TWI443844B - Fabrication method of dye-sensitized solar cells and electrochemical analysis device - Google Patents

Description

Dye sensitized solar cell, manufacturing method thereof and electrochemical analyzing device

The present invention relates to a dye-sensitized solar cell and a method of manufacturing the same, and more particularly to a dye-sensitized solar cell having a dense layer capable of improving conversion efficiency and a method of manufacturing the same.

The crystal energy solar cell developed in the 1970s has a total energy conversion efficiency of more than 25%, but its expensive cost is deterred and limits its practical use, indirectly causing dye-sensitized solar cells (Dye-sensitized solar cells). The development of DSSC) has the advantages of simple process, low material usage and low production cost.

There are three factors that affect the photoelectric conversion efficiency of dye-sensitized solar cells:

1. Sensitizing dyes: The choice of sensitizing dyes is one of the most important factors. The quality of dyes directly affects the photoelectric conversion efficiency of solar cells. Therefore, sensitizing dyes must meet the following conditions: (1) in nano-semiconductors (for example) The surface of the titanium dioxide nanoparticles needs to have good adsorption, that is, it can quickly reach the adsorption equilibrium and is not easy to fall off, so the dye molecules should have groups which are easy to combine with the surface of the nano semiconductor: such as -COOH, -SO ₃ H, -PO ₃ H _{2 ,} etc., (2) has a wide and strong absorption band in the visible light region, (3) has a very high stability in the oxidized state and the excited state, and (4) has a long lifetime in the excited state and requires It has a very high charge transfer efficiency, (5) has a sufficiently negative excited state redox potential to ensure that the dye excited state electrons can be smoothly injected into the titanium dioxide conductive band, and (6) in the redox process (ground state and excited state) Low potential to facilitate loss of free energy in primary and secondary electron transfer.

Second, the semiconductor electrode: the performance of the semiconductor electrode is also related to the efficiency of the solar cell. The dye-sensitized solar cell has the following two requirements for the semiconductor electrode: (1) the larger the surface area of the semiconductor electrode, the better, (2) the appropriate energy level structure, The energy band structure of the semiconductor should match the dye energy level and the redox potential of the electrolyte.

3. Electrolytes: Electrolytes play the role of transporting electrons and regenerating dyes in dye-sensitized solar cells. For a long time, dye-sensitized solar cells are mainly liquid electrolytes. Due to the wide variety of liquid electrolytes, electrode potentials are easy to control, but liquid electrolytes still exist. The following disadvantages: (1) low boiling point of organic solvent, high vapor pressure, easy to volatilize has an impact on long-term stability of dye-sensitized solar cells, (2) liquid electrolyte sealing technology is complicated, long-term placement will cause electrolyte leakage And the sealant may also react with the electrolyte, (3) the toxicity of the organic solvent, (4) the trace water molecules in the liquid electrolyte may cause the dye to desorb, and (5) the shape design of the dye-sensitized solar cell is limited. Although the liquid electrolyte has the above disadvantages, the improvement of the above disadvantages of the dye-sensitized solar cell is a goal of the current efforts, although the conversion efficiency obtained by the liquid electrolyte is still higher than that of the solid electrolyte.

The Republic of China Invention Patent No. I241029 "Dye-sensitized solar cell and its electrode", a metal nanocrystalline film of a dye-sensitized solar cell electrode is added with metal particles including gold, silver, platinum, copper, and the like. By using its own good electrical conductivity, the conductivity of the semiconductor nanocrystals is increased, and the rate of electron migration to the conductive substrate is accelerated, thereby improving the photoelectric conversion efficiency of the entire dye-sensitized solar cell.

The Republic of China Invention Patent No. I274424 "Electrode, photoelectric conversion element, and dye-sensitized solar cell" uses a conductive adhesive to bond carbon particles or platinum particles to form an electrode having a porous structure, thereby increasing the effective area of the electrode. (surface area). The invention can be manufactured at low cost and obtains excellent photoelectric conversion efficiency by increasing the effective area.

The Republic of China new patent No. M323109 "Dye-sensitized solar cells with nano-gold particles as embedded quantum dots" provides a dye-sensitized solar cell with nano-gold particles as embedded quantum dots, which is immersed in nano gold In the particle solution, the absorption band is increased, and the function of photoelectric conversion is improved to obtain a dye-sensitized solar cell structure having a high conversion ratio.

The Republic of China Invention Patent No. I241721 "Dye-sensitized solar cell module and its preparation method" discloses a dye-sensitized solar cell module capable of reducing the cost of a wire process, improving a photoactive region and a process yield, and a method for preparing the same; By adopting the integrated module manufacturing method, by combining two anode plates and cathode plates respectively having an anode and a cathode, the insulator and the wire are shared, so that the cost of the wire process can be reduced, and the manufacturing process of the wire and the insulator is performed at a high temperature. (about 400 ° C) operation to improve the process yield of solar cells; on the other hand, due to the design of the insulator and wire sharing, the light active area per unit area can also be increased.

U.S. Patent No. 7,179,988, "Dye sensitized solar cells having foil electrodes" provides a nanowire or nanopore electrode, thereby reducing the electron transport path. The electrode has a large specific surface area and can increase the dye adsorption area to enhance the performance of the dye-sensitized solar cell.

The present invention provides a dye-sensitized solar cell comprising: a uniform dense layer modified semiconductor electrode comprising: a transparent conductive substrate; a uniform dense layer formed on the transparent conductive substrate; and a porous semiconductor layer formed on the dense layer And a dye formed on the porous semiconductor layer; an electrolyte formed on the dense layer-modified semiconductor electrode; and an auxiliary electrode formed on the electrolyte.

The present invention also provides a method for fabricating a dye-sensitized solar cell, the method comprising: providing a transparent conductive substrate; forming a uniform dense layer on the transparent conductive substrate; forming a porous semiconductor layer on the dense layer; and forming a a dye on the porous semiconductor layer, wherein the transparent conductive substrate, the dense layer, the porous semiconductor layer and the dye constitute a uniform dense layer modified semiconductor electrode; forming an electrolyte on the dense layer modified semiconductor electrode; forming a An auxiliary electrode is on the electrolyte.

The invention further provides an electrochemical analysis device for a dye-sensitized solar cell, comprising: a potentiostat; a dye-sensitized solar cell as described above, connected to the potentiostat; a computer connected to the potentiostat .

The above and other objects, features and advantages of the present invention will become more apparent and understood.

Referring to FIG. 1, there is shown a dye-sensitized solar cell 30 according to an embodiment of the present invention, comprising a uniform dense layer modified semiconductor electrode 10, an electrolyte 31 formed on the dense layer modified semiconductor electrode 10, and an auxiliary electrode ( Counter electrode 20 is formed on the electrolyte 31. The dye-sensitized solar cell 30 of the present invention has high conversion efficiency and is simple in process and environmentally friendly.

Please refer to FIG. 2 , which shows a detailed structure of the uniform-layer-modified semiconductor electrode 10 in the embodiment of the present invention, which comprises a transparent conductive substrate 11 , and a uniform dense layer 12 is formed on the transparent conductive substrate 11 in sequence. The porous semiconductor layer 13 and a dye 14.

The transparent conductive substrate 11 can be any hard or flexible conductive substrate, including but not limited to an indium tin oxide glass substrate, a oxyfluoride glass substrate or an indium tin oxide flexible substrate. The transparent conductive substrate 11 may have a thickness of about 175-2200 μm.

The dense layer 12 can be a dense, high resistance (e.g., 10 Mohm high) film having a similar energy gap to that of titanium dioxide, including, for example, zinc oxide, titanium dioxide or barium metal doped titanium dioxide. The dense layer 12 can be formed on the transparent conductive substrate 11 by a radio frequency sputtering system, such as a radio frequency co-sputtering system. The dense layer 12 can have a thickness of about 16-155 nm.

The porous semiconductor layer 13 may be a semiconductor having a high specific surface area (for example, more than 50 m ² /g), a large band gap (for example, more than 3 eV), and a dye-adsorbing dye, including, for example, titanium oxide (TiO ₂ ) or zinc oxide (ZnO). ). The method for forming the porous semiconductor layer 13 may include the steps of: (a) mixing a semiconductor powder such as titanium dioxide (TiO ₂ ) powder or zinc oxide (ZnO) powder, and the powder may have a particle diameter of about 20-40 nm and a dispersion. Dispersant, such as 2,4-pentanedione or Ethylacetoacetone, a surfactant such as Triton X-100 (C ₁₄ H ₂₂ O(C ₂ H ₄ O) _n , And a solvent, such as Deionized water (DI water), to obtain a semiconductor coating colloid, a weight ratio of each of the above components is about 30:1:1:50; (b) for example, spin coating The coating colloid is uniformly applied to the dense layer 12 by a method such as spin-coating, bar coating or blade coating; (c) in the annealing furnace, The dense layer 12 having the coating colloid thereon is annealed at a constant temperature between 400 and 500 ° C to complete a porous semiconductor layer 13. The thickness of the porous semiconductor layer 13 may be about 5 -15 μm.

Dye 14 includes an organic ruthenium metal complex powder that absorbs light and excites electrons, such as N3 (Ruthenium-535), N719, or Black dye. The method for forming the dye 14 may include the steps of: (a) mixing a dye powder such as N3, N719, and a black dye, and a solvent such as alcohol to obtain a dye mixture; (b) agitating the dye with an ultrasonic oscillator. Mixture. Next, the transparent conductive substrate 11 having the dense layer 12 and the porous semiconductor layer 13 formed thereon in this order is immersed in the dye 14 at about 60-80 ° C for 0.1-2 hours. After the transparent conductive substrate 11 is taken out, a dense layer-modified semiconductor electrode 10 having a dense layer 12, a porous semiconductor layer 13, and a dye 14 sequentially formed on the transparent conductive substrate 11 is obtained.

Returning to Fig. 1, the electrolyte 31 of the dye-sensitized solar cell 30 can be a redox capable electrolyte, which may include a redox couple, an additive that increases the performance of the dye-sensitized solar cell ( Additive) and a solvent. The method for forming the electrolyte 31 may include the following steps: (a) mixing a redox couple, an additive, and a solvent to obtain a mixed solution, the weight ratio of each of the above components is about 1:5:75; (b) The ultrasonic oscillator agitates the mixed solution.

The redox couple of the electrolyte 31 may include I ₃ ^- /I ^- and its source may include iodine (Iodide, I ₂ ). The additive of the electrolyte 31 may include, for example, sodium iodide (NaI), lithium iodide (LiI), 4-tert-butylpyridine (TBP), and 1-propyl iodide. -1,3-dimethylimidazolium iodide (DMPII). The solvent of the electrolytic solution 31 may include, for example, acetonitrile (Acetonitrile), 3-methoxypropionitrile (MPN), and Propylene carbonate (PC).

In an embodiment, the electrolyte 31 may include sodium iodide, iodine, 4-tert-butylpyridine, and propylene carbonate. Alternatively, in another embodiment, the electrolyte 31 may include lithium iodide, iodine, 3-methoxypropionitrile, 4-tert-butylpyridine, and 1-propyl-2,3-dimethylimidazolium iodide. .

Referring to FIG. 3, an auxiliary electrode 20 including a transparent conductive substrate 21 and a catalytic layer 22 formed on the transparent conductive substrate 21 is shown in the embodiment of the present invention.

The transparent conductive substrate 21 of the auxiliary electrode 20 may include an indium tin oxide (ITO) glass substrate, a fluorine fluoride (FTO) glass substrate, or an indium tin oxide flexible substrate. The auxiliary electrode 20 may have a thickness of about 175-2200 μm.

The catalytic layer 22 is a material that catalyzes the redox reaction of the electrolyte, and includes platinum metal, carbon, and nickel metal. The catalytic layer 22 can be formed on the transparent conductive substrate 11 by a radio frequency sputtering system. The thickness of the catalytic layer 22 can be about 100-160 nm.

After forming the dense layer modified semiconductor electrode 10, the electrolyte 31, and the auxiliary electrode 20, the above components are packaged to complete the preparation of the dye-sensitized solar cell, wherein the semiconductor layer 10 and the auxiliary electrode 20 are modified by a thermoplastic film encapsulation dense layer. Then, an electrolyte is injected between the dense layer-modified semiconductor electrode 10 and the auxiliary electrode 20. The thermoplastic film may include, for example, an ultraviolet curable resin or other material that does not react with the electrolyte to prevent the thermoplastic film from reacting with the electrolyte.

Referring to FIG. 4, an electrochemical analysis device 40 for a dye-sensitized solar cell according to an embodiment of the present invention includes a potentiostat 41, a computer 42 and a dye-sensitized solar cell 30 as described above. The dye-sensitized solar cell 30 is connected to a potentiostat 41. The potentiostat 41 is connected to the computer 42. The method of connecting the potentiostat 41 includes the steps of first providing a dye-sensitized solar cell 30, then connecting the working electrode 10 to the working electrode terminal and the reference electrode terminal of the potentiostat 41, and then connecting the back electrode 20 to the constant potential. The auxiliary electrode end of the meter 41.

The invention has the advantages of using a dense layer to suppress the occurrence of a reverse reaction of the dye-sensitized solar cell, thereby achieving the effect of improving the conversion efficiency of the dye-sensitized solar cell.

Preferred embodiments of the invention are disclosed below.

[Example 1] 1. Preparation of dense layer modified semiconductor electrode

An indium tin oxide (ITO) glass substrate was taken, and sequentially washed with acetone, ethanol, and deionized water in an ultrasonic oscillator for 10 minutes. It was again dried with a nitrogen gun and placed in an oven at 100 ° C for 20 minutes to evaporate the water contained in the indium tin oxide glass substrate.

Next, a zinc oxide (ZnO) dense layer is formed on the indium tin oxide glass substrate by RF sputtering, wherein the ZnO target is placed at an RF output with a power of 50 W, a process pressure of about 30 mTorr, and argon (Ar). The flow rate is 40 sccm and the sputtering time is 4 minutes.

After forming a dense layer of zinc oxide on the ITO glass substrate, a porous semiconductor layer is formed on the zinc oxide dense layer. One method of forming the porous semiconductor layer includes the following steps: (a) mixing 3 grams of titanium dioxide powder, 0.1 mL of 0.2 M ethyl acetylacetone dispersant, 0.1 mL of 0.03 M Triton X-100 surfactant, and 5 mL of deionized water. Solvent to obtain a titania coating colloid; (b) uniformly coating the coating colloid on the dense layer; (c) annealing at 450 ° C in an annealing furnace to complete a porous semiconductor layer.

2. Preparation of dyes

A N3 dye (Ruthenium-535, N3) was dissolved in 99.8% absolute alcohol to form a dye solution having a concentration of 3 × 10 ^-4 M, and the dye solution was ultrasonically shaken for 15 minutes.

3. Preparation of electrolyte

Sodium monoiodide (NaI) was taken, and propylene carbonate (PC) was used as a solvent, and the concentration was 0.5 M after mixing.

Iodine (I ₂ ) was taken, and propylene carbonate (PC) was used as a solvent, and the concentration was 0.05 M after mixing.

A 4-tert-butylpyridine (TBP) was taken, and propylene carbonate (PC) was used as a solvent, and the concentration was 0.5 M after mixing.

After mixing the above three solutions, the electrolyte was prepared by ultrasonic vibration for 5 minutes.

4. Preparation of auxiliary electrode

An indium tin oxide glass substrate is taken, and platinum metal is sputtered thereon to form an auxiliary electrode.

5. Preparation and packaging of dye-sensitized solar energy

The dense layer-modified semiconductor electrode was placed in the above dye and placed at 75 ° C for 1 hour.

The above-mentioned dense layer-modified semiconductor electrode and auxiliary electrode are encapsulated by a thermoplastic film, wherein the thermoplastic film is made of DuPont ^TM Surlyn 1706, followed by injection of the electrolyte, that is, preparation and packaging of the dye-sensitized solar cell.

[Example 2] 1. Preparation of dense layer modified semiconductor electrode

An indium tin oxide (ITO) glass substrate was sequentially placed in an ultrasonic oscillator with acetone, ethanol, and deionized water, and each was washed for 10 minutes, dried with a nitrogen gun, and placed in an oven at 100 ° C for 20 minutes. The water contained in the ITO glass substrate is evaporated.

Next, a cesium-doped titanium dioxide (TiO ₂ ) dense layer is formed on the cleaned ITO glass substrate by RF co-sputtering, wherein the TiO ₂ target is placed in the RF output, the bismuth target is placed in the DC output, and the RF power is applied. Set to 100 W, DC power is 2 W, process pressure is approximately 30 mTorr, argon (Ar) flow is 40 sccm, and sputtering time is 2 minutes.

After forming a tantalum-doped titanium dioxide dense layer on the ITO glass substrate, a porous semiconductor layer is formed on the tantalum-doped titanium dioxide dense layer. The method for forming a porous semiconductor layer comprises the steps of: (a) mixing 3 grams of titanium dioxide powder, 0.1 mL of 0.2 M ethyl acetylacetone dispersant, 0.1 mL of 0.03 M Triton X-100 surfactant, and 5 mL of deionized water solvent. To obtain a titania coating colloid; (b) uniformly coating the coating colloid on the dense layer; (c) annealing at 450 ° C in an annealing furnace to complete a porous semiconductor layer.

2. Preparation of dyes

A N3 dye was dissolved in 99.8% absolute alcohol to form a dye solution having a concentration of 3 x 10 ^-4 M, and the dye solution was ultrasonically shaken for 15 minutes.

3. Preparation of electrolyte

Lithium iodide (LiI) was taken, and 3-methoxypropionitrile (MPN) was used as a solvent, and the concentration was 0.5 M after mixing.

1-propyl-2,3-dimethylimidazolium chloride (DMPII) was taken, and MPN was used as a solvent, and the concentration was 0.6 M after mixing.

Iodine (I ₂ ) was taken, and MPN was used as a solvent, and the concentration after mixing was 0.05 M.

A 4-tert-butylpyridine (TBP) was taken, and MPN was used as a solvent, and the concentration was 0.5 M after mixing.

After mixing the above four solutions, the electrolyte was prepared by ultrasonic vibration for 5 minutes.

4. Preparation of auxiliary electrode

An indium tin oxide glass substrate is taken, and platinum metal is sputtered thereon to form an auxiliary electrode.

5. Preparation and packaging of dye-sensitized solar components

The dense layer-modified semiconductor electrode was placed in the above dye and placed at 75 ° C for 1 hour.

The above-mentioned dense layer-modified semiconductor electrode and auxiliary electrode are encapsulated by a thermoplastic film, wherein the thermoplastic film is made of DuPont ^TM Surlyn 1706, followed by injection of the electrolyte, that is, preparation and packaging of the dye-sensitized solar cell.

[Example 3] Tight layer modified semiconductor electrode

A tin oxyfluoride (FTO) glass substrate was taken, and sequentially washed with acetone, ethanol, and deionized water in an ultrasonic oscillator for 10 minutes. It was again dried with a nitrogen gun and placed in an oven at 100 ° C for 20 minutes to evaporate the water contained in the FTO glass substrate.

Next, a titanium dioxide (TiO ₂ ) dense layer was formed on the FTO/glass substrate by RF sputtering, wherein the TiO ₂ target was placed at the RF output with an RF power of 100 W, a process pressure of about 30 mTorr, and argon (Ar). The flow rate is 40 sccm and the sputtering time is 80 minutes.

After the titanium dioxide dense layer is formed on the FTO glass substrate, a porous semiconductor layer is formed on the titanium dioxide dense layer. The formation of the porous semiconductor layer comprises the steps of: (a) mixing 3 grams of titanium dioxide powder, 0.1 mL of 0.2 M ethyl acetylacetone dispersant, 0.1 mL of 0.03 M Triton X-100 surfactant, and 5 mL of deionized water solvent. A titania coating colloid is obtained; (b) the coating colloid is uniformly applied to the dense layer; and (c) annealing is performed at 450 ° C in an annealing furnace to complete a porous semiconductor layer.

2. Preparation of dyes

A N3 dye was dissolved in 99.8% absolute alcohol and vortexed by ultrasonic for 15 minutes at a concentration of 3 x 10 ^-4 M.

3. Preparation of electrolyte

Lithium iodide (LiI) was taken, and 3-methoxypropionitrile (MPN) was used as a solvent, and the concentration was 0.5 M after mixing.

1-propyl-2,3-dimethylimidazolium chloride (DMPII) was taken, and MPN was used as a solvent, and the concentration was 0.6 M after mixing.

Iodine (I ₂ ) was taken, and MPN was used as a solvent, and the concentration after mixing was 0.05 M.

A 4-tert-butylpyridine (TBP) was taken, and MPN was used as a solvent, and the concentration was 0.5 M after mixing.

After mixing the above four solutions, the electrolyte was prepared by ultrasonic vibration for 5 minutes.

4. Preparation of auxiliary electrode

A tin oxyfluoride glass substrate is obtained, and platinum metal is sputtered thereon to form an auxiliary electrode.

5. Preparation and packaging of dye-sensitized solar energy

The dense layer-modified semiconductor electrode was placed in the above dye and placed at 75 ° C for 1 hour.

The above-mentioned dense layer-modified semiconductor electrode and auxiliary electrode are encapsulated by a thermoplastic film, wherein the thermoplastic film is made of DuPont ^TM Surlyn 1706, followed by injection of the electrolyte, that is, preparation and packaging of the dye-sensitized solar cell.

[Embodiment 4] 1. Electrochemical analysis device for dye-sensitized solar cell

A dye-sensitized solar cell is provided wherein the dense layer-modified semiconductor electrode is a working electrode. Next, the working electrode of the dye-sensitized solar cell is connected to the working electrode (W _E ) and the reference electrode end (R _E ) of the potentiostat, and the auxiliary electrode is connected to the auxiliary of the potentiostat. Counter electrode (C _E ). The data measured by the potentiostat is output by the computer.

2. Potentiostat parameter setting

The potentiostat uses a frequency of 10 Hz to 100 kHz, and the potential is the open circuit voltage (V _oc ) of the dye-sensitized solar cell. Using this parameter for electrochemical analysis, a Nyquist plot of the dye-sensitized solar cell can be obtained.

3. AC impedance map (Nyquist diagram)

To ensure that it can be used by DuPont ^TM Surlyn 1706 thermoplastic film encapsulation electrode to control the electrolyte content, measuring the AC impedance of three dye-sensitized solar cells (DSSC) with ZnO, TiO ₂ :Ru (cerium-doped titanium dioxide) and TiO ₂ dense layer, the amount The map is shown in Figure 5. In Fig. 5, R _s is the point at the left of the semicircle in Fig. 5 that intersects the Z _Re axis, and according to TV Nguyen, HC Lee, OB Yang, "The Effect of Pre-thermal Treatment of TiO ₂ Nano-particles on the Performances of Dye-sensitized Solar Cells, "Solar Energy Materials & Solar Cells, vol. 90, pp. 967-981,2006, R s is the resistance of the electrolyte in DSSC. In Fig. 5, the point where the right circle of the semicircle intersects with the Z _Re axis is R _s + R _ct , and according to N. Fuke, A. Fukui, A. Islam, R. Komiya, R. Yamanaka, H. Harima, L. Han, "Influence of TiO2/electrode Interface on Electron Transport Properties in Back Contact Dye-sensitized Solar Cells," Solar Energy Materials & Solar Cells, vol. 93, pp. 720-724, 2009, R _ct reflects TiO ₂ /electrode The interface between.

As can be seen from Fig. 5, the series resistances R _{s of the} three DSSCs are the same, which means that the content of the electrolyte is fixed at different DSSCs, so it can be proved that DuPont ^TM Surlyn is used for packaging. 1706 Controlling electrolyte content is a reliable method. A DSSC using the dense layer of TiO _2, which charge transfer resistance (Charge transfer resistance, R _ct) less than ZnO and TiO _2: Ru, this is due to the conduction band of TiO ₂ is lower than a dense layer with a conductive porous layer of TiO _2, so that the electronic It is smoother when delivered, and can achieve higher photoelectric conversion efficiency. The reason why the R _{ct of the} dense layer of ZnO is large is mainly due to the reaction between ZnO and TiO ₂ colloid, so that the defects between the ZnO/TiO ₂ interface are increased, and the electron transport is not easy to cause R _{ct to} rise. On the other hand, the TiO ₂ :Ru dense layer does not react with the TiO ₂ colloid, but since its conductive band is higher than the TiO ₂ porous layer, R _{ct is} higher than the TiO ₂ dense layer.

[Comparative Example 1]

The preparation method of Comparative Example 1 was similar to that of Example 1, except that Comparative Example 1 did not apply a zinc oxide dense layer on the ITO substrate when forming the working electrode, that is, the working electrode in Comparative Example 1 did not include zinc oxide. Tight layer.

[Comparative Example 2]

The preparation method of Comparative Example 2 is similar to that of Example 2, except that in Comparative Example 2, when the working electrode was prepared, the tantalum-doped titanium dioxide dense layer was not applied to the ITO substrate, that is, the working electrode in Comparative Example 2 was not included. The cerium is doped with a dense layer of titanium dioxide.

[Comparative Example 3]

Comparative Example 3 was prepared in a manner similar to that in Example 3, except that Comparative Example 3 did not apply a titanium dioxide dense layer to the FTO substrate when preparing the working electrode, that is, the working electrode in Comparative Example 3 did not include the titanium dioxide dense layer. .

The function data of the above battery is shown in Table 1:

In Table 1, J _sc , V _oc , FF and η are respectively short-circuit current, open-circuit voltage, fill factor and Photoelectric conversion efficiency. . As can be seen from Table 1, the current density and photoelectric conversion efficiency of Example 1, Example 2 and Example 3 are respectively greater than those of Comparative Example 1, Comparative Example 2 and Comparative Example 3, wherein The zinc oxide dense layer can increase the conversion efficiency from 1.2% (Comparative Example 1) to 1.48% (Example 1). The use of yttrium-doped titanium dioxide dense layer can increase the conversion efficiency from 1.98% (Comparative Example 2) to 2.44% ( Example 2), while using a titanium dioxide dense layer, the conversion efficiency was increased from 4.01% (Comparative Example 3) to 5.11% (Example 3). Since the first, second, and third embodiments of the present invention differ from the comparative examples 1, 2, and 3, respectively, only in the presence of the dense layer, it is understood that the higher current densities of the embodiments 1, 2, and 3 of the present invention are The photoelectric conversion efficiency should be caused by a dense layer. Therefore, the dense layer produced by the preparation method of the present invention can effectively improve the efficiency of the dye-sensitized solar cell.

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

10‧‧‧Dense layer modified semiconductor electrode

11‧‧‧Transparent conductive substrate

12‧‧‧Dense layer

13‧‧‧Porous semiconductor layer

14‧‧‧Dyes

20‧‧‧Auxiliary electrode

21‧‧‧Transparent conductive substrate

22‧‧‧ Catalytic layer

30‧‧‧Dye-sensitized solar cells

31‧‧‧ electrolyte

40‧‧‧Electrochemical analysis device

41‧‧‧potentiostat

42‧‧‧ computer

Fig. 1 is a view showing a dye-sensitized solar cell in an embodiment of the present invention.

Figure 2 is a diagram showing a uniform dense layer modified semiconductor electrode in an embodiment of the present invention.

Figure 3 is a view showing an auxiliary electrode in an embodiment of the present invention.

Fig. 4 is a view showing an electrochemical analysis apparatus for a dye-sensitized solar cell in an embodiment of the present invention.

Figure 5 shows the AC impedance spectra of three dye-sensitized solar cells (DSSC) with ZnO, TiO ₂ :Ru (germanium-doped titanium dioxide) and TiO ₂ dense layers, respectively.

10. . . Dense layer modified semiconductor electrode

11. . . Transparent conductive substrate

12. . . Dense layer

13. . . Porous semiconductor layer

14. . . dye

Claims (20)

A dye-sensitized solar cell comprising: a uniform dense layer modified semiconductor electrode comprising: a transparent conductive substrate; a uniform dense layer formed on the transparent conductive substrate, wherein the dense layer comprises a base metal doped titanium dioxide; a porosity a semiconductor layer formed on the dense layer; and a dye formed on the porous semiconductor layer; an electrolyte formed on the dense layer modified semiconductor electrode; and an auxiliary electrode formed on the electrolyte. The dye-sensitized solar cell of claim 1, wherein the transparent conductive substrate comprises an indium tin oxide glass substrate, an oxyfluoride glass substrate or an indium tin oxide flexible substrate. The dye-sensitized solar cell of claim 1, wherein the porous semiconductor layer comprises titanium dioxide or zinc oxide. The dye-sensitized solar cell according to claim 1, wherein the dye is an organic ruthenium metal complex powder capable of absorbing electrons and absorbing electrons. The dye-sensitized solar cell of claim 4, wherein the dye comprises N3 (Ruthenium-535), N719 or Black dye. The dye-sensitized solar cell of claim 1, wherein the electrolyte comprises a redox couple, an additive, and a solvent. The dye-sensitized solar cell of claim 6, wherein the redox couple is I ^- /I ₃ ^- , the solvent is acetonitrile, 3-methoxypropionitrile, propylene carbonate or any combination thereof . The dye-sensitized solar cell of claim 6, wherein the additive comprises sodium iodide, lithium iodide, 4-tert-butylpyridine iodide, and 1-propyl-2,3-dimethylimidazolium iodide. Or any combination of the above. The dye-sensitized solar cell of claim 1, wherein the auxiliary electrode comprises a catalytic layer formed on another transparent conductive substrate, and the catalytic layer has a material capable of catalyzing a redox reaction of the electrolyte. The dye-sensitized solar cell of claim 1, wherein the material of the catalytic layer comprises platinum metal, carbon or nickel metal. A method for fabricating a dye-sensitized solar cell, comprising the steps of: providing a transparent conductive substrate; forming a uniform dense layer on the transparent conductive substrate, wherein the dense layer comprises a base metal doped titanium dioxide; forming a porous semiconductor layer thereon Forming a dye on the porous semiconductor layer, wherein the transparent conductive substrate, the dense layer, the porous semiconductor layer and the dye constitute a uniform dense layer modified semiconductor electrode; forming an electrolyte in the dense layer Modifying the semiconductor electrode; and forming an auxiliary electrode on the electrolyte. The method for producing a dye-sensitized solar cell according to claim 11, wherein the forming of the electrolyte comprises: (a) mixing a redox couple, an additive, and a solvent to A mixed solution is obtained; and (b) the mixed solution is stirred with an ultrasonic oscillator to form the electrolyte. The method for fabricating a dye-sensitized solar cell according to claim 11, wherein the dense layer is formed on the transparent conductive substrate by radio frequency sputtering. The method for producing a dye-sensitized solar cell according to claim 11, wherein the porous semiconductor layer is formed on the dense layer by a spin coating method, a bar coating method, or a knife coating method. The method for producing a dye-sensitized solar cell according to claim 11, wherein the forming of the porous semiconductor layer comprises the steps of: (a) mixing a semiconductor powder, a dispersant, a surfactant, and a solvent to obtain a semiconductor. Coating the colloid; (b) uniformly coating the above-mentioned coating colloid on the dense layer; and (c) annealing in a annealing furnace at a constant temperature. The method for producing a dye-sensitized solar cell according to claim 11, wherein the dye is adsorbed on the porous semiconductor layer by a dipping method. The method for manufacturing a dye-sensitized solar cell according to claim 11, wherein the forming of the auxiliary electrode comprises: providing a transparent conductive substrate; and forming a catalytic layer on the transparent conductive substrate by radio frequency sputtering. An electrochemical analysis device for a dye-sensitized solar cell, comprising: a potentiostat; A dye-sensitized solar cell as described in claim 1 is connected to the potentiostat; and a computer connected to the potentiostat. The electrochemical analysis device for a dye-sensitized solar cell according to claim 18, wherein the dense layer modified semiconductor electrode of the dye-sensitized solar cell is connected to one of the working electrode terminals of the potentiostat and a reference electrode Extremely, and the auxiliary electrode of the dye-sensitized solar cell is connected to one of the auxiliary electrode terminals of the potentiostat. The electrochemical analysis device for a dye-sensitized solar cell according to claim 18, wherein the potentiostat has an operating frequency of 10 Hz to 100 kHz and an operating potential of an open circuit voltage of the dye-sensitized solar cell.