CN101979315A - Preparation method of monoatomic-layer graphene film - Google Patents
Preparation method of monoatomic-layer graphene film Download PDFInfo
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- CN101979315A CN101979315A CN 201010546602 CN201010546602A CN101979315A CN 101979315 A CN101979315 A CN 101979315A CN 201010546602 CN201010546602 CN 201010546602 CN 201010546602 A CN201010546602 A CN 201010546602A CN 101979315 A CN101979315 A CN 101979315A
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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 rearranged, and 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-multiple 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 be 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 the thickness homogeneous and have the grapheme material of monoatomic layer thickness.
Summary of the invention
The problem to be solved in the present invention provides a kind of preparation method of monoatomic layer graphene film, and this method is simple to operate, the transformation efficiency height, and energy consumption is little, and the graphene film structural integrity that makes, and the thickness homogeneous is monoatomic layer thickness.
In order to achieve the above object, the technical solution used in the present invention 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;
Feed carbon-source gas in described atomic layer deposition apparatus reaction chamber, described 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 described carbon-source gas and feeding, and produce corresponding by product, carbon-source gas completely consumed up to the silicon carbide substrates surface;
After described 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 described silicon carbide substrates is selected crystalline orientation for use, and is terminal with the carbon atom.
In the such scheme, describedly before the step that silicon carbide substrates is positioned 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, described carbon-source gas is diazomethane or ketene.
In the such scheme, described diazomethane or ketene carry out chemisorption on the silicon carbide substrates surface condition is illumination or low-temperature heat, and described diazomethane or ketene have not bonding electrons through the degradation production of illumination or low-temperature heat.
In the such scheme, the described second reaction precursor body is a gaseous iodine simple substance.
In the such scheme, described diazomethane or ketene and described 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, described carbon iodine key ruptures by illumination, and the spontaneous Cheng Jian of carbon atom forms Graphene on the silicon carbide substrates surface.
In the such scheme, described halogenating reaction carries out under illumination condition.
In the such scheme, described 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; Described rare gas element is argon gas or nitrogen.
Compared with prior art, the beneficial effect of technical solution of the present invention generation is as follows:
The present invention utilizes technique for atomic layer deposition to prepare graphene film, and this preparation method is simple to operate, the transformation efficiency height, and energy consumption is little, and the graphene film structural integrity that makes, the thickness homogeneous, 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 drawings and Examples technical solution 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 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; Feeding diazomethane 2 minutes-60 minutes again in reaction chamber, is the UV-irradiation of 270nm-350nm with wavelength simultaneously, and diazomethane is decomposed, and 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, shown in c figure among Fig. 1 on the silicon carbide substrates surface;
Step 103, in the atomic layer deposition apparatus reaction chamber, fed argon gas 5 minutes-20 minutes, discharge unreacted diazomethane, feeding gaseous iodine simple substance again 2 minutes-60 minutes, shown in a figure among Fig. 2, is the high voltage mercury lamp radiation of 350nm-450nm with wavelength simultaneously, make the methyl structural and the gaseous iodine simple substance generation substitution reaction on silicon carbide substrates surface, hydrogen atom 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, 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 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; Feeding ketene 2 minutes-60 minutes again in reaction chamber, is UV-irradiation or the low-temperature heat of 270nm-350nm with wavelength simultaneously, and ketene is decomposed, and 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, shown in c figure among Fig. 1 on the silicon carbide substrates surface;
Step 103, in the atomic layer deposition apparatus reaction chamber, fed argon gas 5 minutes-20 minutes, discharge unreacted diazomethane, feeding gaseous iodine simple substance again 2 minutes-60 minutes, shown in a figure among Fig. 2, is the high voltage mercury lamp radiation of 350nm-450nm with wavelength simultaneously, make the methyl structural and the gaseous iodine simple substance generation substitution reaction on silicon carbide substrates surface, hydrogen atom 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, 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 the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a monoatomic layer graphene film is characterized in that, comprises the steps:
Silicon carbide substrates is positioned in the atomic layer deposition apparatus reaction chamber;
Feed carbon-source gas in described atomic layer deposition apparatus reaction chamber, described 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 described carbon-source gas and feeding, and produce corresponding by product, carbon-source gas completely consumed up to the silicon carbide substrates surface;
After described 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: it is the crystal face of (0001) that described silicon carbide substrates is selected crystalline orientation for use, and is terminal with the carbon atom.
3. the preparation method of monoatomic layer graphene film as claimed in claim 2, it is characterized in that, describedly before the step that silicon carbide substrates is positioned 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.
4. the preparation method of monoatomic layer graphene film as claimed in claim 1 is characterized in that: described carbon-source gas is diazomethane or ketene.
5. the preparation method of monoatomic layer graphene film as claimed in claim 4, it is characterized in that: described diazomethane or ketene carry out chemisorption on the silicon carbide substrates surface condition is illumination or low-temperature heat, and described diazomethane or ketene have not bonding electrons through the degradation production of illumination or low-temperature heat.
6. the preparation method of monoatomic layer graphene film as claimed in claim 5 is characterized in that: the described second reaction precursor body is a gaseous iodine simple substance.
7. the preparation method of monoatomic layer graphene film as claimed in claim 6, it is characterized in that: described diazomethane or ketene and described 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.
8. the preparation method of monoatomic layer graphene film as claimed in claim 7 is characterized in that: described carbon iodine key ruptures by illumination, and the spontaneous Cheng Jian of carbon atom forms Graphene on the silicon carbide substrates surface.
9. the preparation method of monoatomic layer graphene film as claimed in claim 1 is characterized in that: described halogenating reaction carries out under illumination condition.
10. the preparation method of monoatomic layer graphene film as claimed in claim 1 is characterized in that: described 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; Described rare gas element is argon gas or nitrogen.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102181924A (en) * | 2011-03-30 | 2011-09-14 | 苏州纳维科技有限公司 | Growth method of graphene and graphene |
| CN102344134A (en) * | 2011-09-23 | 2012-02-08 | 中国科学院微电子研究所 | Preparation method of graphite |
| CN102728849A (en) * | 2012-05-08 | 2012-10-17 | 清华大学 | Self-supporting noble metal nanosheet with equal thickness of monatomic layer and preparation method of nanosheet |
| CN102936009A (en) * | 2012-10-11 | 2013-02-20 | 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 |
| CN104071780A (en) * | 2014-06-24 | 2014-10-01 | 武汉理工大学 | Preparation method of controllable-layer-number graphene |
| CN104477899A (en) * | 2014-12-12 | 2015-04-01 | 重庆墨希科技有限公司 | Clamp for preparing graphene and method for preparing graphene |
| CN104818526A (en) * | 2015-01-27 | 2015-08-05 | 夏洋 | Preparation method for vapor grown two-dimensional material |
| CN110016803A (en) * | 2019-04-04 | 2019-07-16 | 碳翁(北京)科技有限公司 | A kind of high temperature resistant fibre electroheating and its application |
| CN110022623A (en) * | 2019-04-04 | 2019-07-16 | 碳翁(北京)科技有限公司 | A kind of preparation and application of high temperature resistant fibre electroheating |
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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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| CN102181924B (en) * | 2011-03-30 | 2013-02-06 | 苏州纳维科技有限公司 | Growth method of graphene and graphene |
| CN102181924A (en) * | 2011-03-30 | 2011-09-14 | 苏州纳维科技有限公司 | Growth method of graphene and graphene |
| CN102344134A (en) * | 2011-09-23 | 2012-02-08 | 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 |
| CN102728849A (en) * | 2012-05-08 | 2012-10-17 | 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 |
| CN102936009A (en) * | 2012-10-11 | 2013-02-20 | 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 |
| CN104071780A (en) * | 2014-06-24 | 2014-10-01 | 武汉理工大学 | Preparation method of controllable-layer-number graphene |
| 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 |
| CN104477899A (en) * | 2014-12-12 | 2015-04-01 | 重庆墨希科技有限公司 | Clamp for preparing graphene and method for preparing graphene |
| CN104818526A (en) * | 2015-01-27 | 2015-08-05 | 夏洋 | Preparation method for vapor grown two-dimensional material |
| CN110016803A (en) * | 2019-04-04 | 2019-07-16 | 碳翁(北京)科技有限公司 | A kind of high temperature resistant fibre electroheating and its application |
| CN110022623A (en) * | 2019-04-04 | 2019-07-16 | 碳翁(北京)科技有限公司 | A kind of preparation and application of high temperature resistant fibre electroheating |
| 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 |
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