CN1159217C - Controllable growth process of carbon nanotube in certain diameter and distribution density - Google Patents
Controllable growth process of carbon nanotube in certain diameter and distribution density Download PDFInfo
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- CN1159217C CN1159217C CNB021150966A CN02115096A CN1159217C CN 1159217 C CN1159217 C CN 1159217C CN B021150966 A CNB021150966 A CN B021150966A CN 02115096 A CN02115096 A CN 02115096A CN 1159217 C CN1159217 C CN 1159217C
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- China
- Prior art keywords
- carbon nanotube
- distribution density
- controllable growth
- certain diameter
- substrate
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000012495 reaction gas Substances 0.000 abstract 1
- 238000000427 thin-film deposition Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 239000002238 carbon nanotube film Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The present invention discloses a controllable growth method of a carbon nanotube with a certain diameter and distribution density, which comprises the following processing steps: (1), plating a catalyst thin film on a substrate by a method of the magnetic filtration of vacuum arc plasma thin film deposition or magnetron sputtering; (2), reducing the substrate plated with a catalyst under a hydrogen gas atmosphere in 600 DEG C of temperature; (3), using the mixed gas of acetylene and inert gas of which the flow ratio is 1/10 as reaction gas, and growing the carbon nanotube under 700 DEG C; (4), cooling under an inert gas atmosphere. The controllable growth method is simple; only two parameters of the thickness of the catalyst thin film and the reduction time of the hydrogen gas are controlled, and then, the diameter and the distribution density of the carbon nanotube can be controlled.
Description
Technical field
The present invention relates to the method that a kind of controllable growth has the carbon nanotube of certain diameter and distribution density.
Background technology
Carbon nanotube is a kind of nano-tube material with unique physical chemical property, shows in information, and Chu Qing, there is important application prospects aspects such as nanoelectronics.It generally can discharge with carbon arc, the preparation of pulsed laser deposition or chemical Vapor deposition process methods such as (CVD).With CVD method carbon nano-tube film the time, the diameter of controlling carbon nanotube and distribution density are great for the application value of carbon nanotube on field-transmitting cathode.And general existing method is all complicated, and is not easy the diameter and the distribution density of controlling carbon nanotube.
Summary of the invention
The invention provides a kind of method, can control the diameter of the carbon nano-tube film that uses the preparation of CVD method and distribution density preferably in applicable scope.
A kind of controllable growth of the present invention has the method for the carbon nanotube of certain diameter and distribution density, comprises following processing step:
1. the method with magnetic filtered vacuum arc plasma foil deposition or magnetron sputtering plates one deck catalyst film on substrate.
2. the substrate that will plate catalyzer is under hydrogen atmosphere, and reduction is handled under 600 degrees centigrade temperature;
3. the use traffic ratio is that 1: 10 acetylene and rare gas element mixed gas are reactant gases, at 700 degrees centigrade of following carbon nano-tubes;
4. under inert gas atmosphere, lower the temperature.
Method of the present invention is simple, and these two parameters of the recovery time of the thickness of control catalyst film and hydrogen only can realize the diameter and the distribution density of controlling carbon nanotube.To observing with SEM and TEM with the carbon nanotube of method preparation of the present invention, the thickness of finding catalyzer is thick more, the particle that forms is big more, the diameter of carbon nanotubes grown is big more, and with the increase of catalyst layer thickness, the pellet density that forms increases, and the density of carbon nanotubes grown also increases.And for the catalyst films of different recovery times, it is long more to get the recovery time with hydrogen, and particle is more little, and the carbon nanotubes grown diameter is also more little.
Description of drawings
Fig. 1 is the surface topography of substrate after reduction is handled that has plated catalyzer iron;
Fig. 2 is for having grown the surface topography behind the carbon nanotube on above-mentioned substrate, a, b, c, d, the iron film thickness of e are respectively 5nm, 10nm, 20nm, 30nm, 40nm;
Fig. 3 is the I-V curve of the field emission of above-mentioned sample.
Embodiment
Method of the present invention just may further comprise the steps:
1. magnetic filtered vacuum arc method plasma-deposited or magnetron sputtering plates one deck catalyst film on substrate, and thickness is the 5-100 nanometer.The catalyzer that uses is iron, cobalt or nickel.
2. the substrate that will plate catalyzer is under hydrogen atmosphere, and reduction was handled 15 minutes to 5 hours under 600 degrees centigrade temperature, and the length of recovery time can be controlled the size and the density of the granules of catalyst of formation;
3.The use traffic ratio is that 1: 10 acetylene and argon gas mixed gas is reactant gases, at 700 degrees centigrade of following carbon nano-tubes;
4.Under argon gas atmosphere, lower the temperature.
Use aforesaid method, the carbon nanotube of a series of different diameters of growth and density on silicon substrate:
1. plating catalyzer
Utilize magnetic filtered vacuum arc plasma foil depositing system deposited catalyst (iron) layer on substrate, and carry out real-time thickness monitoring, deposit a series of different thickness 5nm, 10nm, 20nm, 30nm, the iron layer of 40nm;
2. hydrogen is handled
The substrate that is coated with iron reduced under 600 degrees centigrade with hydrogen handled its flow 110ml/min 2 hours;
3. long nanotube
Sample 700 degrees centigrade of reactions down, feeds the mixed gas of argon gas (300ml/min) and acetylene (30ml/min) after reduction is handled, reacted 5 minutes;
4. after reaction finishes, under argon gas atmosphere, be cooled to room temperature.
With SEM the surface topography of prepared sample is observed, and tested their field emission characteristic.Reduction is handled back sample surfaces pattern and is seen Fig. 1, a, and b, c, d, the thickness of the iron of e is respectively 5nm, 10nm, 20nm, 30nm, 40nm; Catalyst particle size, density increases with the increase of catalyst layer thickness.Grown sample topography such as Fig. 2 of carbon nanotube, a, b, c, d, the thickness of the iron film of e is respectively 5nm, 10nm, 20nm, 30nm, 40nm, the diameter of carbon nanotube and density also increase with catalyst layer thickness.When catalyst layer very thin (less than 20nm) time, reduction rear catalyst particle is little and rare, and corresponding carbon nanotubes grown diameter density is little, and canal curvature is lied down (sample 1,2), along with catalyst layer thickness increases, particle becomes big and becomes close, and it is close that the carbon nanotube chap becomes, when catalyst layer reaches certain thickness (greater than 20 nanometers), carbon nanotube just can vertical growth (sample 3,4,5).This is because the easier length of carbon nanotube of thick (greater than 50 nanometers) is straight, and has arrived certain density, because adjacent carbon nanotube squeezes mutually, just grows towards axial direction separately.
The field emission results of each sample as shown in Figure 3, from field emission results, launching best is sample 4, next is a sample 3,5, the poorest is sample 2, and the straight pipe of this explanation is launched, curved pipe emission is poor, comparative sample 1,2, sample 1 is better than sample 2 emissions, this is the pipe range De Taimi because of sample 2, adjacent carbon nanotube generation electrostatic shielding effect.Comparative sample 3,4,5, sample 4 pipe is straight and density is moderate, therefore launches preferably, and sample 3 is because look straight not enough, and sample 5 is because look too close, so emission is not as sample 4.
Claims (3)
1. a controllable growth has the method for the carbon nanotube of certain diameter and distribution density, it is characterized in that: it comprises following processing step:
(a) method with magnetic filtered vacuum arc plasma foil deposition or magnetron sputtering plates one deck catalyst film on substrate, and thickness is the 5-100 nanometer;
(b) substrate that will plate catalyzer is under hydrogen atmosphere, and reduction is handled under 600 degrees centigrade temperature, and the recovery time is 15 minutes to 5 hours;
(c) the use traffic ratio is that 1: 10 acetylene and rare gas element mixed gas are reactant gases, at 700 degrees centigrade of following carbon nano-tubes;
(d) under inert gas atmosphere, lower the temperature.
2. have the method for the carbon nanotube of certain diameter and distribution density by a kind of controllable growth of claim 1, it is characterized in that: the used catalyzer of step (a) is iron, cobalt or nickel.
3. have the method for the carbon nanotube of certain diameter and distribution density by a kind of controllable growth of claim 1, it is characterized in that: the thickness of described catalyzer is the 20-50 nanometer, and the hydrogen reducing time is 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021150966A CN1159217C (en) | 2002-04-17 | 2002-04-17 | Controllable growth process of carbon nanotube in certain diameter and distribution density |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021150966A CN1159217C (en) | 2002-04-17 | 2002-04-17 | Controllable growth process of carbon nanotube in certain diameter and distribution density |
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| Publication Number | Publication Date |
|---|---|
| CN1388059A CN1388059A (en) | 2003-01-01 |
| CN1159217C true CN1159217C (en) | 2004-07-28 |
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| CNB021150966A Expired - Fee Related CN1159217C (en) | 2002-04-17 | 2002-04-17 | Controllable growth process of carbon nanotube in certain diameter and distribution density |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411980C (en) * | 2003-09-30 | 2008-08-20 | 鸿富锦精密工业（深圳）有限公司 | Method for controlling growth density of carbon nanometer tube |
| JP3935479B2 (en) * | 2004-06-23 | 2007-06-20 | キヤノン株式会社 | Carbon fiber manufacturing method, electron-emitting device manufacturing method using the same, electronic device manufacturing method, image display device manufacturing method, and information display / reproducing apparatus using the image display device |
| CN1962427B (en) * | 2005-11-09 | 2010-11-10 | 鸿富锦精密工业（深圳）有限公司 | Production method of nano-carbon tube |
| CN101870591B (en) * | 2009-04-27 | 2012-07-18 | 清华大学 | Carbon nanotube film precursor, carbon nanotube film, manufacturing method thereof, and light-emitting device with carbon nanotube film |
| CN102330069B (en) * | 2011-10-18 | 2013-03-06 | 天津理工大学 | Preparation method of carbon nano tube |
| CN102757033B (en) * | 2012-07-03 | 2014-01-29 | 清华大学 | Method for preparing carbon nanotube with specific quantities of walls and specific diameters |
| CN110950321A (en) * | 2019-12-17 | 2020-04-03 | 哈尔滨金纳科技有限公司 | High-specific-surface-area and high-conductivity carbon nanotube material and preparation method thereof |
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- 2002-04-17 CN CNB021150966A patent/CN1159217C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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