KR101457105B1 - Dye compond for dye sensitized sola cell and sola cell comprising it - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic dye compound and a dye-sensitized solar cell including the organic dye compound, and more particularly, to an organic dye compound having improved photoelectric conversion efficiency and a dye-sensitized solar cell comprising the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a dye-sensitized solar cell and a dye-sensitized solar cell including the dye-

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic dye compound and a dye-sensitized solar cell including the organic dye compound, and more particularly, to an organic dye compound having improved photoelectric conversion efficiency and a dye-sensitized solar cell comprising the same.

A solar cell is a device that converts light energy into electric energy by using photovoltaic effect. Unlike other energy sources, it is an energy source that is infinite in resources and environmentally friendly. It is a silicon solar cell, a dye sensitized solar cell It is known.

Silicon solar cells are difficult to put into practical use because they are expensive to manufacture, and there are many difficulties in improving efficiency. On the other hand, the dye-sensitized solar cell has a possibility to replace the conventional amorphous silicon solar cell because the manufacturing cost is significantly lower than that of the conventional silicon solar cell. The dye-sensitized solar cell is a mechanism for generating electron-hole pairs by absorbing light energy of a visible light ray. The dye-sensitized solar cell is composed of a photo-electrochemical solar cell comprising a photosensitive dye molecule and a transition metal oxide Battery.

Currently, ruthenium metal dyes are known as practical dyes for dye-sensitized solar cells. These ruthenium dyes are problematic not only in terms of expensive production cost, low absorption coefficient, but also in environmental friendliness. Recently, researches on the development of organic dyes which do not use metals have been focused on to solve these problems.

In general, organic dyes that do not use metal complexes are synthesized with a structure in which an electron donor and an electron acceptor are connected by a π-bond. At this time, aromatic amine derivatives are used as the electron donor, 2-cyanoacrylic acid is the most used as the electron acceptor, thiophene or phenyl group is used as the? -Conjugate and long or short wavelength The spectrum can be adjusted.

In general, organic dyes have much room for improvement due to low light conversion efficiency, chemical instability, lack of adsorption with metal oxides, etc., compared with ruthenium metal dyes. Therefore, it is necessary to develop cheap organic dyes which can replace ruthenium metal dyes.

Therefore, in order to solve the problems of the prior art, the present invention provides a method of preventing the open-circuit voltage from being caused by ions in the electrolyte by introducing a substituent capable of preventing recombination between the electron donor and the electrolyte in the compound, An organic dye compound having improved photoelectric conversion efficiency, and a dye-sensitized solar cell comprising the same.

According to an aspect of the present invention, there is provided an organic dye compound represented by Formula 1 below.

≪ Formula 1 >

Another aspect of the present invention provides an organic dye-sensitized solar cell comprising the organic dye represented by Formula 1 above.

According to the present invention, by introducing a substituent having a role of preventing recombination between the electron donor and the electrolyte in the molecule, it is possible to prevent the decrease in open-circuit voltage (Voc) due to ions in the electrolyte and to increase the electron flowability to maximize the photoelectric conversion efficiency have.

1 is a diagram illustrating a schematic structure of a dye-sensitized solar cell.
2 is a graph showing a light absorption spectrum of a dye containing a compound according to an embodiment of the present invention.
3 is a graph showing current-voltage characteristics of a dye-sensitized solar cell including a compound according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to facilitate a person skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

The term " halo "or" halogen "as used herein, on the other hand, includes fluorine, chlorine, bromine, and iodine unless otherwise specified.

The term "alkyl" or "alkyl group ", as used herein, unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

The term "alkenyl" or "alkynyl ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms,

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term "alkoxy group" as used in the present invention has, unless otherwise stated, 1 to 60 carbon atoms, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto.

In the present invention, an aryl group or an arylene group means an aromatic group of a single ring or plural rings, and an adjacent ring includes an aromatic ring formed by bonding or participating in a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 3 to 60 carbon atoms each containing at least one heteroatom, And includes plural rings as well as a single ring, and may be formed by bonding adjacent groups.

The term " heterocycloalkyl ", "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, , And neighboring groups may be combined with each other. Furthermore, the "heterocyclic group" may mean an alicyclic group and / or an aromatic group including a hetero atom.

As used herein, the term "heteroatom " refers to N, O, S, P and Si, unless otherwise indicated.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise indicated, the term "saturated or unsaturated ring" as used herein refers to a saturated or unsaturated aliphatic ring or an aromatic ring or hetero ring having 6 to 60 carbon atoms.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention alkoxy group, C ₁ ~ C ₂₀ alkyl amine group of _20, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron of Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, a germanium group, and a C ₅ to C ₂₀ heterocyclic group, and is not limited to these substituents.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an exemplary diagram showing a schematic structure of a dye-sensitized solar cell. FIG.

In general, the dye-sensitized solar cell 100 includes a transparent substrate 110, a transparent electrode 120, nanoparticles 130, a dye 140, an electrolyte, and a counter electrode 150.

That is, the dye-sensitized solar cell 100 comprises nanoparticles (generally, titanium oxide is used) 130 which absorbs light, which absorbs light, which generates electrons, an electrolyte, and a counter electrode 150, do.

At this time, the dye (140) is a material directly participating in photoelectron generation. It is advantageous that the absorption occurs over the entire visible light region and the light absorption coefficient is large. Dye (140) The thickness of the polymer coating layer is preferably a single molecule, and when two or more molecules are accumulated, the efficiency of the polymer coating layer may be deteriorated due to interference of electrons.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited by the following examples.

A compound according to one aspect of the present invention comprises:

In the above formula, X is a single bond, sulfur (S) or oxygen (O), and n is 0 or 1.

When n = 0, X is absent, and the formula (1) may be represented by the following formula (2).

On the other hand, when n is 1 and X is a single bond, it can be represented by the following chemical formula 3, and when X is S (sulfur), when X is O (oxygen) 5 < / RTI >

In the above Chemical Formulas 1 to 5, R ₁ is a C ₁ to C ₂₀ alkylene group, p is an integer of 1 to 3, and R ₂ is a C ₁ to C ₂₀ alkyl group. For example, when R ₁ is an ethylene group, p is 3, and R ₂ is a methyl group, the formula (1) may be represented by the following formula (6).

In the above formulas (1) to (6), L ₁ , L ₂ and L ₃ independently represent a single bond; A substituted or unsubstituted C ₆ -C ₆₀ arylene group; A substituted or unsubstituted fluorenylene group; A heterocyclic group of the substituted or unsubstituted C ₂ ~ C _60; A substituted or unsubstituted C ₁ to C ₂₀ alkylene group; A substituted or unsubstituted C ₁ -C ₂₀ alkenylene group; An amine group substituted with an aryl group having ₆ to ₂₀ carbon atoms and / or a heterocyclic group having ₂ to ₂₀ carbon atoms.

Illustratively, L ₁ , L ₂ and L ₃ independently of one another are selected from the group consisting of phenylene, naphthylene, divalent biphenyl, bivalent terphenyl, bivalent anthracene, divalent phenanthrene, phenylene (Phenol), a fluorenylene group, a divalent alkyl or arylthiophene, a divalent furan, a divalent pyrrole, a divalent diarylamine, a divalent indole, a divalent indoline and a divalent carbazole . Each of which may be further substituted with a vinyl group, a polyvinyl group or an acetyl group.

That is, when L ₁ , L ₂ and L ₃ are an arylene group or a fluorenylene group,

,

And the like,

When L ₁ , L ₂ and L ₃ are heterocyclic groups,

And the like,

When L ₁ , L ₂ and L ₃ are amine groups,

Lt; / RTI >

On the other hand, phenylene, biphenylene, terphenylene and the like may be represented by the following general formula.

In the above formula, m is an integer of 1 to 3.

When L &_lt; _{1 >} , L &_lt; _{2 >} and L < ₃ &_gt; are arylene groups, they may be substituted with other substituents and more particularly substituted with alkenyl groups or alkenylene groups. For example, L < _{1 &} gt ;, L &_lt; ₂ >, and L < ₃ >

In the above formula, m is an integer of 1 to 3, and when m = 1, it may be represented by the following formula a, and when m = 2, it may be represented by the following formula b.

(Formula a) < Formula b >

When L ₁ , L ₂ and L ₃ are heterocyclic groups, it may be one of the following heterocyclic compounds.

In the above formulas, R ₃ is a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and m is an integer of 1 to 3.

In the formulas (1) to (6), Ar ₁ and Ar ₂ independently represent a substituted or unsubstituted C ₁ to C ₃₀ alkyl group; Alkenyl group of a substituted or unsubstituted C ₂ ~ C _30; A substituted or unsubstituted C ₆ -C ₆₀ aryl group; A heterocyclic group of the substituted or unsubstituted C ₂ ~ C _60; And a substituted or unsubstituted amine group substituted with a C ₆ to C ₃₀ aryl group or a C ₆ to C ₃₀ heterocyclic group, provided that each of these includes an acid group capable of hydrogen bonding .

Illustratively, Ar ₁ and Ar ₂ may comprise (or substitute) a carboxyl group (-COOH), wherein Ar ₁ and Ar ₂ are substituted or unsubstituted 2-cyanoacrylic acid, substituted or unsubstituted rhodanine- 3-acetic acid, and substituted or unsubstituted 5-oxo-1-phenyl-2-pyrazole-1-acetic acid. That is, Ar ₁ and Ar ₂ may be one selected from the following groups.

In the above formula (1), when L ₃ is a phenyl group, R ₁ is C ₂ H ₄ , p is 3, and R ₂ is CH ₃ , it may be represented by one of the following formulas.

         &Lt; Formula 1-1 &gt; > < EMI ID =

,

           <Formula 3-1> Formula 4-1>

,

           <Formula 5-1>

Specifically, formula (1) may be one of the following compounds.

In another aspect, the present invention may be a dye-sensitized solar cell comprising a first electrode, a second electrode, and a dye layer formed between the first electrode and the second electrode, wherein the dye layer is represented by Formula 1 &Lt; / RTI &gt;

Synthetic example

Hereinafter, the synthesis example of the compound of formula (1) of the present invention will be described. The following synthesis examples are merely illustrative, and can be prepared by various methods other than the following methods.

Product  Synthesis method

The compounds according to the present invention can be synthesized by way of illustrative examples.

(1) Sub 1 Preparation: (10- (4- {2- [ 2- (2- Methoxy - ethoxy) - ethoxy] - ethoxy} -phenyl) -10H-phenothiazine (

)

<Reaction Scheme 1>

phenothiazine (3.29 g, 13.75 mmol), 1-Bromo-4- {2- [2- (2- methoxy-ethoxy) -ethoxy] -ethoxy} -benzene (3 g, 16.5 mmol) and sodium tert- , 5.5 mmol) are dissolved in 100 mL of toluene. tri-tert butyl phosphine (8 g, 20.63 mmol) and Pd ₂ (dba) ₃ (0.5 g, 0.55 mmol) were added and sufficiently dissolved at room temperature under nitrogen atmosphere. When the reaction is complete, work-up is carried out with a 1: 1 mixture of water and CHCl ₃ . The work-up organic layer is separated by extraction and the solvent is removed under reduced pressure. After removing the solvent, a light yellow solid product (2.2 g, 48%) was obtained through recrystallization several times with methanol.

The chemical properties of the obtained compound are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.40-7.26 (m, 4H), 7.01-6.99 (d, J = 6.9Hz, 2H), 6.83 (m, 4H), 6.19 (m, 2H), 3.64- 3.62 (m, 15 H)

Since Scheme 1 is based on Buchwald-Hartwig Crossoupling, Even if 10 H -phenoazine is used instead of phenothiazine, the reaction scheme can be proceeded by the same reaction mechanism. That is, even if X is O instead of S, or a single bond or absent, the reaction will proceed by the same mechanism as the above reaction formula. (CH ₂ -CH ₂ -) - ₃ - as defined in Chemical Formula 1 instead of the reactant 1-Bromo-4- {2- [2- (2-methoxy-ethoxy) O-CH ₃ Instead, even if the compound represented by the general formula? - (R ₁ O) -R ₂ is bonded to phenyl, it does not affect the progress of the reaction.

(2) Sub 2 Preparation: 3,7- Dibromo -10- (4- {2- [2- (2- methoxy - ethoxy) - ethoxy] - ethoxy} - phenyl) -10H- phenothiazine (

)

<Reaction Scheme 2>

10- (4- {2- [2- (2-Methoxy-ethoxy) -ethoxy] -ethoxy} -phenyl) -10H-phenothiazine Was dissolved in acetic acid (10 mL), bromine (1.91 g, 12 mmol) was slowly added dropwise at 0 ° C, and the mixture was stirred for 12 hours. When the reaction is complete, titrate with saturated aqueous sodium hydroxide. After the titration is complete, work-up is carried out with a 1: 1 mixture of water and CHCl ₃ . The work-up organic layer is separated by extraction and the solvent is removed under reduced pressure. After removal of the solvent, red solid product (1.5 g, 63.6%) was obtained through several recrystallization steps using methanol and CH2Cl2.

The chemical properties of the obtained compound are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.50-7.18 (d, J = 7.8Hz, 2H), 7.33-7.27 (m, 4H), 7.11-7.07 (dd, J = 2.1Hz, 2H), 6.0 ( d, J = 8.7 Hz, 2H), 3.64-3.62 (m, 15H)

(3) Sub 3 Preparation: 10- (4- {2- [2- (2- Methoxy - ethoxy) - ethoxy] - ethoxy} - phenyl) -3,7- di - thiophen -2- yl -10H- phenothiazine (

)

<Reaction Scheme 3>

3,7-Dibromo-10- (4- {2- [2- (2-methoxy-ethoxy) -ethoxy] -ethoxy} -phenyl) -10H-phenothiazine (0.05 g, 2.1 mmol), Tributyl-thiophene-2-yl-stannane (2.03 g, 5.4 mmol) and PdCl ₂ (PPh ₃ ) ₂ (0.1 g, 0.13 mmol) were dissolved in 50 mL of dried THF Stir for 24 hours while refluxing. When the reaction is complete, work-up is carried out with a 1: 1 mixture of water and CHCl ₃ . The work-up organic layer is separated by extraction and the solvent is removed under reduced pressure. After removing the solvent, yellow solid product (0.75 g, 81.5%) was obtained by silicagel column chromatography (CHCl ₃ : hexane, 1: 3).

The chemical properties of the obtained compound are as follows.

¹ H NMR (300 MHz, CDCl 3):? 7.54-7.47 (dd, J = 8.1 Hz, 4H), 7.40-7.32 J = 3.9 Hz, 2H), 6.14-6.11 (d, J = 8.7 Hz, 2H), 3.64-3.62 (m,

Scheme 3 is based on the SUZUKI CROSS-COUPLING reaction, In the case of tributyl-thiophene-2-yl-stannane in which other heterocyclic compounds or aromatic hydrocarbons are bonded instead of thiophene, the above reaction scheme will proceed by the same mechanism. Therefore, arylene or a heterocyclic group may be present at the positions L1 and L2 in the general formula (1).

(4) Sub 4 Preparation: 5- (10- (4- (2- (2- (2- methoxyethoxy) ethoxy) ethoxy) phenyl) -3- (5- formylthiophen -2- yl) -10 H - phenothiazin -7- yl ) thiophene -2- carbaldehyde (

)

<Reaction Scheme 4>

10-phenothiazine (0.72 g, 1.6 mmol) was added to a solution of 10- (4- {2- [2- (2-Methoxy-ethoxy) -ethoxy] Was dissolved in 15 mL of 1,2-dichloro-ethane, DMF (0.3 g, 4.09 mmol) was added, phosphorus oxychloride (0.62 g, 4.09 mmol) was slowly added dropwise at 0 ° C. and refluxed for 8 hours. When the reaction is complete, work-up is carried out with a 1: 1 mixture of water and CHCl ₃ . The work-up organic layer is separated by extraction and the solvent is removed under reduced pressure. After removing the solvent, an orange solid product (0.5 g, 63.2%) was obtained by silicagel column chromatography (ethyl acetate: hexane, 1: 3)

The chemical properties of the obtained compound are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 9.88 (s, 2H), 7.44 (m, 2H), 7.34 (m, 4H), 7.19-7.17 (m, 6H), 5.93-5.90 (d, J = 8.4 Hz, 2H), 3.64-3.62 (m, 15H)

(5) Product Synthesis Example : Synthesis of Compound 7 (

)

<Reaction Scheme 5>

10- (4- {2- [2- (2-Methoxy-ethoxy) -ethoxy] -ethoxy} -phenyl) -3,7-dithiophen-2-yl-10H-phenothiazine-2- carbaldehyde , 0.807 mmol), 2-cyanoacrylic acid (0.34 g, 3.99 mmol) and piperidine were dissolved in 20 mL of acetonitrile and refluxed for 6 hours. After completion of the reaction, the solid produced in the reactor was filtered to obtain a dark red solid product (0.45 g, 88.5%).

The chemical properties of the obtained compound are as follows.

^{1 H NMR (300MHz, DMSO)} : δ 8.41 (s, 2H), 8.23 (s, 2H), 7.84 (m, 2H), 7.58 (d, J = 3.9Hz, 2H), 7.55-7.48 (dd, J J = 7.8 Hz, 2H), 3.64-3.62 (d, J = (m, 15H)

The dye-sensitized solar cell was prepared using the compound of the present invention prepared by the above Synthesis Example, and the electrochemical characteristics of the produced solar cell were described.

Manufacture of dye-sensitized solar cell

First, a conductive glass substrate (FTO: TEC 8, Pilkington, 8 Ω cm 2, Thickness of 2.3 mm) was washed with ethanol using an ultrasonic wave and then commercialized TiO ₂ paste (20 nm, solarnonix) A TiO ₂ paste prepared in advance on a glass substrate was coated and baked at 500 ° C for 30 minutes. The thickness of the fired TiO ₂ paste layer was measured by Alpha-step IQ surface profiler (KLA Tencor). In order to use another TiO ₂ paste as a scattering layer, the calcined layer was re-coated with TiO ₂ particles having a size of 250 nm and then calcined at 500 ° C for 30 minutes. The prepared TiO ₂ film was immersed in 0.04 M TiCl ₄ aqueous solution at 70 ° C for 30 minutes.

Next, for the dye adsorption, the annealed TiO ₂ electrode was immersed in a 0.3 mM dye solution for 3 hours at 50 ° C., and then the thin film formed from the 0.7 mM H ₂ PtCl ₆ solution dissolved in 2-propanol was heated at 400 ° C. for 20 minutes The Pt counter electrode was prepared through the thermal reduction of the Pt electrode. The dye-adsorbed TiO ₂ electrode and the Pt counter electrode were assembled using 60 μm-thick Surlyn (Dupont 1702) as a binder. A liquid electrolyte was introduced through the perforation holes on the opposite electrode. Electrolyte was prepared by dissolving 3-propyl-1-methyl-imidazolium iodide (PMII, 0.7M), lithium iodide (LiI, 0.2M), iodine dissolved in acetonitrile / valeronitrile (85:15) (I ₂ , 0.05M) and t-butylpyridine (TBP, 0.5M).

The device characteristics of the thus fabricated dye-sensitized solar cell were measured and the results are shown in Table 1 below. The electric characteristic measurement condition using the solar simulator used for the measurement of the embodiment of the present invention is AM 1.5 (1 sun, 100 mW / cm ² ).

Dye Voc  (V) Jsc  ( mAcm ^-2 ) FF  (%) 侶 (%) (7) Example ) 0.649 18.09 68.17 8.01 N719 0.723 16.54 69.15 8.26

In Table 1, N719 is a ruthenium-based dye used in a conventional dye-sensitized solar cell, and has the following structure.

In Table 1, Jsc is short-circuit photocurrent density, Voc is opencircuit photovoltage, ff is a fill factor, and? Indicates the total photoconversion efficiency. At this time, the performance of the dye-sensitized solar cell was measured with a working area of 0.24 cm ² .

As shown in Table 1, it was confirmed that the solar cell using the compound according to the present invention as a dye can obtain high photoelectric conversion efficiency similar to that of the conventional ruthenium-based dye.

The characteristics of the present invention can be seen from FIG. 2 and FIG.

FIG. 2 is a graph showing a light absorption spectrum of a dye containing a compound according to an embodiment of the present invention, and FIG. 3 is a graph showing a current-voltage characteristic of a dye- Fig. 2 and 3, &quot; 7 &quot; represents a compound represented by the formula (7) of the present invention.

The compound of the present invention has a structure in which an O- (R ₁ O) pR ₂ group and an acid group capable of hydrogen bonding are introduced into a molecule to surround Li ⁺ ions in the electrolyte, thereby increasing the open- The short circuit current can be increased to obtain a high photoelectric conversion efficiency, which is also apparent from the graph of FIG.

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.

100: dye-sensitized solar cell 110: transparent substrate
120: transparent electrode 130: nanoparticle
140: dye 150: counter electrode

Claims (8)

An organic dye compound for a dye-sensitized solar cell represented by the following Formula 1:
&Lt; Formula 1 >

In the above formulas,
X is a single bond, sulfur (S) or oxygen (O), n is 0 or 1,
R ₁ is a C ₁ to C ₂₀ alkylene group, p is an integer of 1 to 3, R ₂ is a C ₁ to C ₂₀ alkyl group,
L ₁ , L ₂ and L ₃ independently of one another are a single bond; A substituted or unsubstituted C ₆ -C ₆₀ arylene group; A substituted or unsubstituted fluorenylene group; A heterocyclic group of the substituted or unsubstituted C ₂ ~ C _60; A substituted or unsubstituted C ₁ to C ₂₀ alkylene group; A substituted or unsubstituted C ₁ -C ₂₀ alkenylene group; Is selected from the group consisting of; an amine group substituted with a heterocyclic group of C ₆ ~ C ₂₀ aryl group or a C ₂ ~ C ₂₀ of
Ar ₁ and Ar ₂ are, independently of each other, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group; Alkenyl group of a substituted or unsubstituted C ₂ ~ C _30; A substituted or unsubstituted C ₆ -C ₆₀ aryl group; A heterocyclic group of the substituted or unsubstituted C ₂ ~ C _60; And a substituted or unsubstituted amine group substituted with a C ₆ to C ₃₀ aryl group or a C ₆ to C ₃₀ heterocyclic group, provided that each of these includes an acid group capable of hydrogen bonding ,
The alkyl, alkenyl, aryl and heterocyclic groups of L ₁ , L ₂ and L ₃ of an arylene group, a fluorenylene group, a heterocyclic group, an alkylene group, an alkenylene group, Ar ₁ and Ar ₂ may be deuterium, , an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, a C ₆ ~ of aryl T of C ₂₀ thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ aryl group of C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ of, the C ₆ substituted with deuterium ~ C ₂₀ aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron group, may be substituted with one or more substituents selected from a germanium group, and the group consisting of C ₅ ~ group heterocyclic C ₂₀ . The method according to claim 1,
The organic dye compound for a dye-sensitized solar cell according to claim 1,
&Lt; Formula 2 >< EMI ID =

,

&Lt; Formula 4 &gt;&lt; EMI ID =

,

&Lt; Formula 1-1 >< Formula 1-1 >

,

(2-1) < Formula (3-1) &gt;

,

&Lt; Formula 4-1 &gt;&lt; EMI ID =
,

,

In the above formulas, X, L ₁ , L ₂ , L ₃ , Ar ₁ , Ar ₂ and n are as defined in claim 1. The method according to claim 1,
L ₁ , L ₂ and L ₃ are one of the following compounds:

,

,

,

In the above compounds, R ₃ is an alkyl group of a substituted or unsubstituted C ₁ ~ C _20, m is an integer from 1 to 3, R ₃ alkyl group is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ of alkoxy group the alkyl group of _{C 20, C 1 ~ C 20} , C 1 ~ C 20 alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C _A C ₂ to C ₂₀ alkynyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₆ to C ₆₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ An arylalkenyl group of ₁ to ₂₀ carbon atoms, a silane group, a boron group, a germanium group, and a C5 to C20 heterocyclic group. The method of claim 3,
L ₁ , L ₂ and L ₃ are A vinyl group, a polyvinyl group, or an acetyl group. The method according to claim 1,
The acid group capable of hydrogen bonding of Ar &lt; _{1 &gt;} and Ar &lt; _{2 &} An organic dye compound for a dye-sensitized solar cell, which comprises a carboxylic acid group (-COOH). 6. The method of claim 5,
Ar &lt; _{1 &gt;} and Ar &lt; ₂ &gt; are one of the following compounds:

. The method according to claim 1,
An organic dye compound for a dye-sensitized solar cell, characterized in that it is one of the following compounds:

,

. A dye-sensitized solar cell comprising a first electrode, a second electrode, and a dye layer formed between the first electrode and the second electrode,
The dye-sensitized solar cell according to claim 1, wherein the dye layer comprises the compound of claim 1.

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