CN103193216B - Preparation method of carbon nano composite material - Google Patents
Preparation method of carbon nano composite material Download PDFInfo
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- CN103193216B CN103193216B CN201310126385.1A CN201310126385A CN103193216B CN 103193216 B CN103193216 B CN 103193216B CN 201310126385 A CN201310126385 A CN 201310126385A CN 103193216 B CN103193216 B CN 103193216B
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Abstract
The invention discloses a preparation method of a carbon nano composite material, and belongs to the field of nano material research. The method comprises the following steps of: preparing single layer or multi-layer graphene by using a CVD (Chemical Vapor Deposition) method; subsequently transferring the graphene to a target substrate; coating etching gel on the structure of the graphene and the target substrate; bombarding by using an inductive coupling plasma method so as to denaturalize the etching gel, and subsequently soaking and removing the residual etching gel; carrying out high temperature treatment on the bombarded etching gel, the graphene and the target substrate together so as to carbonize the etching gel and form the carbon nano composite material. The thickness of the obtained intensively distributed carbon nano material with high conduction property and large ratio area is about 50-200nm; the diameter of each carbon nano line is more than about 10 nanometers; and the length is dozens of nanometers.
Description
Technical field:
The invention belongs to the development field of nano material, be specifically related to a kind of preparation method of carbon nano-composite material.
Background technology:
Carbon nanomaterial has important application on the electrode of lithium ion battery, absorbing material, magnetic material, and no matter being applied to this kind, which aspect material all needs specific surface area large, improves conductance property.Wherein Graphene is as a kind of two-dimensional material of monoatomic layer; there is excellent electricity, calorifics, magnetics and mechanical property; particularly carrier mobility is high, thermal conductivity is high; present certain magnetic; existing very high Young's modulus, soft again, in lithium ion battery, absorbing material and magneticsubstance etc., there is potential application prospect (J.Luo et al.; J.Phys.Chem.Lett.3,1824-1829 (2012); J Tang et al., Macromolecules41,493-496 (2008); Diandra L.Leslie-Pelecky, Chem.Mater.8,1770-1783 (1996), although Graphene has above-mentioned excellent specific property, if be applied to above-mentioned field to still have open defect, topmost problem is that its specific surface area is limited.Usually at present, graphenic surface is processed into various figure for increasing its specific surface area, but the electricity of its intrinsic, calorifics, magnetics and mechanical property can be affected, therefore be badly in need of, under the prerequisite do not changed or reduce Graphene intrinsic property as far as possible, increasing substantially the specific surface area of graphenic surface.
Summary of the invention:
The present invention is directed to the problems referred to above, propose a kind of and the preparation big area of CMOS technology compatibility, the carbon nano-composite material of high-specific surface area method.
Technical scheme provided by the invention is as follows:
A preparation method for carbon nano-composite material, as shown in Figure 1, specifically comprises the steps:
1) CVD method is utilized to prepare the Graphene of individual layer, bilayer or multilayer: to flow down at argon gas and hydrogen mixed gas when preparing Graphene and carry out, catalyzer can be the metals such as Cu, Ni, Fe, prepare the temperature range of Graphene at 400 DEG C-1200 DEG C, carbon source can be solid carbon source, gaseous carbon source, liquid carbon source;
2) Graphene is shifted to target substrate: be coated on a side of the metallic film being coated with Graphene by photoresist spinner by polymkeric substance (as: PMMA, PDMS), and the Graphene of its other one side is removed by inductively coupled plasma (ICP) bombardment method, and then by the method such as electrochemical method or wet etching, metal catalyst is etched away, and be placed in target substrate on the surface, finally remove PMMA, the Graphene be transferred to can be obtained.The speed range of whirl coating is 1000r/min-5000r/min, the design parameter of inductively coupled plasma used (ICP) is: RIE:25W-150W, ICP:0W-150W, air pressure: 5mtorr-120mtorr, oxygen flow is: 5sccm-100sccm, remove PMMA organic solvent used and have the multiple organic solvents such as acetone, toluene or chloroform, target substrate can be semi-conductor (as: Si, GaN, GaAs etc.), conductive surface (as: Au, Ag, Pt, Pd metal, conductive polymers etc.) or insulant (as: SiO
2, graphite oxide, glass, plastics etc.).
3) apply photoresist material at the structure of Graphene and target substrate, bombard, make photoresist material sex change by the method for inductively coupled plasma (ICP), then bubble falls remaining light photoresist material; Selected photoresist material can be auspicious red 304-25,5350 etc.The parameter of bombardment: RIE is between 25W-150W, ICP is between 0W-250W, and air pressure is between 5mtorr-120mtorr, and oxygen flow is: 5sccm-100sccm, bombardment time can between 2min-100min, and photoresist thickness can between 50nm-500nm.
4) the more above-mentioned photoresist material through bombardment, Graphene and target substrate are carried out pyroprocessing in the lump, make photoresist material carbonization, carbonization object increases electroconductibility.This process need pyroprocessing in a vacuum or inert atmosphere, its object mainly prevents carbon material to be oxidized.Before and after photoresist material high temperature cabonization, pattern is substantially constant, is as highdensity tufted nano wire film structure.Concrete processing parameter: temperature range is between 300 DEG C-1200 DEG C, and annealing time is between 10min-150min, and annealing can under vacuo, also can be carried out with under rare gas element (as: argon gas).
Advantage of the present invention and technique effect as follows:
The thickness of the nanostructure of the large specific area of higher conductivity that has of the dense distribution that the present invention obtains is probably 50 ~ 200nm, and the diameter of each carbon nano wire bar is probably tens nanometers, and length is tens nanometer.A large amount of carbon nano wire bars is assembled at lines top, and the contact of graphenic surface and carbon nano wire bar is good.Can big area preparation, by the advantages of the excellent electroconductibility of Graphene and the bigger serface of carbon nanotube, thus the adsorptive power of larger lithium ion can be had, improve cell container, the electrology characteristics such as increase load electric density.Therefore very large application prospect is had in the battery improving lithium ion and super capacitor performance.In addition, the present invention's equipment used is comparatively simple, and preparation cost is cheap.
Accompanying drawing illustrates:
Fig. 1 is for preparing preparation flow schematic diagram needed for sample;
Fig. 2 is parameter schematic diagram prepared by Graphene of the present invention
Fig. 3 is the scanning electron microscope diagram of composite nanostructure of the present invention;
Fig. 4 is the Raman spectrogram of composite nanostructure of the present invention.
Embodiment:
Test method described in following example, if no special instructions, is ordinary method, and affiliated reagent and material all can obtain from commercial channels.
(1) prepare Graphene: it is CVD method that the present invention prepares what adopt inside Graphene step, carry out catalyzed reaction with metal and prepare individual layer, double-deck Graphene.For the two-dimensional nanostructure of the large-area Graphene of preparation, as shown in Figure 2, concrete step is specific as follows:
1. by Copper Foil (99.8%, alpha likes Sha, 0.25 μm) put into the silica tube of tube furnace, argon gas and hydrogen (H2:Ar=15sccm:150sccm) is passed into after sealing, exhausted air, drain only until air and heat, generally heat to 1000 DEG C with the speed of 25 DEG C/min, insulation 30min.
2. methane (CH is passed into
4=3sccm), pass into ten minutes, close methane; start cooling and be cooled to room temperature, period uses argon gas and hydrogen shield always, and the object of argon gas is to prevent entering of oxygen; the object passing into hydrogen is to reduce the cupric oxide of copper foil surface, ensureing the cleaning on copper surface.
(2) Graphene is shifted: after preparing large-area Graphene, need Graphene to transfer to SiO
2target substrate is come, and concrete operation steps is as follows:
1. having the side of Graphene to coat PMMA, photoresist spinner rotating speed used is 4000r/min, and the time is 50 seconds.
2. ICP is put in the side of the Copper Foil of non-gluing to etch, RIE is 45W, and the time is 3min, and air pressure is 20mtorr, and the set(ting)value of oxygen flow is 20sccm.The Graphene of the side of non-gluing is etched away, by target substrate Graphene and PMMA composite structure is taken out and naturally dry.
3. sample is put into the acetone of 55 DEG C, Heating Water 3-30 hour, object removes the PMMA glue above Graphene, puts into Virahol successively and deionized water cleans after taking out sample, and naturally dry, now, prepared by the substrate with Graphene.
(3) nanostructured carbon material film is prepared.Gluing on prepared Graphene, prepares nano composite structure with the bombardment of ICP beam-plasma.Coat auspicious red 304-25 photoresist material by transferring to the target Graphene sunk to the bottom above, rotating speed is 4000r/min.Then inductively coupled plasma etching machine is put in the side of gluing, wherein parameter RIE is 55W, selects 25min, and the positively charged ion power of etching and etching time are inversely proportional to, and air pressure is 20mtorr, and the set(ting)value of oxygen flow is 20sccm.
(4) put into acetone after being taken out by the sample of oxygen plasma etch and steep 20min, photoresist material residual above removal.
(5) by the Graphene composite nanostructure high temperature annealing carbonization of preparation.Sample is put into tube furnace, first argon gas (500sccm) is used to lead to 3min, the air of silica tube is ensured to discharge, then heat with the speed of 25 DEG C/min, heating and heat preservation in argon atmospher stream, carbonization temperature is 340 DEG C-1200 DEG C, specifically can determine according to the carbonization temperature of the heat resisting temperature of different matrixes and photoresist material, this example preferentially takes 800 DEG C, and soaking time is 60min.
After above-mentioned process, the nano structure membrane of homogeneous, a large amount of nano-sized carbon nano wires can be found at sample surfaces.
Optimum condition of the present invention is: the Graphene preparation temperature of 1000 DEG C, passes into methane 3min, and the photoresist material used is auspicious red 304-25 type photoresist material, the parameters of ICP: RIE is 55W, and the time selects 25min, and ICP is 0W, air pressure is 20mtorr, and the set(ting)value of oxygen flow is 20sccm; Acetone soak time is 20min, and carbonization temperature is 800 DEG C, and soaking time is 1 hour.Accompanying drawing 3(a), Fig. 3 (b) shows is electron scanning micrograph, there is the carbon nano wire of the homogeneous tufted of homogeneous, a large amount of diameter lengths in sample surfaces as can be seen here, its thickness is about about tens nanometer, and the top of the carbon nano wire of cluster focuses on together.Accompanying drawing 4 is Raman collection of illustrative plates, and the carbon nano wire membrane structure of the cluster as seen after high temperature cabonization is primarily of Graphene and decolorizing carbon composition.
The embodiment of description is above not limited to the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention, can make various changes and amendment, and therefore protection scope of the present invention is that right defined.
Claims (4)
1. a preparation method for carbon nano-composite material, specifically comprises the steps:
1) CVD method is utilized to prepare single or multiple lift Graphene;
2) Graphene is transferred in target substrate;
3) photoresist material is applied at the structure of Graphene and target substrate, bombard with inductance Coupled Plasma Method, make photoresist material sex change, then bubble falls remaining photoresist material, specifically comprises: photoresist material thickness is between 50nm-500nm, the parameter of bombardment: RIE is between 25W-150W, ICP is between 0W-250W, air pressure is between 5mtorr-120mtorr, and oxygen flow is: 5sccm-100sccm, and bombardment time is between 2min-100min;
4) the above-mentioned photoresist material through bombardment, Graphene and target substrate are carried out pyroprocessing in the lump, make photoresist material carbonization, form carbon nano-composite material.
2. the preparation method of carbon nano-composite material as claimed in claim 1, it is characterized in that, step 1) described in CVD method to prepare grapheme material carbon source used be solid-state carbon source, liquid carbon source or gaseous carbon source, catalyzer is Cu, Ni, Fe metallic film, and in heat-processed, furnace temperature is raised between 400 DEG C to 1200 DEG C.
3. the preparation method of carbon nano-composite material as claimed in claim 1, it is characterized in that, step 2) concrete steps are: by photoresist spinner PMMA are coated on the Graphene on metallic film one side, and the Graphene of the another side of metallic film is removed by inductively coupled plasma bombardment, and then by electrochemical method or wet etching method, metallic film is etched away, Graphene is placed in target substrate surface, removes PMMA, obtains the Graphene be transferred in target substrate.
4. the preparation method of carbon nano-composite material as claimed in claim 1, it is characterized in that, step 4) pyroprocessing in a vacuum or inert atmosphere, concrete processing parameter: temperature range is between 300 DEG C-1200 DEG C, and annealing time is between 10min-150min.
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| CN102180439A (en) * | 2011-03-31 | 2011-09-14 | 华中科技大学 | Carbon microtructure with graphene integrated on surface and preparation method thereof |
| CN102719803A (en) * | 2012-07-09 | 2012-10-10 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing and transferring graphene transparent film |
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| CN102180439A (en) * | 2011-03-31 | 2011-09-14 | 华中科技大学 | Carbon microtructure with graphene integrated on surface and preparation method thereof |
| CN102719803A (en) * | 2012-07-09 | 2012-10-10 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing and transferring graphene transparent film |
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