KR20120057959A - Novel ruthenium complex and photoelectric component using the same - Google Patents

Abstract

PURPOSE: A ruthenium complex is provided to ensure suitability as a dye-sensitized solar cell(DSC) and to improve photoelectric property of the DSC. CONSTITUTION: A ruthenium complex is denoted by chemical formula 1. In chemical formula 1, L1 is 2,2'-bipyridyl-4,4'-dicarboxylic acid, 2,2'-bipyridyl-4,4'-disulfonic acid, or 2,2'-bipyridyl-4,4'-diphosphonic acid; and L2 is . 2,2'-bipyridyl-4,4'-dinonyl, or 2,2'-bipyridine-4,4'-ditridecyl. The ruthenium complex is a dye compound for a dye-sensitized solar cell. The dye-sensitized solar cell comprise a photoanode containing ruthenium complex, a cathode, and an electrolytic layer between photoacid and cathodes.

Description

Ruthenium composite and optoelectronic component using same {NOVEL RUTHENIUM COMPLEX AND PHOTOELECTRIC COMPONENT USING THE SAME}

The present invention relates to a ruthenium complex and an optoelectronic component using the same, and more particularly, to a dye-sensitized solar cell (DSC), and a ruthenium complex used in an optoelectronic component using the same.

Regarding the development of industrial technology, the world today faces two serious problems: energy crisis and environmental pollution. One effective means of addressing the global energy crisis and reducing environmental pollution is solar cells that can convert solar energy into electrical energy. Applications of such dye-sensitized solar cells are increasingly attractive because dye-sensitized solar cells can be designed for high volume production and can be applied to buildings with low manufacturing costs, flexibility and optical transparency.

Recently, Gratzel et al . Has published a series of reports to confirm the practicality of dye-sensitized solar cells (eg O 'Regan, B .; Gratzel, M. Nature 1991 , 353, 737). The general structure of the dye-sensitized solar cell includes an anode, a cathode, a nano-porous titanium dioxide layer, a dye and an electrolyte, where the dye plays an important role in the conversion rate of the dye-sensitized solar cell. In charge of. Suitable dyes for the dye-sensitized solar cell must have the characteristics of a broad absorption spectrum, high molar absorption coefficient, thermal stability, and light stability.

Gratzel's lab revealed a series of ruthenium complexes as dyes for the dye-sensitized solar cells. In 1993, Gratzel's laboratory revealed a dye-sensitized solar cell made of N3 dye, the conversion of the dye-sensitized solar cell was 10.0% under the illuminance of AM 1.5 stimulated light. The incident photon-to-current conversion efficiency (IPCE) value of the N3 dye was 80% in the range of 400 to 600 nm. Although numerous ruthenium complexes have been developed, the conversion of these dye complexes has not been superior to N3 dyes. The structure of the N3 dye is represented by the following formula (a).

(A)

In 2003, Gratzel's laboratory revealed in detail a dye-sensitized solar cell made with N719 dye, the conversion of the dye-sensitized solar cell improved to 10.85% under the illumination of AM 1.5 induced light. Here, the structure of the N719 dye is represented by the following formula (b).

[Formula b]

Gratzel's lab also published a dye-sensitized solar cell made of black dye in 2004, with a conversion of 11.04% under the illuminance of AM 1.5 induced light. The black dye can improve the spectral response in the red and near-IR region, so that the conversion rate of the dye-sensitized solar cell can be improved. The structure of the black dye is represented by the following formula (c).

[Formula c]

In addition to ruthenium complexes such as the N3 dye, N719 dye, and black dye, other compounds that can be used in the dye-sensitized solar cell are platinum complexes, osmium complexes, iron complexes, and copper complexes. However, the results of various studies show that the conversion of the ruthenium complex is superior to other kinds of dye compounds.

The dye-sensitized solar cell dye has a great influence on the conversion rate. Therefore, there is a need to provide a dye compound capable of improving the conversion rate of the dye-sensitized solar cell.

The present invention provides a ruthenium composite used in the dye-sensitized solar cell for improving the photoelectric efficiency of the dye-sensitized solar cell.

The present invention also provides a dye-sensitized solar cell having excellent photoelectric properties.

Accordingly, the present invention provides a ruthenium complex represented by Formula 1 below:

here,

L ₁ is 2,2'-bipyridyl-4,4'-dicarboxylic acid, 2,2'-bipyridyl-4,4'-disulfonic acid, or 2,2'-bipyridyl-4 , 4'-diphosphonic acid;

L ₂ is 2,2'-bipyridyl-4,4'-dinonyl, or 2,2'-bipyridine-4,4'-ditridecyl;

,

,

,

, 또는

이고, 여기서 X는 N, 또는 P, R₁, R₂, R₃, 및 R₄는 서로 독립적으로 C_{1 -20} 알킬, 페닐, 또는 벤질, 및 R₅, R₆, R₇은 서로 독립적으로 C_{1 -20} 알킬; 및 m은 1, 또는 2이다. A is X ⁺ R ₁ R ₂ R ₃ R ₄ ,

,

,

,

, or

, Wherein X is N, or P, R _1, R _2, R _3, and R ₄ are independently C _{1 -20} alkyl, phenyl, or benzyl each other, and R _5, R _6, R ₇ independently of each other C _{1 -20} alkyl; And m is 1 or 2.

In Chemical Formula 1, L ₁ is 2,2'-bipyridyl-4,4'-dicarboxylic acid, 2,2'-bipyridyl-4,4'-disulfonic acid, or 2,2 '-Bipyridyl-4,4'-diphosphonic acid. Preferably, L ₁ is 2,2'-bipyridyl-4,4'-dicarboxylic acid.

In Formula 1, L ₂ may be 2,2'-bipyridyl-4,4'-dinonyl, or 2,2'-bipyridine-4,4'-ditridecyl. Preferably, L ₂ is 2,2'-bipyridyl-4,4'-dinonyl.

,

,

,

, 또는

이고, 여기서 X는 N, 또는 P, R₁, R₂, R₃, 및 R₄는 서로 독립적으로 C_{1 -20} 알킬, 페닐, 또는 벤질, 및 R₅, R₆, R₇는 서로 독립적으로 C_{1 -20} 알킬이다. 바람직하게는, A는 P⁺R₁R₂R₃R₄, 여기서 R₁, R₂, R₃, 및 R₄는 서로 독립적으로 C_{1 -20} 알킬, 페닐, 또는 벤질이다. 좀 더 바람직하게는, A는 N⁺R₁R₂R₃R₄, 여기서 R₁, R₂, R₃, 및 R₄는 서로 독립적으로 C_{1 -20} 알킬, 페닐, 또는 벤질이다. 좀 더 바람직하게는, A는 N⁺R₁R₂R₃R₄, 여기서 R₁, R₂, R₃, 및 R₄는 서로 독립적으로 C_{1 -20} 알킬, 페닐, 또는 벤질이다. In Chemical Formula 1, A is X ⁺ R ₁ R ₂ R ₃ R ₄ ,

,

,

,

, or

, Wherein X is N, or P, R _1, R _2, R _3, and R ₄ are independently C _{1 -20} alkyl, phenyl, or benzyl each other, and R _5, R _6, R ₇ are each independently selected from a C _1-20 alkyl. Preferably, A is a ^{_{P + R 1 R 2 R 3}} R 4, wherein _{R 1, R 2, R 3} , and R ₄ are independently of each other C _{1 -20} alkyl, phenyl, or benzyl. In more preferably, A is ^{_{N + R 1 R 2 R 3}} R 4, wherein _{R 1, R 2, R 3} , and R ₄ are independently of each other C _{1 -20} alkyl, phenyl, or benzyl. In more preferably, A is ^{_{N + R 1 R 2 R 3}} R 4, wherein _{R 1, R 2, R 3} , and R ₄ are independently of each other C _{1 -20} alkyl, phenyl, or benzyl.

In Chemical Formula 1, m may be 1 or 2. Preferably, m is one.

Specific examples of the ruthenium complex represented by Formula 1 are as follows:

[Formula 1a]

[Chemical Formula 1b]

[Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

The present invention also provides a dye-sensitized solar cell comprising the above-mentioned ruthenium composite.

Additionally, the dye-sensitized solar cell of the present invention comprises: (a) a photoanode comprising the ruthenium composite mentioned above; (b) a cathode; And (c) an electrolyte layer located between the photoanode and the cathode.

In the dye-sensitized solar cell of the present invention, the photoanode includes a transparent substrate, a transparent conductive film, a porous semiconductor film and a dye of the ruthenium composite.

In the dye-sensitized solar cell according to the present invention, the material of the transparent substrate of the photoanode is not particularly limited as long as the material of the substrate is a transparent material. Preferably, the material of the transparent substrate is a transparent material having excellent moisture resistance, solvent resistance and weather resistance. Thus, the dye-sensitized solar cell may resist moisture and gas from outside the transparent substrate. Examples of the transparent substrate include transparent inorganic substrates such as quartz and glass; And poly (ethylene terephthalate) (PET), poly (ethylene 2,6-naphthalate) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), and polyimide (PI) It includes a transparent plastic substrate. Optionally, the thickness of the transparent substrate is not particularly limited in the range that varies depending on the requirements for the transmittance and characteristics of the dye-sensitized solar cell. Preferably, the material of the transparent substrate is glass.

Furthermore, in the dye-sensitized solar cell of the present invention, the material of the transparent conductive layer is indium tin oxide (ITO), fluorine-doped tin oxide (FTO), ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ , or Tin-based oxides.

Additionally, in the dye-sensitized solar cell of the present invention, the porous semiconductor layer may be made of semiconductor particles. Suitable microparticles can include Si, TiO ₂ , SnO ₂ , ZnO, WO ₃ , Nb ₂ O ₅ , TiSrO ₃ , and mixtures thereof. Preferably, the semiconductor microparticles are TiO ₂ particles. The semiconductor particles may have an average diameter of 5 to 500 nanometers, preferably 10 to 50 nanometers. Furthermore, the thickness of the porous semiconductor layer may be 5 ~ 25 ㎛.

In the dye-sensitized solar cell of the present invention, the ruthenium composite may be the ruthenium composite mentioned above.

In addition, the material of the cathode used in the dye-sensitized solar cell is not particularly limited as long as it can include any conductive material. Optionally, the material of the cathode may be an insulating material, and a conductive layer is formed on the surface of the cathode in contact with the photoanode. The material of the cathode may be an electrochemically stable material. Suitable examples of the material of the cathode include Pt, Au, C, or the like.

Furthermore, the material used for the electrolyte layer of the dye-sensitized solar cell is not particularly limited as long as it can be any material capable of moving electrons and / or holes.

In addition, the present invention further provides a dye solution comprising the above-mentioned ruthenium complex.

The dye solution of the present invention (A) 0.01-1 wt% of the ruthenium complex; And (B) 99-99.99 wt% of an organic solvent, wherein the organic solvent is selected from the group consisting of acetonitrile, methanol, ethanol, propanol, butanol, dimethyl pomide, and N-methyl-2-pyrrolidone do.

Ruthenium composite according to the present invention has the effect of improving the photoelectric efficiency of the dye-sensitized solar cell.

Hereinafter, the features of the present invention will be described in more detail.

Ruthenium complex of the present invention can be synthesized by the following method.

Cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) (Z907 Dye) The Nature It is synthesized according to the method described in Material , 2003 , 2 , 402-407.

Cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) Is dispersed in distilled water, and 10% aqueous tetrabutylammonium hydroxide is added thereto, and the pH of the reaction solution is adjusted to 11. The reaction solution is then stirred until the ruthenium complex is completely dissolved in water. Finally, the pH value of the reaction solution is adjusted to 4.6 with 0.1 M nitric acid _{( aq )} to obtain a ruthenium complex represented by Formula 1a.

The method for producing the dye-sensitized solar cell of the present invention is not particularly limited, and the dye-sensitized solar cell of the present invention can be produced by conventional methods known to those skilled in the art.

The material of the transparent substrate is not particularly limited as long as the substrate material is a transparent material. Preferably, the material of the transparent substrate is a transparent material having excellent moisture resistance, solvent resistance and weather resistance. Thus, the dye-sensitized solar cell may resist moisture and gas from outside the transparent substrate. Examples of the transparent substrate include transparent inorganic substrates such as quartz and glass; And poly (ethylene terephthalate) (PET), poly (ethylene 2,6-naphthalate) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), and polyimide (PI) It includes, but is not limited to, a transparent plastic substrate. Optionally, the thickness of the transparent substrate can be varied according to the requirements for the transmittance and characteristics of the dye-sensitized solar cell is not particularly limited. In certain embodiments, the transparent substrate material is a glass substrate.

Furthermore, in the dye-sensitized solar cell of the present invention, the transparent conductive layer material is indium tin oxide (ITO), fluorine-doped tin oxide (FTO), ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ , or tin It may be a base oxide. In certain embodiments, fluorine-doped tin oxide is used as the transparent conductive layer.

In addition, the porous semiconductor layer is made of semiconductor particles. Suitable microparticles can include Si, TiO ₂ , SnO ₂ , ZnO, WO ₃ , Nb ₂ O ₅ , TiSrO ₃ , and mixtures thereof. First, the semiconductor particles are manufactured in the form of a paste, and the transparent conductive substrate is coated with the paste. Coating methods used here are blade coating, screen printing, spin coating and spray coating. In addition, the coating process may be performed one or more times to obtain a porous semiconductor layer of appropriate thickness. The semiconductor layer can be a single-layer or a multi-layer, wherein each layer of the multi-layer is formed by semiconductor particles having a different diameter. For example, the semiconductor particles having a diameter of 5 to 50 nm are coated to a thickness of 5 to 20 μm, and then the semiconductor particles having a diameter of 200 to 400 nm are coated thereon to a thickness of 3 to 5 μm. . Then, after drying at a temperature of 50 to 100 ° C., sintering is performed for 30 minutes in a temperature range of 400 to 500 ° C. in order to obtain a plurality of semiconductor layers.

The ruthenium complex may be dissolved in a solvent suitable for preparing a dye solution. Suitable solvents include, but are not limited to, acetonitrile, methanol, ethanol, propanol, butanol, dimethyl pomide, N-methyl-2-pyrrolidone or mixtures thereof. Here, the transparent substrate coated with the semiconductor layer is dipped into the dye solution until the semiconductor layer completely absorbs the dye from the dye solution. After dye absorption is completed, the transparent substrate coated with the semiconductor layer is moved and dried to obtain a photoanode for dye-sensitized solar cell.

In addition, the material of the dye-sensitized solar cell cathode is not particularly limited as long as it can include any conductive material. Optionally, the material of the cathode can be an insulating material, and a conductive layer is formed on the surface that abuts the photoanode. The material of the cathode may be an electrochemically stable material. Suitable examples of the material of the cathode include Pt, Au, C, or the like.

Furthermore, the material used for the electrolyte layer of the dye-sensitized solar cell is not particularly limited as long as it can be any material capable of moving electrons and / or holes. Additionally, the liquid electrolyte may be an iodine containing acetonitrile solution, an iodine containing N-methyl-2-pyrrolidone solution, or an iodine containing 3-methoxy propionitrile. In certain embodiments, the liquid electrolyte may be an iodine-containing acetonitrile solution.

One specific embodiment for manufacturing the dye-sensitized solar cell of the present invention is as follows.

First, a glass substrate covered with fluorine-doped tin oxide (FTO) with a paste containing TiO ₂ particles having a diameter of 20 to 30 nm is coated once or several times by screen printing. The glass substrate is then sintered at 450 ° C. for 30 minutes.

In order to prepare a dye solution of the ruthenium complex, the ruthenium complex is acetonitrile and t- butanol Dissolve in a mixture of (1: 1 v / v). Thereafter, the glass substrate with the porous TiO ₂ layer is dipped into the dye solution. After the porous TiO ₂ layer completely absorbs the dye in the dye solution, the final glass substrate is moved and dried to obtain a photoanode.

The glass substrate covered by fluorine-doped tin oxide is perforated to form an inlet having a diameter of 0.75 mm. Here, the injection hole is used to inject the electrolyte composition. The glass substrate covered by the fluorine-doped tin oxide is then coated with a H ₂ PtCl ₆ solution, and then the glass substrate is heated at 400 ° C. for 15 minutes to form a cathode.

Thereafter, a 60 μm thick thermoplastic polymer layer is placed between the photoanode and the cathode. The two electrodes are pressed at a temperature of 120 to 140 ° C. to attach the two electrodes.

The electrolyte is then injected, where the electrolyte is an acetonitrile solution containing 0.03 MI ₂ /0.3 M LiI / 0.5 M t -butyl-pyridine. After the inlet is sealed with a thermoplastic polymer layer, the dye-sensitized solar cell of the present invention is obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples. Units, parts, and percentages used in this example are by weight unless otherwise indicated, and temperatures are expressed in degrees Celsius. The relationship between parts by weight and parts by volume is equal to that between kilograms and liters.

Example 1

Cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) Tetrabutylammonium (Synthesis 1a)

Nature 1 part cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) synthesized according to the method described in Material , 2003 , 2 , 402-407 (2, 2'-bipyridyl-4,4'-dinonyl) ruthenium (II) (Z907 dye) and 10 parts of distilled water are added to the reaction flask, and the reaction solution is stirred to disperse the ruthenium complex. Then, tetrabutylammonium hydroxide in 10% aqueous solution is added dropwise to the reaction solution to adjust the pH of the reaction solution to 11. The reaction solution is continuously stirred until the ruthenium complex is completely dissolved in water. The pH value of the reaction solution is then adjusted to 4.6 using 0.1 M nitric acid _{( aq )} . After stirring the reaction solution for 18 hours, the product is filtered through a sintered glass filter to filter and then the product is washed with 5 parts distilled water having pH 4.1. Finally, 0.43 parts of black solid product (Formula 1a) was obtained, and the yield of the product (Formula 1a) was 85%.

Example 2

Cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) Synthesis of Bis (tetrabutylammonium) (Formula 1b)

Nature 1 part cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) synthesized according to the method described in Material , 2003 , 2 , 402-407 (2, 2'-bipyridyl-4,4'-dinonyl) ruthenium (II) (Z907 dye) and 10 parts of distilled water are added to the reaction flask, and the reaction solution is stirred to disperse the ruthenium complex. Then, tetrabutylammonium hydroxide in 10% aqueous solution is added dropwise to the reaction solution to adjust the pH of the reaction solution to 11. The reaction solution is continuously stirred until the ruthenium complex is completely dissolved in water. The pH value of the reaction solution is then adjusted to 5.5 using 0.1 M nitric acid _{( aq )} . After stirring the reaction solution for 18 hours, the product is filtered through a sintered glass filter to filter and then the product is washed with 5 parts distilled water having pH 4.1. Finally, 0.44 part of a black solid product (Formula 1b) was obtained, and the yield of the product (Formula 1b) was 70%.

Example 3

Cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) Synthesis of (Benzyltriethylammonium) (Formula 1c)

In Example 1, 5 parts of deionized water and 5 parts of methanol were used in place of 10 parts of deionized water, and benzyltriethylammonium hydroxide (TCI Co., Ltd.,) was synthesized in the same manner except for replacing with an aqueous solution. Finally, 0.35 part of a black solid product (Formula 1c) was obtained, and the yield of the product (Formula 1c) was 71%.

Example 4

Cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) Synthesis of Tetrabutylphosphonium (Formula 1d)

In Example 1, 5 parts of deionized water and 5 parts of methanol were used in place of 10 parts of deionized water, and a tetrabutyl phosphonium hydroxide aqueous solution was substituted for aqueous solution of tetrabutylammonium hydroxide. Except for the synthesis. Finally, 0.42 parts of black solid product (Formula 1d) was obtained, and the yield of the product (Formula 1d) was 81%.

Example 5

Cis-di (thiocyanato) (2,2'-bipyridyl-4,4'-dicarboxylic acid) (2,2'-bipyridyl-4,4'-dinonyl) ruthenium (II) Synthesis of (1-dodecylpyridinium) (Formula 1e)

In Example 1, 5 parts of deionized water and 5 parts of methanol were used instead of 10 parts of deionized water, and 98% of 1-dodecylpyridinium chloride reagent (ALDRICH) was used instead of aqueous tetrabutylammonium hydroxide. Synthesis was carried out in the same manner, except that it was replaced with an aqueous 1-dodecylpyridinium hydroxide solution. Finally, 0.32 parts of a black solid product (Formula 1e) was obtained, and the yield of the product (Formula 1e) was 63%.

Example 6

Manufacture of Dye-Sensitized Solar Cell

Glass substrates covered with fluorine-doped tin oxide (FTO) are coated one or several times with a paste containing TiO ₂ particles having a diameter of 20-30 nm. The thickness of the glass substrate is 4 mm, and the electrical resistance of the glass substrate is 10 Ω. The coated glass substrate is then sintered at 450 ° C. for 30 minutes and the thickness of the sintered porous TiO ₂ layer is 10-12 μm.

Ruthenium complex prepared by Example 1 is acetonitrile and t- butanol A dye solution, dissolved in a mixture of (1: 1 v / v) and containing 0.5 M ruthenium complex, is obtained. The glass substrate covered with the porous TiO ₂ layer is then dipped into the dye solution to attach a dye to the porous TiO ₂ layer. After 16 to 24 hours, the final glass substrate is moved and dried to obtain a photoanode.

The glass substrate covered with fluorine-doped tin oxide was perforated to form an injection hole having a diameter of 0.75 mm. Here, the injection hole is used to inject the electrolyte composition. The glass substrate covered by the fluorine-doped tin oxide was then coated with a H ₂ PtCl ₆ solution (2 mg Pt in 1 ml ethanol), and then the glass substrate was heated at 400 ° C. for 15 minutes to form a cathode. do.

Thereafter, a 60 μm thick thermoplastic polymer layer is placed between the photoanode and the cathode. The two electrodes are pressed at a temperature of 120 to 140 ° C. to attach the two electrodes.

The electrolyte is then injected, where the electrolyte is an acetonitrile solution containing 0.03 MI ₂ /0.3 M LiI / 0.5 M t -butyl-pyridine. After sealing the inlet with a thermoplastic polymer layer, the dye-sensitized solar cell of the present invention is obtained.

Example 7

Manufacture of Dye-Sensitized Solar Cell

The process of manufacturing the dye-sensitized solar cell of this embodiment was performed in the same manner as in Example 6, except that the ruthenium composite prepared by Example 2 was replaced with the ruthenium composite prepared by Example 1.

Example 8

Manufacture of Dye-Sensitized Solar Cell

The process of manufacturing the dye-sensitized solar cell of the present embodiment was performed in the same manner as in Example 6, except that the ruthenium composite prepared by Example 3 was replaced with the ruthenium composite prepared by Example 1.

Example 9

Manufacture of Dye-Sensitized Solar Cell

The process of manufacturing the dye-sensitized solar cell of this example was performed in the same manner as in Example 6, except that the ruthenium composite prepared by Example 4 was replaced with the ruthenium composite prepared by Example 1.

Comparative Example 10

Manufacture of Dye-Sensitized Solar Cell

The process of manufacturing the dye-sensitized solar cell of this comparative example was carried out in the same manner except that Z907 was replaced with the ruthenium composite prepared by Example 1 in Example 6.

Test method and result

Test of photoelectric properties

The short circuit current (J _SC ), open circuit voltage (V _OC ), and fill factor of the dye-sensitized solar cells prepared by Examples 6-9 and Comparative Examples ( FF), photoelectric conversion (η) and incident photon-to-current conversion efficiency (IPCE) are measured at the illuminance of the AM 1.5 induced light. The results are shown in Table 1 below.

Test results of dyes and dye-sensitized solar cells dyes J _SC (㎃ / ㎠) V _OC (V) FF η (%) Example 6 Formula 1a 0.739 9.60 64.82 4.60 Example 7 1b 0.728 9.60 61.19 4.28 Example 8 Formula 1c 0.746 9.68 64.88 4.68 Example 9 Formula 1d 0.736 9.53 64.31 4.51 Comparative example Z907 0.740 8.72 65.41 4.22

The results of Table 1 show that the short circuit current (J _SC ), the open circuit voltage (V _OC ) and the fill factor (FF) of the dye-sensitized solar cell manufactured by the ruthenium composite of the present invention are dye-sensitized by the Z907 dye. It shows improvement compared to solar cell.

In conclusion, the present invention differs from the prior art not only in several ways such as object, composition and effect, but also in technology and research and design. Although the present invention has been described in the preferred embodiments, those skilled in the art can make various modifications and changes within the scope of the claims of the present invention.

Claims (18)

Ruthenium complex represented by the following formula (1):
[Formula 1]

here,
L ₁ is 2,2'-bipyridyl-4,4'-dicarboxylic acid, 2,2'-bipyridyl-4,4'-disulfonic acid, or 2,2'-bipyridyl-4 , 4'-diphosphonic acid;
L ₂ is 2,2'-bipyridyl-4,4'-dinonyl, or 2,2'-bipyridine-4,4'-ditridecyl;
A is X ⁺ R ₁ R ₂ R ₃ R ₄ ,

,

,

,

, or

, Wherein X is N, or P, R _1, R _2, R _3, and R ₄ are independently C _{1 -20} alkyl, phenyl, or benzyl each other, and R _5, R _6, R ₇ independently of each other C _{1 -20} alkyl; And m is 1 or 2. The method according to claim 1,
The L ₁ is a ruthenium complex, characterized in that 2,2'-bipyridyl-4,4'-dicarboxylic acid. The method according to claim 1,
The L ₁ is a ruthenium complex, characterized in that 2,2'-bipyridyl-4,4'- disulfonic acid. The method according to claim 1,
The L ₁ is a ruthenium complex, characterized in that 2,2'-bipyridyl-4,4'-diphosphonic acid. The method according to claim 1,
The L ₂ is a ruthenium complex, characterized in that 2,2'-bipyridyl-4,4'-dinonyl. The method according to claim 2,
The L ₂ is a ruthenium complex, characterized in that 2,2'-bipyridyl-4,4'-dinonyl. The method according to claim 2,
And A is ^{_{N + R 1 R 2 R 3}} R 4, R 1, R 2, R 3, and R ₄ are independently C _{1 -20} alkyl, ruthenium complexes, it characterized in that the phenyl or benzyl each other. The method according to claim 2,
A is

,

,

,

, or

, And R _5, R _6, R ₇ is a ruthenium complex, characterized in that independently C _{1 -20} alkyl each other. The method according to claim 2,
Ruthenium composite, characterized in that m is 1. The method of claim 6,
And A is ^{_{N + R 1 R 2 R 3}} R 4, R 1, R 2, R 3, and R ₄ are independently C _{1 -20} alkyl, ruthenium complexes, it characterized in that the phenyl or benzyl each other. The method of claim 6,
A is

,

,

,

, or

, And R _5, R _6, R ₇ is a ruthenium complex, characterized in that independently C _{1 -20} alkyl each other. The method of claim 6,
Ruthenium composite, characterized in that m is 1. The method of claim 11,
Ruthenium composite, characterized in that m is 1. The method according to claim 1,
The ruthenium composite is a ruthenium composite, characterized in that the dye compound for dye-sensitized solar cells. A ruthenium complex represented by the following Formula 1a, 1b, 1c, or 1d.
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

[Formula 1d]

The method according to claim 15,
The ruthenium composite is a ruthenium composite, characterized in that the dye compound for dye-sensitized solar cells. (a) a photoanode comprising a ruthenium complex represented by Formula 1 below;
[Formula 1]

here,
L ₁ is 2,2'-bipyridyl-4,4'-dicarboxylic acid, 2,2'-bipyridyl-4,4'-disulfonic acid, or 2,2'-bipyridyl-4 , 4'-diphosphonic acid;
L ₂ is 2,2'-bipyridyl-4,4'-dinonyl, or 2,2'-bipyridine-4,4'-ditridecyl;
A is X ⁺ R ₁ R ₂ R ₃ R ₄ ,

,

,

,

, or

, Wherein X is N, or P, R _1, R _2, R _3, and R ₄ are independently C _{1 -20} alkyl, phenyl, or benzyl each other, and R _5, R _6, R ₇ independently of each other C _{1 -20} alkyl; And m is 1, or 2;
(b) a cathode; And
(c) a dye-sensitized solar cell comprising an electrolyte layer located between the photoanode and the cathode. (A) 0.01-1 wt% of the ruthenium complex represented by the following Formula 1;
[Formula 1]

here,
L ₁ is 2,2'-bipyridyl-4,4'-dicarboxylic acid, 2,2'-bipyridyl-4,4'-disulfonic acid, or 2,2'-bipyridyl-4 , 4'-diphosphonic acid;
L ₂ is 2,2'-bipyridyl-4,4'-dinonyl, or 2,2'-bipyridine-4,4'-ditridecyl;
A is X ⁺ R ₁ R ₂ R ₃ R ₄ ,

,

,

,

, or

, Wherein X is N, or P, R _1, R _2, R _3, and R ₄ are independently C _{1 -20} alkyl, phenyl, or benzyl each other, and R _5, R _6, R ₇ independently of each other C _{1 -20} alkyl; And m is 1, or 2; And
(B) 99.99-99 wt% of an organic solvent, wherein the organic solvent is a dye solution selected from the group consisting of acetonitrile, methanol, ethanol, propanol, butanol, dimethyl pomide, and N-methyl-2-pyrrolidone .