CN117071077A - Two-dimensional non-layered self-intercalation V 3 S 5 Crystalline material and method for producing the same - Google Patents
Two-dimensional non-layered self-intercalation V 3 S 5 Crystalline material and method for producing the same Download PDFInfo
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- 239000002178 crystalline material Substances 0.000 title claims abstract description 48
- 238000009830 intercalation Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 67
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims abstract description 49
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims abstract description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 239000012159 carrier gas Substances 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 52
- 229910052786 argon Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 5
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 230000008021 deposition Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NGTSQWJVGHUNSS-UHFFFAOYSA-N bis(sulfanylidene)vanadium Chemical compound S=[V]=S NGTSQWJVGHUNSS-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/68—Crystals with laminate structure, e.g. "superlattices"
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a two-dimensional non-lamellar self-intercalation V 3 S 5 A preparation method of crystals belongs to the field of preparation of two-dimensional non-lamellar materials. The preparation method comprises the following steps: placing a sulfur source in an upstream area of a reaction furnace, and controlling the temperature of the upstream area to be 200-300 ℃; placing a vanadium source in the central area of the reaction furnace, and setting the temperature of the central area at 500-600 ℃, wherein the vanadium source is a mixture formed by vanadium chloride and a vanadium-containing substance with a melting point higher than that of the vanadium chloride; placing a substrate in a downstream area of a reaction furnace, introducing mixed gas of reducing gas and inert gas into the reaction furnace as carrier gas, conveying sulfur vapor to a central area of the reaction furnace for reaction, and depositing on the substrate in the downstream area to obtain a two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline material.
Description
Technical Field
The invention relates to the technical field of two-dimensional non-lamellar materials, in particular to a two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline materials and methods of making the same.
Background
Two-dimensional materials have attracted considerable attention since their discovery, exhibiting many excellent physicochemical properties. As many layered two-dimensional materials are successfully synthesized, their related properties have been studied extensively. In order to obtain more excellent physical and chemical properties, two-dimensional materials have been tried to be innovated and structurally modified, including doping, phase change and composition regulation, stacked heterojunction and intercalation studies. After the intercalation regulation and control are carried out on the two-dimensional material, the original layered structure is changed into a non-layered structure, and the original physical and chemical properties of the two-dimensional material are also obviously changed, so that a new path is opened up for the construction and research of the novel two-dimensional material. A non-layered structure is a structure without van der waals structures between layers.
Among non-layered two-dimensional materials, vanadium-based chalcogenides exhibit many physicochemical properties and are therefore of great interest. For example, 1T-VS 2 Has a typical charge density wave and is magnetic. Inserting V atoms into VS 2 The charge density wave of the interlayer is obviously changed, and the magnetic property is also changed. Thus, V atoms enter 1T-VS from intercalation 2 Provides a novel idea for researching charge density waves and magnetic properties.
Disclosure of Invention
To explore new physical properties, V atoms were intercalated into 1T-VS 2 By adjusting the electronic structure between the layers, new charge density waves and magnetic properties can be generated. The vanadium precursor commonly used in the synthesis of two-dimensional non-layered compounds is vanadium chloride. The vanadium chloride has low melting point, high activity and quick volatilization rate, and usually when the reaction temperature is not reached, the vanadium chloride volatilizes in a large amount in the process of heating, so that the vanadium chloride is extremely easy to react with chalcogenide in the process of reaction to generate a vanadium disulfide crystal material, and therefore, the vanadium is regulated and controlledIs very difficult, there is no effective means to synthesize self-intercalated compounds by controlling the vapor pressure of the metal source, and there is no two-dimensional V 3 S 5 The preparation method of the crystal material is reported, so that the preparation method of the material needs to be explored urgently.
To solve the problems existing in the prior art, the embodiment of the invention provides a two-dimensional non-lamellar self-intercalation V 3 S 5 Preparation method of crystal material and two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline material. In the embodiment of the invention, a mixture formed by vanadium chloride and vanadium-containing substances (such as at least one of vanadium powder, potassium vanadate, vanadium trioxide and vanadium pentoxide) with a higher melting point than the vanadium chloride is used as a vanadium source, and the vanadium-containing substances with a high melting point are used for delaying the volatilization of the vanadium chloride and regulating the vapor pressure of the vanadium source. Because the melting points of the vanadium source precursors are inconsistent, when the reaction temperature is reached, multiple vanadium precursors react, the proportion of the vanadium precursors is controlled according to the inconsistent melting points, and the vapor pressure of the vanadium can be regulated and controlled.
According to one aspect of the present invention, there is provided a two-dimensional non-layered self-intercalated V 3 S 5 The preparation method of the crystal material comprises the following steps:
placing a sulfur source in an upstream area of a reaction furnace, and controlling the temperature of the upstream area to be 200-300 ℃;
placing a vanadium source in the central area of the reaction furnace, and setting the temperature of the central area at 500-600 ℃, wherein the vanadium source is a mixture formed by vanadium chloride and a vanadium-containing substance with a melting point higher than that of the vanadium chloride;
placing a substrate in a downstream area of a reaction furnace, introducing mixed gas of reducing gas and inert gas into the reaction furnace as carrier gas, conveying sulfur vapor to a central area of the reaction furnace for reaction, and depositing on the substrate in the downstream area to obtain a two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline material.
According to another aspect of the present invention, there is provided a two-dimensional non-layered self-intercalated V 3 S 5 Crystalline material, whichIn the two-dimensional non-lamellar self-intercalation V 3 S 5 The crystalline material is prepared according to the preparation method described in any one of the preceding embodiments.
Drawings
These and/or other aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a two-dimensional non-layered self-intercalated V according to an embodiment of the invention 3 S 5 A flow chart of a method for preparing a crystalline material;
FIG. 2 is a two-dimensional non-layered self-intercalated V according to an embodiment of the invention 3 S 5 Schematic diagram of a process for preparing a crystalline material;
FIGS. 3a and 3b illustrate a two-dimensional non-layered self-intercalated V according to an embodiment of the invention 3 S 5 Morphology photomicrographs of crystalline materials;
FIG. 4 shows a two-dimensional non-layered self-intercalated V according to an embodiment of the present invention 3 S 5 Raman spectrum of the crystalline material;
FIG. 5 shows a two-dimensional non-layered self-intercalated V according to an embodiment of the present invention 3 S 5 A characterization diagram of the crystal structure of the crystalline material.
Detailed Description
The technical scheme of the invention is specifically described below through examples and with reference to the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of embodiments of the present invention with reference to the accompanying drawings is intended to illustrate the general inventive concept and should not be taken as limiting the invention.
In an embodiment of the present invention, a chemical deposition synthesized two-dimensional non-layered self-intercalated V is provided 3 S 5 The preparation process of crystal includes setting sulfur source in the upstream area of the reactor at 200-300 deg.c, setting the mixture of vanadium chloride and vanadium-containing matter with smelting point higher than that of vanadium chloride in the central area of the reactor at 500-600 deg.c, introducing mixed gas as carrier gas into the reactor, and conveying sulfur vapor to the central area of the reactor for reactionThe deposition is carried out on the substrate to obtain the two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline material.
The embodiment of the invention selects the mixture of vanadium chloride and vanadium-containing substances with the melting point higher than that of the vanadium chloride as the vanadium source, and sets the temperature of the central area to be 500-600 ℃, thus, in a reaction furnace, the volatilization process of the vanadium source (mixture) is delayed due to the existence of the vanadium-containing substances with the melting point higher than that of the vanadium chloride, so that the vapor pressure of the vanadium source is changed (compared with the vapor pressure of pure vanadium chloride), the temperature of the sulfur source in the upstream area is set to be 200-300 ℃, and when the reaction temperature (the temperature of the central area reaches 500-600 ℃), the vapor pressure of the vanadium source is higher than the vapor pressure of the sulfur source, namely enough vanadium chloride reacts with the sulfur vapor, and the two-dimensional non-lamellar self-intercalation V is formed on a substrate in a deposition way 3 S 5 Crystalline material.
Specifically, as can be seen from fig. 1 and 2, the two-dimensional non-layered self-intercalation V according to the embodiment of the present invention 3 S 5 The preparation method of the crystal comprises the following steps:
a sulfur source (e.g., by means of a quartz boat) is placed in an upstream region of the reaction furnace, and the temperature of the upstream region is controlled to 200-300 ℃ (e.g., 250 ℃);
placing a vanadium source (e.g., by means of a quartz boat) in a central region of the reaction furnace, and setting the temperature of the central region at 500-600 ℃ (e.g., 520-580 ℃), wherein the vanadium source is a mixture of vanadium chloride and a vanadium-containing material having a higher melting point than the vanadium chloride;
placing a substrate in a downstream area of a reaction furnace, introducing mixed gas of reducing gas and inert gas into the reaction furnace as carrier gas, conveying sulfur vapor to a central area of the reaction furnace for reaction, and depositing on the substrate in the downstream area to obtain a two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline material.
The two-dimensional non-lamellar self-intercalation V of the invention 3 S 5 The crystal material belongs to a triclinic system and belongs to a P1 space group. Two-dimensional non-layered self-intercalation V 3 S 5 The crystal material has a composition of alternating vanadium atomic layers and 1T-VS 2 Layers of layer compositionThe structure being such that the V atom is self-intercalated into 1T-VS 2 Interlaminar layers.
The embodiment of the invention utilizes vanadium-containing substances with a melting point higher than that of vanadium chloride to adjust the vapor pressure of a vanadium source. Since the vanadium source is composed of substances having different melting points, the volatilization of vanadium in the vanadium source is relatively less compared with pure vanadium chloride. Thus, when the reaction temperature is reached, more vanadium sources (such as vanadium chloride) react with the sulfur sources in the reaction furnace, thereby forming a two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline material. In one example, the vanadium-containing material having a melting point higher than that of vanadium chloride includes at least one of vanadium powder, potassium vanadate, vanadium trioxide, and vanadium pentoxide.
The sulfur source of the embodiment of the invention is positioned in the upstream area of the reaction furnace, and the temperature is set at 200-300 ℃. The temperature of the sulfur source is set to be 200-300 ℃ (lower than the temperature of the central area), on one hand, the melting point of the sulfur source is lower, the temperature can realize that the sulfur source is sufficient in the reaction process, and on the other hand, the vapor pressure of the sulfur source is smaller than that of the vanadium source, so as to be favorable for generating V 3 S 5 Crystalline material. For example, the sulfur source may be placed 8-15 cm (e.g., 10 cm) from the central region of the reactor to achieve a temperature at the sulfur source that is lower than the temperature of the central region, specifically 200-300 ℃.
In one example, the sulfur source is sulfur powder. The mass ratio of the sulfur powder to the vanadium source is 1:1. the use amount of the sulfur source and the vanadium source is regulated, which is helpful to control the vapor pressure of the sulfur source and the vanadium source in the reaction process and ensure the formation of V 3 S 5 Crystalline material. For example, in the case of a large amount of vanadium source, V is generated 5 S 8 A crystalline material; under the condition of less vanadium source, VS is generated 2 Crystalline material.
The vapor pressure of the vanadium source can be effectively regulated by regulating the mass ratio of vanadium chloride to vanadium-containing substances with the melting point higher than that of the vanadium chloride, so that excessive vanadium chloride is prevented from evaporating before reaching the reaction temperature and cannot participate in the reaction. In one example, the mass ratio of vanadium chloride to vanadium-containing material having a higher melting point than vanadium chloride is 3:1.
when the vanadium-containing substance having a melting point higher than that of vanadium chloride includes at least two of vanadium powder, potassium vanadate, vanadium trioxide and vanadium pentoxide, the mass of each vanadium-containing substance is equal. For example, when the vanadium-containing material includes vanadium powder and vanadium pentoxide, the mass ratio of the vanadium powder to the vanadium pentoxide is 1:1, a step of; correspondingly, in the vanadium source, the mass ratio of vanadium chloride, vanadium powder and vanadium pentoxide is 3:0.5:0.5.
the reaction furnace is a single-temperature-zone reaction furnace. The volatilization rate of the vanadium source can also be controlled by controlling the temperature rising rate of the reaction furnace. In one example, the temperature rise rate of the reaction furnace is 40-60 ℃/min. At a heating rate of 40-60 deg.c/min, it is ensured that there is less volatilization of the vanadium source (e.g., less than 10% of the vanadium source volatilizes) before the reaction temperature is reached.
In one example, the sulfur source, vanadium source, and reducing gas are reacted in the central region of the reaction furnace for 1 to 10 minutes. The reaction time needs to be ensured to be long enough to ensure that the reaction source can react completely and to provide sufficient time for intercalation of vanadium. If the reaction time is too short, this results in a smaller sample size to be obtained; if the reaction time is too long, this results in the formation of bulk crystalline material.
The preparation method of the embodiment of the present invention provides a mixed gas of a reducing gas and an inert gas during the reaction. The reducing gas undergoes oxidation-reduction reaction with the sulfur source and the vanadium source. The reducing gas includes at least one of hydrogen and carbon monoxide. Inert gases are used to transport the sulfur source (in particular, sulfur vapor) and carry away byproducts (e.g., water) generated by the reaction. The inert gas includes at least one of argon and nitrogen.
In the argon-hydrogen mixed gas (i.e., hydrogen is used as the reducing gas and argon is used as the inert gas), the argon is 50-100sccm, and the hydrogen is 2-10sccm. The amount of hydrogen is just the amount of hydrogen needed to properly react at this ratio, while argon in this range can provide a suitable source of sulfur for the reaction and can carry away by-products generated by the reaction. If the amount of hydrogen is above this range, this will result in etching the sample; if the amount of hydrogen is less than this range, the sample is insufficiently reacted, intermediate products may be present, and the product is adversely affectedAnd (5) crystallizing. If the amount of argon is above this range, the sulfur supply is excessive, resulting in an excessive sample thickness; otherwise, the supply is insufficient to generate V 3 S 5 Crystalline material.
Before the reaction starts, an inert gas (e.g., argon) is introduced into the reaction furnace. At this time, the inert gas is introduced to remove air in the reaction furnace, so that the reaction of the reactant with water and oxygen in the air is avoided, and the purity and yield of the reaction are ensured. Meanwhile, the pressure, the flow rate and the like of the reaction can be regulated by a proper amount of inert gas so as to meet the reaction requirement and improve the efficiency and the quality of the reaction.
After the reaction is completed, an inert gas (e.g., argon) is introduced into the reaction furnace until the temperature in the reaction furnace is reduced to room temperature. At this time, the inert gas is introduced to remove air in the reaction furnace, so that the reaction of the reactant with water and oxygen in the air is avoided, and the purity and yield of the reaction are ensured.
For example, before the reaction starts, inert gas is introduced into the reaction furnace; when the reaction starts, reducing gas is introduced into the reaction furnace, and meanwhile inert gas is also introduced continuously; and stopping introducing the reducing gas when the reaction is finished, and continuing introducing the inert gas until the reaction furnace is cooled to room temperature.
In an example, the substrate includes S i/SiO 2 At least one of a substrate, a sapphire substrate, and a mica substrate. In one example, si/SiO may be selected 2 A substrate to grow a crystalline material of excellent quality.
In another embodiment of the present invention, a two-dimensional non-layered self-intercalated V is provided 3 S 5 Crystalline material. The two-dimensional non-lamellar self-intercalation V 3 S 5 The crystalline material is prepared according to the preparation method described in any one of the preceding embodiments.
The two-dimensional non-lamellar self-intercalation V of the invention 3 S 5 The crystal material belongs to triclinic system, belongs to P1 space group, has alternating vanadium atomic layers and 1T-VS 2 A layered structure of layers. No van der waals structures exist between all layers.
Embodiments of the present invention will be described in detail below in terms of specific embodiments and in conjunction with the accompanying drawings. It will be appreciated by persons skilled in the art that the invention is not limited to the specific embodiments described and that reasonable modifications may be made after understanding the concepts of the invention.
Example 1
The invention adopts a single-temperature zone tube furnace as a reaction device, and uses a quartz tube with the length of 120cm, the outer diameter of 25cm and the wall thickness of 2mm. The reaction temperature in the central temperature zone was set to 540℃and the heating rate was 50℃per minute, with a reaction time of 10 minutes. Will S i/S iO 2 The substrate is placed downstream of the tube furnace for deposition of the reactants. Then weighing 0.2g of the mixture of vanadium chloride and vanadium powder by using a balance, wherein the mass ratio of the vanadium chloride to the vanadium powder is 3:1, placing the ceramic boat in a central temperature zone. Then, 0.2g of sulfur block was weighed with a balance and placed in a quartz boat and upstream of a tube furnace. Before the temperature-rising reaction, 750sccm of argon gas was introduced into the tube furnace for 1min, and the air in the tube furnace was completely removed. Then, the flow rate of argon gas was adjusted to 100sccm, the flow rate of hydrogen gas was adjusted to 10sccm, and the temperature-rising reaction was performed. After the reaction is finished, closing hydrogen, keeping the flow rate of argon unchanged, and rapidly cooling the tubular furnace to room temperature. Finally take out S i/S iO 2 A substrate, the sample deposited on the substrate is two-dimensional V 3 S 5 Crystalline material.
Example 2
The invention adopts a single-temperature zone tube furnace as a reaction device, and uses a quartz tube with the length of 120cm, the outer diameter of 25cm and the wall thickness of 2mm. The reaction temperature in the central temperature zone was set to 540℃and the heating rate was 50℃per minute, with a reaction time of 5 minutes. Will S i/S iO 2 The substrate is placed downstream of the tube furnace for deposition of the reactants. Then weighing 0.2g of the mixture of vanadium chloride and vanadium powder by using a balance, wherein the mass ratio of the vanadium chloride to the vanadium powder is 3:1, placing the ceramic boat in a central temperature zone. Then, 0.2g of sulfur block was weighed with a balance and placed in a quartz boat and upstream of a tube furnace. Before the temperature-rising reaction, 750sccm of argon gas was introduced into the tube furnace for 1min, and the air in the tube furnace was completely removed. Then, the flow rate of argon gas was adjusted to 100sccm, the flow rate of hydrogen gas was adjusted to 10sccm, and the temperature-rising reaction was performed. After the reaction is finished, the valve is closedClosing hydrogen, keeping the flow rate of argon unchanged, and rapidly cooling the tube furnace to room temperature. Finally take out S i/S iO 2 A substrate, the sample deposited on the substrate is two-dimensional V 3 S 5 Crystalline material.
Example 3
The invention adopts a single-temperature zone tube furnace as a reaction device, and uses a quartz tube with the length of 120cm, the outer diameter of 25cm and the wall thickness of 2mm. The reaction temperature in the central temperature zone was set to 540℃and the heating rate was 50℃per minute, with a reaction time of 3 minutes. Will S i/S iO 2 The substrate is placed downstream of the tube furnace for deposition of the reactants. Then weighing 0.2g of the mixture of vanadium chloride and vanadium powder by using a balance, wherein the mass ratio of the vanadium chloride to the vanadium powder is 3:1, placing the ceramic boat in a central temperature zone. Then, 0.2g of sulfur block was weighed with a balance and placed in a quartz boat and upstream of a tube furnace. Before the temperature-rising reaction, 750sccm of argon gas was introduced into the tube furnace for 1min, and the air in the tube furnace was completely removed. Then, the flow rate of argon gas was adjusted to 100sccm, the flow rate of hydrogen gas was adjusted to 10sccm, and the temperature-rising reaction was performed. After the reaction is finished, closing hydrogen, keeping the flow rate of argon unchanged, and rapidly cooling the tubular furnace to room temperature. Finally take out S i/S iO 2 A substrate, the sample deposited on the substrate is two-dimensional V 3 S 5 Crystalline material.
Example 4
The invention adopts a single-temperature zone tube furnace as a reaction device, and uses a quartz tube with the length of 120cm, the outer diameter of 25cm and the wall thickness of 2mm. The reaction temperature in the central temperature zone was set at 580℃and the heating rate was 50℃per minute, with a reaction time of 5 minutes. Will S i/S iO 2 The substrate is placed downstream of the tube furnace for deposition of the reactants. Then weighing 0.2g of the mixture of vanadium chloride and vanadium powder by using a balance, wherein the mass ratio of the vanadium chloride to the vanadium powder is 3:1, placing the ceramic boat in a central temperature zone. Then, 0.2g of sulfur block was weighed with a balance and placed in a quartz boat and upstream of a tube furnace. Before the temperature-rising reaction, 750sccm of argon gas was introduced into the tube furnace for 1min, and the air in the tube furnace was completely removed. Then, the flow rate of argon gas was adjusted to 100sccm, the flow rate of hydrogen gas was adjusted to 10sccm, and the temperature-rising reaction was performed. After the reaction is completed, the hydrogen is turned offThe argon flow rate is kept unchanged, and the tube furnace is rapidly cooled down to room temperature. Finally take out S i/S iO 2 A substrate, the sample deposited on the substrate is two-dimensional V 3 S 5 Crystalline material.
Example 5
The invention adopts a single-temperature zone tube furnace as a reaction device, and uses a quartz tube with the length of 120cm, the outer diameter of 25cm and the wall thickness of 2mm. The reaction temperature in the central temperature zone is set to 600 ℃, the heating rate is 50 ℃/min, and the reaction time is 5min. Will S i/S iO 2 The substrate is placed downstream of the tube furnace for deposition of the reactants. Then weighing 0.2g of the mixture of vanadium chloride and vanadium powder by using a balance, wherein the mass ratio of the vanadium chloride to the vanadium powder is 3:1, placing the ceramic boat in a central temperature zone. Then, 0.2g of sulfur block was weighed with a balance and placed in a quartz boat and upstream of a tube furnace. Before the temperature-rising reaction, 750sccm of argon gas was introduced into the tube furnace for 1min, and the air in the tube furnace was completely removed. Then, the flow rate of argon gas was adjusted to 100sccm, the flow rate of hydrogen gas was adjusted to 10sccm, and the temperature-rising reaction was performed. After the reaction is finished, closing hydrogen, keeping the flow rate of argon unchanged, and rapidly cooling the tubular furnace to room temperature. Finally take out S i/S iO 2 A substrate, the sample deposited on the substrate is two-dimensional V 3 S 5 Crystalline material.
Example 6
The invention adopts a single-temperature zone tube furnace as a reaction device, and uses a quartz tube with the length of 120cm, the outer diameter of 25cm and the wall thickness of 2mm. The reaction temperature in the central temperature zone was set to 540℃and the heating rate was 50℃per minute, with a reaction time of 2 minutes. Will S i/S iO 2 The substrate is placed downstream of the tube furnace for deposition of the reactants. Then weighing 0.2g of the mixture of vanadium chloride and vanadium powder by using a balance, wherein the mass ratio of the vanadium chloride to the vanadium powder is 3:1, placing the ceramic boat in a central temperature zone. Then, 0.2g of sulfur block was weighed with a balance and placed in a quartz boat and upstream of a tube furnace. Before the temperature-rising reaction, 750sccm of argon gas was introduced into the tube furnace for 1min, and the air in the tube furnace was completely removed. Then, the flow rate of argon gas was adjusted to 100sccm, the flow rate of hydrogen gas was adjusted to 10sccm, and the temperature-rising reaction was performed. After the reaction is finished, closing hydrogen and argonThe flow speed is kept unchanged, and the tube furnace is rapidly cooled down to room temperature. Finally take out S i/S iO 2 A substrate, the sample deposited on the substrate is two-dimensional V 3 S 5 Crystalline material.
In the present invention, the prepared two-dimensional V is observed by an optical microscope 3 S 5 The results are shown in fig. 3a and 3 b. As shown in FIG. 3a, when the reaction temperature was 540℃and the reaction time was 5min (example 2), the obtained sample was large in size but thick. As shown in FIG. 3b, when the reaction temperature was 540℃and the reaction time was reduced to 3 minutes (example 3), the obtained sample was slightly smaller in size but thinner in thickness. It can be seen that the sample size is too small when the growth temperature is too low or the growth time is too short in the process of optimizing the growth temperature and the growth time of the sample; and the growth temperature is increased or the growth time is prolonged, and the thickness of the grown sample is too thick. Thus, by comparison, the sample obtained is optimal at a reaction temperature of 540℃and a growth time of 3min.
Subsequently, samples of different thicknesses obtained in examples 1 to 6 were characterized by raman spectroscopy, and the characterization results are shown in fig. 4. As is evident from FIG. 4, self-intercalated V 3 S 5 The crystalline material has 4 characteristic peaks, 86cm each -1 、126cm -1 、166cm -1 And 325cm -1 . Wherein, 86cm -1 The characteristic peak is most likely due to intercalation of V atoms into 1T-VS 2 Caused by the interlayer; 126cm -1 And 166cm -1 Is a typical binaural sub-peak; 325cm -1 Characteristic peak corresponding to out-of-plane A 1g A mode.
V obtained in example 6 3 S 5 The crystal structure of the crystalline material was characterized by means of a spherical electron microscope, and the results are shown in fig. 5. As can be derived from FIG. 5, at 1T-VS 2 Periodic V atomic layers exist between the layers, and the V atoms are confirmed to enter 1T-VS from intercalation 2 Interlayer formation V 3 S 5 And (5) a crystal.
In conclusion, the embodiment of the technology synthesizes the two-dimensional non-lamellar self-intercalation V with large size and high quality 3 S 5 Crystalline material. The preparation technology is economical and simple, has strong operability, and is beneficial to exploring two-dimensional V 3 S 5 Physical properties of the crystalline material and application route thereof.
Although a few embodiments of the present general inventive concept have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the claims and their equivalents.
Claims (10)
1. Two-dimensional non-lamellar self-intercalation V 3 S 5 A method of preparing a crystalline material, wherein the method of preparing comprises the steps of:
placing a sulfur source in an upstream area of a reaction furnace, and controlling the temperature of the upstream area to be 200-300 ℃;
placing a vanadium source in the central area of the reaction furnace, and setting the temperature of the central area at 500-600 ℃, wherein the vanadium source is a mixture formed by vanadium chloride and a vanadium-containing substance with a melting point higher than that of the vanadium chloride;
placing a substrate in a downstream area of a reaction furnace, introducing mixed gas of reducing gas and inert gas into the reaction furnace as carrier gas, conveying sulfur vapor to a central area of the reaction furnace for reaction, and depositing on the substrate in the downstream area to obtain a two-dimensional non-lamellar self-intercalation V 3 S 5 Crystalline material.
2. Two-dimensional non-layered self-intercalated V according to claim 1 3 S 5 A method for preparing a crystalline material, wherein,
the vanadium-containing material with a melting point higher than that of vanadium chloride comprises at least one of vanadium powder, potassium vanadate, vanadium trioxide and vanadium pentoxide.
3. Two-dimensional non-layered self-intercalated V according to claim 2 3 S 5 A method for preparing a crystalline material, wherein,
the sulfur source is sulfur powder,
the mass ratio of the sulfur powder to the vanadium source is 1:1,
in the vanadium source, the mass ratio of vanadium chloride to vanadium-containing substances with a melting point higher than that of vanadium chloride is 3:1.
4. a two-dimensional non-layered self-intercalated V as claimed in claim 3 3 S 5 A method for preparing a crystalline material, wherein,
when the vanadium-containing substance having a melting point higher than that of vanadium chloride includes at least two of vanadium powder, potassium vanadate, vanadium trioxide and vanadium pentoxide, the mass of each vanadium-containing substance is equal.
5. The two-dimensional non-layered self-intercalated V of claim 4 3 S 5 A method for preparing a crystalline material, wherein,
the sulfur source is placed 8-15 cm from the central region of the reactor,
the temperature rising rate of the reaction furnace is 40-60 ℃/min.
6. Two-dimensional non-lamellar self-intercalating V according to any of the claims 1-5 3 S 5 A method for preparing a crystalline material, wherein,
the sulfur source, the vanadium source and the reducing gas react for 1 to 10 minutes in the central area of the reaction furnace.
7. The two-dimensional non-layered self-intercalated V of claim 6 3 S 5 A method for preparing a crystalline material, wherein,
the reducing gas includes at least one of hydrogen and carbon monoxide;
the inert gas comprises at least one of argon and nitrogen;
in the argon-hydrogen mixed gas, argon is 50-100sccm, and hydrogen is 2-10sccm.
8. The two-dimensional non-layered self-intercalated V of claim 7 3 S 5 A method for preparing a crystalline material, wherein,
the substrate comprises Si/SiO 2 At least one of sapphire and mica substrates,
before the reaction starts, inert gas is introduced into the reaction furnace;
after the reaction is finished, inert gas is introduced into the reaction furnace until the temperature in the reaction furnace is reduced to room temperature.
9. Two-dimensional non-lamellar self-intercalation V 3 S 5 A crystalline material, wherein,
the two-dimensional non-lamellar self-intercalation V 3 S 5 A crystalline material prepared according to the preparation method of any one of claims 1 to 8.
10. Two-dimensional non-layered self-intercalated V according to claim 9 3 S 5 A crystalline material, wherein,
the two-dimensional non-lamellar self-intercalation V 3 S 5 The crystal material belongs to triclinic systemSpace group consisting of alternating vanadium atomic layers and 1T-VS 2 A layered structure of layers.
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