CN101022136A - Alkaline-earth metal salt decorative nano crystal semiconductor optical anode, producing method and application thereof - Google Patents

Alkaline-earth metal salt decorative nano crystal semiconductor optical anode, producing method and application thereof Download PDF

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CN101022136A
CN101022136A CNA2007100569347A CN200710056934A CN101022136A CN 101022136 A CN101022136 A CN 101022136A CN A2007100569347 A CNA2007100569347 A CN A2007100569347A CN 200710056934 A CN200710056934 A CN 200710056934A CN 101022136 A CN101022136 A CN 101022136A
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alkaline
earth metal
metal salt
crystal semiconductor
nano
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陈军
张莉
许炜
蔡锋石
陶占良
梁静
高峰
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Nankai University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

This invention relates to a nm crystal semiconductor light anode decorated by alkaline earth salt and a preparation method and its use in dye sensitized solar cells, which utilizes a dipping-sentering technology to form an alkaline earth salt decoration layer on the surface of nm crystals then to get a nm crystal semiconductor film electrode decorated by alkaline earth salt with a silk screen printing method, which can not only increase the dye adsorption ability and light absorption ability of light anode but also suppress the composition of photogenerated electrons and cavities effectively so as to increase the photoelectric conversion efficiency of dye sensitized soalr cells.

Description

Alkaline-earth metal salt decorative nano crystal semiconductor optical anode and preparation method and application thereof
[technical field]: the invention belongs to technical field of solar batteries, the preparation method of the semiconductor nano light anode material that particularly a kind of alkaline-earth metal salt is modified and the application in DSSC thereof.
[background technology]: since Switzerland Gr  professor tzel in 1991 has reported the research work of DSSC (O ' Regan, B.; Gr  tzel, M.Nature 1991,353,737.), DSSC has caused people's extensive concern as a kind of novel solar battery of efficient, cheap, environmentally safe, is considered to one of developing direction of the tool prospect of photovoltaic generation.
In order further to improve the photoelectric conversion efficiency of DSSC, people have all carried out continuous exploration to the aspects such as light anode, photocathode, electrolyte, production technology and battery structure of battery.Wherein, semiconductor nano film light anode is as the core of DSSC, and its performance directly has influence on the photoelectric conversion efficiency of solar cell.Nano-crystal film has big specific area and high porosity, can absorb a large amount of sensitising agents, thereby effectively utilizes sunlight.Yet, since the loose structure of semiconductor nano make contact between its electronics and hole very tight, and nanocrystalline size is less in the nano crystal semiconductor electrode, can not form space charge layer at electrolyte and interface, thereby, in DSSC, there are two recombination processes in the light induced electron that is injected on the semiconductor conduction band from the dye molecule of excitation state: the compound and light induced electron of redox couple and oxidized dye molecule is compound light induced electron and the electrolyte.These two processes can reduce the light induced electron number of transferring to external circuit, thereby have influence on the photoelectric conversion efficiency of DSSC.
In order to reduce the photoelectric conversion efficiency that charge recombination process that the light anode exists improves solar cell, reported method mainly contains surface chemical modification, ion doping, compound other sull at present, and method (Palomares E. such as pattern design; Clifford, J.N.; Haque, S.A.; .Lutz, T.; Durrant, J.R.J.Am.Chem.Soc.2003,125,475-482).But about reporting also seldom (Diamant, Y. at home and abroad with the research of alkaline-earth metal salt decorative nano crystal semiconductor film light anode; Chen, S.G.; Melamed, O.; Zaban A.J.Phys.Chem.B2003,107,1977-1981).
[summary of the invention]: the objective of the invention is to solve the prior art above shortcomings, a kind of nano crystal semiconductor optical anode and preparation method of alkaline-earth metal salt decorative are provided, so that the recombination probability in electronics and hole in the minimizing battery, the photoelectric properties of raising solar cell.
Another object of the present invention provides the application of semiconductor nano film light anode in constituting DSSC that a kind of above-mentioned alkaline-earth metal salt is modified.
The nano crystal semiconductor optical anode that alkaline-earth metal salt provided by the invention is modified, it comprises base material FTO conductive glass layer, and on fixed successively alkaline-earth metal salt nanometer crystal semiconductor film layer and the photosensitizer layer modified.
Described nano crystal semiconductor is TiO 2
Described photosensitizer is to close ruthenium (being called for short the N3 dyestuff) along one or two (thiocyanate radicals) or two (4,4 one dicarboxylic acids 1,2 one _ bipyridine).
Described alkaline-earth metal salt comprises alkaline-earth metal composite oxides or carbonate.The alkaline-earth metal composite oxides comprise MgTiO 3, SrTiO 3Or BaTiO 3In any one or two kinds; Alkaline earth metal carbonate is BaCO 3
The preparation method of the nano crystal semiconductor optical anode that a kind of alkaline-earth metal salt is modified, by dipping-sintering process, realize through following steps:
The first, the method that adopts silk screen printing is coated in the slurry that nano crystal semiconductor particle or the nano crystal semiconductor particle modified through the alkaline-earth metal salt make on the FTO electro-conductive glass equably, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature, use 50mM TiCl 4Solution-treated 30min, with distilled water, alcohol flushing surface, nitrogen dries up, and through 450 ℃ of high temperature sintering 30min, obtains the semiconductor nano perforated membrane again, or the nanometer crystal semiconductor film of modifying through the alkaline-earth metal salt;
The second, the semiconductor nano perforated membrane that obtained for the last step, at first under 20 ℃, the semiconductor nano perforated membrane is dipped in the soluble alkaline earth salting liquid of 0.5-100mM, wash 3 times and drying with distilled water, absolute ethyl alcohol after leaving standstill 15min, dried semiconductor nano perforated membrane is obtained the nanometer crystal semiconductor film that the alkaline-earth metal salt is modified at 550 ℃ of following sintering 0.5h;
Three, the first step or second is gone on foot the nanometer crystal semiconductor film of the alkaline-earth metal salt modification that obtains 3 * 10 -4Soak 12h in the ethanolic solution of MN3 dyestuff, take out the back and clean with absolute ethyl alcohol, nitrogen dries up, and makes the nano crystal semiconductor optical anode of modifying through the alkaline-earth metal salt.
The nano crystal semiconductor particle of modifying through the alkaline-earth metal salt among the above-mentioned preparation method makes through following steps: under the room temperature, the nano crystal semiconductor particle is dissolved in the soluble alkaline earth saline solution, centrifugation behind the magnetic agitation 1h, to be deposited in the Muffle furnace in 550 ℃ of following sintering 30min, obtain the nano crystal semiconductor particle of modifying through the alkaline-earth metal salt.
Above-mentioned soluble alkaline earth salt is the nitrate or the acetate of alkaline-earth metal.
The mass percent of described slurry consists of 16% semiconductor nano powder, 4% ethyl cellulose, 80% terpinol.
The DSSC that the nano crystal semiconductor optical anode that the above-mentioned alkaline-earth metal salt of a kind of usefulness is modified is made, it comprises light anode, photocathode, thermoplastic barrier film and electrolyte; Described smooth anode is an alkaline-earth metal salt decorative nano crystal semiconductor membrane electrode, described photocathode is a platinum electrode, the prescription of described electrolyte is: in acetonitrile solvent, add 1 of 0.6M, 2-dimethyl-3-propyl imidazole iodine, the lithium iodide of 0.1M and the iodine of 0.05M are made supporting electrolyte.
Advantage of the present invention and beneficial effect:
The invention has the advantages that with forming a passivation layer on the semiconductor grain surface behind the alkaline-earth metal salt modifying semiconductor material, thereby the recombination reaction that effectively suppresses semiconductor surface electronics and hole, improve the efficiency of transmission of electronics, can strengthen simultaneously the light absorpting ability of semi-conducting material and, improve the performances such as photoelectric conversion efficiency of DSSC the adsorption capacity of photosensitizer.
The method that is used to prepare the alkaline-earth metal salt decorative semi-conducting material provided by the present invention, preparation technology is simple, is easy to control, constant product quality, and good process repeatability.Not only can be applied to modify in the DSSC material, but also may be used on fields such as piezoceramic material, catalysis material and gas sensitive material.
[description of drawings]:
Fig. 1 is the BaTiO according to embodiment 2 preparations 3The TiO that modifies 2Nanocrystalline TEM (transmission electron microscope) analysis.
Fig. 2 is the BaTiO according to embodiment 2 preparations 3The TiO that modifies 2Nanocrystalline X-ray diffraction analysis.
Fig. 3 is the BaTiO according to embodiment 3 preparations 3The TiO that modifies 2Nanocrystalline X-ray photoelectron spectroscopic analysis.
Fig. 4 is the absorption spectrum according to the light anode of embodiment 1, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 preparations.
Fig. 5 is the DSSC structural representation according to embodiment 6 assemblings.
Fig. 6 is assembled into photoelectric current (I)-photovoltage (V) curve chart that records behind the battery respectively for the different types of smooth anode that makes according to embodiment 1, embodiment 3, embodiment 4, embodiment 5 and embodiment 6.
The variety classes light anode that Fig. 7 makes for embodiment 1 and embodiment 3 is assembled into the ac impedance spectroscopy of DSSC.
Fig. 8 is different-thickness SrTiO 3Modify photoelectric current (I)-photovoltage (V) curve chart that battery light anode obtains.
[embodiment]:
Embodiment 1, TiO 2The preparation of light anode:
Under the room temperature, the method by silk screen printing is TiO 2Slurry (prescription: 16wt%TiO 2Nano particle (German Degussa company), 4wt% ethyl cellulose, 80wt% terpinol) be coated in equably on the FTO electro-conductive glass, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature.With above-mentioned TiO 2Film 50mM TiCl 4Solution-treated 30min uses distilled water, alcohol flushing surface successively, and nitrogen dries up, again through 450 ℃ of high temperature sintering 30min.Obtain the porous TiO that thickness is about 12 μ m 2Film.Subsequently with the TiO that obtains 2Film is 3 * 10 in concentration -4Soak 12h in the ethanol solution of the N3 dyestuff of M, take out the back and clean with ethanol, nitrogen dries up.
Embodiment 2, BaTiO 3The TiO that coats 2Nanocrystalline preparation:
Under the room temperature, with TiO 2Nano particle (German Degussa company) 1g is in the 0.005mol/L of 20mL Ba (NO 3) 2Centrifugation behind the magnetic agitation 1h in the solution will be deposited in the Muffle furnace in 550 ℃ of following sintering 30min, obtain BaTiO 3The TiO that coats 2Nanocrystalline.Transmission electron microscope (TEM) the analysis showed that: BaTiO 3Be coated on TiO uniformly 2Nanocrystal surface, the thickness of coating layer is about the 2-3nm (see figure 1).(Fig. 2) can prove that this layer film is the BaTiO of cubic phase by X-ray diffraction spectrum (XRD) 3
The method that adopts silk screen printing is BaTiO 3The TiO that modifies 2Nanocrystalline being coated in equably on the FTO electro-conductive glass through 450 ℃ of high temperature sintering 30min, naturally cools to room temperature, uses 50mM TiCl 4Solution-treated 30min, with distilled water, alcohol flushing surface, nitrogen dries up, again through 450 ℃ of high temperature sintering 30min.Be 3 * 10 with the film that obtains in concentration subsequently -4Soak 12h in the ethanolic solution of the N3 dyestuff of M, take out the back and clean with absolute ethyl alcohol, nitrogen dries up.
Embodiment 3, BaTiO 3The TiO that modifies 2The preparation of light anode:
Under the room temperature, the method by silk screen printing is TiO 2Slurry (prescription: 16wt%TiO 2Nano particle (German Degussa company), 4wt% ethyl cellulose, 80wt% terpinol) be coated in equably on the FTO electro-conductive glass, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature.With above-mentioned TiO 2Film is dipped in the Ba (NO of 0.005M 3) 230min in the solution, with distilled water, alcohol flushing surface, nitrogen dries up, and 550 ℃ of following sintering 30min in Muffle furnace obtain BaTiO then 3The TiO that modifies 2Film.According to x-ray photoelectron power spectrum (XPS) (Fig. 3) as can be known, BaTiO 3Film is coated on TiO 2Particle surface.Can get film surface Ti/Ba mol ratio according to XPS result's calculating is 80.5: 19.5.Be 3 * 10 with the laminated film that obtains in concentration subsequently -4Soak 12h in the ethanolic solution of the N3 dyestuff of M, take out the back and clean with absolute ethyl alcohol, nitrogen dries up.
Embodiment 4, SrTiO 3Modify TiO 2The preparation of light anode:
Under the room temperature, the method by silk screen printing is TiO 2Slurry (prescription: 16wt%TiO 2Nano particle (German Degussa company), 4wt% ethyl cellulose, 80wt% terpinol) be coated in equably on the FTO electro-conductive glass, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature.With above-mentioned TiO 2Film is dipped in the Sr (NO of 0.01M 3) 21h in the aqueous solution, 550 ℃ of following sintering 30min in Muffle furnace obtain SrTiO then 3The TiO that modifies 2Film.Subsequently with this SrTiO 3The TiO that modifies 2Film is 3 * 10 in concentration -4Soak 12h in the ethanolic solution of the N3 dyestuff of M, take out the back and clean with absolute ethyl alcohol, nitrogen dries up.
Embodiment 5, MgTiO 3Modify TiO 2The preparation of light anode:
Under the room temperature, the method by silk screen printing is TiO 2Slurry (prescription: 16wt%TiO 2Nano particle (German Degussa company), 4wt% ethyl cellulose, 80wt% terpinol) be coated in equably on the FTO electro-conductive glass, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature.With above-mentioned TiO 2Film is dipped in the Mg (NO of 0.03M 3) 21h in the aqueous solution, 550 ℃ of following sintering 30min in Muffle furnace obtain MgTiO then 3The TiO that modifies 2Film.Be 3 * 10 with this modified membrane in concentration subsequently -4Soak 12h in the ethanolic solution of the N3 dyestuff of M, take out the back and clean with absolute ethyl alcohol, nitrogen dries up.
Embodiment 6, BaCO 3Modify TiO 2The preparation of light anode:
Under the room temperature, the method by silk screen printing is TiO 2Slurry (prescription: 16wt%TiO 2Nano particle (German Degussa company), 4wt% ethyl cellulose, 80wt% terpinol) be coated in equably on the FTO electro-conductive glass, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature.With above-mentioned TiO 2Film is dipped in the Ba (CH of 0.005M 3COO) 21h in the aqueous solution, 550 ℃ of following sintering 30min in Muffle furnace obtain BaCO then 3The TiO that modifies 2Film.Subsequently with this BaCO 3The TiO that modifies 2Film is 3 * 10 in concentration -4Soak 12h in the ethanolic solution of the N3 dyestuff of M, take out the back and clean with absolute ethyl alcohol, nitrogen dries up.
Used electrolyte consists of: 1 of 0.6M, 2-dimethyl-3-propyl imidazole iodine, the lithium iodide of 0.1M, the iodine of 0.05M, the acetonitrile solution of the tert .-butylpyridine of 0.5M.Being formulated in the dry glove box of electrolyte finished.
The different types of dye sensitization TiO of Fig. 4 for making according to embodiment 1, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 2The absorption spectrum of film.Absorption spectrum adopts the Japanese Jasco V-550 UV-vis spectrometer that has integrating sphere to record.As can be seen from the figure, the TiO after modified 2Film has stronger absorption intensity, shows the TiO behind alkaline-earth metal salt decorative 2Film can adsorb more dye molecule, thereby energy more efficient use sunlight increases photoelectric current.
The preparation method of embodiment 7, used platinum electrode is:
Under the room temperature, adopt spin coating technique, with the H of 50mM 2PtCl 6Aqueous isopropanol drips under the rotating speed of 1000r/min and is spun on the electro-conductive glass, in 390 ℃ of sintering 30min, obtains platinum electrode then.
Battery assembling: add diaphragm seal (for example " surlyn " thermoplastic polymer film) between light anode and the platinum electrode (photocathode), under dull and stereotyped forcing press, be heated to 100 ℃, heated sealant 20min, two electrodes are bonded together fully, utilize vacuum or manual method to inject electrolyte solution at the photocathode dorsal pore then, and sealing.The structure of this battery as shown in Figure 5.The number in the figure meaning is: 1, incident sunlight; 2, transparent conducting glass; 3, photosensitizer; 4, alkaline-earth metal salt decorative layer; 5, semiconductor nano; 6, barrier film; 7, electrolyte; 8, platinum; 9, electro-conductive glass.The effective illuminating area of this battery is: 0.16cm 2, at AM1.5-100mW/cm 2Light intensity under test, adopt U.S. Keithley2400 digital source table to gather photoelectric current, photovoltage, obtain short circuit current (Jsc), open circuit voltage (Voc), fill factor, curve factor related datas such as (FF).
Embodiment 8:
Fig. 6 is assembled into photoelectric current (I)-photovoltage (V) curve chart that records behind the battery respectively for the different types of smooth anode that makes according to embodiment 1, embodiment 3, embodiment 4, embodiment 5 and embodiment 6.The short circuit current that provides in the associative list 1 (Jsc), open circuit voltage (Voc), fill factor, curve factor (FF) and photoelectric conversion efficiency data such as (η) are as can be seen: at AM1.5-100mW/cm 2Under the light intensity, adopt the TiO of alkaline-earth metal salt decorative 2The light anode is applied to open circuit voltage, short circuit current and the fill factor, curve factor that DSSC can obviously improve battery.Thereby the TiO of employing alkaline-earth metal salt decorative 2The light anode can obtain higher photoelectric conversion efficiency.Wherein, the battery efficiency after barium salt is modified has improved 46%.
The do not share the same light photoelectric properties of the DSSC that anode forms of table 1
Voc(mV) Jsc(mA/cm 2) FF η(％)
TiO 2 712 12.89 0.61 5.62
TiO 2/MgTiO 3 734 13.67 0.63 6.37
TiO 2/SrTiO 3 769 15.91 0.61 7.46
TiO 2/BaTiO 3 803 16.06 0.64 8.22
TiO 2/BaCO 3 774 17.05 0.62 8.18
Embodiment 9:
Fig. 7 is the TiO that embodiment 1 and embodiment 3 make 2Light anode and BaTiO 3The TiO that modifies 2The light anode is assembled into the ac impedance spectroscopy of DSSC respectively.Measure and adopt U.S. PARSTAT 2273 impedance test systems to carry out, probe temperature is 25 ℃.The semicircle in AC impedance spectrogram medium and low frequency district is corresponding to the charge migration resistance (R at light anode interface Rec), and the semicircle of high frequency region is by the electric charge diffusion control of platinum electrode.As can be seen from the figure: BaTiO 3The charge migration resistance of the photoanode surface after the modification obviously increases, thereby the migration velocity of electronics reduces, and electronics has time enough to move to electrode, thereby has reduced the recombination probability in electronics-hole.Therefore, the photoelectric conversion efficiency of modification back solar cell obtains and can significantly improve.Battery table behind other several alkaline-earth metal salt decoratives reveals similar trend.
Embodiment 10:
Fig. 8 is different-thickness SrTiO 3Modify the I-V curve chart that battery light anode obtains.SrTiO 3Thickness by changing Sr (NO 3) 2The concentration of solution is controlled.Provide data as can be seen in the associative list 2: used alkali salt precursor solution concentration has a significant impact the efficient of modifying the back battery, has only the suitable concentration of selection just can obtain best photoelectric conversion efficiency.
Table 2 variable concentrations SrTiO 3Modify TiO 2The photoelectric properties of the DSSC that the light anode is formed
C(mol/L) Voc(mV) Jsc(mA/cm 2) FF η(％)
0 712 12.89 0.61 5.62
0.001 727 13.66 0.61 6.10
0.005 749 14.55 0.62 6.74
0.01 769 15.91 0.61 7.46
0.05 784 11.94 0.64 5.07
0.1 830 5.79 0.58 2.77
Carry out Optical Electro-Chemistry character and performance test by the DSSC that the light anode of several alkaline-earth metal salt decoratives is formed, as can be seen: the solar cell of alkaline-earth metal salt decorative of the present invention has higher photoelectric conversion efficiency, compare with the battery that does not have to modify, maximal efficiency has improved 46%, can obtain the photoelectric conversion efficiency more than 8%.This modification that comes from alkali salt has increased the adsorption capacity of sensitising agent, more efficient use sunlight on the one hand.On the other hand, alkali salt has reduced the semiconductor nano blemish, has formed an energy barrier that light induced electron is passed through but can not return, thereby has suppressed the electronics-hole-recombination probability of photoanode surface.Method raw material provided by the invention is cheap and easy to get, technology simple, be easy to control, and constant product quality, and good process repeatability can be applicable to association areas such as solar cell, photocatalysis, piezoelectric ceramic and gas sensitive.

Claims (9)

1, the nano crystal semiconductor optical anode modified of a kind of alkaline-earth metal salt, it is characterized in that: it comprises base material transparent conducting glass layer, with and on the TiO that modifies of fixed successively alkaline-earth metal salt 2Nanometer crystal semiconductor film layer and photosensitizer layer.
2, the nano crystal semiconductor optical anode of alkaline-earth metal salt modification as claimed in claim 1 is characterized in that: described photosensitizer is for closing ruthenium dye along one or two (thiocyanate radicals) or two (4,4 one dicarboxylic acids 1,2 one _ bipyridine).
3, the nano crystal semiconductor optical anode of alkaline-earth metal salt modification as claimed in claim 1, it is characterized in that: described alkaline-earth metal salt comprises alkaline earth oxide or carbonate.
4, the nano crystal semiconductor optical anode of alkaline-earth metal salt modification as claimed in claim 3, it is characterized in that: alkaline earth oxide comprises MgTiO 3, SrTiO 3Or BaTiO 3In any one or two kinds; Alkaline earth metal carbonate is BaCO 3
5, the preparation method of the nano crystal semiconductor optical anode of the described alkaline-earth metal salt modification of a kind of claim 1 is characterized in that: by flooding a sintering process, realize through following steps:
The first, the method that adopts silk screen printing is coated in the slurry that nano crystal semiconductor particle or the nano crystal semiconductor particle modified through the alkaline-earth metal salt make on the transparent conducting glass equably, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature, use 50mM TiCl 4Solution-treated 30min, with distilled water, alcohol flushing surface, nitrogen dries up, and through 450 ℃ of high temperature sintering 30min, obtains the semiconductor nano perforated membrane again, or the nanometer crystal semiconductor film of modifying through the alkaline-earth metal salt;
The second, the semiconductor nano perforated membrane that obtained for the last step, at first under 20 ℃, the semiconductor nano perforated membrane is dipped in the soluble alkaline earth salting liquid of 0.5-100mM, wash 3 times and drying with distilled water, absolute ethyl alcohol after leaving standstill 15min, dried semiconductor nano perforated membrane at 550 ℃ of following sintering 0.5h, is obtained the nanometer crystal semiconductor film that the alkaline-earth metal salt is modified;
Three, the first step or second is gone on foot the nanometer crystal semiconductor film of the alkaline-earth metal salt modification that obtains 3 * 10 -4Soak 12h in the ethanolic solution of the N3 dyestuff of M, take out the back and clean with absolute ethyl alcohol, nitrogen dries up, and makes the nano crystal semiconductor optical anode of modifying through the alkaline-earth metal salt.
6, preparation method as claimed in claim 5 is characterized in that the nano crystal semiconductor particle of modifying through the alkaline-earth metal salt makes through following steps:
Under the room temperature, the nano crystal semiconductor particle is dissolved in the soluble alkaline earth salting liquid, centrifugation behind the magnetic agitation 1h will be deposited in the Muffle furnace in 550 ℃ of following sintering 30min, obtain the nano crystal semiconductor particle of modifying through the alkaline-earth metal salt.
7, as claim 5 or 6 described preparation methods, it is characterized in that: nitrate or acetate that described soluble alkaline earth salt is an alkaline-earth metal.
8, preparation method as claimed in claim 5 is characterized in that: the mass percent of described slurry consists of 16% semiconductor nano powder, 4% ethyl cellulose, 80% terpinol.
9, a kind of DSSC of making of the nano crystal semiconductor optical anode of the described alkaline-earth metal salt modification of claim 1, it comprises light anode, photocathode, thermoplastic barrier film and electrolyte, it is characterized in that:
Described smooth anode is the nanometer crystal semiconductor film electrode that the alkaline-earth metal salt is modified,
Described photocathode is a platinum electrode,
The prescription of described electrolyte is: in acetonitrile solvent, add 1 of 0.6M, and 2-dimethyl-3-propyl imidazole iodine, the lithium iodide of 0.1M and the iodine of 0.05M are made supporting electrolyte.
CNA2007100569347A 2007-03-16 2007-03-16 Alkaline-earth metal salt decorative nano crystal semiconductor optical anode, producing method and application thereof Pending CN101022136A (en)

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CN102290529A (en) * 2010-06-18 2011-12-21 海洋王照明科技股份有限公司 Single-layer organic solar cell and preparation method thereof
CN101887804A (en) * 2010-06-29 2010-11-17 彩虹集团公司 Preparation method of large-area dye-sensitized solar battery photo-anode
CN102280264A (en) * 2011-05-20 2011-12-14 常州有则科技有限公司 Titanium/strontium covered nanocrystalline titanium dioxide film for dye-sensitized solar cell and preparation method thereof
CN102280264B (en) * 2011-05-20 2012-12-19 常州有则科技有限公司 Titanium/strontium covered nanocrystalline titanium dioxide film for dye-sensitized solar cell and preparation method thereof
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