CN103456581A - Carbon nanometer tube field emitting cathode and manufacturing method thereof - Google Patents
Carbon nanometer tube field emitting cathode and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a carbon nanometer tube field emitting cathode and a manufacturing method thereof. The carbon nanometer tube field emitting cathode comprises a conductive substrate, a grapheme layer and a carbon nanometer tube layer, wherein the grapheme layer and the carbon nanometer tube layer are sequentially stacked on the conductive substrate. The theory ratio surface area of grapheme reaches up to 2600m<2>/g, the unique two-dimensional structure of the carbon nanometer tube field emitting cathode can conduct effective electric heat transmission, more excellent thermotics and electrics performance is obtained compared with a carbon nanometer tube, the grapheme layer is arranged between the conductive substrate and the carbon nanometer tube layer, the characteristics of the large grapheme ratio surface area and excellent conductive heat dissipation are brought into full play, adhesive force of the carbon nanometer tube layer can be improved, and an emission current and stability are improved.
Description
Technical field
The present invention relates to a lift-off technology field, particularly relate to a kind of carbon nanotube field emission cathode and preparation method thereof.
Background technology
Carbon nano-tube is a kind of Novel Carbon Nanomaterials, it has excellent conductance, the outstanding electron emissivity produced by nano level tip and the stable characteristics such as mechanochemistry characteristic, it is a kind of desirable field emmision material, but show as instant on switch, the unlatching electric field is low, and emission is large, is expected to emission on the scene field and is used widely.
But the key of the application in carbon nano-tube emission on the scene is to prepare continous-stable electron emission, carbon nanotube cathod that emission current is larger.At present, method commonly used comprises chemical vapor deposition (CVD) method, silk screen print method and electrophoresis.Wherein, electrophoresis technique is simple and easy to control, and manufacturing cycle is short, can on the substrate of any shape and size, large tracts of land prepare carbon nanotube field emission cathode, and actual application prospect is wide.It is that carbon nano-tube, dispersant, charge additive etc. are dispersed in water or organic solvent, under direct current or AC field effect, and carbon nano-tube anode or movable cathode, and deposit on electrically-conductive backing plate.The problem that electrophoresis exists is, the adhesion of carbon nanotube layer and electrically-conductive backing plate a little less than, contact resistance is large, causes an emission current less, launches stable not.
Summary of the invention
Based on this, be necessary that a kind of emission current is large, the more stable carbon nanotube field emission cathode of emission for providing.
A kind of carbon nanotube field emission cathode, comprise electrically-conductive backing plate and stack gradually graphene layer and the carbon nanotube layer on described electrically-conductive backing plate.
In embodiment, the material of described graphene layer comprises Graphene and the first charge additive therein.
Therein in embodiment, the quality of described the first charge additive be described Graphene quality 0.13～64%.
In embodiment, described the first charge additive is magnesium ion, aluminium ion, nickel ion, iron ion or silver ion therein.
In embodiment, the material of described carbon nanotube layer comprises carbon nano-tube and the second charge additive therein.
Therein in embodiment, the quality of described the second charge additive be described carbon nano-tube quality 0.13～64%.
In embodiment, described the second charge additive is magnesium ion, aluminium ion, nickel ion, iron ion or silver ion therein.
In embodiment, the thickness of described graphene layer is 0.1 micron～1 micron therein.
In embodiment, the thickness of described carbon nanotube layer is 1 micron～10 microns therein.
A kind of preparation method of carbon nanotube field emission cathode, comprise the steps:
Electrically-conductive backing plate is provided;
The electrophoresis liquid that preparation contains Graphene respectively and the electrophoresis liquid that contains carbon nano-tube;
Described electrically-conductive backing plate is put into to the described electrophoresis liquid that contains Graphene, and the electrophoretic deposition Graphene, on described electrically-conductive backing plate, obtains being laminated with the electrically-conductive backing plate of graphene layer; And
The described electrically-conductive backing plate that is laminated with graphene layer is put into to the described electrophoresis liquid that contains carbon nano-tube, and the electrophoretic deposition carbon nano-tube, to described graphene layer, forms and is laminated in the carbon nanotube layer on described graphene layer, obtains described carbon nanotube field emission cathode.
In embodiment, also comprise the step that described carbon nanotube layer is dried therein.
Therein in embodiment, described described electrically-conductive backing plate is put into to the described electrophoresis liquid that contains Graphene, the electrophoretic deposition Graphene is on described electrically-conductive backing plate, obtain being laminated with in the step of electrically-conductive backing plate of graphene layer, the voltage of described electrophoresis is 100 volts～200 volts, and the time of electrophoresis is 10 seconds～60 seconds.
Therein in embodiment, described described electrically-conductive backing plate is put into to the described electrophoresis liquid that contains Graphene, the electrophoretic deposition Graphene is on described electrically-conductive backing plate, obtain being laminated with in the step of electrically-conductive backing plate of graphene layer, take described electrically-conductive backing plate as negative electrode, conductive substrate is as anode, and the distance of described negative electrode and anode is 0.1 centimetre～5 centimetres.
Therein in embodiment, described the described electrically-conductive backing plate that is laminated with graphene layer is put into to the described electrophoresis liquid that contains carbon nano-tube, the electrophoretic deposition carbon nano-tube is to described graphene layer, formation is laminated in the step of the carbon nanotube layer on described graphene layer, the voltage of described electrophoresis is 100 volts～200 volts, and the time of electrophoresis is 1 minute～5 minutes.
Therein in embodiment, described the described electrically-conductive backing plate that is laminated with graphene layer is put into to the described electrophoresis liquid that contains carbon nano-tube, the electrophoretic deposition carbon nano-tube is to described graphene layer, formation is laminated in the step of the carbon nanotube layer on described graphene layer, using the described electrically-conductive backing plate of Graphene that is laminated with as negative electrode, conductive substrate is as anode, and the distance of described negative electrode and anode is 0.1 centimetre～5 centimetres.
Above-mentioned carbon nanotube field emission cathode comprises electrically-conductive backing plate and stack gradually graphene layer and the carbon nanotube layer on electrically-conductive backing plate, and the theoretical specific area of Graphene is up to 2600m
2/ g, its unique two-dimensional structure can carry out effective electric heating transmission, there is the calorifics more excellent than carbon nano-tube and electric property, between electrically-conductive backing plate and carbon nanotube layer, graphene layer is set, give full play to the characteristic that the Graphene specific area is huge and conductive radiator is excellent, the adhesive force of carbon nanotube layer be can improve, emission current and stability improved.
The accompanying drawing explanation
The structural representation of the carbon nanotube field emission cathode that Fig. 1 is an execution mode;
The preparation method's of the carbon nanotube field emission cathode that Fig. 2 is an execution mode flow chart;
The emission current I of the carbon nanotube field emission cathode that Fig. 3 is embodiment 1 and Comparative Examples 1 is with the change curve of electric field E;
The field emission current I of the carbon nanotube field emission cathode that Fig. 4 is embodiment 1 and Comparative Examples 1 is curve over time.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the carbon nanotube field emission cathode 100 of an execution mode, comprise electrically-conductive backing plate 10 and stack gradually graphene layer 20 and the carbon nanotube layer 30 on conductive laminate 10.
In the present embodiment, electrically-conductive backing plate 10 is the metal substrates such as stainless steel substrate, titanium-base, copper base, aluminium base, chrome substrate or ni substrate.
In another embodiment, electrically-conductive backing plate 10 has the insulated substrate of the metal coatings such as tungsten, molybdenum, titanium, nickel, chromium, gold, silver or platinum for plating, and wherein, insulated substrate is glass, pottery or silicon chip.
In other embodiments, electrically-conductive backing plate 10 is indium tin oxide electro-conductive glass (ito glass).
The material of graphene layer 20 comprises Graphene and the first charge additive.
Graphene is a kind of New Two Dimensional carbon nanomaterial, and its theoretical specific area is up to 2600m
2/ g, make carbon nanometer layer 30 to be attached to more reliably on graphene layer 20, is conducive to improve the launch stability of carbon nanotube field emission cathode 100.
Graphene can be the mixture of single-layer graphene, multi-layer graphene or single-layer graphene and multi-layer graphene.Can be graphene oxide or reduced graphene.
Preferably, the thickness of reduced graphene is 1.1 nanometers～3.7 nanometers, and the thickness of graphene oxide is 5.0 nanometers～8.6 nanometers.
The two-dimensional structure of Graphene uniqueness can carry out effective electric heating transmission, has the thermal property more excellent than carbon nano-tube and electric property, and its thermal conductivity reaches 3000W/ (mK), and the room temperature electron mobility reaches 15000cm
2/ (Vs).Therefore, graphene layer 20 has thermal property and electric property preferably.
The first charge additive is soluble metal ion, is preferably magnesium ion (Mg
2+), aluminium ion (Al
3+), nickel ion (Ni
2+), iron ion (Fe
3+) or silver ion (Ag
+).
Preferably, the quality of the first charge additive be Graphene quality 0.13～64%.
Preferably, the thickness of graphene layer 20 is 0.1 micron～1 micron.In 0.1 micron～1 micron this thickness range, graphene layer 20 can form comparatively evenly continuous film, is conducive to uniform deposition and the conductive and heat-conductive of follow-up carbon nano-tube.
The material of carbon nanotube layer 30 comprises carbon nano-tube and the second charge additive.
Carbon nano-tube can be at least one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, modified Single Walled Carbon Nanotube and modified multi-walled carbon nano-tubes.
The diameter of carbon nano-tube is 2 nanometers～20 nanometers, and length is 1 micron～100 microns, and length is preferably 1～20 micron.
The second charge additive is soluble metal ion, is preferably magnesium ion (Mg
2+), aluminium ion (Al
3+), nickel ion (Ni
2+), iron ion (Fe
3+) or silver ion (Ag
+).
Preferably, the quality of the second charge additive be carbon nano-tube quality 0.13～64%.
Preferably, the thickness of carbon nanotube layer 30 is 1 micron～10 microns.In the thickness range of 1 micron～10 microns, the uniformity of carbon nanotube layer 30 is better, obtains comparatively reasonably carbon nanotube density simultaneously, is conducive to reduce the screen effect in emission process on the scene, thereby improves field emission performance.
Above-mentioned carbon nanotube field emission cathode 100 arranges graphene layer 20 between electrically-conductive backing plate 10 and carbon nanotube layer 30, Graphene and carbon nano-tube are all carbon nanomaterials, make between graphene layer 20 and carbon nanotube layer 30 very strong Van der Waals force is arranged, therefore carbon nanotube layer 30 can be closely and graphene layer 20 combinations, overcome the weak problem of carbon nanotube layer and electrically-conductive backing plate adhesion in conventional carbon nanotube field emission cathode, improved the stability of emission current in an emission process.
And Graphene has huge two-dimensional areas, carbon nanotube layer 30 contacts with electrically-conductive backing plate 10 by graphene layer 20, and because contact area increases, contact resistance obviously reduces, thereby improves emission current.
Because Graphene has excellent heat dispersion, make graphene layer 20 can discharge rapidly the heat that this carbon nanotube field emission cathode 100 produces in emission process, prevent that carbon nanotube layer 30 from damaging rapidly, further is conducive to improve launch stability, and improved useful life.
Refer to Fig. 2, the preparation method of the carbon nanotube field emission cathode of an execution mode, comprise the steps:
Step S110: electrically-conductive backing plate is provided.
Electrically-conductive backing plate can be the metal substrates such as stainless steel substrate, titanium-base, copper base, aluminium base, chrome substrate or ni substrate; The insulated substrate of the metal coatings such as tungsten, molybdenum, titanium, nickel, chromium, gold, silver or platinum is perhaps arranged for plating, and wherein insulated substrate is glass, pottery or silicon chip.
In other execution mode, electrically-conductive backing plate is ito glass.
Electrically-conductive backing plate is used to acetone, ethanol ultrasonic cleaning 10 minutes successively, then dry up with nitrogen, standby.
Step S120: the electrophoresis liquid that preparation contains Graphene respectively and the electrophoresis liquid that contains carbon nano-tube.
By Graphene with the first electric charge additive is ultrasonic is scattered in the first organic solvent, preparation obtains the electrophoresis liquid that contains Graphene.
Graphene can be the mixture of single-layer graphene, multi-layer graphene or single-layer graphene and multi-layer graphene.Can be graphene oxide or reduced graphene.
Can adopt chemical vapour deposition technique and chemical method (Hummer method) to prepare Graphene, also can adopt commercially available Graphene.
The first electric charge additive is the soluble metal inorganic salts, is preferably magnesium nitrate (Mg (NO
3)
2), magnesium chloride (MgCl
2), magnesium sulfate (MgSO
4), aluminum nitrate (Al (NO
3)
3), aluminium chloride (AlCl
3), nickel chloride (NiCl
2), iron chloride (FeCl
3) or silver nitrate (AgNO
3).
Graphene and the first electric charge additive are scattered in the first organic solvent simultaneously, make the first charge additive the adsorption of metal ions in the first electric charge additive on Graphene, make Graphene charged, to realize electrophoresis.
Preferably, the concentration of Graphene is 0.05mg/mL～0.5mg/mL.Select this concentration, make the uniformity of follow-up electrophoretic deposition better, prepare thickness graphene layer comparatively uniformly.Simultaneously, under this concentration, obtain a more suitable deposition rate.When the concentration of Graphene is greater than 0.5mg/mL, the bad dispersibility of the electrophoresis liquid that this contains Graphene, deposition effect is bad; When the concentration of Graphene is less than 0.05mg/mL, deposition rate is too slow, and preparation efficiency is low.
Preferably, the quality of the first electric charge additive be Graphene quality 1～100%, can realize with comparalive ease electrophoretic deposition process in this scope.When the consumption of the first electric charge additive be less than the Graphene quality 1% the time, very little, electrophoresis is difficult to realize the electrically charged amount of Graphene; When the consumption of the first electric charge additive be greater than the Graphene quality 100% the time, in electrophoresis liquid, do not have the ion of absorption to move to electrode, suppressed Graphene to movable cathode, also be unfavorable for electrophoresis.
More preferably, the quality of the first electric charge additive account for Graphene quality 25～50%.
Preferably, the first organic solvent is at least one in methyl alcohol, ethanol, propyl alcohol and acetone, is preferably ethanol.
By carbon nano-tube with the second electric charge additive is ultrasonic is scattered in the second organic solvent, preparation obtains the electrophoresis liquid that contains carbon nano-tube.
Carbon nano-tube can be at least one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, modified Single Walled Carbon Nanotube and modified multi-walled carbon nano-tubes.
The diameter of carbon nano-tube is 2 nanometers～20 nanometers, and length is 1 micron～100 microns.Length is preferably 1～20 micron.
Carbon nano-tube can adopt universal method as preparations such as arc discharge method, chemical vapour deposition technique or laser ablation methods, also can adopt commercially available carbon nano-tube.
The second electric charge additive is the soluble metal inorganic salts, is preferably magnesium nitrate (Mg (NO
3)
2), magnesium chloride (MgCl
2), magnesium sulfate (MgSO
4), aluminum nitrate (Al (NO
3)
3), aluminium chloride (AlCl
3), nickel chloride (NiCl
2), iron chloride (FeCl
3) or silver nitrate (AgNO
3).
Carbon nano-tube and the second electric charge additive are scattered in the second organic solvent simultaneously, make the second charge additive the adsorption of metal ions in the second electric charge additive on carbon nano-tube, make carbon nano-tube charged, to realize electrophoresis.
Preferably, the concentration of carbon nano-tube is 0.01mg/mL～0.1mg/mL.Select this concentration, make the uniformity of follow-up electrophoretic deposition better, prepare thickness carbon nanotube layer comparatively uniformly.Simultaneously, under this concentration, obtain a more suitable deposition rate.When the concentration of carbon nano-tube is greater than 0.1mg/mL, the bad dispersibility of the electrophoresis liquid that this contains carbon nano-tube, deposition effect is bad; When the concentration of carbon nano-tube is less than 0.01mg/mL, deposition rate is too slow, and preparation efficiency is low.
Preferably, the quality of the second electric charge additive be carbon nano-tube quality 1～100%, can realize with comparalive ease electrophoretic deposition process in this scope.When the consumption of the second electric charge additive be less than the carbon nano-tube quality 1% the time, very little, electrophoresis is difficult to realize the electrically charged amount of carbon nano-tube; When the consumption of the second electric charge additive be greater than the carbon nano-tube quality 100% the time, in electrophoresis liquid, do not have the ion of absorption to move to electrode, suppressed carbon nano-tube to movable cathode, also be unfavorable for electrophoresis.
More preferably, the quality of the second electric charge additive account for carbon nano-tube quality 25～50%.
Preferably, the second organic solvent is at least one in methyl alcohol, ethanol, propyl alcohol and acetone, is preferably ethanol.
The electrophoresis liquid that preparation contains Graphene and the electrophoresis liquid ultrasonic dispersing apparatus used that contains carbon nano-tube are supersonic cleaning machine or biomixer.The time of ultrasonic dispersion is preferably 1 hour～and 3 hours.
Step S130: electrically-conductive backing plate is put into to the electrophoresis liquid that contains Graphene, the electrophoretic deposition Graphene, to electrically-conductive backing plate, obtains being laminated with the electrically-conductive backing plate of graphene layer.
Put into the electrophoresis liquid that contains Graphene using the electrically-conductive backing plate of step S110 as negative electrode, put into this electrophoresis liquid that contains Graphene simultaneously using conductive substrate as anode and carry out electrophoresis.Under the effect of direct current or AC field, with the Graphene of electric charge, to movable cathode, make to be deposited on electrically-conductive backing plate with the Graphene of electric charge, form and be laminated in the graphene layer on electrically-conductive backing plate, obtain being laminated with the electrically-conductive backing plate of graphene layer.
Conductive substrate as anode is metal substrate, is preferably anaerobic copper sheet or stainless steel substrates.
The thickness of graphene layer was controlled by voltage and the time of electrophoresis.Preferably, the voltage of electrophoresis is 100 volts～200 volts.The time of electrophoresis is 10 seconds～60 seconds.
Preferably, as the electrically-conductive backing plate of negative electrode be 0.1 centimetre～5 centimetres as the spacing of the conductive substrate of anode.Select this spacing, be conducive to reduce the edge effect existed between negative electrode and anode.More preferably, this spacing is 0.1 centimetre～1 centimetre.
Preferably, when the shape of the shape of required graphene layer and follow-up carbon nanotube layer and electrically-conductive backing plate is different, in order to prepare graphene layer and the carbon nanotube layer with regular shape and accurate dimension, be pre-formed certain photoetching agent pattern on electrically-conductive backing plate, and then the deposition Graphene, form graphene layer.
Step S140: the electrically-conductive backing plate that will be laminated with graphene layer is put into the electrophoresis liquid that contains carbon nano-tube, and the electrophoretic deposition carbon nano-tube, to graphene layer, forms and is laminated in the carbon nanotube layer on graphene layer, obtains carbon nanotube field emission cathode.
The electrically-conductive backing plate that is laminated with graphene layer that step S130 is prepared puts into as negative electrode the electrophoresis liquid that contains carbon nano-tube, puts into this electrophoresis liquid that contains carbon nano-tube simultaneously using conductive substrate as anode and carries out electrophoresis.Under the effect of direct current or AC field, with the carbon nano-tube of electric charge, to movable cathode, make to be deposited on graphene layer with the carbon nano-tube of electric charge, form and be laminated in carbon nanotube layer on graphene layer, obtain carbon nanotube field emission cathode.
Conductive substrate as anode is metal substrate, is preferably anaerobic copper sheet or stainless steel substrates.
The thickness of carbon nanotube layer was controlled by voltage and the time of electrophoresis.Preferably, the voltage of electrophoresis is 100 volts～200 volts.The time of electrophoresis is 1 minute～5 minutes.
Preferably, as the electrically-conductive backing plate that is laminated with graphene layer of negative electrode be 0.1 centimetre～5 centimetres as the spacing of the conductive substrate of anode.Select this spacing, be conducive to reduce the edge effect existed between negative electrode and anode.More preferably, this spacing is 0.1 centimetre～1 centimetre.
While before the electrophoretic deposition Graphene prepares graphene layer, being pre-formed certain photoetching agent pattern on electrically-conductive backing plate, after electrophoresis formation is laminated in the carbon nanotube layer on graphene layer, use again the solution that can dissolve photoresist that photoetching agent pattern is removed, thereby obtain having graphene layer and the carbon nanotube layer of regular shape and accurate dimension.
Preferably, after forming carbon nano-tube, also comprise dry step, to remove organic solvent remaining in carbon nanotube layer, improve the adhesion of carbon nanotube layer and electrically-conductive backing plate, to improve launch stability.
Preferably, dry step be drying 1 hour～5 hours under 50 ℃～100 ℃.
Preparation method's technique of above-mentioned carbon nanotube field emission cathode is simple, and, without HTHP, energy consumption is low, and preparation cost is low, is beneficial to promotion and application, can preparation cost low, emission current is large and the higher carbon nanotube field emission cathode of launch stability.
Below by specific embodiment, further set forth.
Prepare carbon nanotube field emission cathode
(1) reduced graphene of thickness 1.1～3.7nm is added in absolute ethyl alcohol, and add 50%MgCl
2(using Graphene quality), as the first electric charge additive, Graphene concentration is 0.05mg/ml, and ultrasonic dispersion 1h obtains the electrophoresis liquid of graphene-containing;
(2) diameter is less than to 8nm, the multi-walled carbon nano-tubes of length 5～15 μ m adds in absolute ethyl alcohol, and adds 25%MgCl
2(using carbon nano-tube quality), as the second electric charge additive, carbon nano-tube concentration is 0.01mg/ml, and ultrasonic dispersion 1h obtains the electrophoresis liquid of carbon nanotubes;
(3) using ito glass as electrically-conductive backing plate, using this electrically-conductive backing plate as negative electrode, using the anaerobic copper sheet as anode, before using, successively with acetone, ethanol ultrasonic cleaning 10min, nitrogen dries up.Then, clean, dry electrically-conductive backing plate and anaerobic copper sheet are inserted in the electrophoresis liquid of graphene-containing to negative electrode and anode spacing 0.1cm, direct current electrophoretic voltage 120V, electrophoresis time 1min deposits Graphene on electrically-conductive backing plate, forms and is laminated in the graphene layer on electrically-conductive backing plate; Wherein, the thickness of this graphene layer is 1 micron, the first charge additive Mg in graphene layer
2+the quality quality that is Graphene 12%;
(4) using the above-mentioned electrically-conductive backing plate of graphene layer that is laminated with as negative electrode, using the anaerobic copper sheet as anode, the electrically-conductive backing plate and the anaerobic copper sheet that are laminated with graphene layer are inserted in the electrophoresis liquid that contains carbon nano-tube, negative electrode and anode spacing 0.1cm, direct current electrophoretic voltage 100V, electrophoresis time 5min, deposition of carbon nanotubes on graphene layer, form and be laminated in the carbon nanotube layer on graphene layer; Wherein, the thickness of carbon nanotube layer is 10 microns, the second charge additive Mg in carbon nanotube layer
2+the quality quality that is carbon nano-tube 6%;
(5) sample above-mentioned steps (4) prepared, in 60 ℃ of lower vacuumizes 1 hour, obtains carbon nanotube field emission cathode.
Prepare carbon nanotube field emission cathode
(1) graphene oxide of thickness 5.0～8.6nm is added in absolute ethyl alcohol, and add 1%Mg (NO
3)
2(using Graphene quality), as the first electric charge additive, Graphene concentration is 0.5mg/ml, and ultrasonic dispersion 1h obtains the electrophoresis liquid of graphene-containing;
(2) diameter is less than to 10～20nm, the Single Walled Carbon Nanotube of length 10～20 μ m adds in absolute ethyl alcohol, and adds 1%Mg (NO
3)
2(using carbon nano-tube quality), as the second electric charge additive, carbon nano-tube concentration is 0.1mg/ml, and ultrasonic dispersion 3h obtains the electrophoresis liquid of carbon nanotubes;
(3) using deposit layer of titanium metal glass substrate as electrically-conductive backing plate, using this electrically-conductive backing plate as negative electrode, using stainless steel substrates as anode, before using, successively with acetone, ethanol ultrasonic cleaning 10min, nitrogen dries up.Then, clean, dry electrically-conductive backing plate and stainless steel substrates are inserted in the electrophoresis liquid of graphene-containing to negative electrode and anode spacing 5cm, direct current electrophoretic voltage 200V, electrophoresis time 10s deposits Graphene on electrically-conductive backing plate, forms and is laminated in the graphene layer on electrically-conductive backing plate; Wherein, the thickness of this graphene layer is 0.1 micron, the first charge additive Mg in graphene layer
2+the quality quality that is Graphene 0.2%;
(4) using the above-mentioned electrically-conductive backing plate of graphene layer that is laminated with as negative electrode, using stainless steel substrates as anode, the electrically-conductive backing plate and the stainless steel substrates that are laminated with graphene layer are inserted in the electrophoresis liquid that contains carbon nano-tube, negative electrode and anode spacing 5cm, direct current electrophoretic voltage 100V, electrophoresis time 1min, deposition of carbon nanotubes on graphene layer, form and be laminated in the carbon nanotube layer on graphene layer; Wherein, the thickness of carbon nanotube layer is 1 micron, the second charge additive Mg in carbon nanotube layer
2+the quality quality that is carbon nano-tube 0.2%;
(5) sample above-mentioned steps (4) prepared, in 100 ℃ of lower vacuumizes 5 hours, obtains carbon nanotube field emission cathode.
Prepare carbon nanotube field emission cathode
(1) reduced graphene of thickness 1.1～3.7nm is added in acetone, and add 100%Al (NO
3)
3(using Graphene quality), as the first electric charge additive, Graphene concentration is 0.1mg/ml, and ultrasonic dispersion 1h obtains the electrophoresis liquid of graphene-containing;
(2) diameter is less than to 10～20nm, the multi-walled carbon nano-tubes of length 50 μ m adds in acetone, and adds 100%Al (NO
3)
3(using carbon nano-tube quality), as the second electric charge additive, carbon nano-tube concentration is 0.04mg/ml, and ultrasonic dispersion 3h obtains the electrophoresis liquid of carbon nanotubes;
(3) using deposit metallic silver layer glass substrate as electrically-conductive backing plate, using this electrically-conductive backing plate as negative electrode, using stainless steel substrates as anode, before using, successively with acetone, ethanol ultrasonic cleaning 10min, nitrogen dries up.Then, apply the SU-82025 photoresist on clean, dry electrically-conductive backing plate, through whirl coating, front baking, exposure and development, form the circular photoetching agent pattern that diameter is 3mm on electrically-conductive backing plate.Further, electrically-conductive backing plate and the stainless steel substrates that will be formed with circular photoetching agent pattern insert in the electrophoresis liquid of graphene-containing, negative electrode and anode spacing 1cm, direct current electrophoretic voltage 100V, electrophoresis time 30s deposits Graphene on electrically-conductive backing plate, forms and is laminated in the graphene layer on electrically-conductive backing plate; Wherein, the thickness of this graphene layer is 0.6 micron, the first charge additive Al in graphene layer
3+the quality quality that is Graphene 12%;
(4) using the above-mentioned electrically-conductive backing plate of graphene layer that is laminated with as negative electrode, using stainless steel substrates as anode, the electrically-conductive backing plate and the stainless steel substrates that are laminated with graphene layer are inserted in the electrophoresis liquid that contains carbon nano-tube, negative electrode and anode spacing 1cm, direct current electrophoretic voltage 200V, electrophoresis time 1min, deposition of carbon nanotubes on graphene layer, form and be laminated in carbon nanotube layer on graphene layer; Wherein, the thickness of carbon nanotube layer is 7 microns, the second charge additive Al in carbon nanotube layer
3+the quality quality that is carbon nano-tube 12%;
(5) sample above-mentioned steps (4) prepared is put into SU-8 except glue (SU-8Remover, purchase is from U.S. MicroChem company) in solution, 80 ℃ of heating 1min, remove remaining photoresist, and clean with acetone and alcohol flushing, obtain having graphene layer and the carbon nanotube layer of regular shape and accurate dimension;
(6) sample above-mentioned steps (5) prepared, in 60 ℃ of lower vacuumizes 5 hours, obtains carbon nanotube field emission cathode.
Comparative Examples 1
Prepare carbon nanotube field emission cathode
(1) diameter is less than to 8nm, the multi-walled carbon nano-tubes of length 5～15 μ m adds in absolute ethyl alcohol, and adds 25%MgCl
2(using carbon nano-tube quality), as the second electric charge additive, carbon nano-tube concentration is 0.01mg/ml, and ultrasonic dispersion 1h obtains the electrophoresis liquid of carbon nanotubes;
(2) using ito glass as electrically-conductive backing plate, using this electrically-conductive backing plate as negative electrode, using the anaerobic copper sheet as anode, before using, successively with acetone, ethanol ultrasonic cleaning 10min, nitrogen dries up.Then, clean, dry electrically-conductive backing plate and anaerobic copper sheet are inserted in the electrophoresis liquid of carbon nanotubes to negative electrode and anode spacing 0.1cm, direct current electrophoretic voltage 100V, electrophoresis time 5min, deposition of carbon nanotubes on electrically-conductive backing plate, form and be laminated in the carbon nanotube layer on electrically-conductive backing plate; Wherein, the thickness of this carbon nanotube layer is 10 microns, the first charge additive Mg in carbon nanotube layer
2+the quality quality that is carbon nano-tube 6%;
(3) sample above-mentioned steps (2) prepared, in 60 ℃ of lower vacuumizes 1 hour, obtains carbon nanotube field emission cathode.
Adopt diode structure respectively the carbon nanotube field emission cathode for preparing of embodiment 1 and Comparative Examples 1 to be carried out to the electron field emission property test.As shown in Figure 3, the unlatching electric field of the carbon nanotube field emission cathode (curve A) of embodiment 1 preparation is 1.8V/ μ m to test result, and the unlatching electric field of the carbon nanotube field emission cathode (curve B) prepared with Comparative Examples 1 is that 2.9V/ μ m compares, and has descended 38%.When electric field strength is 6V/ μ m, the cathode current emission is increased to 2.3mA from 1mA, has increased by 130%.
Respectively the carbon nanotube field emission cathode of embodiment 1 and Comparative Examples 1 preparation carried out to the field emission stability test, as shown in Figure 4.Result shows, the carbon nanotube field emission cathode of embodiment 1 preparation has good launch stability, emission current kept stable in the DC test time of 8h, illustrate that the carbon nanotube layer of carbon nanotube field emission cathode prepared by embodiment 1 and electrically-conductive backing plate combination are firm.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (15)
1. a carbon nanotube field emission cathode, is characterized in that, comprises electrically-conductive backing plate and stack gradually graphene layer and the carbon nanotube layer on described electrically-conductive backing plate.
2. carbon nanotube field emission cathode according to claim 1, is characterized in that, the material of described graphene layer comprises Graphene and the first charge additive.
3. carbon nanotube field emission cathode according to claim 2, is characterized in that, the quality of described the first charge additive be described Graphene quality 0.13～64%.
4. carbon nanotube field emission cathode according to claim 2, is characterized in that, described the first charge additive is magnesium ion, aluminium ion, nickel ion, iron ion or silver ion.
5. carbon nanotube field emission cathode according to claim 1, is characterized in that, the material of described carbon nanotube layer comprises carbon nano-tube and the second charge additive.
6. carbon nanotube field emission cathode according to claim 5, is characterized in that, the quality of described the second charge additive be described carbon nano-tube quality 0.13～64%.
7. carbon nanotube field emission cathode according to claim 5, is characterized in that, described the second charge additive is magnesium ion, aluminium ion, nickel ion, iron ion or silver ion.
8. carbon nanotube field emission cathode according to claim 1, is characterized in that, the thickness of described graphene layer is 0.1 micron～1 micron.
9. carbon nanotube field emission cathode according to claim 1, is characterized in that, the thickness of described carbon nanotube layer is 1 micron～10 microns.
10. the preparation method of a carbon nanotube field emission cathode, comprise the steps:
Electrically-conductive backing plate is provided;
The electrophoresis liquid that preparation contains Graphene respectively and the electrophoresis liquid that contains carbon nano-tube;
Described electrically-conductive backing plate is put into to the described electrophoresis liquid that contains Graphene, and the electrophoretic deposition Graphene, on described electrically-conductive backing plate, obtains being laminated with the electrically-conductive backing plate of graphene layer; And
The described electrically-conductive backing plate that is laminated with graphene layer is put into to the described electrophoresis liquid that contains carbon nano-tube, and the electrophoretic deposition carbon nano-tube, to described graphene layer, forms and is laminated in the carbon nanotube layer on described graphene layer, obtains described carbon nanotube field emission cathode.
11. the preparation method of carbon nanotube field emission cathode according to claim 10, is characterized in that, also comprises the step that described carbon nanotube layer is dried.
12. the preparation method of carbon nanotube field emission cathode according to claim 10, it is characterized in that, described described electrically-conductive backing plate is put into to the described electrophoresis liquid that contains Graphene, the electrophoretic deposition Graphene is on described electrically-conductive backing plate, obtain being laminated with in the step of electrically-conductive backing plate of graphene layer, the voltage of described electrophoresis is 100 volts～200 volts, and the time of electrophoresis is 10 seconds～60 seconds.
13. the preparation method of carbon nanotube field emission cathode according to claim 10, it is characterized in that, described described electrically-conductive backing plate is put into to the described electrophoresis liquid that contains Graphene, the electrophoretic deposition Graphene is on described electrically-conductive backing plate, obtain being laminated with in the step of electrically-conductive backing plate of graphene layer, take described electrically-conductive backing plate as negative electrode, and conductive substrate is as anode, and the distance of described negative electrode and anode is 0.1 centimetre～5 centimetres.
14. the preparation method of carbon nanotube field emission cathode according to claim 10, it is characterized in that, described the described electrically-conductive backing plate that is laminated with graphene layer is put into to the described electrophoresis liquid that contains carbon nano-tube, the electrophoretic deposition carbon nano-tube is to described graphene layer, formation is laminated in the step of the carbon nanotube layer on described graphene layer, the voltage of described electrophoresis is 100 volts～200 volts, and the time of electrophoresis is 1 minute～5 minutes.
15. the preparation method of carbon nanotube field emission cathode according to claim 10, it is characterized in that, described the described electrically-conductive backing plate that is laminated with graphene layer is put into to the described electrophoresis liquid that contains carbon nano-tube, the electrophoretic deposition carbon nano-tube is to described graphene layer, formation is laminated in the step of the carbon nanotube layer on described graphene layer, using the described electrically-conductive backing plate that is laminated with Graphene as negative electrode, and conductive substrate is as anode, and the distance of described negative electrode and anode is 0.1 centimetre～5 centimetres.
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