CN101619499A - Amorphous titanium oxide nanotube array structure and preparation method thereof - Google Patents
Amorphous titanium oxide nanotube array structure and preparation method thereof Download PDFInfo
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- CN101619499A CN101619499A CN200810012113A CN200810012113A CN101619499A CN 101619499 A CN101619499 A CN 101619499A CN 200810012113 A CN200810012113 A CN 200810012113A CN 200810012113 A CN200810012113 A CN 200810012113A CN 101619499 A CN101619499 A CN 101619499A
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- oxide nanotube
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- oxygen
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 58
- 239000001301 oxygen Substances 0.000 claims abstract description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000035945 sensitivity Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 239000002071 nanotube Substances 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 4
- 230000005518 electrochemistry Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000012916 structural analysis Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to application of a titanium oxide nanotube array structure, in particular to an amorphous titanium oxide nanotube array structure with an excellent low-temperature oxygen sensing characteristic and a preparation method thereof to solve the inert performance of most of metallic oxides including titanium oxide and the like to the oxygen. An n-type semiconductor titanium oxide nanotube array is obtained by adopting an electrochemical anodic oxidation method, which has following the structure and the physical characteristics that: the n-type semiconductor titanium oxide nanotube array has an amorphous structure, the length is between 1.0 and 20.0 microns, the outer diameter is between 40 and 200 microns, the current carrier concentration ranges from 1.0*10<18> to 1.0*10<20>cm<-3>, the measurable oxygen concentration ranges from 200 ppm to 20.0 vol. percent, the working temperature ranges from 50 to 250 DEG C, and the sensibility ranges from 0.1 to 1,000. The amorphous titanium oxide nanotube array is a low-temperature resistance control type oxygen sensor material, has the characteristics of high sensitivity, good linear relation of the resistance changing along with the concentration, wide detection concentration range and easy manufacture of parts, and has important application value.
Description
Technical field:
The present invention relates to the application of titanium oxide nanotube array structure, be specially anonizing and prepare a kind of amorphous titanium oxide nanotube array structure and preparation method thereof, be expected in the novel sensor sensitive material, to use with excellent cryogenic oxygen sensing characteristics.
Background technology:
Along with the development of the modernization of industry and the progress of human society, also more urgent to the application and the specific demand of gas sensor.In recent decades, many occasions all need oxygen concentration is surveyed, and monitor and adjust in real time than gas concentration in control, the fuel cell as the air/fuel of car engine.Up to the present, the oxygen sensor of commercial applications mainly is based on the ZrO of Nernst equation
2Based solid electrolyte system, such transmitter have been successfully applied to the oxygen level of waste gas in ferrous metallurgy and the automotive industry and have surveyed.But still exist some problems: the working temperature height (being not less than 1100K) of (1) solid electrolyte; (2) need reference electrode, be not suitable for measuring oxygen concentration near the reference electrode oxygen partial pressure; (3) device relative complex, maintenance cost is higher.So develop and a kind ofly can work, install simple and easy at low temperatures, and highly sensitive oxygen sensor modulator material is imperative.
The metal oxide semiconductor material of electrons/conduction is to be widely studied as the gas sensing material in recent years, because its resistance is relevant with surface atmosphere, and presenting clear and definite corresponding relation with gas concentration under certain condition, promptly so-called surface resistivity control type sensing is as SnO
2, ZnO, TiO
2, Ga
2O
3, WO
3And In
2O
3Deng, to some specific gas (H
2, NO, NO
2, CO, C
2H
5OH) show tangible susceptibility.These oxide compounds have multiple structure, as film, nanometer rod, nano particle etc., particularly nano tubular structure shows more outstanding advantage aspect gas-sensitive: the nanotube-shaped array of opening ordered arrangement can provide big effective ratio area, many absorption reaction active sites and abundant gas transport passage.But, almost there is not which kind of resistance control type semiconductor material can show higher sensitive property, good restorability and the quantitative variation relation of resistance simultaneously at present for oxygen detection.
Summary of the invention:
For with the metal-oxide semiconductor (MOS) better application in the oxygen sensor aspect, the object of the present invention is to provide a kind of titania nanotube array and constitutional features and suitable preparation method with excellent cryogenic oxygen sensing characteristics, proposed to use the new approaches of amorphous titanium oxide nanotube array structure, solution comprises the inertia performance of most metal oxides of titanium oxide to oxygen sensor.
Technical scheme of the present invention is:
The present invention is a kind of amorphous titanium oxide nanotube array structure with excellent cryogenic oxygen sensing characteristics, prepared n N-type semiconductorN titania nanotube array by the electrochemical anodic oxidation method, and make its surface cleaning and keep unformed microtexture by aftertreatment, the size characteristic that has possessed higher carrier concentration and be fit to, the structure and the physical features of amorphous titanium oxide nanotube array are specially: titanium oxide is an amorphous structure in the nanotube, its nanotube external diameter is 40-200nm, thickness of pipe 5-50nm, nano-tube array thickness (nanotube length) is 1.0-20.0 μ m, and current carrier (electronics) concentration range is 1.0 * 10
18-1.0 * 10
20Cm
-3(be generally 5.0 * 10
18-8.0 * 10
19Cm
-3), this material has splendid detection oxygen scope width (200ppm-20.0vol.%), detection sensitivity height (can reach 1000 under higher oxygen concentration, sensitivity drift scope 0.1-1000), the characteristics of working temperature low (50-250 ℃).
Preparation titania nanotube array method of the present invention is an electrochemistry anodic oxidation, and processing parameter is as follows:
Negative electrode is the inert metal platinized platinum; Anode is that purity 99.5wt% is above, the smooth surface titanium sheet of thickness 10-500 μ m; Electrolytic solution is that concentration is 0.5-1.5M (NH
4)
2SO
4, 0.3-0.8wt.%NH
4The aqueous solution of F; Perhaps, concentration is 0.2-0.8wt.%NH
4F, 1.0-3.0vol.%H
2The ethylene glycol solution of O; Utilize external dc power supply, apply the volts DS of 10-80V, temperature is 15-25 ℃, and oxidization time is 1-24h, is preferably 5-24 hour.Among the present invention, electrolytic solution is preferably 0.9-1.1M (NH
4)
2SO
4, 0.4-0.6wt.%NH
4The aqueous solution of F; Perhaps, 0.3-0.6wt.%NH
4F, 1.5-2.5vol.%H
2The ethylene glycol solution of O.Among the present invention, the volts DS scope that applies is preferably 18-22V or 30-50V respectively, and temperature is preferably 18-20 ℃, and oxidization time is preferably 2-3h or 9-12h respectively.The last handling process of mentioning among the present invention is conventional ultrasonic clean technology.Sample adopts ethanol as solvent finishing anodic oxidation preparation back supersound process, and the sonic oscillation time is preferably 3-4min; Dry the armorphous nano pipe array that can obtain surface cleaning.
The titania nanotube array that the present invention obtains is a undefined structure, so-called unformed (non-crystalline state), i.e. the arrangement aperiodicity of inner atom of material or molecule, unordered, the short range order of long-range, macroscopic property has homogeneity, the physical properties isotropy.Resulting titanium oxide nanotubes is orderly is grown on the titanium matrix and closely links to each other with it, its feature structure is: titanium oxide is an amorphous structure, the nanotube external diameter is 40-200nm, and thickness of pipe 5-50nm, nano-tube array thickness (nanotube length) are 1.0-20.0 μ m.Prepared titanium oxide is the n N-type semiconductorN, and current carrier (electronics) concentration range in the amorphous titanium oxide nanotube is 1.0 * 10
18-1.0 * 10
20Cm
-3, much larger than titanium oxide nanotubes had with crystalline state (anatase octahedrite) after its 450 degree thermal treatment 1.0 * 10
17-1.0 * 10
18Cm
-3Big carrier concentration has bigger change in concentration with oxygen generation absorption reaction the time, thereby obtain higher sensitivity, so the titanium oxide of this undefined structure significantly improves than the crystal form structure for preparing down in same anodic oxidation condition the sensitive property of oxygen at low temperatures, and than other oxide compound such as Ga
2O
3, SrTiO
3Oxygen sensitivity more excellent.In the oxygen susceptibility is measured, the titanium oxide of this undefined structure shows good restorability, higher sensitivity and good resistance-concentration linear corresponding relation, good to oxygen response under 50-250 ℃, it is interval for 200ppm-20.0% to measure oxygen concentration, is 0.1-1000 to its sensitivity drift scope of different oxygen concentrations.Therefore, be expected to as the widespread use in addition of portable surface resistivity control type semiconductor material in the oxygen sensor field.
The invention has the beneficial effects as follows:
The invention provides the application of amorphous titanium oxide nanotube array structure aspect oxygen sensor, be characterized in having splendid detection oxygen wide ranges, detection sensitivity height, linear relationship are good, the restorability excellence, the characteristics that working temperature is low, simultaneously this material is made the gas sensitization device, it is simple to have manufacture craft, advantages such as applied range.
Description of drawings:
Fig. 1 is the unformed TiO of the embodiment of the invention 1 preparation
2The nano-tube array structure electron micrograph.(a) be scanning electron microscope full face and sectional view; (b) be transmission electron microscope photo and diffracting spectrum.
Fig. 2 is the Detitanium-ore-type TiO of comparative example 1 preparation of the present invention
2The nano-tube array electron micrograph.(a) be the scanning electron microscope full face; (b) be transmission electron microscope photo and diffracting spectrum.
Fig. 3 is TiO in the embodiment of the invention
2Nano-tube array structure XRD structural analysis figure.(a) be the unformed TiO of embodiment 1 preparation
2The nano-tube array diffractogram; (b) be the Detitanium-ore-type TiO of comparative example 1 preparation
2The nano-tube array diffractogram.
Fig. 4 is the TiO of embodiment of the invention preparation
2The Mott-Schottky test curve of nano-tube array structure can calculate carrier concentration from linear portion.(a) be the prepared unformed TiO of embodiment 1
2The nano-tube array test curve; (b) be the Detitanium-ore-type TiO of comparative example 1 preparation
2The nano-tube array test curve.
Fig. 5 is the unformed TiO of the embodiment of the invention 1 preparation
2Resistance and the oxygen concentration variation relation figure of nano-tube array when testing the oxygen sensor performance down for 100 ℃.(a) and (b), (c) correspond respectively to the oxygen concentration variation range of 200-1980ppm, 6.1 ‰-9.5 ‰, 1.8%-20.0%.
Fig. 6 is the unformed TiO of the embodiment of the invention 2 preparations
2Nano-tube array is tested oxygen sensor performance response figure down at 50 ℃.(a) and (b) are respectively resistance and oxygen concentration variation relation figure and sensitivity and oxygen concentration change curve.
Fig. 7 is the unformed TiO of the embodiment of the invention 3 preparations
2Nano-tube array is tested oxygen sensor performance corresponding figures down at 100 ℃.(a) and (b) are respectively resistance and oxygen concentration variation relation figure and sensitivity and oxygen concentration change curve.
Fig. 8 is the TiO of embodiment of the invention preparation
2Nano-tube array is sensitivity and oxygen concentration relation curve when testing the oxygen sensor performance down for 100 ℃.(a) be the unformed TiO of embodiment 1 preparation
2The nano-tube array sensitivity curve; (b) be the Detitanium-ore-type TiO of comparative example 1 preparation
2The nano-tube array sensitivity curve.
Embodiment:
Be described in further detail the present invention below by embodiment and accompanying drawing.
Embodiment 1
In the anodic oxidation reactions, negative electrode is 30 * 40 * 1mm inert metal platinized platinum, and the anode substrate material is that purity is the smooth surface titanium sheet that 99.5wt% is above, be of a size of 10 * 30 * 0.25mm; Electrolytic solution is that concentration is 1.0M (NH
4)
2SO
4, 0.5wt.%NH
4The aqueous solution of F; External dc power supply applies 20V voltage, and experimental temperature is 18 ℃, and oxidization time is 2h.Reaction finishes the back and takes out titanium anode substrate, places dehydrated alcohol sonic oscillation 2min, and taking-up is dried, and promptly obtains amorphous titanium oxide nanotube array structure.Fig. 1 is the scanning electronic microscope and the transmission electron microscope photo of nano surface pipe array film.As can be seen from the figure TiO
2The hollow of nanotube, ordered arrangement structure, the external diameter of pipe are about 140nm, and the about 20nm of wall thickness, pipe range are the about 2.3 μ m of nano-tube film thickness; And diffraction pattern is the amorphous ring, illustrates that it is unformed (amorphous) attitude.Among the present invention, sample adopts ethanol as solvent finishing anodic oxidation preparation back supersound process, and the sonic oscillation time is 3-4min, dries the armorphous nano pipe array that can obtain surface cleaning.
(a) is the titanium substrate XRD structural analysis curve of growing nano-tube array in the present embodiment among Fig. 3, the characteristic peak of any titanium oxide do not occur, can determine prepared TiO
2Nanotube is a unformed shape.(a) is the M-S curve of the amorphous titanium oxide nanotube structure that makes in the present embodiment among Fig. 4, and therefrom can calculate carrier concentration is 1.149 * 10
19Cm
-3
To the unformed TiO for preparing in the present embodiment
2Nano-tube array carries out the oxygen sensitive performance test under 100 ℃.As shown in Figure 5, this sample shows the excellent sensitivity energy in the 200ppm-20.0vol.% oxygen concentration scope of test, and the restorability excellence of resistance; Through sensitivity calculations, as shown in Figure 8, curve (a) is the sensitivity of this sample and the relation of oxygen concentration, shows good linear relationship, and this just lays the foundation for the quantitative detection oxygen concentration.
Embodiment 2
Anodic oxidation prepares the method for titania nanotube array and last handling process with embodiment 1, is with the difference of embodiment 1:
To the unformed TiO for preparing in the present embodiment
2Nano-tube array carries out the oxygen sensitive performance test under 50 ℃.Shown in Fig. 6 (a), this sample shows the excellent sensitivity energy in the 1.2%-4.0vol.% oxygen concentration scope of test, and the restorability excellence of resistance; Through sensitivity calculations, as shown in Figure 6, curve (b) is the sensitivity of this sample and the relation of oxygen concentration, shows good linear relationship, and this just lays the foundation for the quantitative detection oxygen concentration.
In the anodic oxidation reactions, electrode materials is with embodiment 1, is with the difference of embodiment 1:
The electrolytic solution that present embodiment adopted is 0.5wt.%NH
4F, 2.0vol.%H
2The ethylene glycol solution of O, external dc power supply apply 40V voltage, and experimental temperature is 18 ℃, and oxidization time is 11h.Reaction finishes the back and takes out titanium anode substrate, places dehydrated alcohol sonic oscillation 2min, and taking-up is dried, and promptly obtains amorphous titanium oxide nanotube array structure.
To the unformed TiO for preparing in the present embodiment
2Nano-tube array carries out the oxygen sensitive performance test under 100 ℃.Shown in Fig. 7 (a), this sample shows the excellent sensitivity energy in the 200ppm-4.0vol.% oxygen concentration scope of test, and the restorability excellence of resistance; Through sensitivity calculations, as shown in Figure 7, curve (b) is the sensitivity of this sample and the relation of oxygen concentration, shows the better linearity relation, and this just lays the foundation for the quantitative detection oxygen concentration.
Embodiment result shows, the present invention is the amorphous titanium oxide nanotube array structure with excellent cryogenic oxygen sensing characteristics, the n N-type semiconductorN titania nanotube array that adopts electrochemistry anodic oxidation to obtain, the structure and the physical features of this amorphous titanium oxide nanotube array are: amorphous structure, length 1.0-20.0 micron; External diameter 40-200 nanometer; Carrier concentration scope 1.0 * 10
18-1.0 * 10
20Cm
-3Can measure the interval 200ppm-20.0vol.% of oxygen concentration; Operating temperature range 50-250 ℃; Sensitivity drift scope 0.1-1000.Amorphous titanium oxide nanotube array provided by the invention, it is a kind of new type low temperature resistance control type oxygen sensor modulator material, be characterized in highly sensitive, resistance is good with the change in concentration linear relationship, the detecting concentration scope is wide, preparation forms device easily, thereby have important use and be worth.
Comparative example 1
Anodic oxidation prepares the method for titania nanotube array with embodiment 1, is with the difference of embodiment 1:
Reaction finishes the back and takes out titanium anode substrate, places dehydrated alcohol sonic oscillation 2min, and taking-up is dried.Heat-treat after drying, thermal treatment in this comparative example is routine techniques: but the sample that embodiment 1 is made places heated quarty tube, temperature rise rate with 5 ℃/min under air atmosphere is heated to 450 ℃, insulation 2h, take out behind the furnace cooling, promptly obtain the titania nanotube array of crystalline state.Figure 2 shows that the scanning electronic microscope and the transmission electron microscope photo of the film of Nano tube array that makes in this comparative example.As can be seen from the figure TiO
2The hollow of nanotube, ordered arrangement structure and embodiment 1 do not change, and the external diameter of pipe, wall thickness do not change yet; Difference is that diffraction pattern is the polycrystalline diffraction spot, and the crystallization of this sample is described.
(b) is the titanium substrate XRD structural analysis curve of growing nano-tube array in this comparative example among Fig. 3, except the peak of titanium matrix, near the characteristic diffraction peak that anatase octahedrite (101) also 25.2 °, occurred, and near the rutile (110) of minute quantity 27.0 °, interpret sample is by unformed the changing into based on anatase octahedrite crystal form mutually among the embodiment 1.(b) is the M-S curve of the prepared crystalline state titanium oxide nanotubes of this comparative example among Fig. 4, and therefrom can calculate carrier concentration is 4.022 * 10
17Cm
-3
To the crystal form TiO for preparing in this comparative example
2Nano-tube array carries out the oxygen sensitive performance test under 100 ℃, also show the restorability of resistance.Through sensitivity calculations, as shown in Figure 8, curve (b) is the sensitivity of this sample and the relation of oxygen concentration, and sensitivity is than the unformed TiO of embodiment 1
2Nano-tube array obviously reduces, and the two does not have linear relationship.Therefore, be not suitable for the quantitative measurment concentration of oxygen.
Claims (5)
1, a kind of amorphous titanium oxide nanotube array structure, it is characterized in that, prepare n N-type semiconductorN titania nanotube array by the electrochemical anodic oxidation method, the structure and the physical features of amorphous titanium oxide nanotube array are: titanium oxide is an amorphous structure in the nanotube, its nanotube external diameter is 40-200nm, thickness of pipe 5-50nm, nano-tube array length is 1.0-20.0 μ m, the carrier concentration scope is 1.0 * 10
18-1.0 * 10
20Cm
-3
According to the described amorphous titanium oxide nanotube array structure of claim 1, it is characterized in that 2, this material tests oxygen scope is 200ppm-20.0vol.%, detection sensitivity variation range 0.1-1000, working temperature 50-250 ℃.
According to the described amorphous titanium oxide nanotube array structure preparation method of claim 1, it is characterized in that 3, the preparation titania nanotube array method that is adopted is an electrochemistry anodic oxidation, processing parameter is as follows:
Negative electrode is the inert metal platinized platinum; Anode is that purity 99.5wt% is above, the smooth surface titanium sheet of thickness 10-500 μ m; Electrolytic solution is that concentration is 0.5-1.5M (NH
4)
2SO
4, 0.3-0.8wt.%NH
4The aqueous solution of F; Perhaps, electrolytic solution is that concentration is 0.2-0.8wt.%NH
4F, 1.0-3.0vol.%H
2The ethylene glycol solution of O; Utilize external dc power supply, apply the volts DS of 10-80V, temperature is 15-25 ℃, and oxidization time is 1-24h.
According to the preparation method of the described amorphous titanium oxide nanotube array structure of claim 3, it is characterized in that 4, electrolytic solution is preferably 0.9-1.1M (NH
4)
2SO
4, 0.4-0.6wt.%NH
4The aqueous solution of F; Perhaps, 0.3-0.6wt.%NH
4F, 1.5-2.5vol.%H
2The ethylene glycol solution of O.
5, according to the preparation method of the described amorphous titanium oxide nanotube array structure of claim 3, it is characterized in that, the volts DS scope that applies is preferably 18-22V or 30-50V respectively, and temperature is preferably 18-20 ℃, and oxidization time is preferably 2-3h or 9-12h respectively.
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ID=41512905
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102778479A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院微电子研究所 | Integratable amorphous metal oxide semiconductor gas sensor |
| CN102778481A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院微电子研究所 | Induction gate type amorphous metal oxide TFT gas sensor |
-
2008
- 2008-07-02 CN CN200810012113A patent/CN101619499A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102778479A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院微电子研究所 | Integratable amorphous metal oxide semiconductor gas sensor |
| CN102778481A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院微电子研究所 | Induction gate type amorphous metal oxide TFT gas sensor |
| CN102778479B (en) * | 2011-05-09 | 2014-03-19 | 中国科学院微电子研究所 | Integratable amorphous metal oxide semiconductor gas sensor |
| CN102778481B (en) * | 2011-05-09 | 2014-06-11 | 中国科学院微电子研究所 | Induction gate type amorphous metal oxide TFT gas sensor |
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