CN115418714A - Universal method for preparing single-crystal two-dimensional material on metal substrate - Google Patents
Universal method for preparing single-crystal two-dimensional material on metal substrate Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000002184 metal Substances 0.000 title claims abstract description 95
- 239000000758 substrate Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 85
- 239000013078 crystal Substances 0.000 title claims abstract description 41
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- 238000000137 annealing Methods 0.000 claims abstract description 58
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- 238000007429 general method Methods 0.000 claims abstract description 15
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 50
- 239000011889 copper foil Substances 0.000 claims description 48
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 22
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052582 BN Inorganic materials 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000012159 carrier gas Substances 0.000 claims description 13
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000004020 conductor Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
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- 238000005229 chemical vapour deposition Methods 0.000 description 8
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- 230000008018 melting Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000004907 flux Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
Abstract
The invention relates to a general method for preparing a single-crystal two-dimensional material on a metal substrate, which comprises the following steps: heating a metal substrate to an annealing temperature, and annealing the metal substrate; after the annealing is finished, heating the metal substrate to a near-molten state; and depositing and growing a two-dimensional material on the metal substrate in the process of heating the metal substrate to a near-molten state. The preparation method is suitable for insulator materials, semiconductor materials and conductor materials which belong to two-dimensional materials, and has the advantages of high universality and universality, easy operation and high quality of the prepared single-crystal two-dimensional materials.
Description
Technical Field
The invention relates to the technical field of preparation of two-dimensional materials, in particular to a general method for preparing a single-crystal two-dimensional material on a metal substrate.
Background
The two-dimensional material refers to a material in which electrons can move freely (planar motion) only on a two-dimensional nanoscale (1-100 nm), and the two-dimensional material mainly comprises a conductor material (such as graphene), a semiconductor material (such as molybdenum disulfide), an insulating material (such as boron nitride) and the like. However, the conventional method for preparing a single-crystal two-dimensional material has a poor practicability because the preparation conditions are severe and the single-crystal two-dimensional material is not easily prepared.
Disclosure of Invention
Based on this, the present invention aims to provide a general method for preparing a single crystal two-dimensional material on a metal substrate, which has low requirements on growth parameters and the growth substrate, is easy to realize single crystal preparation, is suitable for the preparation of two-dimensional conductor materials, semiconductor materials and insulator materials, and has high quality of the prepared single crystal two-dimensional material.
The invention is realized by the following technical scheme:
a general method for preparing a single-crystal two-dimensional material on a metal substrate, comprising the steps of:
heating a metal substrate to an annealing temperature, and annealing the metal substrate; after the annealing is finished, heating the metal substrate to a near-molten state; and depositing and growing a single crystal two-dimensional material on the metal substrate in the process of heating the metal substrate to a near-molten state.
Compared with the prior art, the method has the advantages that the metal substrate is annealed, and is heated to a near-molten state after annealing, so that the growth source is more easily adsorbed on the metal substrate for nucleation, the grown two-dimensional material has orientation consistency, and the high-quality single-crystal two-dimensional material is prepared. The preparation method has universality and universality for different two-dimensional materials, is easy to realize and strong in practicability, and the prepared single-crystal two-dimensional material has high quality.
Further, the two-dimensional material is any one of a two-dimensional insulating material, a two-dimensional semiconductor material, and a two-dimensional conductor material.
Further, when the two-dimensional material is boron nitride, the metal substrate is a copper foil, and the heating of the metal substrate to a near-molten state is heating the copper foil to 1092-1098 ℃.
Further, after completion of annealing, the copper foil was heated to 1098 ℃.
Further, the annealing treatment comprises: introducing carrier gas, heating the copper foil to an annealing temperature under the protection of the carrier gas, and then introducing hydrogen to anneal for a period of time, wherein the annealing temperature is 1050-1070 ℃; depositing growth of a two-dimensional material on the metal substrate during heating of the metal substrate to a near-molten state comprises: weighing ammonia borane, and heating the ammonia borane to be gasified a period of time before the copper foil is annealed; then, hydrogen is introduced into the copper foil, and boron azine, a main decomposition product of ammonia borane, falls on the copper foil through argon gas to deposit and grow monocrystalline boron nitride.
Further, when the two-dimensional material is molybdenum disulfide and the metal substrate is gold foil, the heating to the near-molten state is to heat the gold foil to 1053-1058 ℃.
Further, after completion of annealing, the gold foil was heated to 1055 ℃.
Further, the annealing treatment comprises: introducing carrier gas, heating the gold foil to an annealing temperature under the protection of the carrier gas, and then introducing hydrogen to anneal for a period of time, wherein the annealing temperature is 900-1020 ℃; depositing growth of a two-dimensional material on the metal substrate during heating of the metal substrate to a near-molten state comprises: weighing molybdenum trioxide and sulfur powder, heating the molybdenum trioxide to be gasified within a period of time before growth, and simultaneously heating the sulfur powder to be gasified; and then introducing hydrogen into the gold foil, and allowing gaseous molybdenum trioxide and gaseous sulfur powder to fall on the gold foil through argon gas to deposit and grow single crystal molybdenum disulfide.
Further, when the two-dimensional material is graphene, the metal substrate is copper foil, and the heating to the near-molten state is to heat the metal substrate to 1092-1098 ℃.
Further, after completion of annealing, the copper foil was heated to 1095 ℃.
Further, the annealing treatment comprises: introducing carrier gas, heating the copper foil to an annealing temperature under the protection of the carrier gas, and then introducing hydrogen to anneal for a period of time, wherein the annealing temperature is 1050-1070 ℃; depositing growth of a two-dimensional material on the metal substrate during heating of the metal substrate to a near-molten state comprises: and then introducing hydrogen and a growth carbon source to the copper foil, wherein the growth carbon source falls on the copper foil, and depositing and growing the single crystal graphene.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic view of the production process of the present invention;
FIG. 2 is an optical diagram of 100 μm boron nitride grown in example 1 of the present invention;
FIG. 3 is an optical diagram of 40 μm boron nitride grown in example 1 of the present invention;
FIG. 4 is an optical diagram of boron nitride grown in example 2 of the present invention with a thickness of 100 μm;
FIG. 5 is an optical diagram of 100 μm boron nitride grown in comparative example 1 of the present invention;
FIG. 6 is an optical diagram of 100 μm of molybdenum disulfide grown in example 3 of the present invention;
FIG. 7 is an optical diagram of 100 μm of molybdenum disulfide grown in example 4 of the present invention;
FIG. 8 is an optical image of 50 μm of molybdenum disulfide grown in comparative example 2 of the present invention;
FIG. 9 is an optical diagram of 100 μm graphene grown in example 5 of the present invention;
FIG. 10 is an optical diagram of 100 μm graphene grown in example 6 of the present invention;
fig. 11 is an optical diagram of 100 μm of graphene grown in comparative example 3 of the present invention.
Detailed Description
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
Chemical Vapor Deposition (CVD) is one of the effective methods for producing two-dimensional materials of large area and high quality. When a CVD method is used to prepare a two-dimensional material, a metal substrate is usually heated, annealed, and then a growth source is introduced to deposit and grow the two-dimensional material on the metal substrate. The metal substrate is subjected to surface recrystallization in the high-temperature annealing process to form parallel steps. Since the formation of the steps can reduce the surface energy of the metal substrate, most metal surfaces have steps. However, the applicant found during the research on the two-dimensional material preparation method the phenomenon as shown in fig. 1: after the metal substrate forms the step under the high temperature condition, if the metal substrate is continuously heated until the surface of the metal substrate is gradually melted and is in a near-melting state, the step on the surface of the metal substrate gradually disappears, and the step has a large number of defects and is easier to absorb a growth source, so that the two-dimensional material nucleates in the process from the existence of the step on the surface of the metal substrate to the nonexistence of the step on the surface of the metal substrate, the oriented uniform growth of the two-dimensional material is realized, and the high-quality single crystal two-dimensional material is finally prepared.
Based on the above mechanism research, the applicant has designed a general method for preparing a single crystal two-dimensional material on a metal substrate, comprising the following steps:
heating a metal substrate to an annealing temperature, and then annealing the metal substrate; after the annealing is finished, heating the metal substrate to a near-molten state; and depositing and growing a single crystal two-dimensional material on the metal substrate in the process of heating the metal substrate to a near-molten state.
The general process for the preparation of single-crystal two-dimensional materials on metal substrates according to the invention is further illustrated below by 6 examples and 3 comparative examples.
Example 1
Boron Nitride (BN) is a typical representative of insulator materials in two-dimensional materials, and a method of preparing single crystal boron nitride includes the steps of:
s101: putting copper foil on a high-melting-point metal sheet, then putting the high-melting-point metal sheet on a glass plate, and then putting the glass plate in a tubular furnace of a CVD system; meanwhile, 0.6mg of ammonia borane is weighed and placed in a porcelain boat, and the porcelain boat is placed at an upstream inlet of a tubular furnace wound with a heating belt;
s102: introducing 500sccm argon as a carrier gas and a protective gas, heating the copper foil to 1065 ℃ under the protection of the argon, introducing 100sccm hydrogen for annealing for 90-150min when the temperature reaches 1065 ℃, wherein the annealing time is preferably 150min;
in the step, hydrogen is introduced for annealing, so that the grain size of the copper foil is increased, the appearance of the surface of the copper foil is improved, the copper foil is flattened, the crystallization quality of the surface of the copper foil is improved, and the growth of a single-crystal two-dimensional material is facilitated;
s103: starting the heating belt to heat the ammonia borane in the porcelain boat within 5min before finishing annealing, and heating to 100 ℃ within 5min to gasify the ammonia borane and decompose the ammonia borane into hydrogen, borazine and solid polymeric amino borane;
s104: after the annealing is finished, heating the copper foil from 1065 ℃ to 1098 ℃ within 10min to enable the copper foil to be close to a molten state, adjusting the hydrogen flux to 10sccm, dropping boron azine, a main decomposition product of ammonia borane, on the surface of the copper foil through argon, and depositing and growing monocrystalline boron nitride under the action of intermolecular collision dehydrogenation;
since hydrogen gas can etch boron nitride at high temperature, the flux of hydrogen gas needs to be reduced while the copper foil is further heated to a near-molten state to keep the balance between the growth rate and the etching rate of boron nitride, so that uniform nucleation density and triangular boron nitride domains are obtained.
S105: after the growth is finished, stopping heating, and naturally cooling the boron nitride to room temperature in the atmosphere of 500sccm argon and 10sccm hydrogen;
since ammonia borane continues to decompose and nucleate on the surface of the copper foil due to the high temperature of the growth environment in the early stage of temperature reduction, an etching action of hydrogen is required to suppress unnecessary growth.
Example 2
As another embodiment for preparing single crystal boron nitride, this example is different from example 1 only in that:
in step S102, the copper foil is heated to 1050 ℃, that is, the annealing temperature in this embodiment is 1050 ℃; in this embodiment, the copper foil is heated from 1050 ℃ to 1092 ℃ within 10min in step S104, and other steps and parameters are the same as those in embodiment 1, and therefore, the description thereof will not be repeated.
Example 3
Molybdenum disulfide (MoS) 2 ) Which is a typical representative of semiconductor materials in two-dimensional materials, the method for preparing single crystal molybdenum disulfide comprises the following steps:
s100: heating the gold foil to 1020 ℃ under the protection of argon of 500sccm, and introducing 100sccm hydrogen to anneal for 90-150min when the temperature of the gold foil reaches 1020 ℃; wherein the annealing time is preferably 150min;
s101: placing the gold foil on a metal sheet with a high melting point, then placing the metal sheet with the high melting point on a glass plate, and then placing the metal sheet in a tubular furnace of a CVD system; meanwhile, weighing 360mg of sulfur powder and placing the sulfur powder into a porcelain boat, placing the porcelain boat into an upstream inlet of a tubular furnace wound with a heating belt, weighing 30mg of molybdenum trioxide and placing the molybdenum trioxide into the tubular furnace of a CVD system;
s102: introducing 500sccm argon, and heating the gold foil and the molybdenum trioxide to 1000 ℃ and 575 ℃ respectively within 1h under the protection of the argon to gasify the molybdenum trioxide; heating the sulfur powder to 160 ℃ to gasify the sulfur powder 10min before the temperature of the gold foil and the molybdenum trioxide are respectively raised to 1000 ℃ and 575 ℃;
in this step, the molybdenum trioxide needs to be heated within 1h because the speed of heating the molybdenum trioxide affects the gasification rate of the molybdenum trioxide, thereby affecting the concentration of the molybdenum trioxide in the growth environment. If the temperature rise time is too short, the heating rate is too high, so that the concentration of molybdenum trioxide is too high, and the growth of molybdenum disulfide is not facilitated; if the temperature rise time is too long, the heating rate is too slow, which can result in too low concentration of molybdenum trioxide and is also not beneficial to growth of molybdenum disulfide.
S103: after the annealing is finished, heating the gold foil to 1055 ℃ from 1000 ℃ within 10min to enable the gold foil to be close to a molten state, adjusting the hydrogen flux to 5sccm, and allowing part of gaseous molybdenum trioxide and gaseous sulfur simple substance to fall on the surface of the gold foil through argon gas for reaction to grow molybdenum disulfide; the other part of gaseous molybdenum trioxide reacts with elemental sulfur to generate molybdenum disulfide, and the molybdenum disulfide falls on the surface of the gold foil through argon to form nucleation to grow single-crystal molybdenum disulfide;
s104: after the growth is completed, the heating is stopped, and the molybdenum disulfide is naturally cooled to room temperature under the atmosphere of 300sccm of argon and 5sccm of hydrogen.
In this embodiment, since the annealing temperature of the gold foil is high, if the annealing treatment of the gold foil is performed simultaneously with the heating of the molybdenum trioxide and the sulfur powder, the vaporization temperature of the molybdenum trioxide and the sulfur powder is greatly affected. Therefore, the gold foil needs to be separately annealed before being put into the CVD system to avoid the influence of the excessive annealing temperature on the vaporization of the molybdenum trioxide and sulfur powder.
Example 4
As another embodiment for preparing single crystal molybdenum disulfide, this example differs from example 3 in that:
in step S100, the gold foil is heated to 900 ℃, that is, the annealing temperature in this embodiment is 900 ℃; in this embodiment, the gold foil is heated from 1000 ℃ to 1053 ℃ within 10min in step S103, and other steps and parameters are completely the same as those in embodiment 3, so that the description will not be repeated.
Example 5
Graphene is a typical representative of a conductor material in a two-dimensional material, and a method for preparing single crystal graphene specifically includes the steps of:
s101: placing a copper foil on a metal sheet with a high melting point, then placing the metal sheet with the high melting point on a glass plate, and then placing the glass plate into a CVD system tubular furnace;
s102: introducing 500sccm argon as a protective gas, heating the copper foil to 1065 ℃ under the protection of the argon, introducing 100sccm hydrogen to anneal for 90-150min when the temperature of the copper foil reaches 1065 ℃, wherein the annealing time is preferably 150min;
s103: after the annealing is finished, heating the copper foil from 1065 ℃ to 1095 ℃ within 10min to enable the copper foil to be close to a molten state, adjusting the introduction amount of hydrogen to be 20sccm, introducing 5sccm of methane, and growing single crystal graphene on the copper foil;
s104: and after the growth is finished, stopping introducing methane and stopping heating, and naturally cooling the graphene to room temperature in the atmosphere of 20sccm hydrogen and 500sccm argon.
Example 6
As another embodiment of preparing single crystalline graphene, this example is different from example 5 in that:
in step S102, the copper foil is heated to 1050 ℃, that is, the annealing temperature in this embodiment is 1050 ℃; in this embodiment, the copper foil is heated from 1050 ℃ to 1092 ℃ within 10min in step S104, and other steps and parameters are the same as those in embodiment 5, and therefore, the description thereof will not be repeated.
In the above 6 examples, the time taken for the metal substrate to be heated from the annealing temperature to a near-molten state was the time required for growing the two-dimensional material. In examples 1 to 6, the growth time of the two-dimensional material was 10min, because the crystal domains obtained by growth in this growth time had appropriate size, uniform distribution, and moderate nucleation density, and the phenomenon of uniform orientation could be observed and judged well. If the growth time is less than 10min, the copper foil can not reach a near-melting state, and no difference exists between the growth in a normal state and the growth in a near-melting state. However, in practical applications, the growth time may be extended according to the area of the two-dimensional material, the longer the time, the higher the nucleation density.
In the 6 above examples, in order to obtain and maintain a flat copper or gold surface in a near-molten state, a high melting point metal sheet was used as a carrier to prevent the formation of copper or gold spheres when the surface of the glass, quartz, silicon or other non-wetting carrier is near-molten; wherein the high melting point metal sheet is any one of tungsten sheet, molybdenum sheet or tantalum sheet.
Comparative example 1
As a comparative example of example 1, this comparative example differs from example 1 only in that: in step S103, after completion of the annealing, the temperature of the copper foil is not heated to 1098 ℃, and other steps and parameters are exactly the same as those of example 1, and thus, a description thereof will not be repeated.
Comparative example 2
As a comparative example to example 3, this comparative example differs from example 3 only in that: the manufacturing method of this example does not heat the gold foil to 1055 ℃ after completion of annealing in step S103, and other steps and parameters are exactly the same as those of example 3, and thus, a repeated description thereof will not be made.
Comparative example 3
As a comparative example to example 5, this comparative example differs from example 5 only in that: in step S103, after completion of the annealing, the temperature of the copper foil is not heated to 1095 ℃, and other steps and parameters are exactly the same as those of example 5, and thus, a description thereof will not be repeated.
Analysis of results
Referring to fig. 2 to 5, it can be seen that the boron nitride grown on the metal substrate in examples 1 and 2 has the same orientation, while the boron nitride grown on the metal substrate in comparative example 1 has the random orientation.
Referring to fig. 6-8, it can be seen that the molybdenum disulfide grown on the metal substrate in examples 3 and 4 has a consistent orientation, while the molybdenum disulfide grown on the metal substrate in comparative example 2 has a random orientation.
Referring to fig. 9 to 11, it can be seen that the graphene grown on the metal substrate in examples 5 and 6 has the same orientation, while the graphene grown on the metal substrate in comparative example 3 has random orientation.
The reason why the above results were analyzed is that: when the metal substrate is in a near-melting state at a high temperature close to the melting temperature, the steps on the surface of the metal substrate move and are damaged, a large number of defects are caused, the growth source for growing the two-dimensional material is easier to adsorb on the metal substrate for nucleation, and when the growth nuclei are formed at the steps, the two-dimensional material grows in a consistent orientation, so that the high-quality single crystal two-dimensional material is prepared.
Compared with the prior art, the method has the advantages that the metal substrate is annealed, and is heated to a near-molten state after the annealing treatment, so that the growth source is more easily adsorbed on the metal substrate for nucleation. Because the substrate with the parallel steps is symmetrical in a doublet mode, boron nitride and molybdenum disulfide which are not centrosymmetric or graphene which is centrosymmetric can only have one orientation once nucleation is carried out at the steps, and therefore the preparation of the single crystal material is achieved. The preparation method is suitable for two-dimensional insulator materials, semiconductor materials and conductor materials, and can realize unidirectional growth by the preparation method of the invention no matter non-center inversion symmetric materials or center inversion symmetric materials, the universality and universality are high, the practicability is strong, the realization is easy, and the quality of the prepared single crystal two-dimensional material is high.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that numerous changes and modifications can be made by those skilled in the art without departing from the inventive concepts and it is intended that such changes and modifications be covered by the present invention.
Claims (10)
1. A general method for preparing a single-crystal two-dimensional material on a metal substrate, comprising the steps of:
heating a metal substrate to an annealing temperature, and annealing the metal substrate;
after the annealing is finished, heating the metal substrate to a near-molten state;
and depositing and growing a single crystal two-dimensional material on the metal substrate in the process of heating the metal substrate to a near-molten state.
2. The general method for producing a monocrystalline two-dimensional material on a metal substrate according to claim 1, characterized in that,
when the two-dimensional material is boron nitride, the metal substrate is a copper foil, and the step of heating the metal substrate to a near-melting state is to heat the copper foil to 1092-1098 ℃.
3. The general method for producing a single-crystal two-dimensional material on a metal substrate according to claim 2,
after the annealing was completed, the copper foil was heated to 1098 ℃.
4. The general method for producing a single-crystal two-dimensional material on a metal substrate according to claim 2 or 3,
the annealing treatment comprises the following steps:
introducing carrier gas, heating the copper foil to an annealing temperature under the protection of the carrier gas, and then introducing hydrogen to anneal for a period of time, wherein the annealing temperature is 1050-1070 ℃;
depositing growth of a two-dimensional material on the metal substrate during heating of the metal substrate to a near-molten state comprises:
weighing ammonia borane, and heating the ammonia borane to be gasified a period of time before the copper foil is annealed;
and then introducing hydrogen into the copper foil, and allowing the main decomposition product boron azine of ammonia borane to fall on the copper foil through argon gas to deposit and grow the monocrystalline boron nitride.
5. The general method for producing a single-crystal two-dimensional material on a metal substrate according to claim 1,
when the two-dimensional material is molybdenum disulfide and the metal substrate is gold foil, the heating to the near-molten state is to heat the gold foil to 1053-1058 ℃.
6. The general method for producing a monocrystalline two-dimensional material on a metal substrate according to claim 5, characterized in that,
after the annealing was completed, the gold foil was heated to 1055 ℃.
7. The general method for producing a single-crystal two-dimensional material on a metal substrate according to claim 5 or 6,
the annealing treatment comprises the following steps:
introducing carrier gas, heating the gold foil to an annealing temperature under the protection of the carrier gas, and then introducing hydrogen to anneal for a period of time, wherein the annealing temperature is 900-1020 ℃;
depositing a growth two-dimensional material on the metal substrate during the heating of the metal substrate to a near-molten state comprises:
weighing molybdenum trioxide and sulfur powder, heating the molybdenum trioxide to be gasified within a period of time before growth, and simultaneously heating the sulfur powder to be gasified;
and then introducing hydrogen into the gold foil, and allowing gaseous molybdenum trioxide and gaseous sulfur powder to fall on the gold foil through argon gas to deposit and grow single crystal molybdenum disulfide.
8. The general method for producing a single-crystal two-dimensional material on a metal substrate according to claim 1,
when the two-dimensional material is graphene and the metal substrate is copper foil, heating the metal substrate to a near-molten state is to heat the metal substrate to 1092-1098 ℃.
9. The general method for producing a monocrystalline two-dimensional material on a metal substrate according to claim 8, characterized in that,
after completion of annealing, the copper foil was heated to 1095 ℃.
10. The general method for producing a monocrystalline two-dimensional material on a metal substrate according to claim 8 or 9, characterized in that,
the annealing treatment comprises the following steps:
introducing carrier gas, heating the copper foil to an annealing temperature under the protection of the carrier gas, and then introducing hydrogen to anneal for a period of time, wherein the annealing temperature is 1050-1070 ℃;
depositing growth of a two-dimensional material on the metal substrate during heating of the metal substrate to a near-molten state comprises:
and then introducing hydrogen and a growth carbon source to the copper foil, wherein the growth carbon source falls on the copper foil, and depositing and growing the single crystal graphene.
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