TWI377196B - Ruthenium complex and photoelectric component using the same - Google Patents

Description

1377196 VI. Description of the Invention: [Technical Field] The present invention relates to a base metal complex and a photovoltaic element produced using the same, and in particular to a dye-sensitized solar cell 5 (Dye-Sensitized Solar) CeU, DSSC) bismuth metal complexes and dye-sensitized solar cells. [Prior Art] ® With the development of human civilization, the world faces serious energy crisis and environmental pollution. The photoelectric solar cell directly converts solar energy into electrical energy, which 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 dye-sensitized solar cell related literatures (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 Absorption of a large range of solar spectrum, high absorption coefficient (absorption coefficient), high temperature stability and light stability.

GrStzel 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 1377196 5 with an efficiency of 10.0% (ΑΜ 1.5). The single-wave photo-current conversion efficiency (IPCE) of the N3 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

10 Until 2003, GrStzel 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 1377196 Then, in 2004, the dye-sensitized solar cell prepared by using the black dye was published in the laboratory with 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

In addition to the related series of N3 dyes, N719 dyes and black dyes published by GrStzel Laboratories, other similar compounds are platinum complexes, 锇10 complexes, iron complexes, and copper complexes. ..and many more. However, after many studies, it has been shown that the efficiency of the compound is still better. Because dyes in dye-sensitized solar cells have a critical ® effect 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. 1377196 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:

RuL2(NCS)2Ai (I) where L is 2,2'-double. Than 4,4,-dicarboxylic acid (2,2'-bipyridyl-4,4'-dicarboxylic acid), 2,2'-double ratio bite-4,4,-disulfonic acid (2,2' -bipyridyl-4,4'-disulfonic acid) or 2,2,-bipyridyl 4,4'-dibronic acid (2,2'-bipyridyl-4,4'-diphosphonic acid); n-r5

A is N R1R2R3R4

Let Ri be a C5-20 alkyl group,

15 independently phenyl (phenyl) or benzyl (benzyl), R2, R3, and R4 are each independently Cw alkyl, phenyl or benzyl, and R5, 'and R7 are each CbM alkyl; m is an integer from 1 to 4. In the above formula (I), L may be 2,2'·bis 0-pyridine-M,·dimethyl sulphate, 2 2 bispyridin-4,4′-dicarboxylic acid or 2,2′-bipyridine _ 4,4'-diphosphate. Preferred L is 2,2'-bipyridine-4,4'-dicarboxylic acid. 20 1377196 In the above formula (I), A may be N, RiR2R3R4, Q^Rs

For C5-20 炫, 笨基 & | where R! soil sub-f, R2, R3, and other C, _2G alkyl, stupid 戌 from independent 5

忒 〒 ,, R5, R6, and R7 each of the white molybdenum A is 〇ν20 appearance; respectively, preferably, A is Mm, which makes 10: danic, phenyl or benzene f-based 'R 2, R 3, And r 4 are each independently '., a Cl-20 alkyl group, a phenyl group or a benzyl group; more preferably, A is N+RlR2R3R, wherein R! is a C5-2 alkyl group, a phenyl group or a benzyl group. , Rs, &, and heart 4 from independent knife is C! · 6 alkyl, phenyl or benzyl; optimal, a is N + RlR2R3R4, which makes the heart c52 alkyl, phenyl Or benzyl, I, R3, and R4 are each independently a CN6 alkyl group. In the above formula (I), m may be an integer of 1 to 4; preferably, an integer of 2 or 3. ...

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

(1-1) 15 1377196

(1-2)

1377196

(1-4)

• (1-5)

10 1377196 (1-6)

(1-7) 5

Ο 0=S-0* ^(CHzCHiCHzCHaJjiCHjPh)

(1-8) IS] 11 1377196

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 1377196 - (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 complex. In the dye-sensitized solar cell of the present invention, the material of the transparent substrate of the photoanode 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 which has good barrier properties, solvent resistance, weather resistance, and the like for the moisture or gas invaded by the dye-sensitized solar cell. Listed include: transparent inorganic substrates such as quartz and glass; polyethylene terephthalate (poly), poly(ethylene naphthalate) (ruthenium), polycarbonate (PC), polyethylene (ΡΕ) A transparent plastic substrate such as polypropylene (poly) or polyimine (fluorene), 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. In addition, in the dye-sensitized solar cell of the present invention, the material of the transparent conductive film may be indium tin oxide (yttrium oxide), fluorine-doped tin oxide (FT〇), or oxidized-gallium trioxide (Zn〇_). Ga2〇3), oxidized word_aluminum oxide.20 (Zn〇-A12〇3), or a cerium-based oxide material. Further, in the dye-sensitized solar cell of the present invention, the porous semiconductor film is made of semiconductor fine particles. Suitable semiconductor microparticles may include: ruthenium, titanium dioxide, tin dioxide, zinc oxide, tungsten trioxide, five: two silver, titanium oxide, and combinations thereof; preferably, the semiconductor microparticles are IS1 13 1377196 - 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 can be used as cathodes and are suitable for cathodes. Non-limiting examples of materials include: platinum, gold, carbon, and the like. 10 Further, there is no particular limitation on the electrolyte layer of the dye-sensitized solar cell. Any substrate having electrical and/or hole conductivity can be included. [Embodiment] The base metal complex of the present invention can be synthesized in the following manner. 15-Dithiocyanobis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) (c/i-di(thiocyanato)-iV,i^,-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. Dissolve guangxi-dithiocyano-from bis(2,2,bipyridine-4,4'-dicarboxylic acid) oxime 20 (II) in distilled water, and then add 10% hydroxybenzyl-3-butane 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 concentrated. Viscous liquid. The viscous liquid was dissolved in methanol (methanol), and then the product was precipitated by adding diethyl ether, and 1377196 of the hygroscopic solid product was taken and dried under vacuum for one day. The dried solid was dissolved in distilled water, and the pH was adjusted to 5 or less with a 0.1 Torr aqueous nitric acid solution to obtain a ruthenium metal complex of the formula (1-1). The method for producing the dye-sensitized solar cell of the present invention is not particularly limited to being produced by a generally known method. The material of the transparent substrate is not particularly limited as long as it is a transparent substrate. 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 outside of the dye-dyeing solar cell, and specifically, there are quartz, glass, and the like. Transparent inorganic substrate 'polyethylene terephthalate (PET), poly(ethylene naphthalate) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (pp), poly brewing A transparent plastic substrate such as an imine (PI), but is not limited thereto. 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 the group consisting of indium tin oxide (IT0), fluorine-doped φ tin oxide (FT〇), zinc oxide-diazonium oxide CZnO-Ga^:), zinc oxide _ three-oxide bismuth (ΖηΟ) - Α12〇3), and bismuth-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, zinc oxide, antimony trioxide, antimony pentoxide, titanium oxide, 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 1377196. . In addition, one or more times may be applied in order to obtain a suitable thickness. The semiconductor film layer may be a single layer or a plurality of layers, and the plurality of layers means semiconductor particles having different particle diameters for 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 2 micrometers, and then semiconductor fine particles having a particle diameter of 5 to 4 nanometers are coated. The coating thickness is 3 to 5 μm. Then, after drying at 50 to 100 Torr, a multilayer semiconductor film layer can be obtained by sintering for 3 minutes. The nail metal complex dye can be dissolved in a suitable solvent to prepare a dye solution. Suitable solvents include, but are not limited to, acetonitrile, mercaptan, ethanol, propanol, butanol, monomethylformamide, N-methylpyrrole or a mixture thereof. Here, the transparent substrate coated with the semiconductor film is immersed in the dye solution to fully absorb the dye in the dye solution, and after the absorption is completed, the dried 'a dye-sensitized solar cell: an electric anode can be obtained as the The material of 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: the substance acts as a 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 electrons and hole conductivity. The liquid electrolyte may be an iodine-containing acetonitrile: liquid, an iodine-containing N-methyl ketene solution, or an iodine-containing solution. % methoxypropane solution. In one embodiment, the liquid electrolysis f is - acetonitrile containing iodine [S) 16 1377196 A dye-sensitized solar cell of the present invention is specifically manufactured as follows. First, 'a paste comprising titanium oxide particles having a particle diameter of 20 to 30 nanometers (nm) is coated on a fluorine-doped tin oxide (FTO) glass plate by one or several screen printings. Up and then at 45 baht. (: Sintering for 30 minutes. 5 Dissolving the ruthenium metal complex in a mixture of acetonitrile and i-butanol (1:1 v/v) to form a ruthenium metal The dye solution is then immersed in the dye solution in the above-mentioned glass plate containing the porous titanium oxide film, and then absorbed in the dye solution, and then taken out and dried to obtain a photoanode (photoanode). A fluorine-doped tin oxide glass plate is drilled with a 0.75 mm diameter injection port for injection of electrolyte. The chlorinated platinum acid (H2PtCl^ solution is coated on a fluorine-doped tin oxide glass plate, Then heating to 4 ° C for 15 minutes to obtain a cathode (cath〇de) <> then 'a 60 micron thick thermoplastic polymer film between the photoelectric anode 15 and the cathode, at 120 to 14〇. (: Apply pressure to the two electrodes to bond the two electrodes. • Inject the electrolyte (〇.〇3 Μ I2/〇.3 M LiI/0.5 Μ tri-butylpyridine in acetonitrile), The dye sensitized electricity of the present invention can be obtained by sealing the injection port with a thermoplastic polymer film. The following examples are only intended to illustrate the invention, and the scope of the invention is not limited by the party. If not specified, the temperature is in degrees Celsius, and the parts and percentages are by weight. The relationship between the parts by volume is like the relationship between kilograms and liters. >5 ~ Example 1 17 1377196 Synthetic waste · Dithiocyanatobis(2,2,-bipyridine-4,4'-dicarboxylic acid) ruthenium ( II) bis(benzyltributylammonium) (c&-di(thiocyanato)-_^,7\r-bis(2,2'-bi pyridyl-4,4,-dicarboxylic acid)ruthenium(II) Bis(benzyl tributyl ammonium)(1-1) 5 0.50 parts of broad-dithiocyano-W'-bis(2,2'-bipyridine-4,4'-didecanoyl) ruthenium (II) (c/j-di(thiocyanato)-iV, iV'-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)ruthenium(II), N3 dye) (according to Inorganic Chemistry, Vol. 38 , No 26, 1999, 6298-6305 6-j _ method synthesis) and 10 parts of distilled water was added to the reaction flask, stirred and mixed, and then added dropwise 10 10% aqueous solution of benzyltributylammonium hydroxide (using gasified benzene) Methyl tributylammonium reagent Ylammonium chloride reagent, ACROS, 98%) was added to 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 a vacuum for one day. The dried solid was dissolved in 10 parts of distilled water, and the pH was adjusted to 5 or less with a 0.1 Torr aqueous solution of nitric acid, and the product was continuously collected by a sintered glass niter and used for 20 5 . The product was washed with 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 G-Dithiocyanato-Foo #'-bis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) 25 bis(phenylmercaptotriethylammonium) ( Di-di(thiocyanato)-^#,-bis(2,2,-bi 18 1377196 pyridyl-4,4,-di carboxylic acid)ruthenium(II)bis(benzyl triethyl ammonium) (1-2) The compound of this example was prepared in the same manner as in Example 1 except that an aqueous solution of hydroxytriphenylammonium 5 hydroxide (TCI Co., Ltd.) was used in place of the aqueous solution of oxyhydroidenyltributylammonium. 0.30 parts of a black solid product of the formula (1-2) was obtained in a yield of 41.1%. Example 3 I Synthesis of waste-dithiocyano-state bis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) 10 bis(triethylhexyl) (cz\s- Di(thiocyanato)-iV,_/V'-bis(2,2'-bi pyridyl-4,4,-dicarboxylic acid)ruthenium(II)bis(triethyl hexyl ammonium)) (1-3) will be 0.50 parts wide -Dithiocyano-W,-bis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) and 10 parts of distilled water were added to the reaction flask, stirred and mixed, and then dropped into 10%. An aqueous solution of triethylhexylammonium hydroxide (prepared with triethylhexylammonium bromide reagent (ALDRICH, 99%)) is added to the reaction solution until the pH of the reaction solution reaches 12 Then, the solvent was distilled off by a rotary evaporator to obtain a viscous liquid. Next, the viscous liquid 20 was dissolved in methanol, and then diethyl ether was added to give a precipitate, which was taken out and dried under vacuum for one day. The dried solid was dissolved in 10 parts of distilled water, and the pH was adjusted to 4 or less with a 0.1 Torr aqueous solution of nitric acid, and the product was collected by filtration through a sintered glass filter, and the product was washed with 5 parts of distilled water of pH 4.1 to obtain a formula ( 1-3) Black solid product 0.44 parts, yield 25 81.5%» 1377196 Example 4 Synthesis / #-Dithiocyano-Fool-bis(2,2'-bipyridine-4,4'-dicarboxylic acid ()) bis(II) bis (1-dodecyl group 0 to bite) (£^,di(thiocyanato)-iV,;V'-bis(2,2'-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-oxecylpyridinium was used. Hydroxide _ aqueous solution (formulated with 1-dodecylpyridinium 10 chloride reagent, ALDRICH, 98%) in place of 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-bis(2,2,-bipyridine-4,4'-didecanoyl) ruthenium (II) tris(phenylmethyltriethyl) (cz\s) -di(thiocyanato)-i^,_/V'-bis(2,2'-bi pyridyl-4,4,-dicarboxylic acid)ruthenium(II)tris(benzyl • triethyl ammonium)) (1-5) 0_20 parts 10°/. An aqueous solution of argonoxybenzyltriethylammonium and 100 parts of 20 sterol were added to the reaction flask to mix and mix, and then 0.10 parts of gal-dithiocyanobis(2,2'-bipyridine-4,4'- Dicarboxylic acid) ruthenium (II) bis(benzyltriethylammonium) (1-2) was added to the reaction mixture, and the mixture was stirred and mixed for 2.5 hours. Then, the solvent was distilled off by a rotary evaporator to obtain a precipitated product. The product was collected by filtration using a fritted 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%. [S] 20 1377196 Example 6 Synthesis of waste-dithiocyanobis(2,2'-bipyridine-4,4'-didecanoyl) ruthenium (II) tetrakis(phenylindoletriethyl) Cz\s-di(thiocyanato)-A^iV'-bis(2,2'-bi 5 pyridyl-4,4,-dicarboxylic acid)ruthenium(II)tetrakis (benzyl triethyl ammonium)) (1-6) 0.50 parts of poly-dithiocyano-W'-bis(2,2'-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) and 50 parts of distilled water were added to the reaction flask, stirred and mixed, and then dropped into A 10% aqueous solution of hydroxyphenoxytriethylammonium was added to the reaction solution until the pH of the anti-10 aqueous solution was stabilized to 7, and then the solvent was distilled off by a rotary evaporator to obtain a viscous liquid. The viscous liquid was dissolved in decyl alcohol, and then 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 the formula (1-6) in a yield of 68.0%. . . 15 Example 7 Production of a dye-sensitized solar cell will comprise a paste B having titanium oxide particles having a particle diameter of 20 to 30 nanometers (nm), coated with fluorine by one or several screen printings. On a heterogeneous tin oxide (FTO) glass plate (thickness 4 mm, resistance ΙΟ Ω / port), the thickness of the porous titanium oxide film after sintering is 10 to 12 μm (//m), and then sintered at 450 ° C. minute. The ruthenium metal complex of Example 1 was dissolved in a mixture of acetonitrile and i-butanol (1:1 v/v) to form a ruthenium metal complex concentration of 0.5 Μ dye solution, then, immersing the above glass plate containing porous oxidized 25 titanium film in the dye solution, allowing it to absorb the dyed 21 1377196 material in the dye solution for 16 to 24 hours, and then taking out and drying to obtain a photoanode. (photoanode) 〇 will be covered with a fluorine-doped tin oxide glass plate with a diameter of 〇75 mm' for injection into the electrolyte, and then vaporized platinum acid (H2ptCl6) solution (1 ml of ethanol contains 2 mg of platinum) It was coated on a tin oxide glass plate and then heated to 400 ° C for 15 minutes to obtain a cathode (cath〇de). A thermoplastic polymer film having a thickness of 60 μm was disposed between the photoanode and the cathode. A pressure was applied to the two electrodes at 120 to 140 ° C to bond the electrodes. The dye-sensitized solar cell of the present example can be obtained by injecting an electrolyte (0.03 Μ Ι 2/0·3 M LiI/0.5 Μ tri-butyl pyridine in acetonitrile) into a 're-use thermoplastic polymer film to seal the injection port. 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 base metal complex of Example 2 was used instead of the base metal of Example 1. Things. -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 ruthenium metal complex of Example 3 was used in place of the ruthenium metal complex of Example 1. . [S] 22 25 1377196 Example ί Manufacturing of 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 base metal complex of Example 4 was used instead of Example i 5 Base metal complex. Example 11 Production of Dye-Sensitized Solar Cell I The same procedure as in Example 7 was carried out to prepare a dye-sensitized solar cell of the present example, except that the base metal complex of Example 5 was used instead of the base metal of Example 1. Compound. Example 12 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 ruthenium metal complex of Example 6 was used in place of the ruthenium metal complex of Example i. Comparative Example A dye-sensitized solar cell was prepared in the same manner as in Example 7, except that N719 was used instead of the base metal complex of Example 1. Test Methods and Results Photoelectric Efficiency Test The dye-sensitized solar cells of Examples 7 to 12 and Comparative Examples were tested for short-circuit current (Jsc), open circuit voltage (v〇c) under illumination of τ S] 23 1377196 AM 1.5, Filling factor (FF), photoelectric conversion efficiency (η) and single-wave photocurrent conversion efficiency (Incident Photon to Current Conversion Efficiency > IPCE) 0 The test results are summarized 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 of Table 1 show that the base metal of the embodiment of the present invention is wrong. The dye-sensitized solar cell produced by the compound can improve the short-circuit current and open circuit of the dye-sensitized solar cell as compared with the dye-sensitized solar cell produced by the comparative example using N719. And fill factor 'thereby increasing the photoelectric conversion efficiency of the dye-sensitized solar cell. In summary, the present invention has been shown to be different from 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-mentioned embodiments are merely illustrative for ease of explanation. However, it is not intended to limit the present invention, and any of the techniques [S1 24 1377196

5

The present invention claims to be limited and limited to the above embodiments without departing from the spirit and scope of the invention. . The above-described embodiments are merely examples for the convenience of the description, and the claims are intended to be within the above-described embodiments. 4 is the standard, not limited to [Simple description] None. [Main component symbol description] None. 25

Claims (1)

1377196 No. 97138544 'Amendment in September of the following year VII. Scope of application: 1. A ruthenium metal complex with the following structure (j): RuL2(NCS)2Am (I) 5 where L is 2, 2'-bisbiidine_4,4'-dicarboxylic acid (2,2, 丫1^1-4,4'-dicarboxylic acid); A is N+RiR2R3R4, wherein R丨 is benzyl (benzyl) ), r2, &, and R·4 are each independently Cuoalkyl, phenyl or phenylhydrazine; and 10 m is 2, 3 or 4, and all a are the same. 2. The base metal complex according to claim 1, wherein A is N+R丨R2R3R4' R丨 is a methyl group, and n and R4 are each independently a CN6 alkyl group. 3. The metal complex according to claim 1, wherein the metal complex is a dye for a dye-sensitized solar cell. 4. A base metal complex, the structure of which is as follows (〗 〖) 26 1377196 (1-2). 5. The base metal complex according to claim 4, wherein the base metal complex is a dye compound for use in a dye-sensitized solar cell. 5 6.-(4) A dye-sensitized solar cell comprising: a photoanode comprising a ruthenium metal complex of the following formula (1); RuL2(NCS)2Am (I) 10 L being 2,2'-double Pyridine-4 4, dicarboxylic acid; A is N+R〗 R2R3R4 ' wherein & is benzyl, R2, heart, and & are each independently Ci-2 alkyl, phenyl or phenylhydrazine; And m is 2, 3 or 4, and all eight are the same; (b) - cathode; and 15 (C) an electrolyte layer between the photoanode and the cathode. A dye solution comprising: (A) a ruthenium metal complex of the following formula (1) in an amount of 0.01 to 1% by weight: 20 wherein RuL2(NCS)2Am(I) L is 2,2'-double. Specific biting _4,4' diterpenic acid: A is N+RiR2H, wherein R is benzyl, R2 'r3, and r4 are each independently C, _20 alkyl, phenyl or alum; 25 m is 2, 3 or 4' and all A are the same; and 27 1377196 (B) is an organic solvent having a content of 99.99 to 99% by weight, and the organic solvent is selected from the group consisting of: acetonitrile, methanol, ethanol, and C A group consisting of alcohol, butanol, dimethylformamide, and N-decylpyrrolidone. 28