CN103377831A - Method for preparing TiO2/ZnO compound ordered porous thin film - Google Patents
Method for preparing TiO2/ZnO compound ordered porous thin film Download PDFInfo
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- CN103377831A CN103377831A CN 201210121070 CN201210121070A CN103377831A CN 103377831 A CN103377831 A CN 103377831A CN 201210121070 CN201210121070 CN 201210121070 CN 201210121070 A CN201210121070 A CN 201210121070A CN 103377831 A CN103377831 A CN 103377831A
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Abstract
The invention belongs to the technical field of ordered porous thin film preparation, and particularly relates to a method for preparing a TiO2/ZnO compound ordered porous thin film and related process parameters. The preparation method is a sol dipping template method. Firstly, ordered PS array templates are assembled on a clean glass substrate through the dipping-pulling method; then the PS templates are perpendicularly dipped into hybrid sol composed of TiO2 and ZnO, the sol enters gaps of microspheres under the action of capillary force to form gel, finally, the PS templates are removed through calcinations and the TiO2/ZnO compound ordered porous thin film is obtained. Meanwhile, the influence of the process parameters such as concentration of a solution precursor and dipping time on the thin film structure and properties is discussed, and the optimal process parameters for preparing the TiO2/ZnO compound ordered porous thin film with the high properties are obtained.
Description
Technical field
The invention belongs to the ordered porous thin-film preparing technical field, be specially a kind of TiO of preparation
2The method of/ZnO complex ordered stephanoporate film and related process parameter.
Background technology
Along with the continuous minimizing of physical resources on the earth and going from bad to worse of environment, energy problem more and more becomes the focus that people pay close attention to.The key that addresses this problem is exactly to study new forms of energy and new energy materials, in recent years, the countries such as the U.S., Japan, Switzerland, Canada have all carried out the research of novel energy material, and China " 12 " and " 863 " plan etc. is studied new forms of energy as the primary study funded projects.Solar energy is as a kind of new forms of energy of cleaning, aboundresources, and its development and utilization has become the focus that people pay close attention to.Utilizing one of most important approach of solar energy is exactly research and applied solar energy battery, particularly solar power generation is combined with construction material so that following heavy construction realizes the electric power self-sufficiency, is a great development direction of future architecture.Announce to put into effect the building energy conservation new standard on November 13rd, 2006 such as Spain government, regulation from now on domestic all newly build and build and renovate building and all solar panel must be installed, to promote energy efficiency.
At present, solar cell can be divided into silicon solar cell, inorganic compound thin film solar cell, organic solar batteries, nano-crystalline solar battery etc. by the material difference.Wherein the transformation efficiency of silicon solar cell is higher, but price comparison is expensive; The inorganic compound thin film solar cell relates to some heavy metals and rare metal; The life-span of organic solar batteries is shorter.The NPC battery is nano-crystalline solar battery, claims again Gr/tzel type battery or sensitization solar battery, is the another novel solar battery that grows up behind follow-up silion cell in 1991, hull cell etc.Have simple in structure, lightweight, the advantages such as raw material is cheap, low cost of manufacture, its cost of manufacture only is 1/5～1/10 of silion cell, thereby just be subject to people's extensive concern at world wide once coming out, carried out great many of experiments around improving cell photoelectric transformation efficiency scientists thereafter.Up to the present, external TiO
2The transformation efficiency of nano-crystalline solar battery can be stabilized in more than 12%, and forms production capacity, begins to be applied to solar power generation, demonstrates good application development prospect.Also in succession carried out the research work of this respect in domestic these several years, though obtained certain achievement, on the whole with still have gap abroad.One of three large chief components and the core material of NPC solar cell as the photo-anode film on dye sensitizing agent adsorbent and opto-electronic conversion basis.Existing result of study shows that its structure and performance will directly affect the final electricity conversion of battery.In order to be beneficial to the absorption of dye sensitizing agent, improve the sunlight utilance, need this electrode film to be loose structure, have high specific area; Film defects should lack simultaneously, is beneficial to the transmission of light induced electron.
TiO
2The porous membrane specific area is generally up to 80m
2/ g can adsorb a large amount of sensitizers.The more important thing is, be adsorbed on sensitizer and TiO in the film
2The surface forms the C-O-Ti key, and this electronics that has greatly promoted to excite in the dyestuff is to TiO
2The transfer of film is so that quantum efficiency, becomes the first-selected light anode material of dye sensitized nano crystal photovoltaic solar cell close to 100%.Yet, traditional TiO
2Unordered porous electrode film defective is more, and light induced electron-hole is easy to compound.In addition, TiO
2Energy gap is 3.2eV, only can absorb the ultraviolet light that accounts for solar spectrum 4～5%, greatly reduces the utilance of sunlight.To TiO
2To carry out to be to realize one of its visible light-responded available strategy with modulation Deng wide bandgap semiconductor.The modulation level structure can be by following several strategies: the containing transition metal cation is new for body or donor energy level to form; Element such as C, N, S, P etc. that the doping electronegativity is lower than O improve the valence band current potential; Semiconductor formation solid solution with the width band gap reduces energy gap etc.
To sum up, present TiO
2Light anode material Main Problems as the NPC battery is: how to reduce TiO
2Energy gap, improve that it is visible light-responded; And the defective of minimizing film, and then reduce the compound of light induced electron-hole.The present invention is directed to the problems referred to above, take the photovoltaic performance that improves the NPC solar cell as final purpose, adopt the ordered porous TiO of the high-quality NPC battery of sol impregnation template synthesis
2/ ZnO combination electrode film utilizes orderly pore structure to reduce electrode defects, increases specific area; Utilize simultaneously ZnO wide band gap semiconducter and TiO
2Form solid solution, reduce energy gap, improve visible light-responded.
Summary of the invention
The object of the invention is to propose a kind of TiO
2/ ZnO complex ordered stephanoporate thin film technology method and related process parameter.
A kind of suitable preparation TiO
2The method of/ZnO complex ordered stephanoporate film.The method is the sol impregnation template.At first, on the glass substrate of cleaning, assembled orderly polystyrene microsphere (PS) array mould plate by dipping-pulling method; Then the PS template vertically is impregnated into by TiO again
2In the mixed sols that forms with ZnO, the gap that colloidal sol enters into microballoon under the effect of capillary force forms gel, removes the PS template and obtains porous TiO finally by calcining
2/ ZnO complex ordered stephanoporate film.
The mechanism of action of the present invention is: at first a clean glass substrate of cleaning vertically is impregnated in the PS emulsion, static certain hour is vertically pulled out this glass substrate, namely is assembled into the brilliant array mould plate of PS glue at glass substrate.Whole assembling process is broadly divided into three phases: 1. convection current transports: because emulsion is to the wetability of glass substrate, in the moment that substrate is drawn out, a curved meniscate liquid level will form in glass substrate, emulsion and air triplicity place, under the effect of power, the PS colloidal spheres transports to this place's convection current; 2. crystallization nucleation: along with the evaporation of on-chip PS colloid emulsion, when the thickness of liquid film reaches the colloidal spheres diameter, begin to form concave meniscus between the PS colloidal spheres, under capillary effect, form the two dimensional crystal nucleus of solid matter row; 3. crystal growth: along with the carrying out that lifts process, the PS colloidal spheres continues to transport to nucleation zone convection current, and under capillary effect, around the nucleation region growing, progressively forms large-area colloidal crystal, until continuous crystallization becomes the brilliant array of glue.Then, this PS template is impregnated into by TiO
2In the mixed sols that forms with ZnO, the gap that colloidal sol enters into microballoon under the effect of capillary force forms gel, removes the PS template and obtains ordered porous TiO finally by calcining
2/ ZnO laminated film.
The present invention also proposes above-mentioned preparation method's related process parameter, and is specific as follows:
The brilliant array mould plate of dipping-pulling method assembling PS glue: the concentration of PS emulsion is 13 ± 2vol%, and pull rate is 0.1 ± 0.02cm/min, and dip time is 4 ± 1min; Sol impregnation template synthesis TiO
2/ ZnO complex ordered stephanoporate film: TiO
2With the mol ratio of ZnO colloidal sol be 1: 1, precursor sol concentration is 0.4 ± 0.02mol/L, pull rate is 4 ± 0.1cm/min, dip time is 5 ± 1min.
Characteristics of the present invention:
1, sol impregnation template technical process is comparatively simple, is easy to realize, is convenient to control.
2, the preparation of PS template and TiO
2Be easy to finish with the preparation of ZnO complex sol presoma.
3, the quality of ordered porous thin-film is easy to control and improves, and fault of construction is few, and specific area is high.
This preparation technology's using method is as follows:
1, the technological parameter of the brilliant array mould plate of typical dipping-pulling method assembling PS glue: the concentration of PS emulsion is 13vol%, and pull rate is 0.1cm/min, and dip time is 4min.
2, typical sols dipping template synthesis TiO
2The technological parameter of/ZnO complex ordered stephanoporate film: TiO
2With the mol ratio of ZnO colloidal sol be 1: 1, precursor sol concentration is 0.4mol/L, pull rate is 4cm/min, dip time is 5min.
3, the process parameters range of the brilliant array mould plate of dipping-pulling method assembling PS glue wherein: the concentration of PS emulsion is 13 ± 2vol%, and pull rate is 0.1 ± 0.02cm/min, and dip time is 4 ± 1min.
4, sol impregnation template synthesis TiO wherein
2The process parameters range of/ZnO complex ordered stephanoporate film: precursor sol concentration is 0.4 ± 0.02mol/L, and pull rate is 4 ± 0.1cm/min, and dip time is 5 ± 1min.
5, preparation process is pressed preceding method.
Embodiment
The invention is further illustrated by the following examples.
Embodiment
The concentration of PS emulsion is 13vol%, and pull rate is 0.1cm/min, and dip time is 4min; TiO
2With the mol ratio of ZnO colloidal sol be 1: 1, precursor sol concentration is 0.4mol/L, pull rate is 4cm/min, dip time is 5min.
Press the preceding method preparation.
Nanocrystalline photovoltaic solar cell be can get and 2.8eV, high-quality TiO are about with, energy gap
2/ ZnO complex ordered stephanoporate film.
Used PS particle size directly has influence on the aperture (PS has 30～45% contraction approximately relatively) of film, precursor sol concentration affects dipping process, and general concentration is unsuitable excessive.
Claims (4)
1. one kind is fit to preparation TiO
2The method of/ZnO complex ordered stephanoporate film.The method is the sol impregnation template.At first, on the glass substrate of cleaning, assembled orderly polystyrene microsphere (PS) array mould plate by dipping-pulling method; Then the PS template vertically is impregnated into by TiO again
2In the mixed sols that forms with ZnO, the gap that colloidal sol enters into microballoon under the effect of capillary force forms gel, removes the PS template and obtains porous TiO finally by calcining
2/ ZnO complex ordered stephanoporate film.
2. one kind to require the dipping-pulling method of 1 described suitable assembling PS array mould plate.It is characterized in that detailed process is as follows with technological parameter: will be impregnated in the certain density PS emulsion so that certain speed is vertical by the slide of watery hydrochloric acid, isopropyl alcohol, the ultrasonic processing of absolute ethyl alcohol successively, behind the dipping certain hour, vertically pull out, after the drying at room temperature, repeat aforesaid operations, can get the multilayer template.The concentration of PS emulsion is 13 ± 2vol%, and pull rate is 0.1 ± 0.02cm/min, and dip time is 4 ± 1min.
3. one kind to require the TiO of 1 described suitable dipping
2Preparation with ZnO mixing precursor sol.The preparation and the related process parameter that it is characterized in that colloidal sol are as follows: butyl titanate and the zinc acetate of equimolar ratio are dissolved in certain anhydrous ethanol solvent, and 50 ℃ of heating magnetic agitation 2h obtain stable colloidal sol.TiO
2With the mol ratio of ZnO be 1: 1, precursor sol concentration is 0.4 ± 0.02mol/L.
4. one kind to require 1 described suitable sol impregnation template synthesis TiO
2The related process parameter of/ZnO complex ordered stephanoporate film.It is characterized in that pull rate is 4 ± 0.1cm/min, dip time is 5 ± 1min.
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| CN 201210121070 CN103377831A (en) | 2012-04-24 | 2012-04-24 | Method for preparing TiO2/ZnO compound ordered porous thin film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110261365A (en) * | 2019-07-02 | 2019-09-20 | 吉林大学 | A kind of period crescent nano gap array and preparation method thereof with raising Surface enhanced Raman scattering performance |
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2012
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110261365A (en) * | 2019-07-02 | 2019-09-20 | 吉林大学 | A kind of period crescent nano gap array and preparation method thereof with raising Surface enhanced Raman scattering performance |
| CN110261365B (en) * | 2019-07-02 | 2021-04-02 | 吉林大学 | Periodic crescent-shaped nano-gap array and preparation method thereof |
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Application publication date: 20131030 |