CN101740229A - Preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery - Google Patents
Preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 206010070834 Sensitisation Diseases 0.000 title claims abstract description 14
- 230000008313 sensitization Effects 0.000 title claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000033001 locomotion Effects 0.000 claims abstract description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 140
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000005118 spray pyrolysis Methods 0.000 claims description 11
- 238000003764 ultrasonic spray pyrolysis Methods 0.000 claims description 7
- -1 titanium alkoxide Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 abstract 2
- 150000004703 alkoxides Chemical class 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 121
- 229910010413 TiO 2 Inorganic materials 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 238000005457 optimization Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
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- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of a surface compact titanium dioxide film of a transparency conductive electrode of a dye sensitization solar battery. The preparation method comprises the following steps of: (1) preparing titanium dioxide sol: uniformly mixing the metal alkoxide of titanium, used as a titanium source, diacetone used as a stabilizing agent, ethanol or isopropanol used as a solvent, wherein the concentration of the titanium source is 0.1-1mol/l, and the mole ratio of the diacetone to the titanium source is between 2 and 20; (2) filming: filming by adopting a spraying pyrogenation method, controlling the diameter of fog drops to be between 10mum and 100mum, preparing a large-area film by adopting a mode that a nozzle carries out two-dimensional motion scanning along the track of a tooth wave, increasing the thickness of the film by the reciprocating scanning of the nozzle along the direction of an X axis, and finally obtaining the large-area film by enabling the nozzle to move forward along the direction of a Y axis slowly, wherein the temperature of a substrate is between 150 DEG C and 500 DEG C; and (3) heat treatment. The invention can conveniently obtain a large-area compact TiO2 film with favorable uniformity and enhance the efficiency of the dye sensitization solar battery by 7-10%.
Description
Technical field
The invention belongs to technical field of solar utilization technique, relate in particular to dye-sensitized solar cell anode thin film study field.
Technical background
Nano-TiO
2Dye-sensitized solar cells (abbreviating DSSCs as) is based on the novel photoelectric chemical cell of nanostructure semiconductor and organic dyestuff, has with low cost and the technology characteristic of simple, has been subjected to various countries researcher's extensive concern since its invention.The work electrode of dye-sensitized solar cells is usually by transparent conducting glass, fine and close TiO
2Film, nanocrystalline porous TiO
2Film constitutes, wherein fine and close TiO
2Film mainly plays the effect of inhibition transparency conductive electrode/electrolyte interface electron recombination, and the method for main at present employing magnetron sputtering, sol-gel prepares fine and close TiO
2Film.The film of magnetron sputtering method preparation has the even film layer densification, controls advantages such as thickness, film adhesion are strong easily, but has weak points such as preparation cost is high, equipment complexity; Although sol-gel process has the cheap advantage of preparation cost, need the repeated multiple times film forming, the program complexity be not easy to large tracts of land, serialization production, and uniformity of film is undesirable.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, a kind of preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery is provided.
The preparation method of the said surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery of the present invention comprises the steps:
(a) preparing titanium dioxide colloidal sol: with the titanium alkoxide is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol or isopropyl alcohol, and the three is mixed; The titanium alkoxide can be in butyl titanate or the isopropyl titanate a kind of, the concentration in titanium source is 0.1-1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is between 2-20;
(b) film forming: adopt the method film forming of spray pyrolysis, the nozzle liquid flow is between 60ml/h-480ml/h, and nozzle scan speed is 30-180mm/s, and nozzle increases thickness by reciprocating motion scanning; Fogdrop diameter is between 10 μ m-100 μ m;
(c) heat treatment: through the super-dry after-baking, heat treatment can be under 400 ℃ of-500 ℃ of conditions heat treatment 0.5h.
The concentration of described titanium alkoxide generally can be controlled between the 0.1-1mol/l, and solution concentration is high more, and formed film is thick more, and the concentration of optimization is between 0.1-0.5mol/l.Generally between 2-20, the ratio in acetylacetone,2,4-pentanedione and titanium source is big more for the ratio in acetylacetone,2,4-pentanedione and titanium source, and colloidal sol is stable more, if but acetylacetone,2,4-pentanedione concentration is too big, also cause pore easily, and the ratio of optimization is between 5-6.Described nozzle liquid flow generally can be regulated between 60ml/h-480ml/h, and the nozzle liquid flow is big more, and the thickness of film is thick more.When too big the or collosol concentration of colloidal sol flow was too high, the organic substance in the rete may have little time volatilization, decompose and burning, causes film cracking efflorescence or film portion carbonization easily; In addition, flow is too big, may cause glass substrate to ftracture because of the inequality of being heated, and the colloidal sol flow of optimization is between 100ml/h-150ml/h.Said nozzle scan speed generally is controlled between the 30mm/s-180mm/s, and nozzle scan speed is high more, and film is thin more, and the sweep speed of optimization is between 80mm/s-100mm/s.Said fogdrop diameter generally is controlled between the 10 μ m-100 μ m; The distance of nozzle and substrate is between 15cm-30cm, and underlayer temperature can be between 150 ℃-500 ℃.Film forming generally can be hanged down the resistant to elevated temperatures requirement of entire equipment at low temperatures, but film forming at low temperatures, the porosity of film can be high, and the density of film is poor slightly, and the underlayer temperature of optimization is between 400 ℃-500 ℃.
Under the collosol concentration and film-forming process condition of aforementioned optimization,, can obtain the fine and close TiO of thickness between 100nm-150nm when the film number of plies during at 8 layers-10 layers
2Film makes the efficient of dye-sensitized solar cells improve 7%-10%.
Described employing spray pyrolysis method film forming, can also adopt nozzle to prepare large area film along the mode that tooth ripple track carries out two dimensional motion scanning, nozzle moves back and forth scanning with the increase thickness along X-direction, and slowly moves to obtain large area film along Y direction.Nozzle is 30-180mm/s along the sweep speed of X-direction, nozzle along the rate travel of Y direction between 0.5mm/s-4mm/s.
The method film forming of said employing spray pyrolysis, improving one's methods is the method film forming that adopts ultrasonic spray pyrolysis, and what more optimize is to adopt integrative ultrasonic atomizer film forming, and the uniformity of film forming is best.Said integrative ultrasonic atomizing nozzle structure is open in Chinese invention patent 200710033036.X, its operation principle is to be sent to nozzle head by the ultrasonic wave that transducer produces by the luffing bar, thereby make the colloidal sol that flows out through nozzle in the nozzle face uniform atomizing, deposit film forming then.Compare with traditional ullrasonic spraying mode, its atomizing effect is more even, and supersonic frequency is low, mechanism is simple.Integrative ultrasonic atomizer supersonic frequency is between 30kHz-120kHz, and supersonic frequency is high more, and mist droplet particle size is just more little, and for example for the ultrasonic atomizing nozzle of 60KHz, fogdrop diameter is between 10-100 μ m, and the droplet average diameter is about 40 μ m.Carry out two dimensional motion scanning by nozzle along tooth ripple track and can prepare large area film.Said nozzle is more little at the movement rate of Y direction, and the uniformity of film will be good more, and the number of plies of film stack will be many more, and the rate travel of optimization is between 0.5mm/s-2mm/s.Under the collosol concentration and film-forming process condition of described optimization, when the number of plies of film stack is between 8 layers-10 layers, can obtain thickness between 100nm-150nm, the uniform fine and close TiO of large tracts of land film forming
2Film, wherein the area of film can be regulated by the control of swash width.
The method film forming of described employing spray pyrolysis can also be provided with template at substrate surface as required, to hide the part that does not need to spray plated film, is used for extraction electrode.
The present invention adopts the method for spray pyrolysis to prepare the fine and close TiO on transparency conductive electrode surface
2Film, and can obtain the large area film that has good uniformity easily along the mode of tooth ripple track shuttle-scanning by nozzle, can obtain the fine and close TiO of thickness between 100nm-150nm by the technological parameter of optimizing collosol concentration and spray pyrolysis
2Film makes the efficient of dye-sensitized solar cells improve 7%-10%.
Description of drawings
Fig. 1 is provided with tight TiO
2The J-V curve of dye-sensitized solar cells before and after the film (film thickness is about 150nm).
The formwork structure schematic diagram that Fig. 2 transparency conductive electrode surface is provided with
Below in conjunction with accompanying drawing content of the present invention is further specified
Embodiment
Embodiment 1
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.5mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 10;
(b) film forming: adopt the method film forming of spray pyrolysis, fogdrop diameter is about 60 μ m, and nozzle colloidal sol flow is 120ml/h, nozzle scan speed is 180mm/s, nozzle is 8 times by the reciprocating motion scanning times, and the distance of nozzle and substrate is 20cm, and underlayer temperature is 150 ℃;
(c) heat treatment: through after the super-dry under 400 ℃ of conditions heat treatment 0.5h.
Can obtain the fine and close TiO that thickness is about 150nm
2Film, the dye-sensitized solar cells short circuit current improves, and efficient improves about 8% (as Fig. 1).
Embodiment 2
Being the titanium source with the isopropyl titanate as different from Example 1, is solvent with the isopropyl alcohol.
Can obtain the fine and close TiO that thickness is about 180nm
2Film, dye-sensitized solar cells efficient improves about 6%.
Embodiment 3
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 20;
(b) film forming: adopt the method film forming of ultrasonic spray pyrolysis, fogdrop diameter is about 100 μ m, and nozzle colloidal sol flow is 60ml/h, nozzle scan speed is 180mm/s, nozzle is 10 times by the reciprocating motion scanning times, and the distance of nozzle and substrate is 20cm, and underlayer temperature is 500 ℃;
(c) heat treatment: through after the super-dry under 500 ℃ of conditions heat treatment 0.5h.
Can obtain the fine and close TiO that thickness is about 150nm
2Film, dye-sensitized solar cells efficient improves 7%.
Embodiment 4
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 2;
(b) film forming: adopt the method film forming of ultrasonic spray pyrolysis, fogdrop diameter is about 10 μ m, and nozzle colloidal sol flow is 120ml/h, nozzle scan speed is 30mm/s, nozzle is 9 times by the reciprocating motion scanning times, and the distance of nozzle and substrate is 20cm, and underlayer temperature is 250 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain the fine and close TiO that thickness is about 150nm
2Film, dye-sensitized solar cells efficient improves 7%.
Embodiment 5
Different with embodiment 4, the method film forming of employing spray pyrolysis, nozzle colloidal sol flow is 480ml/h, nozzle scan speed is 180mm/s.
Can obtain the fine and close TiO that thickness is about 180nm
2Film, dye-sensitized solar cells efficient improves 6%.
Embodiment 6
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.3mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 8;
(b) film forming: adopt the method film forming of ultrasonic spray pyrolysis, fogdrop diameter is about 60 μ m, and nozzle colloidal sol flow is 120ml/h, nozzle scan speed is 90mm/s, nozzle is 9 times by the reciprocating motion scanning times, and the distance of nozzle and substrate is 20cm, and underlayer temperature is 400 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain the fine and close TiO that thickness is about 120nm
2Film, dye-sensitized solar cells efficient improves 10%.
Embodiment 7
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.5mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 10;
(b) film forming: the method film forming that adopts spray pyrolysis, fogdrop diameter is about 60 μ m, nozzle colloidal sol flow is 120ml/h, nozzle carries out two dimensional motion scanning along tooth ripple track, and nozzle is 360mm along the X-direction stroke, and sweep speed is 180mm/s, nozzle is 2mm/s along the rate travel of Y direction, be 2 minutes sweep time, and the distance of nozzle and substrate is 20cm, and underlayer temperature is 180 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area and be about 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is between 100nm-200nm, and film forming is inhomogeneous; Dye-sensitized solar cells efficient improves about 7%-8%.
Embodiment 8
Being the titanium source with the isopropyl titanate as different from Example 7, is solvent with the isopropyl alcohol.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is between 100nm-200nm, and film forming is inhomogeneous; Dye-sensitized solar cells efficient improves about 7%-8%.
Embodiment 9
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 20;
(b) film forming: the method film forming that adopts ultrasonic spray pyrolysis, fogdrop diameter is about 100 μ m, nozzle colloidal sol flow is 60ml/h, nozzle is 360mm along the X-direction stroke, sweep speed is 180mm/s, and nozzle is 4mm/s along the rate travel of Y direction, and be 2 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 450 ℃;
(c) heat treatment: through after the super-dry under 500 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is between 150nm-250nm, and film forming is inhomogeneous; Dye-sensitized solar cells efficient improves about 5%-6%.
Embodiment 10
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 5;
(b) film forming: the method film forming that adopts ultrasonic spray pyrolysis, fogdrop diameter is about 10 μ m, nozzle colloidal sol flow is 120ml/h, nozzle is 360mm along the X-direction stroke, sweep speed is 30mm/s, and nozzle is 0.5mm/s along the rate travel of Y direction, and be 10 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 250 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is between 50nm-150nm, and film forming is inhomogeneous, and dye-sensitized solar cells efficient improves about 7%-8%.
Embodiment 11
Different with embodiment 10, the method film forming of employing spray pyrolysis, fogdrop diameter is about 60 μ m, nozzle colloidal sol flow is 480ml/h, and nozzle is 360mm along the X-direction stroke, and sweep speed is 180mm/s, nozzle is 4mm/s along the rate travel of Y direction, and be 2 minutes sweep time.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is between 100nm-250nm, and film forming is inhomogeneous, and dye-sensitized solar cells efficient improves about 6%-7%.
Embodiment 12
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.5mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 10;
(b) film forming: adopt integrative ultrasonic atomizer film forming, fogdrop diameter is about 50 μ m,, nozzle colloidal sol flow is 120ml/h, nozzle carries out two dimensional motion scanning along tooth ripple track, nozzle is 360mm along the X-direction stroke, sweep speed is 180mm/s, and nozzle is 2mm/s along the rate travel of Y direction, and be 3 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 180 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is about 160nm, and film forming is more even, and dye-sensitized solar cells efficient improves about 7%.
Embodiment 13
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.2mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 20;
(b) film forming: adopt integrative ultrasonic atomizer film forming, fogdrop diameter is about 80 μ m, nozzle colloidal sol flow is 60ml/h, nozzle is 360mm along the X-direction stroke, sweep speed is 180mm/s, and nozzle is 4mm/s along the rate travel of Y direction, and be 2 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 450 ℃;
(c) heat treatment: through after the super-dry under 500 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is about 130nm, and film forming is more even, and dye-sensitized solar cells efficient improves about 9%.
Embodiment 14
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 5;
(b) film forming: adopt integrative ultrasonic atomizer film forming, fogdrop diameter is about 30 μ m, nozzle colloidal sol flow is 120ml/h, nozzle is 360mm along the X-direction stroke, sweep speed is 30mm/s, and nozzle is 0.5mm/s along the rate travel of Y direction, and be 5 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 450 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is about 120nm, and film forming is even, and dye-sensitized solar cells efficient improves about 10%.
Embodiment 15
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 5;
(b) film forming: adopt integrative ultrasonic atomizer film forming, fogdrop diameter is about 60 μ m, nozzle colloidal sol flow is 120ml/h, nozzle is 360mm along the X-direction stroke, sweep speed is 90mm/s, and nozzle is 1mm/s along the rate travel of Y direction, and be 6 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 450 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is about 120nm, and film forming is even, and dye-sensitized solar cells efficient improves about 10%.
Embodiment 16
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.5mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 5;
(b) film forming: adopt integrative ultrasonic atomizer film forming, fogdrop diameter is about 60 μ m, nozzle colloidal sol flow is 120ml/h, nozzle is 360mm along the X-direction stroke, sweep speed is 90mm/s, and nozzle is 2mm/s along the rate travel of Y direction, and be 3 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 450 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is about 160nm, and film forming is even, and dye-sensitized solar cells efficient improves about 7%.
Embodiment 17
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.2mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 5;
(b) film forming: adopt integrative ultrasonic atomizer film forming, fogdrop diameter is about 60 μ m, nozzle colloidal sol flow is 120ml/h, nozzle is 360mm along the X-direction stroke, sweep speed is 90mm/s, and nozzle is 2mm/s along the rate travel of Y direction, and be 3 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 400 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area is 30 * 30cm
2Fine and close TiO
2Film, the thickness of film is about 120nm, and film forming is more even, and dye-sensitized solar cells efficient improves about 10%.
Embodiment 18
(a) preparing titanium dioxide colloidal sol: with the butyl titanate is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol; The concentration of butyl titanate is 0.2mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is 5;
(b) film forming: adopt integrative ultrasonic atomizer film forming, fogdrop diameter is about 60 μ m, nozzle colloidal sol flow is 120ml/h, nozzle is 1100mm along the X-direction stroke, sweep speed is 100mm/s, and nozzle is 0.5mm/s along the rate travel of Y direction, and be 20 minutes sweep time, the distance of nozzle and substrate is 20cm, and underlayer temperature is 400 ℃;
(c) heat treatment: through after the super-dry under 450 ℃ of conditions heat treatment 0.5h.
Can obtain area is 100 * 100cm
2Fine and close TiO
2Film, the thickness of film is about 130nm, and film forming is even, and dye-sensitized solar cells efficient improves about 9%.
Embodiment 19
Different with embodiment 16, at substrate surface template (as accompanying drawing 2) is set, result's blank space shown in the figure has plated fine and close TiO
2Film does not plate TiO at the template shelter
2Film can be used for extraction electrode.
Claims (8)
1. the preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery is characterized in that comprising the steps:
(a) preparing titanium dioxide colloidal sol: with the titanium alkoxide is the titanium source, is stabilizer with the acetylacetone,2,4-pentanedione, is solvent with ethanol or isopropyl alcohol, and the three is mixed; The titanium alkoxide is selected from a kind of in butyl titanate, the isopropyl titanate, and the concentration in titanium source is 0.1-1mol/l; The mol ratio in acetylacetone,2,4-pentanedione and titanium source is between 2-20;
(b) film forming: the method film forming that adopts spray pyrolysis, the control fogdrop diameter is between 10 μ m-100 μ m, adopt nozzle to prepare large area film along the mode that tooth ripple track carries out two dimensional motion scanning, nozzle moves back and forth scanning with the increase thickness along X-direction, and slowly moves ahead to obtain large area film along Y direction; Underlayer temperature is between 150 ℃-500 ℃;
(c) heat treatment: through the super-dry after-baking.
2. the preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery according to claim 1, it is characterized in that: the concentration in titanium source is between 0.1-0.5mol/l.
3. the preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery according to claim 1, it is characterized in that: underlayer temperature is between 400 ℃-500 ℃ in step (b) film forming procedure.
4. the preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery according to claim 1, it is characterized in that: in the film forming procedure, the nozzle liquid flow is between 60ml/h-480ml/h, and fogdrop diameter is between 10 μ m-100 μ m.
5. the preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery according to claim 1, it is characterized in that: in the film forming procedure, nozzle is 30-180mm/s along the sweep speed of X-direction, nozzle along the rate travel of Y direction between 0.5mm/s-4mm/s.
6. the preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery according to claim 1 is characterized in that: the method film forming that adopts ultrasonic spray pyrolysis in step (b) film forming procedure.
7. the preparation method of surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery according to claim 6 is characterized in that: adopt integrative ultrasonic atomizer film forming in step (b) film forming procedure.
8. according to the preparation method of the wantonly 1 described surface compact titanium dioxide film of transparency conductive electrode of dye sensitization solar battery of claim 1 to 7, it is characterized in that: in film forming procedure, template is set, to hide the part that does not need to spray plated film at substrate surface.
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