CN103050346B - The preparation method of field emission electron source and carbon nano-tube graphene composite structure thereof - Google Patents
The preparation method of field emission electron source and carbon nano-tube graphene composite structure thereof Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of field emission electron source and carbon nano-tube graphene composite structure thereof, comprise conductive substrates, graphene film layer and the orientation carbon nano pipe array perpendicular to graphene film layer, described graphene film layer sticks in conductive substrates, and one end of the carbon nano-tube in described carbon nano pipe array and graphene film layer are connected to form an overall structure.The present invention improves emissivities and the stability of carbon nano pipe array field emitting electronic source greatly, makes electron source of the present invention obtain the emission current of efficient stable and can bear high emission.
Description
Technical field
The present invention relates to vacuum electronics technology field, be specifically related to a kind of field emission electron source and carbon nano-tube graphene composite structure preparation method thereof.
Background technology
Vacuum electron device is now just in fast-developing trend, and the increase day by day of the market demand, particularly microminiaturized vacuum electron device and integrated vacuum electronic device are the emphasis directions of development at present.Field emitting electronic source is at low temperature or room temperature operation, have compared with the thermionic source in current electron tube that brightness is high, low in energy consumption, energy dispersive is little, fast response time and without advantages such as hot flashings, therefore as vacuum electron device electron source, vacuum electron device performance can be made to increase substantially.
As shown in Figure 1, in figure, 1 is emitter to the schematic diagram of field emissive cathode electron source, as molybdenum tip, carbon nano-tube etc.Under the effect of extra electric field, emitter top end has very high electric field strength, make its surface potential barrier reduce and thinning, due to tunnel effect, a large amount of electronics escapes into vacuum from emitter and forms free electron.
Carbon nano-tube has the characteristics such as nanoscale emission tip, big L/D ratio, high strength, high tenacity, good thermal stability and conductivity, makes it to become desirable field emission material.But utilize carbon nano-tube as field emitting electronic source, the resistance ratio of carbon nano-tube and substrate interface is larger, be significantly less than carbon nano-tube with the capacity of heat transmission of substrate contact part simultaneously, a large amount of Joule heat can be produced make interface temperature too high when high current is launched and burn, even cause carbon nanotube field-emission cathode complete failure.Fig. 2 is the SEM photo after carbon nano pipe array big current is launched, can be seen by Fig. 2, there is many pittings dissolved in carbon nano-tube and substrate contact place, dissolve is exactly a little because when big current is launched, because of carbon nano-tube and bases heat-conductivity conducting performance bad, create a large amount of Joule heat and cannot go out by Quick diffusing, cause local temperature too high and substrate is dissolved.
Graphene is a kind of novel material with carbon element, has excellent electric conductivity, heat conductivility, mechanical mechanics property.Graphene, as field emission material, also shows excellent characteristic.Because Graphene has excellent conductive capability and the capacity of heat transmission, and stable chemical property, also can obtain 10 from the edge of Graphene
7~ 10
8a/cm
2autoelectronic current density.But Graphene requires that edge is erected in substrate and could obtains good emitting performance, technique will realizing Graphene, to be erected in substrate according to certain spatial distribution very difficult, therefore, the effective current density of current Graphene is very little, cannot meet the requirement of vacuum electron device.
Summary of the invention
For above-mentioned prior art, the object of the present invention is to provide a kind of field emission electron source of carbon nano-tube graphene composite structure, it is intended to solve, and the launch stability that existing field emission electron source field emission cathode array exists is poor, always emission current is low and there is contact heat resistance between field emitter and substrate and contact resistance causes very greatly heat conduction and the very poor technical problem of electric conductivity.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of field emission electron source, it is characterized in that, comprise conductive substrates, graphene film layer and the orientation carbon nano pipe array perpendicular to graphene film layer, described graphene film layer sticks in conductive substrates, and one end of the carbon nano-tube in described carbon nano pipe array and graphene film layer are connected to form an overall structure.
The diameter of described carbon nano-tube is 1nm ~ 100nm; The diameter of described carbon nano-tube bundle is 10nm ~ 100 μm; Described carbon nano-tube line width is 10nm ~ 100 μm.
Described graphene film layer is multilayer or individual layer.
Described conductive substrates is metal substrate or the other materials being coated with metal electrode.
The preparation method of the carbon nano-tube graphene composite structure of described field emission electron source, it is characterized in that, carbon nano-tube and graphene film grow simultaneously, and one end of carbon nano-tube forms being connected of atom level with Graphene, form C-C covalent bond, its preparation process comprises the following steps:
1. select silicon chip or other materials as substrate, remove surperficial foul with acetone, ethanol and deionized water, obtain clean silicon face;
2. the continuous film adopting vacuum coating, sputter coating or other film plating process to deposit one deck in substrate to be applicable to graphene growth, as pure metals or associated alloys films such as nickel, copper, iron;
3. adopt high precision lithography, the substrate that plated film is good is prepared the microwell array according to designing requirement or line array;
4. material vacuum evaporation coating, sputter coating or other plated film modes deposit the catalyst stack layer material being applicable to deposition of carbon nanotubes growth respectively in the substrate co-domain that photoetching is good;
5. the CVD method adopting MPCVD method (MWCVD) or gas ions to strengthen chemical vapour deposition technique (PECVD) or other types realizes carbon nano pipe array and Graphene grows simultaneously.
The preparation method of the carbon nano-tube graphene composite structure of described field emission electron source, it is characterized in that, after having grown carbon nano-tube, continuous print Graphene is prepared in gap again between carbon nano pipe array, do not form C-C covalent bond between carbon nano-tube and Graphene, its preparation process comprises the following steps:
1. select silicon chip or other materials as substrate, remove surperficial foul with acetone, ethanol and deionized water, obtain clean silicon face;
2. adopt high precision lithography, the substrate that plated film is good is prepared the microwell array according to designing requirement or line array;
3. vacuum vapor plating, sputter coating or other plated film modes is adopted to deposit the catalyst stack layer material being applicable to deposition of carbon nanotubes growth respectively in the substrate co-domain that photoetching is good;
4. the CVD method adopting MPCVD method (MWCVD) or gas ions to strengthen chemical vapour deposition technique (PECVD) or other types realizes the growth of carbon nano pipe array;
5. the continuous film adopting vacuum coating, sputter coating or other film plating process to deposit one deck in substrate to be applicable to graphene growth, as pure metals or associated alloys films such as nickel, copper, iron;
6. the CVD method adopting MPCVD method (MWCVD) or gas ions to strengthen chemical vapour deposition technique (PECVD) or other types realizes the growth of Graphene continuous film;
Certainly, the 5. with the 3., the 4. step can adjustment order as required.
The preparation method of the carbon nano-tube graphene composite structure of described field emission electron source, is characterized in that, first prepare graphene film, then on graphene film carbon nano tube array grows, do not form C-C covalent bond between carbon nano-tube and Graphene; Its preparation process following steps:
1. select silicon chip or other materials as substrate, remove surperficial foul with acetone, ethanol and deionized water, obtain clean silicon face;
2. the continuous film adopting vacuum coating, sputter coating or other film plating process to deposit one deck in substrate to be applicable to graphene growth, as pure metals or associated alloys films such as nickel, copper, iron;
3. the CVD method adopting MPCVD method (MWCVD) or gas ions to strengthen chemical vapour deposition technique (PECVD) or other types realizes the growth of Graphene continuous film;
4. adopt high precision lithography, Graphene continuous film is prepared the microwell array according to designing requirement or line array;
5. vacuum vapor plating, sputter coating or other plated film modes is adopted to deposit the catalyst stack layer material being applicable to deposition of carbon nanotubes growth respectively in the substrate co-domain that photoetching is good;
6. the CVD method adopting MPCVD method (MWCVD) or gas ions to strengthen chemical vapour deposition technique (PECVD) or other types realizes the growth of carbon nano pipe array.
Compared with prior art, the present invention has following beneficial effect:
One, greatly improve emissivities and the stability of carbon nano pipe array field emitting electronic source, make electron source of the present invention obtain the emission current of efficient stable and high emission can be born;
Two, be applicable to current emission characteristics requirement higher, particularly require the feds of very high currents density, the vacuum microelectronic devices such as such as klystron, travelling wave tube, flat panel display, electron microscope, electron beam exposure apparatus, high frequency power amplifier part and X-ray tube.
Accompanying drawing explanation
Fig. 1 is field emission electron source structural representation;
Fig. 2 is the SEM photo of carbon nano pipe array after the overcurrent of high current density is launched;
Fig. 3 is the field emission electron source structural representation of the composite construction that carbon nano-tube and Graphene grow simultaneously;
Fig. 4 is the field emission electron source structural representation preparing the composite construction of Graphene after first preparing carbon nano pipe array again;
Fig. 5 is for first to prepare Graphene continuous film, then the composite construction field emission electron source structural representation that carbon nano-tube is formed on Graphene;
Reference numeral is: 1 be emitter, 2 be conductive layer, 3 is anode, 4 intermediate layer, 8 that be the pitting, 5 that dissolves formation because of overheated substrate be carbon nano-tube bundle, 6 to be substrate, 7 be between Graphene and substrate is Graphene, 9 be carbon nano pipe array.
Embodiment
Below in conjunction with the drawings and the specific embodiments, the invention will be further described.
A kind of field emission electron source of carbon nano-tube graphene composite structure, comprise conductive substrates, graphene film layer and the orientation carbon nano pipe array perpendicular to graphene film layer, described graphene film layer sticks in conductive substrates, and one end of the carbon nano-tube in described carbon nano pipe array and graphene film layer are connected to form an overall structure.The diameter of described carbon nano-tube is 1nm ~ 100nm.Described graphene film layer is multilayer or individual layer.Described conductive substrates is metal substrate or the other materials being coated with metal electrode.
Take diameter as the carbon nano-tube bundle of 100nm ~ 100 μm be transmitter unit, or take width as micro-carbon nano tube line of 100nm ~ 100 μm, easily realize oriented growth, stable large emission can be obtained, make emission current controllability better, greatly improve stability and the reliability of carbon nanotube field emission; Certain employing single-root carbon nano-tube also likely realizes the directed preparation perpendicular to Graphene, adopts structure of the present invention can obtain better performance.The problem simultaneously introducing graphene layer solution carbon nano-tube bad with substrate contact contacts with thermal conductance with the electrical contact obtaining carbon nano-tube and substrate good.The conductivity of Graphene excellence and heat conductivility, the Joule heat produced when launching by force is very low, and the Joule heat of generation also can conduct to avoid contacting the overheated of interface existence and causing substrate thawing to burn phenomenon as quick as thought.
Claims (1)
1. the preparation method of the carbon nano-tube graphene composite structure of a field emission electron source, it is characterized in that, carbon nano-tube and graphene film grow simultaneously, and one end of carbon nano-tube forms being connected of atom level with Graphene, form C-C covalent bond, its preparation process comprises the following steps:
1. select silicon chip as substrate, remove surperficial foul with acetone, ethanol and deionized water, obtain clean silicon face;
2. vacuum coating, sputtering film coating method is adopted to be applicable to the continuous film of graphene growth at deposited on substrates one deck;
3. adopt high precision lithography, the substrate that plated film is good is prepared the microwell array according to designing requirement or line array;
4. vacuum vapor plating, sputter coating mode is adopted to be applicable to the catalyst stack layer material of carbon nano tube growth at the deposited on substrates that photoetching is good;
5. adopt MPCVD method or gas ions to strengthen chemical vapour deposition technique and realize carbon nano pipe array and Graphene grows simultaneously.
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| CN103436854B (en) * | 2013-09-05 | 2015-09-09 | 吉林大学 | The preparation method of a kind of Graphene and carbon nano tube compound material |
| CN103456581B (en) * | 2013-09-10 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Carbon nanotube field emission cathode and preparation method thereof |
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| CN104241062B (en) * | 2014-09-12 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode |
| CN105551909B (en) * | 2015-12-23 | 2017-12-01 | 深圳先进技术研究院 | Field-transmitting cathode and its preparation method and application |
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| CN108172488B (en) * | 2017-12-26 | 2020-10-23 | 深圳先进技术研究院 | Carbon nano field emission cathode and manufacturing method and application thereof |
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| CN114538420A (en) * | 2022-01-25 | 2022-05-27 | 常州大学 | Preparation method of composite heat dissipation film material |
| CN114655944A (en) * | 2022-03-04 | 2022-06-24 | 深圳石墨烯创新中心有限公司 | Graphene/carbon nanotube composite film and preparation method thereof |
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Denomination of invention: Preparation of field emission electron source and carbon nanotube graphene composite structure Effective date of registration: 20210518 Granted publication date: 20150930 Pledgee: Science City (Guangzhou) Finance Leasing Co.,Ltd. Pledgor: GUANGZHOU HAOZHI IMAGE TECHNOLOGY Co.,Ltd. Registration number: Y2021980003759 |
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Application publication date: 20130417 Assignee: Science City (Guangzhou) Finance Leasing Co.,Ltd. Assignor: GUANGZHOU HAOZHI IMAGE TECHNOLOGY Co.,Ltd. Contract record no.: X2021980009731 Denomination of invention: Field emission electron source and preparation method of carbon nanotube graphene composite structure thereof Granted publication date: 20150930 License type: Exclusive License Record date: 20210923 |