CN103193217A - Method for preparing boron-doped diamond and carbon nanotube composite nanocone - Google Patents
Method for preparing boron-doped diamond and carbon nanotube composite nanocone Download PDFInfo
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- CN103193217A CN103193217A CN2013100773289A CN201310077328A CN103193217A CN 103193217 A CN103193217 A CN 103193217A CN 2013100773289 A CN2013100773289 A CN 2013100773289A CN 201310077328 A CN201310077328 A CN 201310077328A CN 103193217 A CN103193217 A CN 103193217A
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Abstract
Carbon nanotubes have a relatively high geometric field enhancement effect, low threshold voltage and high field emission performance. Diamond has a negative electron affinity and field emission stability. The two materials can be widely used in field emission display devices. The invention provides a method for preparing a boron-doped diamond and carbon nanotube composite nanocone. By an electrostatic spraying method, a suspension of nanodiamond mixed with methanol is sprayed and coated on vertical orientation growth multi-walled carbon nanotube surfaces to pre-deposite nanocrystalline diamond particles. The adjacent carbon nanotube tips gather into a cone structure under the role of static electricity. Further, a hot filament chemical vapor deposition method is used for depositing a layer of boron-doped diamond thin film on carbon nanotube cone structures to form the neat, uniform, and size and density-controllable boron-doped diamond and carbon nanotube composite nanocone. The composite nanocone has the advantages of low field emission threshold voltage, long electron emission life and stable performance, and can be applied to field emission devices, electrochemical electrodes and hydrogen storage devices.
Description
Technical field
The present invention relates to nano material technology, particularly a kind of preparation method who can be applicable to boron-doped diamond and the carbon nanotube composite Nano awl of high-performance and long lifetime feds, electrochemical electrode and hydrogen storage device.
Background technology
Carbon nanotube has the mechanical property that the tip curvature radius is little, length-to-diameter ratio is big, excellent, good chemical stability and electroconductibility, thereby have higher end geometric field reinforcing effect, low threshold voltage and a field emission performance efficiently, since being found, people are applied to field emission display to carbon nanotube as electron source and have produced great interest.Field emission research single and many carbon nanotubes and carbon nano-tube film has obtained common concern, still, the field transmitter current instability of carbon nanotube, work-ing life is shorter, is not suitable for large-scale commercial applications.When working under certain vacuum environment, the surface adsorption gas molecule can cause the damage of carbon nanotube end, and the emission electronic capability weakens, and causes the field emission generation persistence of carbon nanotube to be degenerated.
Along with the fast development of information technology and vaccum microelectronics, less energy-consumption, high-resolution, ultra-thin jumbotron show that visual organ more and more comes into one's own, and vacuum microelectronics technique requires also more and more higher to the cathode material as the device core.Therefore, the material that energy consumption is little, field emission performance is superior and stable becomes more and more important.Be the wide bandgap material (as cBN, AlN etc.) of representative with the diamond owing to have good chemistry and thermostability, high-melting-point and thermal conductivity, little specific inductivity, big carrier mobility and high voltage breakdown and negative electron affinity (NEA) (when the surface is stopped by hydrogen atom), in feds, have broad prospect of application.Document (A comparative study of the field emission properties of aligned carbon nanostructures films, from carbon nanotubes to diamond, Eur. Phys. J. Appl. Phys. 38,115,2007) utilize adamantine negative electron affinity (NEA) to hang down advantages such as effective work function with the surface, prepared the diamond thin with better field emission performance by chemical gaseous phase depositing process.In addition, the field emission characteristic of diamond thin can also further strengthen by other method, as the grain-size that reduces film, mix boron or nitrogen unit usually improve the electroconductibility of film or produce defect level, adopt different functional groups (as CsO, LiO) that diamond surface is carried out that chemically modified increases surperficial negative electron affinity (NEA) and diamond thin constructed and have sharp-pointed end to improve method such as a reinforcing effect in film.Though can improve the diamond field emission performance by these methods, but the diamond thin of chemical vapour deposition preparation exists, and electroconductibility is relatively poor relatively, columnar crystal structure, the contact of the low resistance back of the body and nanostructure prepare problems such as difficulty, cause highlyer than the feds threshold voltage of carbon nanotube based on adamantine feds under the same conditions, emission efficiency is lower.Yet adamantine feds is longer work-ing life, and the electron emission end is difficult for being burnt.
Be prepared into diamond and carbon nano tube compound material in conjunction with characteristics such as the stability on the satisfactory electrical conductivity of carbon nanotube and boron-doped diamond surface and emission lifetime are long, and it is built into cone structure, will be a kind of efficient, long-life field emission cold-cathode material.But the technology of preparing that does not have boron-doped diamond and carbon nanotube composite Nano awl in the prior art.
Summary of the invention
The objective of the invention is by in conjunction with carbon nanotube and boron-doped diamond in the characteristics aspect the field emission performance, the preparation method of a kind of boron-doped diamond and carbon nanotube composite Nano awl is provided.
The technical solution that realizes the object of the invention is: the preparation method of a kind of boron-doped diamond and carbon nanotube composite Nano awl, by the multi-wall carbon nano-tube tube-surface pre-deposition Nano diamond particle of electrostatic coating method at vertical oriented growth, and under electrostatic forcing, make carbon nanotube be gathered into cone structure; Further adopt the hot-wire chemical gas-phase deposition method at carbon mitron cone structure deposition one deck boron-doped diamond film, form boron-doped diamond and carbon nanotube composite Nano awl with good field emission performance, specifically may further comprise the steps:
The present invention compared with prior art, its remarkable advantage is: 1) composite Nano of the present invention awl material is made of the multi-walled carbon nano-tubes that has applied boron-doped diamond; 2) the vertical orientation multi-walled carbon nano-tubes carbon of the present invention's preparation can make the adjacent carbons nanotube assemble by Electrostatic Spray Technology and form the nanocone structure; 3) the present invention adopts the boron-doped diamond film of hot-wire chemical gas-phase deposition method preparation the nanocone end can be covered, and does not influence the configuration of nanocone simultaneously; 4) the technology of the present invention can prepare boron-doped diamond and the carbon nanotube composite Nano awl of neat homogeneous, size and controllable density, and this composite Nano awl has low emission threshold threshold voltage, emission lifetime is long and stable performance; 5) boron-doped diamond of the present invention's preparation and carbon nanotube composite Nano awl are not only applicable to the high-performance field emission display, also can be used for electrochemical electrode and hydrogen storage device simultaneously.
Below in conjunction with accompanying drawing the present invention is done further detailed description.
Description of drawings
Fig. 1 is the carbon nanotube sem photograph of the vertical oriented growth of example 1 preparation of the present invention.
Fig. 2 is the carbon nanotube pyramidal structure sem photograph that forms behind the example 1 process electrostatic spraying Nano diamond particle suspension liquid of the present invention.
Fig. 3 is the boron-doped diamond of example 1 preparation of the present invention and the sem photograph of carbon nanotube composite Nano awl.
Fig. 4 is the field emission characteristic curve of boron-doped diamond and carbon nanotube composite Nano awl array.
Embodiment
The invention provides the preparation method of a kind of boron-doped diamond and carbon nanotube composite Nano awl, by the multi-wall carbon nano-tube tube-surface pre-deposition Nano diamond particle of electrostatic coating method at vertical oriented growth, and under electrostatic forcing, make carbon nanotube be gathered into cone structure; Further adopt the hot-wire chemical gas-phase deposition method at carbon mitron cone structure deposition one deck boron-doped diamond film, form boron-doped diamond and carbon nanotube composite Nano awl with good field emission performance, specifically may further comprise the steps:
Do further detailed description below in conjunction with the present invention of embodiment:
Embodiment 1:
Using plasma strengthens chemical gaseous phase depositing process and prepares multi-walled carbon nano-tubes, by the multi-wall carbon nano-tube tube-surface pre-deposition Nano diamond particle of electrostatic coating method at vertical oriented growth, and under electrostatic forcing, make carbon nanotube be gathered into cone structure; Further adopt the hot-wire chemical gas-phase deposition method at carbon mitron cone structure deposition one deck boron-doped diamond film, form boron-doped diamond and carbon nanotube composite Nano awl with good field emission performance, specifically may further comprise the steps:
Boron-doped diamond and carbon nanotube composite Nano awl to preparation have carried out analysis and characterization, and Fig. 1 is the about 5 μ m of length, diameter 20-50nm, density about 1 * 10
9Cm
-2The multi-walled carbon nano-tubes of vertical oriented growth.Fig. 2 is the sem photograph of array of multi-walled carbon nanotubes behind the electrostatic spraying Nano diamond particle, and residual methyl alcohol is distributed in the carbon nano pipe array end surface, and electrostatic attraction makes 30-40 follow the carbon nanotube tip to be gathered into a little, forms density about 1 * 10
7Cm
-2Conical structure.Fig. 3 is the sem photograph of boron-doped diamond behind the surface deposition diamond thin and carbon nanotube composite Nano awl array, and the top of awl and surface are covered density about 1 * 10 by the skim boron-doped diamond
7Cm
-2Fig. 4 is the field emission characteristic curve of boron-doped diamond and carbon nanotube composite Nano awl array, shows that this composite Nano awl has low threshold electric field (about 3.0V μ m
-1), emitting performance is stable and the life-span is long.
Embodiment 2:
Using plasma strengthens chemical gaseous phase depositing process and prepares multi-walled carbon nano-tubes, by the multi-wall carbon nano-tube tube-surface pre-deposition Nano diamond particle of electrostatic coating method at vertical oriented growth, and under electrostatic forcing, make carbon nanotube be gathered into cone structure; Further adopt the hot-wire chemical gas-phase deposition method at carbon mitron cone structure deposition one deck boron-doped diamond film, form boron-doped diamond and carbon nanotube composite Nano awl with good field emission performance, specifically may further comprise the steps:
Through verification experimental verification, deposited one deck boron-doped diamond film at many walls carbon mitron cone structure of forming core in advance, and formed boron-doped diamond and bore with the carbon nanotube composite Nano.
Embodiment 3:
Using plasma strengthens chemical gaseous phase depositing process and prepares multi-walled carbon nano-tubes, by the multi-wall carbon nano-tube tube-surface pre-deposition Nano diamond particle of electrostatic coating method at vertical oriented growth, and under electrostatic forcing, make carbon nanotube be gathered into cone structure; Further adopt the hot-wire chemical gas-phase deposition method at carbon mitron cone structure deposition one deck boron-doped diamond film, form boron-doped diamond and carbon nanotube composite Nano awl with good field emission performance, specifically may further comprise the steps:
Through verification experimental verification, deposited one deck boron-doped diamond film at many walls carbon mitron cone structure of forming core in advance, and formed boron-doped diamond and bore with the carbon nanotube composite Nano.
Claims (7)
1. the preparation method of a boron-doped diamond and carbon nanotube composite Nano awl, it is characterized in that, by the multi-wall carbon nano-tube tube-surface pre-deposition Nano diamond particle of electrostatic coating method at vertical oriented growth, and under electrostatic forcing, make carbon nanotube be gathered into cone structure; Further adopt the hot-wire chemical gas-phase deposition method at carbon mitron cone structure deposition one deck boron-doped diamond film, form boron-doped diamond and carbon nanotube composite Nano awl with good field emission performance, specifically may further comprise the steps:
Step 1, monocrystalline substrate is carried out surface cleaning processing;
Step 2, on the clean monocrystalline substrate of surface cleaning sputtering sedimentation SiO successively
2Film and Ni film;
Step 3, sample is placed in the plasma enhanced chemical vapor deposition reaction vessel, by heated substrate, makes the fusing of Ni film, form the Ni nanoparticle that disperses at substrate;
Step 4, using plasma strengthen chemical gaseous phase depositing process, are catalyzer with Ni, at C
2H
2/ NH
3Regulate the array of multi-walled carbon nanotubes that direct-current biasing prepares vertical orientation in the mixed gas;
Step 5, with the Nano diamond particles dispersed in methanol solution, be mixed with suspension liquid, afterwards by electrostatic spraying coated with nano diamond particles in advance on the multi-wall carbon nano-tube tube-surface of preparation, and under electrostatic forcing, make carbon nanotube be gathered into cone structure;
Step 6, there is the multi-walled carbon nano-tubes sample of Nano diamond particle to place the hot filament chemical vapor deposition reactor container surface-coated, feeds CH
4/ H
2/ B
2H
6Mixed gas, control hot-wire temperature, CH
4/ H
2Ratio, B/C ratio, deposition pressure and these processing parameters of depositing time at many walls carbon mitron cone structure deposition one deck boron-doped diamond film of forming core in advance, form boron-doped diamond and bore with the carbon nanotube composite Nano.
Boron-doped diamond according to claim 1 and carbon nanotube composite Nano the awl the preparation method, it is characterized in that, step 1 pair silicon substrate carries out surface cleaning processing and is specially: at first substrate is immersed ultrasonic cleaning in the miscible fluid of acetone and ethanol, put into deionized water for ultrasonic then and clean, cold wind dries up afterwards.
3. the preparation method of boron-doped diamond according to claim 1 and carbon nanotube composite Nano awl is characterized in that SiO in the step 2
2Film thickness is 30-50nm, and the Ni film thickness is 5-15nm.
4. the preparation method of boron-doped diamond according to claim 1 and carbon nanotube composite Nano awl is characterized in that underlayer temperature is 650-750 ℃ in the step 3, and be 5-15min heat-up time.
5. the preparation method of boron-doped diamond according to claim 1 and carbon nanotube composite Nano awl is characterized in that, the direct-current biasing of preparation array of multi-walled carbon nanotubes is 550-750V in the step 4, C
2H
2/ NH
3Gas flow is 50sccm/200sccm.
Boron-doped diamond according to claim 1 and carbon nanotube composite Nano the awl the preparation method, it is characterized in that, the Nano diamond particle diameter is 3-10nm in the step 5, electrostatic spraying Nano diamond particle suspension liquid time institute biasing is 35kV, deposits the sample speed of rotation 1500rpm of multi-walled carbon nano-tubes.
Boron-doped diamond according to claim 1 and carbon nanotube composite Nano the awl the preparation method, it is characterized in that hot-wire chemical gas-phase deposition prepares the diamond thin condition in the step 6: deposition pressure is 20-30Torr, CH
4/ H
2Gas ratio is 1-5%, and the B/C ratio is 2000-10000ppm in the mixed gas, and Ta flight lead sample surfaces distance is 3-5mm, and the hot-wire temperature is 2300-2400 ℃, and substrate temperature is about 800-900 ℃, and depositing time is 30-60min.
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Cited By (8)
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CN103496689A (en) * | 2013-09-23 | 2014-01-08 | 同济大学 | Preparation method of boron-doped p type carbon nanotube with high seebeck coefficient |
CN104090011A (en) * | 2014-07-09 | 2014-10-08 | 东南大学 | Preparation method for nanogold-nanofiber functional composite modified electrode |
CN104709872A (en) * | 2015-02-06 | 2015-06-17 | 中国科学院物理研究所 | Diamond nanowire array and preparation method thereof, and electrode for electrochemical analysis |
CN108335916A (en) * | 2017-12-20 | 2018-07-27 | 肇庆市华师大光电产业研究院 | A kind of multi-walled carbon nanotube@X combination electrodes and its preparation method and application |
CN108609695A (en) * | 2018-05-14 | 2018-10-02 | 环境保护部华南环境科学研究所 | A kind of boron-doped diamond thin-film electrode and its preparation method and application of fluorine tin modification |
CN110734726A (en) * | 2018-10-23 | 2020-01-31 | 嘉兴学院 | Preparation method of carbon nanotube/diamond composite heat-conducting adhesive material |
CN111378956A (en) * | 2020-03-24 | 2020-07-07 | 南京航空航天大学 | Preparation method of orderly-arranged diamond micro-nano cone array tool |
CN113604792A (en) * | 2021-06-21 | 2021-11-05 | 北京大学 | Preparation method of diamond nano burr structure |
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Cited By (12)
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CN103496689A (en) * | 2013-09-23 | 2014-01-08 | 同济大学 | Preparation method of boron-doped p type carbon nanotube with high seebeck coefficient |
CN103496689B (en) * | 2013-09-23 | 2015-04-15 | 同济大学 | Preparation method of boron-doped p type carbon nanotube with high seebeck coefficient |
CN104090011A (en) * | 2014-07-09 | 2014-10-08 | 东南大学 | Preparation method for nanogold-nanofiber functional composite modified electrode |
CN104709872A (en) * | 2015-02-06 | 2015-06-17 | 中国科学院物理研究所 | Diamond nanowire array and preparation method thereof, and electrode for electrochemical analysis |
CN108335916A (en) * | 2017-12-20 | 2018-07-27 | 肇庆市华师大光电产业研究院 | A kind of multi-walled carbon nanotube@X combination electrodes and its preparation method and application |
CN108609695A (en) * | 2018-05-14 | 2018-10-02 | 环境保护部华南环境科学研究所 | A kind of boron-doped diamond thin-film electrode and its preparation method and application of fluorine tin modification |
CN108609695B (en) * | 2018-05-14 | 2020-06-30 | 环境保护部华南环境科学研究所 | Fluorine-tin modified boron-doped diamond film electrode and preparation method and application thereof |
CN110734726A (en) * | 2018-10-23 | 2020-01-31 | 嘉兴学院 | Preparation method of carbon nanotube/diamond composite heat-conducting adhesive material |
CN110734726B (en) * | 2018-10-23 | 2021-10-29 | 嘉兴学院 | Preparation method of carbon nanotube/diamond composite heat-conducting adhesive material |
CN111378956A (en) * | 2020-03-24 | 2020-07-07 | 南京航空航天大学 | Preparation method of orderly-arranged diamond micro-nano cone array tool |
CN111378956B (en) * | 2020-03-24 | 2021-08-03 | 南京航空航天大学 | Preparation method of orderly-arranged diamond micro-nano cone array tool |
CN113604792A (en) * | 2021-06-21 | 2021-11-05 | 北京大学 | Preparation method of diamond nano burr structure |
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