CN114735751A - Single-layer CrI prepared based on chemical vapor transport3Sheet and method - Google Patents
Single-layer CrI prepared based on chemical vapor transport3Sheet and method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 54
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- 239000002994 raw material Substances 0.000 claims abstract description 40
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 19
- 239000011630 iodine Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 46
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- 238000006243 chemical reaction Methods 0.000 claims description 30
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- 238000001816 cooling Methods 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 16
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052594 sapphire Inorganic materials 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/04—Chromium halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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Abstract
The invention discloses a single-layer CrI prepared based on chemical vapor transport3A slice and a method, which belong to the technical field of two-dimensional ferromagnetic materials and solve the problem of preparing single-layer CrI at present3The method has the technical problems of high preparation environment requirement, high experiment cost, low efficiency, small size and the like. The invention discloses a method for preparing single-layer CrI based on chemical vapor transport3Method for preparing a single-layered CrI having a large area by programming Cr raw material, crystalline iodine powder and transfer agent powder under controlled temperature conditions3The preparation process of the method is less in material consumption, simple to operate, high in efficiency, low in cost and has the advantage of large-scale production. Single layer CrI prepared by the method3The sheet has large area, high purity and wide application range.
Description
Technical Field
The invention belongs to the technical field of two-dimensional ferromagnetic materials, and particularly relates to a single-layer CrI prepared based on chemical vapor transport3A sheet and a method.
Background
Ferromagnetism is a fundamental quantum property of a substance, specifically referring to electrons in the substanceDue to the interaction, the magnetic moments tend to align and thus exhibit a magnetization phenomenon on a macroscopic scale. The discovery and utilization of the magnetic phenomena in human beings have been for thousands of years, and the origin of the magnetism is studied more and more deeply along with the development of quantum mechanics and solid theory, such as the relationship between the magnetism and the dimension. Scientists in the past theoretically predicted that two-dimensional isotropic ferromagnetism did not exist, however in 2017 scientists were working on two-dimensional chromium triiodide (CrI)3) The long-range order of ferromagnetism is discovered, which opens up a new chapter for the research of magnetics. CrI3Being a layered van der waals ferromagnet, the magnetic material is an ideal platform for researching two-dimensional magnetic materials, and the obvious characteristics of the magnetic material are the existence of intrinsic magnetism under a single-layer structure and ferromagnetic dependence related to the number of layers. Single layer of CrI3Bilayer of CrI in ferromagnetic state3Being interlayer antiferromagnetic, trilayer CrI3And re-assumes a ferromagnetic state, which means that two-dimensional CrI3The method has wide application prospect in data storage, low-temperature magneto-optical electric devices and research and exploration of superconducting topological effect based on ferromagnetic van der Waals heterojunction. Meanwhile, the material is a ferromagnetic insulator, and has potential application value in the research of topological technology, spin electronic devices, energy valley electronics and nonlinear optical measurement technology. In addition thereto CrI3Other excellent properties are also exhibited, for example it is an ideal magnetic substrate in the study of valley electronics; the double-layer structure can detect a second harmonic signal, thereby further expanding the application of the double-layer structure in the field of photoelectric detection; at the same time, CrI3Is a material which is extremely sensitive to external pressure, and related reports indicate that the ferromagnetism of the material can be further regulated by the external pressure.
Currently, large area single layer CrI3The controllable preparation research of (A) is still in the initial stage, CrI with thick atomic layer3The characteristic of easy degradation in atmospheric environment brings great challenges to the preparation of single layer or few layers of the CrI, and the development of a large-size single-layer CrI with good economy and high reliability is urgently needed3The method of (1). In 2019, Martin
Et al report the growth of CrX on Yttrium Stabilized Zirconia (YSZ) substrates using a tube sealing method3(X ═ F, Cl, Br) nanosheets, however CrX prepared by such a process3The sample layer thickness distributions of (X ═ F, Cl, Br) were very different, with the thinnest CrI3The thickness of the sample is 20nm, few layers or even a single layer of CrI is prepared3The methods of (a) still need further exploration. In 2020, Peigen Li and the like respectively prepare single-layer CrI on an Au (111) substrate and an HOPG substrate by using MBE technology3. At present, Molecular Beam Epitaxy (MBE) is used for preparing CrI3Monolayer technology is reported, but CrI is prepared using this method3Has strict requirements on experimental environment and higher experimental cost, and the prepared CrI3The size of the material stays at the nanometer level, and further physical property tests cannot be met. Current Single layer CrI3The commonly adopted preparation method is to carry out mechanical stripping under the inert atmosphere condition, and the method has low efficiency, great uncertainty and large amount of mechanical repeated labor, and is difficult to realize industrialized application.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a single-layer CrI prepared based on chemical vapor transport3Flakes and methods for solving the current problem of preparing a monolayer of CrI3The method has the technical problems of high preparation environment requirement, high experiment cost, low efficiency, small size and the like.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a method for preparing single-layer CrI based on chemical vapor transport3A method of sheeting comprising the steps of:
putting Cr raw materials, crystalline iodine powder and transmission agent powder into a container for mixing to obtain a raw material mixture, vacuumizing, and then putting the container into chemical vapor transmission heating equipment for heat treatment; the transmission agent powder is one or more of potassium fluoride powder, potassium chloride powder and potassium bromide powder;
the chemical vapor transmission heating equipment is provided with a raw material area and a reaction area, wherein the container is placed in the raw material area, and a substrate is placed in the reaction area;
after heat treatment, the raw material mixture in the raw material area is brought into the reaction area in the form of gas flow transmission under the vacuum condition, and after reaction growth on the surface of the substrate, a single-layer CrI is obtained3A sheet.
Further, the usage ratio of the Cr raw material, the crystalline iodine powder and the transmission agent powder is (1-2): (3-14): (1-2); the Cr raw material is in the form of Cr blocks or Cr powder.
Further, after vacuum pumping, the pressure in the container is less than or equal to 1.7 multiplied by 10-4Pa。
Further, the chemical vapor transport heating device is a dual-temperature-zone tube furnace, and a raw material zone and a reaction zone are arranged inside the dual-temperature-zone tube furnace.
Further, when the heat treatment is carried out, the heat treatment parameters of the raw material area are as follows: heating from room temperature to 850-950 ℃ at the heating rate of 6-8 ℃/min, keeping the temperature for 2-3 h, and cooling to room temperature; the heat treatment parameters of the reaction zone are as follows: the temperature is raised from the room temperature to 550-600 ℃ at the temperature raising speed of 4-5 ℃/min, and then the temperature is kept constant for 2-3 h and then the temperature is cooled to the room temperature.
Further, the cooling to room temperature is natural cooling, air cooling or water cooling.
Further, the substrate is mica, amorphous quartz glass, sapphire or highly oriented pyrolytic graphite.
The invention also discloses a method for preparing single-layer CrI based on chemical vapor transport3Method for preparing a lamella3A sheet.
Further, the single layer CrI3The size of the thin slice is 30-50 μm.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a method for preparing single-layer CrI based on chemical vapor transport3The method of flake adopts chemical vapor transport technology, Cr raw material, crystalline iodine powder and transport agent powder are programmed to control temperature conditions,preparation of a monolayer of CrI with Large area3A sheet. Compared with the traditional melting method for preparing the growth material, the preparation method has very limited application to the preparation of compounds with high melting point, mainly because some reactants can be dissociated at the melting point or can be melted only under the condition of continuously increasing the pressure, thus providing higher requirements for experimental conditions; the method disclosed by the invention adopts a chemical vapor transmission technology, so that reaction components are carried to a specific space region by airflow in a transmission mode under a vacuum condition to react and grow, the reaction components are not dissociated even at a melting point, the preparation process efficiency is high, the reaction conditions are easy to control, and the industrialization is favorably realized. Investigation of molten salt species and growth substrates for CrI Using one or more of Potassium fluoride powder, Potassium chloride powder and Potassium bromide powder as transport agent powder3The effect of the epitaxial growth of the thin film crystal; the method solves the problem of CrI from the block3Exfoliation of CrI3The thin layer has the problems of low efficiency, poor controllability and the like, and the single-layer CrI obtained based on the MBE preparation technology is also solved3The method has the advantages of few materials, simple operation, high efficiency, low cost and large-scale production, and can be used for growth of target materials only by setting program parameters and placing reaction materials.
The invention also discloses a single-layer CrI prepared by the preparation method3Flakes, said monolayer CrI3The sheet has large area, high purity, wide application range and can meet various physical property test conditions.
Drawings
FIG. 1 is a temperature rise and constant temperature program graph of a raw material zone and a reaction zone;
FIG. 2 shows a single layer of CrI prepared in example 13Optical micrographs of the flakes;
FIG. 3 shows a single layer of CrI prepared in example 13An optical image of the sheet and its corresponding mask map;
FIG. 4 shows a single layer of CrI prepared in example 23Optical micrographs of the flakes;
FIG. 5 shows a single layer of CrI prepared in example 23An optical image of the sheet and its corresponding mask map;
FIG. 6 shows a single layer of CrI prepared in example 33Optical micrographs of the flakes;
FIG. 7 shows a single layer of CrI prepared in example 33An optical image of the sheet and its corresponding mask map;
FIG. 8 shows a single layer of CrI prepared in example 43An optical image of the sheet and its corresponding mask map;
FIG. 9 shows a single layer of CrI prepared in example 43High resolution electron micrographs of the flakes;
FIG. 10 shows a single layer of CrI prepared in example 43Optical micrographs of the flakes;
FIG. 11 shows a single layer of CrI prepared in example 43Atomic force micrographs of flakes;
FIG. 12 is a single layer of CrI prepared in example 53Optical micrographs of the flakes;
FIG. 13 is a single layer of CrI prepared in example 53A raman spectrum of the sheet;
FIG. 14 is a single layer of CrI prepared in example 53Atomic force micrographs of flakes;
FIG. 15 is a single layer of CrI prepared in example 53A height map of the lamella;
FIG. 16 is a single layer of CrI prepared in example 63Optical micrographs of the flakes;
FIG. 17 is a single layer of CrI prepared in example 63A raman spectrum of the flake;
wherein: a-an optical image; b-mask diagram.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Unless otherwise specified herein, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other, "and" a comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Instrumentation conventional in the art is used in the following examples. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
The invention discloses a method for preparing single-layer CrI based on chemical vapor transport3A method of sheeting comprising the steps of:
putting Cr raw materials, crystalline iodine powder and transmission agent powder into a container for mixing to obtain a raw material mixture, vacuumizing, and then putting the container into chemical vapor transmission heating equipment for heat treatment; the transmission agent powder is one or more of potassium fluoride powder, potassium chloride powder and potassium bromide powder;
the chemical vapor transmission heating equipment is provided with a raw material area and a reaction area, wherein the container is placed in the raw material area, and a substrate is placed in the reaction area;
after heat treatment, the raw material mixture in the raw material area is brought into the reaction area in the form of gas flow transmission under the vacuum condition, and after reaction growth on the surface of the substrate, a single-layer CrI is obtained3A sheet.
The purity of the Cr raw material is preferably 98% or more, more preferably 99.95% or more, and the form of the Cr raw material is not particularly limited, and may be bulk or powder Cr, but preferably, the form of Cr is preferably powder; the purity of the transport agent powder is 98% or more, more preferably 99.9% or more, in order to improve the yield.
FIG. 1 is a graph showing temperature-raising and constant-temperature program curves of a raw material zone and a reaction zone, wherein the temperature of the hot end and the temperature of the cold end of the tube furnace are respectively set to 850 ℃ and 550 ℃, and the temperature raising process needs 120 min.
Example 1
Single-layer CrI prepared based on chemical vapor transport3A method of sheeting comprising the steps of:
placing 5mg Cr powder, 35mg crystal iodine powder and 5mg potassium fluoride powder into the bottom of ampoule (with necking), mixing, and vacuumizing until the vacuum degree reaches 1.7 × 10-4Packaging at Pa, and vacuum sealingFixing the iodine powder by using liquid nitrogen to prevent the iodine powder from volatilizing; then, the ampoule tube is placed in a raw material area in a double-temperature-area tube furnace, and mica (mica) is placed in a reaction area to be used as a growth substrate; then setting the following heating program in a double-temperature-zone tube furnace for heat treatment: heating the raw material area from room temperature to 850 ℃ at a heating rate of 6 ℃/min for 2h, preserving heat for 2h, and naturally cooling to room temperature; heating the reaction zone from room temperature to 550 ℃ at the heating rate of 4 ℃/min, preserving the temperature for 2h, and naturally cooling to room temperature; after the heat treatment is finished, obtaining a large-area single-layer CrI on the surface of the substrate3A sheet.
FIG. 2 shows the single-layer CrI prepared in example 13The optical micrograph of the flakes shows that there are many black particles left on the surface of the sample. FIG. 3 shows a single layer of CrI prepared in example 13Optical image of a lamella and corresponding mask map, wherein the mask is used for identifying and calculating CrI3Coverage on mica, black circles represent monolayer CrI with maximum area in each optical image3Region, it can be seen that when potassium fluoride powder is used as the transport agent, a single monolayer of CrI on the mica substrate3The maximum area of the sample was 1227 μm2The sample coverage was 4.01%.
Example 2
Single-layer CrI prepared based on chemical vapor transport3A method of sheeting comprising the steps of:
placing 5mg Cr powder, 35mg crystal iodine powder and 5mg potassium chloride powder into the bottom of ampoule (with necking), mixing, and vacuumizing until the vacuum degree reaches 1.7 × 10-4Packaging is carried out when Pa, and liquid nitrogen is needed to fix the iodine powder in the vacuum sealing process so as to prevent the iodine powder from volatilizing; then placing the ampoule tube into a raw material area in a double-temperature-area tube furnace, and placing mica as a growth substrate in a reaction area; then setting the following heating program in a double-temperature-zone tube furnace for heat treatment: heating the raw material region from room temperature to 900 ℃ at a heating rate of 7 ℃/min for 2h, then preserving heat for 2.5h, and naturally cooling to room temperature; the reaction zone was raised from room temperature at a ramp rate of 4.5 deg.C/minThe temperature is increased to 580 ℃, and the temperature is preserved for 2.5 hours and then naturally cooled to the room temperature; after the heat treatment is finished, obtaining a large-area single-layer CrI on the surface of the substrate3A sheet.
FIG. 4 shows a single layer of CrI prepared in example 23Optical micrographs of the flakes from which it can be seen that the number of black particles on the surface of the sample decreased, indicating that chloride ions have a better promoting effect on film growth of the sample than fluoride ions; FIG. 5 shows a single layer of CrI prepared in example 23Optical image of a lamella and corresponding mask map, wherein the mask is used for identifying and calculating CrI3Coverage on mica, black circles represent monolayer CrI with maximum area in each optical image3Region, it can be seen that when potassium chloride powder is used as the transport agent, a single monolayer of CrI on the mica substrate3The maximum area of the sample was 1908 μm2Sample coverage was 9.40%.
Example 3
Single-layer CrI prepared based on chemical vapor transport3A method of sheeting comprising the steps of:
placing 5mg Cr powder, 35mg crystal iodine powder and 5mg potassium bromide powder into the bottom of ampoule (with necking), mixing, and vacuumizing until the vacuum degree reaches 1.7 × 10-4Packaging is carried out when Pa, and liquid nitrogen is needed to fix the iodine powder in the vacuum sealing process so as to prevent the iodine powder from volatilizing; then placing the ampoule tube into a raw material area in a double-temperature-area tube furnace, and placing mica as a growth substrate in a reaction area; then setting the following heating program in a double-temperature-zone tube furnace for heat treatment: heating the raw material area from room temperature to 950 ℃ at a heating rate of 8 ℃/min for 2h, preserving heat for 3h, and naturally cooling to room temperature; heating the reaction zone from room temperature to 600 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, and cooling the air to room temperature; after the heat treatment is finished, obtaining a large-area single-layer CrI on the surface of the substrate3A sheet.
FIG. 6 shows a single layer of CrI prepared in example 33Optical micrographs of the flakes, from which it can be seen that the number of black particles on the surface of the sample is reduced, whichThe bromide ions have better promotion effect on the film growth of the sample than the fluoride ions; FIG. 7 shows a single layer of CrI prepared in example 33Optical image of a lamella and corresponding mask map, wherein the mask is used for identifying and calculating CrI3Coverage on mica, black circles represent monolayer CrI with maximum area in each optical image3Region, it can be seen that a single monolayer of CrI on the mica substrate when potassium bromide powder is used as the transport agent3The maximum area of the sample was 643. mu.m2The sample coverage was 10.06%.
Example 4
Preparation of single-layer CrI based on chemical vapor transport3A method of sheeting comprising the steps of:
placing 5mg Cr powder, 35mg crystal iodine powder, 2.5mg potassium bromide powder and 2.5mg potassium chloride powder into the bottom of ampoule (with necking), mixing, and vacuumizing until the vacuum degree reaches 1.7 × 10-4Packaging is carried out when Pa, and liquid nitrogen is needed to fix the iodine powder in the vacuum sealing process so as to prevent the iodine powder from volatilizing; then placing the ampoule tube into a raw material area in a double-temperature-area tube furnace, and placing mica as a growth substrate in a reaction area; then setting the following heating program in a double-temperature-zone tube furnace for heat treatment: heating the raw material area from room temperature to 930 ℃ at a heating rate of 7.5 ℃/min for 2h, then preserving heat for 2.8h, and naturally cooling to room temperature; heating the reaction zone from room temperature to 560 ℃ at a heating rate of 4.8 ℃/min, preserving heat for 2.5h, and cooling the air to room temperature; after the heat treatment is finished, obtaining a large-area single-layer CrI on the surface of the substrate3A sheet.
FIG. 8 shows a single layer of CrI prepared in example 43Optical image of a lamella and corresponding mask map, wherein the mask is used for identifying and calculating CrI3Coverage on mica, black circles represent monolayer CrI with maximum area in each optical image3An area; based on this sample, CrI was observed by STEM3High resolution transmission electron images of both monolayer and bilayer regions, as shown in FIG. 9, can be observed with a representative honeycomb network, which is comparable to the atomic structure of CrI3The simulated diagram keeps high correspondence, and the CrI with thick atomic layer prepared by the method can be inferred3Has high quality. FIG. 10 shows a single layer of CrI prepared in example 43As a result of optical micrograph of the sheet, it can be seen that the single layer CrI obtained in this example3The sample size of the flakes was 40. + -.10 μm, much larger than by mechanical stripping (. about.5 μm) and MBE (. about.5 μm)<1 μm) method to obtain a single layer of CrI3The size of (d); FIG. 11 shows a single layer of CrI prepared in example 43Atomic force micrographs of the flakes from which it can be seen that the sample is uniform in thickness and 0.79nm in height; single monolayer CrI on a mica substrate when potassium bromide and potassium chloride powders are used as transport agents3The maximum area of the sample was 1474 μm2The sample coverage was 8.20%.
Example 5
This example differs from example 2 in that: the substrate is amorphous quartz glass. Single layer CrI obtained in this example3The morphology of the sheet is shown in fig. 12, the sample is polygonal, the sample size is about 30um, and the sheet is a nano sheet with a regular shape. CrI as shown in FIG. 133The Raman characteristic peak position of the crystal is the same as CrI grown on a mica substrate3The characteristic peak positions of the samples are consistent, which
FWHM of the mode is 6.56cm-1This means CrI grown on a quartz glass substrate3Has higher crystallographic quality. The sample was thickness characterized by AFM, figure 14 is an AFM image of the sample, and the height of the sample figure 15 shows the thickness of the sample is 15.28 nm.
Example 6
This example differs from example 2 in that: the substrate is sapphire. Single layer CrI obtained in this example3The morphology of the flakes is shown in FIG. 16, CrI3The sample had a regular shape, but the thickness of the sample was much greater than the CrI on the quartz and mica substrates, as viewed from the optical contrast of the sample3The thickness of the sample. CrI as shown in FIG. 173The Raman characteristic peak position of the crystal is the same as CrI grown on a mica substrate3The characteristic peak positions of the samples are consistent, which
FWHM of the mode is 7.17cm-1。
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. Single-layer CrI prepared based on chemical vapor transport3A method of sheeting, comprising the steps of:
putting Cr raw materials, crystalline iodine powder and transmission agent powder into a container for mixing to obtain a raw material mixture, vacuumizing, and then putting the container into chemical vapor transmission heating equipment for heat treatment; the transmission agent powder is one or more of potassium fluoride powder, potassium chloride powder and potassium bromide powder;
the chemical vapor transmission heating equipment is provided with a raw material area and a reaction area, wherein the container is placed in the raw material area, and a substrate is placed in the reaction area;
after heat treatment, the raw material mixture in the raw material area is brought into the reaction area in the form of gas flow transmission under the vacuum condition, and after reaction growth on the surface of the substrate, a single-layer CrI is obtained3A sheet.
2. The method of claim 1, wherein the single-layer CrI is prepared based on chemical vapor transport3The method for preparing the flake is characterized in that the using amount ratio of the Cr raw material, the crystalline iodine powder and the transmission agent powder is (1-2) to (3-14) to (1-2); the Cr raw material is in the form of Cr blocks or Cr powder.
3. The method of claim 1, wherein the single-layer CrI is prepared based on chemical vapor transport3The method being characterised in that, after evacuation, the container is filled withPressure intensity is less than or equal to 1.7 multiplied by 10-4Pa。
4. The method of claim 1, wherein the single-layer CrI is prepared based on chemical vapor transport3The method for preparing the slices is characterized in that the chemical vapor transport heating equipment is a double-temperature-zone tube furnace, and a raw material zone and a reaction zone are arranged inside the double-temperature-zone tube furnace.
5. The method of claim 1, wherein the single-layer CrI is prepared based on chemical vapor transport3The method of the thin slice is characterized in that when the heat treatment is carried out, the heat treatment parameters of the raw material area are as follows: heating from room temperature to 850-950 ℃ at the heating rate of 6-8 ℃/min, keeping the temperature for 2-3 h, and cooling to room temperature; the heat treatment parameters of the reaction zone are as follows: the temperature is raised from the room temperature to 550-600 ℃ at the temperature raising speed of 4-5 ℃/min, and then the temperature is kept constant for 2-3 h and then the temperature is cooled to the room temperature.
6. The method of claim 4, wherein the single layer CrI is prepared based on chemical vapor transport3The method for preparing the slices is characterized in that the mode of cooling to room temperature is natural cooling, air cooling or water cooling.
7. The method of claim 1, wherein the single-layer CrI is prepared based on chemical vapor transport3A method of flaking, characterized in that the substrate is mica, amorphous quartz glass, sapphire or highly oriented pyrolytic graphite.
8. Preparation of single-layer CrI based on chemical vapor transport by using any one of claims 1-73Method for preparing a lamella3A sheet.
9. Single layer CrI according to claim 83Flakes, characterized in that said monolayer CrI3The size of the thin slice is 30-50 μm.
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| CN115558989A (en) * | 2022-09-23 | 2023-01-03 | 西北工业大学 | Preparation method of band gap adjustable chalcogenide germanide single crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272358A (en) * | 2015-06-01 | 2016-01-27 | 湘潭大学 | Preparation method for a large-area single-layer or few-layer molybdenum disulfide film |
| CN112779597A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院物理研究所 | Method for producing van der waals two-dimensional layered single crystal |
-
2022
- 2022-03-17 CN CN202210264388.0A patent/CN114735751A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272358A (en) * | 2015-06-01 | 2016-01-27 | 湘潭大学 | Preparation method for a large-area single-layer or few-layer molybdenum disulfide film |
| CN112779597A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院物理研究所 | Method for producing van der waals two-dimensional layered single crystal |
Non-Patent Citations (2)
| Title |
|---|
| LIPENG GONG等: "Epitaxial growth of large-grain-size ferromagnetic monolayer CrI3 for valley Zeeman splitting enhancement", 《NANOSCALE》 * |
| 胡大珂: "二维金属硫族化合物的化学气相输运法合成及性质研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558989A (en) * | 2022-09-23 | 2023-01-03 | 西北工业大学 | Preparation method of band gap adjustable chalcogenide germanide single crystal |
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