CN101845664A - Low-temperature preparation method of highly oriented single crystal titanium dioxide nanowire array film - Google Patents
Low-temperature preparation method of highly oriented single crystal titanium dioxide nanowire array film Download PDFInfo
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Abstract
The invention relates to a low-temperature preparation method of a highly oriented single crystal titanium dioxide nanowire array film, which utilizes improved low-temperature heterogeneous phase solvent thermal technology to be combined with interface chemical reaction, and leads the single crystal titanium dioxide nanowire array film with high orientation, good crystallization and adjustable size to be directly deposited on the surface of transparent conductive glass in a large area. The one-dimensional nano-structure array film grows vertically to the surface of the conductive glass, can be taken as a nano-electrode to be assembled into a novel nano device, especially can be directly taken as a photoelectrode of a novel solar battery for use, improves the transmission rate of photoelectrons, and reduces the recombination velocity of the photoelectrons. The preparation process of the materials is simple, environment-friendly and low in cost, and the preparation method is easy for industrialized popularization and use, and is beneficial to developing and utilizing solar energy with low cost.
Description
Technical field
The present invention relates to a kind of low temperature preparation method of conductor nano tube/linear array film, be specifically related to a kind of low temperature preparation method of transparent conductive glass surface highly oriented single crystal titanium dioxide nanowire array film, be applicable to the optoelectronic pole in the solar cell.
Background technology
Increasingly serious along with the energy in the global range and environmental problem, urgent need will be developed and a kind ofly not only obtain but also the new forms of energy of clean environment firendly a kind of so just novel energy of sun power easily.The form of development and use sun power is varied, and solar cell is a kind of principal mode wherein.Traditional solar cell is mainly prepared by silicon-based semiconductor material, the photoelectric transformation efficiency height of this class battery (can reach about 18%), but the purity requirement to material is very high, and material preparation process complexity, cost are very high, and use in the national defence fields such as Aeronautics and Astronautics and military affairs that only are confined to.In order to realize promoting the use of of solar cell, urgent need will be developed a kind of low cost of manufacture, solar cell that efficiency of conversion is high.
Novel sensitization titanium dioxide nanocrystalline conductor oxidate solar cell is subjected to extensive concern with its cheap manufacturing cost and excellent photoelectric properties.The titania nanoparticles film of this battery about with surface adsorption sensitizing agent, size 20 nanometers is optoelectronic pole, under illumination, sensitizing agent absorbs photon and is converted into excited electronic state generation light induced electron, light induced electron injects semi-conductive conduction band by the excited state of sensitizing agent fast, and then passes Nano semiconductor network transitions to external circuit and form photoelectric current.Light induced electron will inevitably run into a large amount of crystal boundaries in passing the Nano semiconductor network development process, cause the scatter loss of electronics, influences device performance.
For this reason, need to optimize the optoelectronic pole structure, improve the transmission speed of light induced electron.Undoubtedly the one dimension Nano structure array can be directly for the transmission of light induced electron provides direct channel, improve the transmission speed of electronics, be a kind of ideal structure form of novel solar battery optoelectronic pole.The one-dimensional titanium dioxide nanostructure array film mainly contains nano-tube array and two kinds of forms of nano-wire array film.At present, the one-dimensional titanium dioxide nano-pipe array thin film is mainly by electrochemical anodic oxidation titanium sheet or be deposited on the titanium film preparation of transparent conductive glass surface, the gained nano-pipe array thin film presents non-crystalline state on the one hand, need the high temperature crystallization to handle, on the other hand, because titanium sheet itself is light tight, influence the illumination mode, the thickness that perhaps is difficult to depositing high-quality surpasses micron-sized titanium film, makes the length of synthesis of nano pipe be restricted.The one-dimensional titanium dioxide nano-wire array film is mainly by the preparation of various CVD (Chemical Vapor Deposition) method, and equipment complexity, cost are higher, and synthesis temperature is higher, is unfavorable for scale operation.
Summary of the invention
The present invention aims to provide a kind of based on the heterogeneous solvent thermal technology of low temperature bonding interface chemical reaction, can be directly at the low temperature preparation method of transparent conductive glass surface big area formation of deposits highly oriented single crystal titanium dioxide nanowire array film.
For achieving the above object, the technical solution used in the present invention is: 1) at first, the fluorine doped tin oxide conductive glass of acetone, ethanol and deionized water ultrasonic cleaning is successively dried and puts into the polytetrafluoroethyllining lining of stainless steel pressure still, press (10-20): (0.5-1.5): volume ratio (0.5-1.5) joins in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after toluene, butyl (tetra) titanate and concentrated hydrochloric acid are mixed; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 160-200 ℃ constant temperature, solvent thermal reaction is carried out in insulation 1-20 hour, and reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and remove the remaining unreacted reactant in surface, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 60-70 ℃ concentration
4In the solution 30 minutes, take out the back and fully rinse well with deionized water, at 450 ℃ of insulation 30min down, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film.
The concentration of concentrated hydrochloric acid of the present invention is 36%-38%; Removing fluorine doped tin oxide conductive glass surface resistates in the described step 3) is fully to wash the fluorine doped tin oxide conductive glass or adopt ultra sonic bath to remove fluorine doped tin oxide conductive glass surface resistates with dehydrated alcohol, Virahol.
The present invention adopts the heterogeneous solvent thermal technology of low temperature, at non-polar solvent and hydrophilic substrate surface, by the controllable interface chemical reaction directly at the nano-wire array film of titanium dioxide vertical substrate of substrate surface preparation, highly crystalline.This membrane deposition method raw materials cost is low, technology is simple, good reproducibility, temperature of reaction are low, be easy to the big area film forming, product is height-oriented, advantages of good crystallization, microscopic dimensions are easily controlled, the substrate height of growing film sees through, and is a kind of desirable approach that directly prepares solar cell photoelectric pole.Use as optoelectronic pole, this nano-wire array film structure is for the radial transport of light induced electron provides direct channel, and the transmission speed that helps improving electronics reduces the recombination losses of electronics simultaneously, also is a kind of good selection of other nano photoelectric device of assembling.
Description of drawings
The vertical view of the nano-wire array film of titanium dioxide of Fig. 1 embodiment of the invention 4 preparations; The front view of the nano-wire array film of titanium dioxide of Fig. 2 embodiment of the invention 3 preparations; The X-ray diffractogram of the nano-wire array film of titanium dioxide of Fig. 3 embodiment of the invention 3 preparations; Fig. 4 is the IPCE figure of the N719 dye sensitization nano-wire array film of titanium dioxide solar cell of the embodiment of the invention 4 preparations.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment 1:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still after the concentrated hydrochloric acid of 36-38% mixes by 10: 0.5: 0.5 volume ratios with toluene, butyl (tetra) titanate and concentration, then the sealing load still; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 160 ℃ constant temperature, be incubated 20 hours, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and fully wash the fluorine doped tin oxide conductive glass with dehydrated alcohol, Virahol, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 70 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
Embodiment 2:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after the concentrated hydrochloric acid of 36-38% mixes by 10: 0.5: 0.5 volume ratios with toluene, butyl (tetra) titanate and concentration; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 180 ℃ constant temperature, be incubated 10 hours, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and adopt ultra sonic bath to remove the resistates of fluorine doped tin oxide conductive glass conductive layer surface, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 60 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
Embodiment 3:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after the concentrated hydrochloric acid of 36-38% mixes by 10: 0.8: 1.0 volume ratios with toluene, butyl (tetra) titanate and concentration; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 180 ℃ constant temperature, be incubated 10 hours, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and fully wash the resistates of fluorine doped tin oxide conductive glass conducting surface with dehydrated alcohol, Virahol, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 65 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
As seen from Figure 2, the one-dimensional titanium dioxide nano-wire array film of FTO conductive glass surface formation of deposits, the vertical FTO of this film surface, the densification that is evenly distributed, specific surface area are big.The diameter of nano wire is tens nanometers in the preparation film, and length can change arbitrarily between tens nanometers to tens micron by controlling reaction time.
As seen from Figure 3, a small amount of diffraction peak only appears in sample, and the diffraction peak intensity of (002) crystal face is big unusually, shows the high oriented growth of product, well-crystallized.
Embodiment 4:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after the concentrated hydrochloric acid of 36-38% mixes by 15: 1: 1.2 volume ratios with toluene, butyl (tetra) titanate and concentration; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 170 ℃ constant temperature, be incubated 15 hours, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and adopt ultra sonic bath to remove the resistates of fluorine doped tin oxide conductive glass conductive layer surface, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 70 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
As seen from Figure 1, the one-dimensional titanium dioxide nano-wire array film of FTO conductive glass surface formation of deposits, the vertical FTO of this film surface, the densification that is evenly distributed, specific surface area are big.The diameter of nano wire is tens nanometers in the preparation film, and length can change arbitrarily between tens nanometers to tens micron by controlling reaction time.
As seen from Figure 4, in the extinction scope of dyestuff, the efficiency of conversion that incident photon is converted into electronics surpasses 50%, shows that this structure helps opto-electronic conversion, is a kind of ideal structure form of high performance solar cells with optoelectronic pole.
Embodiment 5:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after the concentrated hydrochloric acid of 36-38% mixes by 18: 1.2: 1 volume ratios with toluene, butyl (tetra) titanate and concentration; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 200 ℃ constant temperature, be incubated 1 hour, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and fully wash fluorine doped tin oxide conductive glass surface resistates with dehydrated alcohol, Virahol, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 68 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
Embodiment 6:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after the concentrated hydrochloric acid of 36-38% mixes by 19: 1.5: 0.8 volume ratios with toluene, butyl (tetra) titanate and concentration; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 190 ℃ constant temperature, be incubated 5 hours, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and adopt ultra sonic bath to remove the resistates of fluorine doped tin oxide conductive glass conductive layer surface, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 62 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
Embodiment 7:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after the concentrated hydrochloric acid of 36-38% mixes by 20: 1: 1.5 volume ratios with toluene, butyl (tetra) titanate and concentration; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 165 ℃ constant temperature, be incubated 18 hours, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and fully wash fluorine doped tin oxide conductive glass surface resistates with dehydrated alcohol, Virahol, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 67 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
Embodiment 8:1) at first, fluorine doped tin oxide conductive glass (FTO) is cut into 1.5cm * 2.0 sizes, successively after acetone, ethanol and deionized water ultrasonic cleaning are totally dried, the fluorine doped tin oxide conductive glass is put into the polytetrafluoroethyllining lining of stainless steel pressure still, is to join in the polytetrafluoroethyllining lining of stainless steel pressure still the sealing load still after the concentrated hydrochloric acid of 36-38% mixes by 12: 1.5: 1.5 volume ratios with toluene, butyl (tetra) titanate and concentration; 2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 185 ℃ constant temperature, be incubated 7 hours, carry out solvent thermal reaction, reaction naturally cools to room temperature after finishing; 3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and adopt ultra sonic bath to remove the resistates of fluorine doped tin oxide conductive glass conductive layer surface, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film; 4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 66 ℃ concentration
4In the solution 30 minutes, taking out the back fully rinses well with deionized water, at 450 ℃ of following insulation 30min, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film, can be directly as novel high-performance used for solar batteries optoelectronic pole.
The starting material that use are chemical reagent commonly used among the present invention, do not need purification process, and temperature of reaction is lower, are no more than 200 ℃, and preparation process is with low cost; Simultaneously, the preparation film size depends on used FTO conductive glass, realize the large area film preparation easily, so, the present invention is a kind of wet chemical method efficient, low-cost, the large-area preparation highly oriented single crystal titanium dioxide nanowire array film, also is a kind of ideal structure form of novel solar battery with the light electrode materials.
Claims (3)
1. the low temperature preparation method of a highly oriented single crystal titanium dioxide nanowire array film is characterized in that:
1) at first, the fluorine doped tin oxide conductive glass of acetone, ethanol and deionized water ultrasonic cleaning is successively dried and puts into the polytetrafluoroethyllining lining of stainless steel pressure still, press (10-20): (0.5-1.5): volume ratio (0.5-1.5) joins in the polytetrafluoroethyllining lining of stainless steel pressure still after toluene, butyl (tetra) titanate and concentrated hydrochloric acid are mixed, then the sealing load still;
2) secondly, the autoclave pressure of good seal is transferred in the thermostatic equipment, under 160-200 ℃ constant temperature, solvent thermal reaction is carried out in insulation 1-20 hour, and reaction naturally cools to room temperature after finishing;
3) then, open the pressure kettle cover, take out the fluorine doped tin oxide conductive glass and remove the remaining unreacted reactant in surface, drying at room temperature directly is deposited on the TiO of fluorine doped tin oxide conductive glass surface
2Nano-wire array film;
4) last, will deposit TiO
2It is 0.05 mole every liter TiCl that the fluorine doped tin oxide conductive glass of nano-wire array film places 60-70 ℃ concentration
4In the solution 30 minutes, take out the back and fully rinse well with deionized water, at 450 ℃ of insulation 30min down, promptly obtain perpendicular to the fluorine doped tin oxide conductive glass surface, monocrystalline rutile titanium dioxide nano-wire array film.
2. the low temperature preparation method of highly oriented single crystal titanium dioxide nanowire array film according to claim 1, it is characterized in that: the concentration of described concentrated hydrochloric acid is 36%-38%.
3. the low temperature preparation method of highly oriented single crystal titanium dioxide nanowire array film according to claim 1 is characterized in that: removing fluorine doped tin oxide conductive glass surface resistates in the described step 3) is fully to wash the fluorine doped tin oxide conductive glass or adopt ultra sonic bath to remove fluorine doped tin oxide conductive glass surface resistates with dehydrated alcohol, Virahol.
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| CN102060325A (en) * | 2010-11-12 | 2011-05-18 | 北京理工大学 | Tetragonal-phase barium titanate nanorod array and preparation method thereof |
| CN102060325B (en) * | 2010-11-12 | 2012-10-24 | 北京理工大学 | Tetragonal-phase barium titanate nanorod array and preparation method thereof |
| CN101994154A (en) * | 2010-11-26 | 2011-03-30 | 浙江大学 | Preparation method of waist drum shaped single crystal anatase titanium dioxide and gathered microsphere thereof |
| CN101994154B (en) * | 2010-11-26 | 2012-06-06 | 浙江大学 | Preparation method of waist drum shaped single crystal anatase titanium dioxide and gathered microsphere thereof |
| CN102086528A (en) * | 2010-12-14 | 2011-06-08 | 桂林理工大学 | Preparation method for titanium dioxide monocrystalline nano wire array film |
| CN102169962B (en) * | 2011-03-10 | 2012-08-29 | 许昌学院 | Solar cell device based on In2S3 netted nanocrystal array and P3HT hybrid film |
| CN102169962A (en) * | 2011-03-10 | 2011-08-31 | 许昌学院 | Solar cell device based on In2S3 netted nanocrystal array and P3HT hybrid film |
| CN102222573A (en) * | 2011-03-25 | 2011-10-19 | 华中科技大学 | Method for preparing titanium dioxide nanocrystalline electrode |
| CN102222573B (en) * | 2011-03-25 | 2012-06-13 | 华中科技大学 | Method for preparing titanium dioxide nanocrystalline electrode |
| CN102534781A (en) * | 2012-02-25 | 2012-07-04 | 复旦大学 | Ti-doped titanium dioxide nanowire array, as well as preparing method and application of Ti-doped titanium dioxide nanowire array |
| CN103646989A (en) * | 2013-11-27 | 2014-03-19 | 华东师范大学 | Preparation method of p-n type Cu2O/TiO2 nanowire array composite film |
| CN103896208A (en) * | 2014-02-19 | 2014-07-02 | 华中师范大学 | Manganese dioxide nanowire array electrode on titanium substrate and preparation method thereof |
| CN104576074A (en) * | 2015-01-09 | 2015-04-29 | 哈尔滨工业大学 | Preparation method for ultra-long TiO2 nanowire array thin-film photo-anode |
| CN104828863A (en) * | 2015-05-14 | 2015-08-12 | 西南科技大学 | TiO2 nanowire diameter regulating and controlling method and TiO2 nanowire array prepared by same |
| CN105826081A (en) * | 2016-06-13 | 2016-08-03 | 东南大学 | Titanium-dioxide-based nanorod array counter electrode and preparation method and application thereof |
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