CN102262988A - Method for manufacturing carbon nanotube cold cathode and application of method - Google Patents
Method for manufacturing carbon nanotube cold cathode and application of method Download PDFInfo
- Publication number
- CN102262988A CN102262988A CN2010101904240A CN201010190424A CN102262988A CN 102262988 A CN102262988 A CN 102262988A CN 2010101904240 A CN2010101904240 A CN 2010101904240A CN 201010190424 A CN201010190424 A CN 201010190424A CN 102262988 A CN102262988 A CN 102262988A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- tube
- alloy
- cold cathode
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a method for manufacturing a carbon nanotube cold cathode. The method comprises the following steps of: mixing and stirring provided metal powder, a carbon nanotube and an organic adhesion agent to form carbon nanotube slurry, wherein the melting point of metal ranges from 150 to 600 DEG C; screen-printing the carbon nanotube slurry on a substrate; sintering the printed substrate with the carbon nanotube slurry at temperature greater than the melting point of the used metal, so that the metal can be melted and the organic adhesion agent can be volatilized or decomposed; and cooling the substrate to form the carbon nanotube cold cathode. The invention also provides application of the method for manufacturing the carbon nanotube cold cathode. In the manufacturing method, the metal powder, the carbon nanotube and the organic adhesion agent are mixed to form the slurry, the slurry is printed on the substrate by using a screen-printing technology and then the substrate is sintered, so that an adhesive force of the carbon nanotube on the substrate can be increased, the field emission performance can be enhanced, and batch manufacturing of cold cathodes can be realized by using the mature screen-printing technology; therefore, the method has a wide industrial application prospect.
Description
Technical field
The invention belongs to the cold cathode device technical field, be specifically related to a kind of manufacture method and application thereof of carbon nano-tube cold cathode.
Background technology
The device of cold-cathode emitting electron becomes one of present research focus, and for example feds is a kind of device of typical cold-cathode emitting electron, and it need not the target heating only needs to apply certain electric field on its surface, just can launch electronics.Feds can be used for flat panel display, light source, travelling wave tube etc.During as light source applications, have that energy-saving and environmental protection, working range are big, radioresistance, advantage such as frivolous, can be widely used in each lighting field, have great potential.
Electron emitter and phosphor screen are two crucial in field emission light source parts.In the making of cold cathode, the present master that is applied as with carbon nano-tube.The carbon nano-tube cold cathode passes through the carbon nano-tube of the effect direct growth of catalyst generally by the method for chemical vapour deposition (CVD) on backing material.In this method, the adhesion of carbon nano-tube and substrate is relatively poor, can be subjected to ion bombardment and come off from substrate under high electric field action, causes emission current obviously to descend, and emission is unstable.In addition, the temperature during the direct growth carbon nano-tube is higher, generally all is higher than the fusing point of glass, considers cost of manufacture, and this also is unfavorable for its large-area applications on glass substrate.Adopt growth carbon nano-tube earlier, then the carbon nano-tube of preparation is formed on the substrate that will use again.Yet, the carbon nano-tube of on substrate, making by these modes and the problems such as poor adhesive force, poorly conductive and field emission characteristic difference of substrate.
For this reason, people adopt many improving one's methods to improve and the adhesive force of substrate, field emission characteristic etc.For example, existing a kind of chemical etching manufactured cold cathode, this method is mixed metal dust earlier with carbon nano-tube, and compacting sintering, in the method by chemical etching, the metal of etching surface makes carbon nano-tube come out then, this method has improved the adhesive force of carbon nano-tube and substrate, improve its anti-bombardment ability, prolonged its life-span, still, this method is unfavorable for large-area manufacturing, and etching homogeneity is difficult with control.Also have a kind of prior art, scattered carbon nano-tube is sprayed on the electrocondution slurry, through the surface of delineation electrocondution slurry, last sintering.Though this mode improves its emission characteristics through making an end of carbon nano-tube stick up a stroke quarter, draws a ratio of precision of carving and is difficult to control, and can cause scuffing to electrode, is unfavorable for the commercialization making.Also have other to press the mode of handling to improve ohmic contact and heat-conductive characteristic between printed carbon nanotube film and the conductive substrates in addition, adopt the mutual method that combines of czochralski method and heat treatment in addition as scraping.Though these methods can be improved the adhesive force and the field emission characteristic of carbon nano-tube and substrate to a certain extent, all be difficult to guaranteeing that the realization large tracts of land is effectively handled under the good situation of carbon nano-tube emission characteristics.
Summary of the invention
In view of this, the manufacture method of the low carbon nano-tube cold cathode of a kind of strong adhesion, conductivity height, emitting performance excellence and cost is provided.
And, the application of manufacture method in making vacuum electronic source array of this carbon nano-tube cold cathode is provided.
A kind of manufacture method of carbon nano-tube cold cathode, it comprises the steps:
The metal powder, the carbon nano-tube that provide are mixed with organic binder bond, stir, form the carbon nano-tube slurry, wherein melting point metal is 150 ℃～600 ℃;
The carbon nano-tube slurry is formed on the substrate by silk screen printing;
The substrate of printing back carbon nanotubes slurry at the above temperature sintering of the fusing point of used metal, is made the volatilization of metal molten and organic binder bond or decomposes, after the cooling, form described carbon nano-tube cold cathode.
And the manufacture method that above-mentioned carbon nano-tube cold cathode is provided is in the application of making Field Emission Display, field emission light source, travelling wave tube or transducer.
In the manufacture method and application thereof of described carbon nano-tube cold cathode, by being mixed the back, metal powder, carbon nano-tube and organic binder bond be formed on the substrate with silk screen printing side's technology, can be suitable for industrialized mass production, reduce manufacturing cost, be beneficial to large-area applications.By sintering processing, make the carbon nano-tube brute force be attached on the substrate, and make carbon nano-tube come out again, improve its emitting performance, also can utilize the good electric conductivity of metallic particles, improve the electric conductivity of cold cathode, have broad application prospects.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the process step schematic diagram of manufacture method of manufacture method of the carbon nano-tube cold cathode of the embodiment of the invention;
Fig. 2 is silk screen printing and the sinter molding flowage structure schematic diagram in the manufacture method of carbon nano-tube cold cathode of the embodiment of the invention;
Fig. 3 is the feds structural representation that the manufacture method of the carbon nano-tube cold cathode of the application embodiment of the invention is made.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, the flow process of manufacture method of the carbon nano-tube cold cathode of the embodiment of the invention is shown, comprise the steps:
S01: the metal powder that will provide, carbon nano-tube are mixed with organic binder bond, stir, and form the carbon nano-tube slurry, and wherein melting point metal is 150 ℃～600 ℃;
S02: the carbon nano-tube slurry is formed on the substrate by silk screen printing;
S03: the substrate that will print back carbon nanotubes slurry makes volatilization of metal molten and organic binder bond or decomposition at the above temperature sintering of the fusing point of used metal, after the cooling, forms described carbon nano-tube cold cathode.
Among the step S01, the material of metal powder is selected from least a in Sn, Bi, In, Tl, Sn alloy, Bi alloy, In alloy, the Tl alloy.Wherein each metal alloy can be at least a in Sn-Cu alloy, Sn-Ag alloy, Sn-Pb alloy, Sn-Zn alloy, In-Ag alloy, In-Zn alloy, In-Pb alloy, In-Cu alloy, Bi-Cu alloy, Bi-Ag alloy, Bi-Pb alloy or the Bi-Zn alloy for example.The fusing point of these metal or alloy is in 150 ℃～600 ℃ scopes.For example, the fusing point of Sn is 231.89 ℃, and the fusing point of Bi is 271.3 ℃, the fusing point of In is 156.61 ℃, and the fusing point of Tl is 303.5 ℃, and the fusing point of Sn alloy is at 210 ℃～230 ℃, the melting range of Bi alloy is 220～262 ℃, and the melting range of In alloy is 160～180 ℃.Be understandable that the melting range of above-mentioned each metal alloy is not limited to this only as an example.The metal or alloy of present embodiment adopts low-melting-point metal or alloy, for example is preferably fusing point 150 ℃～350 ℃ material.Further, when adopting the alloy material, can adopt low-melting alloy, promptly fusing point is lower than 232 ℃ alloy.By adopting this low melting point material, can reduce manufacturing cost on the one hand, can avoid the adverse effect of high temperature on the other hand to substrate and dependency structure (conductive coating structure that for example relates to later) thereof etc., for example when adopting glass substrate, temperature Gao Shihui makes the softening even fusion of substrate, destroys its original structure shape.
The grain diameter of metal powder is 5 nanometers～300 micron, is specifically as follows 50 nanometers～2 micron.By adopting this powdered metal particles, because size is little even be nano-grade size, can promote its fusion on the one hand, accelerate fusion speed, can make that on the other hand metal powder and carbon nano-tube and organic binder bond mix, and when sintered molten or fusing, make metallic can be scattered in the carbon nano-tube particulate equably, carbon nano-tube comes out more equably after fusion, thereby improves electric conductivity and electron emission capability, and the uniform and stable property that increases the electronics emission.
Carbon nano-tube is preferably Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, many walls ordered carbon nanotube, at least a through in the carbon nano-tube of modifying or the array carbon nano-tube.Carbon nano-tube has higher draw ratio, and big field enhancement factor helps the emission of electronics, has fabulous field-causing electron emission effect.Wherein, the diameter of Single Walled Carbon Nanotube only has 1～2 nanometer usually, length can reach tens to microns up to a hundred, draw ratio is very big, and its structural intergrity is good, and conductivity is fine, stable chemical performance, the basic structural feature that has possessed the high-performance field emmision material, but the preparation of Single Walled Carbon Nanotube and dispersion are difficult.Using more at present is multi-walled carbon nano-tubes or many walls ordered carbon nanotube.In through the carbon nano-tube or array carbon nano-tube of modifying, can adopt the organic decoration mode, for example adopt hydroxyl, carboxyl or other substituting group form carbon nano-tube modified, perhaps carbon nano-tube is carried out macromolecular grafted modification, can strengthen its electrophilic performance and with the adhesion of organic principle, help the dispersion of carbon nano-tube, for example carbon nano-tube that process is modified in the present embodiment or array carbon nano-tube and organic binder bond adhesion are stronger, promote it to be uniformly dispersed.
This organic binder bond is selected the material that volatilizees or decompose for use under metal powder fusing point or sintering temperature, be that the volatilization of organic binder bond or decomposition temperature and metal powder fusing point are approaching, can be lower than the metal powder fusing point, for example can be the organic carrier of ethyl cellulose, terpinol, butyl carbitol acetate fat and ethyl lactate mixed preparing or the organic carrier of ethyl cellulose, terpinol, butyl carbitol and tributyl citrate mixed preparing, but be not limited to the organic binder bond of above dual mode preparation.Organic binder bond is mainly used in carbon nano-tube and substrate and metal powder is combined, in preparation process, make carbon nano-tube and metal powder mix, sintering time volatilization or divide and take off in the back then, so that carbon nano-tube is solidificated in the metal powder, and there is the part carbon nano-tube to be exposed to the surface of metal powder, improves electron emission capability.
In this mixed process, also available supersonic oscillations raw material in the time of stirring because carbon nano-tube is nanometer materials, is easily reunited, and therefore adopts supersonic oscillations to help its dispersing and mixing.The supersonic oscillations incorporation time can be for example 30 minutes-12 hours.Particularly, this mixed process can be carried out in two steps, earlier carbon nanometer tube material was mixed stirring and sonic oscillation 30 minutes-12 hours with organic binder bond, mix, again metal powder is joined in the mixture of front carbon nanometer tube material and organic binder bond, stir and ultrasonic 30 minutes-2 hours, form the carbon nano-tube slurry.By this substep mixed form, can avoid the formation earlier of carbon nano-tube and metal powder to reunite and be difficult to disperses, earlier carbon nanometer tube material is mixed with organic binder bond, can make carbon nano-tube in organic binder bond, disperse in advance earlier, and then when mixing, can not only avoid above-mentioned reunion situation, and can improve degree of scatter between carbon nano-tube and metal powder with metal powder, it is more even that they are disperseed, and dispersion degree is higher.
During mixing, metal powder, carbon nano-tube and organic binder bond three's mixing quality ratio can be (2～15): (5～20): (0.5～3), be that metal powder and carbon nano-tube mixing quality ratio are 1: 10 to 3: 1, carbon nano-tube and organic binder bond mixing quality ratio are 5: 3 to 20: 0.5.
Among the step S02, substrate 10 can have the substrate of conductive structure for one, or comprises substrate and be formed at the composite substrate of suprabasil conductive layer.The substrate material can be glass, pottery, silicon chip or metal.Wherein, the conductive material of conductive structure or conductive layer is selected from ITO, metal or composite conducting material in the substrate, conducting metal can be but be not limited to chromium, aluminium, conductive silver paste etc., and composite conducting material can be a conductive polymeric composite etc., and conductive structure can be the composite conducting structure.When substrate was used composite substrate, conductive layer can be but be not limited to the metal level of ITO layer and chromium, aluminium, conductive silver paste etc.The thickness of conductive layer is preferably 20 nanometers～200 micron, and conductive layer can be a full wafer, also can be list structure, can decide according to the actual requirements.
When employing has the substrate of conductive structure, directly the carbon nano-tube slurry is formed on this substrate by silk screen printing.When comprising, employing the compound substrate of conductive layer can in substrate, prepare conductive layer earlier.See also Fig. 2, Fig. 2 (a) shows the compound substrate 10 that comprises conductive layer 12.Conductive layer 12 can adopt film preparing technology to be formed on the clean substrate of glass 11, shown in Fig. 2 (a).Film preparing technology for example can be but be not limited to sol-gel process, chemical vapour deposition technique, molecular beam epitaxy, pulsed laser deposition sedimentation, magnetron sputtering method etc.
In addition, before forming conductive layer 12 on the substrate of glass 11, earlier the surface of substrate of glass 11 is handled, for example, sheet glass was put into acetone, ethanol, deionized water ultrasonic 5-60 minute respectively successively, dry or dry up, adopt the sputter coating machine with magnetic control again and on sheet glass, deposit the full wafer metal film at the predetermined thick end as conductive layer 12 with inert gas.
Among the step S02, after obtaining substrate, with screen printing technique the carbon nano-tube slurry is applied and to be formed on the substrate, be specially and be formed on substrate conductive structure or the conductive layer 12, present embodiment is an example with the substrate 10 that comprises conductive layer 12.Shown in Fig. 2 (b), during silk screen printing, will be installed on the screen process press according to the web plate 13 of requirements set earlier, on conductive layer 12, scraper 15 can be along same direction blade coating carbon nano-tube slurry 14 with carbon nano-tube slurry 14 blade coatings for usefulness scraper 15.Wherein, web plate 13 pre-set mesh size and distribution situations, for example, it for example can be forms such as array distribution or circular ring type distribution that mesh size 100 orders～500 orders, mesh distribute, and specifically decides according to the actual product demand.After installing web plate 13, the carbon nano-tube slurry 14 that has mixed metal powder and organic binder bond is poured on the web plate 13, the carbon nano-tube slurry 14 on the blade coating web plate 13 is shown in Fig. 2 (c).When blade coating,, carbon nano-tube slurry 14 is printed on the substrate 10 by regulating the angle of inclination and the dynamics of scraper 15.As Fig. 2 (d)) shown in, remove web plate 13 after, promptly localization has formed carbon nano-tube emitter on substrate 10.
Step S03 is a sintering step, for example by the sintering curing carbon nano-tube, and removes organic binder bond.Through the step S02 of front, on substrate 10, prepared the mixture of metallic particles and carbon nano-tube, i.e. the mixture of carbon nano-tube slurry 14 formations.This mixture is carried out sintering in the above temperature of the fusing point of used metal, and the temperature of sintering is higher than the fusing point of selected metallic particles, and sintering range also can specifically be decided according to metal species that is adopted and organic carrier for 150～600 ℃.Specifically the fusing point of the metallic particles that sintering temperature can be selected relatively is high 50 ℃-300 ℃, is preferably 100 ℃-200 ℃.For example, when adopting In metal or its alloy, sintering temperature can be chosen in 160 ℃ of-180 ℃ of lower temperature, but consider and thoroughly remove and divide and take off organic carrier that sintering temperature is chosen in 180 ℃-300 ℃, concrete as during with the In metal, sintering temperature can be 160 ℃, when adopting the In-Ag alloy, sintering temperature can be 180 ℃, other and the like.In addition; also can select corresponding sintering atmosphere as required; sintering atmosphere can be aeriferous protective atmosphere (as air), nitrogen or inert gas; when adopting nitrogen or inert gas; the sintering that helps carbon nano-tube slurry 14, nitrogen or inert gas atmosphere can not produce change to the performance and the structure of carbon nano-tube substantially, for example; when carbon nano-tube adopts the carbon nano-tube material of modifying, adopt nitrogen or inert gas atmosphere especially favourable.
During concrete sintering, the control sintering temperature is constant, under the constant temperature in heating furnace sintering 15 minutes～8 hours, be preferably 30 minutes-2 hours, this moment, organic carrier can thoroughly decompose.Arrive predetermined sintering temperature according to a temperature programming process, for example, be warmed up to predetermined temperature, like this, can prevent to heat up too fast and performance and structure destroying carbon nanometer tube with the heating rate of 15 ℃/min.In sintering process, organic binder bond volatilization or branch are taken off, and expose metal powder and carbon nano-tube.
Sintering cooled after the scheduled time, can be natural cooling, for example cooled to room temperature with the furnace.Through behind the abundant sintering, because organic adhesive volatilization or branch are taken off, the metal powder fusing, after the cooling, metal powder and carbon nano-tube sinter piece into, and metal powder is formed bulk in other words, form array or dot matrix metal derby 16, carbon nano-tube is solidificated in the metal derby 16, and has part carbon nano-tube 18 to be exposed to outside the surface 17 of metal derby 16, shown in Fig. 2 (e).This is exposed to outer carbon nano-tube 18 as emitter, forms cold cathode 100 with metal derby 16 and substrate 10, shown in Fig. 2 (e).
Like this, metal derby 16 and substrate 10, for example combine closely, contact closely with the conductive structure or the conductive layer of substrate 10, thereby improved the electric conductivity of cold cathode, and make the carbon nano-tube brute force be attached on the substrate, and allow carbon nano-tube come out, and reduced the resistance between carbon nano-tube 18 emitters and the conductive layer 12, improved carbon nano-tube 18 emitting performances.And this screen printing technique is suitable for industrialized mass production, reduces manufacturing cost, is beneficial to large-area applications.
The manufacture method of above-mentioned carbon nano-tube cold cathode can be used for making various vacuum electronics source array, main application examples such as Field Emission Display, field emission light source, travelling wave tube or transducer etc.Be example with the feds below, see also Fig. 3, the feds 200 of the cold cathode with above-mentioned manufacture method acquisition is shown.This feds 200 also comprises slider 24 and anode 20 except comprising cold cathode 100, anode 20 comprises glass substrate 21 and the fluorescent material 23 that is formed on the glass substrate 21.Slider 24 also is referred to as divider wall or supporter sometimes, and it is supported between cold cathode 100 and the anode 20, and is surrounded on around carbon nano-tube 18 emission arrays of cold cathode 100, constitutes confined space with cold cathode 100, anode 20.
When this feds 200 is made and is encapsulated, at first can obtain carbon nano-tube cold cathode 100 according to the manufacture method of above-mentioned carbon nano-tube cold cathode, form anode 20 again, be supported between cold cathode 100 and the anode 20 with slider 24 then, and with seal, sealing materials such as low glass powders with three's sealed attachment and vacuumizing and exhausting sealed-off, and then the assembling driving power, thereby obtain feds 200.
When these feds 200 work, under high voltage, be exposed to outer carbon nano-tube 18 and launch electronics, the fluorescent material 23 of bombardment anode 20 makes fluorescent material 23 send the light of pre-color, forms demonstration or illumination.Because in the cold cathode 100 of present embodiment, carbon nano-tube 18 is strong with substrate 10 adhesions, thereby carbon nano-tube 18 can be born high voltage and do not come off, and carbon nano-tube 18 is solidificated in the metal derby 16, help reducing resistance, improve current density, can suitably reduce the voltage that puts on the cold cathode 100, cut down the consumption of energy.In addition, in carbon nano-tube 18 emitting electrons processes, because carbon nano-tube 18 is solidificated in the metal derby 16, the heat that produces can be transmitted to conductive layer by metal derby 16 rapidly and be derived by substrate, substrate this moment can be adopted heat conductivility pottery or metal material preferably, thereby improves the useful life of cold cathode 100 and feds 200.
Below illustrate the manufacture method detailed process of carbon nano-tube cold cathode by instantiation.
Embodiment 1
Be given in the process of printing multi-walled carbon nano-tubes on the substrate of the ito glass that is coated with thickness 20 nanometers in the present embodiment.
Used glass size: 50mm * 70mm * 1.1mm; The emission tagma figure that prints on ito glass is the square figure of 25mm * 25mm, adopts 200 purpose screen printings.At first weighing by ethyl cellulose, terpinol, butyl carbitol acetate fat and ethyl lactate with 1: 4: 12: organic binder bond 10 grams of 13 ratios preparations, pour the 50ml beaker into, taking by weighing diameter is that 10～20 nanometers, length are 5～15 microns multi-walled carbon nano-tubes 1 gram, pouring in the 50ml beaker to mix with organic binder bond and stir and ultrasonic 2 hours, is that 20 nanometers, purity are that 99.9% glass putty 8 grams are poured in the 50ml beaker to mix with carbon nano-tube, organic binder bond and stirred also ultrasonic 24 hours again with average grain diameter.Then ito glass was put into successively acetone, ethanol, deionized water ultrasonic 15 minutes respectively, and dried or dry up with inert gas.Adopt the preparation process of accompanying drawing 2; silk screen printing contains the slurry of tin particles and carbon nano-tube and organic binder bond on ito glass; and under the protection of nitrogen atmosphere, put into heating furnace; heating rate with 15 ℃/min is warmed up to 550 ℃; constant temperature 60 minutes; last cooling naturally forms the carbon nano-tube cold cathode.
Embodiment 2
Be given in the process of printed carbon nanotube cold cathode on the simple glass substrate in the present embodiment.
Used glass size: 50mm * 50mm * 3mm; φ 30mm circular pattern in printing emission on glass tagma adopts 100 purpose screen printings.At first weighing ethyl cellulose, terpinol, butyl carbitol and tributyl citrate were with 1: 4: 12: organic binder bond 20 grams of 13 mixed preparation, pour the 50ml beaker into, taking by weighing diameter is that 10～20 nanometers, length are many walls ordered carbon nanotube 3 grams of 5～15 microns, pouring in the 50ml beaker to mix with organic binder bond and stir and ultrasonic 4 hours, is that 100 nanometers, Sn-Cu alloyed powder 10 grams are poured in the 50ml beaker to mix with carbon nano-tube, organic binder bond and stirred also ultrasonic 24 hours again with average grain diameter.Then glass was put into successively acetone, ethanol, deionized water ultrasonic 15 minutes respectively, and dried or dry up with inert gas.2 preparation process at first adopts magnetron sputtering coater to deposit the full wafer crome metal film of 2 micron thickness as conductive layer on glass substrate with reference to the accompanying drawings.Adopt screen printer print to contain the metallic particles of Sn-Cu alloy and the slurry of carbon nano-tube and organic binder bond then.And under the protection of air, put into heating furnace, be warmed up to 300 ℃ with the heating rate of 15 ℃/min, constant temperature 90 minutes, last cooling naturally, formation carbon nano-tube cold cathode.
Embodiment 3
Provided the process of printed carbon nanotube cold cathode on the potsherd substrate in the present embodiment.
Used potsherd specification: 50mm * 60mm * 0.5mm; On potsherd printing emission tagma 25mm * 40mm rectangular graph, adopt 100 purpose screen printings.At first weighing ethyl cellulose, terpinol, butyl carbitol acetate fat and ethyl lactate were with 1: 4: 12: organic binder bond 15 grams of 13 ratios preparation, pour the 50ml beaker into, taking by weighing diameter is that＜2 nanometers, length are 10～20 microns Single Walled Carbon Nanotube 1.5 grams, pouring in the 50ml beaker to mix with organic binder bond and stir and ultrasonic 8 hours, is that 50 nanometers, Bi-Ag alloyed powder 10 grams are poured in the 50ml beaker to mix with carbon nano-tube, organic binder bond and stirred also ultrasonic 24 hours again with average grain diameter.Then potsherd was put into successively acetone, ethanol, deionized water ultrasonic 15 minutes respectively, and dried or dry up with inert gas.2 preparation process with reference to the accompanying drawings, at first adopting mode full wafer printing on the potsherd substrate of silk screen printing thick is that 200 microns conductive silver paste is as conductive layer.Printing contains the metallic particles of Bi-Ag alloy and the slurry of carbon nano-tube and organic binder bond.And under the protection of air, put into heating furnace, be warmed up to 200 ℃ with the heating rate of 15 ℃/min, constant temperature 120 minutes, last cooling naturally, formation carbon nano-tube cold cathode.
Embodiment 4
Provided the process of printed carbon nanotube cold cathode on the sheet metal substrate in the present embodiment.
Used sheet metal specification: 50mm * 60mm * 0.5mm; 25mm * 40mm the rectangular graph in printing emission tagma adopts 400 purpose screen printings on sheet metal.At first weighing by ethyl cellulose, terpinol, butyl carbitol and tributyl citrate with 1: 4: 12: organic binder bond 15 grams of 13 mixed preparations, pour the 50ml beaker into, taking by weighing diameter is that 15-30 nanometer, length are 10～30 microns array carbon nano-tube 1.2 grams, pouring in the 50ml beaker to mix with organic binder bond and stir and ultrasonic 12 hours, is that 5 nanometers, In-Ag alloyed powder 10 grams are poured in the 50ml beaker to mix with carbon nano-tube, organic binder bond and stirred also ultrasonic 36 hours again with average grain diameter.Then sheet metal was put into successively acetone, ethanol, deionized water ultrasonic 15 minutes respectively, and dried or dry up with inert gas.2 preparation process with reference to the accompanying drawings, the mode that at first adopts silk screen printing are thick according to the list structure printing on the sheet metal substrate to be 100 microns composite conducting layer.Printing contains the metallic particles of In-Ag alloy and the slurry of carbon nano-tube and organic binder bond.And under the protection of air, put into heating furnace, be warmed up to 180 ℃ with the heating rate of 15 ℃/min, constant temperature 120 minutes, last cooling naturally, formation carbon nano-tube cold cathode.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the manufacture method of a carbon nano-tube cold cathode, it may further comprise the steps:
The metal powder, the carbon nano-tube that provide are mixed with organic binder bond, stir, form the carbon nano-tube slurry, wherein melting point metal is 150 ℃～600 ℃;
The carbon nano-tube slurry is formed on the substrate by silk screen printing;
The substrate of printing back carbon nanotubes slurry at the above temperature sintering of the fusing point of used metal, is made the volatilization of metal molten and organic binder bond or decomposes, after the cooling, form described carbon nano-tube cold cathode.
2. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1 is characterized in that, the material of described metal powder is selected from least a in Sn, Bi, In, Tl, Sn alloy, Bi alloy, In alloy, the Tl alloy.
3. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1, it is characterized in that the material of described metal powder is selected from least a in Sn-Cu alloy, Sn-Ag alloy, Sn-Pb alloy, Sn-Zn alloy, In-Ag alloy, In-Zn alloy, In-Pb alloy, In-Cu alloy, Bi-Cu alloy, Bi-Ag alloy, Bi-Pb alloy, the Bi-Zn alloy.
4. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1 is characterized in that, the grain diameter of described metal powder is 5 nanometers～300 micron, and the fusing point of described metal powder is 150 ℃～350 ℃.
5. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1, it is characterized in that described carbon nano-tube is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, many walls ordered carbon nanotube, at least a through in the carbon nano-tube of modifying or the array carbon nano-tube.
6. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1, it is characterized in that, described substrate is one to have the substrate of conductive structure or comprise substrate and be formed at the composite substrate of suprabasil conductive layer, the conductive structure of described substrate or the conductive material of conductive layer are selected from ITO, metal or composite conducting material, and the thickness of described conductive layer is 20 nanometers～200 micron.
7. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1 is characterized in that, described sintering is to carry out 15 minutes～8 hours under the constant temperature containing air or contain in the atmosphere of inert gas shielding.
8. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1, it is characterized in that, the formation step of described carbon nano-tube slurry comprises: carbon nano-tube is mixed with organic binder bond, stirring and sonic oscillation 30 minutes～12 hours, again carbon nano-tube is mixed with metal powder with the mixture of organic binder bond, stirring and sonic oscillation 30 minutes～2 hours obtain described carbon nano-tube slurry.
9. the manufacture method of carbon nano-tube cold cathode as claimed in claim 1, it is characterized in that described organic binder bond is the organic carrier of ethyl cellulose, terpinol, butyl carbitol acetate fat and ethyl lactate mixed preparing or the organic carrier of ethyl cellulose, terpinol, butyl carbitol and tributyl citrate mixed preparing.
10. the application of the manufacture method of carbon nano-tube cold cathode as claimed in claim 1 in preparation Field Emission Display, field emission light source, travelling wave tube or transducer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101904240A CN102262988A (en) | 2010-05-31 | 2010-05-31 | Method for manufacturing carbon nanotube cold cathode and application of method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101904240A CN102262988A (en) | 2010-05-31 | 2010-05-31 | Method for manufacturing carbon nanotube cold cathode and application of method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102262988A true CN102262988A (en) | 2011-11-30 |
Family
ID=45009585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101904240A Pending CN102262988A (en) | 2010-05-31 | 2010-05-31 | Method for manufacturing carbon nanotube cold cathode and application of method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102262988A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794442A (en) * | 2011-12-31 | 2014-05-14 | 四川虹欧显示器件有限公司 | Plasma screen and manufacturing method thereof |
| CN113517164A (en) * | 2021-03-08 | 2021-10-19 | 中国科学院深圳先进技术研究院 | Method for manufacturing carbon nanotube cathode, carbon nanotube cathode and electronic device |
| WO2022188003A1 (en) * | 2021-03-08 | 2022-09-15 | 中国科学院深圳先进技术研究院 | Manufacturing method for carbon nanotube cathode, and carbon nanotube cathode and electronic device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533579A (en) * | 2001-07-18 | 2004-09-29 | ���ṫ˾ | Electron emitter and method for fabricating the same, cold cathode field electron emission element and method for fabricating the same, and cold cathode field electron emission display and method |
| CN1581400A (en) * | 2003-08-04 | 2005-02-16 | 日进金刚石股份有限公司 | Emitter composition using diamond, method of manufacturing the same and field emission cell using the same |
| CN1674192A (en) * | 2005-02-07 | 2005-09-28 | 中山大学 | Printed nano material cold cathode size and producing method and application for field emitting cold cathode thereof |
| CN1812038A (en) * | 2004-11-15 | 2006-08-02 | 三星Sdi株式会社 | Carbon nanotube, electron emitter, electron emission device and manufacture method thereof |
| CN101171379A (en) * | 2005-05-06 | 2008-04-30 | 毫微-专卖股份有限公司 | Ink jet application for carbon nanotubes |
| CN101321687A (en) * | 2005-12-06 | 2008-12-10 | 韩国电子通信研究院 | The manufacturing method of cnt paste and the manufacturing method of cnt emitter with high reliability |
| CN101593568A (en) * | 2008-05-30 | 2009-12-02 | 三星电机株式会社 | The electrocondution slurry and the printed circuit board (PCB) that uses it that contain carbon nano-tube |
-
2010
- 2010-05-31 CN CN2010101904240A patent/CN102262988A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533579A (en) * | 2001-07-18 | 2004-09-29 | ���ṫ˾ | Electron emitter and method for fabricating the same, cold cathode field electron emission element and method for fabricating the same, and cold cathode field electron emission display and method |
| CN1581400A (en) * | 2003-08-04 | 2005-02-16 | 日进金刚石股份有限公司 | Emitter composition using diamond, method of manufacturing the same and field emission cell using the same |
| CN1812038A (en) * | 2004-11-15 | 2006-08-02 | 三星Sdi株式会社 | Carbon nanotube, electron emitter, electron emission device and manufacture method thereof |
| CN1674192A (en) * | 2005-02-07 | 2005-09-28 | 中山大学 | Printed nano material cold cathode size and producing method and application for field emitting cold cathode thereof |
| CN101171379A (en) * | 2005-05-06 | 2008-04-30 | 毫微-专卖股份有限公司 | Ink jet application for carbon nanotubes |
| CN101321687A (en) * | 2005-12-06 | 2008-12-10 | 韩国电子通信研究院 | The manufacturing method of cnt paste and the manufacturing method of cnt emitter with high reliability |
| CN101593568A (en) * | 2008-05-30 | 2009-12-02 | 三星电机株式会社 | The electrocondution slurry and the printed circuit board (PCB) that uses it that contain carbon nano-tube |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794442A (en) * | 2011-12-31 | 2014-05-14 | 四川虹欧显示器件有限公司 | Plasma screen and manufacturing method thereof |
| CN113517164A (en) * | 2021-03-08 | 2021-10-19 | 中国科学院深圳先进技术研究院 | Method for manufacturing carbon nanotube cathode, carbon nanotube cathode and electronic device |
| WO2022188003A1 (en) * | 2021-03-08 | 2022-09-15 | 中国科学院深圳先进技术研究院 | Manufacturing method for carbon nanotube cathode, and carbon nanotube cathode and electronic device |
| CN113517164B (en) * | 2021-03-08 | 2024-03-29 | 中国科学院深圳先进技术研究院 | Manufacturing method of carbon nanotube cathode, carbon nanotube cathode and electronic equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100911370B1 (en) | The Manufacturing Method of CNT Paste and The Manufacturing Method of CNT Emitter with high Reliability | |
| CN101231431B (en) | Indium tin oxide target, method of manufacturing the same and transparent electrode manufactured by using the same | |
| EP1494256A1 (en) | Field electron emission film, field electron emission electrode and field electron emission display | |
| JP2004311407A (en) | Composite particles for electron emission and their manufacturing method, electron emitting source and its manufacturing method, composition for electron emission emitter formation, and electric field emission display device | |
| US20120267581A1 (en) | Method for making carbon nanotube slurry | |
| CN103871802A (en) | Carbon nanotube composite thin film field emission cathode preparation method | |
| CN102262988A (en) | Method for manufacturing carbon nanotube cold cathode and application of method | |
| US20040178713A1 (en) | Emitter composition using diamond, method of manufacturing the same and field emission cell using the same | |
| JP2005074472A (en) | Method of brazing carbon nanotube to base material | |
| EP1505621A1 (en) | Emitter composition using diamond method of manufacturing the same and field emission cell using the same | |
| JPH11265653A (en) | Electrode, and display device having the electrode | |
| CN102398892A (en) | Preparation method and application of zinc oxide nanowires | |
| CN102339712B (en) | Patterned graphene field emission cathode and preparation method thereof | |
| CN102243973B (en) | Carbon nanometer material composite field electron emission membrane and preparation method thereof | |
| CN103198991B (en) | Based on field emission cathode structure and the manufacture method of sea urchin type nickel particles template | |
| US20060103287A1 (en) | Carbon-nanotube cold cathode and method for fabricating the same | |
| US20060012281A1 (en) | Carbon nanotube field emitter and method for producing same | |
| CN103021762A (en) | Method for processing field emission cathode | |
| Li et al. | Screen-printed Dual-Particle-Containing Multicomponent-Blending Carbon Nanotube Cathode: Enhancement of Electron Emission Characteristics, Current Emission Stability, and Uniformity | |
| CN100466145C (en) | Spraying liquid of nanometer carbon tube and spraying method thereof | |
| KR20140142200A (en) | Carbon nanotube paste for field emission device, Emitter using the same and Field emission device using the same | |
| Park et al. | Stable and high emission current from carbon nanotube paste with spin on glass | |
| JP5376197B2 (en) | Method for producing nanocarbon material composite | |
| CN101587805B (en) | Method for preparing composite nano diamond thin film electron emitting cathode | |
| CN102336443B (en) | Preparation method and application of iron oxide nano wire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111130 |