CN115198267A - Preparation method of graphene-like material - Google Patents
Preparation method of graphene-like material Download PDFInfo
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- CN115198267A CN115198267A CN202110385186.7A CN202110385186A CN115198267A CN 115198267 A CN115198267 A CN 115198267A CN 202110385186 A CN202110385186 A CN 202110385186A CN 115198267 A CN115198267 A CN 115198267A
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- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 18
- 238000005695 dehalogenation reaction Methods 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000005641 tunneling Effects 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 4
- 239000002356 single layer Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene-like material, wherein precursor molecules deposited at a high temperature are subjected to dehalogenation reaction to introduce chlorine atoms into a high-temperature copper surface to obtain a graphene-like structure. The method can ensure that precursor molecules are fully subjected to dehalogenation reaction and desorption on the surface of Cu (111), cl atoms are still adsorbed on the surface of Cu (111) and self-assembled to form the hexagonal honeycomb single-layer chlorine-based graphene with high coverage rate, so that the reaction rate of raw materials on the surface is high, and the waste of reactants is reduced.
Description
Technical Field
The invention relates to a preparation method of a graphene-like material, belonging to the technical field of material preparation.
Background
Graphene is a two-dimensional material with excellent physical and chemical properties, and has a wide application prospect in the fields of electronic devices, solar cells and the like. Inspired by graphene, researchers began exploring two-dimensional topological materials with hexagonal honeycomb structures similar to graphene. Graphene-like materials have received much attention due to their excellent electronic properties, including high carrier mobility, etc., brought about by their unique dirac band structures.
As a structural characterization technology of atomic-scale precision, the ultrahigh vacuum scanning tunneling microscope has the advantages of intuition, real-time performance, in-situ characterization and the like, and provides powerful technical support for development and research of graphene-like materials. Graphene-like materials with similar structures and the same electronic properties are obtained by means of a scanning tunneling microscope manipulation technology in a manner of moving atoms or molecules. At present, the technology realizes the preparation of molecular graphene with carbon monoxide on the surface of copper. However, the manipulation technology is very complex, and it is difficult to obtain a more stable and wider range of graphene-like materials, which limits the development of the graphene-like materials in the aspect of practical production and application.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene-like material.
In order to solve the technical problem, the preparation method of the graphene-like material, disclosed by the invention, comprises the following steps of introducing chlorine atoms into the surface of copper by dehalogenation reaction of precursor molecules deposited at high temperature to obtain a graphene-like structure:
1) Heating the Cu substrate to 520K;
2) Depositing precursor molecules on the Cu substrate in the step 1), and carrying out dehalogenation reaction to obtain the hexagonal honeycomb high-coverage-rate chloro-based graphene through self-assembly;
3) Observing the Cu substrate obtained in the step 2) through a scanning tunnel microscope, desorbing precursor molecules after dehalogenation reaction occurs on the surface of the high-temperature Cu (111), breaking C-Cl bonds in the reaction, and adsorbing obtained Cl atoms on the surface of the Cu (111).
Further, the precursor molecule comprises three meta Cl atoms, such as a 2,4, 6-trichloro-1, 3, 5-triazine molecule (TCT molecule).
Further, the precursor molecules were deposited on a 520K high temperature Cu substrate, the temperature of the Cu substrate was maintained at 520K during the deposition, and the deposition time was 10 minutes.
Further, after the reaction is finished, the sample is rapidly conveyed into a scanning table and cooled to the temperature of liquid nitrogen, and the Cu substrate obtained in the step 2) is observed through a scanning tunnel microscope.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method can enable precursor molecules to fully perform dehalogenation reaction and desorption on the surface of Cu (111), and Cl atoms are still adsorbed on the surface of Cu (111) and self-assembled to form the hexagonal honeycomb single-layer chlorine-based graphene with high coverage rate.
(2) Compared with the scanning tunneling microscope manipulation technology, the preparation process is simple and controllable.
(3) The reaction rate of the raw materials on the surface is high, and the waste of reactants is reduced.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of TCT and a schematic diagram of a model of a ball stick used in the present invention.
FIG. 2 is an STM scan image of room temperature deposition (300K) of precursor molecules onto a Cu substrate according to example 1 of the present invention.
FIG. 3 is an image of an STM scan of example 2 of the present invention in which precursor molecules are deposited after heating a Cu substrate to a temperature of 450K by an EBH-150 electron beam heating apparatus, and the sample is rapidly introduced into a scanning stage and cooled to a liquid nitrogen temperature 10 minutes after deposition.
FIG. 4 is an image of an STM scan of example 3 of the present invention in which precursor molecules are deposited after heating a Cu substrate to a temperature of 520K by an EBH-150 electron beam heating apparatus, and the sample is rapidly introduced into the scanning stage and cooled to a liquid nitrogen temperature 10 minutes after deposition.
Detailed Description
The invention is further elucidated with reference to the figures and embodiments.
The desorption temperature of the molecular layer after coupling of the TCT molecules (the structure is shown in figure 1) is lower than that of Cl atoms on the surface of Cu (111), so that high-temperature adsorption of the Cl atoms is realized, the introduction of the Cl atoms under a high-temperature condition is realized by the precursor molecule high-temperature deposition method, the limitation of the temperature on the diffusion of the Cl atoms on the surface is effectively reduced, the conversion kinetics of the adsorption layer is influenced, a new structure of the chlorine-based graphene is obtained, and the single-layer chlorine-based graphene with high coverage rate is prepared by further utilizing dehalogenation reaction and the desorption temperature difference of the coupled molecular layer and the chlorine atoms.
Example 1
Using molecular beam epitaxy system (Germany)specsCompany), depositing TCT molecules on Cu (111) surface for 10 minutes at room temperature, transferring the sample into a scanning stage and cooling to liquid nitrogen temperature, observing and analyzing using Scanning Tunneling Microscope (STM) and DFT calculation. It was observed by Scanning Tunneling Microscope (STM) that no dehalogenation reaction occurred in the precursor molecule at room temperature, no C-Cl bond was broken, the TCT molecular structure was intact and an ordered self-assembled structure was formed, as shown in fig. 2.
Example 2
Heating the Cu (111) surface to 450K by adopting a molecular beam epitaxy system, depositing TCT molecules on the 450K Cu (111) surface, quickly transferring a sample into a scanning table after 10 minutes, cooling to the liquid nitrogen temperature, and observing and analyzing by utilizing a Scanning Tunneling Microscope (STM) and DFT calculation. The method specifically comprises the following steps:
step 1: the electron beam heating device of the system is turned on, the filament current is increased from 0A to 1.8A in an amplification of 300mA, the high-voltage button is turned on, the numerical value is adjusted to 1 KV, the filament current is continuously increased, the emission current reaches 1 mA, then the emission electron current is increased from 1 mA to 5 mA in an increment of 300mA, and the Cu (111) surface is heated from room temperature to 450K in a few minutes.
And 2, step: TCT molecules are deposited on the surface of Cu (111) of 450K, the sample is conveyed into a scanning platform after 10 minutes of deposition and is cooled to the temperature of liquid nitrogen, dehalogenation reaction of precursor molecules on the surface is observed through a scanning tunnel microscope, and the coupled molecules and chlorine atoms coexist on the surface of the Cu (111), as shown in figure 3 a. The surface adsorbed chlorine atoms are in a close-packed structure as shown in FIG. 3 b.
Example 3
Heating the surface of Cu (111) to 520K by adopting a molecular beam epitaxy system, depositing TCT molecules on the surface of the Cu (111) at 520K, quickly transmitting a sample into a scanning table after 10 minutes, cooling to the temperature of liquid nitrogen, and observing and analyzing by utilizing a Scanning Tunneling Microscope (STM) and DFT calculation. The method specifically comprises the following steps:
step 1: the electron beam heating device of the system is turned on, the filament current is increased from 0A to 1.8A in an amplification of 300mA, the high-voltage button is turned on, the numerical value is adjusted to 1 KV, the filament current is continuously increased, the emission current reaches 1 mA, then the emission electron current is increased from 1 mA to 5 mA in an increment of 300mA, and the Cu (111) surface is heated from room temperature to 520K in a few minutes.
Step 2: depositing TCT molecules on the surface of Cu (111) at 520K, transferring the sample into a scanning table after 10 minutes of deposition, cooling to the temperature of liquid nitrogen, observing through a scanning tunneling microscope that dehalogenation reaction occurs on the surface of precursor molecules, desorbing the coupled molecules from the surface while chlorine atoms are still adsorbed on the surface, and forming a graphene-like hexagonal honeycomb structure by the adsorption of the chlorine atoms on the surface of the Cu (111), as shown in FIGS. 4a and 4 b.
Claims (4)
1. A preparation method of a graphene-like material is characterized in that precursor molecules deposited at a high temperature are subjected to dehalogenation reaction to introduce chlorine atoms into the surface of copper to obtain a graphene-like structure, and the preparation method comprises the following steps:
1) Heating the Cu substrate to 520K;
2) Depositing precursor molecules on the Cu substrate in the step 1), keeping the temperature of the Cu substrate at 520K during deposition, and carrying out dehalogenation reaction to obtain the chloro-graphene through self-assembly.
2. The method of claim 1, wherein the precursor molecule is a 2,4, 6-trichloro-1, 3, 5-triazine molecule.
3. The method of claim 1, wherein the precursor molecules are deposited on a Cu substrate, the temperature of the Cu substrate is maintained at 520K during deposition for 10 minutes, and chloro-graphene is obtained by self-assembly through dehalogenation.
4. The method of claim 1, wherein after the deposition reaction is finished, the sample is rapidly transferred into a scanning table and cooled to the temperature of liquid nitrogen, a scanning tunneling microscope is used for observing the Cu substrate, precursor molecules are desorbed after the dehalogenation reaction is carried out on the surface of Cu (111), C-Cl bonds are broken in the reaction, and the obtained Cl atoms are adsorbed on the surface of Cu (111).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186795A (en) * | 1996-08-22 | 1998-07-08 | 罗姆和哈斯公司 | Method for preparing aromatic compounds |
| CN102077060A (en) * | 2008-06-04 | 2011-05-25 | G·帕特尔 | A monitoring system based on etching of metals |
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2021
- 2021-04-09 CN CN202110385186.7A patent/CN115198267A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186795A (en) * | 1996-08-22 | 1998-07-08 | 罗姆和哈斯公司 | Method for preparing aromatic compounds |
| CN102077060A (en) * | 2008-06-04 | 2011-05-25 | G·帕特尔 | A monitoring system based on etching of metals |
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