CN101979707B - Carbon chemical adsorption method for preparing graphene film by using atomic layer deposition - Google Patents
Carbon chemical adsorption method for preparing graphene film by using atomic layer deposition Download PDFInfo
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- CN101979707B CN101979707B CN2010105466048A CN201010546604A CN101979707B CN 101979707 B CN101979707 B CN 101979707B CN 2010105466048 A CN2010105466048 A CN 2010105466048A CN 201010546604 A CN201010546604 A CN 201010546604A CN 101979707 B CN101979707 B CN 101979707B
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Abstract
The invention relates to preparation technology of graphene, in particular to a carbon chemical adsorption method for preparing a graphene film by using atomic layer deposition. A substance containing carbon atoms which have non-bonded electrons is formed, and the carbon atoms and atoms on the surface of a substrate form covalent bonds so that stable chemical adsorption is realized. The adsorption method for preparing the graphene film by using the atomic layer deposition technology is simple and feasible, and can realize stable carbon chemical adsorption.
Description
Technical field
The present invention relates to the technology of preparing of Graphene, be specifically related to a kind of carbon geochemistry adsorption method that ald prepares graphene film that is used for.
Background technology
Graphene is the graphite with monoatomic layer thickness, after successfully being peeled off out in 2004, has received scientist's extensive concern.Because its premium properties aspect electricity, mechanics, calorifics, the performance of semiconductor device of preparing will be superior to silicon-based devices.Grapheme material is a kind of extremely promising material, must replace the status of silicon in semi-conductor, but primary prerequisite is to prepare proper Graphene, promptly has the Graphene of monoatomic layer thickness.Ald (Atomic Layer Deposition; Hereinafter to be referred as ALD) as the novel method for preparing film; Nowadays used widely; The mode that its monoatomic layer is successively grown meets the requirement for preparing Graphene, but will realize that the ALD mode prepares graphene film, and the chemisorption of carbon is the problem that at first will solve.Prepare in the method for Graphene at present; Common gas is that the mode of needs process pyrolytic decompositions such as precursor such as methane obtains carbon atom; And this growth pattern does not meet the requirement of ALD low temperature (200 ℃-450 ℃) growth; Therefore will realize the growth of graphene film with ALD, the chemisorption of carbon atom and substrate then is a key issue.
Summary of the invention
The problem that the present invention will solve provides a kind of carbon geochemistry adsorption method that ald prepares graphene film that is used for, and this method can realize stable carbon geochemistry absorption.
In order to achieve the above object; The technical scheme that the present invention adopts is: a kind ofly be used for the carbon geochemistry adsorption method that ald prepares graphene film; A kind ofly contain carbon atom and carbon atom has the not material of bonding electrons through forming; Form covalent linkage with the substrate surface atom, realize stable chemisorption.
In the such scheme, the said material that contains carbon atom is an intermediate carbon, and said intermediate carbon comprises carbon radicals midbody and carbon diradical midbody.
In the such scheme, said carbon radicals midbody is through the alkyl mercury halide or n alkyl halide hydrocarbon carries out thermolysis or photolysis obtains.
In the such scheme, said alkyl mercury halide is the methyl red mercury iodide.
In the such scheme, said n alkyl halide hydrocarbon is a methyl iodide.
In the such scheme, said carbon diradical midbody is the Cabbeen material, comprises carbene and verivate thereof.
In the such scheme, said carbon diradical midbody is obtained by diazonium salt or ketenes thermolysis or photolysis.
In the such scheme, said diazonium salt is diazomethane (CH
2N
2), said ketenes is a ketene.
In the such scheme, said not bonding electrons has 1-4.
Compared with prior art, the beneficial effect of technical scheme generation of the present invention is following:
The present invention is applied to technique for atomic layer deposition and prepares graphene film, and this adsorption method is simple, can realize stable carbon geochemistry absorption.
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;
The process synoptic diagram that methyl iodide that Fig. 2 provides for the embodiment of the invention and silicon carbide substrates are carried out chemisorption;
The process synoptic diagram that methyl red mercury iodide that Fig. 3 provides for the embodiment of the invention and silicon carbide substrates are carried out chemisorption.
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is described in detail.
Embodiment 1:
A kind ofly be used for the carbon geochemistry adsorption method that ald prepares graphene film, comprise the steps:
Step 101 with hydrogen treat 20 minutes, makes the silicon carbide substrates surface form c h bond, to silicon carbide substrates (0001) crystal face, that with the carbon atom be terminal surface shown in a among Fig. 1 schemes;
Step 102, the silicon carbide substrates that will carry out after the hydrogen treatment is positioned in the atomic layer deposition apparatus reaction chamber, in the atomic layer deposition apparatus reaction chamber, feeds argon gas, and reaction chamber is cleaned; In reaction chamber, feed diazomethane gas again; Use UV-irradiation simultaneously; Diazomethane is decomposed; Degradation production has not bonding electrons; The chemical expression that diazomethane decomposes is:
diazomethane can also decompose through low-temperature heat; Heating temperature is 200 ℃-500 ℃, and chemical expression is:
shown in b figure among Fig. 1;
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; Reach stable chemisorption, shown in c figure among Fig. 1.
Embodiment 2:
Step 101 with hydrogen treat 20 minutes, makes the silicon carbide substrates surface form c h bond, to silicon carbide substrates (0001) crystal face, that with the carbon atom be terminal surface shown in a among Fig. 1 schemes;
Step 102, the silicon carbide substrates that will carry out after the hydrogen treatment is positioned in the atomic layer deposition apparatus reaction chamber, in the atomic layer deposition apparatus reaction chamber, feeds argon gas, and reaction chamber is cleaned; In reaction chamber, feed ketene gas again; Simultaneously with UV-irradiation or low-temperature heat; Ketene is decomposed; Degradation production has not bonding electrons, and the chemical expression that ketene decomposes is:
shown in b figure among Fig. 1;
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; Reach stable chemisorption, shown in c figure among Fig. 1.
Embodiment 3:
Step 101 is fixed on silicon carbide substrates (0001) crystal face, that with the carbon atom be the terminal in the reaction chamber of atomic layer deposition apparatus;
Step 102 fed argon gas 5 minutes in the reaction chamber of atomic layer deposition apparatus, discharge the gas in the reaction chamber;
Step 103; In the reaction chamber of atomic layer deposition apparatus, feed a methyl iodide gas; Shown in a figure among Fig. 2; And use sun exposure, and a methyl iodide is decomposed, the expression formula of decomposition is:
is shown in b figure among Fig. 2; Product that one methyl iodide decomposes and silicon carbide substrates surface form the structure of methyl through carbon atom Cheng Jian, reach stable chemisorption, shown in c figure among Fig. 2.
Embodiment 4:
Step 101 is fixed on silicon carbide substrates (0001) crystal face, that with the carbon atom be the terminal in the reaction chamber of atomic layer deposition apparatus;
Step 102 fed argon gas 5 minutes in the reaction chamber of atomic layer deposition apparatus, discharge the gas in the reaction chamber;
Step 103 feeds methyl red mercury iodide (CH in the reaction chamber of atomic layer deposition apparatus
3HgI) gas shown in a figure among Fig. 3, and carries out low-temperature heat under 50 ℃-200 ℃ condition, the methyl red mercury iodide is decomposed, and decomposes expression formula and is:
Shown in b figure among Fig. 3; Product that the methyl red mercury iodide decomposes and silicon carbide substrates surface form methyl structural through carbon atom Cheng Jian, reach stable chemisorption, shown in c figure among Fig. 3.
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 (4)
1. one kind is used for the carbon geochemistry adsorption method that ald prepares graphene film, it is characterized in that: a kind ofly contain carbon atom and carbon atom has the not material of bonding electrons through forming, form covalent linkage with the substrate surface atom, realize stable chemisorption;
Said carbon atom and the carbon atom of containing has not that the material of bonding electrons is an intermediate carbon, and said intermediate carbon comprises carbon radicals midbody and carbon diradical midbody; Said carbon radicals midbody is through the alkyl mercury halide or n alkyl halide hydrocarbon carries out thermolysis or photolysis obtains; Said carbon diradical midbody carries out thermolysis by diazonium salt or ketenes or photolysis obtains.
2. as claimed in claim 1ly be used for the carbon geochemistry adsorption method that ald prepares graphene film, it is characterized in that: said alkyl mercury halide is the methyl red mercury iodide.
3. as claimed in claim 1ly be used for the carbon geochemistry adsorption method that ald prepares graphene film, it is characterized in that: said n alkyl halide hydrocarbon is a methyl iodide.
4. as claimed in claim 1ly be used for the carbon geochemistry adsorption method that ald prepares graphene film, it is characterized in that: said diazonium salt is a diazomethane, and said ketenes is a ketene.
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| CN102249175B (en) * | 2011-04-13 | 2014-08-13 | 中国航天科技集团公司第五研究院第五一0研究所 | Method for manufacturing nano electronic device and/or circuit based on electron beam stimulated desorption |
| CN102344134B (en) * | 2011-09-23 | 2013-03-06 | 中国科学院微电子研究所 | Preparation method of graphite |
| CN109250706B (en) * | 2018-11-26 | 2022-03-15 | 天元羲王控股有限公司 | Graphene film and preparation method thereof |
| KR102312299B1 (en) * | 2018-12-26 | 2021-10-14 | 한국생명공학연구원 | Graphene Channel Member Comprising the Cadaverine Olfactory Receptor and Sensor Comprising the Same |
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