KR101179696B1 - Novel compounds containing thienothiophene-vinylene-thienothiophene, methods of preparing the compounds and dye-sensitized solar cells using dyes comprising the compounds - Google Patents

Abstract

The present invention discloses a compound of formula (I) which is a compound containing thienothiophene-vinylene-thienothiophene and a process for preparing the same. A dye containing the compound containing thienothiophene-vinylene-thienothiophene can be adsorbed to the metal oxide layer to form a dye-sensitized solar cell having excellent performance.

≪ Formula 1 >

Here, D is an electron doner group, A is an electron acceptor group, and R ₁ to R ₄ are hydrogen (H) selected from the group consisting of alkyl having 1 to 10 carbon atoms. One

Description

Novel compounds containing thienothiophene-vinylene-thienothiophene, methods of preparing the compounds and dye-sensitized Novel compounds containing thienothiophene-vinylene-thienothiophene, methods for preparing the same, and dye-sensitized solar cells using the same solar cells using dyes comprising the compounds}

The present invention relates to a novel thienothiophene-vinylene-thienothiophene-containing compound and a dye-sensitized solar cell using the same as a dye.

Dye-sensitized solar cells, unlike silicon solar cells, are photoelectrochemical solar cells composed of photosensitive dye molecules and transition metal oxides. In detail, the photosensitive dye molecule absorbs visible light to generate an electron-hole pair, and the generated electrons are transferred to the substrate by the transition metal oxide to have photoelectrochemical properties.

Representative examples of dye-sensitized solar cells known to date are dye-sensitized solar cells published by Gratzel et al. (S. Patent No. 4,927,721 and No. 5,350,644). In general, dye-sensitized solar cells made by Gratzel et al. Are composed of a semiconductor electrode composed of nanoparticle titanium dioxide (TiO ₂ ) coated with dye molecules, a platinum electrode, and an electrolyte solution filled therebetween. Such dye-sensitized solar cells have been attracting attention because they are useful as solar cells because the manufacturing cost per power is lower than that of silicon solar cells. The dyes used in dye-sensitized solar cells are divided into two categories. One is an organometallic dye and the other is an organic dye.

<Example of Organic Metal Dye>

Organometallic dyes are known as Ru (dcb) (bpy) ₂ ²⁺ linking Ru (II) -polypyridyl compounds as the main dyes (see US Pat. No. 5,350,644). In addition, there are dyes including various ligands including nitrogen in transition metals such as Ru, Os, Cu, and Zn (US Pat. No. 6,350,946, US Pat. -294306). Among the dyes, compounds of the above formula (red light red color and dark blue color) as Ru based dyes of nanoparticle dye-sensitized solar cells (trade names: 'N719', 'N3', etc.) are most widely used as organometallic dyes.

Organic dyes show high light absorption efficiency in the visible light range, and are increasingly attracting attention because of their low cost synthesis compared to organometallic dyes. However, organic dyes have a short duration in the excited state, agglomeration of the dye occurs, there is a problem that the efficiency is not excellent. Therefore, the need for a novel organic dye which is prevented from agglomeration and has excellent efficiency is increasing.

The technical problem to be solved by the present invention is to provide a compound containing a novel thienothiophene-vinylene-thienothiophene.

Another technical problem to be solved by the present invention is to provide a method for preparing a compound containing a novel thienothiophene-vinylene-thienothiophene.

Another technical problem to be solved by the present invention is to provide a dye-sensitized solar cell having excellent efficiency by using a dye containing the novel compound.

In order to solve the above technical problem, the compound containing thienothiophene-vinylene-thienothiophene (thienothiophene-vinylene-thienothiophene) according to the present invention is a compound of formula (1).

&Lt; Formula 1 >

D in Chemical Formula 1 is an electron doner group, A in Chemical Formula 1 is an electron acceptor group, and R ₁ to R ₄ in Chemical Formula 1 are hydrogen (H), having 1 to 10 carbon atoms. It is any one selected from the group consisting of alkyl.

In a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, R ₁ to R ₄ of Formula 1 may be hexyl, and A of Formula 1 may be represented by Formula 2 below: Can be.

<Formula 2>

In the compound containing thienothiophene-vinylene-thienothiophene according to the present invention, D in Chemical Formula 1 may be any one selected from the group consisting of the following Chemical Formulas 3 to 7.

<Formula 3>

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

<Formula 7>

R ₉ of Chemical Formula 4 and R ₁₃ of Chemical Formula 6 are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms, X ₁ of Chemical Formula 3 and X ₂ of Chemical Formula 5 are the following Chemical Formulas 8 to Chemical Formulas 11 is any one selected from the group consisting of.

(8)

<Formula 9>

<Formula 10>

<Formula 11>

R ₁₅ of Formula 11 is any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, R ₅ and R ₆ of Formula 3, R ₇ and R ₈ of Formula 4, R ₁₀ of Formula 5 And R ₁₁ , R ₁₂ of Chemical Formula 6 and R ₁₄ of Chemical Formula 7 are any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and the following Chemical Formulas 12 to 19: .

<Formula 12>

<Formula 13>

<Formula 14>

&Lt; Formula 15 >

<Formula 16>

<Formula 17>

&Lt; Formula 18 >

(19)

R ₁₆ of Formula 12, R ₁₇ of Formula 13, R ₁₈ of Formula 14, R _{19 of} Formula 15, and R ₂₀ and R ₂₁ of Formula 18 are hydrogen, a group having 1 to 10 carbon atoms Any one selected from.

In the compound containing thienothiophene-vinylene-thienothiophene according to the present invention, the compound of Formula 1 may be at least one of a compound of Formula 20 and a compound of Formula 21.

<Formula 20>

&Lt; Formula 21 >

In order to solve the above other technical problem, the preparation method of the compound containing thienothiophene-vinylene-thienothiophene (thienothiophene-vinylene-thienothiophene) according to the present invention is a compound of formula 22 and a compound of formula 23 To react to form a compound of formula 24 comprises the step of forming a compound of formula (24).

&Lt; Formula 1 >

<Formula 22>

&Lt; Formula 23 >

&Lt; EMI ID =

D in Chemical Formulas 1, 22, and 24 is an electron donor group, A in Chemical Formula 1 is an electron acceptor group, and R ₁ to Chemical Formula 1, Chemical Formula 23, and Chemical Formula 24 may be used. R ₄ is any one selected from the group consisting of hydrogen (H) and alkyl having 1 to 10 carbon atoms.

In the method for preparing a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, the compound of Formula 23 is, by adding a compound of Formula 25 to the THF solution containing TiCl ₄ and Zn Forming a compound of Formula 26; And reacting a compound represented by Chemical Formula 26 with a compound represented by Chemical Formula 27 (pinacol borate) to form the compound represented by Chemical Formula 23.

&Lt; Formula 25 >

<Formula 26>

&Lt; Formula 27 >

R ₂₂ and R ₂₃ of Formula 25 and R ₁ to R ₄ of Formula 26 are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

In the method for preparing a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, D in Chemical Formula 1, Chemical Formula 22 and Chemical Formula 24 may be any one selected from the group consisting of Chemical Formulas 3 to 7. Can be.

<Formula 3>

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

<Formula 7>

R ₉ of Chemical Formula 4 and R ₁₃ of Chemical Formula 6 are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms, X ₁ of Chemical Formula 3 and X ₂ of Chemical Formula 5 are the following Chemical Formulas 8 to Chemical Formulas 11 is any one selected from the group consisting of.

(8)

<Formula 9>

<Formula 10>

<Formula 11>

R ₁₅ of Formula 11 is any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, R ₅ and R ₆ of Formula 3, R ₇ and R ₈ of Formula 4, R ₁₀ of Formula 5 And R ₁₁ , R ₁₂ of Chemical Formula 6 and R ₁₄ of Chemical Formula 7 are any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and the following Chemical Formulas 12 to 19: .

<Formula 12>

<Formula 13>

<Formula 14>

&Lt; Formula 15 >

<Formula 16>

<Formula 17>

&Lt; Formula 18 >

(19)

R ₁₆ of Formula 12, R ₁₇ of Formula 13, R ₁₈ of Formula 14, R ₁₉ of Formula 15, and R ₂₀ and R ₂₁ of Formula 18 are each selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms It is either chosen.

In the method for preparing a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, A in Chemical Formula 1 may be the following Chemical Formula 2.

<Formula 2>

In the method for preparing a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, the compound of formula 22 is a compound of formula 28, the compound of formula 23 is a compound of formula 29, The compound of Formula 1 may be a compound of Formula 20.

<Formula 20>

(28)

<Formula 29>

In the method for preparing a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, the compound of Formula 22 is a compound of Formula 30, the compound of Formula 23 is a compound of Formula 29, The compound of Formula 1 may be a compound of Formula 21.

&Lt; Formula 21 >

<Formula 29>

<Formula 30>

In order to solve the above another technical problem, the dye-sensitized solar cell according to the present invention comprises a conductive substrate;

A semiconductor electrode formed on the conductive substrate and including a metal oxide layer adsorbed with a dye including the compound of Formula 1; Counter electrode; And an electrolyte filling between the semiconductor electrode and the counter electrode.

&Lt; Formula 1 >

D in Chemical Formula 1 is an electron doner group, A in Chemical Formula 1 is an electron acceptor group, and R ₁ to R ₄ in Chemical Formula 1 are hydrogen (H), having 1 to 10 carbon atoms. It is any one selected from the group consisting of alkyl.

In the dye-sensitized solar cell according to the present invention, R ₁ to R ₄ of Formula 1 may be hexyl, and A of Formula 1 may be Formula 2 below.

<Formula 2>

In the dye-sensitized solar cell according to the present invention, D of Chemical Formula 1 may be any one selected from the group consisting of Chemical Formulas 3 to 7.

<Formula 3>

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

<Formula 7>

R ₉ of Chemical Formula 4 and R ₁₃ of Chemical Formula 6 are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms, X ₁ of Chemical Formula 3 and X ₂ of Chemical Formula 5 are the following Chemical Formulas 8 to Chemical Formulas 11 is any one selected from the group consisting of.

(8)

<Formula 9>

<Formula 10>

<Formula 11>

R ₁₅ of Formula 11 is any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, R ₅ and R ₆ of Formula 3, R ₇ and R ₈ of Formula 4, R ₁₀ of Formula 5 And R ₁₁ , R ₁₂ of Chemical Formula 6 and R ₁₄ of Chemical Formula 7 are any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and the following Chemical Formulas 12 to 19: .

<Formula 12>

<Formula 13>

<Formula 14>

&Lt; Formula 15 >

<Formula 16>

<Formula 17>

&Lt; Formula 18 >

(19)

R ₁₆ of Formula 12, R ₁₇ of Formula 13, R ₁₈ of Formula 14, R ₁₉ of Formula 15, and R ₂₀ and R ₂₁ of Formula 18 are each selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms It is either chosen.

In the dye-sensitized solar cell according to the present invention, the compound of Formula 1 may be at least one of the compound of Formula 20 and the compound of Formula 21.

<Formula 20>

&Lt; Formula 21 >

In the dye-sensitized solar cell according to the present invention, an additive (coadsorbent) may be further adsorbed to the metal oxide layer, and the additive may be tetrabutylammonium chenodeoxycholic acid salt (DCA) TBA. The electrolyte may be a solid-state electrolyte, and the solid-state electrolyte is Spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N, N-dimethoxyphenylamine) -9,9'-spiro bifluorene).

The present invention provides a novel thienothiophene-vinylene-thienothiophene compound used as a raw material for dyes and a method for producing the same. The present invention also provides a dye-sensitized solar cell in which a compound containing the novel thienothiophene-vinylene-thienothiophene is used as a dye. The novel thienothiophene-vinylene-thienothiophene-containing compound can use a thin TiO ₂ layer with a high molar extinction coefficient, thereby significantly increasing the photoelectric conversion efficiency to about 9.5%. In addition, since the entire molecule is close to the planar structure, it is possible to absorb long wavelengths, and the introduction of hexyl groups prevents aggregation between molecules and increases thermal and optical stability. In addition, even in the case of using a solid electrolyte, the photoelectric conversion efficiency is about 4.8%.

The present invention relates to a compound containing thienothiophene-vinylene-thienothiophene comprising the compound of formula (1).

&Lt; Formula 1 >

Here, D is an electron doner group, A is an electron acceptor group, and R ₁ to R ₄ are hydrogen (H) selected from the group consisting of alkyl having 1 to 10 carbon atoms. One.

R ₁ to R ₄ of Formula 1 may be hexyl, and A of Formula 1 may be Formula 2.

<Formula 2>

And D of Formula 1 may be any one selected from the group consisting of Formula 3 to Formula 7.

<Formula 3>

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

<Formula 7>

Here, R ₉ and R ₁₃ is any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, X ₁ and X ₂ is any one selected from the group consisting of Formula 8 to Formula 11. And R ₅ , R ₆ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₄ are hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and as represented by Formula 12 to Formula 19. It is any one selected from the group consisting of.

(8)

<Formula 9>

<Formula 10>

<Formula 11>

Here, R ₁₅ is any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms.

<Formula 12>

<Formula 13>

<Formula 14>

&Lt; Formula 15 >

<Formula 16>

<Formula 17>

&Lt; Formula 18 >

(19)

Here, R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ , R ₂₁ are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

Preferred thienothiophene-vinylene-thienothiophene compounds according to the invention are the compounds of formula (20) and compounds of formula (21).

<Formula 20>

&Lt; Formula 21 >

Here, the compound of formula 20 is named JK-112, and the compound of formula 21 is named JK-113.

Compounds containing thienothiophene-vinylene-thienothiophene can use a thin TiO ₂ layer with a high molar extinction coefficient, thereby significantly increasing the photoelectric conversion efficiency. In addition, the compound containing thienothiophene-vinylene-thienothiophene has a planar structure of the entire molecule by a double bond structure formed between two thienothiophenes, so that conjugation is well achieved. For this reason, compared with the compound which two thienothiophene couple | bonded with a single bond, it absorbs long wavelength light well. As the hexyl group is introduced, aggregation between molecules is prevented and thermal and optical stability are increased.

Such thienothiophene-vinylene-thienothiophene-containing compounds are suitable for use as dyes in dye-sensitized solar cells, and the J _sc value is significantly increased compared to compounds formed by combining two thienothiophenes in a single bond. The efficiency is excellent. The compound containing thienothiophene-vinylene-thienothiophene also exhibits excellent photoelectric conversion efficiency even when a solid electrolyte is used.

The present invention also includes a method for producing a compound containing thienothiophene-vinylene-thienothiophene represented by the formula (1). Compound 1 is prepared by reacting a compound of Formula 22 with a compound of Formula 23 to form a compound of Formula 24.

<Formula 22>

&Lt; Formula 23 >

&Lt; EMI ID =

D is an electron donor group, and R ₁ to R ₄ are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

Reaction of the compound of Formula 22 with the compound of Formula 23 to form the compound of Formula 24 is shown in Scheme 1.

<Reaction Scheme 1>

D is an electron donor group, and R ₁ to R ₄ are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

Reaction of Scheme 1 may be performed by adding Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium) and potassium carbonate (K ₂ CO ₃ ) together. The reaction of Scheme 1 can be carried out in tetrahydrofuran (TFH).

The compound of Formula 23 used to form the compound of Formula 24 may be prepared through the following Scheme 2 to Scheme 4 step.

In order to prepare the compound of Formula 23, first, as shown in Scheme 2, the compound of Formula 31 is sequentially reacted with n-BuLi (n-butyllithium) and DMF (dimethylformamie) to form the compound of Formula 25. The reaction of Scheme 2 can be carried out in THF.

<Reaction Scheme 2>

Here, R ₂₂ and R ₂₃ is any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms.

As shown in Scheme 3, the compound of Formula 25 may be added to a THF solution containing TiCl ₄ and Zn to form a compound of Formula 26.

<Reaction Scheme 3>

Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₂₂ and R ₂₃ are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

Next, as shown in Scheme 4, the compound of Formula 26 is reacted with the compound of Formula 27 to form a compound of Formula 23. In this case, the reaction of Scheme 4 may be performed by adding n-BuLi, and the reaction of Scheme 4 may be performed in THF.

<Reaction Scheme 4>

Here, R ₁ to R ₄ is any one selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms.

The reaction of Scheme 1 may be performed using the compound of Formula 23 prepared through the reaction of Schemes 2 to 4.

D represented in Scheme 1 may be any one selected from the group consisting of Chemical Formulas 3 to 7, and R ₁ to R ₄ may be hexyl.

And A in Formula 1 may be Formula 2. The compound of formula 1 wherein A is formula 2 is shown in formula 32.

<Formula 32>

D is an electron donor group, and R ₁ to R ₄ are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

The compound of formula 32 may be formed from the compound of formula 24, the process of which is shown in Scheme 5 and Scheme 6 below.

In order to form the compound of Formula 32, first, as shown in Scheme 5, the compound of Formula 24 is reacted with DMF to form the compound of Formula 33. POCl ₃ may be added at this time.

Scheme 5

D is an electron donor group, and R ₁ to R ₄ are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

As shown in Scheme 6, the compound of Formula 33 is reacted with cyanoacetic acid to form the compound of Formula 32. The reaction of Scheme 6 may be carried out by adding piperidine and acetonitrile (CH ₃ CN) together.

<Reaction Scheme 6>

D is an electron donor group, and R ₁ to R ₄ are any one selected from the group consisting of hydrogen and alkyl having 1 to 10 carbon atoms.

In this case, in order to form the compound of Formula 32, JK-112, which is a compound of Formula 20, the compound of Formula 22 may be a compound of Formula 28, and the compound of Formula 23 may be a compound of Formula 29.

(28)

<Formula 29>

And in order for the compound of Formula 32 to form JK-113, which is a compound of Formula 21, the compound of Formula 22 may be a compound of Formula 30, and the compound of Formula 23 may be a compound of Formula 29.

<Formula 30>

Hereinafter, embodiments of the method for producing JK-112 and JK-113 among the compounds containing thienothiophene-vinylene-thienothiophene according to the present invention will be described in more detail. The present invention is not limited to the following examples and can be embodied in other forms.

First, the method for preparing the compound of formula 29 used in the examples below will be described first.

Of the compound of formula 29 Manufacturing example

Compound of formula 29 ((E) -2- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b ] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) is shown in FIG. 1.

1) 3,6- dihexylthieno [3,2-b] thiophene-2- carbaldehyde (1-2) synthesis

N-BuLi (2.85 ml, 2.5 in THF solution in which 3,6-dihexylthieno [3,2-b] thiophene (1-1) (2 g, 6.48 mmol) was dissolved at 0 ° C. under argon (Ar) M hexane solution). Then, after one hour, DMF (1 g, 6.48 mmol) was added at 0 ° C. under argon atmosphere. The solution was washed with 5% HCl solution, dried over MgSO 4 and the solvent was evaporated to give 3,6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (1-2). The yield was 90%.

¹ H NMR (CDCl ₃ ): δ 10.09 (s, 1H), 7.26 (s, 1H), 3.09 (t, J = 7.8 Hz, 2H), 2.72 (t, J = 7.2 Hz, 2H), 1.72 (br , 4H), 1.36 (m, 12H), 0.89 (t, J = 6.8 Hz, 3H), 0.86 (t, J = 6.8 Hz, 3H) .

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 182.1, 142.1, 141.5, 137.5, 135.6, 131.1, 121.3, 31.7, 31.6, 30.5, 30.0, 29.4, 29.2, 28.9, 28.5, 28.0, 22.7, 14.3, 14.2.

2) (E) -1,2- bis (3,6- dihexylthieno [3,2-b] thiophen-2- yl ) ethene (1-3) synthesis

TiCl ₄ (1.95 ml, 17.82 mmol) was added to a THF solution in which zinc (Zn) powder (1.165 g, 17.82 mmol) was dissolved at 0 ° C. under an argon atmosphere. After an hour, THF solution in which 3,6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (1-2) was dissolved was added under an argon atmosphere at 0 ° C. The mixed solution was stirred at 70 ° C. for 10 hours and then cooled. The organic material was extracted, dried over MgSO ₄ , and the solvent was evaporated to give (E) -1,2-bis (3,6-dihexylthieno [3,2-b] thiophen-2-yl) ethene (1). -3) could be obtained. The yield was 60%.

¹ H NMR (CDCl ₃ ): δ 9.82 (s, 1H), 7.65 (t, J = 6.3 Hz, 2H), 7.09 (s, 1H), 7.08 (s, 1H), 6.95 (s, 1H), 2.97 (t, J = 7.8 Hz, 2H), 2.81 (m, 4H), 2.70 (t, J = 7.8 Hz, 2H), 1.73 (m, 8H), 1.35 (m, 24H), 0.89 (m, 12H) .

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 146.2, 146.0, 140.9, 140.2, 138.4, 138.2, 136.4, 135.6, 137.7, 133.6, 133.2, 125.9, 122.0, 121.3, 83.9, 31.7, 31.6, 30.5, 30.0 , 29.9, 29.4, 28.8, 28.5, 28.1, 22.9, 22.7, 14.2, 14.1.

3) (E) -2- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6- dihexylthieno [3,2-b] thiophen-2- yl ) -4,4,5,5- tetramethyl -1,3,2- dioxaborolane (1-4) synthesis

In an THF solution in which (E) -1,2-bis (3,6-dihexylthieno [3,2-b] thiophen-2-yl) ethene (1-3) is dissolved at -78 ° C under an argon atmosphere. -BuLi (0.24 ml, 2.5 M hexane solution) was added. After an hour, pinacol borate (2-isopropoxy-4,4,5,5, -tetramethyl-1,3,2-dioxaborolane) (0.121 g, 0.655 mmol) was added under an atmosphere of argon at -78 ° C. . The mixed solution was stirred at 20 ° C. for 1 hour and then cooled. The organic material was extracted, dried over MgSO ₄ , the solvent was evaporated, and the compound of formula 33 (E) -2- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen) -2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1-4) Could get The yield was 60%.

¹ H NMR (CDCl ₃ ): δ 9.82 (s, 1H), 7.65 (t, J = 6.3 Hz, 2H), 7.09 (s, 1H), 7.08 (s, 1H), 6.95 (s, 1H), 2.97 (t, J = 7.8 Hz, 2H), 2.81 (m, 4H), 2.70 (t, J = 7.8 Hz, 2H), 1.73 (m, 8H), 1.35 (m, 24H), 0.89 (m, 12H) .

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 146.2, 146.0, 140.9, 140.2, 138.4, 138.2, 136.4, 135.6, 137.7, 133.6, 133.2, 125.9, 122.0, 121.3, 83.9, 31.7, 31.6, 30.5, 30.0 , 29.9, 29.4, 28.8, 28.5, 28.1, 22.9, 22.7, 14.2, 14.1.

Example  One: JK Preparation of -112 (Compound of Formula 20)

The preparation step of JK-112 is shown in FIG. 2.

1) (E) -N- (4- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6- dihexylthieno [3,2-b] thiophen-2- yl ) phenyl ) -N- (9,9- dimethyl -9H- fluoren -2- yl ) -9,9-dimethyl-9H-fluoren-2-amine (2-2) Synthesis

N, N-bis (9,9-dimethylfluoren-2-yl) -4-bromoaniline (2-1) (0.138 g, 0.25 mmol), (E) -2- (5- (2- (3,6- dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3, A THF solution containing 2-dioxaborolane (1-4) (0.191 g, 0.25 mmol), K ₂ CO ₃ (0.20 g, 1.5 mmol) and Pd (PPh ₃ ) ₄ (0.029 g, 0.025 mmol) was dissolved for 12 hours. Reflux for a while. After cooling the solution, the organics were extracted, dried over MgSO ₄ , the solvent was evaporated, and (E) -N- (4- (5- (2- (3,6-dihexylthieno [3,2] -b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine (2-2) was obtained. Yield 70%.

¹ H NMR (CDCl ₃ ): δ 7.65 (t, J = 7.8 Hz, 2H), 7.63 (d, J = 8.2 Hz, 2H), 7.40 (d, J = 8.2 Hz, 2H), 7.35 (t, J = 7.8 Hz, 2H), 7.33-7.25 (m, 6H), 7.24 (s, 2H), 7.16 (d, J = 7.6 Hz, 2H), 7.13 (s, 1H), 7.10 (s, 1H), 7.00 (s, 1H), 2.82 (t, J = 7.8 Hz, 2H), 2.81-2.71 (m, 6H), 1.85-1.71 (m, 8H), 1.43 (s, 12H), 1.34-1.24 (m, 24H ), 0.89 (t, J = 6.8 Hz, 3H), 0.88-0.86 (m, 6H), 0.85 (t, J = 6.8 Hz, 3H).

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 155.2, 153.6, 147.6, 147.2, 140.4, 139.3, 139.0, 136.8, 135.5, 135.3, 134.6, 132.3, 132.1, 132.0, 131.3, 130.8, 130.1, 129.7, 128.8 , 128.7, 128.5, 127.1, 126.7, 125.6, 123.6, 123.3, 122.6, 120.8, 119.6, 119.0, 47.0, 31.8, 31.7, 31.6, 31.5, 30.5, 30.4, 30.0, 29.8, 29.6, 29.4, 29.3, 29.2, 29.0 , 28.9, 28.7, 28.5, 28.3, 28.0, 27.8, 27.6, 27.1, 22.7, 14.3, 14.2, 14.1.

2) (E) -5- (2- (5- (4- ( bis (9,9- dimethyl -9H- fluoren -2- yl ) amino) phenyl ) -3,6- dihexylthieno [3,2-b] thiophen-2- yl ) vinyl ) -3,6- dihexylthieno Synthesis of [3,2-b] thiophene-2-carbaldehyde (2-3)

(E) -N- (4- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-] at 0 ° C. b] thiophen-2-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine (2-2) is dissolved To the DMF (10 mL) solution was added Vilsmeier reagent obtained from DMF (0.1 mL) and POCl ₃ (0.06 mL). The solution was stirred at 70 ° C. for 4 hours and then cooled. After cooling the solution, the organics were extracted, dried over MgSO ₄ , the solvent was evaporated, and (E) -5- (2- (5- (4- (bis (9,9-dimethyl-9H) -fluoren-2-yl) amino) phenyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (2-3) could be obtained. Yield 85%.

¹ H NMR (CDCl ₃ ): δ 10.05 (s, 1H), 7.65 (t, J = 7.2 Hz, 2H), 7.62 (d, J = 8.2 Hz, 2H), 7.36 (d, J = 8.2 Hz, 2H ), 7.35 (t, J = 7.2 Hz, 2H), 7.33-7.25 (m, 5H), 7.24 (s, 2H), 7.19 (d, J = 15.6 Hz, 1H), 7.13 (d, J = 8.1 Hz , 2H), 7.06 (d, J = 15.6 Hz, 1H), 6.98 (s, 1H), 3.08 (t, J = 7.8 Hz, 2H), 2.81-2.82 (m, 4H), 2.71 (t, J = 7.8 Hz, 2H), 1.85-1.71 (m, 8H), 1.43 (s, 12H), 1.34-1.24 (m, 24H), 0.89 (t, J = 6.8 Hz, 3H), 0.88-0.86 (m, 6H ), 0.85 (t, J = 6.8 Hz, 3H).

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 181.2, 155.4, 153.2, 147.3, 147.1, 140.4, 139.3, 139.0, 136.8, 135.7, 135.3, 134.6, 133.4, 132.3, 132.1, 132.0, 130.3, 130.8, 130.1 , 129.7, 128.8, 128.7, 128.5, 128.1, 127.7, 126.6, 124.6, 123.4, 122.6, 120.8, 120.6, 47.0, 31.8, 31.7, 31.6, 31.5, 30.5, 30.4, 30.0, 29.8, 29.6, 29.4, 29.3, 29.2 , 29.0, 28.9, 28.7, 28.5, 28.3, 28.0, 27.8, 27.6, 27.1, 22.7, 14.3, 14.2, 14.1.

3) (Z) -3- (5-((E) -2- (5- (4- (bis (9,9-dimethyl-9H-fluoren-2-) yl ) amino ) phenyl ) -3,6- dihexylthieno [3,2-b] thiophen-2- yl ) vinyl ) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -2-cyanoacrylic acid (2-4) ( JK -112) synthetic

(E) -5- (2- (5- (4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -3,6-dihexylthieno [3,2-b] thiophen -2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (2-3) (0.16 g, 0.140 mmol) and cyanoacetic acid (0.024 g, 0.28 mmol) mixture was dried in vacuo, and then a solution of acetonitrile (MeCN) (60 ml) and piperidine (0.012 g, 0.140 mmol) was added. The solution was refluxed for 6 hours, then cooled and the organic layer was removed to afford (Z) -3- (5-((E) -2- (5- (4- (bis (9,9-dimethyl-9H-) fluoren-2-yl) amino) phenyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -2-cyanoacrylic acid (2-4) (JK-112) was obtained. Yield 51%.

¹ H NMR (DMSO-d ₆ ): δ 8.20 (s, 1H), 7.77 (t, J = 8.1 Hz, 2H), 7.50 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 8.7 Hz , 2H), 7.32 (t, J = 8.1 Hz, 2H), 7.30-7.25 (m, 6H), 7.24 (s, 2H), 7.21 (d, J = 15.6 Hz, 1H), 7.13 (d, J = 8.4 Hz, 2H), 7.10 (d, J = 15.6 Hz, 1H), 7.08 (d, J = 8.4 Hz, 2H), 3.19 (t, J = 7.8 Hz, 2H), 2.93 (t, J = 7.8 Hz , 2H), 2.71-2.68 (m, 4H), 1.81-1.71 (m, 8H), 1.37 (s, 12H), 1.34-1.24 (m, 24H), 0.82-0.79 (m, 12H).

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 166.1, 155.8, 154.9, 153.2, 152.1, 150.1, 147.7, 146.4, 145.5, 145.3, 140.8, 139.8, 139.0, 138.4, 137.2, 137.0, 135.7, 134.6, 133.4 , 132.1, 130.7, 130.1, 129.4, 128.5, 127.8, 127.1, 126.8, 123.6, 123.4, 122.6, 120.3, 119.5, 119.1, 46.4, 31.8, 31.7, 31.6, 31.4, 30.5, 30.4, 30.1, 29.9, 29.7, 29.5 , 29.3, 29.2, 29.0, 28.8, 28.7, 28.5, 28.3, 28.0, 27.8, 27.6, 27.1, 22.6, 14.3, 14.2, 14.1.

Example  2: JK Preparation of -113 (Compound of Formula 21)

A manufacturing step of JK-113 is shown in FIG. 3.

1) (E) -2- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6- dihexylthieno [3,2-b] thiophen-2- yl ) -N, N- bis (9,9- dimethyl -9H- fluoren Synthesis of -2-yl) benzo [b] thiophen-6-amine (3-2)

6- (bis (9,9-dimethylfluoren-2-yl) amino) -2-bromobenzo [ b instead of N, N-bis (9,9-dimethylfluoren-2-yl) -4-bromoaniline (2-1) ] thiophene (3-1) (0.16 g, 0.261 mmol), except for using (E) -2- (5- (2- (3, 6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -N, N-bis (9,9-dimethyl- 9H-fluoren-2-yl) benzo [b] thiophen-6-amine (3-2) was obtained. Yield 51%.

¹ H NMR (CDCl ₃ ): δ 7.64 (d, J = 9.0 Hz, 1H), 7.59 (d, J = 8.1 Hz, 2H), 7.58 (t, J = 8.1 Hz, 2H), 7.56 (s, 1H), 7.39 (t, J = 8.1 Hz, 2H), 7.36 (d, J = 9.0 Hz, 1H), 7.32-7.28 (m, 4H), 7.25 (s, 2H), 7.19 (s, 1H), 7.13 (s, 1H), 7.11 (s, 1H), 7.10 (d, J = 8.1 Hz, 2H), 2.82 (t, J = 7.8 Hz, 2H), 2.81-2.71 (m, 6H), 1.85-1.71 (m, 8H), 1.43 (s, 12H), 1.34-1.24 (m, 24H), 0.89 (t, J = 6.8 Hz, 3H), 0.88-0.86 (m, 6H), 0.85 (t, J = 6.8 Hz, 3H).

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 155.3, 153.7, 147.5, 146.5, 145.4, 143.7, 142.2, 141.1, 139.0, 138.4, 137.5, 136.5, 135.2, 134.8, 134.4, 134.1, 133.9, 133.8, 132.8 , 132.3, 131.2, 130.9, 129.8, 128.7, 127.1, 126.7, 126.5, 126.3, 123.2, 122.7, 120.8, 119.5, 118.6, 116.7, 47.0, 31.8, 31.7, 31.6, 31.5, 30.5, 30.4, 30.0, 29.8, 29.6 , 29.4, 29.3, 29.2, 29.0, 28.9, 28.7, 28.5, 28.3, 28.0, 27.8, 27.6, 27.1, 22.7, 14.3, 14.2, 14.1.

2) (E) -5- (2- (5- (6- (bis (9,9-dimethyl-9H-fluoren-2- yl ) amino ) benzo [b] thiophen -2- yl ) -3,6- dihexylthieno [3,2-b] thiophen-2- yl ) vinyl ) -3,6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (3-3) Synthesis

(E) -N- (4- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen -2-yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine (2-2) instead of (E)- 2- (5- (2- (3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -N Example 1, except that N-bis (9,9-dimethyl-9H-fluoren-2-yl) benzo [b] thiophen-6-amine (3-2) (0.3 g, 0.249 mmol) is used. Using the same method as in step 2), (E) -5- (2- (5- (6- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzo [b] thiophen -2-yl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (3-3) Could get Yield 51%.

¹ H NMR (CDCl ₃ ): δ 10.05 (s, 1H), 7.64 (d, J = 9.0 Hz, 1H), 7.59 (d, J = 8.1 Hz, 2H), 7.58 (t, J = 8.1 Hz, 2H), 7.61 (s, 1H), 7.39 (t, J = 8.1 Hz, 2H), 7.36 (d, J = 9.0 Hz, 1H), 7.32-7.28 (m, 4H), 7.25 (s, 2H), 7.19 (d, J = 15.6 Hz, 1H), 7.10 (d, J = 8.1 Hz, 2H), 7.06 (d, J = 15.6 Hz, 1H ), 6.98 (s, 1H), 3.07 (t, J = 7.8 Hz, 2H), 2.96 (t, J = 7.8 Hz, 2H), 2.82 (t, J = 7.8 Hz, 4H), 1.85-1.71 (m , 8H), 1.43 (s, 12H), 1.34-1.24 (m, 24H), 0.89 (t, J = 6.8 Hz, 3H), 0.88-0.86 (m, 6H), 0.85 (t, J = 6.8 Hz, 3H). ).

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 180.8, 155.6, 154.7, 148.5, 147.5, 145.3, 143.7, 142.2, 141.1, 139.0, 138.4, 137.5, 136.5, 136.2, 134.8, 134.4, 134.1, 133.9, 133.8 , 133.4, 132.8, 132.3, 131.8, 131.2, 130.8, 129.5, 128.5, 127.1, 126.7, 126.5, 126.3, 123.2, 122.7, 120.8, 119.5, 47.0, 31.8, 31.7, 31.6, 31.5, 30.5, 30.4, 30.0, 29.8 , 29.6, 29.4, 29.3, 29.2, 29.0, 28.9, 28.7, 28.5, 28.3, 28.0, 27.8, 27.6, 27.1, 22.7, 14.3, 14.2, 14.1.

3) (Z) -3- (5-((E) -2- (5- (6- (bis (9,9-dimethyl-9H-fluoren-2--2-) yl ) amino ) benzo [b] thiophen -2- yl ) -3,6- dihexylthieno [3,2-b] thiophen-2- yl ) vinyl ) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -2-cyanoacrylic acid (3-4) ( JK -113) synthetic

(E) -5- (2- (5- (4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -3,6-dihexylthieno [3,2-b] thiophen -2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (2-3) instead of (E) -5- (2- (5- (6- (bis ( 9,9-dimethyl-9H-fluoren-2-yl) amino) benzo [b] thiophen-2-yl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3, Using the same method as in 3) of Example 1, except that 6-dihexylthieno [3,2-b] thiophene-2-carbaldehyde (3-3) (0.21 g, 0.175 mmol) was used, ) -3- (5-((E) -2- (5- (6- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzo [b] thiophen-2-yl)- 3,6-dihexylthieno [3,2-b] thiophen-2-yl) vinyl) -3,6-dihexylthieno [3,2-b] thiophen-2-yl) -2-cyanoacrylic acid (3-4) ( JK-113). Yield 53%.

¹ H NMR (CDCl ₃ ): δ 8.19 (s, 1H), 7.77 (d, J = 9.0 Hz, 1H), 7.69 (d, J = 8.1 Hz, 2H), 7.61 (t, J = 8.1 Hz, 2H), 7.58 (s, 1H), 7.39 (t, J = 8.1 Hz, 2H), 7.36 (d, J = 9.0 Hz, 1H), 7.32-7.28 (m, 4H), 7.25 (s, 2H), 7.22 (d, J = 15.6 Hz, 1H), 7.16 (d, J = 15.6 Hz, 1H), 7.13 (d, J = 8.1 Hz, 2H ), 7.10 (s, 1H), 3.07 (t, J = 7.8 Hz, 2H), 2.96 (t, J = 7.8 Hz, 2H), 2.82 (t, J = 7.8 Hz, 4H), 1.85-1.71 (m , 8H), 1.43 (s, 12H), 1.34-1.24 (m, 24H), 0.89 (t, J = 6.8 Hz, 3H), 0.88-0.86 (m, 6H), 0.85 (t, J = 6.8 Hz, 3H).

¹³ C { ¹ H} NMR (CDCl ₃ ): δ 166.2, 156,2, 155.6, 154.7, 148.5, 147.5, 146.5, 145.3, 143.7, 142.2, 141.1, 139.0, 138.4, 137.5, 136.5, 136.2, 134.8, 134.4 , 134.1, 133.9, 133.8, 133.4, 132.8, 132.3, 131.8, 131.2, 130.8, 129.5, 128.5, 127.1, 126.7, 126.5, 126.3, 123.2, 122.7, 120.8, 119.5, 47.0, 31.8, 31.7, 31.6, 31.5, 30.5 , 30.4, 30.0, 29.8, 29.6, 29.4, 29.3, 29.2, 29.0, 28.9, 28.7, 28.5, 28.3, 28.0, 27.8, 27.6, 27.1, 22.7, 14.3, 14.2, 14.1.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of a dye-sensitized solar cell using a dye containing a compound containing a novel thienothiophene-vinylene-thienothiophene according to the present invention. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention and to those skilled in the art to fully understand the scope of the invention. It is provided to inform you.

4 is a view schematically showing a dye-sensitized solar cell according to the present invention.

Referring to FIG. 4, the dye-sensitized solar cell 100 according to the present invention includes a first substrate 110, a semiconductor electrode 120, an opposite electrode 130, a second substrate 140, an electrolyte 150, and a polymer. With layer 160.

The first substrate 110 may be made of conductive glass. Preferably, indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) are coated on a glass substrate. A TiCl ₄ layer (not shown) may be formed between the first substrate 110 and the semiconductor electrode 120.

The semiconductor electrode 120 is formed on the first substrate 110 and is formed of a nanoparticle metal oxide layer on which a dye is adsorbed. The semiconductor electrode 120 may be formed to a thickness of about 5 to 15 μm. The metal oxide constituting the nanoparticle metal oxide layer may be titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ ) or zinc oxide (ZnO), and may have a size of about 5 to 30 nm.

The dye adsorbed on the nanoparticle metal oxide is a compound containing thienothiophene-vinylene-thienothiophene represented by the compound of formula (1). The compound of Formula 1 is as described above, and R ₁ to R ₄ of Formula 1 may be hexyl. And A (electron pull group) of Formula 1 may be Formula 2, D (electron donor group) of Formula 1 may be any one selected from the group consisting of Formula 3 to Formula 7. Preferably at least one of JK-112, a compound of Formula 20, and JK-113, a compound of Formula 21, are used as the dye.

In the nanoparticle metal oxide, a coadsorbent may be further adsorbed together with the compound dye of Chemical Formula 1. This additive may be tetrabutylammonium chenodeoxycholic acid salt (DBA).

The second substrate 140 may be a glass substrate coated with conductive glass, that is, ITO or FTO, like the first substrate 110.

The opposite electrode 130 is formed on the second substrate 140 and may be made of platinum Pt. The counter electrode 130 is disposed to face the semiconductor electrode 120.

The electrolyte 150 is a material that fills the space between the semiconductor electrode 120 and the counter electrode 130. The electrolyte 150 may be an electrolyte solution, a solvent-free ionic-liquid electrolyte, or a solid-state electrolyte. The electrolyte solution may be a solution in which 0.6 M DMPImI, 0.05 I ₂ , 0.1 M LiI and 0.5 M tert-butylpyridine are dissolved in acetonitrile. The solvent-free ionic liquid electrolyte may be an electrolyte containing 0.2 MI ₂ , 0.5 M NMBI and 0.1 M GuNCS in PMMI / EMINCS (13: 7). The solid electrolyte may be Spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N, N-dimethoxyphenylamine) -9,9'-spiro-bifluorene).

Referring to the operation of the dye-sensitized solar cell according to a preferred embodiment of the present invention illustrated in Figure 4 as follows.

First, when the sunlight passing through the first substrate 110 is absorbed by the dye molecules of the compound of formula 1 adsorbed on the nanoparticle metal oxide of the semiconductor electrode 120, the dye molecules excited in the excited state is nano It is injected into the conduction band of the particle metal oxide. Electrons injected into the nanoparticle metal oxide are transferred to the first substrate 110 through the interparticle interface and are moved to the counter electrode 120 through the external wire.

The dye molecules oxidized as a result of electron transfer is an iodine ion redox action of in the electrolyte ^{(150) (3I - → I} 3 - + 2e -) accept electrons provided by the will be reduced again, the oxidized iodine ions (I ₃ ^- ) Is reduced again by the electrons reaching the counter electrode 130 to complete the operation of the dye-sensitized solar cell.

In order to examine the properties when the compound containing thienothiophene-vinylene-thienothiophene according to the present invention is used as a dye of a dye-sensitized solar cell, the thienothiophene-vinylene-thienothiophene according to the present invention Dye-sensitized solar cells were manufactured using JK-112 and JK-113, which are preferred examples of the compound containing, as a dye. And a compound designated as JK-81 below as a comparative example ((Z) -3- (5- (4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -3,3 A dye-sensitized solar cell was fabricated using ', 6,6'-tetrahexyl-2,2'-bithieno [3,2-b] thiophen-5'-yl) -2-cyanoacrylic acid) as a dye.

<Comparative Example (JK-81)>

The compound containing thienothiophene-vinylene-thienothiophene has a double bond structure formed between two thienothiophenes, whereas the compound (JK-81) shown in the comparative example is composed of two thienothiophenes. Bound to a single bond. Due to this difference, when used as a dye of the dye-sensitized solar cell, a difference in characteristics occurs, which is shown in Figures 5 to 10.

5 is a view showing absorption coefficients according to wavelengths when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells.

As shown in FIG. 5, the dye-sensitized solar cell using JK-81 as a dye absorbs only one wavelength (372 nm) of light well, whereas the dye-sensitized solar cell using JK-112 is used as a dye. In the case of dye-sensitized solar cell using the wavelength of 365 nm and 480 nm well, and dye-sensitized solar cell using JK-113 as a dye absorbs light having the wavelength of 365 nm, 490 nm well. That is, the JK-112 and 113 absorb the light of various wavelengths better than the JK-81, and particularly, the light of the long wavelength of the visible light region is well absorbed.

FIG. 6 is a diagram illustrating incident photon-to-current conversion efficiency (IPCE) according to wavelengths when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells.

As shown in FIG. 6, when JK-112 and JK-113 are used as dyes for dye-sensitized solar cells, the IPCE value is significantly larger than that of JK-81, so that the incident light is converted into current. It can be seen that this is excellent.

7 is a diagram showing current density according to voltage when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells.

As shown in FIG. 7, when JK-112 and JK-113 are used as dyes for dye-sensitized solar cells, and JK-81 is used as dyes for dye-sensitized solar cells, V _oc (open circuit voltage) Although the values are similar, it can be seen that there is a large difference in the value of J _sc (short circuit current). In other words, JK-112 and JK-113 show that J _sc is significantly larger than that of JK-81, which indicates that solar cells using JK-112 and JK-113 as dyes produce significantly larger currents. Means that.

Table 1 shows the overall characteristics of the dye-sensitized solar cell using JK-81, JK-112 and JK-113 as dyes, including the results of FIGS. 6 and 7. At this time, the electrolyte 150 used a solution in which 0.6 M DMPImI, 0.05 I ₂ , 0.1 M LiI and 0.5 M tert-butylpyridine are dissolved in acetonitrile, and sunlight of 1 sun was irradiated.

[Table 1]

As shown in Table 1, a dye having a structure in which two thienothiophenes are connected by a double bond structure (JK-112, JK113) has a structure in which thienothiophene is connected by a single bond. It can be seen that the J _sc value and the efficiency (η) were significantly increased compared to (JK-81). In particular, it can be seen that the efficiency of JK-113 is much higher than that of JK-81 (5.1% → 9.1%). In addition, when DCA.TBA (tetrabutylammonium chenodeoxycholic acid salt) additive was adsorbed onto the metal oxide layer with JK-113 dye, the efficiency was increased to 9.5%.

The ionic liquid electrolyte, in which the solvent is removed from the electrolyte 150, is effective in the case of JK-113 even when an electrolyte containing 0.2 MI ₂ , 0.5 M NMBI and 0.1 M GuNCS is included in PMMI / EMINCS (13: 7). It was about 7.9%.

The compound containing thienothiophene-vinylene-thienothiophene according to the present invention can be used not only in a liquid electrolyte but also in a solid electrolyte. Spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N, N-dimethoxyphenylamine) -9,9'-spiro-bifluorene) as a solid electrolyte Table 2 shows the overall characteristics of the dye-sensitized solar cells using JK-112 and JK-113 as dyes.

[Table 2]

In the case of using the solid electrolyte, the overall efficiency was decreased due to the decrease in the value of J _sc compared to the case of using the electrolyte solution, but the efficiency of about 4.8% is the highest efficiency known to the previous efficiency using the solid electrolyte. do.

8 is a view showing the change of J _sc , V _oc , Fill Factor (FF) and efficiency (η) over time when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells. . At this time, the temperature was maintained at 60 ℃, the electrolyte 150 was used as the ionic liquid electrolyte from which the solvent containing 0.2 MI ₂ , 0.5 M NMBI and 0.1 M GuNCS in PMMI / EMINCS (13: 7) .

As shown in FIG. 8, dye-sensitized solar cells using JK-112 and JK-113 as dyes have almost constant J _sc , V _oc , Fill Factor and efficiency values even after 1000 hours, and thus have excellent thermal stability. It can be seen.

9 is a view showing the impedance change when the external light is irradiated when JK-112 and JK-113 is used as a dye of the dye-sensitized solar cell, Figure 10 is a dye-sensitized embodiment of JK-112 and JK-113 When used as a dye of a battery, it is a figure which shows the impedance change, when external light is not irradiated.

As shown in FIG. 9, when the external light is irradiated, the current flows smoothly by having a small impedance value of about 10 Ω, and as shown in FIG. 10, when the external light is not irradiated, 50 Ω or more It can be seen that it has a large impedance value, which makes it difficult to discharge and exhibits excellent characteristics.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation in the embodiment in which said invention is directed. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.

1 is a view briefly showing a method for preparing a compound of formula 29 used in the present invention.

2 is an embodiment of a method for preparing a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, which is a diagram briefly showing a method for preparing JK-112.

3 is an embodiment of a method for preparing a compound containing thienothiophene-vinylene-thienothiophene according to the present invention, which is a view briefly showing a method for producing JK-113.

4 is a view showing a schematic configuration of a dye-sensitized solar cell according to the present invention.

5 is a view showing absorption coefficients according to wavelengths when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells.

FIG. 6 is a diagram illustrating incident photon-to-current conversion efficiency (IPCE) according to wavelengths when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells.

7 is a diagram showing current density according to voltage when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells.

8 is a view showing the change of J _sc , V _oc , Fill Factor (FF) and efficiency (η) over time when JK-112 and JK-113 are used as dyes in dye-sensitized solar cells. .

9 is a view showing the impedance change when the external light is irradiated when JK-112 and JK-113 is used as a dye of the dye-sensitized solar cell.

10 is a view showing the change in impedance when no external light is irradiated when JK-112 and JK-113 are used as a dye of the dye-sensitized solar cell.

Claims (20)

A compound containing thienothiophene-vinylene-thienothiophene of Formula 1 below. &Lt; Formula 1 >

[A in Formula 1 is the following Formula 2, <Formula 2>

D in Chemical Formula 1 is the following Chemical Formula 3, <Formula 3>

X ₁ of Formula 3 is the following Formula 8 or Formula 9, R ₅ and R ₆ is hydrogen, (8)

<Formula 9>

R ₁ to R ₄ of Formula 1 are alkyl having 1 to 10 carbon atoms.] The method of claim 1, R ₁ to R ₄ of Formula 1 is hexyl (hexyl) characterized in that the thienothiophene-vinylene-thienothiophene-containing compound. delete delete The method of claim 1, The compound of Formula 1 is a compound containing thienothiophene-vinylene-thienothiophene, characterized in that at least one of the compound of formula 20 and the compound of formula 21. <Formula 20>

&Lt; Formula 21 >

Thienothiophene-vinylene-thienothiophene, comprising: reacting a compound of Formula 22 with a compound of Formula 23 to form a compound of Formula 24: -vinylene-thienothiophene). &Lt; Formula 1 >

<Formula 22>

&Lt; Formula 23 >

&Lt; EMI ID =

[A in Formula 1 is the following Formula 2, <Formula 2>

D in Formula 1, Formula 22, and Formula 24 is Formula 3, <Formula 3>

X ₁ of Formula 3 is the following Formula 8 or Formula 9, R ₅ and R ₆ is hydrogen, (8)

<Formula 9>

R ₁ to R ₄ in Formula 1, Formula 23, and Formula 24 are alkyl having 1 to 10 carbon atoms.] The method of claim 6, Compound of Formula 23, Adding a compound of Formula 25 to a THF solution containing TiCl ₄ and Zn to form a compound of Formula 26; And Containing thienothiophene-vinylene-thienothiophene, comprising: reacting a compound of Formula 26 with a compound of Formula 27 to form a compound of Formula 23; Method for preparing the compound. &Lt; Formula 25 >

<Formula 26>

&Lt; Formula 27 >

[R ₂₂ and R ₂₃ of Formula 25 and R ₁ to R ₄ of Formula 26 are alkyl having 1 to 10 carbon atoms.] delete delete delete delete Conductive substrates; A semiconductor electrode formed on the conductive substrate and including a metal oxide layer adsorbed with a dye including the compound of Formula 1; Counter electrode; And And a electrolyte filling between the semiconductor electrode and the counter electrode. &Lt; Formula 1 >

[A in Formula 1 is the following Formula 2, <Formula 2>

D in Chemical Formula 1 is the following Chemical Formula 3, <Formula 3>

X ₁ of Formula 3 is the following Formula 8 or Formula 9, R ₅ and R ₆ is hydrogen, (8)

<Formula 9>

R ₁ to R ₄ of Formula 1 are alkyl having 1 to 10 carbon atoms.] The method of claim 12, A dye-sensitized solar cell, characterized in that R ₁ to R ₄ of Formula 1 is hexyl (hexyl). delete delete The method of claim 12, The compound of formula 1 is a dye-sensitized solar cell, characterized in that at least one of the compound of formula 20 and the compound of formula 21. <Formula 20>

&Lt; Formula 21 >

The method according to any one of claims 12, 13 or 16, A dye-sensitized solar cell, wherein an additive is further adsorbed to the metal oxide layer. 18. The method of claim 17, The additive is a dye-sensitized solar cell, characterized in that DCA ... TBA (tetrabutylammonium chenodeoxycholic acid salt). The method according to any one of claims 12, 13 or 16, The electrolyte is a dye-sensitized solar cell, characterized in that the solid-state (solid-state) electrolyte. 20. The method of claim 19, The solid state electrolyte is Spiro-OMeTAD (2,2 ', 7,7'-tetrakis (N, N-dimethoxyphenylamine) -9,9'-spiro-bifluorene) characterized in that the dye-sensitized solar cell.

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