CN102162116A - Growing method and application of semi-metallic titanium dioxide nanotube array film - Google Patents
Growing method and application of semi-metallic titanium dioxide nanotube array film Download PDFInfo
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Abstract
本发明公开了一种半金属二氧化钛纳米管阵列膜的生长方法及其应用，生长时首先清洗纯钛片并制备抛光液；在抛光液中化学抛光清洗的纯钛片；室温下，将石墨和化学抛光后的纯钛片放入电解液，对纯钛片进行氧化；氧化的纯钛片放入乙二醇溶液浸泡后放入耐高温反应器中，在一定真空度、温度和通入混合气氛的条件下保温，然后在氩气气氛下自然冷却至室温,制得半金属二氧化钛纳米管阵列膜。将该阵列膜直接作为场致电子发射冷阴极。本发明生长方法便于工业化生产，能够制得性能优良、价格便宜、具有实用价值的半金属二氧化钛纳米管阵列膜，在场致电子发射显示材料方面有较好的应用价值。
The invention discloses a growth method and application of a semi-metallic titanium dioxide nanotube array film. During growth, the pure titanium sheet is firstly cleaned and a polishing liquid is prepared; the pure titanium sheet is chemically polished in the polishing liquid; at room temperature, graphite and The chemically polished pure titanium sheet is put into the electrolyte to oxidize the pure titanium sheet; the oxidized pure titanium sheet is soaked in ethylene glycol solution and then put into a high temperature resistant reactor, and mixed at a certain vacuum degree, temperature and Insulated under atmospheric conditions, and then naturally cooled to room temperature under argon atmosphere to prepare semi-metallic titanium dioxide nanotube array film. The array film is directly used as a field electron emission cold cathode. The growth method of the invention is convenient for industrialized production, can produce a semi-metal titanium dioxide nanotube array film with good performance, low price and practical value, and has good application value in field electron emission display materials.
Description
Technical field
The invention belongs to the filed emission cathode material technical field, relate to a kind of growth method of the semi-metal film of Nano tube array of titanium dioxide of emission that is directly used in; The invention still further relates to a kind of application of this semi-metal film of Nano tube array of titanium dioxide.
Background technology
Field Emission Display is a kind of vacuum microelectronic device, high image quality, liquid-crystal display frivolous that not only has cathode tube, but also have the advantages such as big area of plasma display, make it have the potential strength that is at war with other display device.In recent years, Field Emission Display has caused people's extensive concern.But Field Emission Display will obtain widespread use, and the filed emission cathode material of excellent performance is one of most important technical support.
The research of field electron emission cold-cathode material concentrated on seek to open that (or threshold value) electric field is low, emission is big, long-life electron emission cold-cathode material.Filed emission cathode material commonly used at present has metallic substance (Mo, W, Ni etc.), conventional semiconductor material (Si, Ge, GaAs etc.), carbide material (ZrC, TaC, SiC etc.), nitride material (TiN, GaN, AlN etc.), carbon-based material (diamond, carbon nanotube, amorphous carbon etc.) and oxide material (CuO, SnO
2, ZnO, In
2O
3, TiO
2, WO
3Deng).Yet studies show that all there is significant disadvantages in above-mentioned a lot of materials: perhaps work function is big, needs very high driving voltage; Perhaps the chemically reactive height causes the radiator deterioration; Perhaps emission is little, does not satisfy the modulation requirement; Perhaps heat radiation difficulty under big electric current influences works better etc., has limited the application of these materials in field emission display.Therefore, study a kind of excellent property, the field electron emission cold-cathode material that more has practical value becomes the task of top priority.
Summary of the invention
In order to overcome above-mentioned problems of the prior art, the object of the present invention is to provide a kind of growth method of semi-metal film of Nano tube array of titanium dioxide, can make a kind of excellent property, have the field electron emission cold-cathode material of practical value.
Another object of the present invention is to provide of the application of a kind of above-mentioned semi-metal film of Nano tube array of titanium dioxide as filed emission cathode material.
For achieving the above object, the technical solution adopted in the present invention is, a kind of growth method of semi-metal film of Nano tube array of titanium dioxide, growth field emission performance excellence, the direct semi-metal film of Nano tube array of titanium dioxide of energy on industrial pure titanium sheet as field emission cold-cathode, this growth method is specifically carried out according to the following steps:
Step 1: clean pure titanium sheet;
The formation polishing fluid is mixed with dense hydrofluoric acid and concentrated hydrochloric acid in 1:4～8 by volume;
Step 2: the pure titanium sheet that cleans in the step 1 is put into polishing fluid chemical rightenning 10 s～180 s that step 1 makes;
Step 3: under the room temperature, the pure titanium sheet after the chemical rightenning in graphite and the step 2 is put into electrolytic solution, this pure titanium sheet is carried out oxidation;
Step 4: the pure titanium sheet after the oxidation in the step 3 is put into ethylene glycol solution soak 4 h～12 h;
Step 5: the pure titanium sheet after soaking in the step 4 is put into high temperature resistant reaction device, in vacuum tightness is that 1 Pa～200 Pa, temperature are that 700 ℃～850 ℃, feeding flow velocity are insulation 10 min～90 min under the condition of 10SCCM～12 SCCM mixed atmospheres, under argon gas atmosphere, naturally cool to room temperature then, make the semi-metal film of Nano tube array of titanium dioxide.
Another technical scheme of the present invention is that a kind of application of above-mentioned semi-metal film of Nano tube array of titanium dioxide is directly launched cold cathode as field-causing electron with it.
Growth 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, be converted into film of Nano tube array of titanium dioxide by subsequent disposal again with semi-metal characteristic, this film of Nano tube array have open that electric field is low, repeatability and the good characteristics of field emission stability, the field emission performance excellence, can be directly as field emission cold-cathode, and combine firmly with the titanium substrate.This growth method is convenient to suitability for industrialized production, is easy to make low-cost semi-metal film of Nano tube array of titanium dioxide, aspect the field-causing electron emission display material using value is preferably being arranged.
Description of drawings
Fig. 1 is the SEM surface topography map of semi-metal film of Nano tube array of titanium dioxide in the embodiment of the invention 1.
Fig. 2 is the SEM sectional drawing of semi-metal film of Nano tube array of titanium dioxide in the embodiment of the invention 1.
Fig. 3 is the XRD spectrum of 2 semi-metal film of Nano tube array of titanium dioxide in the embodiment of the invention.
Fig. 4 is the Ti 2p narrow scan spectrogram in the semi-metal film of Nano tube array of titanium dioxide xps energy spectrum that makes of the embodiment of the invention 2.
Fig. 5 is an O 1s narrow scan spectrogram in the semi-metal film of Nano tube array of titanium dioxide XPS spectrum that makes of the embodiment of the invention 2.
Fig. 6 is a C 1s narrow scan spectrogram in the semi-metal film of Nano tube array of titanium dioxide XPS spectrum that makes of the embodiment of the invention 2.
Fig. 7 is the graph of relation (I-V curve) of the electric current of the semi-metal film of Nano tube array of titanium dioxide that makes of the embodiment of the invention 3 with voltage change.
Fig. 8 is the current density and the strength of electric field performance diagram of the semi-metal film of Nano tube array of titanium dioxide that makes of the embodiment of the invention 4.
Fig. 9 is the F-N performance diagram of the semi-metal film of Nano tube array of titanium dioxide that makes of the embodiment of the invention 4.
Figure 10 is the time dependent performance diagram of current density (field emission stability curve) of the semi-metal film of Nano tube array of titanium dioxide that makes of the embodiment of the invention 5.
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 issue that field emission display is used widely; The semi-metal film of Nano tube array of titanium dioxide not only has the good characteristic of broad-band gap (～3.2 eV) semi-conductor titanium dioxide: good characteristic such as lower work function (～4.3 eV), nontoxic, low-cost, good chemistry and thermostability, and also has its particular performances: lower electron affinity, good electrical conductivity, bigger length-to-diameter ratio, favorable mechanical performance, fabulous structural controllability, and combine firmly etc. with the titanium substrate, almost possessed desired all character of filed emission cathode material.And adopt existing method to prepare the temperature condition that the semi-metal film of Nano tube array of titanium dioxide need be higher than 850 ℃, and do not appear in the newspapers as yet about the research of semi-metal film of Nano tube array of titanium dioxide field emission characteristic.Given this, the invention provides that a kind of the film of Nano tube array of titanium dioxide that makes can be directly as filed emission cathode material in the method that is lower than growth film of Nano tube array of titanium dioxide under 850 ℃ the temperature condition, this growth method is specifically carried out according to the following steps:
Step 1: industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively;
1:4～8 are by volume got the dense hydrofluoric acid of concentration 〉=40% and concentration respectively and are 36%～38% concentrated hydrochloric acid, mix forming polishing fluid;
Step 2: the pure titanium sheet that cleans up in the step 1 is put into polishing fluid chemical rightenning 10～180 s that step 1 makes;
Step 3: adopt the film of Nano tube array of titanium dioxide of growing on the pure titanium sheet of constant voltage dc anodizing method after step 2 is polished: graphite and this pure titanium sheet are put into electrolytic solution, with graphite is negative electrode, this pure titanium sheet is an anode, guarantee that the distance between negative electrode and the anode is 1～5 cm, under the room temperature this pure titanium sheet is carried out oxidation, electrolytic solution is the analytical pure ethylene glycol solution that contains 0.2～0.3wt.% Neutral ammonium fluoride and 0.01～0.05wt.% hydrofluoric acid, oxidation voltage is 30～60 V, oxidization time is 5～600 min, use magnetic stirrer electrolytic solution in the oxidising process, even with guarantee system temperature and electrolytic solution, after finishing, oxidation takes out pure titanium sheet, use deionized water rinsing, nitrogen dries up;
Form the unbodied film of Nano tube array of titanium dioxide of one deck by above-mentioned three steps at pure titanium plate surface, this unbodied film of Nano tube array of titanium dioxide electron affinity is higher, electron transport ability is undesirable, also needs by following step this array film to be converted into the film of Nano tube array of titanium dioxide with semi-metal characteristic.
Step 4: the pure titanium sheet after the oxidation in the step 3 is put into analytically pure ethylene glycol solution soak 4～12 h;
Step 5: the pure titanium sheet after step 4 immersion is put into quartz boat high temperature resistant reaction devices such as (or potteries), and place in the tube furnace, the tube furnace reaction vessel is evacuated to 1～200 Pa, temperature in the reaction vessel is risen to 700 ℃～850 ℃, be incubated 10～90 min feeding under the condition that flow velocity is 10～12 mark condition milliliter per minute (SCCM) mixed atmospheres, this mixed atmosphere is that the argon gas and the acetylene of 9:1～3 is formed by throughput ratio, after the insulation, stop to feed acetylene, make reaction vessel 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 sample for preparing is placed on the emission analysis instrument plummer, and as field-causing electron emission cold cathode, control cathode is 60～200 μ m to the anodic distance, and the system vacuum degree is better than 1.2 * 10
-4Pa, the variation range of anode voltage is 0～3500 V.The unlatching electric field of the semi-metal film of Nano tube array of titanium dioxide that the present invention makes is 3.0 V/ μ m, and bigger field emission is arranged, and good repeatability and field emission stability are arranged.
The semi-metal film of Nano tube array of titanium dioxide that adopts growth method of the present invention to make not only has the good characteristic that broad-band gap (～3.2 eV) semi-conductor titanium dioxide self is had: lower work function (～4.3 eV), nontoxic, low-cost, good chemistry and thermostability etc., and also has its particular performances: lower electron affinity, good electrical conductivity, bigger length-to-diameter ratio, the favorable mechanical performance, fabulous structural controllability, and combine firm etc. with the titanium substrate, almost possessed desired all character of filed emission cathode material, not only have important scientific meaning, and have more practical value.This semi-metal film of Nano tube array of titanium dioxide is grown on the titanium sheet substrate, its top layer is the porous pattern of similar anodic oxidation aluminium formwork, and lower floor is the nanotube oldered array, and the diameter of this nanotube is about 10～300 nm, thickness of pipe is about 10～40nm, length 1～60 μ m.
Industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively; To get the dense hydrofluoric acid of concentration 〉=40% and concentration respectively be 36% concentrated hydrochloric acid to 1:4 by volume, mixes forming polishing fluid, and the pure titanium sheet that cleans up is put into this polishing fluid chemical rightenning 180s; Adopt the constant voltage dc anodizing method film of Nano tube array of titanium dioxide of growing on the pure titanium sheet after the polishing: with graphite is negative electrode, this pure titanium sheet is an anode, put into the analytical pure ethylene glycol solution that contains 0.2wt.% 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 60 min, adopts magnetic stirring apparatus to stir in the oxidising process, and is even with guarantee system temperature and electrolytic solution; Take out the titanium sheet after oxidation is finished, use deionized water rinsing, after nitrogen dries up; Place the analytical pure ethylene glycol solution to soak 12 h; Put into quartz boat then, and place in the middle part of the silica tube of tube furnace, sealed silica envelope, simultaneously silica tube is evacuated to 40 Pa, the temperature in the silica tube is risen to 700 ℃, feeding 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 9:1 is formed by throughput ratio, stop to feed acetylene afterwards, make silica tube under argon gas atmosphere, naturally cool to room temperature, make the semi-metal film of Nano tube array of titanium dioxide.This semi-metal film of Nano tube array of titanium dioxide is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 200 μ m to the anodic distance, and system is evacuated to 1.2 * 10
-4Pa increases anode voltage (0～3500 V), recording voltage and current value then slowly.
The SEM surface topography map and the sectional drawing of the semi-metal film of Nano tube array of titanium dioxide that present embodiment makes are as Fig. 1 and Fig. 2.As can be seen from the figure, the top layer of this semi-metal film of Nano tube array of titanium dioxide is the porous pattern of similar anodic oxidation aluminium formwork, and lower floor is the nanotube oldered array.The average caliber of this nanotube is about 50 nm, the average tube wall thickness is about 30 nm, and length is about 7 μ m, and compares pattern with pure film of Nano tube array of titanium dioxide considerable change does not take place, still keep bigger length-to-diameter ratio, demonstrate fabulous structural controllability.
Industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively; 1:6 by volume gets the dense hydrofluoric acid of concentration 〉=40% and concentration respectively and is 38% concentrated hydrochloric acid, is mixed into polishing fluid; The pure titanium sheet that cleans up is put into this polishing fluid chemical rightenning 120s; Adopt the constant voltage dc anodizing method film of Nano tube array of titanium dioxide of growing on the titanium sheet after the polishing: with graphite is negative electrode, the titanium sheet is an anode, put into the analytical pure ethylene glycol solution that contains 0.3wt.% Neutral ammonium fluoride and 0.05wt.% hydrofluoric acid under the room temperature titanium sheet is carried out oxidation, distance between this negative electrode and the anode is 2cm, oxidation voltage is 45V, oxidization time is 600min, stir with magnetic stirring apparatus in the oxidising process, even with guarantee system temperature and electrolytic solution, after finishing, oxidation takes out the titanium sheet, use deionized water rinsing, after nitrogen dries up; Place the analytical pure ethylene glycol solution to soak 10 h; Put into quartz boat then, and place in the middle part of the silica tube of tube furnace, sealed silica envelope, this silica tube is evacuated to 30 Pa, the temperature of this silica tube is raised to 800 ℃, feeding insulation 60 min under the condition of mixed atmosphere that flow velocity is 11 SCCM, this mixed atmosphere is that argon gas and the acetylene of 9:2 is formed by throughput ratio, stop to feed acetylene afterwards, make silica tube under argon gas atmosphere, naturally cool to room temperature, make the semi-metal film of Nano tube array of titanium dioxide; This semi-metal film of Nano tube array of titanium dioxide is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 100 μ m to the anodic distance, and system is evacuated to 1.2 * 10
-4Pa increases anode voltage (0～3500 V), recording voltage and current value then slowly.
The XRD spectra of the semi-metal film of Nano tube array of titanium dioxide that present embodiment makes, as shown in Figure 3.Show among the figure, this semi-metal film of Nano tube array of titanium dioxide is except diffraction peak with titanium substrate (2 θ=39.76 °, 52.62 °, 70.32 °, 75.82 °) outside, also have titanium dioxide anatase phase diffraction peak (2 θ=25 °, 37.52 °, 47.78 °, 53.68 °, 68.76 °) with rutile diffraction peak (2 θ=27.14 °, 35.76 °, 40.94 ° mutually, 56.34 °, 62.48 °) and titanium hydrocarbon diffraction peak (2 θ=45.76 °, 61.8 °) occur, this semi-metal film of Nano tube array of titanium dioxide is by the rutile phase of titanium dioxide as can be known, anatase phase and titanium hydrocarbon are formed.Ti 2P narrow scan spectrogram in this semi-metal film of Nano tube array of titanium dioxide xps energy spectrum, as shown in Figure 4, as can be seen from the figure, this semi-metal film of Nano tube array of titanium dioxide is except the characteristic peak that has titanium dioxide and have, some other peak also occurred, these peaks have shown the existence of titanium hydrocarbon; This result also can be from xps energy spectrum shown in Figure 5 finds out in the C 1s narrow scan spectrogram of broadening in the O 1s narrow scan spectrogram of broadening and the xps energy spectrum shown in Figure 6, this semi-metal film of Nano tube array of titanium dioxide is by titanium dioxide phase and the phase composite of titanium hydrocarbon as can be known by xps energy spectrum figure in a word, and this result is consistent with the result that XRD obtains.
Embodiment 3
Industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively; 1:8 by volume gets the dense hydrofluoric acid of concentration 〉=40% and concentration respectively and is 36% concentrated hydrochloric acid, is mixed into polishing fluid; The titanium sheet that cleans up is put into this polishing fluid chemical rightenning 10s; Adopt the constant voltage dc anodizing method film of Nano tube array of titanium dioxide of growing on the titanium sheet after the polishing: with graphite is negative electrode, the titanium sheet is an anode, put into the analytical pure ethylene glycol solution that contains 0.25wt.% Neutral ammonium fluoride and 0.02wt.% hydrofluoric acid under the room temperature titanium sheet is carried out oxidation, distance between this negative electrode and the anode is 5cm, oxidation voltage is 60V, oxidization time is 120min, stir with magnetic stirring apparatus in the oxidising process, even with guarantee system temperature and electrolytic solution, after finishing, oxidation takes out the titanium sheet, use deionized water rinsing, after nitrogen dries up; Place the analytical pure ethylene glycol solution to soak 6 h; The titanium sheet that will soak is then put into high-temperature resistant container, and place in the middle part of the silica tube of tube furnace, sealed silica envelope, this silica tube is evacuated to 200 Pa, the temperature in the silica tube is raised to 750 ℃, feeding insulation 40 min under the condition of mixed atmosphere that flow velocity is 12 SCCM, this mixed atmosphere is that argon gas and the acetylene of 9:3 is formed by throughput ratio, stop to feed acetylene afterwards, make silica tube under argon gas atmosphere, naturally cool to room temperature, make the semi-metal film of Nano tube array of titanium dioxide.This semi-metal film of Nano tube array of titanium dioxide is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 60 μ m to the anodic distance, and system is evacuated to 1.2 * 10
-4Pa increases anode voltage (0～3500 V), recording voltage and current value then slowly.
The electric current and the voltage characteristic curve of the semi-metal film of Nano tube array of titanium dioxide that present embodiment makes, as shown in Figure 7.Shown symmetric electric current and voltage relationship among the figure, illustrated that this semi-metal film of Nano tube array of titanium dioxide has semimetallic characteristic.
Industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively; 1:7 by volume gets the dense hydrofluoric acid of concentration 〉=40% and concentration respectively and is 37% concentrated hydrochloric acid, is mixed into polishing fluid, and the titanium sheet that cleans up is put into this polishing fluid chemical rightenning 60s; Adopt the constant voltage dc anodizing method film of Nano tube array of titanium dioxide of growing on the titanium sheet after the polishing: with graphite is negative electrode, the titanium sheet is an anode, in the analytical pure ethylene glycol solution that contains 0.25wt.% Neutral ammonium fluoride and 0.02wt.% hydrofluoric acid, the titanium sheet is carried out oxidation under the room temperature, distance between this negative electrode and the anode is 4 cm, oxidation voltage is 40 V, oxidization time is 200 min, stir with magnetic stirring apparatus in the oxidising process, even with guarantee system temperature and electrolytic solution, after finishing, oxidation takes out the titanium sheet, use deionized water rinsing, after nitrogen dries up; Place the analytical pure ethylene glycol solution to soak 9 h; The titanium sheet that will soak is then put into quartz boat, and place in the middle part of the silica tube of tube furnace, sealed silica envelope, silica tube is evacuated to 1 Pa, the temperature in the silica tube is raised to 750 ℃, feeding insulation 50 min under the condition of mixed atmosphere that flow velocity is 11 SCCM, this mixed atmosphere is that argon gas and the acetylene of 9:2 is formed by throughput ratio, stop to feed acetylene afterwards, make silica tube under argon gas atmosphere, naturally cool to room temperature, make the semi-metal film of Nano tube array of titanium dioxide.This semi-metal film of Nano tube array of titanium dioxide is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 60 μ m to the anodic distance, and system is evacuated to 1.2 * 10
-4Pa increases anode voltage (0～3500 V), recording voltage and current value then slowly.
The current density of the semi-metal film of Nano tube array of titanium dioxide that present embodiment makes and strength of electric field graphic representation, as shown in Figure 8, show among the figure, the current density of this array film increases sharply with the increase of strength of electric field, in addition, the unlatching electric field of this array film (is opened electric field and is meant output 10 μ A/cm
2The needed electric field of electric current) is approximately 3.0V/ μ m.This semi-metal film of Nano tube array of titanium dioxide has higher current density and lower unlatching electric field as can be known.The field emission is meant that under the situation of electric field action, electron tunneling is crossed the quantum-mechanical phenomenon of solid surface potential barrier.Electron tunneling can be described with the Fowler-Nordheim equation by the process of solid surface field emission, is called for short the F-N equation.The F-N performance diagram of this semi-metal film of Nano tube array of titanium dioxide, as shown in Figure 9, as can be seen from the figure, its field emission is approximate linear, it is theoretical to illustrate that classical field emission is satisfied in its emission behavior, also illustrates that current density and strength of electric field curve are index and increase simultaneously.
Industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively; 1:5 by volume gets the dense hydrofluoric acid of concentration 〉=40% and concentration respectively and is 36% concentrated hydrochloric acid, is mixed into polishing fluid, and the titanium sheet that cleans up is put into this polishing fluid chemical rightenning 150s; Adopt the constant voltage dc anodizing method film of Nano tube array of titanium dioxide of growing on the titanium sheet after the polishing: with graphite is negative electrode, the titanium sheet is an anode, put into the analytical pure ethylene glycol solution that contains 0.3wt.% Neutral ammonium fluoride and 0.04wt.% hydrofluoric acid under the room temperature titanium sheet is carried out oxidation, distance between this negative electrode and the anode is 1 cm, oxidation voltage is 30 V, oxidization time is 5 min, stir with magnetic stirring apparatus in the oxidising process, even with guarantee system temperature and electrolytic solution, after finishing, oxidation takes out the titanium sheet, use deionized water rinsing, after nitrogen dries up; Place the analytical pure ethylene glycol solution to soak 4 h; The Nano tube array of titanium dioxide that will soak is put into high-temperature resistant container then, and place in the middle part of the silica tube of tube furnace, sealed silica envelope, this silica tube is evacuated to 180 Pa, temperature in the silica tube is raised to 850 ℃, feeding insulation 70 min under the condition of mixed atmosphere that flow velocity is 11 SCCM, this mixed atmosphere is that argon gas and the acetylene of 9:2 is formed by throughput ratio, stop to feed acetylene afterwards, make silica tube under argon gas atmosphere, naturally cool to room temperature, make the semi-metal film of Nano tube array of titanium dioxide; This semi-metal film of Nano tube array of titanium dioxide is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 60 μ m to the anodic distance, and system is evacuated to 1.2 * 10
-4Pa increases anode voltage (0～3500 V), recording voltage and current value then slowly.
The field emission stability figure of the semi-metal film of Nano tube array of titanium dioxide that present embodiment makes, as shown in figure 10, the field emission of this array film fluctuates in time as can be seen from Figure, and fluctuation range illustrates that its field emission stability is better in 10%.
Industrial pure titanium sheet (purity is 99.9%) is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively; 1:6 by volume gets the dense hydrofluoric acid of concentration 〉=40% and concentration respectively and is 38% concentrated hydrochloric acid, is mixed into polishing fluid; The titanium sheet that cleans up is put into this polishing fluid chemical rightenning 100s; Adopt the constant voltage dc anodizing method film of Nano tube array of titanium dioxide of growing on the titanium sheet after the polishing: with graphite is negative electrode, the titanium sheet is an anode, put into the analytical pure ethylene glycol solution that contains 0.25wt.% Neutral ammonium fluoride and 0.01wt.% hydrofluoric acid under the room temperature titanium sheet is carried out oxidation, distance between this negative electrode and the anode is 4cm, oxidation voltage is 50V, oxidization time is 300min, stir with magnetic stirring apparatus in the oxidising process, even with guarantee system temperature and electrolytic solution, after finishing, oxidation takes out the titanium sheet, use deionized water rinsing, after nitrogen dries up; Place the analytical pure ethylene glycol solution to soak 8 h; The titanium sheet that will soak is then put into high-temperature resistant container, and place in the middle part of the silica tube of tube furnace, sealed silica envelope, this silica tube is evacuated to 100 Pa, the temperature in the silica tube is raised to 775 ℃, feeding insulation 10 min under the condition of mixed atmosphere that flow velocity is 12 SCCM, this mixed atmosphere is that argon gas and the acetylene of 9:3 is formed by throughput ratio, stop to feed acetylene afterwards, make silica tube under argon gas atmosphere, naturally cool to room temperature, make the semi-metal film of Nano tube array of titanium dioxide; This semi-metal film of Nano tube array of titanium dioxide is placed on the emission analysis instrument plummer, and as field emission cold-cathode, control cathode is 150 μ m to the anodic distance, and system is evacuated to 1.2 * 10
-4Pa increases anode voltage (0～3500 V), recording voltage and current value then slowly.
Claims (7)
1. the growth method of a semi-metal film of Nano tube array of titanium dioxide, growth field emission performance excellence, the direct semi-metal film of Nano tube array of titanium dioxide of energy on industrial pure titanium sheet as field emission cold-cathode, it is characterized in that this growth method is specifically carried out according to the following steps:
Step 1: clean pure titanium sheet;
The formation polishing fluid is mixed with dense hydrofluoric acid and concentrated hydrochloric acid in 1:4～8 by volume;
Step 2: the pure titanium sheet that cleans in the step 1 is put into polishing fluid chemical rightenning 10 s～180 s that step 1 makes;
Step 3: the pure titanium sheet after the chemical rightenning in graphite and the step 2 is put into electrolytic solution, this pure titanium sheet is carried out oxidation;
Step 4: the pure titanium sheet after the oxidation in the step 3 is put into ethylene glycol solution soak 4 h～12 h;
Step 5: the pure titanium sheet after step 4 soaked is that 1 Pa～200 Pa, temperature are that 700 ℃～850 ℃, feedings flow velocity are to be incubated 10 min～90 min under the condition of 10SCCM～12 SCCM mixed atmospheres in vacuum tightness, under argon gas atmosphere, naturally cool to room temperature then, make the semi-metal film of Nano tube array of titanium dioxide.
2. the growth method of semi-metal film of Nano tube array of titanium dioxide according to claim 1 is characterized in that, the cleaning in the described step 1 is that pure titanium sheet is cleaned up in acetone, dehydrated alcohol and deionized water for ultrasonic successively.
3. the growth method of semi-metal film of Nano tube array of titanium dioxide according to claim 1, it is characterized in that, oxidation in the described step 3 is: be negative electrode with graphite, pure titanium sheet is an anode, guarantee that the distance between negative electrode and the anode is 1 cm～5 cm, described electrolytic solution is the ethylene glycol solution that contains 0.2 wt.%～0.3wt.% Neutral ammonium fluoride and 0.01 wt.%～0.05wt.% hydrofluoric acid, and oxidation voltage is 30 V～60 V, and oxidization time is 5 min～600 min.
4. the growth method of semi-metal film of Nano tube array of titanium dioxide according to claim 3 is characterized in that, uses magnetic stirrer electrolytic solution in the described oxidising process.
5. the growth method of semi-metal film of Nano tube array of titanium dioxide according to claim 1 is characterized in that, the mixed atmosphere in the described step 5 is that the argon gas and the acetylene of 9:1～3 is formed by throughput ratio.
6. the application of the described semi-metal film of Nano tube array of titanium dioxide of claim 1 is characterized in that, this semi-metal film of Nano tube array of titanium dioxide is directly launched cold cathode as field-causing electron.
7. the application of semi-metal film of Nano tube array of titanium dioxide according to claim 7 is characterized in that, control cathode is 60 μ m～200 μ m to the anodic distance, and the system vacuum degree is better than 1.2 * 10
-4Pa, the variation range of anode voltage is 0 V～3500 V.
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| CN103972007A (en) * | 2014-05-21 | 2014-08-06 | 福州大学 | A kind of TiO2 nanotube triode field emission electron source and its preparation method |
| CN112585302A (en) * | 2018-08-10 | 2021-03-30 | 地方独立行政法人山口县产业技术研究院 | Anodic titanium oxide material and method for producing same |
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| CN112585302A (en) * | 2018-08-10 | 2021-03-30 | 地方独立行政法人山口县产业技术研究院 | Anodic titanium oxide material and method for producing same |
| CN114197014A (en) * | 2021-12-14 | 2022-03-18 | 合肥工业大学 | A method for realizing surface nanometerization of pure titanium parts with complex shapes |
| CN114197014B (en) * | 2021-12-14 | 2023-04-07 | 合肥工业大学 | Method for realizing surface nanocrystallization of pure titanium part with complex shape |
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