TW201211172A - Method for fabricating a counter electrode of dye-sensitized solar cells - Google Patents

Abstract

The invention provides a method for fabricating a counter electrode of dye-sensitized solar cells, which includes: (a) providing a polyamine compound, wherein the polyamine comprises polyimide or polyamine; (b) mixing the polyamine compound, a carbon nanotube, a platinum salt and a solvent to obtain a homogeneous suspension; (c) adding a reducing agent into the homogeneous suspension to obtain a mixing solution, wherein the mixing solution comprises a plurality of platinum nanoparticles; (d) coating the mixing solution on a substrate by coating method; and (e) heating the substrate to form a conductive film on the substrate.

Description

201211172 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of fabricating an electrode, and more particularly to a method of fabricating a counter electrode of a dye-sensitized solar cell. [Prior Art] In recent years, due to the global climate change, environmental pollution problems and the shortage of resources, the solar photovoltaic industry has been booming under the warning of high environmental awareness and energy crisis. Among various solar cells, Dye-Sensitized Solar Cell (DSC) has become a mainstream of the development of new-generation solar cell technology because of its large area, simple process, and low cost. Regarding dye-sensitized solar cells (DSSC) in the field of counter electrodes, since platinum (Pt) has an excellent catalytic effect, it is conventionally known that platinum is formed on the surface of an electrode as a catalytic layer' However, the chain It is expensive, so the cost of dye-sensitized solar cells cannot be reduced. In addition, although reducing the amount of platinum used can reduce the cost, the catalytic performance of the electrode is also reduced. Later, there have been studies to modify platinum nanoparticles (PtNPs) in nanotubes. It is hoped that the surface area of the whole electrode will be increased by the carbon nanotubes to reduce the amount of platinum used. However, there is a strong van der Waals attraction between the carbon nanotube molecules, which requires a chemical modification method or a physisorption method to uniformly disperse the carbon nanotubes. The process of these treatment methods is cumbersome and time consuming, and is not suitable for mass production. Therefore, there is an urgent need to develop a method for the electrode of a dye-sensitized solar cell (DSSC). This method not only allows the carbon nanotubes to be uniformly dispersed, but also reduces the amount of platinum used, and at the same time has an excellent catalytic effect. 201211172 SUMMARY OF THE INVENTION The present invention provides a method for preparing a counter electrode of a dye-sensitized solar cell, which comprises the following steps: (4) providing a polyamine polymer (wherein the polyamine polymer comprises poly Asia)醯amine (p〇lyimi heart) or polyamide; (b) mixing the polyamine polymer, carb〇n nan〇tube (CNT), a platinum salt (platinum salt) a solvent to prepare a homogenous suspension; (c) adding a reducing agent to the homogeneous suspension, φ to prepare a mixed solution, wherein the mixed solution comprises a plurality of platinum nanoparticles; Applying the mixed solution to a substrate by a coating method; and subjecting the substrate to a heat treatment to form a conductive film on the substrate. The above and other objects, features and advantages of the present invention will become more apparent and understood. The method for preparing a counter electrode of a dye-sensitized solar cell includes the following steps (a) to (e), mainly by using a polyamine probe as a dispersing agent for the carbon nanotubes and as a stabilizer for the platinum nanoparticles; The platinum nano particles are uniformly dispersed in the carbon nanotubes, thereby effectively increasing the surface area of the electrode, thereby reducing the amount of platinum used and reducing the cost of the process. First, step (a) is carried out to provide a polyamine polymer, wherein the polyamine polymer comprises a polyimide or a polyamide, and the polyamidene comprises a polyether-containing fragment. Poly(oxyethylene)-segmented imide (POE-imide) having the following formula (I): 201211172

Where η = 1~16 ; and POE has the following formula (II): 2-)-(-och2ch24-(och2ch-^-nh2 CH-i

NH2CHCH2-(-〇CHCH (II), ch3 ch3 where a+c=6, b=39. Polyamide comprises a poly(oxyethylene)-segmented amide, POE -imide), having the following formula (III):

(ΙΠ) where η = 1~2; and the POE is the same as the above formula (II). The above polyimide or polyamide may be obtained by reacting poly(oxyalkylene)-amine with a linker compound, wherein the polyether amine comprises a polyether monoamine ( Poly(oxyalkylene)-monoamine), poly(oxyalkylene)-diamine or poly(oxyalkylene)-triamine are shown in Table 1. Crosslinking molecules include tetraacids such as dianhydride (see Table 2) and epoxy (see Table 3). 201211172

Table 1 Polyether amine structure type Polyether monoamine POP-600-1 x=l, y = 9 POP-2000-1 x=6, y=29 POE-lOOO-1 x=19, y=3 POE-2000 -1 x=31, y=10 polyether diamine Η2(ν^/^Τ^1^/>Γ2 ch3 ch3 ch3 POP-230-1 x+z=25, y=0 POP-400-1 x +z=6.1, y=0 POP-2000-2 x+z=33, y=0 POP-4000-1 x+z=68, y=0 POE-220-1 x+z=1.2, y=2 POE-600-1 x+z=3.6, y=9 POE-900-1 x+z=6, y=l2.5 201211172

Table 2 Chemical name Structural formula Molecular weight

322

3,3',4,4'-Benzophenone tetracarboxylic dianhydride (BTDA) Pyromellitic dianhydride (PMDA) 218 201211172 3, 3,4,4'-Biphenyl tetracarboxylic dianhydride (s-BPDA) 4,4'(hexafluoroisopropyl)bis(phosphonium benzene) 4,4'-(Hexafluorois opropylidene) diphthalic anliydride, 6FDA) 4,4L diphenyl bond tetrahydro acid dianhydride (4,4'-Oxydiphthali c dianliydride, ODPA) 3,3',4,4'- Diphenyl sulfone tetracarboxylic dianhydride 3,3',4,4'-Diphenyl sulfone tetracarboxylic dianhydride (DSDA) 4,4'-bisphenol A dianhydride 4,4'-Biphenol A dianhydride (BPADA) hydroquinone Double (phosphoric acid)

Hydroquinone diphthalic anhydride (HQDA)

9 201211172 Table 3 Chemical name Structure molecular weight double hope A diglycidide <Ί <.H·, Oil CH, (t Diglycidy) ether of 350 bisphenol A (BE188) Polyethylene glycol glycidyl ether Poly (ethylene Glycol) nix 0 乩c-cHcm -ch2ch2o- (Ή, L 八-CH, CH-CH-, 526 diglycidyl ether n " polypropylene glycol glycidol jun 0 "1 0 Poly (propylene / \ HX-CHCHnO- -CH , CH0 - / \ -ch2ch-ch7 640 glycol) diglycidyl ether Ί J CH, n Then, proceed to step (b), mixing the polyamine polymer 'carbon nanotubes', in the white salt (platinum salt) In a solvent, a homogenous suspension in which a carbon nanotube is a single-walled (singie_wall) or a multi-waii carbon nanotube, and a platinum salt includes a six-gas chain acid (HsPtCU), Potassium chlorate (K2PtCl6)'s gaseous ammonium platinate ((NH4)2PtCl6), hexachloroplatinic acid ruthenium (Rb2PtCl6) or hexachloroplatinic acid sulphate (Cs2PtCl6). Here, so-called, homogeneous suspension" Means that the solute is incompletely dissolved' but exhibits "suspended dispersion" in the solvent, where "dissolved" is a molecule The dispersion of the size of the size "suspension dispersion" is as follows, the dispersion of particles above the molecular size size and the dispersion of the present invention is suspension dispersion. The weight ratio of the polyamine polymer, the carbon nanotube to the uranium salt It is about (1:1:])~(99:1:99), preferably about (1:1:99)~(99:1:99), more preferably about 99:1:1)~( 99:1: 99). In a preferred embodiment, the weight ratio of the polyamine polymer, the nanotube and the platinum salt is about 28:1:28. Used in the step (b). Solvents include water, ethanol (ethan〇1, c2h5〇H), acetone (acetone, (CH3)2CO), propylene glycoxime monomethyl ether acetate (PGMEA), toluene, toluene, N-methyl pyrrolidinone (NMP), tetrahydrofuran (THF), 201211172 ethylene glycol (EG), glycerin or a combination thereof. However, the solvent is not limited to the above-mentioned solvents, as long as the above substances can be mixed into a solvent of a homogeneous suspension, and a solvent which can dissolve the platinum salt and the polyamine polymer is within the scope of the present invention. In a preferred embodiment, water can be used as a solvent to meet environmental requirements. Thereafter, step (c) is carried out to add a reducing agent to the homogeneous suspension to prepare a mixed solution, wherein the reducing agent comprises sodium borohydride (NaBH4), decyl alcohol (CH30H), ethylene glycol (〇2Η4 (ΟΗ) 2), monoethanolamine (MEA, C2H4OHNH2), diethanolamine (DEA, (C2H4OH)2NH), or diglycolamine (DGA, QHhNOO) The role of the reducing agent is to reduce the platinum salt to platinum. And the nano particles, wherein the mixed solution comprises a plurality of platinum nanoparticles, wherein the platinum nanoparticles have a particle size of about 8 nm to 30 nm, preferably about 18 nm to 30 nm, more preferably about 8 nm. ~18 nm. It should be noted here that the benzene ring of the polyamine polymer of the present invention forms a 7 Γ -π interaction between the benzene ring on the carbon nanotube and the stupid ring on the carbon nanotube, and is high in polyamine. The negatively charged imide and oxygen on the molecule form a positive and negative electrostatic interaction with the carbon nanotube. Therefore, the present invention uses a polyamine polymer as a dispersing agent. The carbon tube is coated in it to make the carbon nanotubes uniform Disperse to form a homogeneous suspension. In addition, the negative charge in the platinum salt is attracted to the positive charge in the polyamine polymer, so that the platinum salt is uniformly dispersed in the polymer, so after adding the reducing agent in step (c) The platinum salt is reduced to form uniformly dispersed platinum nanoparticles. In one embodiment, when the platinum salt is hexachloroplatinic acid (H2PtCl6), the positive charge of Pt4+ and the ethylene oxide in the polyamine polymer ( -CH2CH20, ethylene oxide) produces positive and negative electrostatic interactions. In summary, the polyamines of the present invention have a dual 201211172 function, which can be used not only as a dispersing agent for carbon nanotubes, but also as a platinum nanocap. Stabilizer for rice particles. Next, 'Step (d), the mixed solution is applied to the substrate by a coating method. The substrate is a transparent conductive substrate, including fluorine-doped tin dioxide. Fluorine-doped tin oxide glass (FTO) 'indium tin oxide glass, poly (ethylene terephthalate), PET or polyimide (PI) Coating method including spin coating Spin coating), bar coating, dip coating, roll coating, spray coating, gravure coating, inkjet printing (ink ^ jet printing) or blade coating. The rotation speed of the coating method is about 500 rpm to 4000 rpm, preferably about 1000 rpm to 3000 rpm, more preferably about 15 〇〇 ι·ρηι to 2000 rpm. The coating time is about 5 seconds to 30 seconds. It should be noted here that the substrate of the present invention is a conductive transparent substrate, and the platinum counter electrode is used in the sputtering method to form a platinum counter electrode. The use of the platinum nanoparticle of the present invention is less than 'completely blocking the light'. With good penetration, the counter electrode of the present invention can be assembled into a front-illuminated dye-sensitized solar cell (fr〇nt_side iUuminateci DSSC) can also be assembled into a back-illuminated dye-sensitized solar cell (back side φ illuminated DSSC) In a preferred embodiment, the mixed solution is applied to fluorine-doped tin dioxide glass (FT0) using spin coating, and coated at a rotation speed of 2 rpm. Cloth 15 seconds. Thereafter, the substrate (e) is subjected to heat treatment to form a conductive film on the substrate. One of the purposes of the heat treatment is to crack the polyamine polymer to expose the platinum nanoparticles and the carbon nanotubes, and another purpose is to help the unreduced platinum salt to be reduced to platinum nanoparticles. The heat treatment temperature is about 170 ° C to 35 ° C, and the heat treatment time is about 1 〇 12 201211172 〜 50 minutes. The film thickness of the finally obtained conductive film is about 400 to 500 nm, preferably about 400 to 450 nm. Thereafter, the counter electrode prepared in the above step can be assembled into a dye-sensitized solar cell with a conventional electrolyte, dye and anode. The open circuit voltage (Voc) of the solar cell is about 0.65 to 0.75 V, short-circuit current. (short-circuit current, Jsc) is about 16~20 mA/cm2, fill factor (FF) is about 0.55~0.65; photoelectric conversion efficiency (7/) is about 7~9 0/〇 . Further, the dye-sensitized solar cell of the present invention has a better short-circuit current (Jsc) and photoelectric conversion efficiency (?7) than the conventional sputtering of a platinum counter electrode. In the method for preparing the counter electrode of the dye-sensitized solar cell of the present invention, the nano carbon tube and the platinum nanoparticle can be uniformly dispersed in the solution by the aid of the polyamine polymer, thereby effectively improving the counter electrode. The surface area, which makes the counter electrode have better catalytic activity, helps to improve the photoelectric conversion efficiency of the dye-sensitized solar cell. [Examples] Comparative Example 1 ® Platinum particles were formed on a fluorine-doped tin oxide glass (FTO) using a sputtering method to obtain a counter electrode. Comparative Example 2 A 0.036 g multi-walled carbon nanotube was dissolved in 7.107 g of dimethyl fumarate (DMF) and placed in a round bottom flask and ultrasonically shaken to obtain an A solution. Add 6.143 g of water to the A solution, and then add 1. 〇g hexachloroplatinic acid (H2PtCl6) to the solution A. After the solution is completely dissolved, sodium borohydride (NaBH4) is used as a reducing agent to obtain ptNPs. /CNT mixed solution. 13 201211172 In Comparative Example 2, since the polyamine polymer of the present invention is not used, as shown in Figs. 1A to 1B (wherein Fig. 1B is an enlarged view of the circle 101 in Fig. 1A), a nanometer is observed. From the phenomenon of aggregation of carbon tubes and platinum, it is understood that the addition of the polyamine polymer of the present invention can be used as a dispersant for carbon nanotubes. Example 1 Preparation of Polyiminamide See Scheme 1, which is a reaction scheme for the formation of polyamidamine. The synthesis procedure was as follows: P〇E-2000-2/dianhydride was synthesized in a ratio of molar ratio of 6:5. Take 100 ml of three-necked flask, dissolve 10 g (0.005 mol) of POE-2000-2 in 10 ml of tetrahydrofuran (THF), and then add 3.3 g (0.0042 mol) of 4,4'-diphenyl. 4,4'-Oxydiphthalic dianhydride (ODPA), mechanically stirred, nitrogen-filled throughout, temperature controlled at 150 °C, continuous reaction for 3 hours. During the reaction, it was monitored by infrared spectroscopy (IR spectra) and sampled at intervals until the anhydride functional group signal disappeared and the imide functional group no longer increased, and a pale yellow viscous solid was obtained. product.

4-4_-Oxvdiphlhalic dianhydride (ODPA) ^

Poly(oxyethylene)-segmented imide (POE-imide) M\v = 39.000 g/mol Scheme 1 201211172 Example 2 Preparation of Polyamines See Flow 2 ' This process is a reaction scheme for the formation of polyamide. Example 2 was similar to the reaction procedure of Example 1, except that the temperature of the reaction of Example 2 was about 30 ° C, and finally a product of a pale yellow viscous solid was obtained.

4,4-Oxydiphthalic dianhydride (ODPA) I | ·& b i c CH? CHa CHj

POE-2000-2, a+c = 6. b = 39; Mw = 2000 g/ntol 30 »C

Scheme 2 Example 3 Preparation of Counter Electrode A solution and B solution were prepared separately. A 0.036 g multi-walled carbon nanotube was dissolved in 7.107 g of dimethyl fumarate (DMF) and placed in a round bottom flask and ultrasonically shaken to obtain a solution A. Take 1.0 g of the polymer of Example 1 dissolved in 5.143 g of water to obtain a B solution. After the A and B solutions are uniformly dispersed, they are then mixed into a C solution, and then 1.0 g of hexahydroxamic acid (H2PtCl6) is added. Using sodium borohydride (NaBEU) as a reducing agent, a mixed solution (POE-imide@Pt@CNT) was finally obtained. This mixed solution was applied onto fluorine-doped tin oxide glass (FT0) at a rotational speed of 2000 rpm by a spin coating method, and subjected to heat treatment at 350 ° C for 20 minutes to finally obtain a counter electrode. Please refer to FIG. 2, which shows the cyclic voltammetry of Example 3 and Comparative Example 1 (with silver/vaporized silver (Ag/AgCl) as a reference electrode), which can be clearly observed from the figure. The reduction current (Ipc) of Example 3 was higher than that of the reduction 15 201211172 of Comparative Example 1, indicating that the catalytic effect of the counter electrode of the present invention was better. Table 4 shows the conductivity (σ), series resistance (Rs), charge transfer lesistance (Ret) and root mean square roughness (rc) C) t_mean_Square Rms of Example 3 and Comparative Example 1. The data 'where the series resistance (Rs) or charge transfer resistance (the smaller U means 'reducing less resistance, which is beneficial to charge transfer; and the square root roughness is ten) is larger, representing the larger surface area of the electrode. As can be seen from Table 4, the charge transfer resistance (Rj of Example 3 of the present invention is smaller than that of Comparative Example 1 and Comparative Example 2, and the square root roughness (Rms) is larger than that of Comparative Example 丨, and thus it is known that the counter electrode of the present invention is It has a large surface area and thus contributes to the improvement of the catalytic effect. Table 4 Counter electrode σ (S cm·1) Rs (Ω cm2) Ret (Ω cm2) Rms (nm) Comparative Example 1 17.15 + 1.26 20.35±0.47 0.50+ 0.04 10.38+0.09 Example 3 1.96+0.09 22.92+0.24 0.28±0.03 22.69±5.01 Example 4 Preparation of Dye-Sensitized Solar Cell The counter electrode of Example 3, the anode (photoanode) containing titanium dioxide (τ〇2), dye Combined with an electrolyte to form a dye-sensitized solar cell, wherein the electrolyte is 〇·6 Μ 1,2-dimercapto-3-propylimidazolium iodide (l,2-dimethyl-3-pr〇pylimidaz〇iiuni i〇dide, DMPII ), 0.1 Μ lithium iodide (Lil), 0.05 Μ moth (12) and 0.5 Μ 4-tert-butylpyridine (TPP) dissolved in (MPN), wherein the dye is N719 dye (RuL2 (NCS) 2: 2TBA). Fig. 3 shows the photocurrent_potential diagram of Example 4, Comparative Example 1 and Comparative Example 2 201211172 (IV), As can be seen, the photocurrent of Example 4 was significantly higher than that of Comparative Example 1 and Comparative Example 2 at the same potential. Table 4 shows dye-sensitized solar cells composed of Example 4, Comparative Example 1 and Comparative Example 2. (DSSC) open-circuit voltage (V.), short-circuit current (Jsc), fill factor (fill factor) and photoelectric conversion efficiency (power conversion efficiency, η) data. It can be seen from the above that the short-circuit current and the photoelectric conversion efficiency of the fourth embodiment of the present invention are higher than that of the comparative example 1 and the comparative example 2, therefore, the method of the invention can not only reduce the amount of platinum used, but also improve by the carbon nanotubes. The surface area of the electrode is effective to improve the short-circuit current and photoelectric conversion efficiency. Table 5 Counter electrode V〇c (V) J SC FF V (mA/cm2) (%) Comparative Example 1 0.74+0.01 14.62±0.19 0.64±0·01 6.92±0.07 Comparative Example 2 0.75 15.29 0.62 7.16 Example 4 0.73+0.01 18.01+0.91 0·61±0.01 8.00±0.23 Although the present invention has been disclosed above in several preferred embodiments, it is not intended to limit the invention. Anyone in the field of technology Knowledge of those in the present invention without departing from the spirit and scope, it can be made to any modifications and variations of the present invention thus protect the scope of protection as defined by the appended claims which are the scope of their equivalents. !7 201211172 [Simple description of the diagram] Figure 1A is a photo to illustrate the phenomenon of aggregation. The example of the polyamine high score of the present invention is shown in Fig. 1B as a photograph for illustrating a circular voltammogram, and an enlarged view of the circle in the figure. The catalytic effect of the electrode on the electrode. Μ明发明发明-料实施例和比 [Main component symbol description] !01~Circle

18

Claims (1)

201211172 VII. Patent Application Range: 1. A method for preparing a counter electrode of a dye-sensitized solar cell, comprising the following steps: (a) providing a polyamine polymer, wherein the polyamine polymer comprises poly Polyimide or polyamide; (b) mixing the polyamine polymer, a carbon nanotube, and a platinum salt in a solvent to prepare a homogeneous a homogenous suspension; a (c) addition of a reducing agent to the homogeneous suspension to prepare a mixed solution, wherein the mixed solution comprises a plurality of platinum nanoparticles; (d) a coating method Applying the mixed solution to a substrate; and (e) subjecting the substrate to a heat treatment to form a conductive film on the substrate. 2. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein the polyamidoamine comprises a poly(oxyethylene)-segmented imide (POE) containing a polyether segment. -imide), having the following formula (I): Wherein n = 1 to 16; and P0E has the following formula (II): NH.CHCH, ^ I - ch3 OCHCH2-)^-(-〇CH2CH2-^OCH2CH^-NH2 ch3 (II), where a+c=6 , b=39. 3. The method for preparing a dye-sensitized solar cell according to claim 1, wherein the polyamide comprises a polyether-containing polyamine ( Poly(oxyethylene)-segmented amide, POE-imide) having the following formula (III): (ΙΠ) where η = 1~2 ; and POE has the following formula (II): nh2chch2—(- ochch2-)-(· OCH2CH2 ch3 CH3 a where a+c=6, b=39. ^(och2ch^nh2 CH , (II), 4. The method for producing a counter electrode of a dye-sensitized solar cell according to claim i, wherein the polyamine polymer has a molecular weight of about 2,000 to 200,000 g/mol. 5. The method of manufacturing a counter electrode for a dye-sensitized solar cell according to claim 1, wherein the carbon nanotube is a single-wall or a multi-wall carbon nanotube. 6. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein the platinum salt comprises hexa-gas platinum acid (H 2 PtCl 6 ), potassium chloroplatinate (K 2 PtCl 6 ), gas platinum Ammonium acid ((NH4)2PtCl6), hexahydrate ruthenium ruthenate (Rb2PtCl6) or hexahydrate ruthenium platinumate (Cs2PtCl6). 7. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein the reducing agent comprises sodium borohydride (NaBH4), decyl alcohol (CH3OH), ethylene glycol ( C2H4(OH)2), monoethanolamine (MEA, C2H4OHNH2), diethanolamine (20 201211172 DEA, (C2H4OH)2NH) or diglycolamine (DGA, QHhNC^). 8. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein in the step (b), the polyamine south molecule, the nanotube and the platinum salt are The mixing weight ratio is about 1: 1: 1 to 99: 1: 99. 9. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein in the step (b), the solvent comprises water, ethanol (C2H5OH), and acetone (acetone, ( CH3)2CO), propylene glycol monomethyl ether acetate (PGMEA), toluene, N-methyl 0 to ^isKN-methyl pyrrolidinone (NMP), tetrahydrofuran (tetrahydrofuran, THF), ethylene glycol (EG), glycerin or a combination thereof. 10. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein in the step (c), the platinum nanoparticles have a particle size of about 8 nm to 30 nm. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein in the step (d), the substrate comprises a fluorine-doped tin oxide glass (fluorine-doped tin oxide glass, FTO) 'Indium tin oxide glass, polyethylene terephthalate, PET or polyimide (PI). 12. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein in the step (d), the coating method comprises spin coating, bar coating ( Bar coating), dip coating, roll coating, spray coating, gravure coating, ink jet printing or doctor blade coating Blade coating. 13. The method for preparing a counter electrode of a dye-sensitized solar cell according to claim 1, wherein in the step (d), the rotation speed of the coating method is about 500 rpm to 4000 21 201211172 卬 1" The cloth time is about 5 seconds to 30 seconds. [4] The method for preparing a cake electrode of a dye-sensitized solar cell according to the invention, wherein in the step (e), the temperature of the heat treatment is about 170t to 35 (TC, . The time is about 3 minutes to 40 minutes. The electrode of the dye-sensitized solar cell of the first aspect of the invention is as described in claim 1. In the step (4), the film thickness of the conductive film is about 400 legs ~ 500 twenty two