CN100481301C - Method for improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method - Google Patents
Method for improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method Download PDFInfo
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- CN100481301C CN100481301C CNB2006101307582A CN200610130758A CN100481301C CN 100481301 C CN100481301 C CN 100481301C CN B2006101307582 A CNB2006101307582 A CN B2006101307582A CN 200610130758 A CN200610130758 A CN 200610130758A CN 100481301 C CN100481301 C CN 100481301C
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Abstract
A method for improving performance of carbon nanotube film electronic field emission by electrophoresis deposit means includes plating transition metal film on conductive substrate material by physical gas phase depositing process, utilizing plated conductive substrate as cathode to deposit carbon nanotube film on said cathode through electrophoresis depositing process and carrying out annealing treatment on cathode deposited with carbon nanotube film for raising field emission current density.
Description
Technical field
The present invention relates to a kind of method of improving the carbon nano-tube performance, more particularly, relate to a kind of method of improving the electronic field emission performance of electrophoresis carbon nano-tube film depositing.
Background technology
The Field Emission Display technology is a kind of new flat panel display that has obtained developing rapidly since the mid-90 in 20th century.Field Emission Display is with the high-definition image quality of cathode ray tube, the thinness of LCD and the advantages such as large tracts of land of plasma display panel (PDP) roll into one, at aspects such as brightness, resolution, response speed, visual angle, power consumption, operating voltage and operating temperature ranges good performance is arranged all, have vast market and good application prospects [Physica B323,165 (2002)] in the flat panel display field.Wherein, cold-cathode material is the core component of Field Emission Display.Traditional Spindt type pointed cone cold cathode processing technology complexity makes that rate of finished products is difficult to improve, and cost is difficult to reduce.The appearance of carbon nanotube cathod is for this Display Technique provides new breakthrough point [Science 270,1179 (1995), Chem.Phys.Lett.233,63 (1995)].The carbon nano-tube caliber generally in several nanometers to tens nanometers, pipe range does not wait to the millimeter magnitude from nanometer scale, it is a kind of desirable one-dimensional material, have very big draw ratio and minimum tip curvature radius, under certain electric field, can obtain a very big field enhancement factor, have very excellent electronic field emission performance.Simultaneously, the carbon nanotube chemical good stability, the mechanical strength height, thereby be a kind of very desirable field emission cold-cathode material.
Prepare Field Emission Display with carbon nano-tube as cathode material, at first must the uniform carbon nano-tube film of preparation.At present, the preparation of carbon nano-tube thin film cathode has two class methods usually: a class is the direct growth method, and another kind of is grafting.The advantage of direct growth method is that carbon nano-tube and substrate caking power are better, and impurity content is low, combines with traditional semiconductor figure technology and can realize the growing patterned of carbon nano-tube, and can obtain directed carbon nano pipe array; But, be equipped with carbon nano-tube film with the direct growth legal system, because the growth temperature of carbon nano-tube need be higher than 600 ℃, be difficult in the simple glass substrate, realize the even growth of large tracts of land carbon nano-tube film.Therefore, present carbon nano-tube field-transmitting cathode adopts grafting to make usually.Grafting comprises electrophoresis, liquid phase deposition, silk screen print method, photoetching process etc.Utilizing electrophoresis carbon nano-tube film depositing on conductive substrates is a kind of method that has application prospect of making carbon nanotube field transmitting cold-cathode.This method technology is simple, with low cost, manufacturing cycle short, can realize the large-area preparation in enormous quantities [Materials Letters, 57,434 (2002)] of graphing carbon nanotube cathode thin film in the substrate of arbitrary shape.But, utilize the carbon nano-tube film and the adhesive force between the substrate of electrophoresis deposition more weak, carbon nano-tube film peels off easily in the emission process of field, cause an emission current shakiness, restricted practical application [the Applied Surface Science of electrophoresis in the carbon nano-tube field-transmitting cathode is made, 215,232 (2003)].
Summary of the invention
The object of the present invention is to provide a kind of method of electronic field emission performance of effective raising electrophoresis carbon nano-tube film depositing, after adopting this method that the carbon nano-tube film of substrate and electrophoretic deposition is handled, can significantly strengthen the adhesive force between carbon nano-tube and the substrate, obviously improve launch stability, reduce the threshold field strength of carbon nano-tube field emission, improve an emission.
Technical scheme of the present invention is carried out according to following steps:
(1) adopt physical vapor deposition coating film method plating transiting metal film on the conductive substrates material, described plating technic:
Vacuum degree is 3 * 10
-4～2 * 10
-6Pa, deposition rate is 0.2～0.8nm/s, transiting metal film thickness is 100～400nm;
(2) with the conductive substrates behind the plating as negative electrode, the electrophoretic deposition carbon nano-tube film, described electrophoretic deposition process: electrophoretic voltage is 30～120V, electrophoresis time is 0.5～10min, the spacing of negative electrode and anode is 1～5cm, 30min～2h of pre-sedimentation time of electrophoresis liquid, the pre-ultrasonic jitter time 1～2h of electrophoresis liquid;
(3) carbon nano-tube thin film cathode to deposition carries out annealing in process, described annealing treating process: vacuum degree is 1 * 10
-5～1 * 10
-7Pa, annealing time are 1～2h, and annealing temperature is 800～1200 ℃.
Wherein the described conductive substrates material of step (1) is a kind of in the glass of the glass of glass, coating surface Fe of glass, the coating surface Ti of glass, the coating surface Ni of ITO electro-conductive glass, Cu, Ni, Ti, Fe, Al, Si, coating surface Cu and coating surface Al.Described physical vapor deposition coating film method is a kind of in vacuum vapor plating, rf magnetron sputtering plated film and the ion film plating.Described transition metal is a kind of among Ti, Zr, Hf, Nb and the Ta.
Wherein the described anode of step (2) is a kind of in copper electrode, platinum electrode, the stainless steel electrode.Described electrophoresis liquid makes a kind of as dispersant in water, isopropyl alcohol, n-butanol and the ethanol.
The employed carbon nanotube powder of carbon nano-tube film depositing can adopt method preparations such as arc discharge method, laser ablation method, chemical vapour deposition technique.
The purpose of high-temperature vacuum annealing is that carbon atom and the transition metal that contacts are taken place is solid-solidifies to learn and reacts, between substrate and carbon nano-tube film, form the transition metal carbide of conductivity, strengthen the adhesive force between carbon nano-tube and the substrate, reduce the contact resistance between carbon nano-tube and the substrate, thereby improve field emission performance.
Beneficial effect of the present invention is the technique processing method by the high-temperature vacuum annealing of carbon nano-tube thin film cathode behind the transition metal pre-plating of substrate surface before the electrophoresis and the electrophoresis, between carbon nano-tube film and substrate, form the conductivity transition metal carbide, on the one hand, adhesive force between carbon nano-tube and the substrate is increased, can significantly improve the wild effect (seeing Fig. 2 and shown in Figure 3) of the emission current that causes owing to peeling off of electrophoresis carbon nano-tube film in the emission process; On the other hand, the ohmic contact of low resistance be can form between carbon nano-tube and the base material by transition metal carbide, interface potential barrier (Science, 285 between carbon nano-tube and the substrate eliminated, 1719 (1999)), a threshold field of emission is obviously reduced.Be mainly reflected in: compare with the carbon nano-tube film of the electrophoresis deposition that does not adopt any method to handle, adopt the threshold field strength of the electrophoretic deposition carbon nano-tube film of the inventive method processing to reduce greater than 25%, emission under the steady electric field increases greater than 400%, and launch stability is obviously improved.
Carbon nano-tube thin film cathode to the electrophoresis preparation adopts diode structure to carry out the electronic field emission performance test.The sample of test is respectively not through the carbon nano-tube film of any processing with by the carbon nano-tube film of the inventive method through substrate transition metal plating and film cathode high-temperature vacuum annealing in process.Test result (Fig. 4) for the electronic field emission performance of embodiment 1 carbon nano-tube thin film cathode shows: the threshold field strength of pressing the carbon nano-tube thin film cathode after the present embodiment method is handled is from 3.1mA/cm
2Be reduced to 2.1mA/cm
2, (among the embodiment, a definition emission reaches 10mA/cm to have reduced about 30%
2The time electric field strength be threshold field strength); When electric field strength was 2.3V/ μ m, the electronic field emission current density was from 1.9mA/cm
2Be increased to 13.5mA/cm
2, increased about 600%; Maximum emission current without the carbon nano-tube film of any processing only is 9.1mA/cm
2, after employing the inventive method was handled, the launch stability of carbon nano-tube film obviously strengthened, and emission reaches 21.3mA/cm then and there
2The time, still can keep stable field emission, as shown in Figure 4.In addition, from the SEM photo of Fig. 3 as seen, before and after the emission, the distribution density of film surface carbon nanotube changes little, and carbon nano-tube film and the also obviously enhancing of the adhesive force between the substrate handled through the inventive method be describeds.
This shows that the inventive method can improve the adhesive force of carbon nano-tube, strengthen the anti-ion bombardment ability of electrophoretic deposition carbon nano-tube thin film cathode, improve launch stability, prolong the useful life of negative electrode.
Description of drawings
Fig. 1 is a process chart of the present invention.
Fig. 2 does not adopt before the electrophoresis carbon nano-tube film depositing cathodic field emission that method of the present invention handles scanning electron microscopy (SEM) photo of the surface topography of (b) behind (a) and an emission.
Fig. 3 is electrophoretic deposition carbon nano-tube thin film cathode (substrate surface plating Ti film) emission preceding (a) of employing method processing of the present invention and scanning electron microscopy (SEM) photo that the surface topography of back (b) is launched in the field.
Fig. 4 is current density-electric field strength curve that launch electrophoretic deposition carbon nano-tube thin film cathode (substrate surface plating Ti film) after employing method of the present invention is handled and the field of not adopting the electrophoretic deposition carbon nano-tube thin film cathode of method processing of the present invention, wherein, abscissa is electric field strength (V/ μ m), and ordinate is current density (mA/cm
2).
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Ti, and base material is p type (a 100) Si sheet.Concrete sputter coating condition is: it is 0.22nm/s that adjusting sputtering power 80W makes deposition rate, sputtering time 15min, and sputter vacuum degree is 3 * 10
-4Pa, the Ti film thickness of plating is 200nm.
(2) with the Si substrate of plating Ti film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 30 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml isopropyl alcohol, sonic oscillation 2h, sedimentation 1h and obtaining then; Process conditions during electrophoresis are: electrophoretic voltage 100V, electrophoresis time 2min, the spacing 2cm of negative electrode and anode; Used anode is a copper electrode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 30nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 2 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 900 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
(1) utilizes vacuum evaporation coating embrane method plating transiting metal film on base material.The employing transition metal is Ta, and base material is p type (a 100) Si sheet.Process conditions are: deposition rate 0.4nm/s, deposition vacuum degree is 6 * 10
-5Pa, sedimentation time 4min, sputter vacuum degree is 3 * 10
-4Pa, the Ta film thickness of plating is 100nm.
(2) with the Si substrate of plating Ta film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 30 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml isopropyl alcohol, sonic oscillation 2h, sedimentation 1h and obtaining then; Used anode is a platinum electrode; Process conditions during electrophoresis are: electrophoretic voltage 60V, electrophoresis time 5min, the spacing 3cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 25nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 2 * 10
-7The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1000 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Hf, and base material is p type (a 100) Si sheet.Process conditions are: it is 0.8nm/s that adjusting sputtering power 200W makes deposition rate, and sputtering time is 8min, and sputter vacuum degree is 3 * 10
-4Pa, the Hf film thickness of plating is 400nm.
(2) with the Si substrate of plating Ta film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 25 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml isopropyl alcohol, sonic oscillation 2h, sedimentation 1h and obtaining then; Used anode is a stainless steel electrode; Process conditions during electrophoresis are: electrophoretic voltage 60V, electrophoresis time 5min, the spacing 3cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 10nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 2 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1100 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 4
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Zr, and base material is the ITO electro-conductive glass.Process conditions are: it is 0.6nm/s that adjusting sputtering power 150W makes deposition rate, and sputtering time is 8min, and sputter vacuum degree is 3 * 10
-4Pa, the Zr film thickness of plating is 288nm.
(2) with the ITO electro-conductive glass of plating Zr film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 10 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml water, sonic oscillation 1h, sedimentation 30min and obtaining then; Used anode is a platinum electrode; Used anode is a stainless steel electrode; Process conditions during electrophoresis are: electrophoretic voltage 120V, electrophoresis time 5min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 15nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-7The 1h that anneals in the vacuum environment of Pa, annealing temperature is 800 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 5
(1) utilizes ion film plating plating transiting metal film on base material.The employing transition metal is Nb, and base material is Cu.Process conditions are: it is 0.6nm/s that adjusting power 150W makes deposition rate, and sputtering time is 8min, and sputter vacuum degree is 2 * 10
-6Pa, the Nb film thickness of plating is 288nm.
(2) with the Cu of plating Nb film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 15 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml ethanol, sonic oscillation 1.5h, sedimentation 1.5h and obtaining then; Used anode is a platinum electrode; Process conditions during electrophoresis are: electrophoretic voltage 100V, electrophoresis time 10min, the spacing 5cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 25nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 1 * 10
-6The 1h that anneals in the vacuum environment of Pa, annealing temperature is 800 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 6
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Nb, and base material is Al.Process conditions are: it is 0.5nm/s that adjusting power 140W makes deposition rate, and sputtering time is 8min, and sputter vacuum degree is 5 * 10
-4Pa, the Nb film thickness of plating is 240nm.
(2) with the Al of plating Nb film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 10 μ m.
Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml n-butanol, and sonic oscillation 1.5h is right
Back sedimentation 2h and obtaining; Used anode is a stainless steel electrode; Process conditions during electrophoresis are: electrophoretic voltage 30V, electrophoresis time 10min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of Prepared with Laser Ablation, diameter 15nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1200 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 7
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Ta, and base material is Fe.Process conditions are: it is 0.2nm/s that adjusting power 70W makes deposition rate, and sputtering time is 10min, and sputter vacuum degree is 5 * 10
-4Pa, the Ta film thickness of plating is 120nm.
(2) with the Fe of plating Ta film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 15 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml water, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a platinum electrode; Process conditions during electrophoresis are: electrophoretic voltage 60V, electrophoresis time 10min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of Prepared with Laser Ablation, diameter 10nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1200 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 8
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Ti, and base material is Ni.Process conditions are: it is 0.6nm/s that adjusting power 100W makes deposition rate, and sputtering time is 10min, and sputter vacuum degree is 5 * 10
-4Pa, the Ti film thickness of plating is 360nm.
(2) with the Ni of plating Ti film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 10 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml water, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a platinum electrode; Process conditions during electrophoresis are: electrophoretic voltage 30V, electrophoresis time 10min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of Prepared with Laser Ablation, diameter 15nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 800 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 9
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Nb, and base material is Ti.Process conditions are: it is 0.7nm/s that adjusting power 70W makes deposition rate, and sputtering time is 5min, and sputter vacuum degree is 5 * 10
-4Pa, the Nb film thickness of plating is 210nm.
(2) with the Ti of plating Nb film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 10 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml water, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a stainless steel electrode; Process conditions during electrophoresis are: electrophoretic voltage 80V, electrophoresis time 0.5min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 10nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1200 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 10
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Zr, and base material is the glass of coating surface Cu.Process conditions are: it is 0.2nm/s that adjusting power 70W makes deposition rate, and sputtering time is 10min, and sputter vacuum degree is 5 * 10
-5Pa, the Zr film thickness of plating is 120nm.
(2) with the glass of the coating surface Cu of plating Zr film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is about 10 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml n-butanol, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a copper electrode; Process conditions during electrophoresis are: electrophoretic voltage 30V, electrophoresis time 10min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 10nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1200 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 11
(1) utilizes vacuum evaporation coating embrane method plating transiting metal film on base material.The employing transition metal is Zr, and base material is the glass of coating surface Ni.Process conditions are: it is 0.6nm/s that adjusting power 100W makes deposition rate, and sedimentation time is 10min, and vacuum degree is 1 * 10
-5Pa, the Zr film thickness of plating is 360nm.
(2) with the glass of the coating surface Ni of plating Zr film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is about 10 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml ethanol, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a copper electrode; Process conditions during electrophoresis are: electrophoretic voltage 30V, electrophoresis time 10min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 10nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 1 * 10
-6The 1.5h that anneals in the vacuum environment of Pa, annealing temperature is 1000 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 12
(1) utilizes vacuum evaporation coating embrane method plating transiting metal film on base material.The employing transition metal is Nb, and base material is the glass of coating surface Ti.Process conditions are: it is 0.2nm/s that adjusting power 70W makes deposition rate, and sedimentation time is 10min, and vacuum degree is 8 * 10
-4Pa, the Nb film thickness of plating is 120nm.
(2) with the glass of the coating surface Ti of plating Nb film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 20 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml n-butanol, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a stainless steel electrode; Process conditions during electrophoresis are: electrophoretic voltage 100V, electrophoresis time 10min, the spacing 5cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 20nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 1 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1200 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Hf, and base material is the glass of coating surface Fe.Process conditions are: it is 0.2nm/s that adjusting power 70W makes deposition rate, and sputtering time is 10min, and sputter vacuum degree is 5 * 10
-4Pa, the Hf film thickness of plating is 120nm.
(2) with the glass of the coating surface Fe of plating Hf film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 12 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml ethanol, sonic oscillation 1.5h, sedimentation 1.5h and obtaining then; Used anode is a copper electrode; Process conditions during electrophoresis are: electrophoretic voltage 80V, electrophoresis time 10min, the spacing 2cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 20nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1200 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 14
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Zr, and base material is the glass of coating surface Al.Process conditions are: it is 0.2nm/s that adjusting power 70W makes deposition rate, and sputtering time is 10min, and sputter vacuum degree is 5 * 10
-4Pa, the Zr film thickness of plating is 120nm.
(2) with the glass of the coating surface Al of plating Zr film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 10 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml water, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a copper electrode; Process conditions during electrophoresis are: electrophoretic voltage 60V, electrophoresis time 10min, the spacing 3cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of chemical vapour deposition technique preparation, diameter 25nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-5The 1.5h that anneals in the vacuum environment of Pa, annealing temperature is 1000 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Embodiment 15
(1) utilizes rf magnetron sputtering coating method plating transiting metal film on base material.The employing transition metal is Nb, and base material is Fe.Process conditions are: it is 0.2nm/s that adjusting power 70W makes deposition rate, and sputtering time is 10min, and sputter vacuum degree is 5 * 10
-4Pa, the Nb film thickness of plating is 120nm.
(2) with the Fe of plating Nb film as negative electrode, utilize the electrophoresis carbon nano-tube film depositing, film thickness is 10 μ m.Electrophoresis liquid is by 0.3g carbon nano-tube and 0.2g Mg (NO
3)
26H
2O is dispersed in the 200ml water, sonic oscillation 1.5h, sedimentation 2h and obtaining then; Used anode is a stainless steel electrode; Process conditions during electrophoresis are: electrophoretic voltage 30V, electrophoresis time 10min, the spacing 1cm of negative electrode and anode; The carbon nano-tube of using is the multi-walled carbon nano-tubes of arc discharge method preparation, diameter 30nm.
(3) after electrophoresis finishes, with carbon nano-tube thin film cathode 5 * 10
-6The 2h that anneals in the vacuum environment of Pa, annealing temperature is 1200 ℃, promptly gets the carbon nano-tube film that improves the electronic field emission performance.
Claims (6)
1. a method of improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method is characterized in that, carries out according to following steps:
(1) adopt physical vapor deposition coating film method plating transiting metal film on the conductive substrates material, described plating technic: vacuum degree is 3 * 10
-4～2 * 10
-6Pa, deposition rate is 0.2～0.8nm/s, film thickness 100～400nm;
(2) with the conductive substrates behind the plating as negative electrode, the electrophoretic deposition carbon nano-tube film, described electrophoretic deposition process: electrophoretic voltage is 30～120V, electrophoresis time is 0.5～10min, the spacing of negative electrode and anode is 1～5cm, 30min～2h of pre-sedimentation time of electrophoresis liquid, the pre-ultrasonic jitter time 1～2h of electrophoresis liquid;
(3) carbon nano-tube thin film cathode to deposition carries out annealing in process, described annealing treating process: vacuum degree is 1 * 10
-5～1 * 10
-7Pa, annealing time are 1～2h, and annealing temperature is 800～1200 ℃.
2. a kind of method of improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method according to claim 1, it is characterized in that described conductive substrates material is a kind of in the glass of the glass of glass, coating surface Fe of glass, the coating surface Ti of glass, the coating surface Ni of ITO electro-conductive glass, Cu, Ni, Ti, Fe, Al, Si, coating surface Cu and coating surface Al.
3. a kind of method of improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method according to claim 1, it is characterized in that described physical vapor deposition coating film method is a kind of in vacuum vapor plating, rf magnetron sputtering plated film and the ion film plating.
4. a kind of method of improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method according to claim 1 is characterized in that, described transition metal is a kind of among Ti, Zr, Hf, Nb and the Ta.
5. a kind of method of improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method according to claim 1 is characterized in that described anode is any one in copper electrode, platinum electrode, the stainless steel electrode.
6. a kind of method of improving emission property of deposited carbon nano-tube thin film electronic field by electrophorisis method according to claim 1 is characterized in that, described electrophoresis liquid makes in water, isopropyl alcohol, n-butanol and the ethanol any one as dispersant.
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| CN101973510B (en) * | 2010-10-24 | 2012-03-07 | 天津大学 | Method for preparing gas-sensitive sensor element based on carbon nano tube microarray/tungsten oxide nano composite structure |
| CN102423168A (en) * | 2011-11-04 | 2012-04-25 | 昆山龙鹰金属制品有限公司 | 201 stainless steel insole production process |
| CN103346051A (en) * | 2013-06-09 | 2013-10-09 | 中国科学院深圳先进技术研究院 | Carbon nanometer tube negative electrode and method for preparing carbon nanometer tube negative electrode |
| CN113380597B (en) * | 2021-05-05 | 2022-08-30 | 温州大学 | Carbon nanotube-based micro-focus field emission electron source and preparation method thereof |
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| 电泳法制备碳纳米管场发射阴极的研究. ***，孙卓，陈婷，陈奕卫.真空科学与技术学报，第26卷第1期. 2006 |
| 电泳法制备碳纳米管场发射阴极的研究. ***，孙卓，陈婷，陈奕卫.真空科学与技术学报，第26卷第1期. 2006 * |
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