CN117446789A - Preparation method of hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material - Google Patents
Preparation method of hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 165
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 151
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000006467 substitution reaction Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 53
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 230000002950 deficient Effects 0.000 claims description 6
- 238000010884 ion-beam technique Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
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- 229910021538 borax Inorganic materials 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 238000001020 plasma etching Methods 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000005538 encapsulation Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- 239000010453 quartz Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000002356 single layer Substances 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 19
- 239000007789 gas Substances 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 11
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- 238000001816 cooling Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- -1 high mobility Chemical compound 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007907 direct compression Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical group O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
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- 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
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0646—Preparation by pyrolysis of boron and nitrogen containing compounds
-
- 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
-
- 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
- C01B32/188—Preparation by epitaxial growth
-
- 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
- C01B32/19—Preparation by exfoliation
-
- 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
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention relates to the field of preparation of two-dimensional materials, in particular to a preparation method of a hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material. And based on a substitution reaction principle, the grapheme with the specific number of layers on the upper surface and the lower surface is respectively converted into hexagonal boron nitride, and meanwhile, the high-quality grapheme of the middle layer is reserved, so that the hexagonal boron nitride/grapheme/hexagonal boron nitride laminated heterojunction material with the specific number of layers and stacking sequence is formed. The hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material prepared by the method has high crystallization quality, and the intermediate layer graphene is not in contact with the outside, so that a clean interface between the hexagonal boron nitride and the graphene is ensured, and a foundation is laid for realizing the encapsulation of the graphene so as to greatly improve the electrical, thermal and chemical properties of the graphene.
Description
Technical Field
The invention relates to a preparation technology of a two-dimensional material laminated heterostructure, in particular to a preparation method of a hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material, which is suitable for preparing the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material with large area, high quality and clean interface and no pollution.
Background
Hexagonal boron nitride is an excellent insulating substrate with a wide band gap, and because the surface of the hexagonal boron nitride has the characteristics of being flat in atomic level, free of dangling bonds or charge impurities and the like, the hexagonal boron nitride can be used as a dielectric layer to effectively isolate charge doping of a substrate material below, so that a series of intrinsic properties of graphene, such as high mobility, unique electronic structure and the like, can be maintained. The mechanical stripping method for preparing hexagonal boron nitride is limited in development due to the fact that the stripping size is small, the thickness is uncontrollable and the like. Chemical vapor deposition is the main method for preparing high-quality large-area hexagonal boron nitride.
Since the thickness of the single layer of hexagonal boron nitride is too small, it is difficult to effectively protect the two-dimensional material from the substrate and the environment. In contrast, multilayer hexagonal boron nitride is a more suitable substrate for maintaining the inherent properties of two-dimensional materials such as graphene. The hexagonal boron nitride/graphene/hexagonal boron nitride vertical heterojunction prepared by the transfer method is complex in preparation procedure, easy to pollute at the interface and difficult to prepare in large scale. At present, the research on large-area high-quality graphene/hexagonal boron nitride vertical heterojunction is mainly focused on the chemical vapor deposition technology. The preparation of the laminated heterostructure by the chemical vapor deposition method needs to grow layer by layer, and high-quality graphene and surface hexagonal boron nitride are difficult to obtain. Thus, preparing high quality and clean interface hexagonal boron nitride/graphene/hexagonal boron nitride remains extremely challenging.
Disclosure of Invention
The invention aims to provide a preparation method of a high-quality hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material with a specific stacking sequence. The method converts the whole graphene into hexagonal boron nitride locally to form a laminated heterostructure, and has the outstanding characteristics of high graphene quality and complete clean interface. Therefore, the method can be used as a preparation method for preparing the high-quality hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material with a specific stacking sequence.
The technical scheme of the invention is as follows:
a preparation method of a hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material adopts high-quality few-layer or multi-layer graphene, and converts graphene with a designated layer number on the upper surface and the lower surface into hexagonal boron nitride in a chemical reaction substitution mode, so that the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material which is stacked in sequence is formed.
The preparation method of the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material comprises the step of preparing high-quality graphene by adopting a stripping method, a chemical vapor deposition method, a silicon carbide pyrolysis method or an epitaxial method.
The precursor for chemical reaction replacement is a reactant for preparing hexagonal boron nitride, including but not limited to ammonia and boric acid, aminoborane, ammonia and sodium tetraborate, ammonia and sodium metaborate, nitrogen and sodium tetraborate.
The preparation method of the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material comprises the following steps of:
1) The first stage: firstly, preparing high-quality few-layer or multi-layer graphene on an initial substrate; for an initial growth substrate chemically reacting with a precursor for preparing hexagonal boron nitride, transferring prepared graphene from the initial growth substrate to an inert substrate;
2) And a second stage: placing graphene on an initial substrate into a high-temperature chemical reaction cavity, introducing a precursor for preparing hexagonal boron nitride at a high temperature to perform substitution reaction with the surface layer of the graphene, wherein the typical heating temperature is 300-600 ℃; the degree of the graphene surface replacement reaction is regulated and controlled by controlling the reaction time, so that a hexagonal boron nitride/graphene vertical heterojunction with a specific layer number and stacking sequence is formed;
3) And a third stage: transferring the prepared hexagonal boron nitride/graphene vertical heterojunction to a secondary substrate, exposing the bottom graphene above, and then repeating the operation steps of the second stage to prepare a hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material; the number of layers of graphene and hexagonal boron nitride in the stacked heterostructure is regulated by changing the number of layers of initial graphene and the degree of substitution reaction.
In the second stage, the precursor for preparing the hexagonal boron nitride is directly arranged on the surface of the graphene or is contacted with the graphene in a mode of direct volatilization or carrier gas carrying; for the latter two modes, the precursor needs to be heated to 300-600 ℃ to form a sufficiently high concentration.
In the preparation method of the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material, in order to promote the replacement of graphene reaction with hexagonal boron nitride, an ion beam bombardment, plasma etching or chemical functionalization etching method is adopted before the second stage to generate defects on the surface layer of the graphene, so that a channel is provided for the subsequent replacement process, and the reaction of replacing the graphene by hexagonal boron nitride is easier to occur.
According to the preparation method of the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material, the defect-containing graphene surface layers with different thicknesses can be obtained on the original high-quality graphene by adjusting and controlling the etching intensity or time.
According to the preparation method of the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material, in the process of replacing surface graphene with hexagonal boron nitride, defective graphene can be gradually converted into hexagonal boron nitride along with the extension of the replacement reaction time, and the graphene which is not etched has high quality and has an isolation effect on a reactant precursor, so that the replacement reaction is finally terminated after all defective graphene layers are converted into hexagonal boron nitride.
The design idea of the invention is as follows:
the invention adopts high-quality multilayer graphene as a precursor material of all laminated heterostructures, converts the specific layer numbers of the upper and lower surfaces of the multilayer graphene into hexagonal boron nitride based on substitution reaction, and simultaneously reserves the intrinsic structure of the high-quality graphene of the intermediate layer, thereby forming the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material with high quality and clean interface.
The invention has the characteristics and beneficial effects that:
1. the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material prepared by the method has high crystallization quality, and meanwhile, the graphene is not contacted with the outside, so that a clean interface between the hexagonal boron nitride and the graphene is ensured.
2. The method has high controllability, and in the process of replacing the defective surface layer graphene with hexagonal boron nitride, the graphene in the middle layer has an isolation effect on the reactant precursor, and the replacement reaction is automatically stopped after the defective graphene layer is completely converted into hexagonal boron nitride.
Drawings
Fig. 1 is a schematic diagram of an apparatus for growing high quality multi-layer graphene by high temperature annealing and chemical vapor deposition. In the figure, 11 gas inlets; a 12 reaction furnace; 13 a high catalytic activity metal substrate; 14 sealing means; 15 gas outlet; 16 quartz tube.
Fig. 2 is a schematic diagram of ion beam bombardment of high quality graphene. In the figure, a 21 argon gas source; 22 slits; 23 gas beams; 24 ionization chamber; a 25 argon ion beam; 26 high quality multilayer graphene; 27SiO 2 A Si substrate.
Fig. 3 is a schematic diagram of an apparatus for preparing a graphene/hexagonal boron nitride heterojunction and a hexagonal boron nitride/graphene/hexagonal boron nitride stacked heterojunction material. In the figure, 31 gas inlet; 32 heating bands; 33 quartz boat; 34 a reaction furnace; 35 high quality multilayer graphene/SiO 2 Si or high quality multilayer graphene/hexagonal boron nitride/SiO 2 Si;36 sealing means; 37 gas outlet; 38 quartz tube.
Detailed Description
In the specific implementation process, high-quality few-layer or multi-layer graphene is adopted, and based on a substitution reaction principle, the graphene with the specific layer number on the upper surface and the lower surface is respectively converted into hexagonal boron nitride, and meanwhile, the high-quality graphene of the middle layer is reserved, so that the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material with the specific layer number and stacking sequence is formed.
The invention is further described below by way of examples and figures.
Example 1
Preparing a multi-layer hexagonal boron nitride/single-layer graphene/multi-layer hexagonal boron nitride laminated heterojunction. Firstly, preparing high-quality 9 layers of graphene on a metal nickel foil by adopting a Chemical Vapor Deposition (CVD) method; as shown in fig. 1, high-quality graphene is grown by an atmospheric pressure hot wall chemical vapor reaction furnace, a gas inlet 11 and a gas outlet 15 are respectively arranged on two sides of a quartz tube 16 of the reaction furnace 12, the length of a central constant temperature area of the quartz tube 16 of the reaction furnace 12 is 50 mm, two ends of the quartz tube 16 are sealed by a sealing device 14, and a high-catalytic-activity metal substrate 13 (metal nickel foil) is placed in the quartz tube 16 (with the diameter of 22 mm). In a standard growth process, the metallic nickel foil is washed with acetone, isopropanol and deionized water, respectively, before use, and the surface is degreased. Then, an electrolyte solution composed of a certain ratio (330 ml of deionized water, 167 ml of ethanol, 167 ml of orthophosphoric acid, 33 ml of isopropyl alcohol and 3.3g of urea) was put in, and electrochemical polishing was performed at a constant voltage of 8V. And cleaning the electrochemically polished metal nickel foil with deionized water and ethanol, drying with nitrogen after cleaning, rapidly placing in a central constant temperature area of a reaction furnace, heating to 1050 ℃ in 30 minutes under mixed carrier gas of 300sccm argon and 200sccm hydrogen to anneal the metal nickel foil for 1 hour, then introducing 10sccm methane to grow for 5 minutes, and growing 9 layers of graphene on the surface of the metal nickel foil. After the growth is finished, the metal substrate is pushed out of the central constant temperature area to be rapidly cooled.
Dripping ethyl lactate solution (polymethyl methacrylate accounting for 4 wt%) of polymethyl methacrylate (PMMA) onto the surface of graphene, spin-coating a layer of polymethyl methacrylate (spin-coating speed is 2500 rpm, spin-coating time is 60 seconds, and spin-coating times are 2 times) on the surface of graphene by spin-coating method, and adding the spin-coated polymethyl methacrylate-The graphene/metal nickel foil was placed on a hot bench and baked at 90 ℃ for 10 minutes. After etching the metal nickel foil with 1mol/L ferric chloride aqueous solution, polymethyl methacrylate/graphene is transferred to SiO 2 Removing polymethyl methacrylate on the surface of graphene on a Si substrate by using acetone at 80 ℃, respectively washing the graphene by using isopropanol and ethanol, and drying at 120 ℃ for 15 minutes to obtain 9 layers of graphene/SiO 2 /Si。
As shown in fig. 2, the invention adopts argon ion bombardment to defecte the specific layer number on the surface of the high-quality graphene, and an argon ion bombardment system is sequentially provided with an argon gas source 21, a slit 22, an ionization chamber 24, high-quality multilayer graphene 26 and SiO 2 A Si substrate 27 (i.e., a silicon wafer substrate having an oxide layer formed on the surface thereof by preliminary oxidation), which is supplied with an argon gas source 21, a high-speed gas beam 23 is ejected from a slit 22, the argon gas beam 23 is ionized into an argon ion beam 25 in an ionization chamber 24, and the ejected argon ion beam 25 ionizes SiO 2 High quality multilayer graphene 26 on/Si substrate 27 specifies layer number defectivity. In this embodiment, "specific number of layers" and "specified number of layers" refer to 4 layers of graphene on the upper and lower surfaces of 9 layers of graphene.
As shown in fig. 3, the present invention employs an atmospheric pressure hot wall chemical vapor reactor with a heating belt 32 to convert the multi-layer graphene into a multi-layer hexagonal boron nitride/single-layer graphene/multi-layer hexagonal boron nitride stacked heterojunction. The two sides of the quartz tube 38 of the reaction furnace 34 are respectively provided with a gas inlet 31 and a gas outlet 37 of carrier gas, the length of the central constant temperature area of the quartz tube 38 of the reaction furnace 34 is 50 mm, and the two ends of the quartz tube 38 are sealed by a sealing device 36, so that the high-quality multilayer graphene/SiO is obtained 2 the/Si 35 (9 layers) was placed in the central constant temperature zone of the quartz tube 38 (22 mm diameter), and solid boric acid was placed in the quartz boat 33 upstream of the central constant temperature zone of the quartz tube 38, and the solid boric acid was heated by the heating belt 32 outside the quartz tube 38 at that position.
The preparation process of the laminated heterojunction is as follows:
1) Transferring 9 layers of graphene/SiO 2 Si was placed in the central constant temperature zone of the quartz tube (diameter 22 mm) of the reactor, and about 120mg of solid was added to the quartz boat upstream of the quartz tubeBoric acid in a state. The reaction chamber (quartz tube cavity) was evacuated and then filled with argon gas, and the internal pressure of the reaction chamber was maintained at about 20 Torr.
2) The reaction furnace is heated to 1000 ℃ within 30 minutes, the solid boric acid precursor is heated to 300-600 ℃, the flow rate of argon is adjusted to 250sccm, 50sccm of ammonia gas is introduced, and the conversion reaction is started along with the heating of the solid boric acid and the introduction of gaseous ammonia gas. After the conversion is finished, the reaction substrate is pushed out of the reaction area (central constant temperature area) by a push-pull rod, so that the rapid cooling is realized, and simultaneously, the ammonia gas is closed and the heating of the solid boric acid is stopped. Introducing 100sccm of hydrogen to maintain the reducing atmosphere in the reaction chamber, cooling the reaction chamber to room temperature, and closing the carrier gas to obtain 4 layers of hexagonal boron nitride/5 layers of graphene/SiO 2 /Si。
3) Direct compression of Polydimethylsiloxane (PDMS) stamp on 4-layer hexagonal boron nitride/5-layer graphene/SiO 2 Si surface, followed by removal of SiO with a 6:1 Buffered Oxide Etch (BOE) solution 2 After cleaning and drying PDMS/hexagonal boron nitride/graphene with deionized water, spin-coating PMMA with the thickness of 50 μm on the surface of graphene by a spin-coating method (the spin-coating speed is 2500 r/min, the spin-coating time is 60 seconds, the spin-coating times are 8-10 times), after spin-coating, placing PMMA/graphene/hexagonal boron nitride/PDMS (PMMA face up) on a hot table, drying at 150 ℃ for 1 hour, directly removing the polydimethylsiloxane layer after drying, and then placing PMMA/graphene/hexagonal boron nitride on SiO 2 Removing polymethyl methacrylate on the surface of graphene on a Si substrate by using acetone at 80 ℃, respectively flushing the graphene by using isopropanol and ethanol, and drying for 15 minutes at 120 ℃ to obtain 5 layers of graphene/4 layers of hexagonal boron nitride/SiO 2 /Si。
4) 5 layers of graphene/4 layers of hexagonal boron nitride/SiO after transfer 2 Si was placed in the central constant temperature zone of the quartz tube (diameter 22 mm) of the reactor, and about 80mg of solid boric acid was added to the quartz boat upstream of the quartz tube. And (3) vacuumizing the reaction chamber, and then filling argon, and keeping the internal pressure of the reaction chamber at about 20 Torr.
5) Heating the reaction furnace to 1000 ℃ in 30 minutes, heating the solid boric acid precursor to 300-600 ℃,simultaneously, the flow rate of argon is regulated to 270sccm, 30sccm of ammonia gas is introduced, and the conversion reaction is started along with the heating of the solid boric acid and the introduction of gaseous ammonia gas. After the conversion is finished, the reaction substrate is pushed out of the reaction area by a push-pull rod, so that the rapid cooling is realized, and simultaneously, the ammonia gas is closed and the heating of the solid boric acid is stopped. Introducing 100sccm hydrogen to maintain the reducing atmosphere in the reaction chamber, cooling the reaction chamber to room temperature, closing the carrier gas, and washing off hexagonal boron nitride/graphene/hexagonal boron nitride/SiO with 80 ℃ hot water 2 Boric acid or boron oxide residue on Si surface, and drying to obtain SiO 2 4-layer hexagonal boron nitride/single-layer graphene/4-layer hexagonal boron nitride stacked heterostructure on Si substrate.
Example 2
Preparing a single-layer hexagonal boron nitride/single-layer graphene/single-layer hexagonal boron nitride laminated heterostructure. The difference from example 1 is that high quality 3-layer graphene is first prepared on copper nickel alloy foil by chemical vapor deposition. The copper-nickel alloy foil is subjected to surface treatment by adopting the method described in the embodiment 1, then is placed in a reaction furnace, is annealed for 1 hour under the mixed carrier gas of 300sccm argon and 200sccm hydrogen at the temperature of 1050 ℃ in 30 minutes, is then introduced into 1sccm methane for reaction for 10 minutes, and 3 layers of graphene are grown on the surface of the metal nickel foil. Then, siO is obtained by transfer 2 3 layers of graphene on a Si substrate.
The preparation process of the single-layer hexagonal boron nitride/single-layer graphene/single-layer hexagonal boron nitride laminated heterostructure is as follows:
1) High-quality 3-layer graphene/SiO after transfer 2 Si is placed in a quartz tube (diameter 22 mm), high quality 3-layer graphene/SiO 2 The position of/Si was located in the central constant temperature zone of the reactor and about 80mg of solid boric acid was added to the quartz boat upstream of the quartz tube. And (3) vacuumizing the reaction chamber, and then filling argon, and keeping the internal pressure of the reaction chamber at about 20 Torr.
2) The reaction furnace is heated to 1000 ℃ within 30 minutes, the solid boric acid precursor is heated to 300-600 ℃, the flow rate of argon is adjusted to 270sccm, 30sccm of ammonia gas is introduced, and the conversion reaction is started along with the heating of the solid boric acid and the introduction of gaseous ammonia gas. Conversion ofAfter the reaction is finished, the reaction substrate is pushed out of the reaction area by a push-pull rod, so that the rapid cooling is realized, and simultaneously, the ammonia gas is closed and the heating of the solid boric acid is stopped. Introducing 100sccm hydrogen to maintain the reducing atmosphere in the reaction chamber, cooling the reaction chamber to room temperature, closing the carrier gas, and washing off hexagonal boron nitride/graphene/SiO with 80 deg.C hot water 2 Residual boric acid or boron oxide on the surface of Si, and drying to obtain single-layer hexagonal boron nitride/2-layer graphene/SiO 2 /Si。
3) Transferring to obtain 2 layers of graphene/single layers of hexagonal boron nitride/SiO by the method described in example 1 2 /Si。
4) 2 layers of graphene/single-layer hexagonal boron nitride/SiO after transfer 2 Si was placed in the central constant temperature zone of the quartz tube (diameter 22 mm) of the reactor, and about 80mg of solid boric acid was added to the quartz boat upstream of the quartz tube. And (3) vacuumizing the reaction chamber, and then filling argon, and keeping the internal pressure of the reaction chamber at about 20 Torr.
5) And (3) repeating the step (2) to finally obtain the single-layer hexagonal boron nitride/single-layer graphene/single-layer hexagonal boron nitride laminated heterostructure.
Example 3
Preparing a multilayer hexagonal boron nitride/2-layer graphene/multilayer hexagonal boron nitride laminated heterostructure. The difference from example 1 is that first a high quality 10-layer graphene is prepared on a metal nickel foil using a chemical vapor deposition method. And (3) placing the surface-treated metal nickel foil in a reaction furnace, heating to 1050 ℃ in 30 minutes under the mixed carrier gas of 300sccm argon and 200sccm hydrogen to anneal the metal nickel foil for 1 hour, introducing 12sccm methane to react for 5 minutes, and growing 10 layers of graphene on the surface of the metal nickel foil. Then, siO is obtained by transfer 2 10 layers of graphene on a Si substrate. Finally, the method described in example 1 was used to convert the upper surface 4 layers and the lower surface 4 layers of 10 layers of graphene into 4 layers of hexagonal boron nitride, respectively, so as to prepare a multilayer hexagonal boron nitride/2 layers of graphene/multilayer hexagonal boron nitride stacked heterostructure.
Example 4
Preparing a single-layer hexagonal boron nitride/single-layer graphene/single-layer hexagonal boron nitride laminated heterostructure. Is different from example 2 in thatDirectly obtaining SiO by adopting a mechanical stripping method 2 High quality tri-layer graphene on Si substrate without CVD growth and transfer steps. Then, a monolayer hexagonal boron nitride/monolayer graphene/monolayer hexagonal boron nitride stacked heterostructure was obtained using the conversion reaction procedure described in example 2.
The example results show that the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material prepared by the method has high crystallization quality, and the intermediate layer graphene is not in contact with the outside, so that a clean interface between the hexagonal boron nitride and the hexagonal boron nitride is ensured, and a foundation is laid for realizing the encapsulation of the graphene so as to greatly improve the electrical, thermal and chemical properties of the graphene.
Claims (8)
1. A preparation method of a hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material is characterized in that high-quality few-layer or multi-layer graphene is adopted, and graphene with the designated layer number on the upper surface and the designated layer number on the lower surface is converted into hexagonal boron nitride in a chemical reaction substitution mode, so that the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material which is stacked in sequence is formed.
2. The method for preparing the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material according to claim 1, wherein the high-quality graphene is prepared by a lift-off method, a chemical vapor deposition method, a silicon carbide pyrolysis method or an epitaxial method.
3. The method of preparing a hexagonal boron nitride/graphene/hexagonal boron nitride stacked heterojunction material of claim 1, wherein the precursors for chemical reaction substitution are reactants for preparing hexagonal boron nitride, including but not limited to ammonia and boric acid, aminoborane, ammonia and sodium tetraborate, ammonia and sodium metaborate, nitrogen and sodium tetraborate.
4. A method for preparing a hexagonal boron nitride/graphene/hexagonal boron nitride stacked heterojunction material according to any one of claims 1 to 3, wherein the preparation process of the hexagonal boron nitride/graphene/hexagonal boron nitride stacked heterojunction material is as follows:
1) The first stage: firstly, preparing high-quality few-layer or multi-layer graphene on an initial substrate; for an initial growth substrate chemically reacting with a precursor for preparing hexagonal boron nitride, transferring prepared graphene from the initial growth substrate to an inert substrate;
2) And a second stage: placing graphene on an initial substrate into a high-temperature chemical reaction cavity, introducing a precursor for preparing hexagonal boron nitride at a high temperature to perform substitution reaction with the surface layer of the graphene, wherein the typical heating temperature is 300-600 ℃; the degree of the graphene surface replacement reaction is regulated and controlled by controlling the reaction time, so that a hexagonal boron nitride/graphene vertical heterojunction with a specific layer number and stacking sequence is formed;
3) And a third stage: transferring the prepared hexagonal boron nitride/graphene vertical heterojunction to a secondary substrate, exposing the bottom graphene above, and then repeating the operation steps of the second stage to prepare a hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material; the number of layers of graphene and hexagonal boron nitride in the stacked heterostructure is regulated by changing the number of layers of initial graphene and the degree of substitution reaction.
5. The method for preparing the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material according to claim 4, wherein in the second stage, the precursor for preparing hexagonal boron nitride is directly placed on the surface of graphene or is contacted with graphene by direct volatilization or by carrier gas carrying; for the latter two modes, the precursor needs to be heated to 300-600 ℃ to form a sufficiently high concentration.
6. The method of preparing a hexagonal boron nitride/graphene/hexagonal boron nitride stacked heterojunction material of claim 4, wherein in order to facilitate replacement of graphene reaction with hexagonal boron nitride, ion beam bombardment, plasma etching or chemical functionalization etching method is used to generate defects on the graphene surface layer prior to the second stage, so as to provide a channel for subsequent replacement process, and the reaction of hexagonal boron nitride to replace graphene is more likely to occur.
7. The method for preparing the hexagonal boron nitride/graphene/hexagonal boron nitride laminated heterojunction material according to claim 6, wherein the defect-containing graphene surface layers with different thicknesses can be obtained on original high-quality graphene by adjusting and controlling the etching intensity or time.
8. The method for preparing a hexagonal boron nitride/graphene/hexagonal boron nitride stacked heterojunction material according to claim 6 or 7, wherein in the process of replacing surface layer graphene with hexagonal boron nitride, defective graphene is gradually converted into hexagonal boron nitride along with the extension of the replacement reaction time, and the replacement reaction is finally terminated after the defective graphene layer is completely converted into hexagonal boron nitride due to the fact that the graphene which is not etched has high quality and has an isolation effect on a reactant precursor.
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