CN1558441A - Method for preparing carbon nanotube on glass substrates - Google Patents
Method for preparing carbon nanotube on glass substrates Download PDFInfo
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- CN1558441A CN1558441A CNA2004100007261A CN200410000726A CN1558441A CN 1558441 A CN1558441 A CN 1558441A CN A2004100007261 A CNA2004100007261 A CN A2004100007261A CN 200410000726 A CN200410000726 A CN 200410000726A CN 1558441 A CN1558441 A CN 1558441A
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Abstract
The invention discloses a method for preparing carbon nanotube on glass substrates, in particular the preparation of carbon nanotube emission cathode, which comprises, using glass as substrate, depositing a fluoride film of II main group metals or rare-earth metals on the glass substrate, then depositing ferrum, cobalt, nickel, palladium or using the alloy film composing these material as catalyst, growing carbon nanotube on the film by utilizing the conventional growing technology, or first depositing a layer of ferrum, cobalt, nickel, palladium on the glass substrate or using the alloy film composing these material as catalyst, then depositing a fluoride film of II main group metals or rare-earth metals, then growing carbon nanotube on the film, wherein the substrate temperature during carbon nanotube growing is 400-650 deg. C.
Description
Technical field
The invention belongs to the carbon nano tube growth technical field, particularly the preparation of carbon nano-tube field-transmitting cathode.
Technical background
An important application of carbon nano-tube is the fabricating yard emitting cathode, this negative electrode can be used in multiple device that needs electron stream and the device, in vacuum microwave pipe, electron accelerator, discharge tube and flat-panel display device, wherein flat panel display is considered to the most promising direction.The method of making at present the carbon nano-tube field-transmitting cathode roughly is divided into two kinds, a kind of is on substrate earlier films such as deposition one deck iron, cobalt or nickel as catalyst, direct growth carbon nano-tube then, and can formation and iron, cobalt, the figure that the nickel film is identical.Another kind method is the figure that methods such as the carbon nanotube powders body and function printing of will make, plating are produced on substrate to be needed.Two kinds of methods respectively have pluses and minuses, are all adopted comparatively widely.
In the direct growth mode, generally need underlayer temperature to reach 700 degree Celsius, so use silicon as substrate, this has seriously limited its practical application more.Though also useful glass is made substrate, at the report of the following direct growth carbon nano-tube of 600 degree, the quality that grows is often relatively poor, and the size of emission current and the uniformity of emission etc. are not very good.In the prior art, used substrat structure as shown in Figure 1, wherein 11 is dielectric substrate, is generally silicon materials.12 is catalyst films such as iron, cobalt, nickel.
Summary of the invention
The purpose of this invention is to provide a kind of on glass substrate the method for low temperature depositing carbon nano-tube, the carbon nano-tube quality that grows can reach the carbon nano-tube level of making substrate and growing with silicon more than 700 degree.Thereby for a feasible route is opened up in the practical application of carbon nano-tube.
Technical scheme of the present invention is as follows:
A kind of carbon nano-tube method that on glass substrate, prepares, it is characterized in that this method carries out as follows: deposition one deck II main group metal calcium, magnesium, strontium, the fluoride of barium or the fluoride film of rare earth metal on glass substrate earlier, the alloy firm of deposited iron, cobalt, nickel, palladium or these materials composition is used conventional growing technology carbon nano-tube thereon then as catalyst thereon again; Or the alloy firm of elder generation deposition one deck iron, cobalt, nickel, palladium or these materials on glass substrate is as catalyst, deposit the fluoride film of one deck II main group metal calcium, magnesium, strontium, barium or rare earth metal more thereon, underlayer temperature when carbon nano-tube thereon then, described carbon nano-tube is 400～650 ℃.
In method of the present invention, after adopting earlier depositing fluorinated thing film during the deposited catalyst film, its fluoride film thickness in the scope of 10 nanometers to 1 micron, catalyst film thickness in 5 nanometers in the scope of 100 nanometers.If first deposited catalyst film, during the depositing fluorinated thing film in back, in the scope of 20 nanometers, catalyst film thickness is in the scope of 5 nanometers to 1 micron in 1 nanometer for its fluoride film thickness.
The present invention compared with prior art, have the following advantages and the high-lighting progress: this method has successfully solved the low temperature carbon nano tube growth problem that perplexs technos for a long time, owing to make substrate with common glass, (can under the temperature of the softening point that is lower than simple glass the good carbon nano-tube of growth performance), can solve the problem of on large tracts of land substrate carbon nano-tube and continuous mass production, thereby can effectively reduce production costs.
Description of drawings
Fig. 1 is for making the substrat structure figure that has iron, cobalt or nickel film of substrate with silicon in the prior art.
Fig. 2 is the substrat structure figure that has fluoride film with glass as substrate of the present invention.
Fig. 3 is another kind of substrat structure figure of the present invention.
Embodiment
Core of the present invention is the surface state that control is used for the catalyst metals film of carbon nano tube growth.Promptly on glass substrate, deposit one deck II main group metal calcium, magnesium, strontium, the fluoride of barium or the fluoride film of rare earth metal earlier, the thickness of its fluoride film is generally in the scope of 10 nanometers to 1 micron, the alloy firm of deposited iron, cobalt, nickel, palladium or these materials composition is as catalyst thereon again, and the thickness of catalyst film is generally 5 nanometers to 100 nanometers; Use conventional growing technology carbon nano-tube thereon then.As shown in Figure 2, wherein 21 is substrate, is substrate with glass.22 is fluoride film, and 23 is catalyst films such as iron, cobalt, Nie, Palladium.The film surface of calcirm-fluoride, strontium fluoride, magnesium fluoride, barium fluoride or rare earth fluoride etc. is very coarse, and having lateral dimension is the fluctuating of number nanometer to tens nanometer.This fluctuating makes deposition catalyst metals film thereon be discontinuous state, is very beneficial for the growth of carbon nano-tube, the underlayer temperature in the time of can reducing growth greatly.Still can normal growth when underlayer temperature drops to the temperature (about 550 degree) that is lower than the simple glass softening point.
The present invention's another kind method is that earlier the alloy firm of deposition one deck iron, cobalt, nickel, palladium or these materials is as catalyst on glass substrate, and the thickness of catalyst film is generally 5 nanometers to 1 micron; Deposit the fluoride film of one deck II main group metal calcium, magnesium, strontium, barium or rare earth metal more thereon, the thickness of fluoride film is generally 1 nanometer between 20 nanometers; Use conventional growing technology carbon nano-tube thereon then, as shown in Figure 3.In this method, catalyst film is under fluoride film, and wherein 31 is glass substrate, and 32 is catalyst film, and 33 is fluoride film.Utilize the discontinuous state of fluoride film, exist many nanometer level microporously on it, these micropores expose out with the part catalyst surface, and carbon nano-tube will be easy to grow from these micropores, thereby greatly reduce growth temperature.
The method of the conventional growing technology carbon nano-tube of the utilization described in the present invention comprises the chemical vapour deposition (CVD) of thermally decomposed carbon hydrogen compound, cracking hydrocarbon, magnetron sputtering graphite deposition, ion beam sputtering graphite deposition, electron beam evaporation graphite deposition, laser ablation method deposition graphite deposition, microwave plasma cyclotron resonance chemical vapour deposition (CVD), direct magnetic control plasma activated chemical vapour deposition and radio frequency plasma body chemical vapor phase growing etc.
Embodiment 1
Substrate general window glass, deposited by electron beam evaporation method deposits the calcium-fluoride thin film that a layer thickness is 100 nanometers on it, deposits the nickel film of about 10 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 400 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 2
Substrate general window glass, deposited by electron beam evaporation method deposits the neodymium fluoride film that a layer thickness is 50 nanometers on it, deposits the nickel film of about 20 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 500 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 3
Substrate high softening-point glass, deposited by electron beam evaporation method deposits the magnesium fluoride film that a layer thickness is 500 nanometers on it, deposits the iron thin film of about 100 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 200 handkerchiefs, and underlayer temperature 650 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 4
Substrate general window glass, deposited by electron beam evaporation method deposits the dysprosium fluoride film that a layer thickness is 50 nanometers on it, deposits the cobalt thin film of about 20 nanometers of one deck again, prepares carbon nano-tube with microwave plasma cyclotron resonance chemical vapour deposition (CVD) in vacuum system.Gas methane, pressure are 3 * 10
-2About handkerchief, underlayer temperature 500 degree obtain the second best in quality carbon nano-tube, and substrate glass softens sign.
Embodiment 5
Substrate general window glass, deposited by electron beam evaporation method deposits the strontium fluoride film that a layer thickness is 50 nanometers on it, deposits the nickel film of about 10 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 450 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 6
Substrate general window glass, deposited by electron beam evaporation method deposits the strontium fluoride film that a layer thickness is 50 nanometers on it, deposit iron, cobalt and the nickel alloy film (with the sputter of kovar alloy target) of about 20 nanometers of one deck again, in vacuum system, prepare carbon nano-tube with ion beam sputtering graphite sedimentation.Underlayer temperature 550 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 7
Substrate general window glass, deposited by electron beam evaporation method deposits the nickel film of one deck 500 nanometers on it, deposits the calcium-fluoride thin film of about 10 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 500 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 8
Substrate general window glass, deposited by electron beam evaporation method deposits the iron thin film of one deck 1000 nanometers on it, deposits the calcium-fluoride thin film of about 20 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 500 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 9
Substrate general window glass, deposited by electron beam evaporation method deposits the nickel film of one deck 10 nanometers on it, deposits the neodymium fluoride film of about 10 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 550 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 10
Substrate general window glass, deposited by electron beam evaporation method deposits the nickel film of one deck 500 nanometers on it, deposits the strontium fluoride film of about 10 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 450 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Substrate general window glass, deposited by electron beam evaporation method deposits one deck 100 nanometer De Palladium films on it, deposits the calcium-fluoride thin film of about 10 nanometers of one deck again, prepares carbon nano-tube with the thermal decomposition chemical vapour deposition technique in vacuum system.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 550 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Substrate general window glass, iron, cobalt and the nickel alloy film of deposited by electron beam evaporation method deposition one deck 10 nanometers (with the sputter of kovar alloy target) on it, deposit the calcium-fluoride thin film of about 1 nanometer of one deck again, in vacuum system, prepare carbon nano-tube with the thermal decomposition chemical vapour deposition technique.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 500 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Embodiment 13
Substrate general window glass, the deposited by electron beam evaporation method deposits chromium-copper-chromium electrode thereon earlier, and it makes time spent increase conductivity, deposits the nickel film of one deck 200 nanometers more thereon, deposits the calcium-fluoride thin film of 5 nanometers again.In vacuum system, prepare carbon nano-tube with heated filament auxiliary heat chemical decomposition vapour deposition process.Gas acetylene, pressure are about 100 handkerchiefs, and underlayer temperature 550 degree obtain the second best in quality carbon nano-tube, and substrate glass is without any softening sign.
Claims (3)
1. one kind prepares the carbon nano-tube method on glass substrate, it is characterized in that this method carries out as follows: deposition one deck II main group metal calcium, magnesium, strontium, the fluoride of barium or the fluoride film of rare earth metal on glass substrate earlier, the alloy firm of deposited iron, cobalt, nickel, palladium or these materials composition is used conventional growing technology carbon nano-tube thereon then as catalyst thereon again; Or the alloy firm of elder generation deposition one deck iron, cobalt, nickel, palladium or these materials on glass substrate is as catalyst, deposit the fluoride film of one deck II main group metal calcium, magnesium, strontium, barium or rare earth metal more thereon, underlayer temperature when carbon nano-tube thereon then, described carbon nano-tube is 400～650 ℃.
2. carbon nano tube growth method according to claim 1, it is characterized in that: after adopting earlier depositing fluorinated thing film during the deposited catalyst film, its fluoride film thickness in the scope of 10 nanometers to 1 micron, catalyst film thickness in 5 nanometers in the scope of 100 nanometers.
3. carbon nano tube growth method according to claim 1, it is characterized in that: deposited catalyst film in the ban, during back depositing fluorinated thing film, in the scope of 20 nanometers, catalyst film thickness is in the scope of 5 nanometers to 1 micron in 1 nanometer for its fluoride film thickness.
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| CNB2004100007261A CN100395857C (en) | 2004-01-16 | 2004-01-16 | Method for preparing carbon nanotube on glass substrates |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100452284C (en) * | 2006-07-07 | 2009-01-14 | 清华大学 | Thin film transistor controlled thin film field emission display device |
| CN102341234A (en) * | 2009-03-03 | 2012-02-01 | 应用纳米结构方案公司 | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
| CN103021763A (en) * | 2012-12-27 | 2013-04-03 | 青岛艾德森能源科技有限公司 | Method for preparing field-emission cathode material |
| CN103043648A (en) * | 2012-12-27 | 2013-04-17 | 青岛艾德森能源科技有限公司 | Preparation method for carbon nanotube |
| US8580342B2 (en) | 2009-02-27 | 2013-11-12 | Applied Nanostructured Solutions, Llc | Low temperature CNT growth using gas-preheat method |
| US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
| US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
| US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US8969225B2 (en) | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
| US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
| CN115057431A (en) * | 2022-06-24 | 2022-09-16 | 中山烯利来设备科技有限公司 | Method for manufacturing carbon nano tube |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| ATE440073T1 (en) * | 1998-09-18 | 2009-09-15 | Univ Rice William M | CHEMICAL DERIVATIZATION OF SINGLE-WALLED CARBON NANO TUBES TO FACILITATE THEIR SOLVATATION AND USE OF DERIVATIZED NANO TUBES |
| EP1059266A3 (en) * | 1999-06-11 | 2000-12-20 | Iljin Nanotech Co., Ltd. | Mass synthesis method of high purity carbon nanotubes vertically aligned over large-size substrate using thermal chemical vapor deposition |
| KR100490527B1 (en) * | 2000-02-07 | 2005-05-17 | 삼성에스디아이 주식회사 | Secondary electron amplification structure applying carbon nanotube and plasma display panel and back light using the same |
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2004
- 2004-01-16 CN CNB2004100007261A patent/CN100395857C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100452284C (en) * | 2006-07-07 | 2009-01-14 | 清华大学 | Thin film transistor controlled thin film field emission display device |
| US9573812B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
| US9574300B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
| US8580342B2 (en) | 2009-02-27 | 2013-11-12 | Applied Nanostructured Solutions, Llc | Low temperature CNT growth using gas-preheat method |
| US10138128B2 (en) | 2009-03-03 | 2018-11-27 | Applied Nanostructured Solutions, Llc | System and method for surface treatment and barrier coating of fibers for in situ CNT growth |
| CN102341234A (en) * | 2009-03-03 | 2012-02-01 | 应用纳米结构方案公司 | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
| CN102341234B (en) * | 2009-03-03 | 2015-05-27 | 应用纳米结构方案公司 | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
| US8969225B2 (en) | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
| US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
| US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
| CN103021763A (en) * | 2012-12-27 | 2013-04-03 | 青岛艾德森能源科技有限公司 | Method for preparing field-emission cathode material |
| CN103043648A (en) * | 2012-12-27 | 2013-04-17 | 青岛艾德森能源科技有限公司 | Preparation method for carbon nanotube |
| CN115057431A (en) * | 2022-06-24 | 2022-09-16 | 中山烯利来设备科技有限公司 | Method for manufacturing carbon nano tube |
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| CN100395857C (en) | 2008-06-18 |
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