CN101979315B - Preparation method of monoatomic-layer graphene film - Google Patents
Preparation method of monoatomic-layer graphene film Download PDFInfo
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- CN101979315B CN101979315B CN201010546602A CN201010546602A CN101979315B CN 101979315 B CN101979315 B CN 101979315B CN 201010546602 A CN201010546602 A CN 201010546602A CN 201010546602 A CN201010546602 A CN 201010546602A CN 101979315 B CN101979315 B CN 101979315B
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Abstract
The invention relates to preparation technology of graphene, in particular to a preparation method of a monoatomic-layer graphene film. The method comprises the following steps of: putting a silicon carbide substrate in the reaction chamber of atomic layer deposition equipment; introducing carbon source gas into the reaction chamber of the atomic layer deposition equipment and chemically adsorbing the carbon source gas serving as a first reaction precursor on the surface of the silicon carbide substrate; performing a helogenation reaction on the carbon source gas and a second introduced reaction precursor so as to produce a corresponding byproduct until the carbon source gas on the surface of the silicon carbide substrate is fully consumed; and after the halogenation reaction is stopped, illuminating the corresponding byproduct so as to form the monoatomic layer grapheme film on the surface of the silicon carbide substrate. In the method, the graphene film is prepared by atomic layer deposition technology; the preparation method is easy to operate, has high conversion rate and low energy consumption; moreover, the prepared graphene film has a complete structure and uniform monoatomic-layer thickness.
Description
Technical field
The present invention relates to the technology of preparing of Graphene, be specifically related to a kind of preparation method of monoatomic layer graphene film.
Background technology
After scientist in 2004 successfully separated Graphene, Graphene had caused that at once everybody pays close attention to widely.This is because Graphene has good mechanical, calorifics and electrical properties.In terms of mechanics: the connection in the Graphene between each carbon atom is very pliable and tough, and when applying external mechanical force, the carbon atom face adapts to external force with regard to flexural deformation thereby carbon atom needn't be arranged again, has also just kept Stability Analysis of Structures.Aspect calorifics: the appearance of Graphene has been broken theoretical and the experiment circle thinks that perfect two-dirnentional structure can't be in the viewpoint of non-zero absolute temperature stable existence, and this ascribes the microcosmic distortion of Graphene on Nano grade to.Aspect electricity: stable crystalline network makes carbon atom have outstanding electroconductibility, and electronics does not have quality in the Graphene, and is to move with constant speed.Graphene has also shown unusual integer quantum Hall behavior, and its Hall electricity is led and equaled 2e2/h, 6e2/h, and 10e2/h ..., the odd of leading for the quantum electricity, and can at room temperature observe.These characteristics of Graphene make it in fields such as electronics, storing hydrogen, nano-device and invented solid gas dependent sensors important use arranged.
Graphene is wanted and can be used widely, and its prerequisite is to make the grapheme material that has thickness in monolayer on the stricti jurise.And the normal at present method of using has mechanically peel method, epitaxial growth method, chemical Vapor deposition process and graphite oxide reduction method.The Graphene sample that the mechanically peel method can obtain to be of high quality, but its complex operation step, efficient is low, and output is little.Epitaxial growth method and chemical Vapor deposition process all are decomposition compound at high temperature, except that energy consumption greatly, substrate also is to need a problem considering to the influence of product.The employed oxygenant of graphite oxide reduction method has destruction to graphite linings, and the Graphene of gained is of poor quality and more defective arranged.Above the whole bag of tricks also has a defective, promptly can not make uniform in thickness and have the grapheme material of monoatomic layer thickness.
Summary of the invention
The problem that the present invention will solve provides a kind of preparation method of monoatomic layer graphene film, and this method is simple to operate, and transformation efficiency is high, and energy consumption is little, and the graphene film structural integrity that makes, and uniform in thickness is monoatomic layer thickness.
In order to achieve the above object, the technical scheme of the present invention's employing is: a kind of preparation method of monoatomic layer graphene film comprises the steps:
Silicon carbide substrates is positioned in the atomic layer deposition apparatus reaction chamber;
In said atomic layer deposition apparatus reaction chamber, feed carbon-source gas, said carbon-source gas carries out chemisorption as the first reaction precursor body on the silicon carbide substrates surface;
The second reaction precursor body generation halogenating reaction of said carbon-source gas and feeding, and produce corresponding by product, carbon-source gas completely consumed up to the silicon carbide substrates surface;
After said halogenating reaction stopped, corresponding by product formed the monoatomic layer graphene film through illumination on the silicon carbide substrates surface.
In the such scheme, it is the crystal face of (0001) that said silicon carbide substrates is selected crystalline orientation for use, and is the terminal with the carbon atom.
In the such scheme, saidly before silicon carbide substrates being positioned over step in the atomic layer deposition apparatus reaction chamber, also comprise: silicon carbide substrates is carried out hydrogen treatment in advance, make substrate surface form hydrocarbon key.
In the such scheme, said carbon-source gas is diazomethane or ketene.
In the such scheme, said diazomethane or ketene carry out chemisorption on the silicon carbide substrates surface condition is illumination or low-temperature heat, and said diazomethane or ketene have not bonding electrons through the degradation production of illumination or low-temperature heat.
In the such scheme, the said second reaction precursor body is a gaseous iodine simple substance.
In the such scheme, said diazomethane or ketene and said gaseous iodine simple substance generation halogenating reaction make that other functional groups beyond the de-carbon are replaced by the iodine atom in diazomethane or the ketene, form unsettled carbon iodine key.
In the such scheme, said carbon iodine key ruptures through illumination, and the spontaneous Cheng Jian of carbon atom forms Graphene on the silicon carbide substrates surface.
In the such scheme, said halogenating reaction carries out under illumination condition.
In the such scheme, said atomic layer deposition apparatus reaction chamber all feeds rare gas element in the front and back that feed the first reaction precursor body or the second reaction precursor body; Said rare gas element is argon gas or nitrogen.
Compared with prior art, the beneficial effect of technical scheme generation of the present invention is following:
The present invention utilizes technique for atomic layer deposition to prepare graphene film, and this preparation method is simple to operate, and transformation efficiency is high, and energy consumption is little, and the graphene film structural integrity that makes, uniform in thickness, and be monoatomic layer thickness.
Description of drawings
Diazomethane that Fig. 1 provides for the embodiment of the invention or ketene and silicon carbide substrates are carried out the process synoptic diagram of chemisorption;
Diazomethane that Fig. 2 provides for the embodiment of the invention or ketene and gaseous iodine simple substance carry out the process synoptic diagram that halogenating reaction forms graphene film;
The vertical view of the graphene film that Fig. 3 provides for the embodiment of the invention with monoatomic layer thickness.
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is described in detail.
Embodiment 1:
A kind of preparation method of monoatomic layer graphene film comprises the steps:
Step 101; Under 50 ℃ of-1000 ℃ of condition of plasma, fed hydrogen 1 minute-60 minutes, crystalline orientation is carried out hydrogen treatment for silicon carbide substrates (0001) crystal face, that with the carbon atom be the terminal; Make the silicon carbide substrates surface form c h bond, shown in a figure among Fig. 1; The silicon carbide substrates that to carry out after the hydrogen treatment is positioned in the atomic layer deposition apparatus reaction chamber;
Step 102 fed argon gas 5 minutes-20 minutes in the atomic layer deposition apparatus reaction chamber, reaction chamber is cleaned; In reaction chamber, fed diazomethane 2 minutes-60 minutes again, use the UV-irradiation of wavelength as 270nm-350nm simultaneously, diazomethane is decomposed, degradation production has not bonding electrons, and the chemical expression that diazomethane decomposes is:
The degradation production carbene (: CH2) with silicon carbide substrates generation insertion reaction; The chemical expression of reaction is:
promptly form methyl structural on the silicon carbide substrates surface, shown in c figure among Fig. 1;
Step 103; In the atomic layer deposition apparatus reaction chamber, fed argon gas 5 minutes-20 minutes; Discharge unreacted diazomethane; Fed gaseous iodine simple substance again 2 minutes-60 minutes, and shown in a figure among Fig. 2, used the high voltage mercury lamp radiation of wavelength simultaneously as 350nm-450nm; Make the methyl structural and the gaseous iodine simple substance generation substitution reaction on silicon carbide substrates surface; Wasserstoffatoms in the methyl structural is replaced by the iodine atom, forms unsettled carbon iodine key, and the chemical expression of substitution reaction is:
shown in b figure among Fig. 2;
Step 104 fed argon gas 5 minutes-20 minutes in the atomic layer deposition apparatus reaction chamber, discharge unreacted gaseous iodine simple substance; With fluorescent lamp irradiation silicon carbide substrates surface; Make the bond rupture of carbon iodine, the spontaneous one-tenth key of remaining carbon atom forms the structure of carbon simple substance, shown in c figure among Fig. 2; The gained material is the graphene film with monoatomic layer thickness, structural integrity, and is as shown in Figure 3.
In the foregoing description, the condition that diazomethane is decomposed is not limited to UV-irradiation, can also carry out low-temperature heat; In the foregoing description, being not limited to argon gas at the rare gas element that front and back fed that feeds diazomethane or gaseous iodine simple substance, can also be helium.
Embodiment 2:
A kind of preparation method of monoatomic layer graphene film comprises the steps:
Step 101 under 50 ℃ of-1000 ℃ of condition of plasma, fed hydrogen 1 minute-60 minutes, and silicon carbide substrates (0001) crystal face, that with the carbon atom be the terminal is carried out hydrogen treatment, made the silicon carbide substrates surface form c h bond, shown in a figure among Fig. 1; The silicon carbide substrates that to carry out after the hydrogen treatment is positioned in the atomic layer deposition apparatus reaction chamber;
Step 102 fed argon gas 5 minutes-20 minutes in the atomic layer deposition apparatus reaction chamber, reaction chamber is cleaned; In reaction chamber, fed ketene 2 minutes-60 minutes again, use UV-irradiation or the low-temperature heat of wavelength as 270nm-350nm simultaneously, ketene is decomposed, degradation production has not bonding electrons, and the chemical expression that ketene decomposes is:
The degradation production carbene (: CH2) with silicon carbide substrates generation insertion reaction; The chemical expression of reaction is:
promptly form methyl structural on the silicon carbide substrates surface, shown in c figure among Fig. 1;
Step 103; In the atomic layer deposition apparatus reaction chamber, fed argon gas 5 minutes-20 minutes; Discharge unreacted diazomethane; Fed gaseous iodine simple substance again 2 minutes-60 minutes, and shown in a figure among Fig. 2, used the high voltage mercury lamp radiation of wavelength simultaneously as 350nm-450nm; Make the methyl structural and the gaseous iodine simple substance generation substitution reaction on silicon carbide substrates surface; Wasserstoffatoms in the methyl structural is replaced by the iodine atom, forms unsettled carbon iodine key, and the chemical expression of substitution reaction is:
shown in b figure among Fig. 2;
Step 104 fed argon gas 5 minutes-20 minutes in the atomic layer deposition apparatus reaction chamber, discharge unreacted gaseous iodine simple substance; With fluorescent lamp irradiation silicon carbide substrates surface; Make the bond rupture of carbon iodine, the spontaneous one-tenth key of remaining carbon atom forms the structure of carbon simple substance, shown in c figure among Fig. 2; The gained material is the graphene film with monoatomic layer thickness, structural integrity, and is as shown in Figure 3.
In the foregoing description, being not limited to argon gas at the rare gas element that front and back fed that feeds ketene or gaseous iodine simple substance, can also be helium.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. the preparation method of a monoatomic layer graphene film is characterized in that, comprises the steps:
Silicon carbide substrates is carried out hydrogen treatment in advance, make substrate surface form hydrocarbon key;
Said silicon carbide substrates is positioned in the atomic layer deposition apparatus reaction chamber, and it is the crystal face of (0001) that said silicon carbide substrates is selected crystalline orientation for use, and is the terminal with the carbon atom;
In said atomic layer deposition apparatus reaction chamber, feed carbon-source gas, said carbon-source gas carries out chemisorption as the first reaction precursor body on the silicon carbide substrates surface, promptly forms methyl structural on the silicon carbide substrates surface; Wherein, Said carbon-source gas is diazomethane or ketene, and said diazomethane or ketene have not bonding electrons through the degradation production of illumination or low-temperature heat, and said have a not degradation production of bonding electrons; With said silicon carbide substrates generation insertion reaction, realize chemisorption;
The second reaction precursor body generation halogenating reaction of said methyl structural and feeding, and produce corresponding by product, methyl structural completely consumed up to the silicon carbide substrates surface; Wherein, the said second reaction precursor body is a gaseous iodine simple substance, and said halogenating reaction carries out under illumination condition;
After said halogenating reaction stopped, corresponding by product formed the monoatomic layer graphene film through illumination on the silicon carbide substrates surface.
2. the preparation method of monoatomic layer graphene film as claimed in claim 1 is characterized in that: said atomic layer deposition apparatus reaction chamber all feeds argon gas or nitrogen in the front and back that feed the first reaction precursor body or the second reaction precursor body.
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| CN102181924B (en) * | 2011-03-30 | 2013-02-06 | 苏州纳维科技有限公司 | Growth method of graphene and graphene |
| CN102344134B (en) * | 2011-09-23 | 2013-03-06 | 中国科学院微电子研究所 | Preparation method of graphite |
| CN102728849B (en) * | 2012-05-08 | 2013-09-18 | 清华大学 | Self-supporting noble metal nanosheet with equal thickness of monatomic layer and preparation method of nanosheet |
| CN102936009B (en) * | 2012-10-11 | 2014-05-21 | 中国电子科技集团公司第五十五研究所 | Method for manufacturing low layer number graphene film on silicon carbide substrate |
| CN103938180A (en) * | 2014-04-23 | 2014-07-23 | 中国科学院山西煤炭化学研究所 | Preparation method of nanocarbon membrane with controllable thickness |
| CN104071780B (en) * | 2014-06-24 | 2016-08-17 | 武汉理工大学 | A kind of preparation method of number of plies controllable grapheme |
| CN104477899B (en) * | 2014-12-12 | 2016-05-25 | 重庆墨希科技有限公司 | A kind ofly prepare the fixture of Graphene and prepare the method for Graphene |
| CN104818526A (en) * | 2015-01-27 | 2015-08-05 | 夏洋 | Preparation method for vapor grown two-dimensional material |
| CN110022623B (en) * | 2019-04-04 | 2020-01-10 | 碳翁(北京)科技有限公司 | Preparation and application of high-temperature-resistant electric heating fiber |
| CN110016803B (en) * | 2019-04-04 | 2019-12-20 | 碳翁(北京)科技有限公司 | High-temperature-resistant electric heating fiber and application thereof |
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| CN101285175A (en) * | 2008-05-29 | 2008-10-15 | 中国科学院化学研究所 | Process for preparing graphenes by chemical vapour deposition method |
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| KR20100129738A (en) * | 2008-03-10 | 2010-12-09 | 고쿠리츠다이가쿠호진 도호쿠다이가쿠 | Graphene or graphite thin film, manufacturing method thereof, thin film structure and electronic device |
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| CN101285175A (en) * | 2008-05-29 | 2008-10-15 | 中国科学院化学研究所 | Process for preparing graphenes by chemical vapour deposition method |
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| Qingsong Huang et al..Epitaxial graphene on 4H-SiC by pulsed electron irradiation.《Chem. Commun.》.2010,第46卷4917-4919. * |
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