CN102963885A - Catalyst-free method for preparing graphene in large area - Google Patents
Catalyst-free method for preparing graphene in large area Download PDFInfo
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- CN102963885A CN102963885A CN2012104689654A CN201210468965A CN102963885A CN 102963885 A CN102963885 A CN 102963885A CN 2012104689654 A CN2012104689654 A CN 2012104689654A CN 201210468965 A CN201210468965 A CN 201210468965A CN 102963885 A CN102963885 A CN 102963885A
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Abstract
The invention relates to a catalyst-free method for preparing graphene in large area. The mechanism of the catalyst-free method is as follows: heat treatment is carried out on an organic matter film on a support at high temperature, and the organic matter film is carbonized in a temperature raising process and further is graphitized at the high temperature, so that the graphene is formed. The catalyst-free method provided by the invention can be realized by virtue of in situ heat treatment or vapour deposition. Compared with the prior art, the catalyst-free method provided by the invention has the advantages that no catalyst is required when the graphene grows, the graphene directly grows on the required support, operation is extremely simple and convenient, operability is strong, reliability is strong, dependency to the support is low, and the catalyst-free method provided by the invention can be applied to mass production.
Description
Technical field
The present invention relates to the method that situ heat treatment or vapour deposition process catalyst-free prepare grapheme material on a large scale.
Background technology
Graphene is by carbon atom SP
2
The monoatomic layer polynuclear plane that hydridization forms, thickness only be 200,000 of hairline/.The grapheme material of individual layer is to be waited by professor Geim of Univ Manchester UK at first to use the high oriented graphite of adhesive tape mechanically peel and obtain the earliest.This material has excellent electronics, calorifics and mechanical property, has broad application prospects.Thereby, since finding, caused very soon widely and paid close attention to.The at present preparation of Graphene mainly contains several method: (Science 2004 for Novoselov, K.S. etc. for the mechanically peel method, 306,666), epitaxy (Berger, C. wait Science 2006,312,1191), graphite chemistry oxidation reduction process (Hernandez, the Nature Nano 2008,3 such as Y., 563) with chemical Vapor deposition process (Li, X. wait Science 2009,324,1312) etc.Wherein chemical Vapor deposition process most possibly is used to prepare the grapheme material of Large-Area-Uniform.But in the method for the present process for preparing graphenes by chemical vapour deposition that develops, mostly need metal to grow as catalyzer, in application, just need to transfer to Graphene in the needed substrate like this.This transfer process can cause Graphene fold, break, the problem such as chemical pollution and cost up.Thereby, need a kind of low cost of development not need the directly technology of large area deposition Graphene on needed upholder of catalyzer.
Summary of the invention
The object of the invention is to overcome shortcomings and deficiencies of the prior art, a kind of technology that does not need catalyzer directly to prepare Graphene at upholder is provided.Mechanism of the present invention is, at high temperature by organic thin film on the thermal treatment upholder, makes organic thin film in the process that heats up carburizing reagent occur, and the greying reaction further occurs when reaching a high temperature, thereby form Graphene.
Based on this mechanism, under the condition that does not need catalyzer, the present invention can realize (being method and technology scheme step) by following technological line: (1) is by some processing mode, such as spin coating, immersion, thermal evaporation, drip etc. or its hybrid mode, organism is attached to forms film on the upholder; (2) thermal treatment is attached with the upholder of organic thin film under high temperature and oxygen-free environment, makes it that carburizing reagent and greying occur.The temperature of processing is not less than 750 degrees centigrade usually.After the cooling, on upholder, can find Graphene.
Adopt the situ heat treatment technology as concrete example, implementation method is: organism is attached to forms film on the upholder, the organism of handling well and upholder are inserted in the anaerobic heating cavity, make it process for some time being not less than under 750 degrees centigrade the temperature, take out after the cooling, obtain Graphene at upholder.
Adopt gas phase deposition technology as concrete example, implementation method is: organism is placed in the anaerobic cavity, it is evaporated under suitable temperature, upholder is put into the anaerobic cavity that this contains organic molecule, upholder places in the warm area that is not less than 750 degrees centigrade, the organism volatile matter is transferred to formed film on the upholder, processes for some time, take out after the cooling, obtain Graphene at upholder.
The arbitrary substance of above support for bearing temperature of reaction (being not less than 750 degrees centigrade) and not reacting with carbon.
Described organism can select can occur arbitrarily the organism of carburizing reagent as reaction raw materials, such as resol, protein, polyethylene terephthalate, and perhaps mixture of their arbitrary combination and any proportioning etc.Again for example, this organic matter raw material can be selected commercially available photoresist material product.
Catalyst-free big area of the present invention prepares the method for Graphene, can or utilize CVD (Chemical Vapor Deposition) method (be that the thermal evaporation organism forms film to the upholder surface, carbonization and greying occur simultaneously) to realize by situ heat treatment organism/upholder.Compared with prior art, the present invention does not need catalyzer in growing graphene, directly grows at needed upholder, operates extremely easyly, workable, and reliability is strong, and not high to the dependency of upholder, can be used for scale operation.
Description of drawings
Fig. 1 situ heat treatment technology is at upholder preparation Graphene device synoptic diagram.
Fig. 2 vapour deposition process prepares Graphene device synoptic diagram.
Fig. 3 is the optical microscope photograph of the Graphene that forms at SiO2/Si among the embodiment 1.
Fig. 4 is the transmission electron microscope photo of prepared product among the embodiment 2.
Fig. 5 is the transmission electron microscope photo of Graphene on carbon nanotube prepared among the embodiment 3.
Fig. 6 by embodiment 4 the optical microscope photograph of acquisition product.
Fig. 7 by embodiment 5 the atomic force microscopy of acquisition product.
Description of symbols among the figure: 1 is process furnace, and 2 is heating chamber, and 34 is organism and upholder mixture, and 3 is organism, and 4 is upholder.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.Participate in all reagent raw materials of reaction among the embodiment and be the commercially available prod, the photoresist material product is commercially available RZJ-304 photoresist material.
The situ heat treatment method
Adhering to of the first step, organism and upholder: can then the organism wiring solution-forming be spun to them in the smooth substrate, perhaps be dipped on the material, it is first-class perhaps to be applied to substrate.Then solvent evaporates is fallen at low temperatures heating.So just sample is disposed in earlier stage.
Second step, the sample that the thermal treatment the first step is handled well.Thermal treatment unit synoptic diagram such as Fig. 1.First thermal treatment unit is raised to and is not less than 750 degrees centigrade, the sample of under oxygen-free environment the first step being handled well is placed on the warm area, heat treated for some time (more than 10 seconds).Then take out after the cooling.Organism on upholder changes Graphene into.
Perhaps adopt vapour deposition process, synoptic diagram such as Fig. 2, step is as follows: organism is put into the boat body, then insert in the anaerobic cavity, the temperature of cavity raises organic molecule can be volatilized, upholder placement location temperature is not less than 750 degrees centigrade, and upholder can be in organism optional position all around.Thermal treatment is more than 0.5 minute, and cooling is taken out.There is Graphene to exist on the upholder.
Oxygen-free environment can form with the common mechanical pump.Can in heat treated process, add non-oxidizing gas, such as nitrogen, argon gas, the protections such as hydrogen or its gas mixture.
The first step, resol is dissolved in the polymethacrylate;
Second step, the phenol resin solution that forms is spun in the SiO2/Si substrate;
Second step, the good resol/SiO2/Si of spin coating 110 degrees centigrade of lower heated bakings 2 minutes;
The 3rd step, heating cavity are warming up to 900 degrees centigrade;
The 4th the step, resol/SiO2/Si is put into cavity, vacuumize, pass into simultaneously 100 SCCM, 5% H2/Ar gas mixture.
The 5th the step, resol/SiO2/Si is inserted 900 degrees centigrade of warm area places, after 10 minutes, sample is dragged away from from warm area in the situation of not destroying original environment, be cooled to room temperature.
Open cavity and take out the SiO2/Si substrate, the above covers a layer graphene, sees that Fig. 3 is its atomic force microscopy.Fig. 3 is got by atomic force microscope (Suzhou Hai Zisi nanosecond science and technology company limited, Nanofirst 3600A AFM) observation post, shows that film thickness is about 1nm, and the typical thickness of this and Graphene is suitable, illustrates that it is Graphene.
Step changes substrate into copper sheet with embodiment 1.The transmission electron microscope result shows that it is Graphene, sees Fig. 4.Fig. 4 is by transmission electron microscope (FEI Co., Tecnai F20) under 200 KV, obtains, can find out significantly that sample has the Graphene lattice fringe, corresponding fourier transformation (interior illustration) shows that it is the crystalline structure of Graphene, illustrates that it is Graphene.
The first step, get resol/polymethacrylate solution 1 ml, carbon nanotube 20 mg mix;
Second step, the oven dry under 110 degrees centigrade mentioned solution and carbon nanotube mixture;
The 3rd one, resol and the carbon nanotube mixture of oven dry in the same manner as in Example 1 method steps processing.The transmission electron microscope result shows that it is the Graphene (see figure 5).Fig. 5 is obtained under 200 KV by transmission electron microscope (FEI Co., Tecnai F20), can find out significantly that sample comprises the crystalline structure of carbon nanotube and Graphene, and wherein Graphene is to be come by the resol transformation that is attached on the carbon nanotube.
The first step, get an amount of resol and insert in the quartz boat;
Second step, heating cavity are warmed up to 900 degrees centigrade;
The 3rd goes on foot, the quartz boat that is placed with resol and clean SiO2/Si substrate is inserted in the cavity, vacuumizes, passes into simultaneously 100 SCCM, 5% H2/Ar gas mixture;
The 4th the step, the quartz boat that is placed with resol and clean SiO2/Si substrate are inserted 900 degrees centigrade of warm area places, after 10 minutes, clean SiO2/Si is dragged away from from warm area in the situation of not destroying original environment, be cooled to room temperature;
The 5th goes on foot, opens cavity takes out the SiO2/Si substrate, the above covers a layer graphene, see Fig. 6, by atomic force microscope (Suzhou Hai Zisi nanosecond science and technology company limited, Nanofirst 3600A AFM) observation post gets, show that film thickness is about 1nm, the typical thickness of this and Graphene is suitable, illustrates that it is Graphene.
The first step, get an amount of photoresist material (for the commercially available prod, model RZJ-304) and be spun in the SiO/Si substrate;
Second step, heating cavity are warmed up to 900 degrees centigrade;
The 3rd goes on foot, photoresist material/SiO2/Si is inserted in the cavity, vacuumizes, passes into simultaneously 100 SCCM, 5% H2/Ar gas mixture;
The 4th the step, photoresist material/SiO2/Si is inserted 900 degrees centigrade of warm area places, after 10 minutes, sample is dragged away from from warm area in the situation of not destroying original environment, be cooled to room temperature;
The 5th goes on foot, opens cavity takes out the SiO2/Si substrate, the above covers a layer graphene, see Fig. 7, by atomic force microscope (Suzhou Hai Zisi nanosecond science and technology company limited, Nanofirst 3600A AFM) observation post gets, show that film thickness is about 1nm, the typical thickness of this and Graphene is suitable, illustrates that it is Graphene.
Embodiment 6
Reactant is replaced into the photoresist material that model is RZJ-304 with the polyethylene terephthalate among the embodiment 1, and the additive method step also can be found a layer graphene with embodiment 5 in the last substrate.
Claims (8)
1. a catalyst-free big area prepares the method for Graphene, it is characterized in that its method steps is:
(1) organism is attached to forms film on the upholder;
(2) thermal treatment is attached with the upholder of organic thin film under high temperature and oxygen-free environment, makes it that carburizing reagent and greying occur, and the temperature of processing is not less than 750 degrees centigrade usually, after the cooling, obtains graphene layer at upholder.
2. the method for claim 1, it is characterized in that, specific implementation method is: organism is attached to forms film on the upholder, the organism of handling well and upholder are inserted in the anaerobic heating cavity, make it process for some time being not less than under 750 degrees centigrade the temperature, take out after the cooling, obtain Graphene at upholder.
3. the method for claim 1, it is characterized in that, specific implementation method is: organism is placed in the anaerobic cavity, it is evaporated under suitable temperature, upholder is put into the anaerobic cavity that this contains organic molecule, and upholder places in the warm area that is not less than 750 degrees centigrade, the organism volatile matter is transferred to formed film on the upholder, take out after the cooling, obtain Graphene at upholder.
4. such as claim 1 or 2 or 3 described methods, it is characterized in that organism is attached to and forms film on the upholder, the employing processing mode is spin coating, immersion, thermal evaporation, drips or its hybrid mode.
5. such as claim 1 or 2 or 3 described methods, it is characterized in that the material of above support is not less than 750 degrees centigrade and the material that do not react with carbon for bearing temperature of reaction.
6. such as claim 1 or 2 or 3 described methods, it is characterized in that described organism is for the organism of carburizing reagent can occur.
7. method as claimed in claim 6 is characterized in that, described organism is resol, protein or polyethylene terephthalate, perhaps the mixture of their arbitrary combination and any proportioning.
8. method as claimed in claim 6 is characterized in that, described organism, and this organic matter raw material is selected commercially available photoresist material product.
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Citations (6)
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| CN101891187A (en) * | 2010-07-26 | 2010-11-24 | 南京理工大学 | Low-temperature soft template one-step synthesis method for graphitized ordered mesoporous carbon material |
| US20110169013A1 (en) * | 2010-01-12 | 2011-07-14 | Cree, Inc. | Growing polygonal carbon from photoresist |
| CN102161482A (en) * | 2011-01-25 | 2011-08-24 | 中国科学院化学研究所 | Method for preparing graphene |
| 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 |
| CN102259849A (en) * | 2011-06-09 | 2011-11-30 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by utilizing solid carbon source |
| CN102543269A (en) * | 2012-01-20 | 2012-07-04 | 中国科学院上海硅酸盐研究所 | High-quality graphene transparent conductive film and production method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110169013A1 (en) * | 2010-01-12 | 2011-07-14 | Cree, Inc. | Growing polygonal carbon from photoresist |
| CN101891187A (en) * | 2010-07-26 | 2010-11-24 | 南京理工大学 | Low-temperature soft template one-step synthesis method for graphitized ordered mesoporous carbon material |
| CN102161482A (en) * | 2011-01-25 | 2011-08-24 | 中国科学院化学研究所 | Method for preparing graphene |
| 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 |
| CN102259849A (en) * | 2011-06-09 | 2011-11-30 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by utilizing solid carbon source |
| CN102543269A (en) * | 2012-01-20 | 2012-07-04 | 中国科学院上海硅酸盐研究所 | High-quality graphene transparent conductive film and production method thereof |
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Application publication date: 20130313 |