CN100538963C - A kind of compound field-causing electron emitter and its production and use - Google Patents
A kind of compound field-causing electron emitter and its production and use Download PDFInfo
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- CN100538963C CN100538963C CNB200710051232XA CN200710051232A CN100538963C CN 100538963 C CN100538963 C CN 100538963C CN B200710051232X A CNB200710051232X A CN B200710051232XA CN 200710051232 A CN200710051232 A CN 200710051232A CN 100538963 C CN100538963 C CN 100538963C
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Abstract
The present invention relates to a kind of compound field-causing electron emitter, comprise conductive substrates, to be matrix attached to the oxide nano thread on the conductive substrates, nano belt or nanometer rods, growth has one-dimensional carbon nano material on the matrix.The preparation method of above-mentioned compound field-causing electron emitter is: grow oxide nanowires, nano belt or nanometer rods on conductive substrates, be coated with transition-metal catalyst in oxide nano thread, nano belt or nanorod surfaces, burnt 1-30 minute in flame then, forming with oxide nano thread, nano belt or nanometer rods is the compound field-causing electron emitter of the one-dimensional carbon nano material of matrix.Preparation technology of the present invention is simple, with low cost, and the composite field electronic emitting material that makes can be used as emitting cathode needs the application of the occasion of electron source at Field Emission Display or illuminating source, X-ray electron source, mass spectrometer electron source and other.
Description
Technical field
The present invention relates to the compound field-causing electron emission of nano-oxide and one-dimensional carbon nano material low-dimension nano material and its production and use, especially relate on a kind of low-dimensional-oxide nanometer material the synthesize nano carbon material and with this as field-transmitting cathode, belong to nano material preparation and application, also belong to the microelectronic vacuum field.
Background technology
Monodimension nanometer material will bring revolutionary change to fields such as traditional material and microelectronics because its peculiar structure and physical property not only for basic physics research provides valuable research object, are also indicating huge market application foreground.Monodimension nanometer material such as nano wire, nanotube has big draw ratio and extremely small tip radius can be used as good field emission source, at flat-panel screens, x-ray source, microwave amplifier, lighting equal vacuum electronic applications the important application prospect is arranged.Carbon nano-tube (Carbon Nanotubes, CNTs) and carbon nano-fiber (Carbon Nanofibers CNFs) is expected to become one of the preferred material of the field emission source of Field Emission Display of future generation.How further to improve emission, reduce and open electric field, improving emission simultaneously stable is that it moves towards to use the key issue that needs to be resolved hurrily.Substrate has significant effects to the growth and the application of carbon nanomaterial, and carbon current nanotube and carbon nano-fiber can be grown in silicon, porous silicon, on the multiple substrates such as quartz, porous alumina lamina membranacea, metal.Recently reported carbon nano-tube on silicon nanowires on the magazine of " Solid State Communication " (2005,133 volumes, the 22 phase, 131-134 page or leaf), this structure has embodied an electron emission capability preferably.But above-mentioned one-dimensional carbon nano material easily produces the electric field shielding effect, has influenced further raising electronic emission performance.
In addition, the problem of growth of one-dimensional carbon nanomaterial existence is on oxide-based nanomaterial: 1. in the traditional chemical vapor deposition growth carbon nanomaterial, because the hydrogen that uses makes the composition of oxide-based nanomaterial be easy to destroyed at high temperature as the reducing agent of catalyst.2. in the plasma reinforced chemical vapour deposition, high-octane plasma plume brightness can destroy the unique texture of oxide-based nanomaterial.3. other method such as equipment requirements height such as lf, arc discharge, the cost costliness.Growth of one-dimensional carbon nanomaterial and do not appear in the newspapers as yet on the low-dimensional nano structure oxide at present as field-transmitting cathode.
Summary of the invention
The purpose of this invention is to provide a kind of one-dimensional carbon nano material field-transmitting cathode emitter based on the low-dimensional-oxide nanometer material and its production and use, its preparation method is simple, with low cost, but and large-area preparation one-dimensional carbon nano material, the density of the one-dimensional carbon nano material that obtains is higher, and can effectively reduce the electric field shielding effect that the high-compactness one-dimensional carbon nano material produces, thereby improve the electronic emission performance of single low-dimension nano material.
Technical scheme provided by the invention is: a kind of compound field-causing electron emitter, comprise conductive substrates, and to be matrix attached to the oxide nano thread on the conductive substrates, nano belt or nanometer rods, growth has one-dimensional carbon nano material on the matrix.
Described oxide is one or more in zinc oxide, tin oxide, tin ash, gallium oxide, indium oxide, titanium oxide, vanadium oxide, tungsten oxide, iron oxide, nickel oxide, molybdenum oxide, the cerium oxide.
Be connected with electrode on the above-mentioned conductive substrates.
Above-mentioned conductive substrates is sheet metal, be coated with the substrate or the silicon chip of conducting film.
The present invention also provides the preparation method of above-mentioned compound field-causing electron emitter, grow oxide nanowires, nano belt or nanometer rods on conductive substrates are (as document [1] .Chun Li, Guojia Fang, Shuang Ma, Xingzhong Zhao, Self-organized ZnO microcombs with cuboid nanobranches by simple thermal evaporation, CrystalGrowth ﹠amp; Design, 2006,6 (11): 2588-2591.[2] .Chun Li, Guojia Fang, Sheng Xu, DongshanZhao, and Xingzhong Zhao, Phase-segregation assisted growth of quasi-aligned ZnO nanorods onMg
0.6Zn
0.4O-coated Si substrate by thermal evaporation, Nanotechnology, 2006,17:5367-5372.[3] .Chun Li, Guoj ia Fang, Qiang Fu, Fuhai Su, Guohua Li, Xiaoguang Wu, Xingzhong Zhao, Synthesis and photoluminescence properties of vertically aligned ZnO nanorods-nanowall junctionarrays on ZnO-coated silicon substrate, Nanotechnology, 2006,17:3740-3744), at oxide nano thread, nano belt or nanorod surfaces are coated with transition-metal catalyst, in flame, burnt 1-30 minute then, form with oxide nano thread, nano belt or nanometer rods are the emitting cathode of the one-dimensional carbon nano material of matrix.
Above-mentioned flame is fuel used to be organic-fuel such as methane, methyl alcohol, acetylene, ethene, ethanol, propyl alcohol or liquefied petroleum gas etc.
Described transition-metal catalyst is iron, cobalt or nickel; Be coated with thickness between 5-50nm.
Described compound field-causing electron emitter of the present invention in Field Emission Display, illuminating source, X-ray electron source or mass spectrometer electron source as the application of emitting cathode.
The present invention prepares carbon nano-tube on the low-dimensional-oxide nanometer material, can be in the density that improves one-dimensional carbon nano material, can effectively reduce the electric field shielding effect that the high-compactness one-dimensional carbon nano material produces again, thereby improve the electronic emission performance of one dimension oxide-based nanomaterial.Because the major diameter of oxide nano thread (bar) distance between when is controlled, easily realizes Position Control and graphical (addressing) of emitter cells.The electronic emission performance of this material can compare favourably with the electronic emission performance of the one-dimensional carbon nano material that adopts the preparation of chemical vapor deposition (CVD) and plasma enhanced chemical vapor deposition complicated technologies such as (PECVD) and main equipment.This field-transmitting cathode emitter material is expected to be used for flat panel display, illuminating source, X-ray electron source, mass spectrometer electron source and other needs the occasion of electron source.
Description of drawings
Fig. 1 is the stereoscan photograph of nanometic zinc oxide rod array of the present invention and one-dimensional carbon nano material composite cathode;
Fig. 2 is the long transmission electron microscope photo that carbon nano-tube and carbon nano-fiber are arranged on the zinc oxide nano rod;
Fig. 3 is based on nanometic zinc oxide rod array and one-dimensional carbon nano material composite cathode field-causing electron launching curve and phosphor screen and lights photo.
Fig. 4 is based on indium oxide nano thread array and one-dimensional carbon nano material composite cathode field-causing electron launching curve.
Fig. 5 is based on tin oxide nano band array and one-dimensional carbon nano material composite cathode field-causing electron launching curve.
Embodiment
The present invention is compound, and the field-causing electron emitting cathode can be prepared by laxative remedy:
1. on conductive substrates, prepare nano materials such as oxide nano-rod, nano belt or nano wire (as document [1], [2], [3] or [4] Shuang Ma, Guojia Fang, Chun Li, Su Sheng, Linggang Fang, Qiang Fu, Xing-Zhong Zhao, Controllable Synthesis of Vertically Aligned ZnO Nanorod Arrays in Aqueous Solution, Journal of Nanoscience ﹠amp; Nanotechnology, 2006,6 (7), 2062-2066.).
On conductive substrates the zone of nano material grown adopt thermal evaporation or methods such as radio frequency sputtering or electron beam evaporation or electroless plating (as: Tang Weizhong work, thin-film material preparation principle, technology and application, metallurgical industry publishing house 1998 front pages) be coated with 10-50nm transition-metal catalyst layer.
3. the catalyst that is coated with substrate faces down, and the carbon-hydrogen flame towards burning burnt 1-30 minute therein, and natural cooling in air can prepare carbon nano-tube, carbon nano-fiber etc.-dimension carbon nanomaterial on the low-dimensional-oxide nanometer structure then.
4. at the coating of the conductive substrates back side, evaporation or splash-proofing sputtering metal electrode, forming oxide nano structure is the compound field-causing electron emitting cathode of one-dimensional carbon nano material of matrix.
Embodiment one:
1. use semiconductor standard cleaning silicon chip technology (as: Yan Zhirui, semi-conductor silicon chip cleaning developing direction, the electronics industry special equipment, 2003, in September, p23-26), the silicon chip of single-sided polishing is cleaned.Use impulse laser deposition system (as Xin Chen, Wenjie Guan, Guojia Fang, Xingzhong Zhao, Influence of substratetemperature and post-treatment on properties of ZnO:Althin films prepared by pulsed laserdeposition, Appl.Surf.Sci., 2005,252 (5): 1561-1567.), deposit thickness is the zinc-oxide film of 100-500nm on cleaned silicon wafer polishing face.
2. the mixture of powders (mol ratio 1: 1) of 0.1-1 gram zinc oxide and graphite is put in the sealing end bottom of the quartz ampoule that at one end seals, and falls the quartz ampoule that the silicon chip that deposits zinc-oxide film is put into this end closure, and apart from sealing end bottom 5-10cm.
3. the quartz ampoule openend of this end closure is put into the tubular type vacuum atmosphere oven in the other direction towards the high-purity argon gas air-flow, the 900-1100 degree kept 5-15 minute, vacuum degree 10-1000Pa, and cooling to normal temperature with stove then can take out, and obtains nanometic zinc oxide rod array.
4. on the zinc oxide nano rod that obtains, use magnetron sputtering thickness to be about the metallic nickel of 10 nanometers.
5. the surface that substrate is coated with nickel is downward, burnt 1-30 minute at flame middle part over against the ethanol (analyzing pure) that burns, carbon nano-tube, carbon nano-fiber can be grown on the zinc oxide nano rod, obtain the one-dimensional carbon nano material cathode emitter based on zinc oxide nano rod.Fig. 1, Fig. 2 are respectively and observe the pattern picture that resulting nanowire surface is wrapped up by radial carbon nano-tube under scanning electron microscopy and projection electron microscopes.
6. electrode preparation.After preparing nanometic zinc oxide rod array and one-dimensional carbon nano material complex cathode emitter, test its field-causing electron emission, must be at silicon chip back side extraction electrode.Electrode adopts the sputtering method preparation, sputter one deck Al or brush indium gallium electrode equably at the silicon chip reverse side.
7. with the emission of Keithley 6517A electrometer test field-causing electron, nanometic zinc oxide rod array/one-dimensional carbon nano material composite cathode emitter electric field strength and current density characteristic curve and anode phosphor screen are luminous as Fig. 3 recording.Obtain opening electric field 2.5V/ μ m (current density 1 μ A/cm
2), threshold field 4.5V/ μ m (current density 1mA/cm
2) nanometic zinc oxide rod array/one-dimensional carbon nano material composite cathode emitter.
Embodiment two: (preparation method is with list of references Qing Wan, Eric N Dattoli, Wayne Y.Fung at the indium oxide nano thread that obtains, et al., Nano Letters, 2006,6 (12): 2909-2915) go up the metallic iron that uses magnetron sputtering thickness to be about 5 nanometers.Burnt 5 minutes in the liquefied petroleum gas flame.Carbon nano-tube, carbon nano-fiber can be grown on the indium oxide nano thread, obtain the one-dimensional carbon nano material cathode emitter based on indium oxide nano thread.(other subsequent treatment is with example 1).Record indium oxide nano thread array/one-dimensional carbon nano material composite cathode emitter electric field strength and current density characteristic curve such as Fig. 4.
Embodiment three: 1. use magnetron sputtering to plate thickness on the silicon wafer polishing face and be about 10 nano-Au films and be catalyst.2. the silicon chip that will be coated with golden film is put into the tubular type atmosphere furnace with the mixture of powders (mol ratio 1:1) of tin ash and graphite, silicon chip is placed on the air-flow below, apart from the about 5cm of mixture of powders place, the 900-1100 degree kept 30-60 minute, argon stream amount 50-200sccm.Cooling to normal temperature with stove then can take out, and can obtain the stannic oxide nanometer band on silicon chip.3. on the stannic oxide nanometer band, plate the cobalt (Co) of 50nm.The surface that substrate is coated with nickel is downward, burns 10 minutes over against the acetylene torch middle part of burning, and carbon nano-tube, carbon nano-fiber can be grown on the tin oxide nano band, obtain the one-dimensional carbon nano material cathode emitter based on the tin oxide nano band.(other subsequent treatment is with example 1).Record tin oxide nano band array/one-dimensional carbon nano material composite cathode emitter electric field strength and current density characteristic curve such as Fig. 5.
Claims (9)
1. a compound field-causing electron emitter comprises conductive substrates, it is characterized in that: to be matrix attached to the oxide nano thread on the conductive substrates, nano belt or nanometer rods, growth has one-dimensional carbon nano material on the matrix.
2. compound field-causing electron emitter as claimed in claim 1 is characterized in that: described oxide is one or more in zinc oxide, tin oxide, tin ash, gallium oxide, indium oxide, titanium oxide, vanadium oxide, tungsten oxide, iron oxide, nickel oxide, molybdenum oxide, the cerium oxide.
3. compound field-causing electron emitter as claimed in claim 1 or 2 is characterized in that: be connected with electrode on the conductive substrates.
4. compound field-causing electron emitter as claimed in claim 1 or 2 is characterized in that: conductive substrates is sheet metal, be coated with the substrate or the silicon chip of conducting film.
5. the preparation method of claim 1 or 2 described compound field-causing electron emitters, it is characterized in that: grow oxide nanowires, nano belt or nanometer rods on conductive substrates, be coated with transition-metal catalyst in oxide nano thread, nano belt or nanorod surfaces, burnt 1-30 minute in flame then, forming with oxide nano thread, nano belt or nanometer rods is the compound field-causing electron emitter of the one-dimensional carbon nano material of matrix.
6. preparation method as claimed in claim 5 is characterized in that: flame is fuel used to be organic-fuel.
7. preparation method as claimed in claim 6 is characterized in that: described organic-fuel is methane, methyl alcohol, acetylene, ethene, ethanol, propyl alcohol or liquefied petroleum gas.
8. require 5 or 6 or 7 described preparation methods as right power, it is characterized in that: described metallic catalyst is iron, cobalt or nickel; Be coated with thickness between 5-50nm.
The described compound field-causing electron emitter of claim 1 in Field Emission Display, illuminating source, X-ray electron source or mass spectrometer electron source as the application of emitting cathode.
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