JP5167531B2 - Method for producing oxide semiconductor electrode of dye-sensitized solar cell and oxide semiconductor electrode - Google Patents

Description

The present invention relates to a method of manufacturing an oxide semiconductor electrode and an oxide semiconductor electrode of a dye-sensitized solar cell, and more particularly to a method of manufacturing an oxide semiconductor electrode using a TiO ₂ oxide and an oxide semiconductor electrode.

  Dye-sensitized solar cells are attracting attention because they can be manufactured at a lower cost and with a lower environmental load than silicon-based solar cells, and solar cells with various colors can be manufactured. However, since dye-sensitized solar cells have low energy conversion efficiency compared to silicon-based solar cells, their improvement is required, and various methods have been disclosed. This is one of the effective methods for improving the energy conversion efficiency.

  For example, in Patent Document 1, in a photoelectric conversion element having a semiconductor fine particle layer and a charge transfer layer sensitized with a dye, the semiconductor fine particle layer includes at least one second metal together with a main first metal element constituting the semiconductor fine particle layer. A photoelectric conversion element that contains 0.01 mol% or more and less than 50 mol% of a main metal element is disclosed. Here, the first metal element is a simple or compound metal element such as silicon or germanium, and the second metal element is an alkali metal, alkaline earth metal, or the like. And it is disclosed that by adding such a second metal element, the conductor energy level of the semiconductor fine particle layer can be controlled, and a dye-sensitized solar cell with excellent conversion voltage and high conversion efficiency can be obtained. ing.

  Non-Patent Documents 1 and 2 disclose a method of adding a pyridine derivative such as 4-tert-butyl pyridine (TBP), chenodeoxycholic acid, or the like that prevents a reverse current and increases an open photovoltaic voltage to an electrolyte solution.

  Patent Document 2 discloses that a tandem dye-sensitized solar cell is intended to improve the open photovoltaic voltage, the particle diameter is 0.1 nm to 1000 nm, and Cu, Al, Ag, Ni, Co, In, Fe An oxide semiconductor electrode made of a p-type inorganic oxide semiconductor containing any one of Zn, Rh, Ga, Sr, Li, and N is disclosed.

JP 2002-8741 A JP 2006-66215 A Electrochimica Acta, 47 (2002) p4213-4225 J. Phys. Chem., 97 (1993) p6272-6277

  However, there is a need for a method and means for further increasing the open photovoltaic voltage or the open photovoltaic voltage improvement rate and improving the energy conversion efficiency compared to conventional methods. And the dye-sensitized solar cell of patent document 1 has the problem that it is not necessarily easy to manufacture the dye-sensitized solar cell which has homogeneous performance. The oxide semiconductor electrode described in Patent Document 2 has a complicated structure and has a problem that it cannot be easily and inexpensively manufactured. The method described in Non-Patent Document 1 or 2 has a problem that only an improvement effect of a certain degree of open photovoltaic voltage or energy conversion efficiency can be obtained.

  The present invention provides a dye-sensitized solar cell that can change colors in a variety of ways and has a simple structure with a high open photovoltage or a high open photovoltage improvement rate and a high energy conversion efficiency and economy. An object of the present invention is to provide a method for manufacturing an oxide semiconductor electrode and an oxide semiconductor electrode obtained by the method.

The method for producing an oxide semiconductor electrode of a dye-sensitized solar cell according to the present invention includes a step of forming a porous layer of TiO ₂ on a conductive surface of a transparent electrode, and intercalating alkali metal ions into the TiO ₂ And a step of adsorbing the dye to the porous layer after discharging and removing the intercalated alkali metal ions.

In the above invention, the process, it is assumed that an electrolytic process for electrolytic reduction the porous layer of TiO ₂ in the non-aqueous electrolyte solution as the solvent dissolves the alkali metal salt to be intercalated alkali metal ions in TiO ₂ The alkali metal salt is preferably LiX, NaX, or KX. Here, X is any one of F, Cl, Br, I, PF ₆ , BF ₄ , and ClO ₄ .

Further, the step of intercalating alkali metal ions in TiO ₂ can be assumed to be the chemical treatment of immersing the porous layer of TiO ₂ to a solution containing an organic alkali metal compound, an organic alkali metal compound, MeLi (methyl lithium), BuLi (butyl lithium), PhLi (phenyl lithium), thienyllithium (thienyl lithium), t-BuOLi (tertiary butoxy lithium), MeONa (sodium methoxide), EtONa (sodium ethoxide), t- It should be one of BuOK (potassium butoxide) .

Further, alkali metal ions intercalated into TiO ₂ is better to be contained 0.001~0.5mol per TiO ₂ 1 mol with an alkali metal salt or an organic alkali metal compound. The dye may be any one of Eosin Y (Rhodamine B), Chicago Sky Blue, Alizarin, and Coumarin 343 .

By the said invention, the oxide semiconductor electrode for dye-sensitized solar cells with a high open photovoltaic voltage or an open photovoltaic voltage improvement rate and a high energy conversion efficiency can be manufactured. That is, an oxide of a dye-sensitized solar cell having a conductive transparent electrode, a porous layer of TiO ₂ formed on the conductive surface of the transparent electrode, and an organic dye adsorbed on the porous layer An oxide semiconductor electrode of a dye-sensitized solar cell, which is a semiconductor electrode and has a work function of TiO ₂ of 5 eV or less, can be manufactured.

  According to the method for manufacturing an oxide semiconductor electrode of a dye-sensitized solar cell according to the present invention, the color can be changed in various ways, and the open photovoltage or the open photovoltage improvement rate is high with a simple structure and economically. An oxide semiconductor electrode for a dye-sensitized solar cell with high energy conversion efficiency can be manufactured. By using this oxide semiconductor electrode, a dye-sensitized solar cell can be manufactured, and a solar cell built-in panel with various colors suitable for building roofs, exteriors, or advertisements can be easily and inexpensively manufactured.

Hereinafter, embodiments of the method for producing an oxide semiconductor electrode of a dye-sensitized solar cell according to the present invention will be described. As shown in FIG. 1, the dye-sensitized solar cell 10 includes an oxide semiconductor electrode 11 in which a porous layer 15 in which a dye 16 is adsorbed is formed on a conductive surface of a transparent electrode 12, and a conductive counter electrode 18. And an electrolyte solution (including a gel or a solid) 17 containing a redox substance interposed between the oxide semiconductor electrode 11 and the counter electrode 18. The manufacturing method of the oxide semiconductor electrode 11 according to the present invention includes a step of forming a porous layer of TiO ₂ on the conductive surface of the transparent electrode 12, a step of intercalating alkali metal ions into the TiO ₂ , And a step of adsorbing the dye to the porous layer after discharging and removing the intercalated alkali metal ions.

A known method can be used for the step of forming the porous layer of TiO ₂ on the conductive surface of the transparent electrode 12. For example, conductive glass in which a conductive film 14 is formed by depositing 95% indium oxide and 5% tin oxide compound (ITO) on a glass substrate 13 or by doping fluorine (FTO) after depositing tin oxide. Apply paste prepared by mixing TiO ₂ powder with polyethylene glycol, 10% acetylacetone, water, etc. on the conductive surface of (TCO) by the doctor blade method, squeegee method, etc., and drying and firing this Thus, a porous layer of TiO ₂ can be formed on the conductive surface of the transparent electrode 12.

Next, in the present invention, a step of intercalating alkali metal ions into TiO ₂ constituting the porous layer formed by the above steps is provided. Here, intercalation means that an alkali metal ion is inserted between the anatase layers of TiO ₂ (titania). For example, in the case of lithium, lithium ions are intercalated until Li _0.5 TiO ₂ (blue). It means to insert into. In the present invention, the alkali metal ions to intercalate into TiO _2, open to obtain the effect of improvement of photovoltaic voltage, 0.001 to 0.5 mol TiO ₂ 1 mol per an alkali metal salt or an organic alkali metal compound to TiO ₂ It is good to intercalate so that it may be contained. This is because the effect is small when the alkali metal salt or the organic alkali metal compound is less than 0.001 mol, and the degree of the effect is saturated when the amount exceeds 0.5 mol.

The present invention intercalates alkali metal ions into the porous layer of TiO ₂ formed on the conductive surface of the transparent electrode 12, changes the structure of TiO ₂ as described below, and changes the changed TiO ₂ In this method, a dye, particularly an organic dye, is effectively adsorbed on the porous layer. Therefore, the dye effectively adsorbed on the porous layer of TiO ₂ and may have the alkali metal ion is then intercalated into TiO _2, also prior to intercalating the alkali metal ions When the dye is adsorbed, the dye may be destroyed or dropped by the electrochemical or chemical treatment described below. In the present invention, the intercalation of alkali metal ions is performed before the dye is adsorbed. It is important to do.

The method for intercalating alkali metal ions into TiO ₂ is not particularly limited, but an electrochemical or chemical method can be used. For example, an electrolytic treatment in which a porous layer of TiO ₂ is electrolytically reduced in an electrolytic solution in which an alkali metal salt is dissolved in a nonaqueous solvent is preferable. Acetonitrile can be used as the non-aqueous solvent. As the alkali metal salt, LiX, NaX, and KX in which X is any of F, Cl, Br, I, PF ₆ , BF ₄ , and ClO ₄ are preferable. LiClO ₄ is particularly preferable.

The nonaqueous solvent refers to, for example, an acetonitrile solvent. In the case of an aqueous solvent, water itself is reduced, and alkali metal ions cannot be intercalated into TiO ₂ , which is not suitable.

The method of intercalating alkali metal ions into TiO ₂ may be a chemical treatment in which a porous layer of TiO ₂ is immersed in a solution containing an organic alkali metal compound. Organic alkali metal compounds are MeLi (methyl lithium), BuLi (butyl lithium), PhLi (phenyl lithium), thienyllithium (thienyl lithium), t-BuOLi (tertiary butoxy lithium), MeONa (sodium methoxide), EtONa (sodium) Ethoxide) or t-BuOK (potassium butoxide) is preferable. In particular, BuLi is preferable.

Next, in the present invention, a step of adsorbing the dye to the porous layer after discharging and removing the intercalated alkali metal ions is provided. Intercalated alkali metal ions in TiO _2, when taken out of the post-treatment liquid for the electrochemical treatment or a chemical treatment, a hydroxide combines with moisture in the atmosphere diffuses into the TiO ₂ surface Form. For this reason, the dye adsorption reaction is hindered by the alkali metal hydroxide adhering to the porous layer 13 or the treatment liquid used for the electrochemical or chemical treatment before the dye adsorption process, which is the next process. First, the porous layer 13 is washed and dried so as to remove these deposits. Drying may be heat drying or natural drying.

After sufficiently washing and drying the porous layer, the dye is adsorbed onto the porous layer. The dye adsorbed on the porous layer is preferably an organic dye. In particular, an organic dye of any one of Eosin Y, Rhodamine B (Rhodamine B), Chicago Sky Blue, Alizarin, and Coumarin 343 is preferable. In the case of a metal complex dye such as a ruthenium complex, an electrochemical treatment or a chemical treatment according to the present invention is not preferable because the effect of improving the open photovoltaic voltage and energy conversion efficiency is small.

  As described above, the oxide semiconductor electrode 11 in which the porous layer 15 in which the dye 16 is adsorbed is formed on the conductive surface of the transparent electrode 12 according to the present invention can be manufactured by such steps. The dye-sensitized solar cell using this oxide semiconductor electrode 11 can improve the open photovoltage without changing or almost reducing the short-circuit photocurrent density, and further improve the energy conversion efficiency. Can do.

A dye-sensitized solar cell shown in FIG. 1 was produced using the oxide semiconductor electrode produced by the above method, and a battery performance test was conducted. The oxide semiconductor electrode 11 was produced as follows. First, 1.3 g of TiO ₂ powder P-25 (produced by Nippon Aerosil Co., Ltd., average particle size 20-30 nm, rutile-anaters mixed crystal) is placed in a zirconia pot, added with 310 μm of water, and a planetary ball mill (Fritsch Japan) Milling was performed for 10 minutes using P-7). Furthermore, the same amount of water was added and the same treatment was repeated 4 times. To this, 310 μl of EtOH was added and milled for 10 minutes. after that. 80 mg of PEG (average molecular weight: 500,000) and an appropriate amount of nitric acid (3-5 drops with a Pasteur pipette) were added and milled for 3-4 hours to prepare a TiO ₂ paste.

The electrochemical treatment of the porous layer of TiO ₂ was performed as follows. First, an electrolytic solution in which 0.1 M of various alkali metal salts were dissolved in acetonitrile (AN) solvent, a platinum wire as a counter electrode, and a two-electrode system reduction treatment at a constant current of −0.5 mA were performed. As the potentiostat, HA-501G manufactured by Hokuto Denko Co., Ltd. was used.

After the electrochemical treatment of the TiO ₂ porous layer, the dye by washing and drying the transparent electrode 12 to form a porous layer of TiO _2, which is immersed in a variety of dye solution shown in Table 1 Was adsorbed on the porous layer, and the oxide semiconductor electrode 11 in which the dye 16 was adsorbed on the porous layer 15 of TiO ₂ was produced.

The oxide semiconductor electrode 11 was provided with an electrolyte solution 17 and a counter electrode 18 to produce a 0.5 cm × 0.5 cm dye-sensitized solar cell, and a battery performance test was performed. As the electrolyte solution 17, a solution obtained by dissolving 0.5 M LiI and 0.05 M I ₂ in an acetonitrile solvent was used. As the counter electrode 18, Cr was deposited on a slide glass by 2 nm and Pt was deposited by 50 nm. As the counter electrode 18, a glass plate provided with a platinum vapor deposition film was used. For comparison, a dye-sensitized solar cell produced without electrochemical treatment of the porous layer of TiO ₂ and a dye-sensitized solar cell produced by adding TBP to the above electrolyte solution 17 A battery performance test was also conducted.

For the battery performance test (measurement of IV characteristics) of the dye-sensitized solar cell, a solar simulator (SERICSXL-500V2, AM1.5, 93mW / cm ² ) manufactured by Celic Co., Ltd. was used as the light source, and a potentiostat (Hokuto Denko Co., Ltd.) HA-501G).

FIG. 2 shows the effect of electrochemical treatment of the porous layer of TiO ₂ . Figure 2 is a porous layer of TiO ₂ and electrolytic reduction in an electrolytic solution of LiClO _4, after intercalating lithium ions into TiO _2, an oxide semiconductor electrode 11 having adsorbed a dye Coumarin 343 dye It is a graph which shows the result of the battery performance test of what produced the sensitized solar cell. In FIG. 2, the horizontal axis represents the electrolytic treatment time, the vertical axis represents the electrolysis of the short-circuit photocurrent density Isc (mA / cm ² ), the open photovoltaic voltage Voc (mV), the fill factor FF, and the energy conversion efficiency η (%). The relative ratio with respect to the case where the electrolytic treatment is not performed when the treatment is performed is shown.

  According to FIG. 2, the short-circuit photocurrent density ratio (Isc) does not change until the processing time is 5 min, the open photovoltaic voltage ratio (Voc) and the energy conversion efficiency ratio (η) increase rapidly, and the open photovoltaic voltage The ratio (Voc) and the energy conversion efficiency ratio are 1.5. The fill factor ratio (FF) is slight but gradually increasing. On the other hand, when the processing time exceeds 5 min, the short-circuit photocurrent density ratio and the energy conversion efficiency ratio gradually decrease, but the open photovoltaic voltage ratio still increases and reaches a relative ratio of 1.9 at the processing time of 15 nim, and then gradually decreases. At the processing time of 15 nim, the short-circuit photocurrent density ratio is 0.5 and the energy conversion efficiency ratio is 1.0. That is, it can be seen that the present invention can provide a dye-sensitized solar cell having a high open photovoltaic voltage and a high energy conversion efficiency.

FIG. 3 shows the results of investigating the effect of an alkali metal intercalated with TiO ₂ . Fig. 3 shows the open photovoltage of a dye-sensitized solar cell fabricated using an oxide semiconductor electrode obtained by electrochemical treatment of a porous layer of TiO ₂ in various alkali metal salt electrolytes, and electrolytic treatment. It is a graph which shows the relationship with the processing time. In FIG. 3, the horizontal axis represents the treatment time and the vertical axis represents the open photovoltage, the Li curve represents the electrolytic treatment performed in the LiClO ₄ electrolyte, and the Na curve represents the electrolytic treatment in the NaClO ₄ electrolytic solution. When performed, the K curve shows the case where the electrolytic treatment was performed in an electrolytic solution of KClO ₄ .

According to FIG. 3, it can be seen that the effect of improving the open photovoltaic voltage is most effective in the electrolytic treatment in the LiClO ₄ electrolytic solution, and then in the electrolytic treatment in the NaClO ₄ electrolytic solution. Further, according to FIG. 3, it can be seen that there is an optimum processing time in which the open photovoltaic voltage is the highest in any processing.

Next, the effect of the pigment in the present invention will be shown. Table 2 shows a dye-sensitized solar cell (with treatment) prepared using an oxide semiconductor electrode obtained by electrochemically treating a porous layer of TiO _{2 in} an electrolyte solution of LiClO ₄ , and such electrochemical It is the result of the battery performance test of the dye-sensitized solar cell (it did not process) produced using the oxide semiconductor electrode which did not perform an organic process. According to Table 2, the effect of improving the open photovoltaic voltage in the present invention is highest in the case of the dye Coumarin 343, followed by Alizarin and Chicago Sky Blue in this order. On the other hand, when the dye is a ruthenium metal complex, it can be seen that the effect of improving the open photovoltaic voltage is small.

Table 3 and FIG. 4 show the results of comparing the effects of the present invention with the effects of adding TBP that prevents reverse current and increases the open photovoltaic voltage to the electrolyte solution 17. FIG. 4 is a graph showing an IV characteristic curve during light irradiation of the dye-sensitized solar cell, in which the horizontal axis represents voltage and the vertical axis represents current density. In Table 3 and FIG. 4, “with treatment” means that an oxide semiconductor electrode in which the dye Coumarin 343 is adsorbed after electrochemical treatment of the porous layer of TiO _{2 in} an electrolyte solution of LiClO ₄ is used. This shows the case of the dye-sensitized solar cell. “No treatment” indicates a case of a dye-sensitized solar cell manufactured using an oxide semiconductor electrode in which the dye Coumarin 343 is adsorbed without performing such an electrochemical treatment.

  Comparing the case with treatment (invention) and the case without treatment (comparative example) in Table 3, in the case of the invention, the open-circuit photovoltage is almost the same as in the comparative example, although the short-circuit photocurrent density Isc is almost the same as in the comparative example. Voc has increased 1.7 times, and energy conversion efficiency η has increased 1.8 times. In contrast, when the TBP addition treatment and the case without treatment are compared, the open photovoltage Voc can be increased by a factor of 1.2 compared to the case without treatment in the case of TBP addition treatment, but the short-circuit photocurrent density Isc and It can be seen that the energy efficiency η decreases to 1/3.

  According to FIG. 4, it can be seen that in the case of TBP addition treatment, the I-V curve is shifted to the negative side by 70 mV compared to the case without treatment, and when the treatment is performed, it is further shifted to the negative side of 170 mV. As described above, as can be seen from Table 3 and FIG. 4, it can be seen that the effect of improving the open photovoltaic voltage and the energy efficiency according to the present invention is high, and those effects are considerably higher than those of the TBP addition treatment.

FIG. 5 is a graph showing the results of obtaining the work function of TiO ₂ using the same oxide semiconductor electrode as produced in the tests of Table 3 and FIG. In FIG. 5, the horizontal axis indicates the sample number, and the vertical axis indicates the work function. The work function was measured using the Kelvin Probe method. Before the measurement, the work function of a sample (HOPG, Au) with a known work function was measured, and the reference electrode was calibrated. As the reference electrode, a cylindrical glass bottom with gold deposited was used. A piezo element (AE023D08 manufactured by NEC Corporation) was fixed to the reference electrode, and was vibrated at 500 Hz using a piezo driver (M-2633 manufactured by Mestek). At this time, the current flowing between the sample and the reference electrode is converted into a voltage using a preamplifier (NF-LI-76, gain: 10 ⁶ V / A), and the lock-in amplifier (NF-LI-574A) is used. Detected. The voltage between the sample and the reference electrode was swept at 10 mV / s or 1 mV / s, and the applied voltage and the output signal of the lock-in amplifier were recorded with an XY recorder (F-57 manufactured by Riken Denshi Co., Ltd.).

According to FIG. 5, the electrochemical treatment of the TiO ₂ porous layer, the work function of the TiO ₂ prior to treatment it can be seen that it is possible to reduce what was 5.1eV to 4.9 eV. This is considered due to the fact that the structure of TiO ₂ was changed by intercalating alkali metal ions into TiO ₂ . That is, according to the present invention, the work function of TiO ₂ forming the porous layer 15 can be lowered, and when a dye-sensitized solar cell is produced using the oxide semiconductor electrode 11 having such a porous layer 15 It is possible to obtain a dye-sensitized solar cell having high energy efficiency and high open photovoltage or open photovoltage improvement rate.

For the oxide semiconductor electrode 11 with treatment, X-ray analysis of the crystal structure of TiO2 constituting the porous layer 15 and analysis of trace elements of alkali metals present in the porous layer 15 are performed by inductively coupled plasma emission spectroscopy (ICP- AES). According to the result, it was found that no alkali metal was present in the porous layer 15 that had been washed and dried and subsequently adsorbed with the dye. However, for example, a porous layer exhibited blue by electrochemical treatment (lithium ions are intercalated into TiO _2, Li _0.5 TiO ₂ are formed) of more than a few minutes in the atmosphere taken out from the electrolyte left -After stabilization (the blue color of the porous layer disappears and becomes white or transparent), when the residual amount of lithium was measured, Li was contained in an amount of 0.14 mol per 1 mol of Ti0 _{2 in} terms of molecular weight. The calibration curve for Li was prepared by ICP-AES analysis of a solution containing 1 ppm and 10 ppm of Li, respectively. X-ray analysis was performed using an XRD measurement apparatus (M18XHF-SRA manufactured by Mac Science). ICP-AES was performed using an ICP emission spectrometer (Optima 3000 manufactured by Perkin-Elmer).

A dye-sensitized solar cell was fabricated using an oxide semiconductor electrode 11 fabricated by chemical treatment of a porous layer of TiO ₂ , and a battery performance test was performed. The dye-sensitized solar cell was prepared and tested in the same manner as described above. The chemical treatment was performed by immersing the TiO ₂ electrode for 10 minutes in a solution in which 1.5 ml of 1.58M BuLi (n-hexane solution) was dissolved in 30 ml of THF.

Table 4 shows the test results of chemical treatment in butyllithium (BuLi) solution. As shown in Table 4, the open photovoltage is improved by intercalating alkali metal ions into TiO ₂ and the energy conversion efficiency is improved by chemical treatment as well as the above electrochemical treatment. You can see that

Electrochemical treatment of porous layer of TiO ₂ using oxide semiconductor electrode in tetramethylammonium perchlorate (TMAP), tetrabutylammonium perchlorate (TBAP), tetraalkylammonium (TEAP) solution A dye-sensitized solar cell was prepared in the same manner as described above, and a battery performance test was performed. All of the short-circuit photocurrent density, the open photovoltage, the fill factor, and the energy conversion efficiency were the same when either treatment was performed as when the treatment was not performed.

It is a schematic diagram which shows the structure of a dye-sensitized solar cell. It is a graph which shows the relationship between the processing time of a dye-sensitized solar cell which consists of an oxide semiconductor electrode which performed the lithium intercalation process, and a battery performance characteristic. It is a graph which shows the relationship between the processing time of the dye-sensitized solar cell which consists of an oxide semiconductor electrode which performed the intercalation process of various alkali metals, and an open photovoltage. It is a graph which shows the IV characteristic curve of the dye-sensitized solar cell which consists of an oxide semiconductor electrode which performed the lithium intercalation process. Is a graph showing the difference in work function of the TiO ₂ with and without lithium intercalating process.

Explanation of symbols

10 Dye-sensitized solar cell
11 Oxide semiconductor electrode
12 Transparent electrode
13 Board
14 Conductive film
15 Porous layer
16 Dye
17 Electrolyte solution
18 counter electrode

Claims (8)

A step of forming a porous layer of TiO ₂ on the conductive surface of the transparent electrode, a step of intercalating alkali metal ions into the TiO ₂ , and discharging and removing the intercalated alkali metal ions And a method for producing an oxide semiconductor electrode of a dye-sensitized solar cell. _{2. The} step of intercalating alkali metal ions into TiO ₂ is an electrolytic treatment for electrolytic reduction of a porous layer of TiO ₂ in an electrolytic solution in which an alkali metal salt is dissolved in a non-aqueous solvent. The manufacturing method of the oxide semiconductor electrode of the dye-sensitized solar cell of description. The method for producing an oxide semiconductor electrode of a dye-sensitized solar cell according to claim 2, wherein the alkali metal salt is any one of LiX, NaX, and KX.
Here, X is any one of F, Cl, Br, I, PF ₆ , BF ₄ , and ClO ₄ . _2. The dye-sensitized solar cell according to claim 1, wherein the step of intercalating alkali metal ions into TiO2 is a chemical treatment in which a porous layer of TiO2 is immersed in a solution containing an organic alkali metal compound. Of manufacturing an oxide semiconductor electrode. Organic alkali metal compounds are MeLi (methyl lithium), BuLi (butyl lithium), PhLi (phenyl lithium), thienyllithium (thienyl lithium), t-BuOLi (tertiary butoxy lithium), MeONa (sodium methoxide), EtONa (sodium) The method for producing an oxide semiconductor electrode of a dye-sensitized solar cell according to claim 4, wherein the oxide semiconductor electrode is either ethoxide) or t-BuOK (potassium butoxide) . Intercalated alkali metal ions in TiO _2, dyes of any one of claims 1 to 5, characterized in that it is contained 0.001 to 0.5 mol TiO ₂ 1 mol per an alkali metal salt or an organic alkali metal compound A method for producing an oxide semiconductor electrode of a sensitized solar cell. The dye is characterized by being an organic dye of any one of Eosin Y, Rhodamine B (Rhodamine B), Chicago Sky Blue, Alizarin, Coumarin 343 The manufacturing method of the oxide semiconductor electrode of the dye-sensitized solar cell in any one of Claims 1-6. An oxide semiconductor electrode for a dye-sensitized solar cell, comprising: a conductive transparent electrode; a porous layer of TiO ₂ formed on the conductive surface of the transparent electrode; and an organic dye adsorbed on the porous layer An oxide semiconductor electrode for a dye-sensitized solar cell, wherein the work function of TiO ₂ is 5 eV or less.

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