CN101079356B - Method for fabricating field emitter electrode using array of carbon nanotubes - Google Patents
Method for fabricating field emitter electrode using array of carbon nanotubes Download PDFInfo
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- CN101079356B CN101079356B CN200710103761XA CN200710103761A CN101079356B CN 101079356 B CN101079356 B CN 101079356B CN 200710103761X A CN200710103761X A CN 200710103761XA CN 200710103761 A CN200710103761 A CN 200710103761A CN 101079356 B CN101079356 B CN 101079356B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/30—Cold cathodes, e.g. field-emissive cathode
- H01J1/304—Field-emissive cathodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/08—Aligned nanotubes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30446—Field emission cathodes characterised by the emitter material
- H01J2201/30453—Carbon types
- H01J2201/30469—Carbon nanotubes (CNTs)
Abstract
The present invention relates to a method for fabricating a field emitter electrode, in which carbon nanotubes (CNTs) are aligned in the direction of a generated magnetic field. Specifically, the method comprises the steps of dispersing a solution of carbon nanotubes (CNTs) diluted in a solvent, on a substrate fixed to the upper part of an electromagnetic field generator, and fixing the carbon nanotubes aligned in the direction of an electromagnetic field generated from the electromagnetic field generator. According to the disclosed method, high-density and high-capacity carbon nanotubes aligned in the direction of a generated electromagnetic field can be fabricated in a simple process and can be applied as positive electrode materials for field emission displays (FEDs), sensors, electrodes, backlights and the like.
Description
Technical field
The present invention relates to a kind of method of making electron emission electrode, wherein carbon nano-tube (CNTs) is arranged according to the direction that generates an electromagnetic field.More specifically, the present invention relates to a kind of manufacturing and comprise method according to the electron emission electrode of the direction arranging nanotube (CNTs) that generates an electromagnetic field, this method may further comprise the steps, on the substrate that is fixed to electromagnetic field generator top, carbon nanotube (CNT) solution that has diluted in solvent is disperseed, and the electromagnetic field direction carbon nanotubes arranged that produces according to electromagnetic field generator is fixed.
Background technology
Usually, field emission apparatus is a kind of light source, and it is based on the electronics in vacuum emission, and relates to particulate that a kind of utilization quickened by highfield and remove to clash into fluorescent material and make its principle of launching electronics come luminous element.Above-mentioned field emission apparatus has the following advantages, and for example high light emission effciency realizes the ability of lightweight, with conventional lighting source for example incandescent lamp bulb specific volume is little mutually, so and because of unlike fluorescent lamp, using the heavy metal environmental sound.Thereby, it has been thought follow-on light source, in various lighting fields and display unit, use.
The performance of field emission apparatus depends on the ability of emission electrode emission electric field to a great extent.In recent years, carbon nano-tube (CNTs) has been widely used as the electronic emission material in the transmitter electrode, it has fabulous electron emission characteristic.
Carbon nano-tube is a kind of allotrope of carbon, is made up of a large amount of carbon that exist in the earth.They are tubular materials, and wherein carbon atom combines with other carbon with hexagon honeycomb structure form.Their diameter is approximately nano-scale (1/10
9Meter), and their length arrives several microns for the hundreds of nanometer.Compare carbon nano-tube with other materials and have bigger length-width ratio.Known carbon nano-tube has fabulous mechanical performance and electroselectivity, and special, owing to bigger length-width ratio has fabulous electromagnetic field generation performance.
By the agency of because the fabulous field emission characteristic of carbon nano-tube and used as the anode material that is Field Emission Display.(Kim, people such as J.M., Applied PhysicsLetters, 75 (20): 3129,1999), utilize mechanical friction that carbon nano-tube and polymer complex are arranged with specific direction, and measure the field emission characteristic of institute's synthesizing carbon nanotubes in the file formerly.Yet, in this situation, there is defective seriously, promptly must in making processing procedure, combustion make the polymer that has mixed, and have a problem, promptly be difficult in the big zone according to the electromagnetic field direction arranging nanotube that produces.
And, a kind of like this method has been proposed, at high temperature directly prepare carbon nano-tube so that according to specific direction arranging nanotube (Wong C.P. waits the people, Carbon, 44:253,2006).Yet, because of it has major defect can not practical application because tin indium oxide (ITO) glass as positive plate can not high temperature resistance in display unit.
Attempt to address the above problem and propose a kind of method that is used to make electron emission electrode, it comprises carbon nano-tube attached on the substrate, coating electrically conductive polymer on this substrate, and according to specific direction arranging nanotube (Korean Patent Publication No. NO.2006-0024725).Yet this method is also failed in big zone with high density according to the direction arranging nanotube that generates an electromagnetic field, and can not overcome make must combustion system polymer during handling defective.
Thus, press for and develop a kind of method that is used to make electron emission electrode, it utilizes simple process, in big zone with high density at specific direction arranging nanotube along the direction that generates an electromagnetic field.
Therefore, the present inventor uses up its effort and solves existing problem in the existing method according to the specific direction arranging nanotube.As a result, the present inventor finds, carbon nanotube is arranged on the substrate that is fixed on the electromagnetic field generator top, when utilizing metal to fix then, might produce electron emission electrode, it is included in the carbon nano-tube of arranging with high density in the big zone, finishes the present invention thus.
Summary of the invention
Thus, the purpose of this invention is to provide a kind of electron emission electrode, wherein the carbon nano-tube of arranging with high density in big zone be fixed on the substrate with metal with fabulous field emission characteristic, with and make the method for electron emission electrode.
To achieve these goals, an aspect, the invention provides a kind of method that is used to make electron emission electrode, wherein include according to the magnetic direction carbon nanotubes arranged, this method may further comprise the steps: (a) on the substrate that is fixed to magnetic field generator top, carbon nano-tube solution of having diluted in organic solvent or the carbon nano-tube solution that combines magnetic particle are disperseed; (b) in the magnetic field that magnetic field generator produced, by from be distributed to the solution on the substrate, evaporating organic solvent, on the substrate according to magnetic direction arranging nanotube that is produced and (c) plated metal on substrate, even make under zero magnetic field condition, can in its orientation, fix according to the magnetic direction carbon nanotubes arranged that produces.
In the present invention, the magnetic direction that is produced preferably is vertical with substrate, level, or form between vertical and horizontal arbitrarily angled, and preferably, by utilizing physical-chemical method magnetic particle to be attached to the carbon nano-tube that obtains to combine magnetic particle on the carbon nano-tube.And, with the method for acid treatment carbon nano-tube, make magnetic particle be reduced the method for reaction and on carbon nano-tube, in the method for plating magnetic particle, preferably select physical-chemical method.
In the present invention, the magnetic field generator in the step (a) is magnet preferably, and the magnetic field size that magnetic field generator produced is preferably 0.005-10 tesla (T).
In the present invention, preferred magnetic particle is the particle of iron content (Fe).Iron content (Fe) particle is preferably from by iron chloride (FeCl
3), ferrous oxide (FeO), iron oxide (Fe
2O
3) and tri-iron tetroxide (Fe
3O
4) selected in the group formed.
On the other hand, the invention provides a kind of electron emission electrode of making according to described method, wherein depositing on the substrate of metal, the carbon nano-tube that combines magnetic particle is arranged with magnetic direction.
Another aspect, the invention provides a kind of method of making electron emission electrode, it comprises according to the direction of an electric field carbon nanotubes arranged, this method may further comprise the steps: (a) on the substrate that is fixed to field generator top, carbon nano-tube solution of having diluted in organic solvent or the solution that combines the carbon nano-tube of magnetic particle are disperseed; (b) in the electric field that field generator produced, by from be distributed to the solution on the substrate, evaporating organic solvent, on substrate according to the direction of an electric field arranging nanotube that is produced; (c) plated metal on substrate even make under zero current field condition, can be fixed in its orientation according to the direction of an electric field carbon nanotubes arranged that produces.
In the present invention, the direction of an electric field that is produced preferably is vertical with substrate, level, or form between vertical and horizontal arbitrarily angled, and the field generator in the step (a) is an electric field.And the size of electric field is preferably 1-500V/ μ m.
In the present invention, preferred, step (a) comprises the interpolation dispersant in addition.This dispersant is from by organic solvent four octyl group ammonium bromides (TOAB), surfactant triton x-100 (TritonX-100), lauryl sodium sulfate (SDS), neopelex (NADDBS) and polyethylene [2-(2 ' ethyl hexyl oxy)-5-(phenylacetylene base)-1,4-phenylene 1, the 2-ethenylidene] (PAPPV, poly[2-(2 ' ethylhexyloxy)-and 5-(phenylethynyl)-1,4-phenylenevinylene]) selected in the group formed.
In the present invention, on the substrate that is fixed to field generator top, in the step (a) that the carbon nano-tube solution of having diluted in organic solvent is disperseed, preferably utilize from spin coating method, injection method, method selected in the group that dip coated method and ink ejecting method are formed realizes.And, preferred repeating step (a) and (b) improve the density of carbon nano-tube for 1-1000 time.In addition, carbon nano-tube is preferably individual layer, bilayer or multilayer carbon nanotube.
In the present invention, the solvent in the step (a) is preferably from by water (H
2O), dimethyl formamide (DMF), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethylacetylamide (DMAc), cyclohexanone, ethanol, chloroform, carrene, 1, selected in the group that 2-dichloro-benzenes and ether are formed.Substrate in the step (a) is preferably from by tin indium oxide (ITO) glass, glass, and quartz, chip glass, silicon wafer, applying silicon, selected in the group that plastics and transparent polymer are formed.Solvent in the step (b) preferably removes by the temperature that solution is heated to 20-300 ℃.In addition, in above-mentioned organic solvent, chloroform, carrene, diethyl ether and analog have good volatility, thereby even also they can be removed at room temperature.
In the present invention, in the step that carbon nano-tube is disperseed (a), the concentration of carbon nano-tube is preferably 0.001-1.0wt%, and the quantity of carbon nanotubes that has been dispersed in the step (a) on the substrate is 1pg/cm
2-1g/cm
2(quantity of carbon nanotubes in the per unit area).
In the present invention, preferably to be deposited as thickness be 1-5000nm to the metal in the step (c).And the metal in the step (c) is preferably from by titanium (Ti), molybdenum (Mo), and gold (Au), silver (Ag), aluminium (Al), calcium (Ca), cadmium (Cd), iron (Fe), nickel (Ni), platinum (Pt) is selected in the group that zinc (Zn) and copper (Cu) are formed.
Another aspect the invention provides a kind of electron emission electrode according to described method manufacturing, wherein deposits thereon on the substrate of metal to produce the direction of an electric field arranging nanotube.
To more be expressly understood above-mentioned and other purpose of the present invention, feature and embodiment by the following detailed description and appended claim.
Description of drawings
Fig. 1 represents the schematic diagram by the applying a magnetic field carbon nanotubes arranged.
Fig. 2 represents that carbon nano-tube purifies before and transmission electron microscope (TEM) photo (left side: 50,000 times of enlargement ratios afterwards; The right side: 100,000 times of enlargement ratios), wherein Fig. 2 (a) is illustrated in the carbon nano-tube that contains impurity before the purification, and Fig. 2 (b) expression purifies the pure carbon nano-tube in back.
Fig. 3 represents that magnetic particle is attached to transmission electron microscope (TEM) photo (left side: 50,000 times of enlargement ratios on the carbon nano-tube; Right side: 100,000 times of enlargement ratios).
Fig. 4 represents to dispose substrate behind the magnet from Fig. 1 (d), and expression is according to ESEM (SEM) photo (upside: 50,000 times of enlargement ratios of the magnetic direction carbon nanotubes arranged that is produced; Downside: 25,000 times of enlargement ratios), wherein Fig. 4 (a) expression is with the substrate of 80 ° of angle tilts, and Fig. 4 (b) expression is with the substrate of 45 degree inclination.
Fig. 5 according to the present invention according to producing magnetic direction carbon nanotubes arranged photo.
Fig. 6 represents according to the present invention according to the chart of the direction of an electric field carbon nanotubes arranged field emission characteristics that is produced.
Embodiment
Carbon nano-tube has distinctive electromagnetic property, when the carbon nano-tube that combines magnetic particle is fixed on the substrate, has electric field or the magnetic field flow through on it on this substrate, can produce the electron emission electrode with better field emission characteristics.
On the one hand, the present invention relates to a kind of method that is used to make electron emission electrode, wherein according to magnetic field that is produced or direction of an electric field arranging nanotube (CNTs).
In the present invention, make electron emission electrode, wherein have magnetic particle and be attached to carbon nano-tube on it, arrange according to magnetic field that is produced or direction of an electric field according to method shown in Figure 1.Concrete, as shown in Figure 1a, at first be ready to the annular magnet that will use in the present invention, magnetic field intensity is 1000 Gausses (G).Afterwards, tin indium oxide (ITO) glass that is arranged with carbon nano-tube on it is connected on the magnet with carbon binder (referring to Fig. 1 b).Then, will have the carbon nano-tube dispersion that magnetic particle is attached on it and be dropped in (referring to Fig. 1 c) on the indium oxide tin glass.After this, at the deposition on glass metal, thereby arrange and fixed carbon nanotube (referring to Fig. 1 d) according to the direction of magnetic field that is produced or electric field.
In five independent processes, the method that is used to make electron emission electrode will be described in further detail.
Step 1: preparation carbon nano-tube
The carbon nano-tube of Shi Yonging and being not particularly limited in the present invention, and can buy from market or can prepare according to any conventional method.For use of the present invention, carbon nano-tube should have clean Surface and not comprise metallic catalyst.And, employed carbon nano-tube individual layer preferably among the present invention, bilayer or multilayer carbon nanotube, and can prepare according to Hipco (high pressure carbon monoxide cracking process).
Step 2: magnetic particle is attached on the carbon nano-tube
For magnetic particle being attached on the carbon nano-tube prepared in the step 1, with iron chloride (FeCl
3), ferrous oxide (FeO), iron oxide (Fe
2O
3) and tri-iron tetroxide (Fe
3O
4) add ethanol to, in the mixture of distilled water and hexane, thereby and heat and prepare the iron oleate complex compound.Prepared iron oleate complex compound mixes with oleic acid and dimethyl formamide (DMF), and carbon nano-tube prepared in the step 1 is added in the mixture.Include the mixture that adds carbon nano-tube wherein to and be dissolved in fully in the 1-vaccenic acid, and again to its heating, thus from this mixture solvent evaporated.With ethanol surplus material is washed 3-4 time, preparation has magnetic particle and is attached to carbon nano-tube on it thus.
Step 3: the carbon nano-tube of on substrate, disperseing to combine magnetic particle
The prepared carbon nano-tube that combines magnetic particle that goes out in the step 2 is diluted in a kind of solvent at least, this solvent is from by dimethyl formamide (DMF), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethylacetylamide (DMAc), cyclohexanone, ethanol, chloroform, carrene, 1, selected in the group that 2-dichloro-benzenes and ether are formed, its concentration is 0.001-1.0wt%.Afterwards, the dispersion that combines the carbon nano-tube of magnetic particle is dripped on tin indium oxide (ITO) glass substrate, this tin indium oxide (ITO) glass substrate is fixed to the magnet top with magnetic field, and can evaporate this solvent.
Step 4: improve the density that combines the carbon nano-tube of magnetic particle on the substrate
On tin indium oxide (ITO) glass substrate of preparation, evaporating solvent adds 1-2 drips the carbon nano-tube that combines magnetic particle of having diluted in solvent dispersion fully, then can be with this solvent evaporation under hot conditions in step 3.In order to improve the density of the magnetic particle carbon nano-tube that combines, can repeat above-mentioned steps 5-20 time, by so doing, arrange according to the magnetic direction that magnet produced according to the carbon nano-tube that combines magnetic particle of method for preparing.
Step 5: the carbon nano-tube that will combine magnetic particle is fixed on the substrate
Even in order under zero magnetic field condition, still to make in its orientation, fixing in the step 4 according to the magnetic direction carbon nanotubes arranged, will be from by titanium (Ti), molybdenum (Mo), gold (Au), aluminium (Al), calcium (Ca), cadmium (Cd), iron (Fe), nickel (Ni), platinum (Pt), a kind of metal deposition of selecting in the group that zinc (Zn) and copper (Cu) are formed produces pure electron emission electrode thus on substrate.
On the other hand, the present invention relates to a kind of method that is used to make electron emission electrode, therein according to the direction of an electric field arranging nanotube (CNTs) that is produced.
In the foregoing description, only describe in detail and include magnet as electromagnetic field generator and by magnetic particle being attached to the method for its arranging nanotube that comes up.Yet, description by the front, field generator is an electric field, and, surfactant makes electron emission electrode with arranging nanotube on substrate by being added in the carbon nano-tube solution, or make electron emission electrode by on the substrate that is fixed on the electromagnetic field generator, arranging pure carbon nano-tube, all be conspicuous to those skilled in the art.Concrete, can produce the electron emission electrode of arranging according to the direction of an electric field that is produced by following steps:
(a) on the substrate that is fixed to field generator top, the carbon nano-tube solution of having diluted in organic solvent is disperseed;
(b) in the electric field that field generator produced, by from be distributed to the solution on the substrate, evaporating organic solvent, on substrate according to the direction of an electric field arranging nanotube that is produced; With
(c) even in its orientation, fix plated metal on substrate in order under zero current field condition, still to make according to producing the direction of an electric field carbon nanotubes arranged.
According to the present invention, can produce electron emission electrode, therein according to the electromagnetic field direction that is produced, be vertical, level, or the align at random angles carbon nano-tube (CNTs) that forms between vertical and horizontal with substrate.And, can utilize in big zone according to generating an electromagnetic field direction and arrange the carbon nano-tube of distinctive field emission performance with high density, make and have the very big electron emission electrode that improves the field emission effect.The electron emission electrode that produces according to the inventive method can be used as the electron emission electrode of display, and also can utilize the field emission phenomenon, uses in scanning electron microscopy (SEM) and transmission electron microscope (TEM).
Embodiment
Below will make a more detailed description the present invention by embodiment.Yet, be understandable that, these embodiment can be revised as other various forms, and scope of the present invention is not subjected to the restriction of these embodiment.Providing embodiment is in order to describe the present invention more all sidedly to those skilled in the art.
Embodiment 1: the preparation carbon nano-tube
Place the carbon nano-tube of 500mg in 365 ℃ smelting furnace, wherein they are carried out 90 minutes heat treatment, the air with 0.1SLM (standard liters of per minute) is injected in the smelting furnace simultaneously.Heat treated carbon nano-tube is added in the hydrochloric acid of 500ml, carry out 1 hour sonicated, and it is filtered by 1 filter.Afterwards, the carbon nano-tube of having filtered is added in the hydrochloric acid of 500ml, carry out 1 hour sonicated, and it is filtered by 1 1-μ m filter.Repeat the hydrochloric acid processing procedure and come purifying carbon nanometre tube 3-5 time.And, demonstrate before purified treatment and afterwards carbon nano-tube (referring to Fig. 2) with transmission electron microscope (TEM) photo.As a result, as shown in Figure 2, carbon nano-tube contains impurity (referring to Fig. 2 a), and they do not contain impurity (referring to Fig. 2 b) after purifying before purification.The carbon nano-tube that has purified is immersed in the mixture (4: 1v/v), thereby and stir and cut them in 9 hours of sulfuric acid and hydrogen peroxide.Afterwards, the resulting carbon nano-tube of dilution is filtered by the 500-nm filter in distilled water, and in 120 ℃ baking oven drying at least 12 hours.
Embodiment 2: magnetic particle is attached on the carbon nano-tube
Iron chloride (FeCl with 10.8g
36H
2O) and the enuatrol (Cl of 36.5g
8H
33NaO
2) add in the mixture of 80ml ethanol, 60ml distilled water and 140ml hexane, and under 70 ℃ condition, heated 4 hours, prepare the iron oleate complex compound thus.With the iron oleate complex compound for preparing of 12g, the oleic acid of 2.83g and 3ml dimethyl formamide (DMF) solvent are mixed with each other, and disperse prepared carbon nano-tube among the 150mg embodiment 1 in this mixture.
Afterwards, at room temperature, in the 1-of 130ml octadecylene, dissolve this mixture fully, and mixture is heated to 320 ℃ temperature, make its reaction of carrying out 30 minutes, cool to room temperature afterwards in that temperature.With ethanol reaction material is carried out 3-4 time washing, the centrifugal supernatant of getting rid of filters by 1-μ m filter afterwards, provides iron oxide (Fe thus
2O
3) be attached to the carbon nano-tube on it.Utilize transmission electron microscope (TEM) photo to observe the prepared carbon nano-tube (referring to Fig. 3) that goes out.As a result, as shown in Figure 3, what can see is that carbon nano-tube has the magnetic particle that is attached on it.
Embodiment 3: disperse magnetic particle-carbon nano-tube on substrate
5mg magnetic particle-carbon nano-tube of preparing among the embodiment 2 is disperseed in the dimethyl formamide (DMF) of 50ml, then the dispersion of dilution 10ml in the pure dimethyl formamide (DMF) of 40ml.
Simultaneously, tin indium oxide (ITO) glass is fixed on the magnet with 1000 gauss magnetic field intensity, and it is placed in 120 ℃ the baking oven.When the temperature of tin indium oxide (ITO) glass is elevated to 120 ℃, the tin indium oxide (ITO) of above-mentioned drips of solution in baking oven of the carbon nano-tube that combines magnetic particle that 1 μ l has been diluted in dimethyl formamide is on glass, and in 120 ℃, kept 10 minutes, dimethyl formamide (DMF) is evaporated.
Embodiment 4: the density that improves the carbon nano-tube that combines magnetic particle on the substrate
The carbon nano-tube solution that combines magnetic particle that about 1 μ l had been diluted in dimethyl formamide further drops on tin indium oxide (ITO) glass substrate of preparation among the embodiment 3, and the dimethyl formamide on this glass substrate (DMF) is evaporated fully.Afterwards, baking oven that glass substrate is housed was kept 10 minutes in 120 ℃ of temperature, thereby evaporate dimethyl formamide (DMF).In order to improve the density of the carbon nano-tube that combines magnetic particle on the substrate, repeat this step tens time.
By the substrate of ESEM (SEM) photo observation according to method for preparing, the result, what can see is that the carbon nano-tube that combines magnetic particle is arranged (referring to Fig. 4) according to the magnetic direction that magnet produced.
Embodiment 5: on substrate secure bond the carbon nano-tube of magnetic particle
Even in order under zero magnetic field condition, still to arrange the carbon nano-tube that combines magnetic particle according to the magnetic direction that is produced, at room temperature, utilize e ray depositing system (MooHan Co., Ltd, Korea S) with the speed of 0.5nm/sec, the deposition total height is the titanium (Ti) of 30nm and 70nm on substrate.After finishing deposition, the magnet of dismantling produces pure electron emission electrode (referring to Fig. 5) thus.As shown in Figure 5, what can see is that the carbon nano-tube in electron emission electrode is arranged according to the magnetic direction that is produced.
And,, the current density of carbon nano-tube is measured (referring to Fig. 6) according to an electric field in order to detect the field emission characteristics of carbon nanotube electrode in the electron emission electrode of making.As shown in Figure 6, what can see is that electron emission electrode according to the present invention has fabulous field emission characteristics.
Commercial Application
As previously mentioned, according to the present invention, can the simple steps manufacturing comprise that high density and high performance carbon nano-tube (CNTs) are according to the electron emission electrode of arranging in the electromagnetic field direction that is produced.Electron emission electrode according to the present invention can be used as the electron emission electrode of display, also can utilize the field emission phenomenon to use in scanning electron microscopy (SEM) and transmission electron microscope (TEM).
Though invention has been described with reference to the embodiment that specifies, and be not subjected to the restriction of these embodiment, but the claim of passing through to be added limits.Be understandable that those skilled in the art can change and revises execution mode under the condition that does not exceed scope and spirit of the present invention.
Claims (20)
1. method of making electron emission electrode, this electron emission electrode comprises that according to the magnetic direction carbon nanotubes arranged, this method may further comprise the steps:
(a) on the substrate that is fixed to magnetic field generator top, the solution of the solution of the carbon nano-tube of having diluted in organic solvent or the carbon nano-tube that combines magnetic particle of having diluted in organic solvent is disperseed;
(b) in the magnetic field that magnetic field generator produced, be dispersed in organic solvent in the solution on the substrate by evaporation, on substrate according to the magnetic direction arranging nanotube; With
(c) plated metal on substrate, even it is make under zero magnetic field condition, fixing in its orientation according to the magnetic direction carbon nanotubes arranged that produces.
2. according to the method for the manufacturing electron emission electrode described in the claim 1, it is characterized in that the magnetic direction that is produced is to be vertical with substrate, level, or form between vertical and horizontal arbitrarily angled.
3. according to the method for the manufacturing electron emission electrode described in the claim 1, it is characterized in that utilizing physical-chemical method magnetic particle to be attached to the carbon nano-tube that obtains to combine magnetic particle on the carbon nano-tube.
4. according to the method for the manufacturing electron emission electrode described in the claim 3, it is characterized in that physical-chemical method be from the method for acid treatment carbon nano-tube, make magnetic particle be reduced the method for reaction and the group that the method for carbon nano-tube plating magnetic particle is formed, select.
5. according to the method for the manufacturing electron emission electrode described in the claim 1, it is characterized in that magnetic particle is iron content (Fe) particle.
6. according to the method for the manufacturing electron emission electrode described in the claim 1, it is characterized in that the magnetic field size that magnetic field generator produces is 0.005-10 tesla (T).
7. method of making electron emission electrode, this electron emission electrode comprises that according to the direction of an electric field carbon nanotubes arranged, this method may further comprise the steps:
(a) on the substrate that is fixed to field generator top, the carbon nano-tube solution of having diluted in organic solvent is disperseed;
(b) in the electric field that field generator produced, be dispersed in organic solvent in the solution on the substrate by evaporation, on substrate according to the direction of an electric field arranging nanotube; With
(c) plated metal on substrate, even it is make under zero current field condition, fixing in its orientation according to the direction of an electric field carbon nanotubes arranged that produces.
8. according to the method for the manufacturing electron emission electrode described in the claim 7, it is characterized in that the direction of an electric field that is produced is vertical with substrate, level, or form between vertical and horizontal arbitrarily angled.
9. according to the method for the manufacturing electron emission electrode described in the claim 7, it is characterized in that electric field level is 0.1V/ μ m～500V/ μ m.
10. according to the method for the manufacturing electron emission electrode described in the claim 7, it is characterized in that step (a) also comprises the interpolation dispersant.
11. method according to the manufacturing electron emission electrode described in the claim 10, it is characterized in that dispersant is from organic solvent four octyl group ammonium bromides (TOAB), surfactant triton x-100 (Triton X-100), lauryl sodium sulfate (SDS), neopelex (NADDBS) and PAPPV (polyethylene [2-(2 ' ethyl hexyl oxy)-5-(phenylacetylene base)-1,4-phenylene 1,2-ethenylidene]) selected in the group formed.
12. the method according to the manufacturing electron emission electrode described in claim 1 or 7 is characterized in that, described step (a) is, utilized from spin coating method, and injection method, method selected in the group that dip coated method and ink ejecting method are formed realizes this step.
13. according to the method for the manufacturing electron emission electrode described in claim 1 or 7, it is characterized in that repeating step (a) and (b) 1-1000 time, thereby improve the density of carbon nano-tube.
14., it is characterized in that the solvent in the step (a) is from water (H according to the method for the manufacturing electron emission electrode described in claim 1 or 7
2O), dimethyl formamide (DMF), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethylacetylamide (DMAc), cyclohexanone, ethanol, chloroform, carrene, 1, select in the group that 2-dichloro-benzenes and ether are formed.
15., it is characterized in that the substrate in the step (a) is from tin indium oxide (ITO) glass, glass according to the method for the manufacturing electron emission electrode described in claim 1 or 7, quartz, chip glass, silicon wafer, applying silicon is selected in the group that plastics and transparent polymer are formed.
16., it is characterized in that the carbon nano-tube concentration of dispersed carbon nano tube solution in the step (a) is 0.001-1.0wt% according to the method for the manufacturing electron emission electrode described in claim 1 or 7.
17., it is characterized in that the solvent in the step (b) is made a return journey and removed by solution being heated to 20-300 ℃ of temperature according to the method for the manufacturing electron emission electrode described in claim 1 or 7.
18. according to the method for the manufacturing electron emission electrode described in claim 1 or 7, the quantity of carbon nanotubes that it is characterized in that being dispersed in the step (a) in the per unit area on the substrate is lpg/cm
2-1g/cm
2
19., it is characterized in that the metal deposition thickness in the step (c) is 1-5000nm according to the method for the manufacturing electron emission electrode described in claim 1 or 7.
20. method according to the manufacturing electron emission electrode described in claim 1 or 7, it is characterized in that the metal in the step (c) is from titanium (Ti), molybdenum (Mo), gold (Au), silver (Ag), aluminium (Al), calcium (Ca), cadmium (Cd), iron (Fe), nickel (Ni), platinum (Pt) is selected in the group that zinc (Zn) and copper (Cu) are formed.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020060047655 | 2006-05-26 | ||
| KR1020060047655A KR100785377B1 (en) | 2006-05-26 | 2006-05-26 | Method for Manufacturing a Field Emitter Electrode Using the Vertical Alignment of Carbon Nanotubes |
| KR10-2006-0047655 | 2006-05-26 | ||
| KR10-2006-0074791 | 2006-08-08 | ||
| KR1020060074791 | 2006-08-08 | ||
| KR1020060074791A KR100801131B1 (en) | 2006-08-08 | 2006-08-08 | Method for manufacturing a field emitter electrode using the array of cabon nanotubes |
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| CN102081067A (en) * | 2011-02-16 | 2011-06-01 | 西安交通大学 | Carbon nanotube (CNT) film based ionization nitrogen dioxide sensor and method for measuring concentration by adopting same |
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| KR101054354B1 (en) * | 2008-12-22 | 2011-08-05 | 한국과학기술원 | Arrangement method of nanomaterials using solution evaporation |
| CN106556589A (en) * | 2017-01-12 | 2017-04-05 | 重庆大学 | The preparation method and its substrate of high duplication surface enhanced Raman scattering substrate |
| CN113078038B (en) * | 2021-03-23 | 2022-06-07 | 电子科技大学 | Large-current cold cathode of oriented carbon nanotube and preparation method thereof |
| CN115767804B (en) * | 2022-11-24 | 2023-06-30 | 宁波韧和科技有限公司 | Electric heating unit and electric heater with power self-regulating function |
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| US6538367B1 (en) * | 1999-07-15 | 2003-03-25 | Agere Systems Inc. | Field emitting device comprising field-concentrating nanoconductor assembly and method for making the same |
| US6741019B1 (en) * | 1999-10-18 | 2004-05-25 | Agere Systems, Inc. | Article comprising aligned nanowires |
| US6890230B2 (en) * | 2001-08-28 | 2005-05-10 | Motorola, Inc. | Method for activating nanotubes as field emission sources |
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| JP2004234865A (en) * | 2003-01-28 | 2004-08-19 | Sony Corp | Carbon nanotube array material, its process of manufacture, carbon fiber array material, its process of manufacture and electric field emission display element |
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| US6538367B1 (en) * | 1999-07-15 | 2003-03-25 | Agere Systems Inc. | Field emitting device comprising field-concentrating nanoconductor assembly and method for making the same |
| US6741019B1 (en) * | 1999-10-18 | 2004-05-25 | Agere Systems, Inc. | Article comprising aligned nanowires |
| US6890230B2 (en) * | 2001-08-28 | 2005-05-10 | Motorola, Inc. | Method for activating nanotubes as field emission sources |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102081067A (en) * | 2011-02-16 | 2011-06-01 | 西安交通大学 | Carbon nanotube (CNT) film based ionization nitrogen dioxide sensor and method for measuring concentration by adopting same |
| CN102081067B (en) * | 2011-02-16 | 2013-01-02 | 西安交通大学 | Carbon nanotube (CNT) film based ionization nitrogen dioxide sensor and method for measuring concentration by adopting same |
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| CN101079356A (en) | 2007-11-28 |
| KR20070113841A (en) | 2007-11-29 |
| KR100785377B1 (en) | 2007-12-18 |
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