention is characterized by being represented by any one of Chemical Formulas 1 to 4 below.

In the above Chemical Formula 1-4, the donor group, Ar, Ar ₁ , Ar ₂ , Ar ₃ , A, B, C, R ₁ to R ₄ , and n are as defined above.

The dye compound of Chemical Formula 1 of the present invention is suitably represented by any one of the following structural formulae:

Further, the present invention can produce the dye of any one of Chemical Formulas 1 to 4 which is a compound represented by the following Chemical Formula D-5 or Chemical Formula D-6 and A defined in the above Chemical Formulas 1 to 4. , B, A and B or B and A and A precursor compound are sequentially reacted to obtain a terminal bond C of the compound.

Among the above, the donor group is as defined above.

Specifically, the compound of the present invention can be produced, for example, by the following steps: (1) The Suzuki coupling reaction of the compound of the following chemical formula 5-1 with the compound of the following chemical formula 6 is carried out to prepare the following chemical formula 7-1: Compound (2) The compound of Chemical Formula 7-1 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Formula 1.

[Reaction formula 1]

In the above formula, B is as defined above.

Further, the compound of the present invention can be produced, for example, by the following steps: (1) The compound of the chemical formula 5-1 described below is subjected to a Suzuki coupling reaction with a compound of the following Chemical Formula 8 to prepare a compound of the following Chemical Formula 9-1; (2) reacting a compound of the formula 9-1 with trifluoroacetic acid in tetrahydrofuran (THF) to prepare a compound of the following chemical formula 10-1, (3) formulating the chemical formula 10-1 in the presence of piperidine in CH ₃ CN The compound is reacted with cyanoacetic acid. A specific example thereof can be shown in the following Reaction Formula 2.

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) Suppressing a compound of the following chemical formula 5-1 with a compound of the following chemical formula 11 to prepare a compound of the following chemical formula 12-1, 2) reacting a compound of Chemical Formula 12-1 with N-bromosuccinimide to prepare a compound of the following Chemical Formula 13-1, (3) a compound of Chemical Formula 13-1 and a compound of Chemical Formula 6 below The Suzuki coupling reaction occurs to prepare a compound of the following Chemical Formula 14-1, and (4) the compound of Chemical Formula 14-1 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Formula 3.

[Chemical Formula 11]

(HO) ₂ BA

In the above formula, A and B are as defined above.

The compound of the chemical formula 4 of the present invention can be produced, for example, by the following steps: (1) a compound of the following chemical formula 15-1 and a compound of the following chemical formula 16 in potassium tetrahydrofuran (pottasium tert-butoxide) a reaction occurs in the presence of a compound of the following chemical formula 17, (2) a compound of the formula 17-1 is reacted with N-bromosuccinimide to prepare a compound of the following formula 18, (3) The compound of Chemical Formula 18-1 is subjected to Suzuki coupling reaction with a compound of Chemical Formula 6 below to prepare a compound of the following Chemical Formula 19-1, and (4) a compound of Chemical Formula 19-1 and Cyanide are present in the presence of piperidine in CH ₃ CN. Acetic acid reaction. A specific example thereof can be shown in the following Reaction Formula 4.

[Chemical Formula 16]

OHC-A

In the above formula, A and B are as defined above.

Further, the compound of the present invention can be produced, for example, by the following steps: (1) The compound of the chemical formula 5-2 described below is subjected to a Suzuki coupling reaction with a compound of the following chemical formula 6 to prepare a compound of the following chemical formula 7-2; (2) The compound of the formula 7-2 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Formula 5.

In the above formula, A and B are as defined above.

Further, the compound of the present invention can be produced, for example, by the following steps: (1) The compound of the following chemical formula 5-2 is reacted with the compound of the following chemical formula 8 to prepare a compound of the following chemical formula 9-2; (2) reacting a compound of the formula 9-2 with trifluoroacetic acid in tetrahydrofuran to prepare a compound of the following chemical formula 10-2, (3) a compound of the formula 10-2 in the presence of piperidine in CH ₃ CN and Cyanoacetic acid reaction. A specific example thereof can be shown in the following Reaction Formula 6.

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) Suppressing a compound of the following Chemical Formula 5-2 with a compound of the following Chemical Formula 11 to prepare a compound of the following Chemical Formula 12-1, 2) reacting a compound of Chemical Formula 12-2 with N-bromosuccinimide to prepare a compound of the following Chemical Formula 13-2, (3) a compound of Chemical Formula 13-2 and a compound of Chemical Formula 6 below The Suzuki coupling reaction occurs to prepare a compound of the following chemical formula 14-2, and (4) the compound of the chemical formula 14-2 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Scheme 7.

[Chemical Formula 11]

(HO) ₂ BA

In the above formula, A and B are as defined above.

The compound of Chemical Formula 4 of the present invention can be produced, for example, by the following steps: (1) reacting a compound of the following Chemical Formula 15-2 with a compound of the following Chemical Formula 16 in the presence of potassium t-butylate in tetrahydrofuran, The following compound of the formula 17-2 is prepared, (2) the compound of the formula 17-2 is reacted with N-bromosuccinimide to prepare a compound of the following formula 18-2, (3) the formula 18 The compound of -2 is subjected to a Suzuki coupling reaction with a compound of the following chemical formula 6 to prepare a compound of the following chemical formula 19-2, and (4) a compound of the formula 19-2 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. . A specific example thereof can be shown in the following Reaction Scheme 8.

[Chemical Formula 16]

OHC-A

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) subjecting a compound of the following Chemical Formula 5-3 to a Suzuki coupling reaction of a compound of the following Chemical Formula 6 to prepare a compound of the following Chemical Formula 7-3, 2) The compound of the formula 7-3 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Scheme 9.

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) subjecting a compound of the following Chemical Formula 5-3 to a Suzuki coupling reaction of a compound of the following Chemical Formula 8 to prepare a compound of the following Chemical Formula 9-3, 2) reacting a compound of the formula 9-3 with trifluoroacetic acid in tetrahydrofuran to prepare a compound of the following chemical formula 10-3, (3) a compound of the formula 10-3 and a cyanoacetic acid in the presence of piperidine in CH ₃ CN reaction. A specific example thereof can be shown in the following Reaction Formula 10.

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) subjecting a compound of the following Chemical Formula 5-3 to a Suzuki coupling reaction of a compound of the following Chemical Formula 11 to prepare a compound of the following Chemical Formula 12-3, 2) reacting a compound of the formula 12-3 with N-bromosuccinimide to prepare a compound of the following formula 13-3, (3) a compound of the formula 13-3 and a compound of the following chemical formula 6 The Suzuki coupling reaction occurs to prepare a compound of the following chemical formula 14-3, and (4) the compound of the chemical formula 14-3 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Formula 11.

[Chemical Formula 11]

(HO) ₂ BA

In the above formula, A and B are as defined above.

The compound of Chemical Formula 4 of the present invention can be produced, for example, by the following steps: (1) reacting a compound of the following Chemical Formula 15-3 with a compound of the following Chemical Formula 16 in the presence of potassium t-butylate in tetrahydrofuran, The following compound of the formula 17-3 is prepared, (2) the compound of the formula 17-3 is reacted with N-bromosuccinimide to prepare a compound of the following formula 18-3, (3) the formula 18 The compound of -3 is subjected to a Suzuki coupling reaction with a compound of the following chemical formula 6 to prepare a compound of the following chemical formula 19-3, and (4) a compound of the formula 19-3 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. . A specific example thereof can be shown in the following Reaction Formula 12.

[Chemical Formula 16]

OHC-A

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) subjecting a compound of the following Chemical Formula 5-4 to a Suzuki coupling reaction of a compound of the following Chemical Formula 6 to prepare a compound of the following Chemical Formula 7-4, 2) The compound of the formula 7-4 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Formula 13.

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) subjecting a compound of the following Chemical Formula 5-4 to a Suzuki coupling reaction with a compound of the following Chemical Formula 8 to prepare a compound of the following Chemical Formula 9-4, 2) reacting a compound of the formula 9-4 with trifluoroacetic acid in tetrahydrofuran to prepare a compound of the following chemical formula 10-4, (3) a compound of the formula 10-4 and a cyanoacetic acid in the presence of piperidine in CH ₃ CN reaction. A specific example thereof can be shown in the following Reaction Formula 14.

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) Suppressing a compound of the following Chemical Formula 5-4 with a compound of the following Chemical Formula 11 to prepare a compound of the following Chemical Formula 12-4, 2) reacting a compound of the formula 12-4 with N-bromosuccinimide to prepare a compound of the following chemical formula 13-4, (3) a compound of the formula 13-4 and a compound of the following chemical formula 6; The Suzuki coupling reaction occurs to prepare a compound of the following Chemical Formula 14-4, and (4) the compound of Chemical Formula 14-4 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Formula 15.

[Chemical Formula 11]

(HO) ₂ BA

In the above formula, A and B are as defined above.

The compound of the present invention can be produced, for example, by the following steps: (1) reacting a compound of the following Chemical Formula 15-4 with a compound of the following Chemical Formula 16 in the presence of potassium t-butylate in tetrahydrofuran to prepare the following a compound of the formula 17-4, (2) reacting a compound of the formula 17-4 with N-bromosuccinimide to prepare a compound of the following formula 18-4, (3) a chemical formula 18-4 The compound is subjected to a Suzuki coupling reaction with a compound of Chemical Formula 6 below to prepare a compound of the following Chemical Formula 19-4, and (4) a compound of Chemical Formula 19-4 is reacted with cyanoacetic acid in the presence of piperidine in CH ₃ CN. A specific example thereof can be shown in the following Reaction Formula 16.

[Chemical Formula 16]

OHC-A

In the above formula, A and B are as defined above.

Further, the present invention provides a dye-increasing/decreasing photoelectric conversion element characterized in that the dye-increasing/decreasing photoelectric conversion element is loaded with a dye represented by any one of the above Chemical Formulas 1 to 4 in oxide semiconductor fine particles. In addition to the dyes shown in any one of the above Chemical Formulas 1 to 4, the dye-added or subtracted photoelectric conversion element of the present invention may of course be applied to a method for preparing a dye-adding or subtracting photoelectric conversion element for a solar cell by using a conventional dye. According to the method described in Korean Patent Publication No. 10-2009-38377 (Applicant: Dong Jin Semichem Co., Ltd.), it is suitable that the dye addition and subtraction photoelectric conversion element of the present invention utilizes an oxide. The semiconductor fine particles are used to prepare a thin film of an oxide semiconductor on a substrate, and it is preferred that the dye of the present invention is loaded on the film.

Hereinafter, the present invention will be specifically described based on examples. However, the embodiments are merely illustrative of the inventors, and the invention is not limited thereto.

Example 1 1-1) Synthesis of intermediate (1a)

Mixing 2,7-dibromo-9-phenyl acridine with (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid, Pd in dimethylformamide (DMF) After (PPh ₃ ) ₄ and 2M K ₂ CO ₃ aqueous solution, the mixture was refluxed for 12 hours. As a result, the obtained reaction solution was cooled, and after adding water (30 ml) and brine, the organic layer was separated and purified to obtain an intermediate having the following chemical structural formula.

[Intermediate 1a]

1-2) Synthesis of Compound 1

The intermediate (1a) prepared in the foregoing Example 1-1) was mixed with cyanoacetic acid to prepare a mixture, and the mixture was vacuum dried, and then mixed with MeCN and piperidine, and refluxed for 6 hours. As a result, after the obtained reaction solution was cooled, the organic layer was removed under vacuum. As a result, the obtained solid matter was purified by silica gel chromatography to give the following compound 1. As a result of performing a field desorption mass spectrum on the obtained compound, it was confirmed that C ₃₅ H ₁₉ N ₃ O ₄ S ₂ = 610, m/z (measured value) = 610.

Example 2:

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 1, (E)-(5-oxythieno[3,2-b]thiophene- The same procedure as in Example 1 was carried out in the order of 2 (5H)-yield)methylboronic acid to give the compound 2 below. As a result of performing field desorption mass spectrometry on the above compound, it was confirmed that C ₃₉ H ₁₉ N ₃ O ₄ S ₄ = 722, m/z (measured value) = 721.

Example 3:

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 1, (E)-(7-oxy-2,3-dihydrothieno[3] was used. The following compound 3 was obtained in the same manner as in Example 1 except that 4-b][1,4]dioxin-5(7H)-ylidene)methylboronic acid was obtained. As a result of performing field desorption mass spectrometry on the above compound, it was confirmed that C ₃₉ H ₂₃ N ₃ O ₈ S ₂ = 726, m/z (measured value) = 725.

Example 4

Mixing 3,6-dibromo-N,N-bis(4-methoxyphenyl)-10-phenylindole-9-amine with (E)-(5-oxyl) in dimethylformamide After thiophene-2(5H)-ylidene)methylboronic acid, Pd(PPh ₃ ) ₄ and 2M K ₂ CO ₃ aqueous solution, the mixture was refluxed for 12 hours. As a result, the obtained reaction solution was cooled, and after adding water (30 ml) and brine, the organic layer was separated and purified to obtain an intermediate.

The intermediate prepared above was mixed with cyanoacetic acid to prepare a mixture, and the resulting mixture was vacuum dried, mixed with MeCN and piperidine, and refluxed for 6 hours. As a result, after the obtained reaction solution was cooled, the organic layer was removed under vacuum. As a result, the obtained solid matter was purified by silica gel chromatography to give the following compound 4. The results of field desorption mass spectrometry of the obtained Compound 4 were confirmed to be C ₅₀ H ₃₃ N ₃ O ₆ S ₂ = 836, m/z (measured value) = 835.

Example 5:

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 4, (E)-(5-oxythieno[3,2-b]thiophene- The same procedure as in Example 4 was carried out in the order of 2 (5H)-yield)methylboronic acid to give the compound 5 below. As a result of performing field desorption mass spectrometry on the above compound 5, it was confirmed that C ₅₄ H ₃₃ N ₃ O ₆ S ₄ = 948, m/z (measured value) = 947.

Example 6

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 4, (E)-(7-oxy-2,3-dihydrothieno[3] was used. The following compound 6 was obtained in the same manner as in Example 4 except that 4-b][1,4]dioxin-5(7H)-ylidene)methylboronic acid was obtained. The results of field desorption mass spectrometry of the above compound were confirmed to be C ₅₄ H ₃₇ N ₃ O ₁₀ S ₂ = 952, m/z (measured value) = 951.

Example 7

Mixing 3,6-dibromo-9-(4-methoxyphenyl)-9H-carbazole with (E)-(5-oxythiophene-2(5H)- sub in dimethylformamide After a solution of methylboronic acid, Pd(PPh ₃ ) ₄ and 2M K ₂ CO ₃ , the mixture was refluxed for 12 hours. As a result, the obtained reaction solution was cooled, and after adding water (30 ml) and brine, the organic layer was separated and purified to obtain an intermediate.

The intermediate prepared above was mixed with cyanoacetic acid, and the resulting mixture was vacuum dried, mixed with MeCN and piperidine, and refluxed for 6 hours. As a result, after the obtained reaction solution was cooled, the organic layer was removed under vacuum. As a result, the obtained solid matter was purified by silica gel chromatography to give the following compound 7. As a result of performing field desorption mass spectrometry on the obtained compound 7, it was confirmed that C ₃₅ H ₂₁ N ₃ O ₅ S ₂ = 628, m/z (measured value) = 627.

Example 8

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 7, (E)-(5-oxythieno[3,2-b]thiophene- The same procedure as in Example 7 was carried out in the order of 2 (5H)-yield)methylboronic acid to give the compound 8 below. The result of performing field desorption mass spectrometry on the above-mentioned compound 8 was confirmed to be C ₃₉ H ₂₁ N ₃ O ₅ S ₄ = 740, m/z (measured value) = 739.

Example 9

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 7, (E)-(7-oxy-2,3-dihydrothieno[3] The following compound 9 was obtained in the same manner as in Example 7 except that 4-b][1,4]dioxin-5(7H)-ylidene)methylboronic acid was obtained. As a result of performing field desorption mass spectrometry on the above compound, it was confirmed that C ₃₉ H ₂₅ N ₃ O ₉ S ₂ = 744, m/z (measured value) = 743.

Example 10

Mixing 3,7-dibromo-10-(4-methoxyphenyl)-10H-phenothiazine with (E)-(5-oxythiophene-2(5H)- in dimethylformamide After the subunit) methylboronic acid, Pd(PPh ₃ ) ₄ and 2M K ₂ CO ₃ aqueous solution, the mixture was refluxed for 12 hours. As a result, the obtained reaction solution was cooled, and after adding water (30 ml) and brine, the organic layer was separated and purified to obtain an intermediate.

The intermediate prepared above was mixed with cyanoacetic acid, and the resulting mixture was vacuum dried, mixed with MeCN and piperidine, and refluxed for 6 hours. As a result, after the obtained reaction solution was cooled, the organic layer was removed under vacuum. As a result, the obtained solid matter was purified by silica gel chromatography to give the following compound 10. As a result of performing field desorption mass spectrometry on the obtained compound 10, it was confirmed that C ₃₅ H ₂₁ N ₃ O ₅ S ₃ = 660, m/z (measured value) = 659.

Example 11

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 10, (E)-(5-oxythieno[3,2-b]thiophene- The same procedure as in Example 10 was carried out in the order of 2 (5H)-yield)methylboronic acid to give the compound 2 below. As a result of performing field desorption mass spectrometry on the above compound 11, it was confirmed that C ₃₉ H ₂₁ N ₃ O ₅ S ₅ = 772, m/z (measured value) = 771.

Example 12

Instead of (E)-(5-oxythiophene-2(5H)-ylidene)methylboronic acid in the foregoing Example 10, (E)-(7-oxy-2,3-dihydrothieno[3] was used. In the same manner as in Example 10 except that 4-b][1,4]dioxin-5(7H)-ylidene)methylboronic acid was obtained, the following compound 12 was obtained. As a result of performing field desorption mass spectrometry on the above compound, it was confirmed that C ₃₉ H ₂₅ N ₃ O ₉ S ₃ = 776, m/z (measured value) = 775.

Preparation of dye-sensitized solar cells

To evaluate the current-voltage characteristics of the dye of the present invention, a dye-sensitized solar cell was prepared using a 13+10 μm TiO ₂ transparent layer.

Specifically, the washed FTO (Pilkington, 8 Ωsq-1) glass substrate was immersed in a 40 mM TiCl ₄ aqueous solution. A TiO ₂ paste (Solaronix, 13 nm anatase) was screen-printed to prepare a 13 μm thick first TiO ₂ layer, and a 10 μm thick second TiO ₂ scattering was prepared for other light paste (CCIC, HWP-400) for light scattering. Floor. A solution prepared by immersing the prepared TiO ₂ electrode in the dye of the present invention (dissolving 0.3 mM of the compound prepared in the foregoing Examples 1-12 in 10 mM ethanol containing 3a, 7a-dihydroxy-5b-cholic acid, respectively) After 1-12), it was allowed to stand at room temperature for 18 hours. A pair of electrodes was prepared by coating a F ₂ substrate with a H ₂ PtCl ₆ solution (containing 2 mg of Pt in 1 mL of ethanol). Next, 0.6 M of 3-hexyl-1,2-dimethylimidazolium iodide, 0.04 M of I ₂ , 0.025 M of LiI, 0.05 M of guanidium thiocyanate, and 0.28 M were dissolved in acetonitrile. The tert-butylpyridine forms an electrolyte, and the electrolyte is injected into a battery to prepare a dye-sensitized solar cell. The photocell performance of the dye-sensitized solar cell was measured by a 1000 W xenon light source, and the results are shown in Table 1 below.

As shown in the above Table 1, the novel dye of the present invention exhibited excellent photoelectric conversion efficiency. Therefore, the novel dye compound of the present invention can greatly improve the efficiency of the solar cell, and can be purified without using a high-priced column, thereby reducing the unit price of the dye synthesis as never before.

Claims (5)

An organic dye represented by any one of Chemical Formulas 1 to 4 below: In the above Chemical Formulas 1-4, the Donor group is one of the following Chemical Formulas D-1 to D-4, In the above formula, Ar, Ar ₁ , Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-12 aryl group, * is a linking moiety, X is sulfur, and A is a system. or Or a combination of these; B series or Or a combination of these; C Series R ₁ to R ₄ are each independently hydrogen, a C _1-12 alkyl group or a substituted or unsubstituted C _6-21 aryl group; n is an integer of 1 to 5. The organic dye according to claim 1, wherein the dye is any one of the following structural formulas, wherein R is hydrogen, C _1-12 alkyl or substituted or unsubstituted C _6-21 The aryl group: A method for producing an organic dye as shown in any one of Chemical Formulas 1 to 4 of Claim No. 1, which is a compound represented by the following Chemical Formula D-5 or Chemical Formula D-6 and a patent application scope Prepared by the terminal bond C of the compound obtained by sequentially reacting A, B, A and B or B as defined in the first item with the precursor compound of A: [Chemical Formula D-5] In the foregoing, the donor group is as defined in the first item of the patent application. A dye addition-reduction photoelectric conversion element characterized by comprising oxide semiconductor fine particles loaded with an organic dye of claim 1 of the patent application. A dye-sensitized solar cell characterized by comprising the dye addition and subtraction photoelectric conversion element of claim 4 of the patent application.