CN115074695A - Novel two-dimensional CrX 2 Method for producing a material - Google Patents
Novel two-dimensional CrX 2 Method for producing a material Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 19
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- 238000002360 preparation method Methods 0.000 claims abstract description 15
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- 239000000654 additive Substances 0.000 claims abstract description 12
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
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- 239000002135 nanosheet Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- PICQSJQNJSMSNL-UHFFFAOYSA-N [S--].[S--].[Cr+4] Chemical compound [S--].[S--].[Cr+4] PICQSJQNJSMSNL-UHFFFAOYSA-N 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 8
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 0.000 description 8
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- 238000012512 characterization method Methods 0.000 description 5
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- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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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
- C23C16/22—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
-
- 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
- C23C16/44—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 method of coating
-
- 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
- C23C16/44—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 method of coating
- C23C16/46—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 method of coating characterised by the method used for heating the substrate
Abstract
The invention discloses a novel two-dimensional CrX 2 A method of preparing a (X ═ S or Se) material, comprising: 1) the reaction chamber was evacuated to a background vacuum of 1.0x10 0 Pa–1.0x10 ‑3 Pa; 2) mixing a chromium source with an additive material, forming the mixture into a first gaseous precursor, treating the X source to form a second gaseous precursor, wherein CrCl is used 3 ，CrBr 3 Or CrI 3 As chromium source, sulfur powder, selenium powder or H 2 S is taken as an X source; 3) under reducing or oxidizing atmosphere, the first gaseous precursor and the second gaseous precursor are transferred to the substrate for chemical reaction to form two-dimensional CrX 2 And (3) adopting sectional heating and constant temperature treatment for the substrate during the chemical reaction, wherein X is S or Se. The preparation method provided by the invention can effectively improve the preparation of CrX 2 Yield of material.
Description
Technical Field
The invention relates to the field of preparation of two-dimensional materials, in particular to a novel two-dimensional CrX 2 A method for preparing the material.
Background
Since 2004, under the influence of graphene, two-dimensional materials have become hot research in the fields of condensed physics, material science, optoelectronic information science and the like.
The two-dimensional nano material such as graphene, transition metal chalcogenide (TMDS), h-BN, black phosphorus, silylene and other two-dimensional atomic crystal layered materials has unique photoelectric characteristics, such as extremely high carrier mobility and thermal conductivity of graphene, physical properties of energy valley, spinning electron state and the like of TMDS, electric insulation of atomically smooth h-BN, energy gap adjustability, anisotropy, optical rotation and the like of the black phosphorus material along with the change of the number of layers, quantum spinning Hall effect of silylene and the like.
The two-dimensional material has potential application prospects in the aspects of information, micro-nano electronics and the like, and can be used for controlling the characteristics of the two-dimensional material to develop novel electronics and photoelectronic devices; the planar nature of the two-dimensional material makes it easier to integrate into existing semiconductor processing technologies.
For two-dimensional chromium sulfide materials, the theory reports [ j.phys. chem.c 116,8983 (2012); appl.phys.lett.104,022116 (2014); j.phys.chem.c 118,7242 (2014); j.alloys Compd.47,47020554(2015)]CrS indicating a monolayer 2 Energy band structure and two-dimensional MoS 2 Similarly, the photoelectric characteristics of the light source include valley scattering (valley polarization). Theoretical studies show that CrS follows two dimensions 2 The number of layers of the material is different, the energy band width of the material is changed from about 0.5eV to 1.3eV, and the energy range covers the wave band from visible light to intermediate infrared light in the spectrum, so that the material has great significance for the development of a series of photoelectric technologies such as remote communication, sensors, solar cells and the like. Meanwhile, the energy range is matched with the band gaps of silicon and III-V group semiconductors in the prior semiconductor technology, so that the material with the band gap has great research value and application potential. Experimentally, the inventor of the invention has synthesized CrS by taking metal Cr as a Cr source and S powder as an S source in Nanoscale 11,20123(2019) and patent publications of ZL201711268412.3 and ZL201811399316.7 in 2019 2 However, CrS obtained by the above-mentioned technique 2 The yield is relatively low. At the same time, CrSe is currently prepared 2 The material yield is also low.
Disclosure of Invention
The invention aims toAiming at the defects of the prior art, a novel two-dimensional CrX is provided 2 The preparation method of the material provided by the invention can effectively improve the preparation of CrX 2 Yield of material.
The technical scheme provided by the invention is as follows:
novel two-dimensional CrX 2 A method of preparing a (X ═ S or Se) material, comprising:
1) the reaction chamber was evacuated to a background vacuum of 1.0x10 0 Pa–1.0x10 -3 Pa；
2) Mixing a chromium source with an additive material, forming the mixture into a first gaseous precursor, treating the X source to form a second gaseous precursor, wherein CrCl is used 3 ，CrBr 3 Or CrI 3 As chromium source, sulfur powder, selenium powder or H 2 S is taken as an X source;
3) under reducing or oxidizing atmosphere, the first gaseous precursor and the second gaseous precursor are transferred to the substrate for chemical reaction to form two-dimensional CrX 2 And (3) adopting sectional heating and constant temperature treatment for the substrate during the chemical reaction, wherein X is S or Se.
The chromium source in the step 2) of the invention refers to a compound (solid, liquid or gas) containing chromium element, and the mass ratio of the chromium source to the material of the additive is 1: 0.5-6.
Preferably, the chromium source in step 2) is CrCl 3 、CrBr 3 Or CrI 3 . Considering the problem that metallic chromium has a high melting point (1907 deg.C) and is difficult to form gaseous substances, CrCl having a lower melting point is used 3 (1152℃)、CrBr 3 Or CrI 3 As a source of chromium. Simultaneously preparing two-dimensional CrX 2 Can reduce two-dimensional CrX in the process 2 Additive material capable of forming energy capable of further reducing two-dimensional CrX 2 The function of which is to lower the melting point of the chromium source in combination with the chromium source and to form two-dimensional CrX 2 The material has a catalytic effect.
The X source in step 2) of the invention refers to a solid, gaseous or liquid substance or simple substance which is easy to form gas and contains sulfur or selenium. Preferably, the sulfur isThe source being sulfur powder or H 2 S gas, selenium source is selenium powder.
The CrX can be reduced in the step 2) of the invention 2 The additive materials that form the energy include: metals (e.g., gold, etc.), non-metals (e.g., tellurium, iodine), and salts containing sodium, potassium ions (e.g., NaCl, KI, etc.). Preferably, the material is one or more selected from gold, tellurium, sodium salt and potassium salt.
In the invention, in the step 2), the X source is transferred to the substrate through the carrier gas mass to carry out chemical reaction. Preferably, the carrier gas is N 2 Or Ar. In addition to the carrier gas, optionally, a reducing hydrogen gas may be passed, and the chemical reaction may be carried out in an oxidizing atmosphere.
The method for forming the first gaseous precursor and the second gaseous precursor in step 2) of the present invention may employ heating or energetic particle beam treatment. Subjecting the mixture and the X source to energy to become a gaseous material, i.e. to form a gaseous precursor; the energetic particle beam includes laser, plasma, electron beam, etc.
The step 3) of the invention for the temperature rise and constant temperature treatment comprises a multi-stage temperature rise and constant temperature treatment, and 1-5 stages can be selected. Wherein the two stages of heat treatment are as follows: firstly heating up, carrying out constant temperature treatment, then heating up, and then carrying out constant temperature treatment. Preferably, the substrate is processed by two-stage temperature rise and two-stage constant temperature treatment in the chemical reaction, wherein the constant temperature of the first stage is 200-500 ℃, and the constant temperature of the second stage is 600-950 ℃. The two temperature rising rates can be different and can be respectively 2-80 ℃/min.
The substrate in the invention comprises an insulating material, a semiconductor material, a noble metal, graphite or graphene and other two-dimensional layered materials such as TMDs and the like. Wherein the semiconductor material and the insulator material include, but are not limited to ZrB 2 、SiC、SiO 2 、BN、Si 3 N 4 、HfO 2 、Al 2 O 3 One or a combination of more than two of sapphire, mica, graphene oxide, ZnO, MgO, Si, Ge, GaN, GaAs and InP; noble metals include Au, Pt, Pd, Ir, etc., which refer to metals that do not form alloys with Cr and do not react with S; TMDs include MoS 2 、WS 2 、MoSe 2 、WTe 2 And so on, so that van der waals heterojunctions can be formed.
According to the invention, the Cr source is mixed with the additive material, so that the melting point of the Cr source can be reduced, and the temperature of chemical reaction can be reduced, thereby effectively controlling the reaction rate and improving the preparation efficiency, quality and yield of the Cr source.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares two-dimensional CrX 2 The method for preparing the (X ═ S or Se) material is simple, and the preparation efficiency, quality and yield can be effectively improved.
Drawings
FIG. 1 shows two-dimensional layered CrX 2 A schematic structural diagram of a material;
FIG. 2 is a two-dimensional CrX 2 A schematic diagram of a material preparation method;
figure 3 is an OM image of the two-dimensional chromium disulfide material prepared in example 1;
figure 4 is an OM image of the two-dimensional chromium disulfide material prepared in example 2;
figure 5 is an OM image of the two-dimensional chromium disulfide material prepared in example 3;
figure 6 is an SEM image and EDS image of the two-dimensional chromium disulfide material prepared in example 3;
figure 7 is an XPS spectrum of a two-dimensional chromium disulfide material prepared in example 3;
figure 8 is an AFM image of the two-dimensional chromium disulfide material prepared in example 3;
figure 9 is a Raman spectrum of a two-dimensional chromium disulfide material prepared in example 3;
figure 10 is an OM image of the two-dimensional chromium disulfide material prepared in comparative example 1;
figure 11 is an OM image of the two-dimensional chromium disulfide material prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by the following specific examples.
The two-dimensional chromium sulfide material contains chromium and sulfur or selenium, the atomic structure of the two-dimensional chromium sulfide material is planar, and the single-layer two-dimensional chromium sulfide material consists of sulfur, chromium and sulfurThe sandwich structure of the three atomic layers and the structure of the layered two-dimensional chromium sulfide material are shown in fig. 1, wherein white represents X (X ═ S or Se) atoms, and black represents Cr atoms. The single-layer two-dimensional chromium sulfide is piled into two-dimensional chromium sulfide materials with different layers, and the chemical structural formula of the two-dimensional chromium sulfide materials is CrS 2 . Two-dimensional CrX in the present invention 2 The material comprises CrX with 1-100 layers 2 The film material is more preferably 1 to 50 layers. The preparation method is schematically shown in figure 2.
Example 1
First, CrCl was weighed separately with an electronic balance 3 30mg of powder, 15mg of Te powder and 300mg of S powder. Adding CrCl 3 Mixing powder and Te powder uniformly, placing into quartz boat 1 together with mica substrate, keeping the substrate at a proper distance from chromium source, placing S powder into quartz boat 2, placing the two quartz boats into two temperature zones of tube furnace respectively (figure 2), and vacuumizing with mechanical pump to make background vacuum of quartz tube reach 1.0 × 10 -3 Pa。
The temperature of the quartz boat 1 provided with the chromium source is firstly raised to 200 ℃ at the speed of 5 ℃/min, the constant temperature is maintained for 1 min, then raised to 600 ℃ at the speed of 25 ℃/min, the constant temperature is maintained for about 10 min, and the chromium source is vulcanized into two-dimensional CrS 2 Nanosheets.
The temperature of the quartz boat 1 filled with elemental sulfur powder was kept at about 130 ℃ from the reaction start temperature. The whole process of the high-temperature tube furnace is kept at normal pressure, and inert gas such as argon is introduced as carrier gas in the whole process, and the flow rate is about 30 sccm.
After the vulcanization reaction is finished, the temperature of the high-temperature furnace is reduced to room temperature at the cooling rate of 40 ℃/min to obtain the two-dimensional CrS 2 Nanosheets. For the obtained two-dimensional CrS 2 The nanosheet is subjected to optical OM characterization, as shown in FIG. 3, it can be known that the introduction of tellurium powder can effectively reduce CrCl 3 Melting point to obtain high-quality two-dimensional CrS 2 A material having an average size of about 3 μm. Two-dimensional CrS prepared in this example 2 The OM image of the material is shown in fig. 3.
Example 2
Firstly, accurately weighing CrCl respectively by using an electronic balance 3 30mg of powder, 120mg of Te powder and 300mg of S powder. Adding CrCl 3 Powder andte powder is mixed uniformly, and is placed in a quartz boat 1 together with a Si substrate, the substrate and a chromium source are kept at a proper distance, S powder is placed in the quartz boat 2, the two quartz boats are respectively placed in two temperature areas of a tube furnace, and the quartz tube is pumped by a mechanical pump to vacuum, so that the background vacuum of the quartz tube reaches 1.0 multiplied by 10 -2 Pa。
The temperature of the quartz boat 1 with the chromium source is firstly raised to 200 ℃ at the speed of 5 ℃/min, the constant temperature is maintained for 8 minutes, then raised to 700 ℃ at the speed of 25 ℃/min, the constant temperature is maintained for about 10 minutes, and the chromium source is vulcanized into two-dimensional CrS 2 Nanosheets.
The temperature of the quartz boat 1 filled with elemental sulfur powder is kept at about 130 ℃ from the reaction starting temperature. The whole process of the high-temperature tube furnace is kept at normal pressure, and inert gas such as argon is introduced as carrier gas in the whole process, and the flow rate is about 30 sccm.
After the vulcanization reaction is finished, the temperature of the high-temperature furnace is reduced to room temperature at the cooling rate of 40 ℃/min to obtain the two-dimensional CrS 2 Nanosheets. For the obtained two-dimensional CrS 2 The nanosheet is subjected to optical OM characterization, as shown in FIG. 4, it is known that CrS can be increased by increasing the growth temperature 2 To obtain high quality two-dimensional CrS 2 Material, CrS obtained by reaction at 700 ℃ 2 The average size of the nanoplatelets is about 5 μm. Two-dimensional CrS prepared in this example 2 The OM image of the material is shown in fig. 4.
Example 3
Firstly, accurately weighing CrCl respectively by using an electronic balance 3 30mg of powder, 180mg of Te powder and 300mg of S powder. CrCl is added 3 Mixing powder and Te powder uniformly, placing mica substrate in quartz boat 1 at a proper distance from chromium source, placing S powder in quartz boat 2, placing the two quartz boats in two temperature zones of tube furnace respectively, and vacuumizing with mechanical pump to make background vacuum of quartz tube reach 1.0 × 10 0 Pa。
The quartz boat 1 with the chromium source is heated to 200 ℃ at a temperature of 5 ℃/min, is maintained at a constant temperature for 4 min, is heated to 950 ℃ at a temperature of 25 ℃/min, and is maintained at the constant temperature for about 10 min, so that the Cr is vulcanized into two-dimensional CrS 2 Nanosheets.
The temperature of the quartz boat 1 filled with elemental sulfur powder was kept at about 130 ℃ from the reaction start temperature. The whole process of the high-temperature tube furnace is kept at normal pressure, and inert gas such as argon is introduced as carrier gas in the whole process, and the flow rate is about 30 sccm.
After the vulcanization reaction is finished, the temperature of the high-temperature furnace is reduced to room temperature at the cooling rate of 40 ℃/min to obtain the two-dimensional CrS 2 Nanosheets. For the obtained two-dimensional CrS 2 The nanosheet is subjected to optical OM characterization, as shown in FIG. 5, it can be known that CrS can be remarkably improved by increasing the growth temperature 2 Yield and size of CrS obtained by reaction at 950 ℃ 2 The nanosheets have an average size greater than 10 μm. Further on the obtained two-dimensional CrS 2 SEM and EDS energy spectrum analysis of the material, as shown in FIG. 6, hexagonal two-dimensional CrS can be found 2 In the nano-sheet, Cr and S elements are uniformly distributed, and the atomic coefficient ratio is about 1: 2 with CrS 2 The chemical formula is consistent. Te does not exist in the obtained material, which also indicates that the Te only plays the roles of reducing the melting point of the chromium source and catalyzing in the synthesis process and does not participate in chemical reaction. An X-ray photoelectron spectrum was used to further confirm the elemental composition of the resulting material, as shown in FIG. 7, which indicates that the product contains Cr and S, indicating that the invention results in two-dimensional CrS 2 。
The hexagonal two-dimensional CrS prepared by the invention 2 The thickness of the nanosheets was about 19nm as measured by atomic force microscopy, as shown in fig. 8. For the prepared hexagonal two-dimensional CrS 2 The nanosheets were subjected to Raman characterization, the results of which are shown in FIG. 9, having a depth of 176cm -1 ，251cm -1 ，283cm -1 ，358cm -1 Four Raman peaks in total, corresponding to a two-dimensional CrS of 1T or 1T' phase 2 。
Comparative example 1
First, 30mg of Cr powder, 180mg of Te powder and 300mg of S powder were precisely weighed on an electronic balance, respectively. Mixing Cr powder and Te powder uniformly, placing the mixture and mica substrate in quartz boat 1 with proper distance between the substrate and chromium source, placing S powder in quartz boat 2, placing the two quartz boats in two temperature zones of tube furnace respectively, and vacuumizing by mechanical pump to make background vacuum of quartz tube reach 1.0 × 10 0 Pa。
The quartz boat 1 with the chromium source is heated to 200 ℃ at a temperature of 5 ℃/min, is maintained at a constant temperature for 4 min, is heated to 950 ℃ at a temperature of 25 ℃/min, and is maintained at the constant temperature for about 10 min, so that the Cr is vulcanized into two-dimensional CrS 2 A film.
The temperature of the quartz boat 1 filled with elemental sulfur powder was kept at about 130 ℃ from the reaction start temperature. The whole process of the high-temperature tube furnace is kept at normal pressure, and inert gas such as argon is introduced as carrier gas in the whole process, and the flow rate is about 60 sccm.
After the vulcanization reaction is finished, the temperature of the high-temperature furnace is reduced to room temperature at the cooling rate of 40 ℃/min to obtain the two-dimensional CrS 2 A film. For the two-dimensional CrS prepared by adopting metal Cr powder as a chromium source 2 The nanosheets were characterized by optical OM, as shown in fig. 10, with greater variability in product size and thickness and non-uniform sample mass. By comparison, CrCl was used 3 As a chromium source, two-dimensional CrS with higher quality and yield can be obtained 2 A material.
Comparative example 2
Firstly, accurately weighing CrCl respectively by using an electronic balance 3 Powder 30mg and S powder 180 mg. Adding CrCl 3 Placing the powder and mica substrate in quartz boat 1 at a proper distance from the chromium source, placing S powder in quartz boat 2, placing the two quartz boats in two temperature zones of tube furnace respectively, and vacuumizing by mechanical pump to make background vacuum of quartz tube reach 1.0 × 10 0 Pa。
The temperature of the quartz boat 1 containing the chromium source is raised to 200 ℃ at a rate of 5 ℃/min, and is maintained at the constant temperature for 4 minutes, and then raised to 950 ℃ at a rate of 25 ℃/min, and is maintained at the constant temperature for about 10 minutes, so that the chromium source is vulcanized into two-dimensional CrS 2 A film.
The temperature of the quartz boat 1 filled with elemental sulfur powder was kept at about 130 ℃ from the reaction start temperature. The whole process is kept at normal pressure, and inert gas such as argon is introduced as carrier gas in the whole process, and the flow rate is about 60 sccm.
After the vulcanization reaction is finished, the temperature of the high-temperature furnace is reduced to room temperature at the cooling rate of 40 ℃/min to obtain the two-dimensional CrS 2 A film. For only CrCl 3 The powder is used as a chromium source to prepare the obtained two-dimensional CrS 2 Nanosheet for optical applicationsOM characterization, as shown in fig. 11, the product yield and size were small. This is probably due to CrCl 3 The melting point of the powder is higher, if no additive is used for reducing the melting point, CrCl is generated during reaction 3 The powder is difficult to melt, resulting in a lower concentration of the first gaseous precursor and a final two-dimensional CrS 2 The yield of the material is low.
Although the present invention provides XPS studies and Raman spectra only in example 3, samples obtained from other examples also have the same XPS and Raman spectral characteristics.
Meanwhile, the invention only provides CrCl 3 As Cr source, but CrBr is principally 3 And CrI 3 Other Cr-containing compounds may also be used as Cr sources for the production of CrS 2 A material.
Also, the invention discloses a method for synthesizing CrS by taking a Cr compound as a Cr source and Te as an additive 2 Materials, but similar principles can also be used to prepare other transition metal chalcogenides containing Cr, such as CrSe 2 And the like.
The above examples simply illustrate the preparation of two-dimensional CrX of the invention 2 Basic principle of the nano-sheet, wherein each parameter can be according to the CrX required to be prepared 2 But rather mediated and the parameters in the different embodiments may be referred to one another. The examples are intended to better understand the idea of the invention and do not limit the scope of the claims of the invention.
Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the appended claims.
Claims (6)
1. Novel two-dimensional CrX 2 The preparation method of the material is characterized by comprising the following steps:
1) the reaction chamber was evacuated to a background vacuum of 1.0x10 0 Pa–1.0x10 -3 Pa；
2) Mixing a chromium source with a catalyst capable of reducing CrX 2 Mixing the energy-forming additive materials together to form the mixtureFirst gaseous precursor, treating the X source to form a second gaseous precursor, wherein CrCl is used 3 ，CrBr 3 Or CrI 3 As chromium source, sulfur powder, selenium powder or H 2 S is taken as an X source;
3) under reducing or oxidizing atmosphere, the first gaseous precursor and the second gaseous precursor are transferred to the substrate for chemical reaction to form two-dimensional CrX 2 And (3) adopting sectional heating and constant temperature treatment for the substrate during the chemical reaction, wherein X is S or Se.
2. Novel two-dimensional CrX according to claim 1 2 The preparation method of the material is characterized in that in the step 2), the additive material is selected from one or more of gold, tellurium, iodine, sodium salt and potassium salt.
3. Novel two-dimensional CrX according to claim 1 2 The preparation method of the material is characterized in that in the step 2), CrCl is contained in the chromium source 3 、CrBr 3 Or CrI 3 The ratio of the additive material to the additive material is 1: 0.5-6.
4. Novel two-dimensional CrX according to claim 1 2 The method for preparing the material is characterized in that in the step 2), the method for forming the first gaseous precursor and the second gaseous precursor adopts heating or energy particle beam treatment.
5. Novel two-dimensional CrX according to claim 1 2 The preparation method of the material is characterized in that in the step 3), the substrate is processed by two-stage temperature rise and two-stage constant temperature treatment in the chemical reaction, wherein the constant temperature of the first stage is 200-500 ℃, and the constant temperature of the second stage is 600-950 ℃.
6. Novel two-dimensional CrX according to claim 1 2 The preparation method of the material is characterized in that the substrate is selected from insulating materials, semiconductor materials, noble metals, graphite or graphene or two-dimensional layered materials TMDs.
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| GB201605121D0 (en) * | 2016-03-24 | 2016-05-11 | Isis Innovation | Process |
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| CN110079823A (en) * | 2019-05-15 | 2019-08-02 | 中山大学 | Electrode material, using and preparation method thereof |
| CN110295357A (en) * | 2018-03-21 | 2019-10-01 | 北京大学 | A kind of quick magnanimity prepares the method and device of oversize two-dimensional material film |
| CN111206283A (en) * | 2020-02-19 | 2020-05-29 | 湖南大学 | Preparation and application of chromium diselenide two-dimensional material |
| CN111206230A (en) * | 2018-11-22 | 2020-05-29 | 浙江大学 | Preparation method of novel two-dimensional chromium sulfide material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB201605121D0 (en) * | 2016-03-24 | 2016-05-11 | Isis Innovation | Process |
| KR20190070852A (en) * | 2017-12-13 | 2019-06-21 | 한양대학교 에리카산학협력단 | Transition metal dichalcogenide thin film and manufacturing method of the same |
| CN110295357A (en) * | 2018-03-21 | 2019-10-01 | 北京大学 | A kind of quick magnanimity prepares the method and device of oversize two-dimensional material film |
| CN111206230A (en) * | 2018-11-22 | 2020-05-29 | 浙江大学 | Preparation method of novel two-dimensional chromium sulfide material |
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