CN100515935C - Carbon nano-tube growth apparatus and method - Google Patents
Carbon nano-tube growth apparatus and method Download PDFInfo
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- CN100515935C CN100515935C CNB2005100370457A CN200510037045A CN100515935C CN 100515935 C CN100515935 C CN 100515935C CN B2005100370457 A CNB2005100370457 A CN B2005100370457A CN 200510037045 A CN200510037045 A CN 200510037045A CN 100515935 C CN100515935 C CN 100515935C
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- tube growth
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Abstract
The invention discloses a carbon nanometer pipe growing device and growing method, which comprises the following parts: reacting cavity with inlet, at least micro-flow pipe to connect inlet and heating device to heat and dissociate through carbon source gas of micro-flow pipe, wherein the micro-flow pipe pre-dissociates carbon source gas of carbon nanometer pipe, which reduces growing temperature of carbon nanometer pipe.
Description
[technical field]
The present invention relates to a kind of carbon nano-tube growth apparatus and method, especially about utilizing chemical Vapor deposition process to carry out the carbon nano-tube growth apparatus and the method for carbon nano tube growth.
[background technology]
Carbon nanotube is a kind of new carbon, is found in 1991 by Japanology personnel Iijima, sees also " Helical microtubules of graphitic carbon ", S Iijima, Nature, vol.354, p56 (1991).Carbon nanotube has extremely excellent conductivity, and it has almost, and long-pending (tip end surface is long-pending littler near the tip end surface of theoretical limit, its internal field more concentrates), so carbon nanotube is one of known best field emmision material, it has extremely low field emission voltage, can transmit great current density, and the electric current stabilizer pole, thereby be fit to very much do the field emmision material of feds.
At present, the preparation method of carbon nanotube is a lot, and it is broadly divided into Graphite Electrodes arc-over sedimentation, laser evaporation sedimentation, reaches chemical Vapor deposition process etc.Wherein, chemical Vapor deposition process becomes one of present topmost method because of the carbon nano tube growth that it can be applicable to high surface area.
Disclosed a kind of chemical Vapor deposition process-thermal chemical vapor deposition method in the prior art, it is that the substrate that the surface is formed with catalyzer (as iron, cobalt, nickel or its alloy) is placed a silica tube, adopts a process furnace that the catalyzer in this silica tube is heated to high temperature (as 700～1200 degrees centigrade (℃)); Again with CH
4, C
2H
2, C
2H
4React Deng in the hydrocarbon reaction gas feeding pyritous silica tube, grow carbon nanotube.Yet, the carbon nano tube growth temperature of this kind thermal chemical vapor deposition method too high (being generally 700～1200 ℃), it causes the obstruction in many application.For example, the cold-cathode field emission display is generally selected glass for use with cathode substrate, and the strain point of this kind glass (Strain Point) is up to 666 ℃; Therefore above-mentioned thermal chemical vapor deposition method just is not suitable at this kind direct growth carbon nanotube on glass to be used for the cold-cathode field emission display.
Disclosed another kind of chemical Vapor deposition process-plasma auxiliary chemical vapor deposition method in the prior art, it is to utilize a high frequency electric source (as radio-frequency power supply and microwave power supply) to inspire plasma body to substitute the process furnace that thermal chemical vapor deposition method uses and come heatable catalyst to carry out carbon nano tube growth.The carbon nano tube growth temperature of this kind plasma auxiliary chemical vapor deposition method can reach below 600 ℃, and it can overcome the too high defective of thermal chemical vapor deposition method carbon nano-tube temperature to a certain extent.Yet utilize plasma exciatiaon that catalyzer is heated required plasma power and generally be required to be 1～5 kilowatt (kW), its power is higher, causes energy consumption bigger.
In view of this, be necessary to provide a kind of improved carbon nano-tube growth apparatus and method, it can have characteristics such as growth temperature is lower.
[summary of the invention]
To a kind of carbon nano-tube growth apparatus and method be described with specific embodiment below, it can have characteristics such as growth temperature is lower.
For realizing foregoing, a kind of carbon nano-tube growth apparatus is provided, it comprises: a reaction chamber, it has an inlet mouth; At least one microflow channels, the diameter scope of this microflow channels is 100～1000 microns, and the one end is connected with this inlet mouth, its other end feeds and is used for carbon source gas that carbon nano tube growth uses and this carbon source gas is carried out predissociation; And a heating unit, in order to the carbon source gas by this microflow channels is added thermal dissociation.
Among first embodiment, described carbon nano-tube growth apparatus can be the plasma auxiliary chemical vapor deposition carbon nano-tube growth apparatus, and it further comprises: the electrode of pair of opposing, and it is positioned at this reaction chamber; And a high frequency electric source, it is used for applying a voltage to this electrode.
Among another embodiment, described carbon nano-tube growth apparatus can be the thermal chemical vapor deposition carbon nano-tube growth apparatus, and it further comprises: one for the heating unit that is loaded into the catalyst for growth of carbon nano-tube heating in this reaction chamber.
And, a kind of carbon nano tube growth method is provided, it may further comprise the steps:
The substrate that one surface is formed with a catalyst layer is loaded in the reaction chamber;
Be heated and the diameter scope is that 100～1000 microns microflow channels feeds predissociation carbon source gas in a reaction chamber by at least one;
With this predissociation carbon source gas is carbon source, carries out the chemical vapor deposition growth carbon nanotube in this reaction chamber.
Described carbon nano tube growth temperature can be 300～600 degrees centigrade (℃); Described chemical Vapor deposition process comprises thermal chemical vapor deposition method and plasma auxiliary chemical vapor deposition method.Described microflow channels is to be heated to 600～1200 ℃ by a heating unit.
With respect to prior art, carbon nano-tube growth apparatus that the embodiment of the invention provided and method, it provides the microflow channels of carbon source gas and for carry out the heating unit of heat by the carbon source gas of this microflow channels by being provided with one to reaction chamber, because microflow channels has less caliber area, it will provide the carbon source gas of a predissociation in reaction chamber, and then can effectively reduce the carbon nano tube growth temperature.If the auxiliary vapour deposition process of using plasma carries out carbon nano tube growth, also can effectively reduce plasma power.
[description of drawings]
Fig. 1 is the synoptic diagram of first embodiment of the invention carbon nano-tube growth apparatus.
Fig. 2 is the synoptic diagram of second embodiment of the invention carbon nano-tube growth apparatus.
[embodiment]
To be described in further detail the embodiment of the invention below in conjunction with accompanying drawing.
Referring to Fig. 1, the carbon nano-tube growth apparatus 10 that first embodiment of the invention provided is used for the plasma auxiliary chemical vapor deposition carbon nano-tube, and it comprises reaction chamber 12, microflow channels 16, and heating unit 18.
Wherein, reaction chamber 12 tops are provided with an inlet mouth 128, provide a carbon nano tube growth carbon source to feed to this reaction chamber 12.These reaction chamber 12 bottoms also are provided with an air outlet 129, and it can an external pumping, pressure in the chamber of this reaction chamber 12 when keeping carbon nano tube growth.
In this reaction chamber 12, second electrode 122 that also is provided with one first electrode 120 and is oppositely arranged with this first electrode 120; Inlet mouth 128 is to be arranged between this first electrode 120 and second electrode 122 to good.Be provided with a high frequency electric source 14 in reaction chamber 12 outsides, this first electrode 120 and second electrode 122 are connected with high frequency electric source 14.This high frequency electric source 14 can apply a high-frequency voltage between first electrode 120 and second electrode 122, it can be a radio-frequency power supply or microwave power supply.In the present embodiment, high frequency electric source is meant that its output frequency is 50 kilohertzs (kHz) and above power supply; For radio-frequency power supply, its reference frequency output is 50kHz～300 megahertzes (MHz); For microwave power supply, its reference frequency output is 300MHz～300 Gigahertzs (GHz).Wherein, the output frequency of typical microwave power supply is 2.45GHz and 915MHz; The output frequency of typical radio-frequency power supply is 13.56MHz.
This carbon nano-tube growth apparatus 10 carries out predissociation by microflow channels 16 and 18 pairs of carbon source gas of heating unit, and it can effectively reduce the required plasma power of carbon nano tube growth in the reaction chamber 12, and it can be 200～600W (watt).
To specifically describe the working process of carbon nano-tube growth apparatus 10 in the present embodiment below:
(1) substrate 123 is placed between first electrode 120 and second electrode 122 in the reaction chamber 12, or on first electrode 120, and this reaction chamber 12 is vacuumized.These first electrode, 120 ground connection (as shown in Figure 1), its surface is formed with a catalyst layer 124, and this catalyst layer 124 will be as the catalyst layer of carbon nano tube growth.This substrate 123 can be selected materials such as quartz, glass, silicon for use.The material of this catalyst layer 124 can be selected iron, cobalt, nickel or its alloy etc. commonly used in the prior art for use.
(2) provide a carbon source gas via gas inlet 121 to microflow channels 16 by a gas supply device (figure does not show), and to microflow channels 16 heating, this carbon source gas should be heated and predissociation takes place.Described carbon source gas can be CH
4, C
2H
2, C
2H
4In hydrocarbon polymer; Preferably, feed the mixed gas of carbon source gas and ammonia in microflow channels 16, the feeding of ammonia can promote the decomposition of carbon source gas and improve the nucleation rate of catalyzer, and then quicken the growth of carbon nanotube.The flow control of carbon source gas is 20～60 standard cubic centimeter per minutes (sccm), if select the mixed gas that feeds carbon source gas and ammonia for use, the throughput ratio of may command carbon source gas and ammonia is 1: 10～1: 2.Present embodiment selects for use the mixed gas of carbon source gas and ammonia as carbon nano tube growth gas.Gas mixture by microflow channels 16 is heated to high temperature (being generally 600～1200 ℃) through heating unit 18, because the caliber area less (be generally 1mm and following, be preferably 100～1000 μ m) of microflow channels 16; This mixed gas will be by predissociation in the process of this microflow channels 16 of flowing through.
(3) open high frequency electric source 14, between first electrode 120 and second electrode 122, apply a high-frequency voltage and carry out carbon nano tube growth with the plasma auxiliary chemical vapor deposition method.The high frequency electric source 14 that present embodiment is selected for use is microwave power supply, and its output frequency is set to 2.45GHz, and output rating is 500W.Enter between first electrode 120 and second electrode 122 through the mixed gas of microflow channels 16 predissociations inlet mouth by reaction chamber 12, under the high-frequency electric field effect, produce a plasma body 126, carry out plasma auxiliary chemical vapor deposition method carbon nano-tube, the position with catalyst layer 124 of substrate 123 will grow carbon nanotube.The generation zone covering catalyst layer 124 of described plasma body 126.In the process of growth of carbon nanotube, bleed by air outlet 129 external pumpings (figure does not show), be 10～100Torr (holder) to keep the pressure in the reaction chamber 12; Temperature range in the reaction chamber 12 is 300～550 ℃.
(4) treated carbon nano tube growth 30 seconds～30 minutes after, close high frequency electric source 14; The growth time of carbon nanotube can be determined according to the length of required carbon nanotube.After carbon nanotube stops growing, first stop supplies carbon source gas, after the question response cavity temperature reaches room temperature again, the stop supplies ammonia.Take out substrate 123, can obtain required carbon nanotube.
Second embodiment
Referring to Fig. 2, the carbon nano-tube growth apparatus 20 that second embodiment of the invention provided is used for the thermal chemical vapor deposition carbon nano-tube, and it comprises reaction chamber 22, microflow channels 26, and heating unit 28.
Wherein, reaction chamber 22 1 ends are provided with an inlet mouth 228, provide a carbon nano tube growth carbon source to feed to this reaction chamber 22.These reaction chamber 12 bottoms also are provided with an air outlet 229, and it can an external pumping, pressure in the chamber of this reaction chamber 22 when keeping carbon nano tube growth.
Outer setting at this reaction chamber 22 has a heating unit 24, in order to the catalyst for growth of carbon nano-tube that is loaded in this reaction chamber 22 is heated.This heating unit 24 can be selected thermal chemical vapor deposition method carbon nano-tube High Temperature Furnaces Heating Apparatus in the prior art for use; Or select high frequency furnace for use, it can help forming obvious thermograde at catalyst position, and then can be beneficial to the quick growth of carbon nanotube only to the conductor heating.
This carbon nano-tube growth apparatus 20 carries out predissociation by microflow channels 26 and 28 pairs of carbon source gas of heating unit, and it is temperature required that it can effectively reduce reaction chamber 12 interior thermal chemical vapor deposition carbon nano-tubes, and it can be 300～600 ℃.
To specifically describe the working process of carbon nano-tube growth apparatus 20 in the present embodiment below:
(1) substrate 223 that a surface is formed with a catalyst layer 224 places in the reaction chamber 22, and feeds shielding gas (as rare gas elementes such as helium, argon gas) to get rid of the air in the reaction chamber 22 to reaction chamber 22.This catalyst layer 124 will be as the catalyst layer of carbon nano tube growth, and its material can be selected iron, cobalt, nickel or its alloy etc. commonly used in the prior art for use.This substrate 223 can be selected materials such as quartz, glass, silicon for use.
(2) via heating unit 24 heatable catalyst layers 224 to the carbon nano tube growth temperature.This heating unit 24 can be a High Temperature Furnaces Heating Apparatus, and it rises to 600 ℃ with temperature in the reaction chamber 22.
(3) provide the mixed gas of a carbon source gas and shielding gas via gas inlet 221 to microflow channels 26 by a gas supply device (figure do not show), and to microflow channels 26 heating, this carbon source gas should be heated and predissociation takes place; The thermal chemical vapor deposition carbon nano-tube is carried out in catalyst layer 224 positions that this predissociation carbon source gas arrives in the reaction chamber 22.In the carbon nano tube growth process, keeping the pressure in the reaction chamber 22 is 400～600Torr.Described carbon source gas can be CH
4, C
2H
2, C
2H
4In hydrocarbon polymer; The flow control of carbon source gas is 20～60sccm, and the throughput ratio of carbon source gas and shielding gas is 1: 10～1: 2.Gas mixture by microflow channels 26 is heated to high temperature (being generally 600～1200 ℃) through heating unit 28, because the caliber area less (be generally 1mm and following, be preferably 100～1000 μ m) of microflow channels 26; This mixed gas will be by predissociation in the process of this microflow channels 26 of flowing through.
In addition, those skilled in the art also can do other and change in spirit of the present invention, as the shape of suitable change microflow channels, and the position of inlet mouth, the shape of first electrode and second electrode is not as long as it departs from technique effect of the present invention and all can.The variation that these are done according to spirit of the present invention all should be included within the present invention's scope required for protection.
Claims (12)
1. carbon nano-tube growth apparatus, it comprises:
One reaction chamber, it has an inlet mouth;
At least one microflow channels, the diameter scope of this microflow channels is 100～1000 microns, and the one end is connected with this inlet mouth, its other end feeds and is used for carbon source gas that carbon nano tube growth uses and this carbon source gas is carried out predissociation; And
One heating unit is in order to add thermal dissociation to the carbon source gas by this microflow channels.
2. carbon nano-tube growth apparatus as claimed in claim 1 is characterized in that described heating unit is a High Temperature Furnaces Heating Apparatus, and it is surrounded on this microflow channels.
3. carbon nano-tube growth apparatus as claimed in claim 1 is characterized in that described reaction chamber is provided with an air outlet, and it is connected with a pumping.
4. carbon nano-tube growth apparatus as claimed in claim 1, it is characterized in that described carbon nano-tube growth apparatus is a plasma body assistant chemical vapor deposition carbon nano-tube growth apparatus, it further comprises: the electrode of pair of opposing, and it is positioned at this reaction chamber; And a high frequency electric source, it is used for applying a voltage to this electrode.
5. carbon nano-tube growth apparatus as claimed in claim 4 is characterized in that described high frequency electric source is microwave power supply or radio-frequency power supply.
6. carbon nano-tube growth apparatus as claimed in claim 1, it is characterized in that described carbon nano-tube growth apparatus is a thermal chemical vapor deposition carbon nano-tube growth apparatus, it further comprises: another heating unit, and in order to the catalyst for growth of carbon nano-tube that is loaded in this reaction chamber is heated.
7. carbon nano-tube growth apparatus as claimed in claim 6 is characterized in that described another heating unit comprises High Temperature Furnaces Heating Apparatus and high frequency furnace.
8. carbon nano tube growth method, it may further comprise the steps:
The substrate that one surface is formed with a catalyst layer is loaded in the reaction chamber;
Be heated and the diameter scope provides a predissociation carbon source gas for 100～1000 microns microflow channels in a reaction chamber by at least one;
With this predissociation carbon source gas is carbon source, carries out the chemical vapor deposition growth carbon nanotube in this reaction chamber.
9. carbon nano tube growth method as claimed in claim 8, the growth temperature that it is characterized in that carbon nanotube is 300～600 degrees centigrade.
10. as claim 8 a described carbon nano tube growth method, it is characterized in that described microflow channels is to be heated to 600～1200 degrees centigrade by a High Temperature Furnaces Heating Apparatus.
11. carbon nano tube growth method as claimed in claim 8 is characterized in that described chemical vapour deposition comprises thermal chemical vapor deposition and plasma auxiliary chemical vapor deposition.
12. carbon nano tube growth method as claimed in claim 11, the plasma power that it is characterized in that described plasma auxiliary chemical vapor deposition is 200～600 watts.
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| CNB2005100370457A CN100515935C (en) | 2005-09-02 | 2005-09-02 | Carbon nano-tube growth apparatus and method |
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| CNB2005100370457A CN100515935C (en) | 2005-09-02 | 2005-09-02 | Carbon nano-tube growth apparatus and method |
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| CN1923677A CN1923677A (en) | 2007-03-07 |
| CN100515935C true CN100515935C (en) | 2009-07-22 |
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| CN105217599B (en) * | 2015-10-22 | 2017-03-08 | 华北电力大学 | A kind of system and method for synthesizing carbon nanotubes |
| CN106185876A (en) * | 2016-08-31 | 2016-12-07 | 无锡东恒新能源科技有限公司 | The reaction unit of a kind of band heat treatment and the method preparing CNT |
| CN106185871A (en) * | 2016-08-31 | 2016-12-07 | 无锡东恒新能源科技有限公司 | A kind of reaction unit with grid electrode and the preparation method of CNT |
| CN106185872A (en) * | 2016-08-31 | 2016-12-07 | 无锡东恒新能源科技有限公司 | Method prepared by the reaction unit of a kind of band lifting substrate and CNT |
| CN109338459B (en) * | 2018-12-12 | 2021-01-12 | 中国电子科技集团公司第四十六研究所 | Nitrogen doping method for preparing low COP defect silicon single crystal |
| CN110331382A (en) * | 2019-07-04 | 2019-10-15 | 暨南大学 | The pouring-in vacuum vapor deposition apparatus of liquid reaction solution miniflow and method |
| CN112456471B (en) * | 2020-12-23 | 2022-04-12 | 郑州轻工业大学 | Device and method for preparing oriented carbon nanotube array by using combustible solid waste as solid carbon source |
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| CN1389394A (en) * | 2001-06-01 | 2003-01-08 | 富士施乐株式会社 | Production apparatus and production method for producing carbon structure |
| JP2004243477A (en) * | 2003-02-14 | 2004-09-02 | Sharp Corp | Manufacturing method of carbonaceous nanostructure, carbonaceous nanostructure and electron source using it |
| CN1539731A (en) * | 2003-10-28 | 2004-10-27 | 黄德欢 | Method and equipment for preparing Nano carbon tube with multiple walls |
| US6855376B2 (en) * | 2002-03-25 | 2005-02-15 | Industrial Technology Research Institute | Process of direct growth of carbon nanotubes on a substrate at low temperature |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389394A (en) * | 2001-06-01 | 2003-01-08 | 富士施乐株式会社 | Production apparatus and production method for producing carbon structure |
| US6855376B2 (en) * | 2002-03-25 | 2005-02-15 | Industrial Technology Research Institute | Process of direct growth of carbon nanotubes on a substrate at low temperature |
| JP2004243477A (en) * | 2003-02-14 | 2004-09-02 | Sharp Corp | Manufacturing method of carbonaceous nanostructure, carbonaceous nanostructure and electron source using it |
| CN1539731A (en) * | 2003-10-28 | 2004-10-27 | 黄德欢 | Method and equipment for preparing Nano carbon tube with multiple walls |
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