KR20140082569A - Novel organic dye and method for preparing thereof - Google Patents

Abstract

The present invention relates to an organic dye and a manufacturing method thereof. More specifically, a dye compound represented by chemical formula 1 given in the present invention is used for a dye-sensitized solar cell (DSSC) and has improved mole light absorption coefficient, open voltage, and photoelectric conversion efficiency compared with an existing dye, thereby improving the efficiency of the solar cell significantly. In the formula, A, B, C, and m are the same as described in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel organic dye and a method for producing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel organic dye used in a dye-sensitized solar cell (DSSC) and a method for producing the same.

Much research has been done in this area since the development of dye-sensitized nanoparticle titanium dioxide solar cells by Michael Gratzel of the Swiss National Lozan Institute for Technology (EPFL) in 1991. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because they have higher efficiency and lower manufacturing costs than conventional silicon solar cells. Unlike silicon solar cells, dye-sensitized solar cells have the potential to replace visible silicon A dye molecule capable of absorbing and generating an electron-hole pair, and a transition metal oxide transmitting the generated electrons as main constituent materials.

Ruthenium metal complexes exhibiting high photoelectric conversion efficiency have been widely used as dyes for dye-sensitized solar cells, and these ruthenium metal complexes have been disadvantageous in that they are too expensive.

Recently, metal-free organic dyes, which exhibit excellent physical properties in terms of absorption efficiency, redox stability and intramolecular charge-transfer (CT) absorption, can replace expensive ruthenium metal complexes It has been found that the dye can be used as a dye for a solar cell, and studies on an organic dye lacking a metal have been focused on.

Organic dyes generally have the structure of an electron donor-electron acceptor moiety linked by a pi-bonding unit. In most organic dyes, the amine derivative acts as an electron donor, and the 2-cyanoacrylic acid or rhodanine moiety serves as an electron acceptor, and these two moieties are linked via a π-bond system such as a meta in unit or thiophene chain Lt; / RTI >

In general, the structural change of the electron-predominant amine unit leads to a change in the electron characteristics, for example, a shift in the absorption spectrum toward blue, and changes the? -Bond length to change the absorption spectrum and the redox potential, Can be adjusted.

However, most of the organic dyes known so far exhibit lower conversion efficiency and lower driving stability than ruthenium metal complex dyes, and thus, by changing the kind or? -Bond length of the electron donor and electron acceptor, Efforts have been made to develop new dyes having an improved molar extinction coefficient and high photoelectric conversion efficiency.

Accordingly, it is an object of the present invention to provide an organic dye capable of significantly improving the efficiency of a solar cell by introducing a novel electron donor group into a molecule and exhibiting an improved molar extinction coefficient and photoelectric conversion efficiency, and a process for producing the same.

Another object of the present invention is to provide a dye-sensitized photoelectric conversion element and a dye-sensitized solar cell including the dye and having excellent molar extinction coefficient, open-circuit voltage and photoelectric conversion efficiency.

In order to accomplish the above object, the present invention provides an organic dye represented by the following general formula (1) including an electron donating group of the following general formula (2)

[Chemical Formula 1]

In this formula,

A is an electron donor group and is a compound of the formula:

(2)

At this time,

X is each independently selected from the group consisting of sulfur; Oxygen; Hydrogen; heavy hydrogen; Tritium; Or alkyl, alkenyl, or alkynyl having 1 to 50 carbon atoms, optionally substituted with deuterium or tritium;

Y is each independently sulfur or oxygen;

Z is each independently sulfur, oxygen or selenium;

R ₁ , and R _a1 to R _a12 each independently represent hydrogen; heavy hydrogen; Tritium; Or alkyl having 1 to 50 carbon atoms which is unsubstituted or substituted with hydrogen, deuterium or tritium, isoalkyl (branched alkyl), aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxyl , Nitro, amine, acyl, cycloalkene or cycloalkyne;

R ₂ is, each independently, selected from the group consisting of hydrogen, deuterium, alkyl having 1 to 50 carbon atoms optionally substituted with tritium, tricyclic alkyl, aryl, alkoxy, heteroaryl, alkene, , Cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne, and when R ₂ is one or more, the adjacent groups may fuse together to form a ring;

n is an integer from 1 to 10;

B is a spacer group, substituted or unsubstituted divalent hydrocarbons having at least two conjugated P-orbits;

C is an electron acceptor group;

m is an integer of 0 to 10;

The present invention also relates to a process for preparing a compound containing an electron donating group (A) by a Stille reaction or a Suzuki reaction in an organic solvent together with a compound containing a spacer group (B) or an electron donating group (C) Reacting a compound containing an electron donating group (A) with a compound including a spacer group (B) and a compound containing an electron donating group (C) in the order of a Stille reaction or a Suzuki reaction in an organic solvent . ≪ / RTI >

Further, the present invention provides a dye-sensitized photoelectric conversion device comprising oxide semiconductor microparticles in which the dye is supported.

The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.

The novel organic dyes of the present invention have a molar extinction coefficient significantly higher than that of conventional dyes and can be efficiently used as dyes for thin films by including the compound of formula 2 having an absorption wavelength in the wide area as an electron donor group, The efficiency of the solar cell can be greatly improved and the efficiency of the dye-sensitized solar cell can be maximized by applying it to various electrolytes having different energy levels.

In addition, the dye-sensitized photoelectric conversion device and the solar cell using the dye of the present invention can be produced by using a novel dye having a molar extinction coefficient, an open-circuit voltage and a photoelectric conversion efficiency significantly improved compared to conventional dyes, The efficiency of the solar cell is excellent even by the use of the semiconductor fine particles, the production of the solar cell device is facilitated, and the manufacturing cost of the solar cell can be remarkably reduced.

The dye of the present invention is represented by the following general formula (1) and is characterized by including a compound represented by the following general formula (2) as an electron donative group (A).

≪ Formula 1 >

In this formula,

A is an electron donor group which is at least one heteroaromatic group containing at least one heteroatom selected from nitrogen,

(2)

At this time,

X is each independently selected from the group consisting of sulfur; Oxygen; Hydrogen; heavy hydrogen; Tritium; Or alkyl, alkenyl, or alkynyl having 1 to 50 carbon atoms, optionally substituted with deuterium or tritium;

Y is each independently sulfur or oxygen;

Z is each independently sulfur, oxygen or selenium;

R ₁ , and R _a1 to R _a12 each independently represent hydrogen; heavy hydrogen; Tritium; Or alkyl having 1 to 50 carbon atoms which is unsubstituted or substituted with hydrogen, deuterium or tritium, isoalkyl (branched alkyl), aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxyl , Nitro, amine, acyl, cycloalkene or cycloalkyne;

R ₂ is, each independently, selected from the group consisting of hydrogen, deuterium, alkyl having 1 to 50 carbon atoms optionally substituted with tritium, tricyclic alkyl, aryl, alkoxy, heteroaryl, alkene, , Cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne, and when R ₂ is one or more, the adjacent groups may fuse together to form a ring;

n is an integer from 1 to 10;

B is a spacer group, substituted or unsubstituted divalent hydrocarbons having at least two conjugated P-orbits;

C is an electron acceptor group; Preferably at least one acidic hydrogen which is capable of hydrogen bonding;

m is an integer of 0 to 10;

In the present invention, the spacer group (B) may be at least one selected from the group consisting of the following structural formulas:

In this formula,

R ₃ to R ₈ are each independently selected from hydrogen, deuterium, tritium, or substituted or unsubstituted alkyl having 1 to 50 carbon atoms, isoalkyl (branched alkyl), aryl, alkoxy, heteroaryl, Wherein the hydrogen contained in the spacer group (B) is deuterium, tritium, or a substituted or unsubstituted 1 to 50 carbon atoms, (Branched alkyl), aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne .

In the present invention, the electron acceptor group (C) preferably includes at least one acidic hydrogen capable of hydrogen bonding, and may be at least one selected from the group consisting of the following structural formulas:

In this formula,

R ₉ is hydrogen, deuterium, tritium, or an optionally substituted 1-50 alkyl having a number of C, iso-alkyl (branched alkyl), aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano , Hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne.

The dye compound of formula (I) of the present invention may be represented by any one of the following formulas 1-1 to 1-51:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Chemical Formula 1-25]

[Chemical Formula 1-26]

[Chemical Formula 1-27]

[Chemical Formula 1-28]

[Chemical Formula 1-29]

[Chemical Formula 1-30]

[Chemical Formula 1-31]

(1-32)

[Chemical Formula 1-33]

[Chemical Formula 1-34]

[Chemical Formula 1-35]

[Chemical Formula 1-36]

[Chemical Formula 1-37]

[Chemical Formula 1-38]

[Chemical Formula 1-39]

[Chemical Formula 1-40]

[Chemical Formula 1-41]

[Chemical Formula 1-42]

[Chemical Formula 1-43]

[Chemical Formula 1-44]

[Chemical Formula 1-45]

[Chemical Formula 1-46]

[Chemical Formula 1-47]

[Chemical Formula 1-48]

[Chemical Formula 1-49]

[Chemical Formula 1-50]

[Formula 1-51]

The dye compound of the formula (1) of the present invention can contain the compound of the formula (2) having an absorption wavelength at the broad wavelength side as an electron donor compound to secure an improved molar extinction coefficient, an open circuit voltage and a photoelectric conversion efficiency.

The compound of formula (1) according to the present invention can be produced by reacting a compound containing an electron donating group (A) with a compound containing a spacer group (B) or an electron donating group (C) in a stille reaction or a Suzuki reaction Suzuki), or reacting a compound containing the electron donating group (A) with a compound containing the spacer group (B) and a compound containing the electron donating group (C) in the organic solvent in the order of a Stille reaction or a Suzuki Suzuki). When the terminal of the electron donor of the compound of formula (1) comprises cyanoacetic acid group, the reaction can be carried out in the presence of piperidine in CHCl ₃ or CH ₃ CN Lt; / RTI > with cyanoacetic acid in the presence of a base.

Further, the present invention provides a dye-sensitized photoelectric conversion element, wherein the dye-sensitized photoelectric conversion element is characterized in that the organic dye according to the present invention, preferably the organic dye represented by Formula 1, is supported on the oxide semiconductor fine particles . In addition to using the organic dye according to the present invention, the dye-sensitized photoelectric conversion device of the present invention can also be applied to methods for producing dye-sensitized photoelectric conversion devices for solar cells using conventional dyes. For example, The dye-sensitized photoelectric conversion device of the present invention can be applied to a thin film of an oxide semiconductor on a substrate using oxide semiconductor microparticles, And then the dye of the present invention is carried on the thin film.

The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element, wherein the dye-sensitized photoelectric conversion element using the oxide semiconductor fine particles carrying the organic dye represented by Formula 1 is used A conventional method for manufacturing a solar cell using a conventional photoelectric conversion element may be applied. For example, a method described in Korean Patent Publication No. 10-2009-38377 (filed by Dongjin Semichem Co., Ltd.) (Cathode), a counter electrode (anode), a redox electrolyte, a hole transporting material, a p-type semiconductor, or the like, which is formed by supporting the organic dye represented by Chemical Formula 1 on the oxide semiconductor fine particles Lt; / RTI >

Hereinafter, the present invention will be described in more detail with reference to examples. It is to be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example 1: Preparation of the compound of formula (1-1)

[Reaction Scheme 1]

<1-1> Preparation of Compound (1-1-1)

3,4-Ethylenedioxythiophene (10 g, 0.07 mol) was dissolved in THF, and 1.6 M n-BuLi (37 ml, 0.074 mol) was slowly added dropwise at -78 ° C and stirred at low temperature for 1 hour. 2-Ethylhexyl bromide (16.3 g, 0.84 mol) was slowly added dropwise thereto at -78 占 폚, and further stirred at room temperature for 6 hours. (20 ml), extracted with ether (10 ml) and then subjected to column purification using hexane to obtain 5- (2-ethylhexyl) -2,3-dihydrothieno [3,4-b] 4] dioxin (Compound 1-1-1) was synthesized.

&Lt; 1-2 > Preparation of Compound (1-1-2)

The compound 1-1-1 (5.7 g, 22.38 mmol) synthesized in the above step was dissolved in THF, and 1.6 M n-BuLi (15.4 ml, 24.65 mmol) was slowly added dropwise at -78 ° C. Respectively. Then, 1.0 M trimethyltin chloride (26.86 ml, 26.86 mol) was slowly added dropwise at -78 ° C, and the mixture was further stirred at room temperature for 6 hours. Brine (20 ml) was added thereto and extracted with ether (10 ml) 2,4-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) trimethylstannane .

&Lt; 1-3 > Preparation of compound of formula 1-1-3

The compound 1-1-2 (7.8 g, 18.7 mmol), tris (4-bromophenyl) amine (4.5 g, 9.35 mol) and tetrakis (triphenylphosphine) palladium mmol) were dissolved in anhydrous toluene (30 ml), and the reaction was carried out at 120 ° C under a nitrogen atmosphere for 8 hours. (20 ml), extracted with EA (10 ml) and subjected to column purification under MC / hexane to obtain 4-bromo-N, N-bis [4- (7- 3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) phenyl) aniline (Compound 1-1-3) was synthesized.

&Lt; 1-4 >

The compound 1-1-3 (2 g, 2.4 mmol) synthesized in the above step was dissolved in THF, and 1.6 M n-BuLi (1.7 ml, 2.7 mmol) was slowly added dropwise thereto at -78 ° C, followed by stirring at low temperature for 1 hour . 1.0 M trimethyltin chloride (2.7 ml, 2.7 mmol) was slowly added dropwise at -78 ° C, and the mixture was further stirred at room temperature for 6 hours. Brine (20 ml) was added thereto and extracted with ether (10 ml) ((4- (7- (2-ethylhexyl) -2,3-dihydrothieno [3,4-b] [1,4] dioxin- Phenyl) dimethylstannyl) methylium (Compound 1-1-4) was synthesized.

&Lt; 1-5 > Preparation of Compound (1-1-5)

(1 g, 1.1 mmol), 2-bromo-3-hexylthiophene (0.27 g, 1.1 mol) and tetrakis (triphenylphosphine) palladium (6.3 mg) Was dissolved in anhydrous toluene (5 ml), and the mixture was reacted at 120 ° C under a nitrogen atmosphere for 8 hours. (20 ml), extracted with EA (10 ml), and subjected to column purification under MC / hexane to obtain 4- (7- (2-ethylhexyl) -2,3-dihydrothieno [ b] [1,4] dioxin-5-yl) -N- (4- (7- (2-ethylhexyl) -2,3- dihydrothieno [ Dioxin-5-yl) phenyl) -N- (4- (3-hexylthiophen-2-yl) phenyl) aniline (Compound 1-1-5) was synthesized.

<1-6> Preparation of compound of formula 1-1-6

(0.5 g, 0.55 mmol) synthesized in the above step and DMF (0.51 ml) were added to 1,2-dichloroethane (3 ml) and stirred. Then, phosphorus oxychloride (0.06 ml , 0.66 mmol) was added dropwise thereto, followed by reaction at 80 ° C for 4 hours. A sodium acetate aqueous solution was added thereto and stirred. Then, the mixture was extracted with MC and subjected to column purification under MC / hexane to give 5- (4- (bis (4- (7- (2- ethylhexyl) -2,3-dihydrothiere (3,4-b] [1,4] dioxin-5-yl) phenyl) amino) phenyl) -4-hexylthiophene-2-carbaldehyde (Compound 1-1-6).

<1-7> Preparation of compound of formula 1-1

The compound 1-1-6 (0.3 g, 0.32 mmol) synthesized above, cyanoacetic acid (81 mg, 0.95 mmol) and piperidine (189 mg, 2.22 mmol) were dissolved in chloroform and refluxed for 4 hours Respectively. (20 ml) was added thereto, and the mixture was extracted with chloroform (10 ml) and subjected to column purification under chloroform / MeOH to obtain (E) -3- (5- (4- ) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) phenyl) amino) phenyl) -4-hexylthiophen- To obtain non-acrylic acid (Compound 1-1).

Example 2: Preparation of the compound of the formula 1-47

[Reaction Scheme 2]

<2-1> Preparation of the compound of the formula 1-47-1

3,4-Ethylenedioxythiophene (10 g, 0.07 mol) was dissolved in THF, and 1.6 M n-BuLi (37 ml, 0.074 mol) was slowly added dropwise at -78 ° C and stirred at low temperature for 1 hour. Sulfur (2.48 g, 9.7 mmol) was added thereto at -78 占 폚, and 2-ethylhexyl bromide (16.3 g, 0.84 mol) was slowly added dropwise thereto at -78 占 폚 and further stirred at room temperature for 6 hours. (20 ml) was added thereto, followed by extraction with ether (10 ml) and column purification using hexane to obtain 5- (2-ethylhexylthio) -2,3-dihydrothieno [3,4- b] [1 , 4] dioxin (Compound 1-47-1) was synthesized.

<2-2> Preparation of Compound 1-47-2

The compound 1-47-1 (8 g, 27.93 mmol) synthesized in the above step was dissolved in THF, and 1.6 M n-BuLi (19.2 ml, 30.72 mmol) was slowly added dropwise at -78 ° C. Respectively. 1.0 M trimethyltin chloride (30.72 ml, 30.72 mmol) was slowly added dropwise at -78 ° C, and the mixture was further stirred at room temperature for 6 hours. Brine (20 ml) was added thereto and extracted with ether (10 ml) Synthesis of 7- (2-ethylhexylthio) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) trimethylstannane (Compound 1-47-2) Respectively.

<2-3> Preparation of Compound 1-47-3

(8 g, 17.81 mmol), tris (4-bromophenyl) amine (4.3 g, 8.9 mmol) and tetrakis (triphenylphosphine) palladium (102.88 mg, 0.09 mmol) were dissolved in anhydrous toluene, and then reacted at 120 ° C for 8 hours in a nitrogen atmosphere. (20 ml), extracted with EA (10 ml), and subjected to column purification under MC / hexane to obtain 4-bromo-N, N-bis [4- (7- (2-ethylhexylthio) , 3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) phenyl) aniline (Compound 1-47-3) was synthesized.

&Lt; 2-4 > Preparation of compound 1-47-4

The compound 1-47-3 (3 g, 3.36 mmol) synthesized in the above step was dissolved in THF, and 1.6 M n-BuLi (2.31 ml, 3.7 mmol) was slowly added dropwise at -78 ° C. and the mixture was stirred at low temperature for 1 hour . 1.0 M trimethyltin chloride (3.7 ml, 3.7 mmol) was slowly added dropwise thereto at -78 ° C, and the mixture was further stirred at room temperature for 6 hours. Brine (20 ml) was added thereto and extracted with ether (10 ml) Dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -N- (4- (7- ( 4-dioxin-5-yl) phenyl) -N- (4- (trimethylstannyl) phenyl) aniline (Compound 1-47-4) was synthesized.

&Lt; 2-5 > Preparation of compound of formula 1-47-5

(1 g, 1.02 mmol), 5'-bromo-2,2'-bithiophene-5-carbaldehyde (280 mg, 1.02 mmol) synthesized in the above step and tetrakis Phosphine) palladium (6 mg) were placed in a reactor and dissolved in anhydrous toluene (3 ml), followed by reaction at 120 ° C under a nitrogen atmosphere for 8 hours. (20 ml) was added thereto, and the mixture was extracted with EA (10 ml) and subjected to column purification under MC / hexane to obtain 5 '- (4- (bis (4- (7- (2-ethylhexylthio) -Dihydrothieno [3,4-b] [1,4] dioxin-5-yl) phenyl) amino) phenyl) -2,2'-bithiophene-5-carbaldehyde (Compound 1-47-5 ) Were synthesized.

&Lt; 2-6 >

The compound 1-47-5 (0.3 g, 0.3 mmol), cyanoacetic acid (76 mg, 0.9 mmol) and piperidine (178.8 mg, 2.1 mmol) were dissolved in chloroform (3 ml) Was stirred while refluxing. (20 ml) was added thereto, and the mixture was extracted with chloroform (10 ml) and subjected to column purification under chloroform / MeOH to obtain (E) -3- (5- (4- Dihydrothieno [3,4-b] [1,4] dioxin-5-yl) phenyl) amino) phenyl) -2,2'- 2-cyanoacrylic acid (Compound 1-47) was obtained.

Example 3: Preparation of the compound of the formula 1-48

[Reaction Scheme 3]

&Lt; 3-1 > Preparation of the compound of the formula 1-48-1

Compound 1-47-3 synthesized in the above step was dissolved in toluene, and then 2- (3,4'-dihexyl- [2,2 '] bithiophenyl-5-yl-4,4,5,5- (30 ml) was added and extracted with EA (50 ml). After silica column, [4- (3,4 ', 5'- Yl) -phenyl] -bis- {4- [7 [(1-ethyl-hexylsulfanyl) -2,3-dihydro-cyanomethyl- 3,4-b] [1,4] dioxin-5-yl] -phenyl} -amine (compound 1-48-1).

&Lt; 3-2 > Preparation of compound of formula 1-48-2

The compound 1-48-1 synthesized in the above step was dissolved in DMF, and phosphoryl chloride was added thereto to synthesize it using a bis-Mayer reaction. Sodium acetate aqueous solution (30 ml) was added, and the mixture was extracted with MC (50 ml). After silica column chromatography, 5 '- [4- (bis- {4- [7- (1-ethylhexylsulfonyl) -Cyano [3,4-b] [1,4] dioxin-5-yl] -phenyl} -amino) -phenyl] -4,3'-dihexyl- [2,2 '] bithiophenyl -5-carbaldehyde (compound 1-48-2).

&Lt; 3-3 >

Compound 1-48-2 synthesized in the above step was dissolved in chloroform and then reacted with cyanoacetic acid in the presence of piperidine to obtain 4- {5 '- [4- (bis- {4- [7- 3,4-b] [1,4] dioxin-5-yl] -phenyl} - amino) -phenyl] -4,3'-dihexyl- [2,2 '] bithiophenyl-5-yl} -2-ceno-but-3-enoic acid (Compound 1-48) was synthesized.

Example 4: Preparation of the compound of the formula 1-49

[Reaction Scheme 4]

&Lt; 4-1 > Preparation of the compound of the formula 1-49-1

Compound 1-1-3 synthesized in the above step was dissolved in toluene, and then 2- (3,4'-dihexyl- [2,2 '] bithiophenyl-5-yl) -4,4,5,5 - tetramethyl [1,3,2] dioxaborolane was synthesized by Suzuki reaction. Salt (30 ml) was added and extracted with EA (50 ml). After silica column, Compound 1-49-1 was synthesized.

&Lt; 4-2 > Preparation of Compound 1-49-2 Compound

The compound 1-49-1 synthesized in the above step was dissolved in DMF, and then phosphoryl chloride was added thereto to synthesize it using a bis-mer reaction. A sodium acetate aqueous solution (30 ml) was added and extracted with MC (50 ml). After silica column, Compound 1-49-2 was synthesized.

&Lt; 4-3 >

The compound 1-49-2 synthesized in the above step was dissolved in chloroform and reacted with cyanoacetic acid in the presence of piperidine, and the compound 1-49 was synthesized in accordance with the method described in Example 1-1.

Example 5: Preparation of the compound of the formula 1-22

[Reaction Scheme 5]

Compound 1-22 was synthesized by following the synthesis method described in Example 1 in accordance with Reaction Scheme 5 above.

Example 6: Preparation of the compound of the formula 1-6

[Reaction Scheme 6]

Compound 1-6 was synthesized by using the synthetic method described in Example 1 in accordance with Reaction Scheme 6 above.

Example 7: Preparation of the compound of the formula 1-50

[Reaction Scheme 7]

Compounds of the formula 1-50 were synthesized in accordance with the above-described Scheme 7 using the methods described in Example 1 and Example 2, respectively.

Example 8: Preparation of the compound of the formula 1-51

[Reaction Scheme 8]

The compound of the formula 1-51 was synthesized according to the method of Examples 1 and 2 in accordance with the above-mentioned Reaction Scheme 8.

Manufacture of dye-sensitized solar cell

In order to evaluate the current-voltage characteristics of the dye according to the present invention, a dye-sensitized solar cell was fabricated using a 13 + 10 탆 TiO ₂ transparent layer.

Specifically, the washed FTO (Pilkington, 8 Ωsq-1 ) the glass substrate was immersed in 40 mM aqueous solution of TiCl _4. TiO ₂ paste (Solaronix, 13 nm anatase) a screen-printed by 13 ㎛ thickness of Claim 1 TiO preparing the _second layer, and the other paste for the light scattering (CCIC, HWP-400) of claim 2, TiO of 10 ㎛ thickness of ₂ scattering layer . The prepared TiO ₂ electrode was dissolved in a solution of the dye according to the present invention (0.3 mM each of the compounds 1-3 prepared in Example 1-3) in ethanol containing 10 mM of 3a, 7a-dihydroxy-5b-cholic acid ), And then allowed to stand at room temperature for 18 hours. A counter electrode was prepared by coating a solution of H ₂ PtCl ₆ (containing 2 mg of Pt in 1 mL of ethanol) on the FTO substrate. Then, an electrolyte in which 0.6 M 3-hexyl-1,2-dimethylimidazolium iodide, 0.04 MI ₂ , 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert -butylpyridine were dissolved in acetonitrile was used as a battery To prepare a dye-sensitized solar cell. The photovoltaic performance of the dye-sensitized solar cell was measured using a 1000 W xenon light source, and the results are shown in Table 1 below.

division Efficiency (?) (%) Compound 1 5.02 Compound 47 6.01 Compound 48 6.52 Compound 49 7.22 Compound 22 5.22 Compound 6 4.72 Compound 50 6.11 Compound 51 6.65

As shown in Table 1, the novel dyes of the present invention exhibited excellent photoelectric conversion efficiency. Therefore, the novel dye compound of the present invention can greatly improve the efficiency of a solar cell, and can be refined without using an expensive column, thereby dramatically lowering the dye synthesis cost.

Claims (8)

An organic dye represented by the following formula (1):
[Chemical Formula 1]

In this formula,
A is an electron donor group and is a compound of the formula:
(2)

At this time,
X is each independently selected from the group consisting of sulfur; Oxygen; Hydrogen; heavy hydrogen; Tritium; Or alkyl, alkenyl or alkynyl having 1 to 50 carbon atoms which is unsubstituted or substituted by deuterium or tritium;
Y is each independently sulfur or oxygen;
Z is each independently sulfur, oxygen or selenium;
R ₁ , and R _a1 to R _a12 each independently represent hydrogen; heavy hydrogen; Tritium; Or alkyl having 1 to 50 carbon atoms which is unsubstituted or substituted with hydrogen, deuterium or tritium, isoalkyl (branched alkyl), aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxyl , Nitro, amine, acyl, cycloalkene or cycloalkyne;
R ₂ is, each independently, selected from the group consisting of hydrogen, deuterium, alkyl having 1 to 50 carbon atoms optionally substituted with tritium, tricyclic alkyl, aryl, alkoxy, heteroaryl, alkene, , Cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne, and when R ₂ is one or more, the adjacent groups may fuse together to form a ring;
n is an integer from 1 to 10;
B is a spacer group, substituted or unsubstituted divalent hydrocarbons having at least two conjugated P-orbits;
C is an electron acceptor group;
m is an integer of 0 to 10; The method according to claim 1,
Wherein B is at least one selected from the group consisting of the following structural formulas:

In the above,
R ₃ to R ₈ are each independently selected from hydrogen, deuterium, tritium, or substituted or unsubstituted alkyl having 1 to 50 carbon atoms, isoalkyl (branched alkyl), aryl, alkoxy, heteroaryl, Wherein the hydrogen included in B is selected from the group consisting of deuterium, tritium, or a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms Alkyl, arylalkyl, alkoxy, heteroaryl, alkenyl, alkynyl, siloxy, cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne. The method according to claim 1,
Wherein said C contains at least one acidic hydrogen capable of hydrogen bonding. The method according to claim 1,
Wherein said C is at least one selected from the group consisting of the following structural formulas:

In this formula,
R ₉ is hydrogen, deuterium, tritium, or an optionally substituted 1-50 alkyl having a number of C, iso-alkyl (branched alkyl), aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano , Hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne. The method according to claim 1,
The organic dye according to claim 1, wherein the compound represented by the formula (1) is represented by any one of the following formulas (1-1) to (1-47)
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Chemical Formula 1-14]

[Chemical Formula 1-15]

[Chemical Formula 1-16]

[Formula 1-17]

[Chemical Formula 1-18]

[Chemical Formula 1-19]

[Chemical Formula 1-20]

[Formula 1-21]

[Formula 1-22]

[Formula 1-23]

[Formula 1-24]

[Chemical Formula 1-25]

[Chemical Formula 1-26]

[Chemical Formula 1-27]

[Chemical Formula 1-28]

[Chemical Formula 1-29]

[Chemical Formula 1-30]

[Chemical Formula 1-31]

(1-32)

[Chemical Formula 1-33]

[Chemical Formula 1-34]

[Chemical Formula 1-35]

[Chemical Formula 1-36]

[Chemical Formula 1-37]

[Chemical Formula 1-38]

[Chemical Formula 1-39]

[Chemical Formula 1-40]

[Chemical Formula 1-41]

[Chemical Formula 1-42]

[Chemical Formula 1-43]

[Chemical Formula 1-44]

[Chemical Formula 1-45]

[Chemical Formula 1-46]

[Chemical Formula 1-47]

[Chemical Formula 1-48]

[Chemical Formula 1-49]

[Chemical Formula 1-50]

[Formula 1-51]

A compound containing an electron donating group (A) is subjected to a Stille reaction or a Suzuki reaction in an organic solvent together with a compound containing a spacer group (B) or an electron donating group (C) A) is reacted with a compound including the spacer group (B) and a compound including the electron donating group (C) in the order of a Stille reaction or a Suzuki reaction in an organic solvent (1). &Lt; / RTI &gt; A dye-sensitized photoelectric conversion element comprising the oxide semiconductor fine particles carrying the organic dye of claim 1. A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of claim 7.