Solar cell with ruthenium complex
Context of invention 1. Field of invention the present invention refers to a photoelectric member who uses a ruthenium complex, in particular a solar cell which awakened with coloring (DSSC). 2. Description of the technique correlated With I development of the industrial technology, the serious problems that the entire world is facing at present am constituted from the energetic crisis and from the environmental pollution them. Al fine to find a solution to the total energetic crisis and to reduce the environmental pollution them, one of effective means is a solar cell, the duale can convert the solar energy in electricity. Since the solar cell which awakened with coloring introduces the advantages of contained production costs, production on wide scale, great flexibility, trasmittanza of the light, and of being in a position to being used in the buildings, the application of the solar cell which awakened with coloring becomes more and more interesting. Currently, Grätzel ET to has illustrated a literature article series, as an example, O'Regan, B.; Grätzel, M. Natures 1991,353,737, that it illustrates the suitability to the concrete employment of the solar cell which awakened with coloring. The general structure of the solar cell which awakened with coloring comprises an anode, a cathode, a layer of titanium dioxide dwarf-poroso, coloring, and an electrolyte, in which coloring it carries out a crucial role in the conversion efficiency of the solar cell which awakened with coloring. Suitable coloring for the solar cell which awakened with coloring must introduce characteristics of wide absorption spectrum, elevated coefficient of absorption molar, thermal stability, and stability to the light. the laboratory of Grätzel has published a series of complexes of ruthenium in qualities of coloring for the solar cell which awakened with coloring. In 1993, the laboratory of Grätzel has published a solar cell which awakened with coloring prepared with a coloring N3, and the conversion efficiency of the solar cell which awakened with coloring was of 10.0% with the lighting system of a stimulated light to 1,5 AM. The value of conversion efficiency from photon incident to current (IPCE) of the coloring N3 is of 80% in the interval between 400 and 600 nm. Although they have been developed hundred of coloring complexes of, the conversion efficiency of these coloring complexes of is not excellent as that of the coloring N3. The coloring structure of N3 comes represented by means of the following formula (a). COOH I/NCS u NCS COOH (a) In 2003, the laboratory of Grätzel has published a solar cell which awakened with coloring prepared with a coloring N719, and the conversion efficiency of the solar cell which awakened with coloring is improved to 10.85% with a lighting system of light stimulated to 1,5 AM, in which the coloring structure of N719 it comes represented by means of the following formula (b). 693 CH 699 B1 OOTBA HOOC COOTBA (b) Ne12004, the laboratory of Grätzel have published a solar cell which awakened with coloring prepared with black coloring, and the conversion efficiency of the solar cell which awakened with coloring was of l 1.04% with a lighting system of light stimulated to 1,5 AM. Black coloring can improve the spectral answer in the red region edel close infrared, so that refficienza of conversic of the solar cell which awakened with coloring can they improved. The black coloring structure of comes represented by means of the following formula (c). COOTBA TBAO (HOOC /NCS NCS NCS (c) Besides the complexes of the coloring ruthenium corne N3, the coloring N719, and black coloring, other tipologie of coloring compounds, which can be used in the solar cell which awakened with coloring, are the platinum complexes, the osmium complexes, the iron complexes, and the copper complexes. However, the result of varied searches show that the conversion efficiency of the ruthenium complexes remains the best respect to other tipologie of coloring compounds. coloring for the solar cell which awakened with coloring influences the conversion efficiency remarkablly. Therefore, he is favorable to supply a coloring compound, the duale can improve the conversion efficiency of the solar cell which awakened with coloring. Summary of invention the present invention is destined to supply a sensitized solar cell with coloring, the duale introduces an excellent property searchlight. the cell of the present invention uses a ruthenium complex, the duale comes represented by means of the following formula (i): RuL2 (NCS) 2Am (i) in which L it is acid 2,2 " - bipiridil-4,4 " - dicarbossilico, acid 2,2 " - bipiridil-4,4 " - disolfonico, or acid 2,2 " - bipiridil-4,4 " - difosfonico; To it is a quaternario cation fosfonio; and m are 1,2, 3, or 4. In the formula (i) of which over, L can be acid 2,2 " - bipiridil-4,4 " - dicarbossilico, acid 2,2 " - bipiridil-4,4 " - disolfonico, or acid 2,2 " - bipiridil-4,4 " - difosfonico. Preferibilmente, L is acid 2,2 " - bipiridil-4,4 " - dicarbossilico. In the formula (i) of which over, To it can be a quaternario cation fosfonio. Preferibilmente, To is P--R1 R2 R3 R4, in which R1, R2, R3, and R4 C1 is everyone independently -20 alkyl, fenile, or benzyl. More preferibilmente, To it is tetraalchilfosfonio, benzil trialchilfosfonio, or fenil trialchilfosfonio, and the alkyl is 20 C alkyl. In the formula (i) of which over, m can be 1,2, 3, or 4. Preferibilmente, m is 2 or 3. More preferibilmente, m are 2. 693 CH 699 B1 [the 0014] specific examples of complex of ruthenium represented by means of the formula (i) of which over they are: Or or OP+ (ÇIt2 C [- I2 CH2 ÇH3) 4 0-1) or • Or " P÷ (CH2 CH3) 3 (Ph) ““% " %s 9” P+ (CH2 CH3) 3 (Ph) (I-2) P÷ (CH2CH3) 3 ((CH2) I1CH3) OR Or OP” (CH2 CH3) 3 ((CH2) CH3) (>3) CH 699 693 B1 OH the O= P--Or” P+ ('CH2 CHzCHz CH3) 4 O'=-- P-- Or” P+ (CH2 CH2 CHzCH3) 4 OH (1-4) the present invention supplies a solar cell which awakened with coloring, that ruthenium comprises the aforesaid complex dl. In addition, the solar cell which awakened with coloring of the present invention comprises: a fotoanodo, comprising the aforesaid complex of ruthenium; a cathode; and a layer electrolyte posizionato between fotoanodo and the cathode. In the solar cell which awakened with coloring of the present invention, the fotoanodo it comprises: a transparent substrate, a transparent conductive layer, a poroso semiconductive layer, and coloring of the ruthenium complex. In the solar cell which awakened with coloring of the present invention, the material of the transparent substrate is not particularly limited, on condition that the material of the substrate is a transparent material. Preferibilmente, the material of the transparent substrate is a transparent material with resistance to the humidity, resistance to the solventie resistance to the excellent climatic conditions. Therefore, the solar cell which awakened with coloring can resist alrumidità or to gas coming dalresterno thanks to the transparent substrate. The specific examples of the transparent substrate include transparent inorganic substrates, corne quartz and glass; substrates in transparent plastic, corne poles (tereftalato ethylene) (PET), poles (2,6-naftalato ethylene) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), and poliimmide (DEVOUT), also not being limited to they. In addition, I thickness of the transparent substrate am not particularly limited, and can be modified based on the trasmittanza and to requirement of the properties of the solar cell which awakened with coloring. Preferibilmente, the material of the transparent substrate is glass. [the 0019] noltre, in the solar cell which awakened with coloring of the present invention, the material of the transparent conductive layer can be oxide of Indian and pond (ITO), oxide of pond drugged with fluorine (FTO), ZnO-Ga2 03, ZnO-AI2 03, or oxides made up of pond. In addition, in the solar cell which awakened with coloring of the present invention, I0 poroso semiconductive layer is constituted from semiconductor particles. Suitable particles of semiconductor can include, TiO2, SnO2, ZnO, WO3, Nb2 Os, TiSrO3, and a Ioro combination. Preferibilmente, the semiconductor particles are constituted from TiO2. The medium diameter of semiconductor particles can be comprised between 5 and 500 nm. Preferibilmente, the medium diameter of semiconductor particles is comprised between 10 and 50 nm. Moreover, I thickness of the poroso semiconductive layer am of 5-25 tJm. In the solar cell which awakened with coloring of the present invention, the ruthenium complex can be the aforesaid complex of ruthenium. Moreover, the material of the cathode for the solar cell which awakened with coloring is not particularly limited, and can include a any endowed material of conductivity. Various, the material of the cathode can be an insulating material, on condition that you is a formed conductive layer on the surface of the cathode, in which the surface of the cathode it is turned towards the fotoanodo. The material of the cathode can be a material with electrochemical stability. Suitable the limitless examples for the material of the cathode include Pt, Au, C, or similar. [the 0023] noltre, the material used in the electrolyte layer of the solar cell which awakened with coloring particularly is not limited, and can be a any material that can transfer electrons and/or holes. Other scopes, advantages and innovative characteristics of the invention will turn out more obvious from the following detailed description. Detailed description of the form of preferred realization the complex of ruthenium of the present cell invention pub to be synthetized by means of the following methods. 693 CH 699 B1 cis-of (tiocianato) - N, N'- bis (acid 2,2 " - bipiridil-4,4 " - dicarbossilico) ruthenium (ll) (coloring N3) come synthetized according to the method described in Inorganic Chemistry, Vol. 38, Not. 26, 1999, 6298-6305. cis-of (tiocianato) - N, N'- bis (acid 2,2 " - bipiridil-4,4 " - dicarbossilico) ruthenium (ll) comes disciolto in distilled water, and to it an aqueous solution to 10% of reagent comes addition idrossido of tetrabutilfosfonio (TCI Co. Ltd.) for regulating the value of the pH of the solution of reaction to 11. Successively, the reaction solution comes concentrated in order to obtain a viscous liquid. The viscous liquid comes disciolto in methanol, and to it comes added dietil ether in order to make to throw down a product. After to have extracted and essiccato the humid solid product vacuum packed for 1 day, the essiccato solid product comes disciolto in distilled water, and successively the turning out value of pH of solution comes regulated under with nitric acid (aq) 0.1 M. At last, obtains the complex of ruthenium of the formula (I-1). the method for the production of the solar cell which awakened with coloring of the present invention is not particularly limited, and the solar cell which awakened with coloring of the present invention can be produced by means of the famous methods in the technique. the material of the transparent substrate is not particularly limited, on condition that the material of the substrate is a transparent material. Preferibilmente, the material of the transparent substrate is a transparent material with resistance to the humidity, resistance to the solventie resistance to the excellent climatic conditions. Therefore, the solar cell which awakened with coloring can resist to the humidity or gas coming from the outside thanks to the transparent substrate. The specific examples of the transparent substrate include transparent inorganic substrates, corne quartz and glass; substrates in transparent plastic, like poles (tereftalato ethylene) (PET), poles (2,6-naftalato ethylene) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), and poliimmide (DEVOUT), also not being limited to they. In addition, I thickness of the transparent substrate am not particularly limited, and can be modified based on the trasmittanza and to requirement of the properties of the solar cell which awakened with coloring. In a specific form of realization, the material of the transparent substrate is a glass substrate. Moreover, the material of the transparent conductive layer can be oxide of Indian and pond (ITO), oxide of pond drugged with fluorine (FTO), ZnO-Cìa2 03, ZnO-AI2 03, or oxides made up of pond. In a specific form of realization, for I transparent conductive layer come used oxide of pond drugged with fluorine. In addition, I poroso semiconductive layer am constituted from semiconductor particles. Suitable particles of semiconductor can include, TiO2, SnO2, ZnO, WO3, Nb2 Os, TiSrO3, and a Ioro combination. In the first instance, the semiconductor particles are prepared under paste form, and successively the paste comes used in order to cover the transparent conductive substrate. The method of covering used in the present can be a covering to blade, a covering for spin, a covering for atomizaton, or a covering to humid. In addition, the covering can be deposited once or varied times, to the aim to obtain a poroso semiconductive layer with a suitable thickness. The semiconductive layer can be a single layer or multiple layers, in which every layer of the multiple layers it is formed from particles of semiconductor with different diameters. As an example, the particles of semiconductor with diameters comprised between 5 and 50 nm are used for a covering with a thickness comprised between 5 and 20 tJm, and the particles of semiconductor with diameters comprised between 200 and 400 nm are used for a covering with a thickness comprised between 3 and 5 tJm on dl they. After to have essiccato the substrate covered to 50-100° C, the covered substrate multilayer comes sinterizzato to 400-500° C for 30 minuteren in order to obtain a semiconductive layer. the ruthenium complex can be disciolto in a suitable dissolvent in order to prepare a solution of coloring. Suitable dissolvents include the acetonitrile, the methanol, the ethanol, the propanolo, the butanolo, the dimetilformammide, rN-metil-2-pirrolidinone and Ioro combinations, also not being limited to they. In the present, the covered transparent substrate with I semiconductive layer comes dipped in a solution of coloring in order to induce I semiconductive layer to completely absorb coloring in the coloring solution of. After to have completed the absorption of coloring, the covered transparent substrate with I semiconductive layer comes extracted and essiccato. At last, a fotoanodo is obtained for a solar cell which awakened with coloring. Moreover, the material of the cathode for the solar cell which awakened with coloring is not particularly limited, and can include a any endowed material of conductivity. Various, the material of the cathode can be an insulating material, on condition that you is a formed conductive layer on the surface of the cathode, in which the surface of the cathode it is turned towards the fotoanodo. The material of the cathode can be a material with electrochemical stability. Suitable the limitless examples for the material of the cathode include Pt, Au, C, or similar. [the 0034] noltre, the material used in the electrolyte layer of the solar cell which awakened with coloring particularly is not limited, and can be a any material that can transfer electrons and/or holes. In addition, the liquid electrolyte can be a solution of containing acetonitrile iodine, a solution of containing N-metil-2-pirrolidinone iodine, or a containing solution dl propionitrile 3-metossi iodine. In a specific form dl realization, the liquid electrolyte can be a solution of containing acetonitrile iodine. a specific method for the production of the solar cell which awakened with coloring of the present invention comes introduced corne follows. 693 CH 699 B1 In the first instance, a containing paste particles of Ti02 with diameter of 20~30 nm come used in order to cover, once or varied times, a substrate of covered oxide glass of pond drugged with fluorine (FTO). Successively, the substrate of covered glass comes sinterizzato to 450° C for 30 minuteren. the ruthenium complex comes disciolto in a mixture of acetonitrile and t-butanolo (1: 1 v/v) in order to formulate a solution of coloring of the ruthenium complex. Successively, the aforesaid substrate of glass with a layer of poroso Tl02 comes dipped in the coloring solution of. After that I layer of poroso Ti02 have absorbed coloring in the coloring solution of, the turning out substrate of glass comes extracted and essiccato. At last, a fotoanodo is obtained. a substrate of glass covered with oxide of pond drugged with fluorine comes pierced in order to form an income with a diameter of 0,75 tJm, in which the income it is used for iniettare the electrolyte. Successively, a solution of H2 PtCI6 comes used in order to cover the substrate of veto covered with oxide of pond drugged with fluorine, and the glass substrate comes heated to 400° C for 15 minuteren in order to obtain a cathode. In sequence, a thermoplastic polymer layer with a thickness of 60 pm comes disposed between fotoanodo and the cathode. These two electrodes come pressati to a temperature between 120 and 140° C so that they join one to the other. Successively, it comes iniettato an electrolyte, in which the electrolyte M/Lil 0,3 M/t-butil-piridina 0,5 M is a solution of containing acetonitrile 12 0,03. After that the income comes closed to held with I thermoplastic polymer layer, a solar cell which awakened is obtained with coloring of the present invention. [the 0041] following examples are destined to the illustrative aims of the present invention. However, the within of the present invention will have to be defined the attached rivendicazioni to it second, and the following examples will not have to be interpreted in some way like limiting the within of the present invention. Without specific explanations, runità of the parts and the percentages used in the examples are calculated in weight, and latemperatura is represented in Celsius degrees (°C). The relation between the parts in weight and the parts in volume is identical to the relation between kilogram and liter. Example 1 Synthesis of cis-of (tiocianato) - N, N'- bis (acid 2,2 " - bipiridil-4,4 " dicarbossilico) ruthenium (ll) bis (tetrabutilfosfonio) (I-1) 0,50 parts of cis-of (tiocianato) - N, N'- bis (acid 2,2 " - bipiridil-4,4 " - dicarbossilico) ruthenium (ll) (coloring N3), that it has been prepared according to the method described in Inorganic Chemistry, Vol. 38, Not. 26, 1999, 6298-6305, and 10 parts dl distilled water have been added in a flask of reaction, and the reaction solution has been churned. Successively, an aqueous solution to 10% of reagent idrossido of tetrabutilfosfonio (TCI Co. Ltd.) has been addition drop to drop in the solution of reaction for regulating the value of pH of the solution of reaction to 11. In order to remove the dissolvent from the reaction solution in order to obtain a viscous liquid, it has been used the rotary evaporator. The viscous liquid has been disciolto in methanol, to it has been added dietil ether in order to obtain a hasty one, and hasty solid the humid one has been extracted and essiccato vacuum packed for 1 day. The solid one essiccato has been disciolto in 10 distilled water parts, and has been used nitric acid (aq) 0.1 M for regulating the turning out value of pH of solution under 5. The filter of sinterizzato glass is used in order to filter the product, and has been used 5 distilled water parts to pH 5 in order to wash the product. At last, they have been obtained 0,39 parts of black solid product (I-1), and the yield of the product (I-1) has been of 75.9%. Example 2 Preparation of a solar cell which awakened with coloring a containing paste particles of Ti02 with a diameter of 20~30 nm is used in order to cover once or varied times a substrate of glass covered with oxide of pond drugged with fluorine (FTO), in which I thickness of the substrate of 4 glass was of milimeter and the electric resistance of the substrate of 10 glass was/. Successively, the substrate of covered glass has been sinterizzato to 450° C for 30 minuteren, and I thickness of the layer of poroso Ti02 sinterizzato era comprised between 10 and 12 tJm. the complex of ruthenium prepared by means of Example 1 has been disciolto in a mixture of acetonitrile and f-butanolo (1: 1 v/v), and it has been prepared a solution of coloring with complex of 0,5 ruthenium milimeter Successively, the aforesaid substrate of glass covered with a layer of poroso Ti02 has been dipped in the solution of coloring in order to induce coloring to join to the layer dl poroso Tl02. After a period of 16-24 hours, the turning out substrate dl glass has been extracted and essiccato, and has been obtained a fotoanodo. a substrate of glass covered with oxide of pond drugged with fluorine is pierced in order to form an income with a diameter of 0,75 IJm, in which the income it is used in order to iniettare the electrolyte. Successively, it has been used a solution of H2 PtCle (2 mg of Pt in 1 me of ethanol) in order to cover the substrate of glass covered with oxide of pond drugged with fluorine, and the glass substrate has been heated to 400° C for 15 minuteren in order to obtain a cathode. In sequence, a thermoplastic polymer layer with a thickness of 60 tJm has been decided between fotoanodo and the cathode. These two electrodes have been pressati to a temperature comprised between 120 and 140° C so that aderissero runo to the other. 693 CH 699 B1 Successively, have been iniettato an electrolyte, in which the electrolyte M/Lil 0,3 M/t-butil-piridina 0,5 M was a solution of containing acetonitrile 12 0,03. After to have closed to held the income with I thermoplastic polymer layer, have been obtained a solar cell which awakened with coloring of the present invention. Comparative example the process in order to prepare the sensitized solar cell with coloring of the present comparative example is identical to that one described in Example 2, except for the fact that the complex of ruthenium prepared by means of Example 1 is replaced with N719. Methods of analysis and result Test for characteristic 0049 searchlights [] the current of short circuit (Jsc), the tension of the open circuit (Voc), the factor of filling (FF), the conversion efficiency searchlight (q), and the conversion efficiency from photon incident to current (IPCE) of the solar cells which awakened with coloring prepared by means of 2 Example and the comparative Example have been measured with lighting system of light stimulated to 1,5 AM. The result of the test are shown in following Table 1: Table 1. Result of test of coloring and the solar cell which awakened with coloring Coloring Jsc Voc FF q (%) (mA/cm2) (v) 2 Example 4,44 I-1 9,02 0,78 0,83 N719 Example the 7,36 0,76 0.61 3,38 coin parat ivo result of the test of Table 1 show that the current of short circuit (Jsc), the tension of the open circuit (Voc) and the factor of filling (FF) of the solar cells which awakened with coloring prepared with the complex of ruthenium of the present invention are improved regarding the solar cell which awakened with coloring prepared with the coloring N719. This means that the complex of ruthenium of the present invention can improve the conversion efficiency searchlight of the solar cell which awakened with coloring. In conclusion, the present invention differs from the front techniques for varied ways, corne for the scopes, the methods and the efficiency, or even for the technology, the search and the realization. Although the present invention has been explained in relation to its form of preferred realization, it is strengthened that they can be brought moite other possible modifications and variations without discostarsi from the within of the rivendicato invention corne of continuation. Therefore, the within of the present invention will have to be defined the attached rivendicazioni to it second, and the examples precedence will not have to be interpreted in some way corne limiting the within of the present invention. The present invention relates to a ruthenium complex represented by the following formula (I): RuL2(NCS)2Am (I) wherein L, A and m are defined the same as the specification, and a photoelectric component using the same. The ruthenium complex of the present invention can be used in a Dye-Sensitized Solar Cell (DSSC). Hence, the photoelectric characteristics of the DSSC manufactured with the ruthenium complex of the present invention can be improved. 1. Solar cell which awakened with coloring, comprising:
(a) a fotoanodo that it comprises a complex of ruthenium represented by means of the following formula (i):
RuL2 (NCS) 2Am (i) in which L it is acid 2,2 " - bipiridil-4,4 " - dicarbossilico, acid 2,2 " - bipiridil-4,4 " - disolfonico, or acid 2,2 " - bipiridil-4,4 " - difosfonico; To it is a quaternario cation fosfonio; and me 1,2,3, o4; (b) a cathode; and (c) a disposed electrolyte layer between fotoanodo and the cathode. 2. Solution coloring for the preparation of one to solar second rivendicazione 1, comprising:
(a) a complex of ruthenium represented by means of the following formula (i), in which the content of the ruthenium complex it is of the 0,01-1% in weight:
RuL2 (NCS) 2Am (i) in which L it is acid 2,2-bipiridil-4,4 " - dicarbossilico, acid 2,2 " - bipiridil-4,4 " - disolfonico, or acid 2,2 " - bipiridil-4,4 " - difosfonico; To it is a quaternario cation fosfonio; and 693 CH 699 B1 me 1,2,3, o4; and (b) an organic solvent, in which the content of the organic solvent it is of the 99,99-99% in weight, and the organic solvent is selected from the group constituted from acetonitrile, methanol, ethanol, propanolo, butanolo, dimetilformammide, and N-metil-2-pirrolidinone.