CN103613094A - Method for preparing graphene and porous amorphous carbon films simultaneously - Google Patents
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- CN103613094A CN103613094A CN201310624078.6A CN201310624078A CN103613094A CN 103613094 A CN103613094 A CN 103613094A CN 201310624078 A CN201310624078 A CN 201310624078A CN 103613094 A CN103613094 A CN 103613094A
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Abstract
The invention discloses a method for preparing graphene and porous amorphous carbon films simultaneously. The method comprises the following steps: S1, ultrasonically cleaning a metal nickel sheet substrate, drying the metal nickel sheet substrate and placing the metal nickel sheet substrate into a tube furnace; S2, introducing inert gases into the tube furnace; S3, heating the tube furnace to 750 to 1,000 DEG C and maintaining for 10 to 50 minutes, introducing hydrogen into the tube furnace, and performing heat treatment on the metal nickel sheet substrate; and S4, introducing hydrocarbon compounds with the flow quantity of 20 to 100 sccm into the tube furnace, cracking the hydrocarbon compounds under the catalysis of the metal nickel sheet substrate subjected to heat treatment, dissolving carbon by a nickel sheet, and growing graphene and porous amorphous carbon films simultaneously; and S5, cooling the tube furnace, soaking the nickel sheet, on which the graphene and the porous amorphous carbon films grow, into corrosive liquid, and corroding the substrate nickel sheet to obtain the graphene and the porous amorphous carbon films. The hydrocarbon compounds serve as carbon sources, the adsorption cracking of the carbon sources on the surface of the substrate nickel sheet under the high temperature condition is controlled, and carbon atoms are dissolved into the nickel sheet, so that the graphene and the porous amorphous carbon films can be obtained simultaneously.
Description
Technical field
The invention belongs to chemical vapour deposition and prepare thin film technique field, more specifically, relate to a kind of method of simultaneously preparing Graphene and porous amorphous carbon film.
Background technology
Carbon is one of the abundantest element of nature content, and the carbon materials being comprised of carbon has a variety of isomers.The Geim of Univ Manchester UK in 2004 etc. utilizes mechanical separation method to prepare first on a graphite and observes a kind of special carbon film---mono-layer graphite (Graphene), Open from This Side the research boom of grapheme material.Graphene is comprised of individual layer atom, has bi-dimensional cellular structure, and this special structure has been given optics, electricity, calorifics and the mechanical property of grapheme material uniqueness.These superior performances make it at aspects such as nano electron device, lithium ion battery electrode material, ultracapacitor, electrode of solar battery material, hydrogen storage material, sensor, optical material, pharmaceutical carriers, show huge application potential.The fundamental and applied research of Graphene has entered the fast development stage, and Graphene has become " super " material in current novel material.
At present, the preparation method of grapheme material mainly contains: mechanically peel method, chemical oxidization method, crystal epitaxy method, chemical Vapor deposition process, organic synthesis method and carbon nanotube stripping method etc.Chemical vapour deposition as a kind of quick and easy, cost is low and the technique means that can prepare big area Graphene enjoys scientist's concern.Chemical Vapor deposition process utilizes hydrocarbon polymer for carbon source conventionally, under hot conditions, and carbon source cracking formation of deposits Graphene on transition metal.Under conventional technical qualification, can only obtain individual layer and multi-layer graphene film.
Amorphous carbon-film is a kind of in numerous carbon materialses, and this material just begins one's study in eighties of last century the forties, and eighties of last century starts application the sixties.Amorphous carbon-film can be described as the intermediate state of diamond (carbon atom only has sp3 hydridization) and graphite (carbon atom only has sp2 hydridization) structure.Different with sp3 content according to contained hydridization carbon atom sp2, amorphous carbon-film is generally divided into quasi-diamond amorphous carbon-film (sp3 content > sp2 content) and class graphite amorphous carbon-film (sp2 content > sp3 content).Amorphous carbon-film demonstrates excellent mechanics, Optical and frictional properties etc., as high rigidity, good chemical stability and biocompatibility, especially ultra-low friction factor and high-wearing feature can wait it is had a wide range of applications at machinery, electronics, communication and aerospace field.Porous amorphous carbon-film, except having above advantage, also has specific surface area greatly and the abundant feature of pore size distribution, can be widely used in the energy and biomedical sector.
At present, the method for preparing amorphous carbon-film has: particle beam (ion, electronics, photon etc.) assistant depositing technology, Vacuum Arc deposition technique, magnetron sputtering technique, plasma enhanced chemical vapor deposition technology and thermal chemical vapor deposition technology etc.But all there are several problems in all these technology, one is exactly that carbon film preparation process environment temperature is high, so, general amorphous carbon-film is all prepared in rigid substrate (such as silica glass, mica, silicon chip or directly at workpiece surface) upper, makes the application of amorphous carbon-film be subject to certain restriction; It two is that the prepared amorphous carbon-film of these technology is all dense film, cannot obtain vesicular structure carbon film; Its three be these technology prepared be mostly quasi-diamond amorphous carbon-film; It four is self-supporting amorphous carbon-films that these technology cannot obtain special construction, and self-supporting amorphous carbon-film can easily be transferred to any substrate.This shows, amorphous carbon film technology of preparing exists some defects to restrict its fundamental research and application at present.
Summary of the invention
For above defect or the Improvement requirement of prior art, the object of the present invention is to provide a kind of method of simultaneously preparing Graphene and porous amorphous carbon film.
For achieving the above object, according to one aspect of the present invention, provide a kind of method of simultaneously preparing Graphene and porous amorphous carbon film, comprised the steps:
S1: metallic nickel sheet substrate is carried out to ultrasonic cleaning, and be positioned in tube furnace after drying;
S2: pass into rare gas element in described tube furnace;
S3: described tube furnace is carried out to hyperthermic treatment and make it reach 750 ℃～1000 ℃ and keep 10 minutes～50 minutes, pass into hydrogen in described tube furnace, and described metallic nickel sheet substrate is heat-treated;
S4: pass into the hydrocarbon polymer that flow is 20sccm～100sccm in described tube furnace, make after metallic nickel sheet substrate catalytic hydrocarbon cracking after Overheating Treatment and the molten carbon of nickel sheet growing graphene and amorphous carbon film simultaneously;
S5: to the processing of lowering the temperature of described tube furnace, and obtain Graphene and porous amorphous carbon film after growth is had the nickel sheet of Graphene and amorphous carbon film to be immersed in to erode substrate nickel sheet in corrosive fluid.
Further, in step S3, the flow that passes into hydrogen is 50sccm～200sccm.
Further, in step S5, described corrosive fluid is ferric chloride in aqueous solution.
Further, in step S2, described rare gas element is at least one in argon gas or helium.
Further, in step S2, the flow that passes into rare gas element is 50sccm～500sccm.
Further, described hydrocarbon polymer is any one or arbitrarily multiple combination in methane, ethane, propane, butane, hexane, pentane, heptane, octane, propylene, ethene, butylene, amylene, acetylene.
The present invention utilizes chemical vapour deposition technique, take hydrocarbon polymer as carbon source, by controlling carbon source under hot conditions, in the absorption cracking on substrate nickel sheet surface and nickel sheet, dissolve in carbon atom, and follow-up cooling and last substrate etching obtain Graphene and amorphous carbon film.The present invention has the following advantages: (1) equipment is simple and cost is low; (2) simple to operate quick with preparation process; (3) one secondary growths can obtain high-quality graphene and two kinds of products of amorphous carbon film simultaneously; (4) Graphene and amorphous carbon film all have self-supporting, can transfer to respectively on any substrate; (5) can prepare the double-deck composite carbon film of big area Graphene/amorphous carbon film/Graphene sandwich structure or Graphene/amorphous carbon film.Therefore there is important potential research using value.
Accompanying drawing explanation
Fig. 1 is the structural representation that the embodiment of the present invention is provided when providing by the device of Graphene and porous amorphous carbon film;
Fig. 2 is the realization flow figure that the embodiment of the present invention is provided when providing by the method for Graphene and porous amorphous carbon film;
Fig. 3 is passing through of providing of the embodiment of the present invention 2 Graphene that a secondary growth prepared simultaneously and the fluorescence Raman spectrogram of porous amorphous carbon film;
Fig. 4 is the picture of the scanning electronic microscope of the Graphene simultaneously prepared by a secondary growth of the embodiment of the present invention 2 and porous amorphous carbon film;
Fig. 5 is the picture of the transmission electron microscope of the Graphene simultaneously prepared by a secondary growth of the embodiment of the present invention 2 and porous amorphous carbon film.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can not combine mutually as long as do not form each other conflict.
The present invention relates to chemical vapour deposition and prepare thin film technique field.More particularly, the present invention relates to utilize chemical vapour deposition by a secondary growth, to prepare big area graphene film and porous amorphous carbon film in nickel metal substrate simultaneously.Simple and the easy handling control of chemical vapour deposition technique equipment, this technology not only can be prepared big area Graphene but also can prepare amorphous carbon film, and its advantage is self-evident.The present invention utilizes chemical vapour deposition technique to prepare Graphene and amorphous carbon film and compound carbon film material thereof by a secondary growth simultaneously will greatly promote the fundamental research of carbon film material and application widely.
In the method for simultaneously preparing Graphene and porous amorphous carbon film provided by the invention, by a secondary growth, big area Graphene and porous amorphous carbon film have been obtained simultaneously, Graphene can be naturally flawless intact separated with amorphous carbon film, and the Graphene after separation and amorphous carbon film can be transferred to respectively on any substrate, also Graphene and amorphous carbon film can be stacked together, preparation big area Graphene/amorphous carbon film/Graphene sandwich structure or the double-deck composite carbon film of Graphene/amorphous carbon film.Therefore, this technology, for quick and easy and low-cost preparation big area Graphene and porous amorphous carbon film and composite carbon film thereof provide a kind of brand-new thinking, can promote the fundamental research of carbon film material and application widely greatly.
The present invention realizes the technical scheme that above-mentioned technical purpose takes to be: utilize chemical vapour deposition technique, take hydrocarbon polymer as carbon source, by controlling carbon source under hot conditions, in the absorption cracking on substrate nickel sheet surface and nickel sheet, dissolve in carbon atom, and follow-up cooling and last substrate etching obtain Graphene and amorphous carbon film.
According to the Technology Need of preparing Graphene and porous amorphous carbon film simultaneously, Graphene thickness is between which floor is to tens layers, and amorphous carbon film has the constructional feature of porous, and pore diameter distribution, between 10nm～S0nm, and has certain light transmission.Graphene and carbon film all have self-supporting.
A kind of method of simultaneously preparing Graphene and porous amorphous carbon film provided by the invention is: utilize chemical vapour deposition technique, take hydrocarbon polymer as carbon source, by controlling absorption cracking and the carbon atom of carbon source on substrate nickel sheet surface under hot conditions, dissolve in nickel sheet, and follow-up cooling and last substrate etching acquisition Graphene and amorphous carbon film, detailed process is:
First by the ultrasonic cleaning in acetic acid and ethanolic soln of metallic nickel sheet substrate, after oven dry, be positioned over tube furnace central authorities, in tube furnace, pass into rare gas element argon gas.Then, with the temperature rise rate of 10～40 ℃ of per minutes, be warmed up to 750～1000 ℃, pass into hydrogen simultaneously, nickel sheet is heat-treated to heat treatment time 10～50 minutes.Then pass into hydrocarbon polymer, this process process that to be hydrocarbon polymer dissolve in nickel sheet at the surface adsorption cracking of substrate nickel sheet and carbon atom, this process temperature is growth temperature, 750～1000 ℃ of scopes, the growth temperature hold-time is 10～50 minutes, and the gas pressure intensity in this process is normal pressure.Then the rate of temperature fall with 5～20 ℃ of per minutes is cooled to room temperature, finally the nickel sheet after growth is immersed in and in corrosive fluid ferric chloride Solution, erodes substrate nickel sheet, obtain Graphene and porous amorphous carbon film simultaneously, Graphene and amorphous carbon film can naturally flawless intact separating, through washed with de-ionized water, several times, can be transferred to respectively in any substrate, also Graphene and amorphous carbon film can be stacked together, preparation big area Graphene/amorphous carbon film/Graphene sandwich structure or the double-deck composite carbon film of Graphene/amorphous carbon film.
Utilizing chemical vapour deposition technique process of growing graphene and amorphous carbon-film on nickel sheet is the process of molten carbon in nickel sheet catalytic cracking of hydrocarbon and nickel sheet under hot conditions.Owing to could obtain high-quality Graphene under higher temperature condition, by optimizing temperature range, determine within the scope of 750～1000 ℃ can growing high-quality Graphene.In order to obtain high-quality amorphous carbon film simultaneously, employing passes into the hydrocarbon gas that flow range is 20～100sccm scope under condition of normal pressure, both guaranteed in 750～1000 ℃ of temperature ranges, in nickel sheet, be dissolved with a large amount of carbon atoms, growth when impelling Graphene and porous amorphous carbon-film, can suppress again disordered carbon in the deposition on nickel sheet surface, thereby guarantee the quality of Graphene.Finally by control, lower the temperature, the surface growth of nickel sheet has high-quality Graphene, is dissolved with a large amount of carbon atoms and forms amorphous carbon film in nickel sheet, after corroding nickel sheet, can obtain high-quality graphene and amorphous carbon film in ferric chloride Solution simultaneously.
Wherein, substrate is the thick metallic nickel plate sheet of 1 μ m～500 μ m.When substrate nickel sheet is carried out to ultrasonic cleaning processing, as preferentially, can adopt acetic acid and alcohol, clean 10～40 minutes.It is simple that chemical vapour deposition technique has equipment, easy to operate, and the low and good advantage of controllability of cost, therefore as technology of preparing of the present invention.
In the embodiment of the present invention, substrate nickel sheet cleans and intensification thermal treatment, carbon source are adsorbed cracking and the molten carbon of nickel sheet, cooling and last substrate nickel sheet corrosion under hot conditions on nickel sheet, and these processes are prepared in Graphene and porous amorphous carbon film technology indispensable at the same time.In intensification heat treatment process, heat-up rate is controlled at 10～40 ℃ of per minute scopes, and top temperature is 750～1000 ℃ of scopes, and when top temperature, heat treatment time was 10～50 minutes scopes or longer.In heat treatment process, hydrogen flowing quantity scope is 50～200sccm.Carbon source adsorbs on nickel sheet under hot conditions that in cracking and the molten carbon process of nickel sheet, temperature is 750～1000 ℃ of scopes, and the hold-time is 10～50 minutes or longer.
Dissolve in carbon atom process in the surface adsorption cracking of nickel sheet and nickel sheet under hot conditions carbon source in, hydrocarbon polymer flow range is 20～100sccm.In temperature-fall period, with 5～20 ℃ of per minute speed, be cooled to room temperature.In above process, operating air pressure is normal pressure, than being easier to realization, cost-saving and simple to operate.In substrate nickel sheet corrosion process, corrosive fluid is ferric chloride in aqueous solution, because ferric chloride in aqueous solution is very fast with reacting of nickel sheet, and in reaction process, can not produce the structure that gas destroys amorphous carbon film, so can choose ferric chloride in aqueous solution, does corrosive fluid.
Adopt preparation method of the present invention less demanding to envrionment temperature, simple and quick, by a secondary growth, can prepare the smooth Graphene of big area and Large-Area-Uniform porous amorphous carbon film, the area of Graphene and amorphous carbon film is controlled simultaneously, can easily be transferred to any substrate.Adopt preparation method of the present invention can prepare big area Graphene/amorphous carbon film/Graphene sandwich structure or the double-deck composite carbon film of Graphene/amorphous carbon film.Therefore there is important potential research and using value.
The embodiment of the present invention has obtained Graphene and amorphous carbon film by a secondary growth simultaneously, and Graphene thickness can be at which floor to tens layers of control, and amorphous carbon film has transparent and constructional feature porous.What is more important, Graphene can be naturally flawless intact separated with amorphous carbon film, and the Graphene after separation and amorphous carbon film can be transferred to respectively on any substrate.The embodiment of the present invention provides a kind of new way for preparing Graphene and amorphous carbon film and composite structure thereof; Be specially: in the cleaning of substrate metal nickel sheet, tube furnace, pass into that hydrogen passes into the high-temperature heat treatment of nickel sheet, under hot conditions that hydrocarbon gas is grown on nickel sheet, cooling and ferric chloride Solution etching nickel sheet obtain Graphene and amorphous carbon film.This method of simultaneously preparing Graphene and amorphous carbon film is not in the news at present, and the present invention has the following advantages: (1) equipment is simple and cost is low; (2) simple to operate quick with preparation process; (3) one secondary growths can obtain high-quality graphene and two kinds of products of amorphous carbon film simultaneously; (4) Graphene and amorphous carbon film all have self-supporting, can transfer to respectively on any substrate; (5) can prepare the double-deck composite carbon film of big area Graphene/amorphous carbon film/Graphene sandwich structure or Graphene/amorphous carbon film.Therefore there is important potential research using value.
Below in conjunction with accompanying drawing and specific examples, method provided by the invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.Table one shows the list of important parameter in the present invention:
Table one
A kind of method of simultaneously preparing Graphene and porous amorphous carbon film is provided in the present embodiment, and the present embodiment relates to and utilizes chemical vapour deposition to take hydrocarbon polymer in nickel metal substrate, by a secondary growth, to prepare big area graphene film and porous amorphous carbon film as carbon source simultaneously.Chemical vapor depsotition equipment as shown in Figure 1, as shown in Figure 2, existing take embodiment 2 details are as follows as example by embodiment flow process:
(1) take 200 microns of polycrystalline nickel sheets is substrate, by the ultrasonic cleaning 10 minutes in acetic acid and ethanolic soln of metallic nickel sheet substrate, dries up and is placed on (Fig. 1) in tube furnace silica tube, is evacuated to base vacuum (lower than 10
-3torr).
(2) in silica tube, pass into the argon gas that flow is 100sccm, until stable gas pressure is normal pressure, heat-up rate is 20 ℃ of per minutes.Temperature is closed argon gas after reaching 900 ℃, passes into the hydrogen that flow is 80sccm simultaneously.
(3) in temperature, be under 900 ℃, the flow hydrogen condition that is 80sccm, nickel foil to be heat-treated, the treatment time is 10 minutes.
(4) in silica tube, pass into the methane gas that flow is 50sccm, and reduce hydrogen flowing quantity to 5sccm, air pressure remains normal pressure, and methane starts on nickel sheet, to adsorb in cracking and nickel sheet and dissolves in carbon atom, and this process time is 25 minutes.
(5) with 10 ℃ of per minute speed, be cooled to 450 ℃, open tube furnace bell, make temperature be down to room temperature, in temperature-fall period, methane and hydrogen flowing quantity and air pressure are constant.
(6) take out substrate nickel sheet, with deionized water, configure ferric chloride Solution, the substrate nickel sheet taking out is immersed in ferric chloride Solution, erode after nickel sheet, obtain Graphene and porous amorphous carbon film simultaneously, Graphene and amorphous carbon film can naturally flawless intact separating, and can transfer to and on any substrate, carry out applied research (as Fig. 3～5).
(7) Graphene and amorphous carbon film can be transferred to respectively in any substrate through washed with de-ionized water several times, also Graphene and amorphous carbon film can be stacked together, preparation big area Graphene/amorphous carbon film/Graphene sandwich structure or the double-deck composite carbon film of Graphene/amorphous carbon film.
Fig. 3 shows embodiment 2 by the prepared Graphene of a secondary growth and the fluorescence Raman spectrogram of amorphous carbon film.Wherein (a) is the fluorescence Raman spectrum picture of Graphene, and Raman spectrum picture shows D peak (1350cm
-1) substantially do not have, show that gained graphene-structured is orderly, G peak (1580cm
-1) sharp-pointed, broadening is little, shows that graphene-structured is intact, by 2D (2700cm
-1) the known gained Graphene of ratio at peak and G peak is multi-layer graphene; (b) be the fluorescence Raman spectrum picture of amorphous carbon film, Raman spectrum picture shows G peak (1580cm
-1) higher than D peak (1400cm
-1), there is not 2D peak (2700cm
-1), but there is D+G peak (2970cm
-1), show that amorphous carbon film structure is obviously different from Graphene.
Fig. 4 shows embodiment 2 by the picture of the scanning electronic microscope of the prepared Graphene of a secondary growth and amorphous carbon film.Wherein (a) be Graphene the picture of scanning electronic microscope, Graphene surface continuously and also inclusion-free particle adhere to; (b) be the picture of the scanning electronic microscope of amorphous carbon film, amorphous carbon film has the constructional feature of porous, and pore diameter distribution is at 10nm-50nm, and surface does not have impurity.Fig. 4 shows that Graphene and amorphous carbon film are intact separated, and noresidue, does not influence each other each other.
Fig. 5 shows embodiment 2 by the picture of the high resolution transmission electron microscopy of the prepared Graphene of a secondary growth and amorphous carbon film and chooses accordingly electron diffraction picture (upper right corner).Wherein (a) is picture and the corresponding selected area electron diffraction (upper right corner) of the high resolution transmission electron microscopy of Graphene, inclusion-free between number layer graphene, and structural integrity is orderly; (b) be picture and the corresponding selected area electron diffraction (upper right corner) of the high resolution transmission electron microscopy of amorphous carbon film, carbon film inclusion-free adheres to, and selected area electron diffraction shows that carbon film is amorphous carbon film.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. a method of simultaneously preparing Graphene and porous amorphous carbon film, is characterized in that, comprises the steps:
S1: metallic nickel sheet substrate is carried out to ultrasonic cleaning, and be positioned in tube furnace after drying;
S2: pass into rare gas element in described tube furnace;
S3: described tube furnace is carried out to hyperthermic treatment and make it reach 750 ℃～1000 ℃ and keep 10 minutes～50 minutes, pass into hydrogen in described tube furnace, and described metallic nickel sheet substrate is heat-treated;
S4: pass into the hydrocarbon polymer that flow is 20sccm～100sccm in described tube furnace, make after metallic nickel sheet substrate catalytic hydrocarbon cracking after Overheating Treatment and the molten carbon of nickel sheet growing graphene and amorphous carbon film simultaneously;
S5: to the processing of lowering the temperature of described tube furnace, and obtain Graphene and porous amorphous carbon film after growth is had the nickel sheet of Graphene and amorphous carbon film to be immersed in to erode substrate nickel sheet in corrosive fluid.
2. the method for claim 1, is characterized in that, in step S3, the flow that passes into hydrogen is 50sccm～200sccm.
3. the method for claim 1, is characterized in that, in step S5, described corrosive fluid is ferric chloride in aqueous solution.
4. preparation method as claimed in claim 1, is characterized in that, in step S2, described rare gas element is at least one in argon gas or helium.
5. the preparation method as described in claim 1-4 any one, is characterized in that, in step S2, the flow that passes into rare gas element is 50sccm～500sccm.
6. preparation method as claimed in claim 1, is characterized in that, described hydrocarbon polymer is any one or arbitrarily multiple combination in methane, ethane, propane, butane, hexane, pentane, heptane, octane, propylene, ethene, butylene, amylene, acetylene.
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| CN105355465A (en) * | 2015-11-13 | 2016-02-24 | 哈尔滨工业大学 | Preparation method of amorphous carbon/vertical graphene composite electrode material |
| CN105779965A (en) * | 2016-01-21 | 2016-07-20 | 北京师范大学 | Method for preparing porous doped diamond-like carbon thin film by utilizing particle beam control technology |
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