TW201014821A - Ruthenium complex and photoelectric component using the same - Google Patents

Abstract

The present invention relates to a ruthenium complex and a photoelectric component using the same, and the ruthenium complex is represented by the following formula (I): RuL2(NCS)2Am (I) wherein L, L' and X are defined the same as the specification. The ruthenium complex of the present invention is suitable for Dye-Sensitized Solar Cell (DSSC). Hence, the photoelectric characteristics of the DSSC manufactured with the ruthenium complex of the present invention can be improved.

Description

201014821 VI. Description of the Invention: [Technical Field] The present invention relates to a base metal complex and a photovoltaic element produced using the same, in particular to a dye-sensitized solar cell 5 (Dye-Sensitized Solar) Cell, DSSC) metal complex and dye-sensitized solar cells. [Previous technology] • With the development of human civilization, the world faces serious energy crisis and environmental pollution, and the direct conversion of solar energy into electrical energy by photoelectric solar cells is one of the important methods to solve the global energy crisis and reduce environmental pollution. Among them, the dye-sensitized solar cell has become a promising new type of solar cell because of its low manufacturing cost, large area, flexibility, and light transmittance for use in buildings. 15 In recent years, Gratzel et al. published a series of related literatures on dye-sensitized solar cells (eg 0' Regan, B.; GrStzel, M. Nature 1991, 353, _ 737), showing the utility of dye-sensitized solar cells. In general, the structure of a dye-sensitized solar cell includes a cathode/anode electrode, a nano titanium dioxide, a dye, and an electrolyte; a dye in a dye-sensitized solar cell has a critical influence on the efficiency of the battery 20, and an ideal dye has an Absorbs a wide range of solar spectrum, high absorption coefficient, high temperature stability and light stability.

Gratzel Laboratories has published a series of complexes as dyes in dye-sensitized solar cells. In 1993, GrStzel Laboratories published a dye-sensitized solar cell prepared using N3 Dye 4 201014821 with an efficiency of 10.0 ° / 〇 (ΑΜ 1.5). The single-wave photo-current conversion efficiency (IPCE) of the Ν3 dye can reach 80% in the range of 400 nm to 600 nm, and hundreds of dye complexes developed thereafter cannot exceed the N3 dye. The structure of the N3 dye is as shown in the following formula (a).

COOH

Ίο φ Until 2003, Gratzel Laboratories published a dye-sensitized solar cell prepared using N719 dye, which increased its efficiency to 10.85% (AM 1.5). The structure of the N719 dye is as shown in the following formula (b).

COOTBA

(b) 5 201014821 Then in 2004, the same laboratory published a dye-sensitized solar cell using Black dye, which achieved an efficiency of 11.04% (AM 1.5). The black dye enhances the spectral response of the red and infrared regions, thereby improving the performance of the dye-sensitized solar cell. The structure of the black dye is as shown in the following formula (c).

COOTBA

TBAOOC

HOOC

/NCS RU\

'NCS

NCS (C) 10

In addition to the related series of N3 dyes, N719 dyes and black dyes published by GrStzel Laboratories, other similar platinum-compounds, hungry complexes, iron complexes, copper complexes, etc. Wait. However, after many studies, the efficiency of the ruthenium complex is still better. Dyes in dye-sensitized solar cells have a critical impact on cell efficiency. Therefore, finding dye molecules that can improve the efficiency of dye-sensitized solar cells is one of the important methods to improve the efficiency of dye-sensitized solar cells. SUMMARY OF THE INVENTION The present invention provides a novel base metal complex which is suitable for dye-sensitized solar cells and which can increase the photoelectric efficiency of dye-sensitized solar cells. 15 201014821 Μ The present invention further provides a dye-sensitized solar cell having a high photoelectric efficiency. The base metal complex of the present invention has the following structure (1): 5

RuL2(NCS)2Am (I) where L is 2,2'-double mouth ratio _4,4'_ dicarboxylic acid (2,2'-1)1?3^(1丫1-| 4,4, -dicarboxylic acid), 2,2,-bipyridine-4,4'-disulfonic acid 10 (2,2'-bipyridyl-4,4'-disulf〇nic acid) or 2,2'-bipyridine-4 , 4'-discalic acid (2,2,-bipyridyl-4,4,-ciiphosphonic acid);

❹ Phenyl or benzyl, R2, R3, and 尺4 are each independently 15 as Cwo alkyl, phenyl or benzyl 'R5, Re, and 尺7 are each independently C ^oalkyl; m is an integer from 1 to 4. In the above formula (I), L may be 2,2'-bipyridine-4,4,-dicarboxylic acid, 2,2,-bipyridine-4,4,-disulfonic acid or 2,2'-double Pyridine-4,4,-diphosphate. Preferably, 20 L is 2,2'-bipyridine-4,4,-dicarboxylic acid 201014821

In the above formula (1), A can be,

Ίο is alkyl, phenyl or benzyl, 'R3, and & are each independently Cwo, phenyl or benzyl, and &, & and ruler 7 are each independently (: 丨_ 2〇alkyl; preferably, a is n+R^H, wherein R丨 is C5-2〇, phenyl or benzyl, and &, R3, and R4 are each independently C^o More preferably, a is N+Ril^n, wherein R is a C5-2 decyl group, a phenyl group or a phenyl fluorenyl group, and R2, R3, & R4 are each independently Cw alkyl 'stupyl or benzyl; best, a is N + HH 'wherein R 1 is C 5 2 alkyl, phenyl or phenyl fluorenyl, ^, R 3 , and R 4 are each independently cN 6 alkyl In the above formula (I), m may be an integer of 1 to 4; preferably, 〇1 is an integer of 2 or 3.

Specific examples of the ruthenium metal complex of the above formula (I) are:

15 201014821

(1-2)

(1-3) 9 201014821 ❿

(1-4)

4 (I_5)

Οο 201014821 (1-6) 〇., /O'N^CI^CHWPh)

5 0^0- N+(CH2CH3)3CPh) (1-7) ο

11 201014821

The dye-sensitized solar cell provided by the present invention contains the above-described ruthenium metal complex. Further, the dye-sensitized solar cell of the present invention comprises: a photoanode containing 10 of the above-described base metal complex; a cathode 12 201014821 (cathode); and an electrolyte layer between the photoanode and the cathode (electrolyte) Layer). 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 ruthenium 5 conjugate dye; in the dye-sensitized solar cell of the present invention, photoelectric The material of the transparent substrate of the anode is not particularly limited, and any substrate can be used as long as it is transparent. Preferably, the material of the transparent substrate is a transparent substrate having good barrier properties, solvent resistance, weather resistance, and the like for moisture or gas invaded by the φ portion of the dye-sensitized solar cell. Specific examples of the transparent substrate include: transparent inorganic substrates such as quartz and glass; polyethylene terephthalate (PET), poly(ethylene naphthalate) (PEN), polycarbonate (PC), A transparent plastic substrate such as polyethylene (pE), polypropylene (PP), or polyimine (PI), but is not limited thereto. Further, the thickness of the transparent substrate is not particularly limited, and can be freely selected in accordance with the light transmittance and the characteristics of the dye-sensitized solar cell. Preferably, the transparent substrate is made of glass. Further, in the dye-sensitized solar cell of the present invention, the material of the transparent conductive film may be indium tin oxide (ITO), fluorine-doped tin oxide (FT〇), oxidized-gallium-gallium oxide (Zn0-Ga203). ), zinc oxide, antimony oxide 20 (Ζη〇-Α12〇3), or oxide-based oxide materials. Further, in the dye-sensitized solar cell of the present invention, the porous semiconductor film is made of semiconductive particles. Suitable semiconductor microparticles may include: ruthenium, titanium dioxide, tin dioxide, zinc oxide, tungsten trioxide, pentoxide, bismuth oxide, and combinations thereof; preferably, the semiconductor microparticles are 13 201014821 'titanium dioxide. The semiconductor fine particles have an average particle diameter of 5 to 500 nm, preferably 10 to 50 nm. The thickness of the porous semiconductor film is 5 to 25 μm. In the dye-sensitized solar cell of the present invention, the base metal complex dye is a base metal complex as described above. Further, the cathode material of the dye-sensitized solar cell is not particularly limited and may include any material having conductivity. Alternatively, the cathode material may be an insulating material as long as a conductive layer is formed on the surface facing the photoanode. Electrochemically stable materials are available as cathodes, and non-limiting examples of materials suitable for use in the cathode φ material include platinum, gold, carbon, and the like. Further, the electrolyte layer as the dye-sensitized solar cell is not particularly limited and may include any substrate having electron and/or hole conductivity. [Embodiment] The base metal complex of the present invention can be synthesized in the following manner. 15 bis-dithiocyanobis(2,2,-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) (cz'i-di(thiocyanato)-Ar,iV,-bis(2,2 ,-bipyridyl-4,4,-dicarboxylic .acid)ruthenium (II), N3 dye) was synthesized according to the method of Inorganic, Vol. 38, No. 26, 1999, 6298-6305. Dissolving gal-dithiocyano-MiT-bis(2,2'-bipyridine-4,4'-dicarboxylic acid) oxime 20 (II) in distilled water, and then dropping 10% hydroxybenzoyl group An aqueous solution of benzyltributylammonium hydroxide (formulated with benzyltributylammonium chloride reagent (ACROS, 98%)) is added to the reaction solution until the pH of the reaction solution reaches 10, and then Concentrate to obtain a viscous liquid. The viscous liquid was dissolved in methanol (methanol), and then diethyl ether was added to precipitate the product, which was taken to dryness and dried under vacuum for one day. The dried solid is dissolved in steaming water, and the pH is adjusted to 5 or less with an aqueous solution of ο] M acid (nitHe aeid) to obtain a metal complex of the formula (M). The method for producing the dye-sensitized solar cell of the present invention is not particularly limited, and it can be produced by a generally known method. The material of the transparent substrate is not particularly limited, and any transparent substrate can be used. Preferably, the material of the transparent substrate is a transparent substrate having good barrier properties, solvent resistance, weather resistance, etc., for moisture or gas invaded by the exterior of the dye-sensitized solar cell, and specifically, quartz, glass, etc. Through 10 inorganic substrates, polyethylene terephthalate (PET), poly(ethylene naphthalate) (PEN), polycarbonate (PC), polyethylene (pE), polypropylene (pp), The transparent plastic substrate such as polyimide (PI) is not limited to these. The thickness of the transparent substrate is not particularly limited, and can be freely selected by the light transmittance and the characteristics of the dye-sensitized solar cell. In a specific example, the transparent substrate 15 is a glass substrate. The material of the transparent conductive film may be selected from indium tin oxide (ITO), fluorine-doped Φ-tin oxide (FT〇), oxidized-di-gallium oxide (ZnO-Ga2〇3), and oxidized word_2 ΖηΟ-Α12〇3), and yttrium-based oxide materials. In a specific example, the transparent conductive film is tin oxide doped with fluorine. 20 The porous semiconductor film is made of semiconductor fine particles. Suitable semi-conducting particles include antimony, titanium dioxide, tin dioxide, oxidized, tungsten trioxide, antimony pentoxide, antimony trioxide, and combinations thereof. First, the semiconductor microparticles are first formulated into a paste, which is then applied to a transparent conductive substrate. The coating method can be applied by a doctor blade, screen printing, spin coating, spraying, etc. or a general wet type 15 201014821 ' cloth. Further, in order to obtain an appropriate film thickness, the β semiconductor film layer may be applied one or more times in a single layer or a plurality of layers, and the multilayer layer means semiconductor particles having different particle diameters in each layer. For example, semiconductor particles having a particle diameter of 5 to 5 nanometers may be coated first, and the coating thickness is 5 to 20 micrometers, and then semiconductor particles having a particle diameter of 2 to 5 to 400 nm are coated and coated. The cloth has a thickness of 3 to 5 microns. Then, after drying at 50 to 100 C, and sintering at 400 to 500 ° C for 30 minutes, a multilayer semiconductor film layer can be obtained. The ruthenium metal complex dye can be dissolved in a suitable solvent to form a dye lysate. Suitable solvents include acetonitrile, methanol, ethanol, propanol, butanol, 10 decyl decylamine, N-decyl pyrrolidone or a mixture thereof, but are not limited thereto. Here, the transparent substrate coated with the semiconductor film is immersed in the dye solution to sufficiently absorb the dye in the dye solution, and is taken out and dried after the dye absorption is completed, whereby a photoelectrode anode of a dye-sensitized solar cell can be obtained. The material as the cathode is not particularly limited and may include any material having conductivity. Alternatively, the cathode material may be an insulating material as long as a conductive layer is formed on the surface facing the photoanode. In addition, electrochemically stable materials can serve as the cathode, and non-limiting examples of suitable cathode materials include platinum, gold, carbon, and the like. The electrolyte layer is not particularly limited and may include any substrate having electron and/or hole conductivity. Further, the liquid electrolyte may be an iodine-containing acetonitrile solution, an iodine-containing N-methylpyrrolidone solution, or an iodine-containing 3-methoxypropionitrile solution. In one embodiment, the liquid electrolyte is an acetonitrile solution containing iodine. 16 201014821 Dye sensitivity of the present invention First, a solar cell will be included as follows. The granule paste is grounded by tin oxide micro-tin oxide (FTO) with a particle size of 20-30 nanometers (nm) and/or several times of screen printing on the gas-filled (10) 瑕It was then sintered at 450 ° C for 30 minutes. #钌metal complex dissolved in acetonitrile (acet〇nitrile) and final butanol ibutan'l solution (1:1 v / v) into a ruthenium metal complex dye soluble 10 followed by 'the above containing porous titanium oxide The glass plate of the film is immersed in the dye, and after it absorbs the dye in the dye solution, it is taken out and dried to obtain a photoanode. A fluorine-doped tin oxide glass plate was drilled with an injection port having a diameter of 0.75 mm for injection into the electrolyte. The vaporized platinum acid (H2PtCl6) solution was coated on a fluorine-doped tin oxide glass plate and then heated to 400 C for 15 minutes to obtain a cathode. Then, a thermoplastic polymer film having a thickness of 60 μm was placed between the photovoltaic anode and the cathode, and a pressure was applied to the two electrodes at 120 to 140 ° C to bond the two electrodes. The dye-sensitized battery of the present invention is obtained by injecting an electrolyte (0.03 M I2/0.3 M LiI/0.5 Μ tri-butylpyridine in acetonitrile) and sealing the injection port with a thermoplastic polymer film. The following examples are merely illustrative of the invention, and the scope of the invention is not limited thereby. Unless otherwise stated, the temperature is in degrees Celsius and the parts and percentages are by weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters. 25 Lean application 1 17 201014821 Synthesis of hydrazine-dithiocyano-state bismuth-bis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) bis(benzyltributylammonium) (cz\s-di(thiocyanato)-7V,7V,-bis(2,2'-bi pyridyl-4,4,-dicarboxylic acid)ruthenium(II)bis(benzyl tributyl ammonium) (1-1) 5 0.50 parts of poly-dithiocyano-state bis(2,2'-bipyridine-4,4'-didecanoyl) hydrazine (cz) (cz\s-di(thiocyanato)-W'-bis (2,2'-bipyridyl-4,4'-dicarboxylic acid)ruthenium(II), N3 dye) (according to Inorganic Chemistry, Vol. 38, No. 26, 1999, 6298-6305 ^ by synthesis) and 10 parts Distilled water was added to the reaction flask, stirred and mixed, and then dropped into 10 10% aqueous solution of benzyltributylammonium hydroxide (benzyl tributary lammonium chloride reagent (ACROS, 98%). ) was prepared in the reaction solution until the pH of the reaction solution was stabilized to 10, and then the solvent was distilled off by a rotary-evaporator to obtain a viscous liquid. Next, the viscous liquid was dissolved in methanol, and then diethyl ether was added to produce a precipitate, which was taken out and dried under vacuum for one day. The dried solid mash was dissolved in 10 parts of distilled water, and the pH was adjusted to 5 or less with a 0.1 ni aqueous solution of nitric acid, and the product was collected by a sintered glass filter and used. The product was washed with 20 parts of distilled water of pH 4.1 to give 0.52 part of a white solid product of formula (1-1), yield 61.5%. Example 2 Synthesis of hydrazine-dithiocyanobis(2,2'-bipyridine-4,4'-didecanoyl) ruthenium (II) 25 bis(benzyltriethyl hydroxy-Kc/j-diGhiocyanatcO- A^A^'-bisQJ'-bi 18 201014821 pyridyl-4,4,-dicarboxylic acid)ruthenium(II)bis(benzyl triethyl ammonium) (1-2) The same procedure as in Example 1 was carried out to prepare the present example. The compound was replaced by an aqueous solution of hydroxytriphenylammonium tributylammonium using an aqueous solution of benzyltriethylammonium 5 hydroxide (TCI Co., Ltd.). 0.30 parts of a black solid product of the formula (1-2) was obtained in a yield of 41.1%. Example 3 Synthesis of bis-dithiocyano bis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) % bis(triethylhexyl ammonium Xch-dKthiocyanato) - see i\T -bis(2,2',bi pyridyl-4,4,-dicarboxylic acid)ruthenium(II)bis(triethyl hexyl ammonium)) (1-3) 0.50 parts of 膺-dithiofluoro-AT, #,- Bis(2,2'-bipyridyl-4,4'-didecanoyl) ruthenium (Π) and 1 part distilled water were added to the reaction flask and stirred to mix 're-drop 15 into 10% triethylhexyl hexahydrochloride (triethylhexylammonium hydroxide) aqueous solution (prepared with triethylhexylammonium bromide reagent (ALDRICH, 993⁄4) 0) into the reaction solution 'until the pH of the reaction solution stabilizes to 12' and then distilled off with a rotary evaporator The solvent gave a viscous liquid. Then the viscous liquid 2 was dissolved in methanol, and then a precipitate was added to produce a precipitate. The solid product was taken out and dried under vacuum for one day. The dried solid was dissolved in 10 parts of steaming water, and the pH was adjusted to below 4 with a 0.1 Torr aqueous solution of nitric acid. The product was collected by filtration through a sintered glass filter, and the product was washed with 5 parts of steamed water of pH 4.1. 0.44 parts of a black solid product of the formula (1-3) was obtained in a yield of 25 81.5%. 19 201014821 Example 4 Synthesis of broad-dithiocyanato-AT, #'-bis(2,2'-bipyridine-4,4'-didecanoyl) ruthenium (II) bis(1-dide) 0 ratio bite Xc/s-diGhiocyanatc^-T^iV'-bispe'-bi 5 pyridyl-4,4,-dicarboxylic acid)ruthenium(II)bis(l-dodecyl pyridinium)) (1-4) The same procedure as in Example 3 was carried out except that the compound of the present example was used, except that 1-dodecylpyridinium hydroxide was used (aqueous solution of 1-dodecylpyridinium hydroxide) (1-dodecylpyridinium) 1 〇 chloride reagent, ALDRICH, 98%) was prepared by substituting an aqueous solution of triethylhexylammonium hydroxide. 0.20 parts of a black solid product of the formula (1-4) was obtained in a yield of 32.8%. Example 5 15 Synthesis of bis-dithiocyano-state #,-bis(2,2'-bipyridine-4,4,-dicarboxylic acid) ruthenium (Π) Tris(benzyltriethylep) Ci5_di(thiocyanato)-iV,iV'-bis(2,2',bi pyridyl-4,4,-dicarboxylic acid)ruthenium(II)tris(benzyl gintriethyl ammonium) (1-5) 0.20 parts 10% An aqueous solution of hydroxybenzylidene triethylammonium and 100 parts of 20 methanol were added to the reaction flask, stirred and mixed, and then 〇.1 〇 part of bis-dithiocyano bis(2,2'-bipyridine-4,4, - bis(decanoic acid) ruthenium (II) bis(phenylmercaptotriethylammonium) (1-2) into the reaction mixture, and the mixture is stirred and stirred for 2.5 hours. Then the solvent is distilled off by a rotary evaporator to obtain a precipitated product. The product was collected by filtration through a sintered glass filter, and the product was washed with 10 parts of distilled water to obtain 0.08 parts of a black solid product of formula (1-5) in a yield of 74.0%. 20 201014821 Example 6 Synthesis of broad-dithiocyano-state bis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) tetrakis(phenylmethyltriethyl bond Xc^-diGhiocyanatcO -iV^iV'-bisPJ'-bi 5 pyridyl-4,4,-dicarboxylic acid)ruthenium(II)tetrakis(benzyl triethyl ammonium) (1-6) 0.50 parts of broad-dithiocyano-state double 2,2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium (II) and 50 parts of distilled water were added to the reaction flask, stirred and mixed, and then added with 10% aqueous solution of hydroxyoxybenzyltriethylammonium. In the reaction solution, until the pH of the reaction solution was stabilized to 7, the solvent was distilled off by a rotary evaporator to obtain a viscous liquid. The viscous liquid was dissolved in methanol, and diethyl ether was added to give a precipitate. The hygroscopic solid product was taken out and dried under vacuum for one day to obtain 0.43 parts of a black solid product of formula (1-6) in a yield of 68.0%. . 15 Example 7 Production of a dye-sensitized solar cell A paste β comprising 'oxidized granules having a particle diameter of 20 to 30 nanometers (nm) was coated with fluorine by one or several times of screen printing. a heterogeneous tin oxide (FTO) glass plate (thickness 4 mm, resistance ΙΟ Ω / port), so that the thickness of the porous titanium oxide film after sintering is 10 to 12 μm (ym), and then sintered at 450 ° C for 30 minutes. . The ruthenium metal complex of Example 1 was dissolved in a mixture of acetonitrile and butaneol (ΐ··ΐν/ν) to prepare a dye solution having a ruthenium metal complex concentration of 0.5 Μ. Next, the above-mentioned glass plate containing the porous oxide 25 immersion film is immersed in the dye solution, and it is absorbed in the dye solution. After 16 to 24 hours, the film is taken out and dried to obtain a photoanode. ° A fluorine-doped tin oxide glass plate is drilled to a diameter of 0.75 mm for injection into the electrolyte, and then a solution of platinum oxynitride (H2PtCl6) (1 mg of platinum in 1 liter of ethanol) is applied. The cathode was placed on a tin oxide glass plate and then heated to 400 ° C for 15 minutes to obtain a cathode. A thermoplastic polymer film having a thickness of 60 μm was placed between the photoanode and the cathode, and a pressure was applied to the two electrodes at 120 to 140 ° C to bond the electrodes. 10 Injecting an electrolyte solution (0.03 Μ Ι 2/0·3 M LiI/0.5 Μ tri-butyl pyridine in acetonitrile), and sealing the injection port with a thermoplastic polymer film, the dye-sensitized solar cell of the present embodiment can be obtained. Example 8 15 Preparation of Dye-Sensitized Solar Cell The dye-sensitized solar cell of this example was prepared in the same manner as in Example 7, except that the ruthenium metal complex of Example 2 was used in place of the ruthenium metal complex of Example 1. . 20 Example 9 Production of dye-sensitized solar cell The dye-sensitized solar cell of this example was prepared in the same manner as in Example 7, except that the base metal complex of Example 1 was used instead of the base metal complex of Example 1. 22 25 201014821 Example ί Manufacturing a dye-sensitized solar cell The same procedure as in Example 7 was carried out to prepare the dye-sensitized solar cell of the present example, except that the ruthenium metal complex of Example 4 was used instead of the ruthenium metal of Example 15. Compound. Example 11 Production of Dye-Sensitized Solar Cell φ The dye-sensitized solar cell of the present Example was prepared in the same manner as in Example 7 except that the ruthenium metal complex of Example 5 was used instead of the ruthenium metal of Example 1. Compound. Example 12 Production of Dye-Sensitized Solar Cell 15 A dye-sensitized solar cell of this example was prepared in the same manner as in Example 7, except that the metal-metal complex of Example 6 was used in place of the nail metal complex of Example 1. φ Comparative Example 20 A dye-sensitized solar cell was prepared in the same manner as in Example 7 except that N719 was used instead of the ruthenium metal complex of Example 1. Test Methods 舆 Results Photoelectric Efficiency Test 25 The dye-sensitized solar cells of Examples 7 to 12 and Comparative Examples were tested for short-circuit current (Jsc), open circuit voltage (Voc), and fill factor under illumination of 23 201014821 ' AM 1.5 ( FF), photoelectric conversion efficiency (η) and single-photon photo-current conversion efficiency (IPCE) 〇 test results are organized as follows: Table 1 Test results of dye-sensitized solar cells Dye Jsc (mA/cm2) V 〇 c (V) FF η (%) Example 7 1-1 8.22 0.78 0.64 4.09 Example 8 1-2 9.42 0.79 0.62 4.54 Example 9 1-3 8.46 0.80 0.64 4.33 Example 10 1-4 6.98 0.68 0.63 3.00 Example 11 1-5 7.84 0.81 0.65 4.12 Example 12 1-6 7.99 0.75 0.62 3.74 Comparative Example N719 7.36 0.76 0.61 3.38 The test results shown in Table 1 show that the ruthenium metal complex of the present invention was used. The dye-sensitized solar cell of the present invention can improve the short-circuit current and open circuit voltage of the dye-sensitized solar cell as compared with the dye-sensitized solar cell manufactured by N719 in Comparative Example. Fill factor, thereby increasing the photoelectric conversion efficiency of the dye-sensitized solar cell. In summary, the present invention exhibits its characteristics different from those of the prior art in terms of purpose, technique, and efficacy, or in terms of its technical level and R&D design. It should be noted that the above-described embodiments are merely illustrative for the sake of convenience of description, and are not intended to limit the invention, and that the skilled artisan will be able to do so without departing from the spirit and scope of the invention. The invention may be modified and modified, and the scope of the claims is intended to be limited to the above embodiments. The above-described embodiments are merely exemplified for the convenience of the description, and the claims are intended to be within the scope of the above-mentioned embodiments. ‘,“平’ instead of only [圏式说明] ❹无. 10 [Main component symbol description] None. ❹ 25

Claims (1)

201014821 VII. Patent application scope: 1. A ruthenium metal complex with the following structure (I): RuI>2(NC S)2Am (I) 5 wherein L is 2,2,-bipyridine _4,4 '_Dicarboxylic acid (2,2,-bipyridyl-4,4'-dicarboxylic acid), 2,2'-dipyridyl 4,4'-disulfonic acid (2,2'-bipyridyl-4,4'- Disulfonic acid) or 2,2'_double" than 2,2'-bipyridyl-4,4'-diphosphonic acid; Phenyl or benzyl, R_2, R_3, and R_4 are each independently a Cuoxyl group, a phenyl group or a benzyl group, and each of R7 is independently C1.2. An alkyl group; and 15 m is an integer from 1 to 4. 2. The metal complex according to claim 1, wherein L is 2,2'-double β ratio _4,4'·dicarboxylic acid. 3. The base metal complex according to claim 1, wherein L is 2,2'-double n to bite 4,4'-dihydro acid. 2. The base metal complex according to claim 1, wherein L is 2,2'-bipyridine-4,4'-diphosphate. 26 201014821 5. The metal ruthenium complex as described in claim 1, wherein N+RlR2R3R4 'R! is C5.20 alkyl, phenyl or benzyl, and R2, r3, and R4 are each independently It is an alkyl group, a phenyl group or a benzyl group. 6. The ruthenium metal complex according to claim 2, wherein A is N+RlR2R3R4 'RAC5_20 alkyl, phenyl or benzyl, and R2, r3, and R4 are each independently a C6 alkyl group. 7 7· The ruthenium metal complex as described in claim 2, wherein And R5 is a c-based group. 8. The ruthenium metal complex as described in claim 2, wherein 9. The ruthenium metal complex according to claim 3, wherein Α is 'r^C5 2〇 alkyl, phenyl or benzyl, and r2, ^, and R4 are each independently a C6 alkane. base. 10. The base metal complex according to claim 3, wherein 15 m is 2 or 3 » 11. The base metal complex according to claim 4, wherein And 5 is Ci 2 oxime. 12. The base metal complex as described in claim 4, wherein in is 2 or 3. 13. The nail metal complex according to claim 1, wherein the metal complex is a dye compound for a dye-sensitized solar cell. 0 27 201014821 14. A base metal complex, The structure is as follows (1-2) or the following formula (1-3), (1-3). 15. The base metal complex according to claim 14, wherein the base metal complex is a dye compound for a dye-sensitized solar cell. 16. A dye-sensitized solar cell comprising: (a) a photoanode comprising a sulphide complex of the following formula (I); RuL2 (NCS) 2Am 28 (i) 201014821 wherein disulfonic acid or L is 2,2'-double bite-4,4,-dicarboxylic acid, 2,2,_biguanide 唆4,4,2,2'-bipyridine-4,4,_diphosphate; 10 4 »5 , R? , n-R5 R5 N, Rs, wherein, R! is c benzyl, and m R4 are each independently Ci2. The alkyl group, the phenyl group or the benzyl group 'R5, R6, and R7 are each independently Ci-2. And: (b) a cathode; and (c) an electrolyte layer between the photoanode and the cathode. 17. A dye solution comprising: (A) - a ruthenium metal complex of the following formula (I) in an amount of owq weight @ percentage: 15 RuL2(NCS)2Am (I) wherein L is 2, 2' -bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4,-disulfonic acid or 2,2'-bipyridine-4,4'-diphosphate; 29 20 201014821 Re-N- , 5 ' ' where 'Rl is C5-2. The alkyl group, the phenyl group or the methyl group, and R2 and m are each independently Ci2. The alkyl group, the phenyl group or the benzyl group 'R5, R6, and r7 are each independently 12. And m is an integer of from 1 to 4; and 5 (B) an organic solvent in an amount of from 99% to 99% by weight, the organic solvent being selected from the group consisting of: acetonitrile, methanol, ethanol, propanol, butyl A group consisting of an alcohol, methyl amanta, and N. methyl ketone. 30 201014821 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: RuL2(NCS)2Am (I) where L, A, and m are as defined in the specification. 3