CN103668389B - The preparation method of the ultra-thin bilateral titanium dioxide nano-pore array thin film that aperture and thickness are adjustable - Google Patents
The preparation method of the ultra-thin bilateral titanium dioxide nano-pore array thin film that aperture and thickness are adjustable Download PDFInfo
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Abstract
The invention discloses 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 anodizings can make complete, large-area ultra-thin bilateral titanium dioxide nano-pore film, then by regulation and control oxidization time, the pore-enlargement of hydrofluoric acid, can realize the regulation and control to film thickness and aperture. The present invention adopts twice pre-oxidation, has effectively avoided the formation of surperficial bifurcate holes, ensure that the duct of the nano-porous thin film of preparation is straight, and preparation method is simple, with low 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, macromolecule template etc. But these methods or growth and preparation in certain severe rugged environment, or needing 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, but 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 thickness, the aperture of prepared film are all adjustable, be a kind of well mask material, and preparation method are simple, and with low cost, current laboratory is prepared area and can be reached 1cm2。
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 anodizings, prepare 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 DEG C of oven dry in air through acetone, absolute ethyl alcohol, deionized water for ultrasonic successively;
(2) preparation of ultra-thin bilateral titanium dioxide nano-pore film
First by titanium sheet after treatment containing in water glycol electrolyte, pre-oxidation 2-3 hour under 60V constant voltage and 15 DEG C of constant temperatures, obtains titania nanotube layer, then by ultrasonic processing, removes the titanium dioxide layer of formation; Then the titanium sheet through a pre-oxidation is carried out to pre-oxidation for the second time, oxidizing condition is identical with a pre-oxidation, 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 will carry out film forming oxidation through the titanium sheet of secondary pre-oxidation, oxidizing condition is identical with a pre-oxidation, 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 bottom lock; Finally titanium sheet is placed on without in water glycol electrolyte at 120V high pressure, under 20 DEG C 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 treatment step (2) is inserted 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% ammonium fluoride containing water glycol electrolyte, and adds the deionized water of 2-3vol%; Described is the ethylene glycol solution of 0.2～0.4wt% ammonium fluoride without water glycol electrolyte.
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, can realize the reaming to ultra-thin bilateral titanium dioxide nano-pore film by controlling the flotation time.
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 oxidizing process, obtained ultra-thin bilateral titanium dioxide nano-pore film, because film is at electrolyte situ through hole, peels off, thereby can obtain complete, large-area film.
2, adopt twice pre-oxidation, effectively avoided the formation of surperficial bifurcate holes, ensure 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.
Brief description of the drawings
Fig. 1 is oxidation schematic flow sheet, wherein, (a) pre-oxidation, (b) ultrasonic deoxidation layer, (c) secondary pre-oxidation, (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 (8s) obtains, (h-i) increase the bi-pass nano pipe film that film forming oxidization time (30min) obtains, side view (h) and ground plan are (i).
Detailed description of the invention
1, process the early stage of titanium sheet
High purity titanium sheet (purity is 99.6%, purchased from Baoji Tian Mai Tai Ye Co., Ltd) cleans 10 minutes through acetone, absolute ethyl alcohol, deionized water for ultrasonic successively, then 50 DEG C 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 pre-oxidation, film forming oxidation and high pressure through hole. First by titanium sheet after treatment containing in water glycol electrolyte (0.3wt%NH4F, 2vol%H2O), under 60V constant voltage and 15 DEG C of constant temperatures, pre-oxidation 2 hours, obtains titania nanotube layer, then by ultrasonic processing, removes the titanium dioxide layer of formation. By an above-mentioned pre-oxidation, cut that can floating titanium plate surface, and be formed with regularly arranged pit at titanium plate surface, but 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 time pre-oxidation for the second time. Titanium sheet through a pre-oxidation is carried out to pre-oxidation for the second time, and oxidizing condition is identical with a pre-oxidation, 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 will carry out film forming oxidation through the titanium sheet of secondary pre-oxidation, oxidizing condition is identical with a pre-oxidation, 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 bottom lock. Then titanium sheet is placed on without in water glycol electrolyte (0.3wt%NH4F) at 120V high pressure, under 20 DEG C 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 oxidizing process is corroded, and substrate separates with titanium, 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 35nm, and thickness is 200nm. Because film is at electrolyte 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
To insert in 0.4wt% hydrofluoric acid solution through the titanium sheet of four step oxidations, ultra-thin bilateral titanium dioxide nano-pore film will float on hydrofluoric acid solution surface, after reaming in 3 minutes, film is picked up with silicon chip, the ultra-thin bilateral titanium dioxide nano-pore film obtaining is as Fig. 2 d, shown in 2e, its borehole enlargement is to 70nm.
4, thickness regulation and control
Can regulate and control the thickness of the bilateral titanium dioxide nano-pore film of final formation by changing the time of film forming oxidation. Be less than the film of 100nm in order to prepare thickness, 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 pre-oxidation for the second time, only carry out three step oxidations: a pre-oxidation (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 70nm, and its surface and side pattern be as Fig. 2 f, 2g.
Be 30 minutes by the time lengthening of the film forming oxidation in above-mentioned four step oxidations, 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. (Fig. 2 i), we can see, the bottom of film is all opened, and has formed the nano-tube film of bilateral for bottom photo by film.
Claims (3)
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 DEG C of oven dry in air through acetone, absolute ethyl alcohol, deionized water for ultrasonic successively;
(2) preparation of ultra-thin bilateral titanium dioxide nano-pore film
First by titanium sheet after treatment containing in water glycol electrolyte, pre-oxidation 2-3 hour under 60V constant voltage and 15 DEG C of constant temperatures, obtains titania nanotube layer, then by ultrasonic processing, removes the titanium dioxide layer of formation; Then the titanium sheet through a pre-oxidation is carried out to pre-oxidation for the second time, oxidizing condition is identical with a pre-oxidation, 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 will carry out film forming oxidation through the titanium sheet of secondary pre-oxidation, oxidizing condition is identical with a pre-oxidation, 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 bottom lock; Finally titanium sheet is placed on without in water glycol electrolyte at 120V high pressure, under 20 DEG C of constant temperatures, be oxidized 30-50 second, titanium plate surface has formed ultra-thin bilateral titanium dioxide nano-pore film;
(3) reaming in hydrofluoric acid
Titanium sheet after treatment step (2) is inserted in hydrofluoric acid solution, ultra-thin bilateral titanium dioxide nano-pore film floating is in hydrofluoric acid solution surface, can realize the reaming to ultra-thin bilateral titanic oxide nano tube thin-film by controlling the flotation time, finally obtain the adjustable ultra-thin bilateral titanium dioxide nano-pore array thin film of aperture and thickness.
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% ammonium fluoride containing water glycol electrolyte, and adds the deionized water of 2-3vol%; Described is the ethylene glycol solution of 0.2～0.4wt% ammonium fluoride without water glycol electrolyte.
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, is characterized in that, its concentration of hydrofluoric acid solution described in step (3) is 0.3-0.5wt%.
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| CN104328389B (en) * | 2014-10-24 | 2016-08-03 | 中国科学院合肥物质科学研究院 | The 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 |
| CA3073008A1 (en) * | 2016-08-17 | 2018-02-22 | Cirrus Materials Science Limited | Method to create thin functional coatings on light alloys |
| 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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