KR101791161B1 - Organic Dye and Dye-Sensitized Solar Cell - Google Patents

Abstract

INDUSTRIAL APPLICABILITY The present invention can provide organic dyes excellent in light absorption and photoelectric conversion efficiency, their photoelectric elements, and dye-sensitized solar cells.

Description

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

The present invention relates to an organic dye and a photoelectric device and a dye-sensitized solar cell comprising the organic dye.

A photoelectric element is a device that converts light energy into electrical energy. A typical photoelectric device is a solar cell.

A representative example of a dye-sensitized solar cell, which is a type of solar cell, has been disclosed by Gratzel et al., Switzerland. Dyes used in dye-sensitized solar cells can be largely classified into organic metal dyes and organic dyes depending on the use of organic metals.

Organic dyes are required to have high light absorption and wide absorption band characteristics.

The first object to be achieved by the present invention is to provide an organic dye having a high light absorption rate and an absorption band at a long wavelength.

A second problem to be solved by the present invention is to provide a photoelectric device and a dye-sensitized solar cell having improved characteristics by employing the organic dye.

The present invention provides an organic dye represented by the following formula.

The present invention also provides a photoelectric device and dye-sensitized solar cell including the organic dye represented by the above formula.

INDUSTRIAL APPLICABILITY The present invention can provide organic dyes excellent in light absorption and photoelectric conversion efficiency, their photoelectric elements, and dye-sensitized solar cells.

1 is a view illustrating a dye-sensitized solar cell according to an embodiment of the present invention.
FIG. 2 is a graph showing the light conversion efficiency of the comparative example and Formula 26 according to an embodiment of the present invention.
FIG. 3 is a graph showing an absorption spectrum of Formula 26 according to an embodiment of the present invention. Referring to FIG.
4 is a diagram illustrating an emission spectrum of the compound of Formula 26 according to an embodiment of the present invention.
FIG. 5 is a graph showing an NMR spectrum of Formula 16 according to an embodiment of the present invention. FIG.
6 is a graph showing a MALDI_TOF spectrum of Formula 16 according to an embodiment of the present invention.
7 is a diagram showing an NMR spectrum of the chemical formula 26 according to an embodiment of the present invention.
8 shows a MALDI_TOF spectrum of Formula 26 according to an embodiment of the present invention.
Figure 9 is a graphical representation of solids in the visible light of Formula 26 according to one embodiment of the present invention.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals whenever possible, even if they are shown in different drawings. In the following description of the embodiments 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.

In describing the components of the embodiment of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected,""coupled," or "connected."

Unlike silicon solar cells, dye-sensitized solar cells are mainly composed of photo-sensitive dye molecules capable of absorbing visible light to form electron-hole pairs and transition metal oxides transferring generated electrons Photovoltaic solar cells. Since the photoelectric conversion efficiency of a dye-sensitized solar cell is proportional to the amount of electrons generated by the absorption of sunlight, in order to increase the efficiency, it is necessary to increase the absorption of sunlight, increase the amount of dye, Or the excited electrons generated may be prevented from being eliminated by electron-hole recombination, thereby increasing the efficiency.

The present inventors have developed organic dyes represented by the formula (1) in order to obtain a higher light absorption rate.

The present invention provides an organic dye represented by the following formula (1).

[Chemical Formula 1]

In Formula (1), A to B each independently represent a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

R ₁ to R ₆ each independently represent a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C20 alkylsilyl group, a substituted or unsubstituted C1-C20 alkyl group A substituted or unsubstituted C6-C40 cycloalkylene group, and a substituted or unsubstituted C1-C20 alkylene group.

o may be an integer from 0 to 4; When o is 2 or more, two or more R < ₆ > may be independently the same or different. For example, when o is 2 or more, one of the two or more R < ₆ > and the other may be the same or different from each other.

C is a COO-, PO ₃ ^2-, PO ₄ ^2-, SO ₃ ^2-, SO ₄ ^2-, and CONHO- or a group of fixing (anchoring group) is selected from those of the dehydrogenated form (deprotonated form) 1 gae Or more. As the dehydrogenated form, one or more terminal groups of the dye may form an anion, and the terminal group of the dye may form a salt with the cation. The cation may be selected from the group consisting of ammonium, phosphonium, sulfonium, imidazolium, pyrrolidonium and pyridinium groups without any particular limitation

The substituent used in the above formula (1) may be an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, , A halogen group, an aryloxy group having 6 to 24 carbon atoms, a silyl group having 1 to 24 carbon atoms, hydrogen and deuterium (deuterium including triple-branched channels, the same applies hereinafter).

Specific examples of the alkyl group as a substituent include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl, ethylhexyl, ethyloxyl and the like. The hydrogen atom may be substituted with a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group (in this case, an alkylsilyl group), a substituted or unsubstituted amino group (-NH2, -NH (R) A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, A halogenated alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms An alkyl group, a heteroaryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms By Loa Le alkyl group it may be substituted.

Specific examples of the alkoxy group as the substituent include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, ethylhexyloxy, ethyloctyloxy and the like. And at least one of the hydrogen atoms in the alkoxy group may be substituted with the same substituent as in the case of the alkyl group.

An aryl group means an aromatic system comprising at least one ring, which rings may be attached together or fused together by a pendant method. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, biphenyl, terphenylanthracenyl, phenanthryl, pyrenyl, fluorenyl, chrysenyl and fluoranthenyl, and at least one The hydrogen atom may be substituted with the same substituent as the alkyl group (for example, an "arylamino group" when it is substituted with an amino group, an "arylsilyl group" when it is substituted with a silyl group, Quot; aryloxy group ").

Heteroaryl group as a substituent means a ring aromatic system having 3 to 40 carbon atoms in which the remaining ring atoms contain 1, 2 or 3 hetero atoms selected from N, O, P, and S and the rings are bonded together by a pendant method Attached or fused. Specific examples of the heteroaryl group include thiophene, furan, pyrrole, thiazole, oxazole, imidazole, pyridine, benzothiophene, benzofuran, benzopyrrole, benzothiazole, benzoxazole, benzoimidazole, Pyridazine, pyrazine, triazine, aziridine azaindolin, indolidine, imidazole, indole, naphthalidine, quinoxaline, terpyridine, bipyridine, phenanthroline, phenazinquinoline, carbazole, And sol. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the alkyl group.

The anchoring group used in formula (I) may be selected from COOH, PO3H2, PO4H2, SO3H2, SO4H2, CONHOH and the deprotonized form thereof.

As the dehydrogenated form, one or more end groups of the dye may form an anion, that is to say in the form of COO-, PO2-3, PO2-4, SO2-3, SO2-4 and CONHO- In which case the terminal group of the dye may form a salt with the cation. The cation can be selected from the group consisting of ammonium, phosphonium, sulfonium, imidazolium, pyrrolidonium and pyridinium groups without any particular limitation.

Specific examples of organic dyes including carbazole amine derivatives according to one embodiment of the present invention include compounds represented by the following formulas (2) to (100), but the present invention is not limited to these exemplified compounds. In other words, the compounds represented by the general formula (1) are exemplified by representative compounds, since it is practically difficult to exemplify all the compounds in a wide range of the substituted or unsubstituted substituents of A, B, R ₁ to R ₆ and C, The compounds represented by the formula (1) which are not described in the above may also form a part of the present specification.

[Chemical Formula 2] < EMI ID =

[Chemical Formula 5] < EMI ID =

[Chemical Formula 8]

[Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 18] [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62]

[Chemical Formula 65]

[Chemical Formula 70] [Chemical Formula 70]

[Chemical Formula 71] [Chemical Formula 72]

[Chemical Formula 75] [Chemical Formula 75]

[Formula 77] [Formula 79]

[Formula 80] [Formula 81]

[Chemical Formula 84]

[Chemical Formula 86]

[Chemical Formula 90] [Chemical Formula 90]

[Chemical Formula 93] [Chemical Formula 94]

[Formula 97] [Formula 97]

[Chemical Formula 99] [Chemical Formula 100]

As described above, the present inventors have developed an organic dye represented by the formula (1) including a carbazolamine derivative in order to obtain a higher light absorption rate.

On the other hand, the inventors of the present invention have found that a light emitting device having a first electrode, a light absorbing layer formed on one surface of the first electrode, a second electrode arranged opposite to the first electrode having the light absorbing layer formed thereon, A dye-sensitized solar cell including an electrolyte embedded in a space has been developed. At this time, the dye-sensitized solar cell can carry the organic dye represented by the formula (1) in the oxide semiconductor fine particles in the light absorption layer.

Hereinafter, the dye-sensitized solar cell using the organic dye represented by the general formula (1) will be described by way of example, but the organic dye is not limited thereto. For example, the organic dye may be a photoelectric tube and a photomultiplier using a light front, a photoelectric cell using an internal photoelectric effect, a photovoltaic cell, a photodiode or a photo And may be used in photoelectric devices using various dyes such as phototransistors, photo sensors and the like. At this time, the photoelectric device basically has the same or substantially the same basic structure as the dye-sensitized solar cell described below, but a part of the component may be added, deleted, modified or changed in accordance with the application.

1 is a view illustrating a layered structure of a dye-sensitized solar cell according to an embodiment of the present invention.

The dye-sensitized solar cell according to an embodiment of the present invention includes a first electrode 101, a light absorbing layer 102 formed on one surface of the first electrode 101, a first electrode 102 formed with a light absorbing layer 102 A second electrode 104 disposed opposite to the first electrode 101 and an electrolyte 103 interposed in a space between the first electrode 101 and the second electrode 104. However,

The first electrode 101 is one of the two electrodes of the solar cell, and may be a conductive substrate.

The surface of the conductive substrate 101 may have conductivity. The conductive substrate 101 may be formed of a conductive metal oxide such as tin oxide coated with indium, fluorine or antimony, or a thin metal film of steel, silver or gold formed on the surface of a glass or transparent polymer material.

The light absorbing layer 102 includes a porous oxide semiconductor particle film to be produced on the conductive substrate 101 and an organic gold particle adsorbed on the oxide semiconductor particle film.

The porous oxide semiconductor particulate film is formed on the conductive substrate 101 as fine particles of an oxide semiconductor and the oxide semiconductor particulate film specifically includes oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, Can be used. The porous oxide semiconductor particulate film may be used alone, or may be mixed or coated on the surface of a semiconductor. The fine particles of the porous oxide semiconductor may have an average particle diameter of 1-500 nm, and a mixture of large and small particle sizes may be used, or multiple layers may be used. When the porous oxide semiconductor particulate film is used in a multilayer structure, the porosity of the porous oxide semiconductor film having a small particle size is made 0 to 10% on the first conductive substrate 101 to form a recombination blocking layer, Thereby forming a porous oxide semiconductor film layer having a large particle size with a porosity of 40-60%.

The porous oxide semiconductor particle film can be formed by applying a paste containing semiconductor fine particles on the conductive substrate 101, followed by drying, curing and firing. In this method, a paste containing a semiconductor is dispersed in various solvents such as water and ethanol to form a slurry and applied onto a substrate. The substrate coated with the slurry is baked at 400-600 DEG C for about 4 hours. In the dye-sensitized solar cell according to an embodiment of the present invention, the thickness of the porous oxide semiconductor particulate film on the substrate may be 1-2,000 nm, or 1-500 nm.

The photo sensitive organic dye represented by Chemical Formula 1 is adsorbed on the semiconductor particulate film formed. The method for adsorbing the photosensitive organic dye represented by Chemical Formula 1 to the semiconductor particulate film is not particularly limited, but specifically, a solution obtained by dissolving the compound represented by Chemical Formula 1 in a solvent capable of dissolving the compound, or a solution obtained by dispersing a dye A method in which the oxide semiconductor particulate film is supported on the dispersion to adsorb the dye can be used.

At this time, the concentration of the dye used in the solution or dispersion may be suitably adjusted according to the characteristics of the dye. In addition, the holding time for adsorbing the dye to the porous oxide after carrying the semiconductor particulate film is about 1 to 48 hours. The solvent used to dissolve or disperse the dye may be ethanol, water, acetonitrile, acetone, dimethylformaldehyde, and the like, but is not limited thereto.

Fixing of the dye adsorbed in the oxide group can be selected from _{COOH, PO 3 H2, PO 4} H 2, SO 3 H 2, SO 4 H 2, CONHOH and their dehydrogenated form (deprotonized form). There is one or more of the terminal groups of the dye as a dehydrogenated form to form an anion, i.e., COO ^-, PO ₃ ^2-, PO ₄ ^2-, SO ₃ ^2-, SO ₄ ^2-, and CONHO ^- in the form of In which case the terminal group of the dye may form a salt with the cation. The cation may be selected from the group consisting of ammonium, phosphonium, sulfonium, imidazolium, pyrrolidonium and pyridinium groups without any particular limitation.

The second electrode 104 is formed opposite to the first electrode 101 and includes a conductive layer and a conductive electrode which are the same as or similar to the first electrode 101. The conductive layer may be made of carbon black, a carbon material such as carbon nanotubes, or platinum. One or both of the first electrode 101 and the second electrode 104 may be transparent.

The electrolyte layer 103 is sealed by the partition wall interposed between the first electrode 101 and the second electrode 104. [ Examples of the redox electrolyte used in the electrolyte layer 103 include a halogen oxidizing / reducing agent electrolyte composed of a halogen compound and a halogen molecule having a halogen ion as a counter ion, a metal complex such as ferrocenate, ferrocene-ferricinium ion, and cobalt complex An organic redox electrolyte such as a metal oxide redox electrolyte, an alkylthiol-alkyl disulfide, a viologen dye, or a hydroquinone-quinone, or a halogen redox electrolyte. It may also be an iodine molecule. In addition, the LiI, NaI, KI, CaI _2, a halogenated metal or a tetraalkylammonium iodide, such as CuI, imidazolium iodine, the organic ammonium salt of halogen such as flutes Stadium iodine, or I ₂ as the halogen compound to a halogen ion as a counter ion Can be used.

Specific examples of the electrolyte layer 103 include, but are not limited to, the following.

The electrolyte layer 103 is made of an iodine based oxidation-reduction liquid electrolyte such as 1-vinyl-3-hexyl-3-immidazolium iodide, 0.1M LiI , An electrolyte solution of I ₃ ^- / I ^- in which 40 mM I 2 (Iodine) and 0.2 M tert-butyl pyridine were dissolved in 3-methoxypropionitrile Lt; / RTI >

<Examples>

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Comparative Experimental Examples. However, the following Synthesis Examples and Comparative Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

&Lt; Synthesis Example 1 > Preparation of the compound represented by the formula (16)

1) Synthesis of the compound represented by the formula 1-a

The compound represented by the formula (1-a) was synthesized by the following Reaction Scheme 1.

[Reaction Scheme 1]

[Chemical Formula 1-a]

(0.598 mol) of carbazole, 122.1 g (0.777 mol) of bromobenzene, 248 g (1.794 mol) of potassium carbonate, 14.8 g (0.149 mol) of copper chloride and 600 mL of dimethylsulfoxide were placed in a 1 L round bottom flask, And the mixture was refluxed and stirred at 160 캜 for 24 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure. The residue was purified by column chromatography using hexane as a developing solvent to obtain 118.0 g (72%) of the compound represented by the formula 1-a.

2) Synthesis of the compound represented by the formula 1-b

A compound represented by the formula 1-b was synthesized by the following Reaction Scheme 2

[Reaction Scheme 2]

[Chemical Formula 1-b]

78.9 g (0.324 mol) of the compound represented by the formula 1-a obtained from the above reaction formula 1, 44.4 g (0.175 mol) of iodine, 11.1 g (0.0486 mol) of periodic acid and 500 mL of acetic acid were placed in a 1 L round bottom flask, Lt; / RTI &gt; for 2 hours. The reaction was cooled to room temperature and extracted with diethyl ether and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and subjected to column chromatography using hexane as a developing solvent to obtain 88.0 g (85%) of a compound represented by the formula (1-b).

3) Synthesis of the compound represented by the formula 1-c

The compound represented by the formula 1-c was synthesized by the following Reaction Scheme 3

[Reaction Scheme 3]

[Chemical Formula 1-c]

(0.126 mol) of the compound represented by the formula 1-b obtained from the above reaction formula 2, 7.2 g (0.042 mol) of 4-bromoaniline, 1.59 g (0.008 mol) of copper iodide, 27.3 g (0.083 mol) of cesium carbonate, and 180 mL of tetraethylorthosilylate were placed and reacted at 145 DEG C for 38 hours. When the reaction was completed, the reaction mixture was concentrated under reduced pressure to a minimum amount, and recrystallized from methylene chloride and hexane to obtain 8.3 g (30%) of a compound represented by the formula 1-c.

4) Synthesis of the compound represented by the formula (1-d)

The compound represented by the formula 1-d was synthesized by the following Reaction Scheme 4

[Reaction Scheme 4]

[Chemical formula 1-d]

22.2 g (0.09 mol) of the compound represented by the formula 1-c obtained from the above reaction formula 3 was dissolved in 20 mL of acetic acid, and 20.2 g (0.09 mol) of N-iodoacridinimide was added to a 100 mL round- For 4 hours. After the temperature was lowered to room temperature, 50 mL of water was added and the mixture was extracted with methylene chloride. The mixture was extracted again with 1 M aqueous sodium hydroxide solution and brine, and the organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, (80%) of the title compound.

5) Synthesis of the compound represented by the formula 1-e

The compound represented by the formula 1-e was synthesized by the following Reaction Scheme 5

[Reaction Scheme 5]

[Formula 1-e]

5.3 g (0.018 mol) of the compound represented by the formula 1-d obtained from the above reaction formula 4 and 0.83 g (0.72 mol) of tetrakistriphenylphosphine palladium were dissolved in 80 mL of methyl ether in a 100 mL round bottom flask, 6.71 g (0.018 mol) of 3-hexyl-2-thiopheneborate and 54 mL of 1M sodium hydrogencarbonate were added, and the mixture was stirred under reflux for 24 hours. After the reaction was completed, the reaction mixture was extracted with water and ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography using hexane as eluent to obtain 6.7 g (90 %).

6) Synthesis of the compound represented by the formula 1-f

The compound represented by the formula 1-f was synthesized according to the following Reaction Scheme 6 .

[Reaction Scheme 6]

[Chemical Formula 1-f]

5.0 g (0.012 mol) of the compound represented by the formula 1-e obtained from the above reaction formula 5 was dissolved in 25 mL of tetrahydrofuran, and 8.3 mL (0.013 mol) of n-butyllithium was slowly added to the 50 mL round- And 2.56 g (0.13 mol) of triisopropylborate is added thereto over 30 minutes. After the temperature was raised to room temperature, 1.71 g (0.014 mol) of pinacol was added and reacted for 24 hours. When the reaction is completed, the reaction solution is completely removed and petroleum ether is added to precipitate crystals. After the precipitated crystals were filtered off, the solution was concentrated under reduced pressure to obtain 4.9 g (98%) of a compound represented by the formula (1-f).

7) Synthesis of the compound represented by the formula (1-g)

The compound represented by the formula 1-g was synthesized by the following Reaction Scheme 7.

[Reaction Scheme 7]

[Formula 1-g]

After dissolving 4.0 g (0.006 mol) of the compound represented by the formula 1-c obtained in the above reaction formula 3 and 0.49 g (0.0004 mol) of tetrakistriphenylphosphine palladium in 50 mL of toluene in a 100 mL round-bottomed flask, 3.4 g (0.007 mol) of the compound represented by the formula 1-f obtained from the reaction scheme 6 and 1 M sodium hydrogencarbonate were added and reacted for 24 hours. When the reaction was completed, 50 ml of water was added, and the mixture was extracted with water and ethyl acetate. The mixture was concentrated under reduced pressure and the residue was separated by column chromatography to obtain 3.4 g (62%) of the compound represented by the formula (1-g).

8) Synthesis of the compound represented by the formula 1-h

The compound represented by the formula 1-h was synthesized according to the following Reaction Scheme 8.

[Reaction Scheme 8]

[Chemical Formula 1-h]

3.0 g (0.003 mol) of the compound represented by the formula 1-g obtained from the above reaction formula 7 was dissolved in 25 mL of tetrahydrofuran, and 2.48 mL (0.004 mol) of n-butyllithium was added at -20 ° C to a 50 mL round bottom flask And stirred for 15 minutes, 1.2 mL (0.016 mol) of N, N-dimethylformamide was added at -10 DEG C, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, an ammonium chloride aqueous solution was added and the mixture was extracted with methyl ether. The organic layer was concentrated and separated by column chromatography using methylene chloride and hexane as eluent to obtain 1.5 g (47%) of the compound represented by the formula (1-h) .

9) To 16  Synthesis of displayed compounds

The compound represented by the formula (16) was synthesized by the following reaction scheme (9).

[Reaction Scheme 9]

[Chemical Formula 16]

1.2 g (0.001 mol) of the compound represented by the formula 1-h obtained from the above reaction formula 8, 0.17 g (0.002 mol) of cyanoacetic acid, 0.15 g (0.0019 mol) of piperidine obtained in the above reaction formula 8, 15 mL And the mixture was stirred under reflux for 10 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and subjected to column chromatography using methylene chloride and methanol to obtain 0.7 g (55.4%) of the compound represented by the formula (16).

MS: m / z calcd 1002.40; found 1002. Anal. Calcd. for C ₆₆ H ₅₈ N ₄ O ₂ S ₂ : C, 79.01 H, 5.83 N; 5.88; O, 3.19, 6.39. Found: C, 78.56 H, 5.68 N, 6.01.

Synthesis Example 2 Synthesis of Compound Represented by Formula 26

1) Synthesis of the compound represented by the formula 2-a

A compound represented by the formula 2-a was synthesized according to the following Reaction Scheme 10.

[Reaction Scheme 10]

[Chemical Formula 2-a]

4.1 g (0.010 mol) of the compound represented by the formula 1-e obtained in the above Reaction Scheme 5 and 25 mL of tetrahydrofuran were added to a 50 mL round bottom flask and 6.6 mL (0.0105 mol) of normal butyl lithium was slowly added thereto at -80 ° C. for 1 hour Lt; / RTI &gt; 12.6 g (0.0105 mol) of 1M zinc chloride was added at the same temperature, and then the temperature was raised to room temperature. Then, 3.9 g (0.0105 mol) of the compound represented by the formula 1-d obtained from the reaction formula 4, 1.1 g mol) and 25 mL of tetrahydrofuran, and the mixture was stirred at room temperature for 24 hours. The mixture was extracted with methylene chloride and water. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography using methylene chloride and hexane to obtain 2.2 g (38%) of the compound represented by the formula (2-a).

2) Synthesis of the compound represented by the formula 2-b

The compound represented by the formula (2-b) was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

[Formula 2-b]

In a 100 mL round bottom flask, the compound represented by the formula 2-a obtained from the above reaction formula 10 was used instead of the compound represented by the formula 1-e obtained from the above reaction formula 5, (67%) of the title compound.

3) Synthesis of the compound represented by the formula 2-c

The compound represented by the formula 2-c was synthesized by the following Reaction Scheme 12.

[Reaction Scheme 12]

[Chemical Formula 2-c]

In a 100 mL round bottom flask, the compound of the formula 2-a obtained from the above reaction formula 10 was used instead of the compound of the formula 1-f obtained from the above reaction formula 6, (52%) of the title compound.

4) Synthesis of the compound represented by the formula 2-d

The compound represented by the formula (2-d) was synthesized according to the following reaction scheme (13).

[Reaction Scheme 13]

[Chemical Formula 2-d]

2-d was prepared in the same manner as in the reaction scheme 8, except that the compound represented by the formula 2-c obtained from the above-mentioned reaction formula 12 was used instead of the compound represented by the formula 1-g obtained from the above reaction formula 7 in a 100 mL round bottom flask (41%) of the title compound.

5) Synthesis of Compound Represented by Chemical Formula 26

The compound represented by Chemical Formula 26 was synthesized by the following Reaction Scheme 14.

[Reaction Scheme 14]

(26)

In the same manner as in the reaction scheme 9, except that the compound represented by the formula 2-d obtained from the above reaction formula 13 was used instead of the compound represented by the formula 1-h obtained from the above reaction formula 8 in a 100 mL round bottom flask, the compound (32%).

MS: m / z calcd 1168.48; found 1168. Anal. Calcd. for C ₇₆ H ₇₂ N ₄ O ₂ S ₃ : C, 78.04 H, 6.20 N; 4.79; O, 2.74; S, 8.22. Found: C, 77.16H, 6.01 N, 4.93.

Synthesis Example 3: Preparation of a compound represented by the formula (32)

  1) Synthesis of Compound Represented by Formula 3-a

A compound represented by the general formula (3-a) was synthesized by the following Reaction Scheme (15).

[Reaction Scheme 15]

[Formula 3-a]

After adding 100.0 g (1.188 mol) of thiophene and 71 mL of chloroform to a 2 L round bottom flask, 269.6 g (5.229 mol) of bromine was slowly added thereto, and the mixture was stirred under reflux. After the temperature was lowered to room temperature, 25.2 g (0.630 mol) of sodium hydroxide was dissolved in 250 mL of water, added to the reaction solution, and refluxed with stirring for 4 hours. The temperature was lowered to room temperature, filtered, and recrystallized from methylene chloride and ethanol to obtain 362.3 g (76.3%) of the compound represented by the formula (3-a).

  2) Synthesis of the compound represented by the formula 3-b

The compound represented by the formula (3-b) was synthesized according to the following reaction scheme (16).

[Reaction Scheme 16]

[Formula 3-b]

362.3 g (0.906 mol) of the compound represented by the formula 3-a obtained from the above reaction formula 15 and 5.4 L of tetrahydrofuran were added to a 10 L round bottom flask, and the temperature was lowered to -78 ° C. Then, 1189.6 mL (1.903 mol) Slowly added and stirred for 1 hour. 230.7 g (2.25 mol) of 1-morphylpyridine was added at the same temperature, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. After the temperature was lowered to 0 ° C, 2.2 L of 6M hydrochloric acid was poured, filtered, washed with water, and dried to obtain 187.6 g (69.5%) of a compound represented by the formula 3-b.

  3) Synthesis of the compound represented by the formula 3-c

The compound represented by the formula 3-c was synthesized according to the following Reaction Scheme 17.

[Reaction Scheme 17]

[Chemical Formula 3-c]

187.6 g (0.630 mol) of the compound represented by the formula 3-b obtained from the above reaction formula 16 and 5.8 L of N, N-dimethylformamide were added to a 10 L round bottom flask, and 226.3 g (1.637 mol) of potassium carbonate was added 155.1 g (1.291 mol) of ethyl-2-mercaptoacetate were added and stirred for 3 days. The reaction mixture was poured into water and extracted with methylene chloride. The organic layer was separated, concentrated under reduced pressure, and dried to obtain 152.0 g (70.9%) of the compound represented by the formula 3-c.

  4) Synthesis of Compound Represented by Formula 3-d

The compound represented by the general formula (3-d) was synthesized by the following Reaction Scheme 18.

[Reaction Scheme 18]

[Chemical formula 3-d]

152.0 g (0.446 mol) of the compound represented by the formula 3-c obtained from the above reaction formula 17 and 2.3 L of tetrahydrofuran were added to a 5 L round bottom flask, and then 95.5 g (2,277 mol) of lithium hydroxide was dissolved in 2.3 L of water. The reaction mixture was stirred for 30 minutes and then refluxed for 6 hours. After the temperature was lowered to room temperature, 3 L of 1 N hydrochloric acid was poured, and the solid was filtered, washed with methanol and dried to obtain 112.0 g (88.2%) of the compound represented by the formula 3-d.

  5) Synthesis of the compound represented by the formula 3-e

The compound represented by the general formula (3-e) was synthesized by the following reaction scheme (19).

[Reaction Scheme 19]

[Formula 3-e]

113.0 g (0.397 mol) of the compound represented by the formula 3-d obtained from the above reaction scheme 18, 24.0 g (0.378 mol) of copper and 791 mL of quinoline were placed in a 1 L round bottom flask and refluxed with stirring at 230 ° C until the evolution of carbon dioxide was complete . After the temperature was lowered to room temperature, the product was separated by column chromatography using hexane to obtain 58.8 g (75.4%) of the compound represented by the formula 3-e.

  6) Synthesis of the compound represented by the formula 3-f

The compound represented by the formula 3-f was synthesized by the following Reaction Scheme 20.

[Reaction Scheme 20]

[Chemical Formula 3-f]

22.0 g (0.112 mol) of the compound represented by the formula 3-e obtained in the above reaction scheme 19 and 440 mL of N, N-dimethylformamide were added to a 1 L round bottom flask, and then 43.9 g (0.247 mol) of N-bromosuccinimide, Was added slowly and stirred for 30 minutes. 1 L of water was poured and the resulting solid was filtered and dried to obtain 37.0 g (93.2%) of a compound represented by the formula 3-f.

  7) Synthesis of the compound represented by the formula 3-g

The compound represented by the formula (3-g) was synthesized by the following Reaction Scheme (21).

[Reaction Scheme 21]

[Formula 3-g]

10.0 g (0.0152 mol) of the compound represented by the formula 1-c obtained from the above reaction formula 3 and 5.4 g (0.0183 mol) of 3-hexyl-2-thiophene borate were added to a 100 mL round bottom flask, to obtain 7.7 g (68.2%) of a compound represented by -g.

  8) Synthesis of the compound represented by the formula 3-h

The compound represented by the formula 3-h was synthesized according to the following Reaction Scheme 22.

[Reaction Scheme 22]

[Chemical Formula 3-h]

7.0 g (0.0094 mol) of the compound represented by the formula 3-g obtained from the reaction formula 21 and 3.0 g (0.0085 mol) of the compound represented by the formula 3-f obtained from the reaction formula 20 were added to a 1 L round bottom flask, To obtain 4.4 g (51.2%) of the compound represented by the formula (3-h).

9) Synthesis of the compound represented by the formula 3-i

The compound represented by the formula (3-i) was synthesized according to the following reaction scheme (23).

[Reaction Scheme 23]

[Chemical Formula 3-i]

3-h was prepared in the same manner as in Reaction Scheme 8, except that the compound represented by Formula 3-h obtained from Reaction Formula 23 was used instead of the compound represented by Formula 1-g obtained from Reaction Formula 7, in a 100 mL round bottom flask. (44.7%) of the title compound.

10) Synthesis of compound represented by formula (32)

The compound represented by the general formula (32) was synthesized by the following reaction scheme (24).

[Reaction Scheme 24]

(31)

Except that the compound represented by the formula 3-i obtained from the above reaction scheme 30 was used instead of the compound represented by the formula 1-h obtained from the above scheme 8 in a 100 mL round bottom flask, to obtain the compound represented by the formula 32 (39.2%).

MS: m / z Calcd 1030.25; found 1030. Anal. Calcd. for C ₆₄ H ₄₆ N ₄ O ₂ S ₄ : C, 74.53H, 4.50 N; 5.43; O, 3.10; S, 12.44. Found: C, 74.99; H, 4.62; N, 5.49.

&Lt; Synthesis Example 4 > Preparation of a compound represented by the formula (41)

  1) Synthesis of the compound represented by the formula 4-a

A compound represented by the formula 4-a was synthesized by the following Reaction Scheme 25.

[Reaction Scheme 25]

[Chemical Formula 4-a]

20 g (0.050 mol) of 3-iodo-9- (4-methoxyphenyl) carbazole and 4.2 g (0.0227 mol) of 4-bromo-3-methylaniline were added to a 500 mL round bottom flask, 16.5 g (89.6%) of the compound represented by the formula 4-a was obtained.

  2) Synthesis of the compound represented by the formula 4-b

The compound represented by the formula 4-b was synthesized by the following Reaction Formula 26.

[Reaction Scheme 26]

[Formula 4-b]

50.0 g (0.307 mol) of 3-bromothiophene, 11.28 g (0.491 mol) of sodium metal, 174.5 g (1.717 mol) of 1-hexanol and 4.09 g (0.021 mol) of iodopropane were dissolved in N, N-dimethyl Formamide, and the mixture was stirred under reflux. When the reaction was completed, the organic layer was collected, concentrated under reduced pressure, and vacuum distilled to obtain 46.0 g (81.4%) of the compound represented by the formula 4-b.

  3) Synthesis of the compound represented by the formula 4-c

The compound represented by the formula 4-c was synthesized according to the following Reaction Scheme 27.

[Reaction Scheme 27]

[Chemical formula 4-c]

In the same manner as in Reaction Scheme 4, except that a 3-hexyloxhi thiophene compound was used in place of 2-bromo-3-hexylthiophene in the above Reaction Formula 4, a compound represented by the formula 4-c was added in an amount of 22.8 g (80.0%).

  4) Synthesis of the compound represented by the formula 4-d

The compound represented by the formula 4-d was synthesized according to the following Reaction Scheme 28.

[Reaction Scheme 28]

[Chemical formula 4-d]

21.0 g (74.0%) of the compound represented by the formula 4-d was obtained in the same manner as in the reaction scheme 4, with 20.0 g (0.0757 mol) of the compound represented by the formula 4-c obtained in the above reaction formula 27 in a 500 mL round bottom flask.

  5) Synthesis of the compound represented by the formula 4-e

The compound represented by the formula 4-e was synthesized by the following Reaction Scheme 29.

[Reaction Scheme 29]

[Chemical Formula 4-e]

Except that the compound represented by the formula 4-c obtained from the above reaction formula 27 was used instead of the compound represented by the formula 1-e obtained from the above reaction formula 5 in a 100 mL round bottom flask, (69.0%) of the title compound.

  6) Synthesis of the compound represented by the formula 4-f

The compound represented by the formula 4-f was synthesized by the following Reaction Scheme 30.

[Reaction Scheme 30]

[Chemical Formula 4-f]

In a 100 mL round-bottomed flask, the compound represented by the formula 4-d obtained from the reaction formula 28 and the compound represented by the formula 4-e obtained from the reaction formula 29 were used in place of the compound represented by the formula 1-d obtained from the reaction formula 4 To obtain 9.7 g (53.0%) of the compound represented by the formula (4-f).

  7) Synthesis of the compound represented by the formula 4-g

The compound represented by the formula 4-g was synthesized by the following Reaction Scheme 31.

[Reaction Scheme 31]

[Formula 4-g]

(72.0%) of the compound represented by the formula 4-g was obtained in the same manner as in the reaction scheme 6, with 9 g (0.0202 mol) of the compound represented by the formula 4-f obtained from the above reaction formula 30, in a 100 mL round bottom flask.

  8) Synthesis of the compound represented by the formula 4-h

The compound represented by the formula 4-f was synthesized according to the following Reaction Formula 32.

[Reaction Scheme 32]

[Chemical Formula 4-h]

3.0 g (0.00411 mol) of the compound represented by the formula 4-a obtained from the reaction formula 25 and 2.4 g (0.00494 mol) of the compound represented by the formula 4-g obtained from the reaction formula 31 were added to a 100 mL round- To obtain 3.7 g (89.1%) of the compound represented by the formula (4-h).

  9) Synthesis of the compound represented by the formula 4-i

The compound represented by the formula (4-i) was synthesized by the following reaction scheme (33).

[Reaction Scheme 33]

[Chemical formula 4-i]

4-i was prepared in the same manner as in the reaction scheme 8, except that the compound represented by the formula 4-h obtained from the above scheme 32 was used instead of the compound represented by the formula 1-g obtained from the above scheme 7 in a 100 mL round bottom flask. (46.2%) of the title compound.

  10) Synthesis of the compound represented by the formula (41)

A compound represented by the formula (41) was synthesized by the following reaction scheme (34).

[Reaction Scheme 34]

(41)

In a similar manner to scheme 9, except for using the compound of formula 4-i obtained from the above scheme 33 instead of the compound of formula 1-h obtained from the above scheme 8 in a 100 mL round bottom flask, the compound of formula 41 (40.2%).

MS: m / z Calcd 1108.43; found 1108. Anal. Calcd. for C ₆₉ H ₆₄ N ₄ O ₆ S ₂ : C, 74.70 H, 5.81 N; 5.05; O, 8.65; S, 5.78. Found: C, 74.26; H, 5.65; N, 5.27.

Synthesis Example 5 Synthesis of Compound Represented by Formula 70

  1) Synthesis of Compound Represented by Formula 5-a

A compound represented by the formula 5-a was synthesized by the following Reaction Scheme 35.

[Reaction Scheme 35]

[Formula 5-a]

17.3 g (0.124 mol) of thiophene-2,3-dicarboxyaldehyde, 6.6 g (0.059 mol) of 1,4-cyclohexanedione and 70 mL of ethanol were added to a 250 mL round bottom flask, and 70 mL of 15% Lt; / RTI &gt; After completion of the reaction, the reaction mixture was filtered and dried to obtain 17.5 g (92.8%) of the compound represented by the formula 5-a.

  2) Synthesis of the compound represented by the formula 5-b

The compound represented by the formula 5-b was synthesized according to the following Reaction Formula 36.

[Reaction Scheme 36]

[Chemical Formula 5-b]

17.5 g (0.055 mol) of the compound represented by the formula 5-a, 7.9 g (0.120 mol) of zinc, 70 mL of ethanol and 262 mL of 20% sodium hydroxide obtained from the above reaction formula 35 were added to a 500 mL round bottom flask and the mixture was stirred for 1 hour 46.6 g (0.164 mol) of octyl p-toluene sulfonate was added, and the mixture was stirred under reflux for 1 hour. The organic layer was separated using ethyl ether and water, concentrated under reduced pressure, and then subjected to column chromatography using hexane and acetone to obtain 21.2 g (70.9%) of the compound represented by the formula 5-b.

  3) Synthesis of the compound represented by the formula 5-c

The compound represented by the formula 5-c was synthesized by the following Reaction Scheme 37.

[Reaction Scheme 37]

[Chemical Formula 5-c]

20.0 g (0.0364 mol) of the compound represented by the formula 5-b obtained from the above reaction formula 36 and 200 mL of tetrahydrofuran were added to a 500 mL round bottom flask and 18.3 g (0.0437 mol) of n-butyllithium was slowly added thereto at the same temperature And stirred for 30 minutes. 8.7 g (0.0364 mol) of trimethyltin chloride was slowly added thereto, and the mixture was stirred at room temperature for 12 hours. The organic layer was separated by using water and hexane, and the residue was recrystallized from 2-propanol by concentration under reduced pressure. 22.0 g (72.2%) of the compound was obtained.

  4) Synthesis of the compound represented by the formula 5-d

The compound represented by the formula 5-d was synthesized by the following Reaction Scheme 38.

[Reaction Scheme 38]

[Chemical formula 5-d]

(0.0061 mol) of the compound represented by the formula 1-c obtained from the above reaction formula 3, 6.1 g (0.0073 mol) of the compound represented by the formula 5-c obtained from the above-mentioned reaction formula 37, 0.001 mol of the tetrakistriphenylphosphine 0.1 g (0.0001 mol) of palladium palladium and 50 mL of toluene were placed, and the mixture was stirred under reflux for 16 hours. After the temperature was lowered to room temperature, the organic layer was separated using water and ethyl acetate, and the filtrate was concentrated under reduced pressure. Then, 5.9 g (87.1%) of the compound represented by the formula (5-d) was obtained by column chromatography using methylene chloride and hexane as eluent. ).

  5) Synthesis of the compound represented by the formula 5-e

The compound represented by the formula 5-e was synthesized by the following Reaction Scheme 39.

[Reaction Scheme 39]

[Chemical Formula 5-e]

(0.0050 mol) of the compound represented by the formula 5-d obtained from the above reaction scheme 38 and 1.5 g (0.0059 mol) of 2-bromo-3-hexylthiophene were added to a 100 mL round bottom flask, 3.1 g (47.9%) of the compound represented by the formula 5-e was obtained.

  6) Synthesis of the compound represented by the formula 5-f

The compound represented by the formula (5-f) was synthesized by the following reaction scheme (40).

[Reaction Scheme 40]

[Chemical Formula 5-f]

Except that 3.0 g (0.0023 mol) of the compound represented by the formula 5-e obtained from the above reaction formula 39 was used instead of the compound represented by the formula 1-g obtained from the above-mentioned reaction formula 7 in a 100 mL round bottom flask 2.0 g (64.9%) of the compound represented by the formula 5-f was obtained.

  7) To 70  Synthesis of displayed compounds

The compound represented by the general formula (70) was synthesized by the following reaction scheme (41).

[Reaction Scheme 41]

(70)

Except that 2.0 g (0.0015 mol) of the compound represented by the formula 5-f obtained from the above reaction scheme 40 was used instead of the compound represented by the formula 1-h obtained from the above reaction formula 8 in a 100 mL round bottom flask 1.0 g (48.5%) of the compound represented by the general formula (70) was obtained.

MS: m / z Calcd 1382.58; found 1382. Anal. Calcd. for C ₉₀ H ₈₆ N ₄ O ₄ S ₃ : C, 78.11 H, 6.26 N; 4.05; O, 4.62; S, 6.95. Found: C, 77.83 H, 5.91; N, 4.29.

Synthesis Example 6 Synthesis of Compound Represented by Formula 80

  1) Synthesis of the compound represented by the formula 6-a

A compound represented by the formula 6-a was synthesized by the following reaction scheme 42. [

[Reaction Scheme 42]

[Chemical Formula 6-a]

20.0 g (0.0848 mol) of 1,4-dibromobenzene and 200 mL of tetrahydrofuran were added to a 500 mL round-bottomed flask and 28.2 g (0.1017 mol) of n-butyllithium was slowly added thereto at -78 ° C and stirred at the same temperature for 1 hour Then, 11.0 g (0.1017 mol) of trichloromethylsilane was added and stirred at room temperature for 12 hours. The mixture was extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and then hexane was separated by column chromatography to obtain 17.3 g (89.5) of the compound represented by the formula 6-a.

2) Synthesis of the compound represented by the formula 6-b

The compound represented by the formula 6-b was synthesized according to the following reaction scheme 42.

[Reaction Scheme 43]

[Chemical Formula 6-b]

17.0 g (0.0742 mol) of the compound represented by the formula 6-a obtained from the reaction formula 41 and 16.4 g (0.0667 mol) of 3-bromocarbazole were added to a 500 mL round bottom flask and reacted with the compound represented by the formula 6-b (85.6%) was obtained.

  3) Synthesis of the compound represented by the formula 6-c

The compound represented by the formula 6-c was synthesized according to the following reaction scheme 44.

[Reaction Scheme 44]

[Chemical formula 6-c]

(0.0507 mol) of 3-bromo-9- (4-trimethylphenyl) carbazole and 3.6 g (0.0211 mol) of 4-bromo-3-methylaniline in a 500 mL round bottom flask, 32.0 g (79.1%) of the compound represented by the formula 6-c was obtained.

  4) Synthesis of the compound represented by the formula 6-d

The compound represented by the formula (6-d) was synthesized by the following reaction scheme (45).

[Reaction Scheme 45]

[Chemical formula 6-d]

10.0 g (0.0125 mol) of the compound represented by the formula 6-c obtained in the above reaction scheme 44 and 9.4 g (0.0150 mol) of the compound represented by the formula 2-b obtained from the above reaction scheme 11 were added to a 100 mL round- To obtain 11.7 g (77.1%) of the compound represented by the formula (6-d).

  5) Synthesis of the compound represented by the formula 6-e

The compound represented by the formula 6-e was synthesized by the following Reaction Scheme 46.

[Reaction Scheme 46]

[Chemical Formula 6-e]

Except that 5.0 g (0.0041 mol) of the compound represented by the formula 6-c obtained from the above-mentioned reaction formula 45 was used instead of the compound represented by the formula 1-g obtained from the above-mentioned reaction formula 7 in a 100 mL round bottom flask To obtain 3.1 g (61.6%) of the compound represented by the formula 6-e.

  6) Synthesis of Compound Represented by Formula 80

The compound represented by the general formula (80) was synthesized by the following reaction scheme (47).

[Reaction Scheme 47]

(80)

Except that 3.0 g (0.0025 mol) of the compound represented by the formula 6-e obtained from the above reaction scheme 46 was used instead of the compound represented by the formula 1-h obtained from the above reaction formula 8 in a 100 ml round bottom flask 1.5 g (47.9%) of the compound represented by the general formula (80) was obtained.

MS: m / z Calcd 1312.56; found 1313. Anal. Calcd. for C ₈₂ H ₈₈ N ₄ O ₂ S ₃ Si ₂ : C, 74.95 H, 6.75 N; 4.26; O, 2.44 S, 7.32; Si, 4.27. Found: C, 75.81 H, 6.94; N, 4.09.

Herein, the compounds represented by formulas (1) and (2) are exemplified by the synthesis examples of some of the compounds represented by the formula (2) in a wide range of the substituents of the substituents of A, B, R 1 to R 6 and C Compounds represented by formulas (1) and (2), which are not exemplarily shown in the synthesis examples,

.

< Comparative Experimental Example >

Production of solar cell (Examples 1 to 6)

An indium-doped tin oxide transparent conductor was coated with a titanium oxide dispersion having a particle size of about 5 to 15 nm in a 1 cm ² area using a doctor blade method, and a titanium oxide thick film having a thickness of 18 μm was formed through thermal treatment and firing at 450 ° C. for 30 minutes Respectively. After holding the specimen at 80 DEG C, the compound represented by Chemical Formulas 16 and 26, 32, 41, 70, and 80 according to Examples 1 to 6 was immersed in a 0.3 mM dye dispersion in ethanol to perform dye adsorption treatment For more than 12 hours. The dye-adsorbed porous titanium oxide thick film was washed with ethanol and dried at room temperature to prepare a first electrode having a light absorbing layer.

As the second electrode, a Pt layer was deposited on the indium-doped tin oxide transparent conductor to a thickness of about 200 nm by using a sputter. For the injection of the electrolyte, the second electrode was prepared by making a micro hole using a drill having a diameter of 0.75 mm.

A thermoplastic polymer film having a thickness of 60 탆 was sandwiched between the first electrode and the second electrode at 100 캜 for 9 seconds to bond the two electrodes. The redox electrolyte was injected through the micropores formed in the second electrode, and the micropores were sealed using a cover glass and a thermoplastic polymer film to prepare a dye-sensitized solar cell. The oxidation-reduction electrolyte used herein was 0.62M of 1,2-dimethyl-3-hexylimidazolium iodide, 0.5M of 2-aminopyrimidine (2- aminopyrimidine), 0.1 M LiI and 0.05 M I2 dissolved in acetonitrile were used.

Comparative Example

As a comparative example, the dye-sensitized solar cell was produced in the same manner as in Examples 1 to 6, except that N719 (formula 88), which is generally well known, was used in place of the organic dye described above.

In this case, N719 is a ruthenium-based dye used in conventional dye-sensitized solar cells, and a synthetic method thereof is disclosed in literature (Nazeeruddin MK, et al., "Acid-base equilibriaof (2,2'-bipyridyl- dicarboxylic acid ruthenium (II) complexes and the effect of protonation on charge-transfer sensitization of nanocrystalline titania ", Inorganic Chemistry, Vol. 38, No. 26, pp 6298-6305, 1999).

(101)

In order to measure the light conversion efficiency of the dye-sensitized solar cell according to Examples 1 to 6 and Comparative Example of the present invention, optical voltage and photocurrent were measured. The Xenon lamp (Oriel, 01193) was used as the light source and the solar condition (AM 1.5) of the xenon lamp was a standard solar cell (Frunhofer Institute Solare Engeriessysteme, Certificate No. C-ISE369, Type of material: Mono-Si + KG filter). The light conversion efficiency was calculated from the measured photocurrent voltage curve according to the following formula (1), and it is shown in Table 1 below.

In Equation (1), η _e denotes a light conversion efficiency, Jsc denotes a current density, Voc denotes a voltage, FF denotes a fill factor, and Pinc denotes 100 mw / cm ² (1 sun).

Dye Solvent Jsc (mA / cm ² ) Voc (V) FF 侶 (%) Comparative Example (N719) Ethanol 14.89 0.70 0.58 6.13 Formula 16 Ethanol 15.17 0.70 0.62 6.58 26 Ethanol 16.04 0.65 0.59 7.43 (32) Ethanol 16.16 0.71 0.60 6.88 Formula 41 Ethanol 15.11 0.69 0.60 6.25 70 Ethanol 16.48 0.69 0.61 6.94 80 Ethanol 15.99 0.71 0.62 7.04

The molar absorptivity and band gap of the dye-sensitized solar cell according to Examples 1 to 6 of the present invention were measured using an absorption spectrophotometer (UV / Vis absorption spectrometer) and a cyclic voltammetry.

Dye Abs _max [nm] [M ^-1 cm ^-1 ] HOMO (eV) LUMO (eV) Bandgap (eV) Comparative Example (N719) 524 12,329 5.45 3.85 1.60 Formula 16 452 12,813 3.45 1.08 2.37 26 469 13,113 3.32 1.00 2.32 (32) 473 13,313 3.60 1.15 2.45 Formula 41 452 12,892 3.80 1.13 2.67 70 442 12,836 3.82 1.21 2.61 80 456 12,571 3.93 1.16 2.77

As can be seen from Tables 1 and 2, the compounds used in Examples 1 to 6 of the present invention showed a molar extinction coefficient higher than that of an organic metal complex using a conventional bipyridine derivative as a ligand and exhibited excellent light conversion efficiency Could know.

INDUSTRIAL APPLICABILITY As described above, the present invention provides a photosensitive organic dye having a high molar absorptivity and exhibiting excellent light conversion efficiency, and the dye-sensitized solar cell using the organic dye has an excellent light absorptivity and photoelectric conversion efficiency .

The compounds represented by formulas (1) and (2) are exemplified by comparative experimental examples of some of the compounds represented by formula (2) in a wide range of substituents of the substituents of A, B, R 1 to R 6 and C However, as a comparative example,

The compounds represented by the general formulas (1) to (3) have the same effects as those of the above-mentioned comparative examples because they have the above-described general formulas (1) and (2), and the result can be a part of the present specification.

It is to be understood that the terms "comprises", "comprising" or "having" as used in the foregoing description mean that a component can be implanted unless explicitly stated to the contrary. But should be construed to include other elements. All terms, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. Commonly used terms, such as predefined terms, should be interpreted to be consistent with the contextual meanings of the related art, and are not to be construed as ideal or overly formal, unless expressly defined to the contrary.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (8)

Wherein the organic dye is any one selected from the group consisting of the following formulas (2) to (100).

[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 5] &lt; EMI ID =

[Chemical Formula 8]

[Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 18] [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62]

[Chemical Formula 65]

[Chemical Formula 70] [Chemical Formula 70]

[Chemical Formula 71] [Chemical Formula 72]

[Chemical Formula 75] [Chemical Formula 75]

[Formula 77] [Formula 79]

[Formula 80] [Formula 81]

[Chemical Formula 84]

[Chemical Formula 86]

[Chemical Formula 90] [Chemical Formula 90]

[Chemical Formula 93] [Chemical Formula 94]

[Formula 97] [Formula 97]

[Chemical Formula 99] [Chemical Formula 100] delete delete delete 10. A photoelectric device comprising a porous oxide semiconductor film comprising an organic dye according to any one of claims 1 to 9. 6. The method of claim 5,
Wherein the porous oxide semiconductor film is composed of fine particles mainly composed of oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, and vanadium. 6. The method of claim 5,
Wherein the porous oxide semiconductor film is used for a photoabsorption layer formed between a first electrode and a second electrode facing the first electrode. A first electrode;
A second electrode disposed on one surface of the first electrode and disposed opposite the first electrode including a porous film and a light absorbing layer comprising the organic dye of claim 1 formed on the porous film;
And an electrolyte embedded in a space between the first electrode and the second electrode.

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