CN103668389A - Preparation method of ultra-thin two-way titanium-dioxide nanopore-array film with adjustable aperture and thickness - Google Patents
Preparation method of ultra-thin two-way titanium-dioxide nanopore-array film with adjustable aperture and thickness Download PDFInfo
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- CN103668389A CN103668389A CN201310596186.7A CN201310596186A CN103668389A CN 103668389 A CN103668389 A CN 103668389A CN 201310596186 A CN201310596186 A CN 201310596186A CN 103668389 A CN103668389 A CN 103668389A
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Abstract
The invention discloses a preparation method for a preparation method of ultra-thin two-way titanium-dioxide nanopore-array film with an adjustable aperture and thickness. The preparation method adopts an electrochemical anodic oxidation method with four steps to prepare the integral ultra-thin two-way titanium-dioxide nanopore-array film with a large area; then the oxidation time and the pore broadening time of hydrofluoric acid are adjusted so as to adjust the aperture and thickness of the film. According to invention, two-time oxidation is adopted so as to effectively avoid generation of bifurcate pores in the surfaces of the film and ensure that the pore channels of the prepared nanopore film are straight. The preparation method is simple and low in cost.
Description
technical field
The preparation method who the present invention relates to the adjustable ultra-thin bilateral titanium dioxide nano-pore array thin film of a kind of aperture and thickness, belongs to technical field of nano material.
background technology
The preparation method of hole array film mainly contains ion beam etching, photoengraving, molecular beam epitaxy, polymer template etc.Yet these methods or growth and preparation in certain severe rugged environment, or need large-scale valuable equipment, cost is all higher.Adopting electrochemistry anodic oxidation to prepare ultra-thin bilateral titanium dioxide nano-pore array thin film is a kind of simple and cheap approach.
Ultra-thin bilateral titanic oxide nano tube thin-film is widely studied in the front application according to solar cell and high catalytic performance thereof because of it.Although at present existing accomplished in many ways the preparation of bi-pass nano pipe film, yet still there is very large difficulty in the preparation of ultra-thin bilateral titanium dioxide nano-pore film.At this, we have proposed a kind of method of preparing ultra-thin bilateral titanium dioxide nano-pore film, and the thickness of prepared film, aperture are all adjustable, be a kind of good mask material, and preparation method are simple, with low cost, and current laboratory is prepared area and can be reached 1cm
2.
summary of the invention
The object of the present invention is to provide the preparation method of the adjustable ultra-thin bilateral titanium dioxide nano-pore array thin film of a kind of aperture and thickness, the method adopts four one-step electrochemistry anonizings, prepared bilateral titanium dioxide nano-pore film, by regulation and control oxidization time, the pore-enlargement of hydrofluoric acid, can realize to film thickness the regulation and control in aperture.
The technical solution used in the present invention is as follows:
A preparation method for the ultra-thin bilateral titanium dioxide nano-pore array thin film that aperture and thickness are adjustable, comprises the following steps:
(1) process the early stage of titanium sheet
High purity titanium sheet is cleaned to 10-15 minute, then 50-60 ℃ of oven dry in air through acetone, dehydrated alcohol, deionized water for ultrasonic successively;
(2) preparation of ultra-thin bilateral titanium dioxide nano-pore film
First by the titanium sheet after processing containing in water glycol electrolytic solution, preoxidation 2-3 hour under 60V constant voltage and 15 ℃ of constant temperatures, obtains titania nanotube layer, then by supersound process, removes the titanium dioxide layer of formation; Then the titanium sheet through a preoxidation is carried out to preoxidation for the second time, oxidizing condition is identical with a preoxidation, oxidization time is 10-15 minute, and the titanium dioxide layer obtaining, again through ultrasonic removing, is obtained to surface is regular arranges and the titanium sheet of sizeable pit; Then the titanium sheet through secondary preoxidation is carried out to film forming oxidation, oxidizing condition is identical with a preoxidation, and oxidization time is 8-60 second, and after film forming oxidation, titanium plate surface has formed the ultra-thin titanium dioxide nano-pore film of closed bottom; Finally titanium sheet is placed on without in water glycol electrolytic solution at 120V high pressure, under 20 ℃ of constant temperatures, be oxidized 30-50 second, titanium plate surface has formed ultra-thin bilateral titanium dioxide nano-pore film;
(3) shift
Titanium sheet after step (2) is processed inserts in water, and ultra-thin bilateral titanium dioxide nano-pore film floating, in the water surface, then picks up film with silicon chip, after drying, obtains ultra-thin bilateral titanium dioxide nano-pore film.
Described in step (2) is the ethylene glycol solution of 0.2～0.4wt% Neutral ammonium fluoride containing water glycol electrolytic solution, and adds the deionized water of 2-3vol%; Described is the ethylene glycol solution of 0.2～0.4wt% Neutral ammonium fluoride without water glycol electrolytic solution.
Titanium sheet after four step oxidations described in step (2) is inserted in 0.3-0.5wt% hydrofluoric acid solution, ultra-thin bilateral titanium dioxide nano-pore film will float on hydrofluoric acid solution surface, by controlling the flotation time, can realize the reaming to ultra-thin bilateral titanium dioxide nano-pore film.
The change of the film forming oxidization time described in step (2) can realize the regulation and control of ultra-thin bilateral titanium dioxide nano-pore film thickness.
Beneficial effect of the present invention:
1, adopt four step oxidation style, obtained ultra-thin bilateral titanium dioxide nano-pore film, because film is at electrolytic solution situ through hole, peels off, thereby can obtain complete, large-area film.
2, adopt twice preoxidation, effectively avoided the formation of surperficial bifurcate holes, guarantee that the duct of the nano-porous thin film of preparation is straight.
3, take the way at hydrofluoric acid liquid level by film floating, realized the reaming to ultra-thin bilateral titanium dioxide nano-pore film.
4, by changing the time of film forming oxidation, the regulation and control to ultra-thin bilateral titanium dioxide nano-pore film thickness have been realized.
Accompanying drawing explanation
Fig. 1 is oxidation schematic flow sheet, wherein, (a) preoxidation, (b) ultrasonic deoxidation layer, (c) secondary preoxidation, (d) ultrasonic deoxidation layer, (e) film forming oxidation, (f) high pressure through hole, (g) liquid level is floating, and (h) silicon chip is fished for.
Fig. 2 is the scanned photograph of ultra-thin bilateral titanium dioxide nano-pore film; Wherein, (a-c), without reaming film, (d-e) film after reaming, (f-g) shortens the film that film forming oxidization time (8 s) obtains, (h-i) increase the bi-pass nano pipe film that film forming oxidization time (30 min) obtains, side elevational view (h) and ground plan are (i).
Embodiment
1, process the early stage of titanium sheet
High purity titanium sheet (purity is 99.6%, purchased from Baoji Tian Mai Tai Ye company limited) cleans 10 minutes through acetone, dehydrated alcohol, deionized water for ultrasonic successively, then 50 ℃ of oven dry in air.
2, the preparation of ultra-thin bilateral titanium dioxide nano-pore film
Preparation flow as shown in Figure 1, is specifically divided into four steps: twice preoxidation, film forming oxidation and high pressure through hole.First by the titanium sheet after processing containing in water glycol electrolytic solution (0.3 wt%NH4F, 2 vol%H2O), under 60V constant voltage and 15 ℃ of constant temperatures, preoxidation is 2 hours, obtains titania nanotube layer, then by supersound process, removes the titanium dioxide layer of formation.By an above-mentioned preoxidation, cut that can floating titanium plate surface, and be formed with regularly arranged pit at titanium plate surface, yet its diameter of pit forming through long period oxidation is excessive, carry out on this basis new oxidation and can form bifurcate holes, thereby be not suitable for guiding new hole to form, therefore need to carry out short period of time preoxidation for the second time.Titanium sheet through a preoxidation is carried out to preoxidation for the second time, and oxidizing condition is identical with a preoxidation, and oxidization time is 10 minutes, and the titanium dioxide layer obtaining, again through ultrasonic removing, is obtained to surface is regular arranges and the titanium sheet of sizeable pit.Then the titanium sheet through secondary preoxidation is carried out to film forming oxidation, oxidizing condition is identical with a preoxidation, and oxidization time is 50 seconds, and after film forming oxidation, titanium plate surface has formed the ultra-thin titanium dioxide nano-pore film of closed bottom.Then titanium sheet is placed on without in water glycol electrolytic solution (0.3 wt%NH4F) at 120V high pressure, under 20 ℃ of constant temperatures, be oxidized 40 seconds.Under impacting with high pressure and corrosion, the bottom of the nano-pore membrane forming in film forming oxidising process is corroded, and separated with titanium substrate, forms bi-pass nano pore membrane.
3, shift
After four step oxidations, titanium plate surface has formed ultra-thin bilateral titanium dioxide nano-pore film, titanium sheet is inserted in water, and this layer of ultra-thin bilateral titanium dioxide nano-pore film will float on the water surface, then with silicon chip, film be picked up, after drying, ultra-thin bilateral titanium dioxide nano-pore film will tightly stick to silicon chip surface, and its surface topography is as Fig. 2 a, shown in 2b, aperture is 35 nm, and thickness is 200 nm.Because film is at electrolytic solution situ through hole, peel off, be not subject to the impact of external force, thereby can obtain complete nano-porous thin film, its size depends on the oxidation area of titanium sheet, as Fig. 2 c, area is prepared in laboratory can reach 1cm2.
3, reaming in hydrofluoric acid
Titanium sheet through four step oxidations is inserted in 0.4 wt% hydrofluoric acid solution, ultra-thin bilateral titanium dioxide nano-pore film will float on hydrofluoric acid solution surface, after reaming in 3 minutes, with silicon chip, film is picked up, the ultra-thin bilateral titanium dioxide nano-pore film obtaining is as Fig. 2 d, shown in 2e, its borehole enlargement to 70 nm.
4, thickness regulation and control
By changing the time of film forming oxidation, can regulate and control the thickness of the bilateral titanium dioxide nano-pore film of final formation.In order to prepare thickness, be less than the film of 100 nm, the time of film forming oxidation only has several seconds conventionally, in the oxidization time of several seconds, entry is also not enough to form, thereby can carry out above-mentioned preoxidation for the second time, only carry out three step oxidations: a preoxidation (60V-2h), film forming oxidation (60V-8s), high pressure through hole (120V-40s).Then by the film forming after three steps oxidations reaming 1 minute in hydrofluoric acid, can obtain thickness is only the ultra-thin bilateral titanium dioxide nano-pore film of 70 nm, and its surface and side pattern are as Fig. 2 f, 2g.
By the time lengthening of the film forming oxidation in above-mentioned four step oxidations, be 30 minutes, can make thicker bi-pass nano pipe film.The side scanned picture of obtained film is as Fig. 2 h, and thickness is about 5 μ m.By the bottom photo (Fig. 2 i) of film, we can see, the bottom of film is all opened, and has formed the nano-tube film of bilateral.
Claims (4)
1. a preparation method for the adjustable ultra-thin bilateral titanium dioxide nano-pore array thin film of aperture and thickness, is characterized in that comprising the following steps:
(1) process the early stage of titanium sheet
High purity titanium sheet is cleaned to 10-15 minute, then 50-60 ℃ of oven dry in air through acetone, dehydrated alcohol, deionized water for ultrasonic successively;
(2) preparation of ultra-thin bilateral titanium dioxide nano-pore film
First by the titanium sheet after processing containing in water glycol electrolytic solution, preoxidation 2-3 hour under 60V constant voltage and 15 ℃ of constant temperatures, obtains titania nanotube layer, then by supersound process, removes the titanium dioxide layer of formation; Then the titanium sheet through a preoxidation is carried out to preoxidation for the second time, oxidizing condition is identical with a preoxidation, oxidization time is 10-15 minute, and the titanium dioxide layer obtaining, again through ultrasonic removing, is obtained to surface is regular arranges and the titanium sheet of sizeable pit; Then the titanium sheet through secondary preoxidation is carried out to film forming oxidation, oxidizing condition is identical with a preoxidation, and oxidization time is 8-60 second, and after film forming oxidation, titanium plate surface has formed the ultra-thin titanium dioxide nano-pore film of closed bottom; Finally titanium sheet is placed on without in water glycol electrolytic solution at 120V high pressure, under 20 ℃ of constant temperatures, be oxidized 30-50 second, titanium plate surface has formed ultra-thin bilateral titanium dioxide nano-pore film;
(3) shift
Titanium sheet after step (2) is processed inserts in water, and ultra-thin bilateral titanium dioxide nano-pore film floating, in the water surface, then picks up film with silicon chip, after drying, obtains ultra-thin bilateral titanium dioxide nano-pore film.
2. the preparation method of the adjustable ultra-thin bilateral titanium dioxide nano-pore array thin film of a kind of aperture according to claim 1 and thickness, it is characterized in that, described in step (2) is the ethylene glycol solution of 0.2～0.4wt% Neutral ammonium fluoride containing water glycol electrolytic solution, and adds the deionized water of 2-3vol%; Described is the ethylene glycol solution of 0.2～0.4wt% Neutral ammonium fluoride without water glycol electrolytic solution.
3. the preparation method of the adjustable ultra-thin bilateral titanium dioxide nano-pore array thin film of a kind of aperture according to claim 1 and thickness, it is characterized in that, titanium sheet after four step oxidations described in step (2) is inserted in 0.3-0.5wt% hydrofluoric acid solution, ultra-thin bilateral titanium dioxide nano-pore film will float on hydrofluoric acid solution surface, by controlling the flotation time, can realize the reaming to ultra-thin bilateral titanium dioxide nano-pore film.
4. the preparation method of the adjustable ultra-thin bilateral titanium dioxide nano-pore array thin film of a kind of aperture according to claim 1 and thickness, it is characterized in that, the change of the film forming oxidization time described in step (2) can realize the regulation and control of ultra-thin bilateral titanium dioxide nano-pore film thickness.
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| CN104328389A (en) * | 2014-10-24 | 2015-02-04 | 中国科学院合肥物质科学研究院 | Preparation method of graphene nano-net |
| CN106925307A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing isopropanol by propylene hydration and application of catalyst |
| CN107723778A (en) * | 2017-09-06 | 2018-02-23 | 太原理工大学 | A kind of method for preparing Ni Ti O richness Ni nano-pores in NiTi alloy surfaces |
| CN110114517A (en) * | 2016-08-17 | 2019-08-09 | 席勒斯材料科学有限公司 | The method of thin functional coating is generated on light-alloy |
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| CN110114517A (en) * | 2016-08-17 | 2019-08-09 | 席勒斯材料科学有限公司 | The method of thin functional coating is generated on light-alloy |
| CN107723778A (en) * | 2017-09-06 | 2018-02-23 | 太原理工大学 | A kind of method for preparing Ni Ti O richness Ni nano-pores in NiTi alloy surfaces |
| CN107723778B (en) * | 2017-09-06 | 2020-01-07 | 太原理工大学 | Method for preparing Ni-Ti-O Ni-rich nano-pores on surface of NiTi alloy |
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