CN103060880A - Preparation method and application of hydrogenated titanium dioxide nanotube array film - Google Patents
Preparation method and application of hydrogenated titanium dioxide nanotube array film Download PDFInfo
- Publication number
- CN103060880A CN103060880A CN2013100059528A CN201310005952A CN103060880A CN 103060880 A CN103060880 A CN 103060880A CN 2013100059528 A CN2013100059528 A CN 2013100059528A CN 201310005952 A CN201310005952 A CN 201310005952A CN 103060880 A CN103060880 A CN 103060880A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- nano tube
- tube array
- film
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a preparation method and an application of a hydrogenated titanium dioxide nanotube array film. The preparation method comprises the following steps: cleaning an industrial titanium sheet, and chemically polishing; oxidizing at room temperature through a constant-voltage direct-current anodizing method; and carrying out heat treatment in a vacuum environment in a hydrogen-containing atmosphere, stopping the let-in of hydrogen, and naturally cooling to room temperature in an argon atmosphere to prepare the hydrogenated titanium dioxide nanotube array film. The hydrogenated titanium dioxide nanotube array film can be directly used as a field electron emission cold cathode. The preparation method enables the hydrogenated titanium dioxide nanotube array film having the characteristics of low turn-on field, large emission current density, good field emission stability, high repeatability and the like and directly used as the field electron emission to be prepared; and the preparation method can be used for the industrial production, enables the cold cathode field emitters having low prices to be prepared, and can be well applied in the field electron emission display cathode material field.
Description
Technical field
The invention belongs to filed emission cathode material manufacturing technology field, relate to a kind of preparation method of field emission body, be specifically related to a kind of preparation method of hydrogenation film of Nano tube array of titanium dioxide; The invention still further relates to a kind of with the application of this film of Nano tube array as filed emission cathode material.
Background technology
Field Emission Display has the advantages such as reduce power consumption, high brightness, wide visual angle, time of response weak point, good stability, life-span length, full-color demonstration, is a kind of New flat panel display spare with broad prospect of application.And Field Emission Display will obtain widespread use, and the filed emission cathode material of excellent performance is one of technical support of most critical.Filed emission cathode material commonly used has carbon nanotube, metallic substance (Mo, W, Co etc.), nitride material (TiN, GaN, AlN etc.) and wide band gap semiconducter oxide material (CuO, SnO at present
2, ZnO, In
2O
3, TiO
2, WO
3Deng).Carbon nanotube is considered to first-selected filed emission cathode material owing to have low unlatching electric field, large emission, good mechanical property and high specific conductivity.Yet, a little less than the large and resistance of oxidation of the contact resistance between carbon nanotube and the substrate, so that field emission stability is relatively poor, limited its application in Field Emission Display.The anodic oxidation film of Nano tube array of titanium dioxide itself is a kind of oxide material, has stronger resistance of oxidation, and and substrate between contact resistance little, have excellent field emission stability; On the other hand, also has unique performance, such as easy, the good structural controllability of low work function (4.3～4.5 eV), larger length-to-diameter ratio, preparation technology, cheap etc.Therefore, film of Nano tube array of titanium dioxide is considered to a kind of very promising filed emission cathode material.
Research finds that pure titinium dioxide film of Nano tube array electron affinity is higher, greater band gap (3.1～3.2 eV), and therefore, it is higher to open electric field, and current density is little.By optimizing the modes such as appearance structure and element doping (Fe, N, C), its field emission performance obviously improves, but still can not satisfy the requirement of production application.Patent " a kind of growth method of semi-metal film of Nano tube array of titanium dioxide and application thereof " (patent No. ZL201110084992.7, publication number CN102162116, an open day 2011.08.24) a kind of film of Nano tube array of titanium dioxide of semi-metal characteristic is disclosed, this array films has the characteristics such as favorable repeatability, field emission stability is excellent, preparation technology is easy, almost satisfies all requirements as field emission body.But there is following technical difficulty in actual applications in this growth method: at first, preparation temperature is relatively high, and is harsh to the requirement of equipment; Secondly, the acetylene of cracking can pollute production unit; At last, its unlatching electric field is still higher.These technical difficulties can limit its application in display device.Therefore, research and develop a kind of easy, with low cost, nonpolluting method, for the preparation of high performance film of Nano tube array of titanium dioxide field emission body, not only have scientific value, have more important realistic meaning.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of hydrogenation film of Nano tube array of titanium dioxide, the field electron emission cold-cathode material that can make excellent property, have practical value.
Another object of the present invention provides a kind of above-mentioned hydrogenation film of Nano tube array of titanium dioxide in the application of field-transmitting cathode.
For achieving the above object, the technical solution adopted in the present invention is: a kind of preparation method of hydrogenation film of Nano tube array of titanium dioxide, can make a kind of performance film of Nano tube array of titanium dioxide better, that can be used for field emission body, this preparation method specifically carries out according to the following steps:
Step 1: industrial titanium sheet is cleaned in acetone, dehydrated alcohol and deionized water successively;
Step 2: be titanium sheet after the mixed chemical solution polished and cleaned that forms of the dense hydrofluoric acid of 1 ︰ 4～8 and concentrated hydrochloric acid with volume ratio;
Step 3: adopt constant voltage dc anodizing method, the titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after chemical rightenning: graphite is negative electrode, and the titanium sheet is anode, and the distance of two interpolars remains on 1～5 cm; Electrolytic solution is the ethylene glycol solution that contains 0.20～0.50 wt.% Neutral ammonium fluoride and 0.01～0.05 wt.% hydrofluoric acid, and oxidation voltage is 30～60 V, and oxidization time is 5～600 min, and use magnetic stirrer electrolytic solution, after oxidation is finished, deionized water rinsing titanium sheet, nitrogen dries up;
Step 4: the titanium sheet after step 3 oxidation is put into high temperature resistant reactor, and place in the tube furnace, the tube furnace reaction vessel is evacuated to 1～200 Pa, pass into the mixed gas that is formed by argon gas and hydrogen that flow velocity is 15～18 mark condition milliliter per minutes to the tube furnace reaction vessel, reaction vessel is warming up to 400～550 ℃, and insulation 3～6 h stop to pass into hydrogen, make reaction vessel under argon gas atmosphere, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide.
Another technical scheme of the present invention is: a kind of application of above-mentioned hydrogenation film of Nano tube array of titanium dioxide, with it directly as the Field Electron Emission cold cathode.
Preparation method of the present invention adopts constant voltage dc anodizing method at the industrial pure titanium plate surface unbodied film of Nano tube array of titanium dioxide of growing, and processes being converted into the hydrogenation film of Nano tube array of titanium dioxide by follow-up hydrogenation again.This film of Nano tube array has opens that electric field is low, emission is large, field emission stability good and repeatable high, shows the field emission performance of excellence, and is combined firmly with the titanium substrate, can be directly as field emission cold-cathode.This preparation method can be used for suitability for industrialized production simultaneously, can make cheap cold-cathode field radiator, aspect the Field Electron Emission demonstration cathode material preferably application prospect is being arranged.
Description of drawings
Fig. 1 is the SEM surface topography map of hydrogenation film of Nano tube array of titanium dioxide in the embodiment of the invention 1.
Fig. 2 is the SEM sectional drawing of SEM surface topography map shown in Figure 1.
Fig. 3 is the SEM surface topography map of the semi-metal film of Nano tube array of titanium dioxide that makes of existing method.
Fig. 4 is the XRD spectrum of hydrogenation film of Nano tube array of titanium dioxide in the embodiment of the invention 2.
Fig. 5 and Fig. 6 are the comparison diagrams of the Raman spectral curve of the Raman spectral curve of the hydrogenation film of Nano tube array of titanium dioxide that makes of the embodiment of the invention 2 and the semi-metal film of Nano tube array of titanium dioxide that existing method makes.
Fig. 7 is the O 1s XPS scanning spectrogram of semi-metal film of Nano tube array of titanium dioxide.
Fig. 8 is the Ti 2p XPS scanning spectrogram of semi-metal film of Nano tube array of titanium dioxide.
Fig. 9 is hydrogenation film of Nano tube array of titanium dioxide and adopt the electric current of the semi-metal film of Nano tube array of titanium dioxide that existing method makes with relation curve (I-V curve) figure of voltage change in the embodiment of the invention 3.
Figure 10 is current density and the strength of electric field rational curve of hydrogenation film of Nano tube array of titanium dioxide in the embodiment of the invention 4.
Figure 11 is the F-N rational curve of hydrogenation film of Nano tube array of titanium dioxide in the embodiment of the invention 4.
Figure 12 is the time dependent rational curve of the current density of hydrogenation film of Nano tube array of titanium dioxide in the embodiment of the invention 5, i.e. its field emission stability curve.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
At present, the new filed emission cathode material of research and development remains the key problem that field emission display is used widely.Adopt constant voltage dc anodizing method at the industrial pure titanium plate surface unbodied film of Nano tube array of titanium dioxide of growing, thermal treatment is translated into the film of Nano tube array of titanium dioxide with semi-metal characteristic in 700 ℃～850 ℃ acetylene atmosphere again.Although this film of Nano tube array has the characteristics such as favorable repeatability, field emission stability is excellent, preparation technology is easy, it exists in actual applications: 1) preparation temperature is relatively high, and is harsh to the requirement of equipment; 2) acetylene of cracking can cause the pollution of production unit; 3) compare with carbon nanotube, it is still higher that it opens electric field.These technical difficulties can limit its application in display device.In order to overcome problems of the prior art, the invention provides a kind of preparation method of hydrogenation film of Nano tube array of titanium dioxide, can make a kind of performance film of Nano tube array of titanium dioxide better, that be used for field emission body by this preparation method.This preparation method specifically carries out according to the following steps:
Step 1: get purity and be 99.9% industrial titanium sheet, successively at acetone, dehydrated alcohol and deionized water ultrasonic cleaning 3～15 min respectively;
Step 2: be titanium sheet 10～180 s after the mixed chemical solution polished and cleaned that forms of the dense hydrofluoric acid (concentration 〉=40%) of 1 ︰ 4～8 and concentrated hydrochloric acid (concentration is 36%～38%) with volume ratio;
Step 3: adopt constant voltage dc anodizing method, the titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after chemical rightenning: graphite is negative electrode, and the titanium sheet is anode, and the distance of two interpolars remains on 1～5 cm; Electrolytic solution is the ethylene glycol solution (analytical pure) that contains 0.20～0.50 wt.% Neutral ammonium fluoride and 0.01～0.05 wt.% hydrofluoric acid, oxidation voltage is 30～60 V, oxidization time is 5～600 min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, taking-up titanium sheet was used deionized water rinsing after oxidation was finished, and nitrogen dries up;
Form the unbodied film of Nano tube array of titanium dioxide of one deck by above-mentioned three steps at titanium plate surface, this unbodied film of Nano tube array of titanium dioxide work function is higher, electron transport ability is undesirable, also needs by following step this array films to be converted into the hydrogenation film of Nano tube array of titanium dioxide.
Step 4: the titanium sheet after step 3 oxidation is put into the high temperature resistant reactors such as quartz boat (or pottery), and place in the tube furnace, the tube furnace reaction vessel is evacuated to 1～200 Pa, passing into flow velocity to the tube furnace reaction vessel is 15～18 mark condition milliliter per minute (SCCM) mixed gass, and this mixed gas is that argon gas and the hydrogen of 10 ︰ 5～8 forms by throughput ratio; The reaction vessel temperature is risen to 400 ℃～550 ℃ from room temperature, and after being incubated 3～6 h, stop to pass into hydrogen, make reaction vessel under argon gas atmosphere, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide.
The hydrogenation film of Nano tube array of titanium dioxide that makes is placed on the emission analysis instrument plummer, and as the Field Electron Emission cold cathode, control cathode is 30～200 μ m to the distance of anode, when the system vacuum degree is better than 1.2 * 10
-4During Pa, the variation range of anode voltage is 0～3500 V, recording voltage and current value.The unlatching electric field of the hydrogenation film of Nano tube array of titanium dioxide that employing the inventive method makes is 1.75 V/ μ m, and has good repeatability and field emission stability.
Growth method preparation technology of the present invention is simple, cost is low, be convenient to suitability for industrialized production, it is relatively high to have overcome the preparation temperature that exists in the semi-metal film of Nano tube array of titanium dioxide preparation process, the acetylene of equipment requirements harshness and cracking is polluted easily the problem of production unit.Owing in hydrogen atmosphere is arranged, in the structure of the hydrogenation film of Nano tube array of titanium dioxide of thermal treatment preparation a large amount of oxygen rooms is arranged, these oxygen rooms can form oxygen room energy level by 0.75～1.18 eV under the titanium dioxide conduction band, thereby raising fermi level, so that the work function of hydrogenation film of Nano tube array of titanium dioxide significantly reduces, make it have lower unlatching electric field and larger current density.Therefore, hydrogenation film of Nano tube array of titanium dioxide field emission body has more wide application prospect.The hydrogenation film of Nano tube array of titanium dioxide is nontoxic, chemistry and good thermal stability, have lower work function, good conductivity, large length-to-diameter ratio, good mechanical property, good structural controllability, and be combined the performance that firmly waits uniqueness with the titanium substrate, almost possessed desired all character of filed emission cathode material, it is a kind of eco-friendly field emission body, this not only has important scientific meaning, and has more practical value.
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15 min in acetone, dehydrated alcohol and deionized water; Be that the dense hydrofluoric acid (concentration 〉=40%) of 1:8 and concentration are titanium sheet 180 s after the mixed chemical solution polished and cleaned that forms of 36% concentrated hydrochloric acid with volume ratio; Adopt the titanium plate surface growth film of Nano tube array of titanium dioxide after polishing under the constant voltage dc anodizing method room temperature: graphite is negative electrode, the titanium sheet is anode, the distance of two interpolars remains on 3 cm, electrolytic solution is the ethylene glycol solution (analytical pure) that contains 0.30 wt.% Neutral ammonium fluoride and 0.03 wt.% hydrofluoric acid, oxidation voltage is 40 V, oxidization time is 500 min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, taking-up titanium sheet after oxidation is finished, use deionized water rinsing, nitrogen dries up; Titanium sheet after the oxidation is put into the quartz boat reactor, and place in the tube furnace, the tube furnace reaction vessel is evacuated to 100 Pa, then pass into the mixed gas that flow velocity is 18 SCCM to the tube furnace reaction vessel, this mixed gas is that argon gas and the hydrogen of 10 ︰ 8 forms by throughput ratio, and the reaction vessel temperature is risen to 450 ℃ from room temperature, after being incubated 5 h, stop to pass into hydrogen, make reaction vessel under argon gas atmosphere, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide; The hydrogenation film of Nano tube array of titanium dioxide for preparing is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 200 μ m to the distance of anode, and system is evacuated to 1.2 * 10
-4Then Pa increases anode voltage (0～3500 V), recording voltage and current value slowly.
Fig. 1 and Fig. 2 are respectively SEM surface topography map and the SEM sectional drawing of the prepared sample of present embodiment; As can be seen from the figure, the top layer of the hydrogenation film of Nano tube array of titanium dioxide that makes is the porous pattern of similar anodic oxidation aluminium formwork, and lower floor is Nanotube Array, and pipe density is 2.2 * 10
9Cm
-2, the average tube internal diameter is about 56.6 nm, and the average tube wall thickness is about 10.2 nm, and length is about 4 μ m.The appearance structure of hydrogenation film of Nano tube array of titanium dioxide is similar to the appearance structure of pure film of Nano tube array of titanium dioxide, has kept larger length-to-diameter ratio, demonstrates good structural controllability.
Comparative Examples 1
By patent " a kind of growth method of semi-metal film of Nano tube array of titanium dioxide and application thereof " (patent No. ZL201110084992.7, publication number CN102162116, open day 2011.08.24) disclosed method is at industrial pure titanium sheet growth semi-metal film of Nano tube array of titanium dioxide.Be specially: industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively; To get respectively the dense hydrofluoric acid of concentration 〉=40% and concentration be 36% concentrated hydrochloric acid to 1 ︰ 8 by volume, mixes forming polishing fluid, and the pure titanium sheet that cleans up is put into this polishing fluid chemical rightenning 180 s; Adopt the pure titanium sheet of constant voltage dc anodizing method after the polishing film of Nano tube array of titanium dioxide of growing: take graphite as negative electrode, this pure titanium sheet is anode, put into the analytical pure ethylene glycol solution that contains 0.30wt.% Neutral ammonium fluoride and 0.03wt.% hydrofluoric acid under the room temperature pure titanium sheet is carried out oxidation, distance between this negative electrode and the anode is 3 cm, oxidation voltage is 40 V, oxidization time is 40 min, adopts magnetic stirring apparatus to stir in the oxidising process, and is even with guarantee system temperature and electrolytic solution; Taking-up titanium sheet was used deionized water rinsing after oxidation was finished, after nitrogen dries up; Place the analytical pure ethylene glycol solution to soak 12 h; Then put into quartz boat, and place in the middle part of the silica tube of tube furnace, sealed silica envelope, simultaneously silica tube is evacuated to 100 Pa, and with the heat-up rate of 5 ℃/min the temperature in the silica tube is risen to 750 ℃, passing into insulation 90 min under the condition of mixed atmosphere that flow velocity is 10 SCCM, this mixed atmosphere is that argon gas and the acetylene of 9 ︰ 3 forms by throughput ratio, stop afterwards passing into acetylene, make silica tube under argon gas atmosphere, naturally cool to room temperature, make the semi-metal film of Nano tube array of titanium dioxide.
The semi-metal film of Nano tube array of titanium dioxide SEM surface topography map that makes, as shown in Figure 3, can find out, except having the similar appearance structure to hydrogenation film of Nano tube array of titanium dioxide that embodiment 1 makes, its surfaceness increases to some extent, but it still keeps larger length-to-diameter ratio.In a word, with regard to appearance structure, hydrogenation film of Nano tube array of titanium dioxide and semi-metal film of Nano tube array of titanium dioxide have all shown larger length-to-diameter ratio, and this will be conducive to increase the local field intensity of emission tip, strengthen the field emission performance of radiator.
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15 min in acetone, dehydrated alcohol and deionized water; Be that the dense hydrofluoric acid (concentration 〉=40%) of 1 ︰ 6 and concentration are titanium sheet 150 s after the mixed chemical solution polished and cleaned that forms of 38% concentrated hydrochloric acid with volume ratio; Adopt constant voltage dc anodizing method, titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after polishing: graphite is negative electrode, the titanium sheet is anode, the distance of two interpolars remains on 2 cm, electrolytic solution is the ethylene glycol solution (analytical pure) that contains 0.20 wt.% Neutral ammonium fluoride and 0.05 wt.% hydrofluoric acid, oxidation voltage is 50 V, oxidization time is 600 min, use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, taking-up titanium sheet was used deionized water rinsing after oxidation was finished, and nitrogen dries up; The tube furnace reaction vessel is evacuated to 50 Pa, then pass into the mixed gas that flow velocity is 16 SCCM to the tube furnace reaction vessel, this mixed gas is that argon gas and the hydrogen of 10 ︰ 6 forms by throughput ratio, the reaction vessel temperature is risen to 480 ℃ from room temperature, after being incubated 4 h, stop to pass into hydrogen, make reaction vessel under argon gas atmosphere, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide; The hydrogenation film of Nano tube array of titanium dioxide of preparation is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 100 μ m to the distance of anode, and system is evacuated to 1.2 * 10
-4Then Pa increases anode voltage (0～3500 V), recording voltage and current value slowly.
Fig. 4 is the XRD spectrum of the sample of present embodiment preparation, can find out, except diffraction peak with titanium substrate (2 θ=38.08 °, 39.84 °, 52.68 °, 62.62 °, 70.36 °) outside, also have titanium dioxide Anatase diffraction peak (2 θ=25.02 °, 37.54 °, 47.68 °, 53.76 °, 68.54 °, 75.90 °), this sample is comprised of the Anatase of titanium dioxide as can be known.
Fig. 5 is hydrogenation film of Nano tube array of titanium dioxide (the hydrogenation TiO of present embodiment preparation
2) Raman spectral curve and semi-metal film of Nano tube array of titanium dioxide (semi-metal TiO
2) Raman spectral curve comparison diagram.Can find out that the hydrogenation film of Nano tube array of titanium dioxide is at ~ 143 cm
-1(E
g), 197 cm
-1(E
g), 399 cm
-1(B
1g), 519 cm
-1(B
1g), 639 cm
-1(E
g) Raman peaks is all arranged, illustrate that the hydrogenation film of Nano tube array of titanium dioxide mainly is comprised of the titanium dioxide of Anatase, and the semi-metal film of Nano tube array of titanium dioxide is not only at ~ 143 cm
-1(E
g), 197 cm
-1(E
g), 399 cm
-1(B
1g), 519 cm
-1(B
1g), 639 cm
-1(E
g) located Raman peaks, and at Raman shift place (~ 440 cm corresponding to the titanium dioxide Rutile Type
-1(E
g), 613 cm
-1(A
1g)) also there is Raman peaks, illustrate that the semi-metal film of Nano tube array of titanium dioxide is comprised of the mixed phase of Anatase and red schorl phase titanium dioxide.Different is the E of hydrogenation film of Nano tube array of titanium dioxide
g(~ 143 cm
-1) peak is compared with the semi-metal film of Nano tube array of titanium dioxide blue shift has been occured, and the halfwidth increase, as shown in Figure 6.This mainly is owing to hydrogenation so that formed a large amount of oxygen rooms in the film of Nano tube array of titanium dioxide, and these oxygen rooms can form oxygen room energy level by 0.75～1.18 eV under the titanium dioxide conduction band, thereby raise fermi level; So that the work function of hydrogenation film of Nano tube array of titanium dioxide reduces, be conducive to reduce it and open electric field and increase its emission.
And the improvement of the field emission performance of semi-metal titania nanotube mainly is because under high temperature acetylene atmosphere, has formed the titanium hydrocarbon (TiO that mixes in its structure
xC
y), as shown in Figure 7 and Figure 8.These titanium hydrocarbons form doped energy-band in the band gap of titania nanotube, so that its work function reduces, field emission performance improves.Usually, the titanium hydrocarbon (TiO of formation
xC
y) concentration larger, its work function is less, field emission performance is more excellent.But because forming this titanium hydrocarbon (TiO in the titania nanotube
xC
y) heavy doping be difficulty relatively, so the field emission performance of semi-metal titania nanotube is desirable not enough.Comparatively speaking, lower energy can form the oxygen room of high density, so that the work function of film of Nano tube array of titanium dioxide reduces.Therefore, the hydrogenation film of Nano tube array of titanium dioxide shows more excellent field emission performance.
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15 min in acetone, dehydrated alcohol and deionized water; Be that the dense hydrofluoric acid (concentration 〉=40%) of 1 ︰ 4 and concentration are titanium sheet 100 s after 37% concentrated hydrochloric acid forms the mixed chemical solution polished and cleaned with volume ratio; Adopt constant voltage dc anodizing method, titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after polishing: graphite is negative electrode, the titanium sheet is anode, the distance of two interpolars remains on 5 cm, electrolytic solution is the ethylene glycol solution (analytical pure) that contains 0.25 wt.% Neutral ammonium fluoride and 0.02 wt.% hydrofluoric acid, oxidation voltage is 30 V, oxidization time is 315 min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, taking-up titanium sheet after oxidation is finished, deionized water rinsing, nitrogen dries up; The tube furnace reaction vessel is evacuated to 25 Pa, then passes into the mixed gas that flow velocity is 15 SCCM to the tube furnace reaction vessel, this mixed gas is that argon gas and the hydrogen of 10 ︰ 5 forms by throughput ratio.Then the reaction vessel temperature is raised to 400 ℃ from room temperature, be incubated 6 h after, stop to pass into hydrogen, make reaction vessel under argon gas atmosphere, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide; The hydrogenation film of Nano tube array of titanium dioxide for preparing is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 3 μ m to the distance of anode, and system is evacuated to 1.2 * 10
-4Then Pa increases anode voltage (0～3500 V), recording voltage and current value slowly.
Hydrogenation film of Nano tube array of titanium dioxide (the hydrogenation TiO of present embodiment preparation
2) and semi-metal film of Nano tube array of titanium dioxide (the semi-metal TiO that adopts existing method to make
2) electric current and voltage response comparison diagram, as shown in Figure 9.The hydrogenation film of Nano tube array of titanium dioxide has demonstrated the semi-conductive electric current of typical N-shaped and voltage relationship, and the semi-metal film of Nano tube array of titanium dioxide has demonstrated almost electric current and the voltage relationship of symmetry, illustrates that it has the semi-metal characteristic.Simultaneously, compare with the semi-metal film of Nano tube array of titanium dioxide, the hydrogenation film of Nano tube array of titanium dioxide has larger specific conductivity, and this is conducive to inject electronics and transmits along titania nanotube, increase the effective field intensity of emission tip, will improve the field emission performance of sample.
Embodiment 4
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15 min in acetone, dehydrated alcohol and deionized water; Be that the dense hydrofluoric acid (concentration 〉=40%) of 1 ︰ 5 and concentration are titanium sheet 10 s after the mixed chemical solution polished and cleaned that forms of 36.5% concentrated hydrochloric acid with volume ratio; Adopt constant voltage dc anodizing method, titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after polishing: graphite is negative electrode, the titanium sheet is anode, the distance of two interpolars remains on 4 cm, electrolytic solution is the ethylene glycol solution (analytical pure) that contains 0.5 wt.% Neutral ammonium fluoride and 0.01 wt.% hydrofluoric acid, oxidation voltage is 60 V, oxidization time is 40 min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, taking-up titanium sheet after oxidation is finished, deionized water rinsing, nitrogen dries up; The tube furnace reaction vessel is evacuated to 1 Pa, then pass into the mixed gas that flow velocity is 17 SCCM to the tube furnace reaction vessel, this mixed gas is that argon gas and the hydrogen of 10 ︰ 7 forms by throughput ratio, the reaction vessel temperature is raised to 500 ℃ from room temperature, after being incubated 3 h, stop to pass into hydrogen, make reaction vessel under argon atmospher, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide; The hydrogenation film of Nano tube array of titanium dioxide for preparing is placed on the emission analysis instrument plummer, as field emission cold-cathode,, control cathode is 40 μ m to the distance of anode, and system is evacuated to 1.2 * 10
-4Then Pa increases anode voltage (0～3500 V), recording voltage and current value slowly.
Figure 10 is current density and the strength of electric field curve of the hydrogenation film of Nano tube array of titanium dioxide that makes of present embodiment, and current density increases sharply with the increase of strength of electric field as we know from the figure, and in addition, its unlatching electric field (is opened electric field and referred to output 10 μ A/cm
2The needed electric field of electric current) is approximately 1.75 V/ μ m.Therefore, the hydrogenation film of Nano tube array of titanium dioxide has lower unlatching electric field and larger current density.
The field emission refers to that under the effect of DC Electric Field, electron tunneling is crossed the quantum-mechanical phenomenon of solid surface potential barrier.This Tunneling Phenomenon can be described with the Fowler-Nordheim equation, is called for short the F-N equation; Figure 11 is the F-N curve of hydrogenation film of Nano tube array of titanium dioxide, can find out that it is almost linear, and it is theoretical to illustrate that classical field emission is satisfied in its emission behavior, illustrates that also current density and strength of electric field curve are exponential relationship simultaneously.It should be noted that at high field region to have different slopes with low place F-N curve, this mainly is because be in the result of the electron emission of different energy states.
Embodiment 5
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15 min in acetone, dehydrated alcohol and deionized water; Be that the dense hydrofluoric acid (concentration 〉=40%) of 1 ︰ 7 and concentration are titanium sheet 30 s after the mixed chemical solution polished and cleaned that forms of 37.5% concentrated hydrochloric acid with volume ratio; Adopt constant voltage dc anodizing method, titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after polishing: graphite is negative electrode, the titanium sheet is anode, the distance of two interpolars remains on 1 cm, electrolytic solution is the ethylene glycol solution (analytical pure) that contains 0.4 wt.% Neutral ammonium fluoride and 0.04 wt.% hydrofluoric acid, oxidation voltage is 35 V, oxidization time is 50 min, and use magnetic stirrer electrolytic solution, even with guarantee system temperature and electrolytic solution, taking-up titanium sheet after oxidation is finished, deionized water rinsing, nitrogen dries up; The tube furnace reaction vessel is evacuated to 200 Pa, then passes into the mixed gas that flow velocity is 18 SCCM to the tube furnace reaction vessel, this mixed gas is that argon gas and the hydrogen of 10 ︰ 8 forms by throughput ratio.Then the reaction vessel temperature is raised to 420 ℃ from room temperature, behind insulation 5.5 h under this atmosphere, stops to pass into hydrogen, makes reaction vessel naturally cool to room temperature under argon gas atmosphere, namely gets the hydrogenation film of Nano tube array of titanium dioxide; The hydrogenation film of Nano tube array of titanium dioxide for preparing is placed on the emission analysis instrument plummer, as field emission cold-cathode,, control cathode is 60 μ m to the distance of anode, and system is evacuated to 1.2 * 10
-4Then Pa increases anode voltage (0～3500 V), recording voltage and current value slowly.
Figure 12 is the field emission stability figure of hydrogenation film of Nano tube array of titanium dioxide.Can find out in originally 100 min current densities increases to some extent, keeps subsequently stable, and fluctuation range is in 2%.Originally the increase of current density mainly is because cleaning surfaces effect ion implantation and that emission of ions causes.In case the radiator surface is cleaned, an emission will keep stable.The fluctuation of current density mainly is because the surface sorption desorption.In a word, the hydrogenation film of Nano tube array of titanium dioxide has excellent field emission stability.
Embodiment 6
Get industrial titanium sheet (purity is 99.9%), successively difference ultrasonic cleaning 15 min in acetone, dehydrated alcohol and deionized water; Be that the dense hydrofluoric acid (concentration 〉=40%) of 1 ︰ 4 and concentration are titanium sheet 160 s after the mixed chemical solution polished and cleaned that forms of 36% concentrated hydrochloric acid with volume ratio; Adopt constant voltage dc anodizing method, titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after polishing: graphite is negative electrode, the titanium sheet is anode, the distance of two interpolars remains on 5 cm, electrolytic solution is the ethylene glycol solution (analytical pure) that contains 0.35 wt.% Neutral ammonium fluoride and 0.01 wt.% hydrofluoric acid, oxidation voltage is 55 V, oxidization time is 5 min, experiment is carried out at ambient temperature, and use magnetic stirrer electrolytic solution, and even with guarantee system temperature and electrolytic solution, taking-up titanium sheet after oxidation is finished, deionized water rinsing, nitrogen dries up; The tube furnace reaction vessel is evacuated to 150 Pa, then pass into the mixed gas that flow velocity is 15 SCCM to the tube furnace reaction vessel, this mixed gas is that argon gas and the hydrogen of 10 ︰ 5 forms by throughput ratio, the reaction vessel temperature is raised to 440 ℃ from room temperature, after being incubated 4.5 h, stop to pass into hydrogen, make reaction vessel under argon gas atmosphere, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide; The hydrogenation film of Nano tube array of titanium dioxide for preparing is placed on the emission analysis instrument plummer, as field emission cold-cathode,, control cathode is 150 μ m to the distance of anode, and system is evacuated to 1.2 * 10
-4Then Pa increases anode voltage (0～3500 V), recording voltage and current value slowly.
Adopt the comparison of the inventive method the hydrogenation film of Nano tube array of titanium dioxide that makes and the semi-metal film of Nano tube array of titanium dioxide that adopts existing method to make:
First, the hydrogenation film of Nano tube array of titanium dioxide is a kind of eco-friendly field emission body, can overcome in the preparation semi-metal film of Nano tube array of titanium dioxide field emission body process to exist preparation temperature acetylene relatively high and cracking to pollute easily the problem of production unit.
The second, improve the aspect from field emission performance, the hydrogenation film of Nano tube array of titanium dioxide shows more excellent field emission performance, comprises low unlatching electric field, large current density, the field emission stability of excellence during larger emission.
The 3rd, the improvement mechanism of the two is different.The hydrogenation film of Nano tube array of titanium dioxide mainly is the field emission that improves film of Nano tube array of titanium dioxide by the approach of introducing defective, and the semi-metal film of Nano tube array of titanium dioxide mainly is the approach by the C element doping.Specifically, there is a large amount of oxygen rooms in the hydrogenation film of Nano tube array of titanium dioxide of thermal treatment preparation in its structure in the atmosphere of hydrogen is arranged; The oxygen room that produces can form oxygen room energy level by 0.75 ~ 1.18 eV under the titanium dioxide conduction band, thereby raise fermi level, so that the work function of hydrogenation film of Nano tube array of titanium dioxide reduces greatly, be conducive to reduce it and open electric field and increase its emission.And the improvement of the field emission performance of semimetallic film of Nano tube array of titanium dioxide mainly is because under high temperature acetylene atmosphere, has formed the titanium hydrocarbon (TiO that mixes in its structure
xC
y), these titanium hydrocarbons form doped energy-band in the band gap of titania nanotube, so that its work function reduces, field emission performance improves.Usually, the oxygen room of formation and titanium hydrocarbon (TiO
xC
y) concentration larger, the work function of film of Nano tube array of titanium dioxide is less, field emission performance is more excellent.But because forming titanium hydrocarbon (TiO in the titania nanotube
xC
y) required energy is higher, so realize this titanium hydrocarbon (TiO
xC
y) heavy doping be difficulty relatively, so the field emission performance of semimetallic titania nanotube is desirable not enough.Comparatively speaking, lower energy can form the oxygen room of high density, causes the work function of film of Nano tube array of titanium dioxide to reduce.Therefore, the hydrogenation film of Nano tube array of titanium dioxide shows more excellent field emission performance.
The 4th, the field emission performance of hydrogenation film of Nano tube array of titanium dioxide has better controllability.The concentration in oxygen room only depends on hydrogenation time and temperature in the hydrogenation film of Nano tube array of titanium dioxide, thereby can realize controlled to its field emission performance by only changing hydrogenation time and temperature.Simultaneously, in actual production, the control ratio of hydrogenation time and temperature is easier to realize, lower to the requirement of equipment.And the field emission performance of semimetallic film of Nano tube array of titanium dioxide is not only relevant with treatment time and temperature, also depends on the flow of acetylene and argon gas.Will strictly control the flow of acetylene and argon gas in the production of reality, this can increase the production unit requirement.
At last, from the application prospect aspect, the hydrogenation film of Nano tube array of titanium dioxide is the device on basis except can be used for the cold cathode electron emitters such as Field Emission Display, microwave amplifier, X-x ray tube, field emission scanning electron microscope, because it has characteristic of semiconductor, high specific conductivity and the characteristic such as corrosion-resistant, also can be used for photochemical catalysis, solar cell, the devices such as super capacitor.Take the hydrogenation film of Nano tube array of titanium dioxide as the basis, be expected to realize the compound of these functional devices, thereby realize the integrated of multifunction device.
Therefore, hydrogenation film of Nano tube array of titanium dioxide field emission body has more excellent performance and more wide application prospect.
Claims (6)
1. the preparation method of a hydrogenation film of Nano tube array of titanium dioxide can make a kind of performance film of Nano tube array of titanium dioxide better, that can be used for field emission body, it is characterized in that this preparation method specifically carries out according to the following steps:
Step 1: industrial titanium sheet is cleaned in acetone, dehydrated alcohol and deionized water successively;
Step 2: be titanium sheet after the mixed chemical solution polished and cleaned that forms of the dense hydrofluoric acid of 1 ︰ 4～8 and concentrated hydrochloric acid with volume ratio;
Step 3: adopt constant voltage dc anodizing method, the titanium plate surface growth film of Nano tube array of titanium dioxide under the room temperature after chemical rightenning: graphite is negative electrode, and the titanium sheet is anode, and the distance of two interpolars remains on 1～5 cm; Electrolytic solution is the ethylene glycol solution that contains 0.20～0.50 wt.% Neutral ammonium fluoride and 0.01～0.05 wt.% hydrofluoric acid, and oxidation voltage is 30～60 V, and oxidization time is 5～600 min, and use magnetic stirrer electrolytic solution, after oxidation is finished, deionized water rinsing titanium sheet, nitrogen dries up;
Step 4: the titanium sheet after step 3 oxidation is put into high temperature resistant reactor, and place in the tube furnace, the tube furnace reaction vessel is evacuated to 1～200 Pa, pass into the mixed gas that is formed by argon gas and hydrogen that flow velocity is 15～18 mark condition milliliter per minutes to the tube furnace reaction vessel, reaction vessel is warming up to 400～550 ℃, and insulation 3～6 h stop to pass into hydrogen, make reaction vessel under argon gas atmosphere, naturally cool to room temperature, namely get the hydrogenation film of Nano tube array of titanium dioxide.
2. the preparation method of hydrogenation film of Nano tube array of titanium dioxide as claimed in claim 1 is characterized in that, in the described step 2, and the concentration of dense hydrofluoric acid 〉=40%, the concentration of concentrated hydrochloric acid is 36%～38%.
3. the preparation method of hydrogenation film of Nano tube array of titanium dioxide as claimed in claim 1 is characterized in that, in the described step 2, with titanium sheet chemical rightenning 10～180 s.
4. the preparation method of hydrogenation film of Nano tube array of titanium dioxide as claimed in claim 1 is characterized in that, the throughput ratio of argon gas and hydrogen is 10 ︰ 5～8 in the described step 4.
5. the application of the described hydrogenation film of Nano tube array of titanium dioxide of claim 1 is characterized in that, with the hydrogenation film of Nano tube array of titanium dioxide that makes directly as the Field Electron Emission cold cathode.
6. the application of hydrogenation film of Nano tube array of titanium dioxide as claimed in claim 5, it is characterized in that, the hydrogenation film of Nano tube array of titanium dioxide is placed on the emission analysis instrument plummer, as the Field Electron Emission cold cathode, control cathode is 30～200 μ m to the distance of anode, when the system vacuum degree is better than 1.2 * 10
-4During Pa, the variation range of anode voltage is 0～3500 V, recording voltage and current value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005952.8A CN103060880B (en) | 2013-01-08 | 2013-01-08 | A kind of preparation method of hydrogenation film of Nano tube array of titanium dioxide and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005952.8A CN103060880B (en) | 2013-01-08 | 2013-01-08 | A kind of preparation method of hydrogenation film of Nano tube array of titanium dioxide and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103060880A true CN103060880A (en) | 2013-04-24 |
| CN103060880B CN103060880B (en) | 2016-01-27 |
Family
ID=48103764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310005952.8A Expired - Fee Related CN103060880B (en) | 2013-01-08 | 2013-01-08 | A kind of preparation method of hydrogenation film of Nano tube array of titanium dioxide and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103060880B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614759A (en) * | 2013-11-22 | 2014-03-05 | 西北师范大学 | Preparation method and application of N-doped titanium dioxide nano-composite structure |
| CN105734642A (en) * | 2016-03-29 | 2016-07-06 | 上海博友金属制品有限公司 | Preparing method for high-strength and large-specific-surface-area titanium black coating |
| CN106958033A (en) * | 2017-03-17 | 2017-07-18 | 南开大学 | Magn é li phases TinO2n‑1The preparation method of nanotube electrode |
| CN111408360A (en) * | 2020-03-12 | 2020-07-14 | 安徽大学 | Photocatalytic material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102162116A (en) * | 2011-04-06 | 2011-08-24 | 西北师范大学 | Growing method and application of semi-metallic titanium dioxide nanotube array film |
| US8299699B2 (en) * | 2011-04-01 | 2012-10-30 | National Chung Cheng University | Double-sided light emitting field emission device and method of manufacturing the same |
-
2013
- 2013-01-08 CN CN201310005952.8A patent/CN103060880B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8299699B2 (en) * | 2011-04-01 | 2012-10-30 | National Chung Cheng University | Double-sided light emitting field emission device and method of manufacturing the same |
| CN102162116A (en) * | 2011-04-06 | 2011-08-24 | 西北师范大学 | Growing method and application of semi-metallic titanium dioxide nanotube array film |
Non-Patent Citations (1)
| Title |
|---|
| WEI-DONG ZHU ET AL.: "Enhanced field emission from hydrogenated TiO2 nanotube arrays", 《NANOTECHNOLOGY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614759A (en) * | 2013-11-22 | 2014-03-05 | 西北师范大学 | Preparation method and application of N-doped titanium dioxide nano-composite structure |
| CN105734642A (en) * | 2016-03-29 | 2016-07-06 | 上海博友金属制品有限公司 | Preparing method for high-strength and large-specific-surface-area titanium black coating |
| CN106958033A (en) * | 2017-03-17 | 2017-07-18 | 南开大学 | Magn é li phases TinO2n‑1The preparation method of nanotube electrode |
| CN106958033B (en) * | 2017-03-17 | 2019-03-26 | 南开大学 | Magn é li phase TinO2n-1The preparation method of nanotube electrode |
| CN111408360A (en) * | 2020-03-12 | 2020-07-14 | 安徽大学 | Photocatalytic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103060880B (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Metal–organic framework derived Co3O4/TiO2/Si heterostructured nanorod array photoanodes for efficient photoelectrochemical water oxidation | |
| CN107117831B (en) | Preparation method of WO3 nanosheet array | |
| Liu et al. | Efficient photoelectrochemical water splitting by gC 3 N 4/TiO 2 nanotube array heterostructures | |
| CN107574456B (en) | Preparation method of ultrathin molybdenum disulfide nanosheet/silicon nanowire heterojunction structure | |
| US9748581B2 (en) | Functionalized graphene-Pt composites for fuel cells and photoelectrochemical cells | |
| CN103614759B (en) | Nitrogen-doped titanium dioxide nano composite structure preparation method and application | |
| CN106521547A (en) | Preparing method and application of TiO2, RGO and C3N4 compound electrode | |
| CN103060880B (en) | A kind of preparation method of hydrogenation film of Nano tube array of titanium dioxide and application | |
| CN103657624B (en) | A kind of grey nanometer titanic oxide material and its preparation method and application | |
| CN105498773A (en) | Preparation method for doped iron oxide nanorod catalyst | |
| CN107268024B (en) | Compound α type iron oxide vermiform nano-structure array light anode of cobaltosic oxide and its preparation method and application | |
| Khosrow-pour et al. | Large-scale synthesis of uniform lanthanum oxide nanowires via template-free deposition followed by heat-treatment | |
| CN110396701A (en) | A kind of efficient electro-catalysis reduction carbon dioxide prepares catalyst of formic acid and preparation method thereof | |
| CN108465465A (en) | A kind of semiconductive thin film and preparation method thereof | |
| Ma et al. | A self-powered photoelectrochemical ultraviolet photodetector based on Ti3C2T x/TiO2 in situ formed heterojunctions | |
| Guo et al. | Synthesis of Cu, N-doped TiO2 nanotube by a novel magnetron sputtering method and its photoelectric property | |
| Liu et al. | Ultrafast fabrication of nanostructure WO3 photoanodes by hybrid microwave annealing with enhanced photoelectrochemical and photoelectrocatalytic activities | |
| CN103695874A (en) | Preparation method of intelligent temperature control color changing vanadium oxide film | |
| Li et al. | Enhanced photoelectrochemical water splitting from Si quantum dots/TiO2 nanotube arrays composite electrodes | |
| Gu et al. | Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps | |
| CN106929830B (en) | The preparation method of the controllable metal oxide semiconductor films electrode material of nanostructure under a kind of high temperature | |
| CN109183124B (en) | Narrow-forbidden-band black zirconia nanotube film and preparation method thereof | |
| CN110310891A (en) | The preparation method and thin film transistor (TFT) of metal nanometer line conductive film | |
| CN102162116B (en) | Growing method and application of semi-metallic titanium dioxide nanotube array film | |
| CN110993355B (en) | Preparation method of two-dimensional titanium carbide substrate layer optimized alpha-phase iron oxide photo-anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160127 Termination date: 20170108 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |