CN202473819U - Zinc oxide nano wire emitter on orientation carbon nanotube array die plate - Google Patents
Zinc oxide nano wire emitter on orientation carbon nanotube array die plate Download PDFInfo
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- CN202473819U CN202473819U CN2011202840852U CN201120284085U CN202473819U CN 202473819 U CN202473819 U CN 202473819U CN 2011202840852 U CN2011202840852 U CN 2011202840852U CN 201120284085 U CN201120284085 U CN 201120284085U CN 202473819 U CN202473819 U CN 202473819U
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- zinc oxide
- carbon nanotube
- nanotube array
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Abstract
The utility model relates to a zinc oxide nano wire emitter on an orientation carbon nanotube array die plate, comprising a conductive substrate, an orientation carbon nanotube array die plate growing on the conductive substrate, a zinc oxide nano wire emitter growing on the surface of the orientation carbon nanotube array die plate, wherein the length of the zinc oxide nano wire emitter is 100 nm-2 microns. The growing methods of the orientation carbon nanotube array die plate can be a thermal chemical vapor deposition method, and a plasma enhanced chemical vapor deposition method, etc. The zinc oxide nano wire emitter on an orientation carbon nanotube array die plate can enable the current emission of a composite structure array to be more uniform, thereby further increasing emission current density and stability.
Description
Technical field
The utility model relates to a kind of field emission component.
Background technology
Nano zinc oxide material is used for emission field beginning of this century just, and having benefited from the researcher, constantly to attempt new material synthetic and use.Before zinc oxide was applied to emission, such as gallium nitride, a lot of semiconductor material with wide forbidden band such as aluminium nitride were all attempted being used for an emission, but because variety of issue and not by extensive employing.Before the several years; Some researchers turn to sight the zinc oxide material of various structures; A large amount of research is put on the preparation method and an emission characteristic of various zinc oxide structures, makes zinc oxide become the focus of another field emmision material research behind CNT.
C. people such as J. Lee (550 ℃) mode through vapour deposition on silicon substrate under situation about reporting at low temperature in 2002 prepares the very high zinc oxide nanowire of orientation (nanowire) array [Appl. Phys. Lett.; 2002. 81; 3648-3650]; And the zinc oxide array for preparing done the unlatching field intensity (current density is made as 0.1 μ A/cm2) that a transmission test obtains 6V/ μ m, threshold field strength then needs 11V/ μ m (current density is 1mA/cm2).
In order to increase the field enhancement factor of zinc oxide emitter from geometry; Y. people such as W. Zhu is acicular texture (nanoneedle) [Appl. Phys. Lett., 2003. 83,144-146] with the architecture advances of zinc oxide nanowire or rod; It is elongated pin shape; The top is thinner, and such structure has significantly increased the field enhancement factor on emitter top, will open field intensity and once drop to 2.4V/ μ m.
Q. people's reported first such as Wang four needle shape zinc oxide nano structure (tetrapod-like nanostructure) [Appl. Phys. Lett.; 2006. 88; 153123-153125.], the emitter top of this structure is similar to above-mentioned nanoneedle structure, but then caters to very much the requirement of large tracts of land printing by the overall structure that four pins are formed; Because after the preparation and printing treatment through the printing slurry; Tripod structure was supported on the substrate under the four-needle-like zinc oxide structure can make, and a pin was arranged straight up, constituted very big field, top and strengthened factor.After this, the four-needle-like zinc oxide structure is adopted by a large amount of at silk screen printing type cold cathode.
Compare with other nano structural material, with CNT as the heterojunction of substrate since its unique geometry and excellent electricity, calorifics and mechanical property by extensive concern; On the other hand, nano structure of zinc oxide shows the sub-performance of excellent photoelectric owing to its structural form is similar to CNT, and nano structure of zinc oxide is because its good performance has also become the research focus at present.Yet above-mentioned two kinds of materials all have the shortcoming of self, and CNT is owing to be carbon-based material, and easy and oxygen reacts and is destroyed, and therefore makes field emission body with it and requires very high to vacuum degree; Zinc oxide itself is oxide, and it can overcome the shortcoming of above-mentioned CNT, yet because zinc oxide is semiconductor, and it is poor that conductivity is compared CNT, therefore the field emissive porwer of most of zinc oxide emitter is than CNT difference.In view of CNT and nano structure of zinc oxide very strong complementarity arranged aspect field emission characteristic, some scientific research personnel have launched this two kinds of material combined type studies on Cathode Materials, have obtained the achievement that attracts people's attention.People such as Ren [Appl. Phys. Lett., 2004. 85,1407-1409] have reported and have been grown in zinc oxide nanowire on the carbon fiber that it is opened field intensity and is merely 0.7V/ μ m.The homogeneous orientation of CNT good electron transport properties and zincite crystal structure is combined, improved the character of combined type negative electrode greatly.
More than these achievements proved that tentatively the field emission performance of zinc oxide/CNT composite nanostructure is to be superior to simple CNT or zinc oxide emitter.Because zinc oxide/carbon nano tube composite nano material has novel structure, unique stable chemical property, the field emission performance of its composite nanostructure also more and more causes people's attention.Its composite structure can be divided into three types: one, different zinc oxide structures are directly grown in the CNT wall; Two, CNT is directly grown in the zinc oxide structure; Three, the prepared hybrid combination through silk screen printing.
But; The research in early stage mainly is growth of zinc oxide nano structure on CNT (or carbon nano-fiber) film at random orientation; And the randomness of carbon-base film orientation will cause the lack of homogeneity of field emission body pattern, size, thereby causes shortcomings such as emission current is little, poor stability, life-span weak point.
Summary of the invention
The purpose of the utility model is to overcome deficiency of the prior art, proposes a kind of zinc oxide nanowire emitter of on the directional carbon nanotube array template, growing.In view of zinc oxide nanowire is a semiconductor; Has certain resistance; Can play the effect of current-limiting resistance; A kind of zinc oxide nanowire that the utility model proposes and the composite construction of carbon nano pipe array can make the current emission of this composite construction array more even, and then improve emission and stability.The utility model is applicable to the feds higher to the current emission stability requirement, for example, and the electron source in x-ray source, microwave amplifier, the field emission scanning electron microscope etc.
The technical scheme of the utility model is: the zinc oxide nanowire emitter on the directional carbon nanotube array template; Comprise conductive substrates, the directional carbon nanotube array template on conductive substrates, at the superficial growth zinc oxide nanowire emitter of directional carbon nanotube array template; The length of zinc oxide
nano wire emitter is 100nm-2 μ m.
Growing oriented carbon nano pipe array template conductive substrates can be heavily doped silicon, the glass substrate that is coated with metal electrode, metal substrate etc.
The chemical vapor deposition that the growing method of directional carbon nanotube array template can strengthen for hot phase chemical deposition, plasma etc.
The growing method of zinc oxide nanowire can be aqua-solution method, chemical gaseous phase transfer method, chemical vapour deposition technique etc.
Be grown on the directional carbon nanotube array template the preparation method of zinc oxide nanowire emitter:
The utility model is realized by following steps:
Mainly be on the CNT template, to prepare zinc oxide nanowire.
Aqua-solution method: the catalyst solution of growth of zinc oxide nano line is spun to the surface of carbon nano-tube film array, and dry; The preparation growth solution is dissolved in zinc nitrate hexahydrate and the hexa (hexamethylenetetramine) of equivalent molal quantity in the deionized water, and only mistake stirs ultrasonic concussion, and it is fully dissolved; The carbon nano-tube film array of the good catalyst of spin coating is immersed in the growth solution, insert in the vacuum furnace, be heated to 80 ± 10 ℃.Take out through 2 ± 1 hours growth times, use washed with de-ionized water, dry the zinc oxide nanowire/directional carbon nanotube array composite construction that obtains preparing then.
The directional carbon nanotube array template can also adopt the higher technology of efficient on electrically-conductive backing plate.
In view of zinc oxide nanowire is a semiconductor, have certain resistance, can play the effect of current-limiting resistance.
The beneficial effect of the utility model is: a kind of zinc oxide nanowire of proposition and the composite construction of carbon nano pipe array can make the current emission of this composite construction array more even, and then improve emission and stability.The utility model is applicable to the feds higher to the current emission stability requirement, for example, and the electron source in x-ray source, microwave amplifier, the field emission scanning electron microscope etc.Especially adopt the zinc oxide nanowire of aqua-solution method and the composite construction working stability of carbon nano pipe array, working life reaches practical requirement fully.
Description of drawings
Fig. 1 is the directional carbon nanotube array template.
Fig. 2 is the zinc oxide nanowire emitter of the growth on the CNT template.
Specific embodiments
Embodiment in the face of the utility model elaborates down, and present embodiment provided detailed execution mode and process, but the scope that the utility model is protected is not limited to following embodiment being to implement under the prerequisite with the utility model technical scheme.
Embodiment, the preparation process of the zinc oxide nanowire of on the directional carbon nanotube array template, growing is following:
(1) at first, select for use heavy mixed silicon slices, silicon chip was cleaned two minutes in acetone (acetone) and isopropyl alcohol (IPA) respectively, remove surface organic matter and other impurity, be baked to 180 ℃ and keep two minutes to remove the moisture on surface as substrate.
(2) then at surperficial spin coating (spin-coat) one deck electron beam resist, post bake is 90 seconds under 180 ℃ of temperature.
(3) make photoresist by lithography needed pattern,, just prepared photoresist mask with pattern through developing.
(4) method through magnetron sputtering is at the surface sputtering catalyst film of sample then, and the catalyst here is made up of double-layer films, below one deck be the Al film, thickness 10nm is the Fe film above, thickness 1nm.
(5) peel off, sample is immersed in the acetone, the photoresist that is not made public is just by acetone solution, and the catalyst layer on photoresist surface comes off automatically.So, sample surfaces just only has been left to have the catalyst film of pattern.
(6) adopt the growing oriented CNT of hot phase chemical deposition then, just can prepare carbon nano-tube film array with pattern.
(7) prepare the required catalyst solution of growth of zinc oxide nano line then, in the just bright alcohol of 5mL (1-propanol), ultrasonic concussion fully dissolved it in 2 hours with 11 mg zinc acetate dissolution of crystals.
(8) then this solution is spun to the surface of carbon nano-tube film array, is baked to 120 ℃ and kept two minutes then.According to the density of needed zinc oxide nanowire, control the number of times of spin coating, the spin coating number of times is many more, and the density of the zinc oxide that grows out is big more.
(9) the preparation growth solution is dissolved in zinc nitrate hexahydrate (Zn (NO3) 2 6H2O) and the hexa (hexamethylenetetramine) of equivalent molal quantity in the deionized water, and only mistake stirs ultrasonic concussion, and it is fully dissolved.
(10) last, in the carbon nano-tube film array immersion growth solution with the good catalyst of spin coating, insert in the vacuum furnace, be heated to 80 ℃.Take out through 2 hours growth times, use washed with de-ionized water, dry then to 120 ℃ of removal moisture.The zinc oxide nanowire that can obtain preparing at last/directional carbon nanotube array composite construction.
Claims (1)
1. the zinc oxide nanowire emitter on the directional carbon nanotube array template; Comprise conductive substrates, be grown in the directional carbon nanotube array template on the conductive substrates; It is characterized in that the superficial growth zinc oxide nanowire emitter in the directional carbon nanotube array template, the length of zinc oxide
nano wire emitter is 100nm-2 μ m.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011202840852U CN202473819U (en) | 2011-08-07 | 2011-08-07 | Zinc oxide nano wire emitter on orientation carbon nanotube array die plate |
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| CN2011202840852U CN202473819U (en) | 2011-08-07 | 2011-08-07 | Zinc oxide nano wire emitter on orientation carbon nanotube array die plate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324349A (en) * | 2011-08-07 | 2012-01-18 | 张研 | Zinc oxide (ZnO) nanowire emitter growing on aligned carbon nanotube (ACNT) array template |
| CN106939413A (en) * | 2017-03-14 | 2017-07-11 | 中国人民解放军63971部队 | A kind of zinc nano line array electrode preparation method |
-
2011
- 2011-08-07 CN CN2011202840852U patent/CN202473819U/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324349A (en) * | 2011-08-07 | 2012-01-18 | 张研 | Zinc oxide (ZnO) nanowire emitter growing on aligned carbon nanotube (ACNT) array template |
| CN102324349B (en) * | 2011-08-07 | 2013-08-28 | 上海康众光电科技有限公司 | Zinc oxide (ZnO) nanowire emitter growing on aligned carbon nanotube (ACNT) array template |
| CN106939413A (en) * | 2017-03-14 | 2017-07-11 | 中国人民解放军63971部队 | A kind of zinc nano line array electrode preparation method |
| CN106939413B (en) * | 2017-03-14 | 2020-04-14 | 中国人民解放军63971部队 | Preparation method of zinc nanowire array electrode |
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| C14 | Grant of patent or utility model | ||
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Owner name: SHANGHAI KANGZHONG OPTOELECTRONIC TECHNOLOGY CO., Free format text: FORMER OWNER: ZHANG YAN Effective date: 20130517 Free format text: FORMER OWNER: LI CHI Effective date: 20130517 |
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Free format text: CORRECT: ADDRESS; FROM: 210096 NANJING, JIANGSU PROVINCE TO: 200000 YANGPU, SHANGHAI |
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Effective date of registration: 20130517 Address after: 200000 room A102, exhibition hall, No. 11 Cathay Pacific Road, Shanghai, Yangpu District Patentee after: Shanghai Kangzhong Optoelectronic Technology Co., Ltd. Address before: 210096 Room 101, display technology research center, four arch 2, Nanjing, Jiangsu Patentee before: Zhang Yan Patentee before: Li Chi |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121003 Termination date: 20200807 |
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