CN107381539A - 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 PDF

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Publication number
CN107381539A
CN107381539A CN201610326454.7A CN201610326454A CN107381539A CN 107381539 A CN107381539 A CN 107381539A CN 201610326454 A CN201610326454 A CN 201610326454A CN 107381539 A CN107381539 A CN 107381539A
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preparation
carbon nano
nano tube
film
reaction
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CN107381539B (en
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张伟
吉小超
于鹤龙
王红美
杜军
郭蕾
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Beijing Rui Mann Technology Co., Ltd.
Hebei Beijing Tianjin Hebei remanufacturing industry technology research Co., Ltd.
Academy of Armored Forces Engineering of PLA
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention provides a kind of preparation method of array carbon nano tube film, comprise the following steps:Substrate is placed in the metal net mask in PECVD cavitys, two blocks of catalyst metals plates being sequentially overlapped are placed above metal net mask;Reacting gas is passed through in PEVCD cavitys, switches on power after heating, catalyst film is obtained in substrate surface after reaction;Carbon source and carrier gas are passed through after PEVCD cavitys are heated, switches on power, array carbon nano tube film is obtained in substrate surface after reaction.The application catalyst film and array carbon nano tube film are completed in same PECVD cavitys, and can realize continuous preparation, improve the efficiency of array carbon nano tube film preparation;On the other hand, low temperature preparation enable array carbon nano tube film be applied to many non-refractories field.

Description

A kind of preparation method of array carbon nanocapsule thin film
Technical field
The present invention relates to carbon nanotube technology field, more particularly to a kind of array carbon nanocapsule thin film Low temperature preparation method.
Background technology
CNT (CNT) is used as monodimension nanometer material, and its special structure makes it have excellent Different calorifics, mechanics and electric property so that CNT is in material science, physics, electricity The fields such as son show good application prospect.At present, the application study on CNT Be concentrated mainly on composite, Field Emission Display, hydrogen storage, sensor, super capacitor and The fields such as conducting polymer, many application fields have all made important progress.Yet with by The limitation of preparation technology, preparation condition is harsh, yield is few, preparation efficiency is low, order is poor, The factors such as impurity is more all hinder the research and application of CNT.
The method for preparing CNT at present mainly has:Arc process, laser evaporization method and chemistry Vapour deposition process (CVD) etc..The preparation method of CNT is different, then the carbon nanometer obtained The structure of pipe is also different.Arc process and laser evaporization method are generally all the catalyst in unordered accumulation On the basis of prepare CNT, it is difficult to control the orientation of growth of CNT;And CVD method The orientation of carbon nano tube growth can be effectively controlled, so as to prepare array carbon nano tube film. The array carbon nano tube film of acquisition has the performances such as many excellent electricity, Flied emission, micro- The fields such as electronics have huge application prospect.
At present, prepare array carbon nano tube film using hot CVD method and be primarily present two not Foot:First, it, which prepares the surface of substrate, needs one layer of catalyst nano film, the film generally needs To use the preparation technologies such as evaporation or sputtering method;On the other hand, hot CVD method prepares carbon Generally all more than 600 DEG C, exacting terms limits array carbon and received the reaction temperature of nanotube The application field of mitron film so that can not be in the material table to fields such as thermo-responsive microelectronics Face directly prepares array carbon nano tube film.
The content of the invention
Present invention solves the technical problem that it is to provide a kind of low temperature of array carbon nano tube film In-situ preparation method.
In view of this, this application provides a kind of preparation method of array carbon nano tube film, bag Include following steps:
A), substrate is placed in the metal net mask in the cavity of PECVD device on negative plate, Two blocks of catalyst metals plates of superposition are placed above metal net mask;
B), reacting gas is passed through in the cavity of PEVCD equipment, is switched on power after heating, After reaction catalyst film is obtained in substrate surface;
C), carbon source and carrier gas will be passed through after the cavity heating of PEVCD equipment, switched on power, After reaction array carbon nano tube film is obtained in substrate surface.
Preferably, the distance between described two blocks of catalyst metals plates are 1~5cm, the catalysis The material of agent metallic plate is iron, cobalt, nickel or composite material.
Preferably, step A) described in the reacting gas hydrogen and argon gas that are, the reaction temperature Spend for 300~500 DEG C, the power of the 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 methane, acetylene and normal butane in one kind Or it is a variety of, the flow of the carbon source 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 is 30~80sccm.
Preferably, step C) described in the temperature reacted be 350~500 DEG C, the power supply Power is 10~200W, and the time of the reaction is 10~100min.
Preferably, the substrate is the substrate with smooth surface, preferably silicon chip, glass or Metal after the polishing of surface.
Preferably, step B) described in the thickness of catalyst film be 1~50nm.
Preferably, the metal net mask is cylindric stainless steel guard or cylindric copper mesh cover.
This application provides a kind of preparation method of array carbon nano tube, substrate is placed in first Two be sequentially overlapped are placed in metal net mask in the cavity of PEVCD equipment, above metal net mask Block catalyst metals plate, then reacting gas is passed through into cavity, heating cavity, switch on power sharp The reacting gas in cavity is sent out, so that it becomes plasma, passes through air pressure and electricity in control chamber body Source power, make to produce hollow cathode effect between metallic plate, strengthen the plasma between metallic plate Density, highdensity high-energy ion bombardment metal sheet surface so that nano-metal particle sputters Deposition forms catalyst film to substrate surface, continues after heating reaches reaction temperature, to chamber Be passed through carbon source and carrier gas in vivo, using catalyst film decompose caused by nano particle in substrate table Look unfamiliar and grow array carbon nano tube film.It is first during the application array carbon nano tube film First the preparation process of catalyst film is integrated into PECVD reaction cavity, realized in situ The preparation of catalyst film and the growth of array carbon nano tube film, not only reduce preparation Array carbon nano tube thin-film technique also greatly reduces it and prepares cost to device dependence; On the other hand, the assistant metal guard that this method uses, the effective activity for improving plasma, Carbon-source gas are more effectively decomposed, realize low temperature preparation of the array carbon nano tube at 350~500 DEG C, This causes the electronic device surface in situ in non-refractory prepares that array carbon nano tube film becomes can OK, its application prospect has been widened.
Brief description of the drawings
Fig. 1 is the PECVD device and the schematic diagram of metal net mask device that the present invention uses;
Fig. 2 is that the ESEM of array carbon nano tube film prepared by the embodiment of the present invention 1 shines Piece;
Fig. 3 is the saturating of the CNT of array carbon nano tube film prepared by the embodiment of the present invention 1 Penetrate electromicroscopic photograph;
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.
Embodiment
For a further understanding of the present invention, with reference to embodiment to the preferred embodiment of the invention It is described, but it is to be understood that these descriptions are simply the feature of the further explanation present invention And advantage, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of array carbon nano tube film, including with Lower step:
A), substrate is placed in the metal net mask in the cavity of PECVD device on negative plate, Two blocks of catalyst metals plates being sequentially overlapped are placed above metal net mask;
B), reacting gas is passed through in the cavity of PEVCD equipment, is switched on power after heating, After reaction catalyst film is obtained in substrate surface;
C), carbon source and carrier gas will be passed through after the cavity heating of PEVCD equipment, switched on power, After reaction array carbon nano tube film is obtained in substrate surface.
This application provides a kind of preparation method of array carbon nano tube film, this method passes through liter The density of high PECVD cavitys plasma, urged using the plasma bombardment metal of high energy Agent thin plate so that the Nano metal particles deposition sputtered is catalyzed in substrate surface Agent film, on this basis, using the booster action of metal net mask, realize arrayed nanotube The low temperature preparation of film.
The preparation method of the application array carbon nano tube film, including catalyst film preparation with Two steps of preparation of low temperature carbon nano-tube film, and two steps are in same PECVD It is continuously finished in reaction cavity.
The application carries out the preparation of catalyst film first.As shown in figure 1, Fig. 1 is the present invention The schematic device of the PECVD device of array carbon nano tube film preparation.The application first will Substrate is placed in the cavity of PECVD device among the cylindrical metal guard on negative plate, Two blocks of catalyst metals plates for being sequentially overlapped placement are placed above metal net mask.It is herein described PECVD cavitys are the reaction cavity of PECVD device, and the PECVD device is this area Equipment known to technical staff, this application is had no particular limits, what the application used PECVD device preferably as shown in figure 1, metal net mask in PECVD reaction cavities, substrate with The setting of two blocks of catalyst metals plates is specially:The substrate is positioned on bottom crown, and described Substrate is arranged in the metal net mask, the top of the metal net mask and direct with metal net mask Contact is provided with two blocks of catalyst metals plates being sequentially overlapped, the metal net mask, substrate with Catalyst sheet may be contained between top crown and bottom crown.Herein described metal net mask can be with For cylindric stainless steel guard or cylindric copper mesh cover.The material of the substrate is art technology Base material known to personnel, for the substrate with smooth surface, more preferably silicon chip, glass Or the metal after the polishing of surface.The spacing of herein described two blocks of catalyst metals plates is preferably 1~5cm.The catalyst metals plate is preferably iron, cobalt, nickel or composite material, this Shen Please the catalyst metals plate be preferably same metal material.
During catalyst film is prepared, reacting gas is passed through into PECVD cavitys, Heating makes cavity reach predetermined temperature, the reacting gas to switch on power in excitation cavity body, makes it It is changed into plasma, by controlling the distance between two pieces of catalyst sheets to be produced to control in gold Belong to the plasma density between plate, under certain reaction pressure and power, obtain density very High plasma is used for bombarding metal surface, and sputtering prepares catalyst film.Above-mentioned acquisition is high The phenomenon of density plasma is referred to as hollow cathode effect, utilizes height caused by hollow cathode effect Density plasma bombardment metal surface could obtain catalyst film, otherwise due to plasma Density it is relatively low, the efficiency for bombarding metallic plate is low, it is difficult to effectively prepares catalyst film.Herein During, metal net mask is used for the effect for turning on minus plate and catalytic metal plate so that metallic plate Between can produce hollow cathode effect.In above process, the reacting gas is preferably argon Gas and hydrogen, the reaction temperature are preferably 300~500 DEG C, more preferably 400~450 DEG C. The power of the power supply is preferably 500~1000W.The thickness of catalyst film prepared by said process Spend for 1~50nm.
After catalyst film is prepared, the application then continues raw in PECVD cavitys Array carbon nano tube film is grown.This process utilizes the influence of metal net mask plasma field, Realize the low temperature preparation of array carbon nano tube film.In preparation process, by PECVD chambers Body heats, and is passed through carbon source and carrier gas thereto, switches on power, 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, another Aspect can adsorb high energy particle, reduce corrasion, and be beneficial to grow array carbon nano tube Film.The application has no particular limits to the carbon source with carrier gas, is those skilled in the art Well known carbon source and carrier gas, the carbon source be preferably one kind in methane, acetylene and normal butane or A variety of, the carrier gas is preferably argon gas and hydrogen.Argon gas and hydrogen mainly play two sides as carrier gas Face acts on, on the one hand, by being passed through for carrier gas, controls the air pressure in reaction cavity so that etc. Gas ions field is easily excited;On the other hand, it is passed through carrier gas and effectively dilutes carbon-source gas and favourable In the growth of array carbon nano tube film, this is due to the ratio in reaction cavity when carbon-source gas When example is higher, reaction preparation is tended to generate amorphous carbon, rather than CNT.Preparing carbon During nanotube, the ratio of carbon-source gas is controlled preferably 5%-20%, the hydrogen Flow is 30~80sccm, and the flow of the argon gas is 30~80sccm.Used in the application The carbon-source gas that PECVD device is passed through in preparation process are preferably 5sccm~50sccm, In embodiment, the flow of the carbon source is preferably 5~10sccm.The time of the reaction is preferably 10~100min, in embodiment, the reaction time is preferably 30~60min;The reaction Temperature be preferably 350~500 DEG C, power is preferably 10~200W, in embodiment, The power is preferably 30~100W.
The present invention is by changing related test parameters, such as reaction temperature, power, reaction Time and reaction gas flow ratio etc., the thickness and list of array carbon nano tube can be controlled The thickness of root CNT.The argon gas and hydrogen being passed through can suppress amorphous as protective gas The generation of carbon, ensure the continued propagation of array carbon nano tube film.
Although those skilled in the art should be noted that plasma enhancing used by the technical program Chemical vapor depsotition equipment is radio frequency, but the method for the present invention is equally applicable to such as direct current, micro- Ripple plasma enhanced chemical vapor deposition equipment.Other metal net mask of the present invention One layer is not limited only to, the mesh size and shape of metal net mask are also not limited to circle.Utilize this Method can also realize the batch growth of array carbon nano tube film, the i.e. gold by designing multilayer Belong to mesh cover device.
A kind of knot that the simply this method shown in this example obtains under the conditions of established temperature Fruit.The density of CNT, thickness and length in array film, all can be by this example Parameter basis on by suitably adjusting acquisition.Test result indicates that array prepared by the present invention The thickness of carbon nano-tube film is 0.5~50 μm.
This application provides a kind of preparation method of array carbon nano tube film, and it utilizes plasma Body enhancing chemical vapour deposition technique (PECVD), using the hollow cathode effect of plasma field, One layer of metallic catalyst film is prepared on the surface of provided substrate, on this basis, Using metal net mask technology, realize that array carbon nano tube is thin under 350~500 DEG C of cryogenic conditions The preparation of film.
For a further understanding of the present invention, with reference to embodiment to array carbon provided by the invention The preparation method of nano-tube film is described in detail, and protection scope of the present invention is not by following reality Apply the limitation of example.
Embodiment 1
Step 1:Si substrates are provided, are placed on the lower shoe of PECVD device, then Be two pieces of sheet metals above metal net mask by metal net mask side placed on it, below one layer be Stainless steel, above one layer be nickel, the spacing between double layer of metal plate is 1cm;
Step 2:Reaction cavity is closed, reaches the back end air pressure in cavity using vavuum pump 10-4Pa.Argon gas and hydrogen are passed through, and to being heated in cavity, when cavity temperature reaches 450 DEG C Afterwards, switch on power, power is set to 600W, electric field the gas in cavity is excited for wait from Daughter state, control the air pressure in reaction cavity so that hollow cathode is produced between sheet metal Effect, catalyst granules is inspired, catalyst nano film is formed in sample surfaces.This example In the argon flow amount that is passed through be 50sccm, hydrogen flowing quantity 50sccm, reaction time 10min, Catalyst film thickness is about 20nm.
Step 3:After the completion of prepared by catalyst film, continue to be passed through argon gas and hydrogen into cavity, Acetylene is passed through into cavity simultaneously, its gas flow is 10sccm.The sample temperature is controlled to be 450 DEG C, adjust carrier gas so that argon flow amount 50sccm, hydrogen flowing quantity 30sccm, adjust Whole power, it is reduced to 50W, reaction time 60min, obtained array carbon nano tube The thickness of film is about 3 μm, and the diameter of CNT is about 20~30nm.
Step 4:After the completion of reaction, power supply is closed, stops heating and stops being passed through carbon-source gas, Room temperature is cooled to the furnace under the protection of argon gas and hydrogen.
Embodiment 2
With essentially identical in embodiment 1, difference is for the step 1 of this implementation, 2,4:Step It is passed through argon gas and hydrogen in 3 into cavity, flow is respectively 50sccm and 30sccm, simultaneously Acetylene 5sccm is passed through, adjusts power, is reduced to 30W, reaction temperature is 500 DEG C, Time is 20min, and the thickness for the carbon nano-tube film being prepared is about 600nm, and tube wall is straight Footpath is about 20-50nm.The SEM photograph of array carbon nano tube film manufactured in the present embodiment is as schemed Shown in 4.
Embodiment 3
With essentially identical in embodiment 1, difference is for the step 1 of the present embodiment, 2,4:Step It is passed through argon gas and hydrogen in rapid 3 into cavity, flow is respectively 50sccm and 30sccm, together When be passed through acetylene 5sccm, adjust power, be reduced to 30W, reaction temperature is 400 DEG C, Time is 30min, and the thickness for the carbon nano-tube film being prepared is about 1.2 μm, and tube wall is straight Footpath is about 20-50nm.The SEM photograph of array carbon nano tube film manufactured in the present embodiment.
The explanation of above example is only intended to help method and its core think of for understanding the present invention Think.It should be pointed out that for those skilled in the art, this hair is not being departed from On the premise of bright principle, some improvement and modification can also be carried out to the present invention, these improve and Modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize Or use the present invention.A variety of modifications to these embodiments come to those skilled in the art Say and will be apparent, generic principles defined herein can not depart from the present invention's In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by The embodiments shown herein is limited to, and is to fit to and principles disclosed herein and new The consistent most wide scope of clever feature.

Claims (10)

1. a kind of preparation method of array carbon nano tube film, comprises the following steps:
A), substrate is placed in the metal net mask in the cavity of PECVD device on negative plate, Two blocks of catalyst metals plates of superposition are placed above metal net mask;
B), reacting gas is passed through in the cavity of PEVCD equipment, is switched on power after heating, After reaction catalyst film is obtained in substrate surface;
C), carbon source and carrier gas will be passed through after the cavity heating of PEVCD equipment, switched on power, After reaction array carbon nano tube film is obtained in substrate surface.
2. preparation method according to claim 1, it is characterised in that described two pieces are urged The distance between agent metallic plate is 1~5cm, the material of the catalyst metals plate is iron, cobalt, Nickel or composite material.
3. preparation method according to claim 1, it is characterised in that step A) in institute Hydrogen and argon gas that reacting gas is are stated, the reaction temperature is 300~500 DEG C, the power supply Power be 500~1000W.
4. preparation method according to claim 3, it is characterised in that the hydrogen Flow is 30~80sccm, and the flow of the argon gas is 30~80sccm.
5. preparation method according to claim 1, it is characterised in that step C) in institute Stating carbon source includes the one or more in methane, acetylene and normal butane, and the flow of the carbon source is 5~50sccm.
6. preparation method according to claim 1, it is characterised in that the carrier gas is Hydrogen and argon gas, the flow of the hydrogen is 30~80sccm, and the flow of the argon gas is 30~80sccm.
7. preparation method according to claim 1, it is characterised in that step C) in institute The temperature for stating reaction is 350~500 DEG C, and the power of the power supply is 10~200W, the reaction Time be 10~100min.
8. preparation method according to claim 1, it is characterised in that the substrate is Metal after substrate with smooth surface, preferably silicon chip, glass or surface polishing.
9. preparation method according to claim 1, it is characterised in that step B) in institute The thickness for stating catalyst film is 1~50nm.
10. preparation method according to claim 1, it is characterised in that the wire netting Cover for cylindric stainless steel guard or cylindric copper mesh cover.
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