CN107381539B - A kind of preparation method of array carbon nanocapsule thin film - Google Patents
A kind of preparation method of array carbon nanocapsule thin film Download PDFInfo
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of preparation methods of array carbon nano tube film, comprising the following steps: substrate is placed in the metal net mask in PECVD cavity, two blocks of catalyst metals plates being sequentially overlapped are placed above metal net mask；It is passed through reaction gas in PEVCD cavity, powers on after heating, obtains catalyst film in substrate surface after reaction；It will be passed through carbon source and carrier gas after the heating of PEVCD cavity, powers on, obtain array carbon nano tube film in substrate surface after reaction.The application catalyst film and array carbon nano tube film are completed in same PECVD cavity, and can be realized continuous preparation, improve the efficiency of array carbon nano tube film preparation；On the other hand, low temperature preparation makes array carbon nano tube film can be applied to the fields of many non-refractories.
Description
Technical field
The present invention relates to carbon nanotube technology field more particularly to a kind of low temperature preparing methods of array carbon nanocapsule thin film.
Background technique
Carbon nanotube (CNT) is used as monodimension nanometer material, and special structure makes it have excellent calorifics, mechanics and electricity
Performance is learned, so that carbon nanotube is shown good application prospect in fields such as material science, physics, electronics.Currently, closing
In the application study of carbon nanotube be concentrated mainly on composite material, Field Emission Display, hydrogen storage, sensor, super capacitor and
The fields such as conducting polymer, many application fields have all made important progress.However due to being limited by preparation process, prepare
The factors such as condition is harsh, yield is few, preparation efficiency is low, order is poor, impurity is more all hinder the research and application of carbon nanotube.
The method of preparation carbon nanotube mainly has at present: arc process, laser evaporization method and chemical vapour deposition technique (CVD)
Deng.The preparation method of carbon nanotube is different, then the structure of the carbon nanotube obtained is also different.Arc process and laser evaporization method are usual
It is all to prepare carbon nanotube on the basis of the catalyst of unordered accumulation, it is difficult to control the orientation of growth of carbon nanotube；And CVD method
The orientation of carbon nano tube growth can be effectively controlled, to prepare array carbon nano tube film.The array carbon nano tube of acquisition
Film has the performances such as many excellent electricity, Flied emission, has huge application prospect in fields such as microelectronics.
Currently, preparing array carbon nano tube film using hot CVD method is primarily present two deficiencies: first is that it prepares substrate
Surface need one layer of catalyst nano film, it is usually necessary to use the preparation processes such as evaporation or sputtering method for the film；It is another
Aspect, hot CVD method prepare the reaction temperature of carbon nanotube usually all at 600 DEG C or more, and exacting terms limits array carbon
The application field of nano-tube film, so that array carbon can not directly be prepared in the material surface to fields such as thermo-responsive microelectronics
Nano-tube film.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of low-temperature in-site preparation method of array carbon nano tube film.
In view of this, this application provides a kind of preparation methods of array carbon nano tube film, comprising the following steps:
A), substrate is placed in the cavity of PECVD device in the metal net mask on negative plate, is placed above metal net mask folded
The two blocks of catalyst metals plates added；
B), it is passed through reaction gas in the cavity of PEVCD equipment, powers on after heating, is obtained after reaction in substrate surface
To catalyst film；
C), it is passed through carbon source and carrier gas after the cavity of PEVCD equipment being heated, powers on, is obtained after reaction in substrate surface
To array carbon nano tube film.
Preferably, the distance between described two blocks of catalyst metals plates are 1~5cm, the material of the catalyst metals plate
For iron, cobalt, nickel or composite material.
Preferably, step A) described in the reaction gas hydrogen and argon gas that are, the reaction temperature is 300~500 DEG C, institute
The power for stating power supply is 500~1000W.
Preferably, the flow of the hydrogen is 30~80sccm, and the flow of the argon gas is 30~80sccm.
Preferably, step C) described in carbon source include one of methane, acetylene and normal butane or a variety of, the carbon source
Flow is 5~50sccm.
Preferably, the carrier gas is hydrogen and argon gas, and the flow of the hydrogen is 30~80sccm, the flow of the argon gas
For 30~80sccm.
Preferably, step C) described in the temperature of reaction be 350~500 DEG C, the power of the power supply is 10~200W, institute
The time for stating reaction is 10~100min.
Preferably, the substrate is the substrate with smooth surface, the preferably gold after silicon wafer, glass or surface polishing
Belong to.
Preferably, step B) described in catalyst film with a thickness of 1~50nm.
Preferably, the metal net mask is cylindric stainless steel mesh enclosure or cylindric copper mesh cover.
This application provides a kind of preparation methods of array carbon nano tube, and substrate is placed in the cavity of PEVCD equipment first
In metal net mask in, two blocks of catalyst metals plates being sequentially overlapped are placed above metal net mask, then reaction is passed through into cavity
Gas, heating cavity power on the intracorporal reaction gas of excitation cavity, so that it becomes plasma, passes through gas in control chamber body
Pressure and power make to generate hollow cathode effect between metal plate, enhance the plasma density between metal plate, highdensity
High-energy ion bombardment metal sheet surface forms catalyst film so that nano-metal particle is sputter deposited to substrate surface, after
After continuous heating reaches reaction temperature, it is passed through carbon source and carrier gas into cavity, the nano particle generated is decomposed using catalyst film
Array carbon nano tube film is grown in substrate surface.During the application array carbon nano tube film, first by catalyst
The preparation process of film is integrated into the reaction cavity of PECVD, realizes that the preparation of catalyst film in situ and array carbon are received
The growth of mitron film not only reduces and prepares array carbon nano tube thin-film technique to device dependence, also greatly reduces
Its preparation cost；On the other hand, the assistant metal mesh enclosure that this method uses, the effective activity for improving plasma, more effectively
Decomposition carbon-source gas, realize low temperature preparation of the array carbon nano tube at 350~500 DEG C, this makes the electronics in non-refractory
Array carbon nano tube film, which is prepared in situ, in device surface becomes feasible, has widened its application prospect.
Detailed description of the invention
Fig. 1 is the schematic diagram of the PECVD device that the present invention uses and metal net mask device；
Fig. 2 is the stereoscan photograph of array carbon nano tube film prepared by the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope photo of the carbon nanotube of array carbon nano tube film prepared by the embodiment of the present invention 1；
Fig. 4 is the SEM photograph of array carbon nano tube film prepared by the embodiment of the present invention 2；
Fig. 5 is the SEM photograph of array carbon nano tube film prepared by the embodiment of the present invention 3.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation methods of array carbon nano tube film, comprising the following steps:
A), substrate is placed in the cavity of PECVD device in the metal net mask on negative plate, place above metal net mask according to
Two blocks of catalyst metals plates of secondary superposition；
B), it is passed through reaction gas in the cavity of PEVCD equipment, powers on after heating, is obtained after reaction in substrate surface
To catalyst film；
C), it is passed through carbon source and carrier gas after the cavity of PEVCD equipment being heated, powers on, is obtained after reaction in substrate surface
To array carbon nano tube film.
This application provides a kind of preparation methods of array carbon nano tube film, and this method is by increasing in PECVD cavity
The density of plasma, using the plasma bombardment metallic catalyst thin plate of high energy, so that the nano-metal particle sputtered
It is deposited on substrate surface, obtains catalyst film, on this basis, using the booster action of metal net mask, realizes array
The low temperature preparation of nano-tube film.
The preparation method of the application array carbon nano tube film, preparation and low temperature carbon nanotube including catalyst film are thin
Two steps of preparation of film, and two steps are continuously finished in the same PECVD reaction cavity.
The application carries out the preparation of catalyst film first.As shown in FIG. 1, FIG. 1 is array carbon nano tube films of the present invention
The schematic device of the PECVD device of preparation.Substrate is placed in the cavity of PECVD device the circle on negative plate by the application first
Among cylindrical metallic mesh enclosure, two blocks of catalyst metals plates for being sequentially overlapped placement are placed above metal net mask.It is herein described
PECVD cavity is the reaction cavity of PECVD device, and the PECVD device is equipment well known to those skilled in the art, to this
Application is not particularly limited, and the PECVD device that the application uses is preferably as shown in Figure 1, metal mesh in PECVD reaction cavity
The setting of cover, substrate and two blocks of catalyst metals plates specifically: the substrate is placed on bottom crown, and the substrate is set to
In the metal net mask, the top of the metal net mask and urged with two pieces be sequentially overlapped that are provided with that metal net mask directly contacts
Agent metal plate, the metal net mask, substrate and catalyst sheet are all set between top crown and bottom crown.It is herein described
Metal net mask can be cylindric stainless steel mesh enclosure or cylindric copper mesh cover.The material of the substrate is that those skilled in the art are ripe
The base material known, for the substrate with smooth surface, the more preferably metal after silicon wafer, glass or surface polishing.The application
The spacing of two blocks of catalyst metals plates is preferably 1~5cm.The catalyst metals plate is preferably iron, cobalt, nickel or compound gold
Belong to material, herein described catalyst metals plate is preferably same metal material.
During preparing catalyst film, reaction gas is passed through into PECVD cavity, heating makes cavity reach predetermined
Temperature, power on the intracorporal reaction gas of excitation cavity, so that it becomes plasma, by two pieces of catalyst sheets of control it
Between distance generate plasma density between metal plate to control, under certain reaction pressure and power, obtain close
It spends very high plasma to be used to bombard metal surface, sputtering prepares catalyst film.Above-mentioned acquisition high-density plasma
Phenomenon is known as hollow cathode effect, and the high-density plasma bombardment metal surface generated using hollow cathode effect could obtain
Catalyst film bombards the low efficiency of metal plate otherwise since the density of plasma is lower, it is difficult to which it is thin effectively to prepare catalyst
Film.In the process, metal net mask is used to be connected the effect of cathode plate and catalytic metal plate, so that can generate between metal plate
Hollow cathode effect.In above process, the reaction gas is preferably argon gas and hydrogen, and the reaction temperature is preferably 300
~500 DEG C, more preferably 400~450 DEG C.The power of the power supply is preferably 500~1000W.The catalysis of above process preparation
Agent film with a thickness of 1~50nm.
After catalyst film is prepared, the application then continues to grown array carbon nano tube in PECVD cavity
Film.This process utilizes the influence of metal net mask plasma field, realizes the low temperature preparation of array carbon nano tube film.?
In preparation process, PECVD cavity is heated, is passed through carbon source and carrier gas thereto, is powered on, array carbon is grown after reaction and is received
Mitron film.During this, on the one hand metal net mask improves the temperature of conversion zone, on the other hand can adsorb high energy grain
Son reduces corrasion, and is conducive to grow array carbon nano tube film.The application is not special to the carbon source and carrier gas
Limitation is carbon source well known to those skilled in the art and carrier gas, and the carbon source is preferably one of methane, acetylene and normal butane
Or it is a variety of, the carrier gas is preferably argon gas and hydrogen.Argon gas and hydrogen mainly play two aspects as carrier gas, on the one hand, logical
Being passed through for carrier gas is crossed, the intracorporal air pressure of reaction chamber is controlled, so that plasma field is easy to be excited；On the other hand, it is passed through carrier gas
Effective growth for diluting carbon-source gas and being conducive to array carbon nano tube film, this is because when carbon-source gas is in reaction cavity
Ratio it is higher when, reaction preparation is tended to generate amorphous carbon, rather than carbon nanotube.During preparing carbon nanotube,
The ratio of carbon-source gas is controlled preferably 5%-20%, the flow of the hydrogen is 30~80sccm, and the flow of the argon gas is
30~80sccm.The carbon-source gas that the PECVD device used in the application is passed through during the preparation process be preferably 5sccm~
50sccm, in embodiment, the flow of the carbon source are preferably 5~10sccm.The time of the reaction is preferably 10~
100min, in embodiment, the reaction time are preferably 30~60min；The temperature of the reaction is preferably 350~500 DEG C,
Power is preferably 10~200W, and in embodiment, the power is preferably 30~100W.
The present invention is by changing relevant test parameters, such as reaction temperature, power, reaction time and reaction gas
Flow proportional etc. can control the thickness of array carbon nano tube and the thickness of single-root carbon nano-tube.The argon gas and hydrogen being passed through
As protective gas, the generation of amorphous carbon can be inhibited, guarantee the continued propagation of array carbon nano tube film.
Although those skilled in the art should be noted that plasma enhanced chemical vapor deposition used by the technical program is set
It is standby for radio frequency, but method of the invention is equally applicable to such as direct current, microwave plasma enhanced chemical vapor depsotition equipment.Separately
Outer metal net mask of the present invention is also not limited to one layer, and the mesh size and shape of metal net mask are also not limited to circle
Shape.It can also realize that the batch of array carbon nano tube film is grown using this method, that is, pass through the metal net mask dress of design multilayer
It sets.
A kind of result that only this method obtains under the conditions of established temperature shown in this example.Carbon in array film
Density, thickness and the length of nanotube, all can be by being obtained on the parameter basis of this example by appropriate adjustment.Experiment knot
Fruit show array carbon nano tube film prepared by the present invention with a thickness of 0.5~50 μm.
This application provides a kind of preparation methods of array carbon nano tube film, utilize plasma enhanced chemical vapor
Sedimentation (PECVD) is prepared for one layer of nanogold on the surface of provided substrate using the hollow cathode effect of plasma field
Metal catalyst film using metal net mask technology, realizes that array carbon is received under 350~500 DEG C of cryogenic conditions on this basis
The preparation of mitron film.
For a further understanding of the present invention, below with reference to embodiment to the system of array carbon nano tube film provided by the invention
Preparation Method is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Step 1: Si substrate is provided, is placed it on the lower plate of PECVD device, it is then that metal net mask is placed on it
Side is two pieces of sheet metals above metal net mask, below one layer be stainless steel, above one layer be nickel, between double layer of metal plate
Spacing is 1cm；
Step 2: closing reaction cavity, so that the intracorporal back end air pressure of chamber is reached 10 using vacuum pump-4Pa.It is passed through argon gas and hydrogen
Gas, and to being heated in cavity, after cavity temperature reaches 450 DEG C, power on, power is set as 600W, and electric field makes chamber
Intracorporal gas excitation is plasmoid, the intracorporal air pressure of reaction chamber is controlled, so that generating hollow yin between sheet metal
Polar effect inspires catalyst granules, forms catalyst nano film in sample surfaces.The argon flow being passed through in this example is
50sccm, hydrogen flowing quantity 50sccm, reaction time 10min, catalyst film thickness are about 20nm.
Step 3: after the completion of catalyst film preparation, continuing to be passed through argon gas and hydrogen into cavity, while leading into cavity
Enter acetylene, gas flow 10sccm.Controlling sample temperature is 450 DEG C, adjusts carrier gas, so that argon flow is 50sccm,
Hydrogen flowing quantity is 30sccm, adjusts power, is reduced to 50W, reaction time 60min, and obtained array carbon nano tube is thin
The thickness of film is about 3 μm, and the diameter of carbon nanotube is about 20~30nm.
Step 4: after the reaction was completed, closing power supply, stop heating and stop being passed through carbon-source gas, in the guarantor of argon gas and hydrogen
Room temperature is cooled to the furnace under shield.
Embodiment 2
The step 1 of this implementation, 2,4 with it is essentially identical in embodiment 1, difference is: being passed through argon gas in step 3 into cavity
And hydrogen, flow is respectively 50sccm and 30sccm, while being passed through acetylene 5sccm, adjusts power, is reduced to 30W, is reacted
Temperature is 500 DEG C, time 20min, and the thickness for the carbon nano-tube film being prepared is about 600nm, and tube wall diameter is about 20-
50nm.The SEM photograph of array carbon nano tube film manufactured in the present embodiment is as shown in Figure 4.
Embodiment 3
The step 1 of the present embodiment, 2,4 with it is essentially identical in embodiment 1, difference is: being passed through argon in step 3 into cavity
Gas and hydrogen, flow is respectively 50sccm and 30sccm, while being passed through acetylene 5sccm, adjusts power, is reduced to 30W, instead
Answering temperature is 400 DEG C, time 30min, and the thickness for the carbon nano-tube film being prepared is about 1.2 μm, and tube wall diameter is about
20-50nm.The SEM photograph of array carbon nano tube film manufactured in the present embodiment.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (8)
1. a kind of preparation method of array carbon nano tube film, comprising the following steps:
A), substrate is placed in the cavity of PECVD device in the metal net mask on negative plate, superposition is placed above metal net mask
Two blocks of catalyst metals plates；
B), it is passed through reaction gas in the cavity of PEVCD equipment, powers on after heating, utilizes the hollow yin between catalyst plates
Polar effect sputters at substrate surface and obtains catalyst film；
C), it is passed through carbon source and carrier gas after the cavity of PEVCD equipment being heated, powers on, obtains battle array in substrate surface after reaction
Column carbon nano-tube film；
Step A) described in the reaction gas hydrogen and argon gas that are, the reaction temperature is 300~500 DEG C, the function of the power supply
Rate is 500~1000W；
The flow of the hydrogen is 30~80sccm, and the flow of the argon gas is 30~80sccm.
2. preparation method according to claim 1, which is characterized in that the distance between described two blocks of catalyst metals plates are
1~5cm, the material of the catalyst metals plate are iron, cobalt, nickel or composite material.
3. preparation method according to claim 1, which is characterized in that step C) described in carbon source include methane, acetylene and
One of normal butane is a variety of, and the flow of the carbon source is 5~50sccm.
4. preparation method according to claim 1, which is characterized in that the carrier gas be hydrogen and argon gas, the hydrogen
Flow is 30~80sccm, and the flow of the argon gas is 30~80sccm.
5. preparation method according to claim 1, which is characterized in that step C) described in reaction temperature be 350~500
DEG C, the power of the power supply is 10~200W, and the time of the reaction is 10~100min.
6. preparation method according to claim 1, which is characterized in that the substrate is the substrate with smooth surface, excellent
Metal after being selected as silicon wafer, glass or surface polishing.
7. preparation method according to claim 1, which is characterized in that step B) described in catalyst film with a thickness of 1
~50nm.
8. preparation method according to claim 1, which is characterized in that the metal net mask be cylindric stainless steel mesh enclosure or
Cylindric copper mesh cover.
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| CN2723423Y (en) * | 2004-03-15 | 2005-09-07 | 西安交通大学 | Plasma reinforced photo-thermal chemical gas phase depositing device for preparing carbon nano tube film |
| TWI404675B (en) * | 2004-07-27 | 2013-08-11 | Nat Inst Of Advanced Ind Scien | Single layered carbon nanotube and oriented single layered carbon manotube-bulk structure, and manufacturing method, manufacturing apparatus and use thereof |
| KR20060091521A (en) * | 2005-02-15 | 2006-08-21 | 삼성에스디아이 주식회사 | Method for growing carbon nanotubes and manufacturing method of field emission device therewith |
| JP4678687B2 (en) * | 2006-02-24 | 2011-04-27 | 公立大学法人大阪府立大学 | Method and apparatus for producing carbon nanostructure |
| TWI429585B (en) * | 2006-05-29 | 2014-03-11 | Ulvac Inc | Carbon nanotubes growth substrate, carbon nanotubes growth method, carbon nanotubes growth catalyst with particle size control method, and nano-carbon tube diameter control method |
| JP5574265B2 (en) * | 2009-02-10 | 2014-08-20 | 日本ゼオン株式会社 | Equipment for producing aligned carbon nanotubes |
| JP5775705B2 (en) * | 2011-02-25 | 2015-09-09 | 東京エレクトロン株式会社 | Carbon nanotube formation method and pretreatment method |
| 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 |
| CN202755057U (en) * | 2012-08-31 | 2013-02-27 | 合肥永信等离子技术有限公司 | Plasma vacuum film coating chamber |
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