CN115094397B - Non-layered two-dimensional material and preparation method and application thereof - Google Patents

Non-layered two-dimensional material and preparation method and application thereof Download PDF

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CN115094397B
CN115094397B CN202210662427.2A CN202210662427A CN115094397B CN 115094397 B CN115094397 B CN 115094397B CN 202210662427 A CN202210662427 A CN 202210662427A CN 115094397 B CN115094397 B CN 115094397B
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layered
sulfide
metal
dimensional
dimensional material
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CN115094397A (en
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刘碧录
谭隽阳
李晟楠
王经纬
成会明
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Tsinghua-Berkeley Shenzhen Institute
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Tsinghua-Berkeley Shenzhen Institute
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/10—Deposition of chromium only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/14—Deposition of only one other metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a non-layered two-dimensional material and a preparation method and application thereof. The preparation method comprises the steps of taking a metal source containing a metal compound and a metal simple substance as raw materials, preparing the non-layered two-dimensional material through a chemical vapor deposition method, and regulating and controlling the volatilization speed of the metal source through a normalization reaction between the simple substance and the compound in the chemical vapor deposition process, wherein the metal comprises transition metal. The preparation method has the characteristic of good controllability.

Description

Non-layered two-dimensional material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of two-dimensional materials, and particularly relates to a non-layered two-dimensional material, and a preparation method and application thereof.
Background
In recent years, two-dimensional materials have received extensive attention from researchers due to their unique band structure and photoelectric properties. Besides common layered two-dimensional materials (such as graphene, molybdenum disulfide and the like), non-layered two-dimensional materials (strong covalent bonds or ionic bonds between layers) have great application potential due to the unique structure and properties. This is because the unsaturated chemical bonds on the surface of the non-layered two-dimensional material can induce the non-layered two-dimensional material to generate a high-activity surface, so that the non-layered two-dimensional material is expected to be used in the fields of chemical catalysis, energy conversion and the like. Because the non-lamellar material crystal does not have interlayer weak van der Waals acting force inside, all atoms of the non-lamellar material crystal are connected through strong chemical bonds, so that the preparation of the non-lamellar material with a two-dimensional ultrathin structure is difficult. At present, preparation methods of the non-lamellar two-dimensional material comprise a hydrothermal method, a chemical vapor deposition method and the like, however, the traditional chemical vapor deposition method is adopted to prepare the non-lamellar two-dimensional material, so that uniform nucleation and growth of the two-dimensional material are difficult to control, and the controllability is poor.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method of the non-layered two-dimensional material, which has the characteristic of good controllability.
The invention also provides a non-layered two-dimensional material.
The invention also provides an electronic device.
The invention also provides application of the non-layered two-dimensional material.
According to a first aspect of the invention, a preparation method of a non-layered two-dimensional material is provided, wherein a metal source containing a metal compound and a metal simple substance is used as a raw material, the non-layered two-dimensional material is prepared through a chemical vapor deposition method, and in the chemical vapor deposition process, the volatilization speed of the metal source is regulated and controlled through a normalization reaction of the simple substance and the compound, wherein the metal comprises transition metal.
The preparation method of the non-layered two-dimensional material has at least the following beneficial effects:
according to the invention, the metal source comprises a metal simple substance and a compound containing the metal, the volatilization process of the metal source is regulated through the return-to-middle reaction of the simple substance and the compound in the reaction process, and the uniform nucleation of the two-dimensional material is promoted, so that the controllable preparation of the non-layered two-dimensional material is realized. The preparation method has the advantages of simple preparation process, easy operation, low preparation cost and high speed. The obtained non-layered two-dimensional material has strong uniformity and large size, no van der Waals acting force exists in the material, the surface of the material has rich dangling bonds and rich chemical active sites, and the material has good application prospect in the fields of chemical catalysis, energy conversion and the like. Preferably, by the preparation method and the control of reaction parameters (such as preferred temperature, preferred gas flow rate and the like), the controllable preparation of the large-area non-layered two-dimensional material can be realized, and the obtained material can be uniformly distributed on the substrate, the thickness is adjustable, the area is controllable and the like.
In some embodiments of the invention, the non-layered two-dimensional material comprises a non-layered two-dimensional transition metal sulfide material and the metal compound comprises a metal chloride.
Through the embodiment, the method has at least the following beneficial effects:
in the traditional preparation method, pure metal or metal oxide is often used as a metal precursor, and the problem is that high-melting-point metals/metal oxides such as iron, cobalt, nickel and the like are difficult to volatilize below 1000 ℃ and cannot be used for growth. In order to solve this problem, the use of metal chlorides with low melting points is a solution, which has the problem that the volatilization speed of the chlorides is too high and the growth is difficult to control.
In the invention, sulfur powder is used as a nonmetallic precursor, metal powder and chloride powder thereof are used as bimetallic precursors, and the non-lamellar two-dimensional transition metal sulfide is prepared on a substrate by a chemical vapor deposition method. The method and the control of reaction parameters (such as better temperature, better gas flow rate and the like) can realize the controllable preparation of the large-area non-lamellar two-dimensional transition metal sulfide, particularly can realize the thickness adjustment through the regulation and control of the reaction parameters, and the obtained non-lamellar two-dimensional transition metal sulfide is uniformly distributed on the substrate and has wide application prospects in the fields of electronic devices, photoelectric devices, energy catalysis and the like.
In some preferred embodiments of the invention, the metal comprises at least one of iron, cobalt, nickel, vanadium or chromium.
The smaller band gap of narrow bandgap semiconductors has attracted continued interest to researchers. The narrow band gap two-dimensional material has unique response to the photo-electrons, the narrow band gap characteristics of the energy band structure endow the material with higher detection sensitivity to long wave bands and wide light absorption range, and the application potential of the material in the field of photoelectric devices is shown. Currently, narrow bandgap two-dimensional semiconductors (e.g., black phosphorus, 1T' -MoTe 2 Etc.), severely restricting the application of such materials in the semiconductor industry.
The prepared non-layered two-dimensional transition metal sulfide has the advantages of small energy band gap (narrow band gap), excellent air stability and higher quality, and has good application prospect in the technical field of semiconductors.
In some preferred embodiments of the present invention, the non-layered two-dimensional transition metal sulfide includes at least one of iron sulfide, cobalt sulfide, nickel sulfide, vanadium sulfide, or chromium sulfide.
In some preferred embodiments of the present invention, the non-layered two-dimensional transition metal sulfide comprises at least one of ferrous sulfide, cobalt sulfide, nickel sulfide, vanadium sulfide, or chromium sulfide.
In some preferred embodiments of the present invention, the elemental metal includes at least one of iron powder, cobalt powder, nickel powder, vanadium powder, or chromium powder.
In some preferred embodiments of the present invention, the metal chloride comprises at least one of ferric chloride, cobalt dichloride, nickel dichloride, vanadium tetrachloride or chromium dichloride.
In some preferred embodiments of the present invention, the mass ratio of the elemental metal to the metal chloride is (0.1-1): 1.
in some more preferred embodiments of the invention, the mass ratio of the elemental metal to the metal chloride is about 1:1.
in some preferred embodiments of the present invention, the starting material for the preparation of the non-layered two-dimensional transition metal sulfide material further comprises a sulfur source.
In some more preferred embodiments of the invention, the sulfur source comprises elemental sulfur.
In some more preferred embodiments of the invention, the sulfur source is sulfur powder.
In some more preferred embodiments of the invention, the mass ratio of the sulfur source to the metal source is (50-120): 1.
in some embodiments of the invention, the method of preparation comprises the steps of: and carrying out chemical vapor deposition reaction on the metal source and the sulfur source in the carrier gas atmosphere, and obtaining the non-layered two-dimensional transition metal sulfide material on the surface of the substrate.
In some preferred embodiments of the invention, the substrate is placed above the metal source.
Placing a substrate right above the metal source powder to improve the growth efficiency of the non-layered two-dimensional transition metal sulfide; specifically, the silicon oxide substrate can be placed at a position 5-50mm above the mixed powder.
In some preferred embodiments of the invention, the substrate is a silicon oxide substrate.
The sulfur powder and the metal source powder are respectively placed in a quartz boat or other high Wen Chang mouth resistant containers and then are placed in a corresponding temperature zone in a tube furnace. In the preparation process, sulfur materials evaporated in a low temperature zone are carried to a high temperature zone by carrier gas and react with the materials evaporated in the high temperature zone; in the reaction process, high-valence metal chloride can react with zero-valence metal powder in a centering way at high temperature to generate intermediate products in intermediate valence states, and the volatilization speed of the metal precursor can be obviously modulated, so that the growth of non-lamellar two-dimensional transition metal sulfide is facilitated.
In some preferred embodiments of the present invention, the chemical vapor deposition reaction process comprises: and gasifying a sulfur source in a low-temperature area and a metal source in a high-temperature area, and performing chemical vapor deposition to obtain the non-layered two-dimensional transition metal sulfide material.
In some more preferred embodiments of the invention, the preparation method comprises the steps of:
s1, respectively placing the metal source and the sulfur source in a high temperature area and a low temperature area;
s2, introducing carrier gas, respectively increasing the temperature of the high temperature region and the temperature of the low temperature region to T1 and T2, and carrying out heat preservation reaction, wherein T1 and T2 are positive numbers and T1 is more than T2.
In some more preferred embodiments of the invention, the T1 is 480-600 ℃.
In some more preferred embodiments of the invention, the T1 is 480-520 ℃.
In some more preferred embodiments of the invention, the T2 is 140-160 ℃.
In some preferred embodiments of the present invention, the preparation of the non-layered two-dimensional transition metal sulfide material is performed in a CVD apparatus that includes a low temperature zone and a high temperature zone therein.
In some more preferred embodiments of the invention, the CVD apparatus is a tube furnace.
In some preferred embodiments of the invention, the carrier gas is a reducing mixture.
In some preferred embodiments of the invention, the carrier gas comprises an inert gas and hydrogen.
In some more preferred embodiments of the invention, the inert gas has a flow rate of 10-500sccm.
In some more preferred embodiments of the invention, the inert gas flow rate is about 300sccm.
In some more preferred embodiments of the invention, the hydrogen gas has a flow rate of 1-50sccm.
In some more preferred embodiments of the invention, the hydrogen gas has a flow rate of about 10sccm.
In some more preferred embodiments of the invention, the hydrogen gas has a flow rate of 1-50sccm.
In some more preferred embodiments of the invention, the temperature of the high temperature zone during the warm-up phase is at a rate of 10-50 ℃/min.
In some more preferred embodiments of the invention, the temperature of the high temperature zone during the warm-up phase is at a rate of about 40 ℃/min.
In some more preferred embodiments of the present invention, the incubation time is 10-30min in step S2.
In some more preferred embodiments of the present invention, the incubation time is about 20 minutes in step S2.
In some more preferred embodiments of the present invention, in step S2, the reaction pressure in the CVD apparatus is 1 to 760Torr during the soak reaction.
In some more preferred embodiments of the present invention, in step S2, the reaction pressure in the CVD apparatus during the soak reaction is about 760Torr.
In some more preferred embodiments of the present invention, the metal source and the sulfur source are placed in a high temperature region and a low temperature region of the CVD apparatus, respectively, and then the inert gas is used to evacuate the air in the CVD apparatus, and then the carrier gas is introduced into the CVD apparatus.
In some more preferred embodiments of the present invention, the inert gas includes, but is not limited to, nitrogen, helium, argon, carbon dioxide.
In some more preferred embodiments of the present invention, in step S2, the temperature of the high temperature region is raised to 520 ℃, and the temperature of the sulfur powder in the low temperature region is raised to 150 ℃ by a heating jacket during the temperature raising process, so as to perform a soak reaction.
In some more preferred embodiments of the present invention, in step S2, the temperature of the high temperature region is raised to 500 ℃, and the temperature of the sulfur powder in the low temperature region is raised to 150 ℃ by a heating jacket during the temperature raising process, so that the incubation reaction is performed.
In a second aspect of the invention, a non-layered two-dimensional material is proposed, which is produced according to the above-described production method.
In some embodiments of the invention, the non-layered two-dimensional material is a non-layered two-dimensional transition metal sulfide material. The non-layered two-dimensional transition metal sulfide material includes, but is not limited to, any one or more of ferrous sulfide, cobalt sulfide, nickel sulfide, vanadium sulfide, or chromium sulfide.
In some embodiments of the invention, the non-layered two-dimensional transition metal sulfide material has a size of 1 to 100 μm.
It should be noted that, for two-dimensional materials, thin fragments similar to some irregular shapes are usually used, and the dimensions herein refer to the size of the non-layered two-dimensional transition metal sulfide material in the two-dimensional plane.
In some preferred embodiments of the present invention, the non-layered two-dimensional transition metal sulfide material has a thickness of from 2 to 100nm.
In some embodiments of the invention, the shape of the non-layered two-dimensional transition metal sulfide material comprises a polygon.
In some preferred embodiments of the invention, the polygon comprises a curved edge.
In some preferred embodiments of the present invention, the shape of the non-layered two-dimensional transition metal sulfide material includes at least one of a triangle, a quadrilateral, a pentagon, or a hexagon.
In some more preferred embodiments of the present invention, the shape of the non-layered two-dimensional transition metal sulfide material includes at least one of a triangle with arcuate sides, a quadrilateral with arcuate sides, a pentagon with arcuate sides, or a hexagon with arcuate sides.
In a third aspect of the invention, an electronic device is presented comprising the non-layered two-dimensional material described above.
In some embodiments of the invention, the electronic device is an optoelectronic device.
In a fourth aspect of the invention, the use of the non-layered two-dimensional material described above in an electronic device is presented.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic view of the preparation process of a non-layered two-dimensional material according to example 1 of the present invention;
FIG. 2 is a graph showing the results of optical microscopy of the non-layered two-dimensional material of example 1 of the present invention;
FIG. 3 is a graph showing the results of atomic force microscopy of the non-layered two-dimensional material of example 1 of the present invention;
FIG. 4 is an X-ray diffraction spectrum of a non-layered two-dimensional material of example 1 of the present invention;
FIG. 5 is a graph showing the results of energy dispersive X-ray spectroscopy on a non-layered two-dimensional material according to example 1 of the present invention;
FIG. 6 is a graph showing the result of a cross-sectional spherical aberration transmission electron microscope test of a non-layered two-dimensional material of example 1 of the present invention;
FIG. 7 is a graph showing the results of high resolution transmission electron microscopy of the non-layered two-dimensional material of example 1 of the present invention;
FIG. 8 is a graph showing the result of a spherical aberration transmission electron microscope test of a non-layered two-dimensional material of example 1 of the present invention;
FIG. 9 is a graph of thermogravimetric analysis of the metal source of example 1, comparative examples 1-2 in accordance with the present invention;
FIG. 10 is an X-ray diffraction spectrum of the post-reaction residue of the metal source of example 1 of the present invention;
fig. 11 is an atomic force microscope test result chart and an electrical test result chart of the electronic device of example 1 of the present invention;
FIG. 12 is a graph showing the results of optical microscopy of the non-layered two-dimensional material of example 2 of the present invention;
FIG. 13 is a graph showing the thickness statistics of the non-layered two-dimensional material of example 2 according to the present invention;
FIG. 14 is a graph showing the results of optical microscopy of the non-layered two-dimensional material of example 3 of the present invention;
FIG. 15 is a graph showing the results of optical microscopy and atomic force microscopy of the non-layered two-dimensional material of example 4 of the present invention;
FIG. 16 is a graph showing the results of optical microscopy and atomic force microscopy of the non-layered two-dimensional material of example 5 of the present invention;
FIG. 17 is a graph showing the results of optical microscopy and atomic force microscopy of the non-layered two-dimensional material of example 6 of the present invention;
FIG. 18 is a graph showing the results of optical microscopy and atomic force microscopy of the non-layered two-dimensional material of example 7 of the present invention;
FIG. 19 is a graph showing the results of optical microscopy of the material of comparative example 1 in accordance with the present invention;
FIG. 20 is a graph showing the results of optical microscopy of the material of comparative example 2 in the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment discloses a non-layered two-dimensional material, which is a ferrous sulfide nano-sheet, wherein a preparation process schematic diagram is shown in fig. 1, and the preparation process comprises the following steps:
(I) mixing pure metal Fe powder and FeCl 3 Mixing the powder serving as a bimetallic precursor and a metal source according to a mass ratio of 1:1 (each of which is about 0.5 mg), and placing the mixed powder in a high-temperature zone of a double-temperature zone tube furnace; placing an excess of S powder (greater than 100 mg) in a low temperature zone of a double temperature zone tube furnace; placing a silicon oxide substrate at 15-20mm above the mixed powder;
(II) repeatedly cleaning the tube furnace with argon (Ar), and then raising the temperature of a high-temperature region in the tube furnace to 520 ℃ at a heating rate of 40 ℃/min; when the temperature of the tube furnace is increased to 400 ℃, the temperature of the S powder is increased to 150 ℃ by a heating sleeve at a heating rate of 30 ℃/min; continuously introducing a mixed gas of argon and hydrogen (the flow rate of the argon is 300sccm, and the flow rate of the hydrogen is 5 sccm) in the whole process, and transporting S vapor to a high-temperature area to react with the volatilized metal precursor vapor; and (3) carrying out heat preservation reaction for 10min at the temperature, naturally cooling the product after the reaction to 25 ℃ under the protection of argon, and obtaining uniformly distributed ferrous sulfide nano-sheets on the surface of the substrate.
The embodiment also provides an electronic device, which comprises the non-layered two-dimensional material prepared by the embodiment.
Example 2
The present example discloses a non-layered two-dimensional material, which is a ferrous sulfide nanosheet, and differs from example 1 in that:
in step (II) of this example, the tube furnace was heated to 500℃at 520℃at 540℃at 560℃at 580℃at 600℃at a heating rate of 40℃per minute, respectively, to prepare non-layered two-dimensional materials.
The embodiment also provides an electronic device, which comprises the non-layered two-dimensional material prepared by the embodiment.
Example 3
The present example discloses a non-layered two-dimensional material, which is a ferrous sulfide nanosheet, and differs from example 1 in that:
in step (II) of this embodiment, H is introduced 2 The flow rates were 1sccm, 5sccm, 10sccm, 25sccm, and 50sccm, respectively, to prepare non-layered two-dimensional materials.
The embodiment also provides an electronic device, which comprises the non-layered two-dimensional material prepared by the embodiment.
Example 4
The present example discloses a non-layered two-dimensional cobalt sulfide material, which is a nanosheet, and differs from example 1 in that: in this example, cobalt powder and cobalt chloride were used instead of the iron powder and iron chloride in example 1, respectively.
The embodiment also provides an electronic device, which comprises the cobalt sulfide nano-sheet prepared by the embodiment.
Example 5
The present example discloses a non-layered two-dimensional nickel sulfide material, which is a nanosheet, and differs from example 1 in that: in this example, nickel powder and nickel chloride were used instead of the iron powder and the iron chloride in example 1, respectively.
The embodiment also provides an electronic device, which comprises the nickel sulfide nanosheets prepared by the embodiment.
Example 6
The embodiment discloses a non-lamellar two-dimensional vanadium sulfide material which is a nano sheet and is different from the embodiment 1 in that: in this example, vanadium powder and vanadium chloride were used in place of the iron powder and iron chloride in example 1, respectively.
The embodiment also provides an electronic device, which comprises the vanadium sulfide nanosheets prepared by the embodiment.
Example 7
The present example discloses a non-layered two-dimensional chromium sulfide material, which is a nanosheet, and differs from example 1 in that: in this example, chromium powder and chromium chloride were used in place of the iron powder and iron chloride in example 1, respectively.
The embodiment also provides an electronic device, which comprises the chromium sulfide nanosheets prepared by the embodiment.
Comparative example 1
This comparative example discloses a material which differs from example 1 in that: the metal source in this comparative example, excluding FeCl 3 And (3) powder.
Comparative example 2
This comparative example discloses a material which differs from example 1 in that: the metal source in this comparative example does not include Fe powder.
Test examples
The test example tests the non-layered two-dimensional material obtained in the example and the material obtained in the comparative example, and specifically includes:
(1) For the non-layered two-dimensional material (nanoplatelets) prepared in example 1:
the prepared nanosheets were tested using an optical microscope, and the test results are shown in fig. 2. As can be seen from FIG. 2, the prepared nanosheets comprise trapezoid-like, pentagonal-like or hexagonal-like structures (irregular polygons with arc edges), have uniform thickness, have a size average of about 15 μm, and are uniformly distributed on the substrate.
The obtained nanosheets were tested by atomic force microscopy, and the test results are shown in fig. 3. As can be seen from FIG. 3, the thickness of the prepared nanoplatelets was about 10 nm.
The prepared nano-sheets were tested by an X-ray diffractometer, and the test results are shown in fig. 4. As can be seen from fig. 4, the nano-sheet of ferrous sulfide prepared in example 1 is ferrous sulfide.
The prepared nano-sheet was tested by using an energy dispersive X-ray spectrometer, and the test results are shown in fig. 5. As can be seen from fig. 5, the composition of the nano-sheet prepared in example 1 was ferrous sulfide, and the measured elemental ratio was approximately 1:1.
The obtained nanosheets were subjected to cross-sectional imaging analysis by transmission electron microscopy, and the test results are shown in fig. 6. As can be seen from fig. 6, the nanoplatelets prepared in example 1 are non-lamellar, i.e., covalent bonds between layers rather than van der waals bonds.
The image of the nano-sheet obtained in example 1 on the high-power transmission electron microscope and the corresponding electron diffraction image of the selected area are shown in fig. 7, and the image of the nano-sheet on the high-precision spherical aberration correction scanning transmission electron microscope is shown in fig. 8. As can be seen from fig. 7 and 8, the nano-sheet prepared in example 1 has extremely high crystallinity.
As can be seen from fig. 2 to 8, the non-layered two-dimensional material prepared by using the metal-metal chloride as the bimetallic precursor in the embodiment of the invention has the advantages of thin material thickness and good crystal phase. Example 1 the growth of nanoplatelets enabled benefits from the bimetallic precursor in example 1.
Furthermore, to further illustrate the Fe powder and FeCl 3 Effect of powder on volatilization rate of metal source thermogravimetric analysis was performed on the metal source raw materials in example 1 and comparative examples 1-2, and the resulting thermogravimetric analysis curves are shown in fig. 9: it proves that during the growth of the nano-sheet, fe powder and FeCl are added 3 The combined use of the powders has remarkable growth advantages, and the Fe powder is difficult to volatilize at the growth temperature of the example 1 due to the characteristic of high melting point (1535 ℃); and FeCl 3 The melting point (315 ℃) is far lower than the growth temperature of example 1, so that a large amount of volatilization can be generated at the growth temperature, and the nucleation and growth of ferrous sulfide are difficult to control.
The post-reaction residue of the metal source of example 1 was tested using an X-ray polycrystalline diffractometer and the test results are shown in fig. 10: when Fe powder and FeCl are used 3 When the powder is used as a bimetallic precursor, the metal at high Wen Xiatie can generate a centering reaction to generate a divalent intermediate product of iron, and the volatilization rate of the divalent intermediate product is well controlled, so that the nanosheets can be obtained.
(2) For the electronic device produced in example 1:
the electronic device obtained in example 1 was characterized, and the atomic force microscope test results and the electrical test results thereof are shown in fig. 11. As can be seen from fig. 11 (a), the non-layered two-dimensional material-nanoplatelets in the electronic device have a thickness of 13.5nm. As can be seen from fig. 11 (b), the non-layered two-dimensional material-nanoplatelets in the electronic device exhibit a narrow bandgap semiconductor characteristic, a bandgap of about 20meV, which exhibits a metallic type electrical behavior at room temperature under thermal excitation.
(3) For the non-layered two-dimensional material (nanoplatelets) prepared in example 2:
the nanoplates obtained in example 2 were each examined by an optical microscope, and the results of the examination are shown in fig. 12. In FIG. 12, (a), (b), (c), (d), (e) and (f) are optical photomicrographs of the nanoplatelets obtained in example 2 by raising the temperature in the high temperature region to 500℃520℃540℃560℃580℃600 ℃.
The thickness of the nanoplatelets prepared in example 2 was measured using an atomic force microscope, and the test results are shown in fig. 13: the thickness of the nanosheets obtained at 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃ and 600 ℃ is 5.9nm, 11.5nm, 18.1nm, 39.8nm, 62.7nm and 112.4nm respectively.
Examples 1 and 2 show that the thickness of the non-layered two-dimensional material (nanoplatelets) can be controlled by adjusting the growth temperature using the preparation method of the present invention.
(4) For the non-layered two-dimensional material (nanoplatelets) prepared in example 3:
the nanoplates obtained in example 3 were each examined by an optical microscope, and the results of the examination are shown in fig. 14. In FIG. 14, (a), (b), (c), (d) and (e) are H in example 3, respectively 2 The flow rates were set to 1sccm, 5sccm, 10sccm, 25sccm, and 50sccm for the optical microscope photographs of the produced nanoplatelets. The nanoplatelets obtained in example 3 have a thickness ranging from 5 to 15nm.
Comparative example 1 and example 3 show that the size of the nanoplatelets can be controlled by adjusting the growth temperature using the preparation method of the present invention.
(5) For the non-layered two-dimensional sulfide nanoplatelets prepared in examples 4-7:
the cobalt chloride nano-sheet prepared in example 4 was characterized, and the optical microscope and atomic force microscope test results are shown in fig. 15, and it can be seen from fig. 15 that the thickness of the two-dimensional cobalt sulfide nano-sheet obtained in example 4 is 8.9nm.
The nickel chloride nano-sheet prepared in example 5 is characterized, the optical microscope and atomic force microscope test results are shown in fig. 16, and as can be seen from fig. 16, the thickness of the two-dimensional nickel sulfide nano-sheet obtained in example 5 is 9.5nm.
Characterization is performed on the vanadium chloride nano-sheet prepared in example 6, the optical microscope and atomic force microscope test results are shown in fig. 17, and as can be seen from fig. 17, the thickness of the two-dimensional vanadium sulfide nano-sheet obtained in example 6 is 7.3nm.
Characterization is performed on the chromium chloride nano-sheet prepared in example 7, the optical microscope and atomic force microscope test results are shown in fig. 18, and as can be seen from fig. 18, the thickness of the two-dimensional chromium sulfide nano-sheet obtained in example 7 is 10.6nm.
(5) The materials prepared for comparative examples 1-2:
the material obtained in comparative example 1 was examined by an optical microscope, and the results of the examination are shown in FIG. 19. As can be seen from fig. 19, comparative example 1 hardly had any deposit on the substrate, and thus nano-sheets could not be grown. From this, feCl 3 The powder plays a key role in the preparation process of the nano-sheet, and can promote the volatilization of the metal precursor, so that the metal precursor is easier to nucleate and grow.
The material obtained in comparative example 2 was examined by an optical microscope, and the results of the examination are shown in FIG. 20. As can be seen from fig. 20, comparative example 2 produced a large amount of particle deposition on the substrate, and thus the growth of the nanoplatelets could not be completed. It can be seen that only FeCl is used 3 Excessive iron volatilization as a precursor occurs. As is clear from comparative example 1, only metallic Fe powder and its chloride FeCl were used 3 When the mixture of the powder is used as a bimetallic precursor, the ferrous sulfide nanosheets can be prepared.
The "room temperature" herein is about 25℃unless otherwise specified.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (11)

1. The preparation method is characterized in that a metal source containing a metal compound and a metal simple substance is used as a raw material, the non-layered two-dimensional material is prepared by a chemical vapor deposition method, and in the chemical vapor deposition process, the simple substance and the compound regulate and control the volatilization speed of the metal source through a centering reaction, wherein the metal comprises transition metal;
the non-layered two-dimensional material is a non-layered two-dimensional transition metal sulfide material;
the metal source is iron and ferric trichloride, cobalt and cobalt dichloride, nickel and nickel dichloride, vanadium and vanadium tetrachloride, or chromium and chromium dichloride.
2. The method of claim 1, wherein the non-layered two-dimensional transition metal sulfide comprises iron sulfide, cobalt sulfide, nickel sulfide, vanadium sulfide, or chromium sulfide.
3. The method of claim 2, wherein the non-layered two-dimensional transition metal sulfide comprises ferrous sulfide, cobalt sulfide, nickel sulfide, vanadium sulfide, or chromium sulfide.
4. The method for producing a non-layered two-dimensional material according to claim 1, wherein the mass ratio of the metal simple substance to the metal chloride is (0.1-1): 1.
5. a method of preparing a non-layered two-dimensional material according to claim 1, comprising the steps of: and carrying out chemical vapor deposition reaction on the metal source and the sulfur source in the carrier gas atmosphere, and obtaining the non-layered two-dimensional transition metal sulfide material on the surface of the substrate.
6. The method of claim 5, wherein the chemical vapor deposition reaction process comprises: and gasifying a sulfur source in a low-temperature area and a metal source in a high-temperature area, and performing chemical vapor deposition to obtain the non-layered two-dimensional transition metal sulfide material.
7. The method for preparing a non-layered two-dimensional material according to claim 5, wherein the method comprises the steps of:
s1, respectively placing the metal source and the sulfur source in a high temperature area and a low temperature area;
s2, introducing carrier gas, respectively increasing the temperature of the high temperature region and the temperature of the low temperature region to T1 and T2, and carrying out heat preservation reaction, wherein T1 and T2 are positive numbers and T1 is more than T2.
8. The method of claim 7, wherein T1 is 480-520 ℃.
9. The method of claim 7, wherein T2 is 140-160 ℃.
10. The method for preparing a non-layered two-dimensional material according to claim 7, wherein the heating rate of the high temperature region in the heating stage is 10-50 ℃/min.
11. Use of a non-layered two-dimensional material made by the method of any one of claims 1-10 in an electronic device.
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CN104058458A (en) * 2014-07-07 2014-09-24 中国科学技术大学 Method for preparing high-quality single/double-layer controllable molybdenum disulfide
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