CN1304631C - Technology for preparing nano tube of carbon by direct current glow plasma chemical vapour phase deposition process - Google Patents
Technology for preparing nano tube of carbon by direct current glow plasma chemical vapour phase deposition process Download PDFInfo
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- CN1304631C CN1304631C CNB2004100110489A CN200410011048A CN1304631C CN 1304631 C CN1304631 C CN 1304631C CN B2004100110489 A CNB2004100110489 A CN B2004100110489A CN 200410011048 A CN200410011048 A CN 200410011048A CN 1304631 C CN1304631 C CN 1304631C
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Abstract
The present invention relates to a process for preparing carbon nanotubes via direct current glow plasma by a chemical vapor deposition method, which belongs to a technical method for preparing carbon nanotubes. A silicon slice or a quartz slice with a catalyst layer on the surface is used as a substrate, a mixed gas of methane and hydrogen gas is used as a raw material, and carbon nanotubes grow by a chemical vapor deposition method. Firstly, the raw material gas is led into a vacuum chamber with vacuum degree of about 2 Pa and interelectrode distance of 4 to 5mm; when pressure intensity achieves 200 to 500 Pa, discharge current is kept to be about 2 A; when gas pressure intensity achieves 5 to 10 KPa, the discharge current is adjusted to 5 to 10 A, the interelectrode distance is from 20 to 40mm, and the raw material is deposited for 5 to 600 s. The plasma produced by direct current glow discharge is stable, so the present invention has high gas ionization rate and uniform substrate surface, and can greatly and uniformly prepare the carbon nanotubes with high purity and uniform tube diameters. Distributed nanometer grade catalyst particles are formed on the substrate surface, and the vertically-arranged ordered carbon nanotubes can be deposited.
Description
Technical field
The invention belongs to the processing method of preparation carbon nanotube, the particularly preparation technology of the carbon nanotube of high purity, uniform diameter, and the preparation technology of the carbon nanotube of orderly arranged vertical.
Background technology
The tubular fiber material that carbon nanotube is made up of carbon, its caliber in several nanometers to tens nanometers.Carbon nanotube has excellent electronics character and mechanical property, is a kind of good field emmision material, is electronic device material of new generation, is excellent hydrogen storage material and novel filamentary material, and therefore, people have set up several different methods and prepare carbon nanotube for many years.
It is generally acknowledged that the prerequisite of chemical vapor carbon deposition nanotube is: 1. have carbonaceous gas to participate in reaction.2. carbonaceous gas is decomposed, and then produce ion or the atom and the active group thereof of carbon.3. the existence of catalyzer is arranged, and general catalyzer is iron group or some rare earth element etc.4. suitable substrate temperature, substrate temperature are generally between 650 ℃ to 900 ℃.The key distinction of various chemical gaseous phase depositing process is the decomposition means differences to reactant gases.
The method close with the present invention is plasma-assisted heat filament decomposition method.
It is a kind of chemical vapor deposition (CVD) method that the hot filament decomposition method prepares carbon nanotube, feeds reactant gasess such as methane, hydrogen in vacuum chamber, and gas is deposition of carbon nanotubes on the substrate that decomposes and containing catalyzer under the pyritous hot filament.In order to prepare the carbon nanotube of oriented growth, Z.P.Huang, Z.F.Ren, Deng people (Growth of highly oriented carbon nanotubes by plasma-enhanced hotfilament chemical vapor deposition, APPLIED PHYSICS LETTERS, VOLUME73, NUMBER26,1998.) biasing voltage and formed the method for plasma-assisted heat filament deposition of carbon nanotubes between filament and substrate.
But because the filament alignment characteristics makes that the state of substrate surface and discharge are inhomogeneous, carbon nanotubes grown can not guarantee that big area is even on the substrate surface, and caliber is also inhomogeneous, has influenced the carbon nanotube quality.
Summary of the invention
The technical problem to be solved in the present invention is: adopt the DC glow plasma CVD method of plate electrode to prepare carbon nanotube, by setting up the experimental technique of optimizing, be coated with deposition of carbon nanotubes on the substrate of catalystic material.
In order to prepare uniform diameter, high purity and the carbon nanotube of arranged vertical in order, the contriver has set up the technology that direct current glow discharge plasma activated chemical vapour deposition method prepares carbon nanotube.From the decomposition aspect to gas, the plasma body that the direct current glow discharge method produces is more stable, and higher to the ionization level of gas, the state of substrate surface is even, has bigger advantage aspect the preparation of high quality carbon nanotube.
Owing to adopt this method to prepare carbon nanotube, at several KPa in the pressure range of tens KPa, it is very difficult directly to light aura, produce down to discharge into from lower air pressure and produce predetermined discharge result and need long steady time, during this period, substrate surface can produce the settling of non-carbon nanotube and substrate surface is polluted, in the discharge afterwards, even discharging condition satisfies the carbon nanotube deposition, on substrate, still can not get carbon nanotube.
Equipment and starting material that preparation carbon nanotube of the present invention adopts are:
Vacuum system: opposed circular flat negative electrode and the anode of being placed with in vacuum chamber, logical respectively water coolant indirect water-cooling, negative electrode up and anode below, flat circular tantalum cathode is tightened under the cathode copper seat of water-cooled, substrate places on the anode copper seat of water-cooled, substrate can in company with the anode copper seat under the effect of jacking system lifting to regulate interelectrode distance.Be placed with suitable heat shield between substrate and the anode copper seat, can make substrate reach predetermined depositing temperature.
Substrate: adopt the substrate preparation carbon nanotube that is coated with catalyst layer.Make substrate with silicon chip or quartz plate, be coated with 5 nanometers on it to 60 nanocatalyst layers.Can select iron, cobalt or nickel for use, or their alloy can adopt also nickel/golden composite film material as catalyst layer as catalystic material.The catalyst layer of substrate surface can adopt catalyzer rete or surface to have the layer of catalyst particles of nano-scale particle.
Raw material: the mixed gas with methane and hydrogen is a raw material.
The technology of made of carbon nanotubes of the present invention is:
1, the substrate wiped clean is placed on the anode copper seat in the vacuum chamber capping of building vacuum chamber.
2, the vacuum tightness in the vacuum chamber is evacuated to about 1～3Pa, and the distance of regulating between negative electrode and the anode is 4～5mm.
3, the master who closes vacuum system takes out valve, feeds the mixed gas of hydrogen and methane in vacuum chamber by a certain percentage, and the feeding gas flow ratio is a hydrogen flowing quantity: methane gas flow=100: 10～40.When pressure in vacuum tank reaches 200～500Pa, between negative electrode and anode, add volts DS and make geseous discharge, keeping discharging current is 1.5～2.5A.When the indoor gas pressure intensity of vacuum reaches between 5～10KPa, open the fine setting needle-valve of bleeding, metering pin valve, it is constant to keep the vacuum chamber internal gas pressure.In this process, electric discharge phenomena are arranged between the electrode, but do not have plasma body, discharge gas is decomposed hardly, therefore, and can deposition of carbon nanotubes or other settling on the substrate, and temperature is very low, and substrate does not have any variation, and discharge condition as shown in Figure 1.
4, increase discharging current, regulate interelectrode distance simultaneously, make discharging current be increased to 5～10A, interelectrode distance is increased to 20～40mm, substrate temperature can reach 600～900 ℃ simultaneously, produces the plasma body of glow discharge between negative electrode and anode, as shown in Figure 2.At this moment, the deposition of carbon nanotube will be arranged, keep this sedimentation state 5 second～10 minute at substrate surface.
5, close discharge power supply, can on substrate, obtain carbon nanotube after the shutdown.
In the carbon nano tube growth process, the catalyst type of gas pressure intensity, discharging current, substrate temperature, substrate surface and thickness, interelectrode distance etc. are main processing parameters, regulate these processing parameters within the specific limits, can prepare polytype carbon nanotube.
Above the certain limit of said processing parameter be meant: the gas pressure intensity scope is 5KPa～12KPa; Discharging current is 5～10A; 600 ℃～900 ℃ of substrate temperatures; Interelectrode distance is 20mm～40mm; Gas flow ratio is: the hydrogen gas flow: the methane gas flow is between 100: 10～100: 40; The catalyst type and the thickness of substrate surface are meant: can select iron, cobalt, nickel respectively for use, and their alloy, also can adopt nickel/golden composite membrane etc. as the catalyzer rete, the catalyst film layer thickness of substrate surface coating is generally between 5nm～60nm.
The less carbon nanotube of preparation diameter: can select the substrate of thin catalyzer rete for use, under lower temperature, grow.And the condition of the thicker carbon nanotube of preparation caliber is with last opposite.
Hydrogen flowing quantity can be selected 50～500sccm, and correspondingly, the methane gas flow is elected 5～200sccm as.
Because the plasma body that the direct current glow discharge method produces is more stable, ionization level to gas is higher, therefore the state of substrate surface is even, and the characteristics of the carbon nanotube for preparing with this processing method are: purity height, uniform diameter, can be on large area substrates the uniform preparation carbon nanotube.
The employed substrate surface of carbon nanotube for preparing orderly arranged vertical has discrete nano-scale particle layer, and catalyzer is iron, cobalt, nickel or its alloy.Substrate with nano-scale particle layer can obtain with following method, to the substrate of the catalyzer coating that is coated with 5～20 nanometers, adopts the glow plasma pre-treatment of nitrogen, and the pretreated method of substrate is:
1,, places on the anode copper seat in the vacuum chamber capping of building vacuum chamber the substrate wiped clean of the catalyzer coating that is coated with 5～20 nanometers.
2, the vacuum tightness in the vacuum chamber is evacuated to about 1～3Pa, and the distance of regulating between negative electrode and the anode is 4～5mm.
3, the master who closes vacuum system takes out valve, stops logical hydrogen in vacuum chamber behind feeding hydrogen to 200～500Pa, adds volts DS between electrode, lights aura, keeps discharging current at 1.5～2.5A.
4, feed nitrogen to 5KPa in vacuum chamber, increase discharging current and interelectrode distance branch are clipped to 5A and 30mm, keep this state 5～10 minutes.
5, can obtain having the substrate of isolating nano-scale particle layer after the shutdown.
Make substrate surface form discrete nm-class catalyst particle,, can deposit in order upright carbon nanotubes arranged again according to the preparation technology of aforesaid carbon nanotube.There is wide application prospect the carbon nanotube emission on the scene aspect of orientation arranged vertical in order.
Description of drawings
Fig. 1 is the discharge condition of growth deposition not in the vacuum chamber of the present invention.
Fig. 2 is the discharge condition that produces in the vacuum chamber of the present invention in the plasma-grown carbon nanotube process of glow discharge.
Embodiment
Embodiment 1 provides the example of a concrete preparation carbon nanotube.
Employing is coated with the silicon chip of 5nm thickness nickel and does deposition substrate, places on the anode base in the vacuum chamber, and the vacuum tightness in the vacuum chamber is evacuated to 2Pa, and the distance of regulating between negative electrode and the anode is 4mm.The master who closes vacuum system takes out valve, in vacuum chamber, feed the mixed gas of hydrogen and methane, hydrogen flowing quantity is 500sccm, methane flow is 200sccm, when pressure in vacuum tank reaches 500Pa, between negative electrode and anode, add volts DS and make geseous discharge, keeping discharging current is 2A, when the indoor gas pressure intensity of vacuum reached 5KPa, it was constant to keep the vacuum chamber internal gas pressure.Discharging current is increased to 5A, makes interelectrode distance be increased to 30mm simultaneously, and substrate temperature reaches 800 ℃, keeps 30 seconds of this sedimentation state.Obtain the carbon nanotube of purity height, uniform diameter after shutting down at substrate surface.
Embodiment 2 provides the example of a concrete preparation carbon nanotube.
Employing is coated with the silicon chip of 60nm or 30nm thickness nickel film and does deposition substrate, repeat the process of example 1, has also obtained the carbon nanotube of purity height, uniform diameter.
Embodiment 3 provides the example of a concrete preparation carbon nanotube.
Make operating air pressure be respectively 7KPa and 10KPa, repeat the process of example 1, on substrate, obtain carbon nanotube.
Embodiment 4 provides the example of a concrete preparation carbon nanotube.
The discharging current of keeping deposition of carbon nanotubes is respectively 7A and 9A, repeats the experimentation of example 1, has obtained carbon nanotube on substrate.
Embodiment 5 provides the example of a concrete preparation carbon nanotube.
The depositing temperature of regulating substrate is 600 ℃ or 900 ℃, repeats the experimentation of example 1, has obtained carbon nanotube on substrate.
Embodiment 6 provides the example of a concrete preparation carbon nanotube.
Distance adjustment between substrate and the negative electrode to 20mm or 40mm, is repeated the experimentation of example 1, on substrate, obtained carbon nanotube.
Embodiment 7 provides the example of a concrete preparation carbon nanotube.
Catalyzer rete with iron or cobalt replacement nickel film repeats above 1～6 embodiment, has obtained carbon nanotube on substrate.
Embodiment 8 provides the example of a concrete preparation carbon nanotube.
Nickel/golden composite membrane is as the catalyzer rete, and the catalyst film layer thickness of substrate surface is: nickel 20 nanometers, golden 20 nanometers.Adopt such substrate, repeat the experimentation of embodiment 1, on substrate, obtained carbon nanotube.
Embodiment 9 provides the example that a concrete preparation has the substrate of discrete nm-class catalyst particle surface.
The silicon chip wiped clean that is coated with the thick nickel film of 10nm is placed on the interior anode copper seat of vacuum chamber; Vacuum tightness in the vacuum chamber is evacuated to about 1～3Pa, and the distance of regulating between negative electrode and the anode is 4～5mm; Close the main valve of taking out; In vacuum chamber, feed H
2, when air pressure rises to 200～500Pa, between negative electrode and anode, add volts DS and make geseous discharge, keeping discharging current is 1.5～2.5A; In vacuum chamber, feed N
2Gas makes the air pressure in the vacuum chamber rise to 2～10KPa; Increase discharging current to 7A, increase interelectrode distance simultaneously to 30mm; Kept this discharge condition 8 minutes.N
2Under plasma body, decompose and ionization, and substrate surface is carried out etching.Prepare and have discrete nm-class catalyst particulate substrate on the surface.
Employing has discrete nm-class catalyst particulate substrate, according to the preparation technology of above-mentioned carbon nanotube, can deposit the upright carbon nanotubes arranged of high orientation.
Embodiment 10 provides the example of an in order upright carbon nanotubes arranged of concrete preparation.
Adopt the discrete nm-class catalyst particulate substrate that has of embodiment 9 preparations.Place on the anode seat,, can prepare the upright carbon nanotubes arranged of orderly orientation according to the technology of embodiment 1～7.
Claims (3)
1, a kind of DC glow plasma chemical gaseous phase depositing process prepares the technology of carbon nanotube, makes substrate with silicon chip or quartz plate, be coated with iron, cobalt or nickel or their alloy on it and be material or nickel/golden composite membrane be the catalyst layer of material; Mixed gas with methane and hydrogen is a raw material, adopts the method carbon nano-tube of chemical vapour deposition, it is characterized in that, said catalyst layer is the layer of catalyst particles that catalyzer rete or surface have nano-scale particle, and thickness is that 5 nanometers are to 60 nanometers; Technological process is, the substrate wiped clean placed on the planar anode copper seat in the vacuum chamber capping of building vacuum chamber; Vacuum tightness in the vacuum chamber is evacuated to 1～3Pa, and the distance of regulating between flat negative electrode and the planar anode is 4～5mm; The master who closes vacuum system takes out valve, in vacuum chamber, feed the mixed gas of hydrogen and methane, the feeding gas flow ratio is a hydrogen flowing quantity: methane gas flow=100: 10～40, when pressure in vacuum tank reaches 200～500Pa, between flat negative electrode and planar anode, add volts DS, keeping discharging current is 1.5～2.5A, and it is constant to keep the vacuum chamber internal gas pressure when the indoor gas pressure intensity of vacuum reaches between 5～10KPa; Regulate discharging current to 5～10A, distance is increased to 20～40mm between plate electrode, and substrate temperature reaches 600～900 ℃, keeps this state and closes discharge power supply after 5～600 seconds, obtains carbon nanotube on substrate.
2, the technology for preparing carbon nanotube according to the described DC glow plasma chemical gaseous phase depositing process of claim 1, it is characterized in that, the layer of catalyst particles that said surface has a nano-scale particle is the substrate to the catalyzer coating that is coated with 5～20 nanometers, adopts the glow plasma pre-treatment of nitrogen to obtain.
3, prepare the technology of carbon nanotube according to claim 1 or 2 described DC glow plasma chemical gaseous phase depositing process, it is characterized in that, said gas flow is that hydrogen flowing quantity is 50～500sccm, and the methane gas flow is 5～200sccm.
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| CN100442438C (en) * | 2006-12-20 | 2008-12-10 | 南京大学 | Manufacturing method of amorphous carbon-film semiconductor |
| CN102625729B (en) * | 2009-06-09 | 2015-09-09 | 黑达勒石墨工业公共有限公司 | With the method and apparatus of plasma treatment particle |
| ES2560466T3 (en) | 2010-12-08 | 2016-02-19 | Haydale Graphene Industries Plc | Particle-shaped materials, composite materials that comprise them, preparation and uses thereof |
| CN102267693B (en) * | 2011-07-06 | 2013-03-06 | 天津理工大学 | Low-temperature preparation method of carbon nanotube |
| CN102330069B (en) * | 2011-10-18 | 2013-03-06 | 天津理工大学 | Preparation method of carbon nano tube |
| JP7133975B2 (en) * | 2018-05-11 | 2022-09-09 | 東京エレクトロン株式会社 | Etching method and etching apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237648A (en) * | 1999-07-02 | 1999-12-08 | 中国科学院物理研究所谷东梅 | Method for growing high-oriented BCN nanometer tube material |
| WO2003027350A1 (en) * | 2001-09-26 | 2003-04-03 | Fundação De Amparo À Pesquisa Do Estado de São Paulo | Amorphous hydrogenated carbon film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237648A (en) * | 1999-07-02 | 1999-12-08 | 中国科学院物理研究所谷东梅 | Method for growing high-oriented BCN nanometer tube material |
| WO2003027350A1 (en) * | 2001-09-26 | 2003-04-03 | Fundação De Amparo À Pesquisa Do Estado de São Paulo | Amorphous hydrogenated carbon film |
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