CN113718227B - Two-dimensional layered ternary compound and preparation method thereof - Google Patents
Two-dimensional layered ternary compound and preparation method thereof Download PDFInfo
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- CN113718227B CN113718227B CN202010446362.9A CN202010446362A CN113718227B CN 113718227 B CN113718227 B CN 113718227B CN 202010446362 A CN202010446362 A CN 202010446362A CN 113718227 B CN113718227 B CN 113718227B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 20
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- 239000010410 layer Substances 0.000 claims abstract description 79
- 239000010949 copper Substances 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 239000010408 film Substances 0.000 claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 claims abstract description 62
- 239000002356 single layer Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 26
- 150000003624 transition metals Chemical class 0.000 claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 9
- 238000005411 Van der Waals force Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
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- 238000006243 chemical reaction Methods 0.000 claims description 74
- 239000010703 silicon Substances 0.000 claims description 74
- 229910016006 MoSi Inorganic materials 0.000 claims description 67
- 239000007789 gas Substances 0.000 claims description 59
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 54
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 229910052785 arsenic Inorganic materials 0.000 claims description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
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- 239000010937 tungsten Substances 0.000 claims description 9
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- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910000078 germane Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
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- 239000001257 hydrogen Substances 0.000 description 50
- 229910052739 hydrogen Inorganic materials 0.000 description 50
- 238000010438 heat treatment Methods 0.000 description 42
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- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 5
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- 229910007991 Si-N Inorganic materials 0.000 description 1
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- 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
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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
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- 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
- C23C16/34—Nitrides
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- 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
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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- 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
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- 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
- C30B29/38—Nitrides
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to the field of two-dimensional layered ternary compound materials and Chemical Vapor Deposition (CVD) preparation thereof, in particular to a two-dimensional layered ternary compound and a preparation method thereof. In the two-dimensional layered ternary compound, each layer is composed of 7 atomic layers of Y-X-Y-M-Y-X-Y, and Van der Waals force bonding is formed between the layers. Adopting a copper/transition metal double-metal layer substrate, introducing a fourth main group element and a fifth main group element, and growing a single layer or a few layers of MX (MX) by CVD (chemical vapor deposition) at a high temperature not higher than the melting point of copper 2 Y 4 Ternary compounds, which are subsequently transferred to any substrate by etching the copper substrate. The invention has the characteristics of simple preparation process, easy regulation and control of product components, thickness and size, suitability for large-area high-quality thin film preparation and the like, and is two-dimensional MX 2 Y 4 Lays a foundation for research and application in the fields of electronic devices, photoelectronic devices, millet electronic devices, high-strength films, high-light-transmittance films, proton/ion exchange membranes, separation membranes and the like.
Description
The technical field is as follows:
the invention relates to a two-dimensional layered ternary compound material and the field of Chemical Vapor Deposition (CVD) preparation thereof, in particular to a two-dimensional layered MX 2 Y 4 (M is transition metal element, X is fourth main group element, Y is fifth main group element) ternary compound and preparation method thereof, and is suitable for preparing large-area high-quality single-layer and few-layer MX 2 Y 4 Crystals and thin films.
The background art comprises the following steps:
the successful exfoliation of graphene opens the door to the study of two-dimensional layered materials. The two-dimensional layered material has wide application prospect in the fields of electronics, photoelectrons, information, energy, environment, aerospace and the like due to excellent electrical, optical, thermal, mechanical and other properties. The two-dimensional layered material can show different physical and chemical properties and bring new physical effects due to different components and structures, so that the exploration of the novel two-dimensional layered material is always the most active research frontier in the field of two-dimensional materials, and has great significance for expanding the physical properties of the two-dimensional layered material and developing new applications. At present, in addition to graphene, a variety of novel two-dimensional layered materials are also successively prepared, including h-BN, transition metal chalcogenides, oxides, black phosphenes, and the like. However, the two-dimensional layered materials are relatively simple in composition and structure, mainly single-element and binary, and mostly have corresponding layered bulk materials, and can be obtained by peeling off the bulk materials.
The invention content is as follows:
the invention aims to provide a two-dimensional layered ternary compound and a preparation method thereof, wherein each layer of the two-dimensional layered ternary compound consists of 7 atomic layers of Y-X-Y-M-Y-X-Y, and Van der Waals force is bonded between the layers.
The technical scheme of the invention is as follows:
a two-dimensional layered ternary compound with molecular formula MX 2 Y 4 Wherein: m is a transition metal element including, but not limited to, molybdenum, tungsten, titanium, zirconium, hafnium, vanadium, niobiumTantalum or chromium; x is a group iv element including, but not limited to, silicon or germanium; y is a group v element including, but not limited to, nitrogen, phosphorus, or arsenic; each layer of the compound consists of 7 atomic layers of Y-X-Y-M-Y-X-Y, which are bonded to each other by van der waals forces.
A two-dimensional layered ternary compound is prepared through preparing growth substrate from dual-metal layer consisting of upper Cu layer and bottom transition metal M layer, providing M element by diffusion channel of transition metal M, introducing X and Y elements in carrier gas atmosphere, and catalytic reaction on Cu surface to obtain MX under the condition of not higher than Cu smelting point 2 Y 4 Single crystal or thin film, MX being subsequently etched away Cu 2 Y 4 Transfer to any substrate.
The preparation method of the two-dimensional layered ternary compound comprises the following steps that a laminated Cu foil and a transition metal M foil are adopted as a double-metal-layer growth substrate; or the coating is obtained by adopting a coating method of magnetron sputtering or thermal evaporation; the thickness of the upper layer copper is 100 nm-100 μm.
The preparation method of the two-dimensional layered ternary compound introduces X, Y elements by using X, Y-containing precursors, wherein the precursors are solids, powders, liquids or gases which volatilize or decompose X or Y at high temperature.
In the preparation method of the two-dimensional layered ternary compound, X is a fourth main group element including but not limited to silicon or germanium, a silicon element precursor includes but not limited to a silicon wafer, a quartz plate or silane, and a germanium element precursor includes but not limited to a germanium plate or germane; y is a group v element including, but not limited to, nitrogen, phosphorus or arsenic, precursors of nitrogen include, but are not limited to, ammonia, precursors of phosphorus include, but are not limited to, white phosphorus or red phosphorus, and precursors of arsenic include, but are not limited to, elemental arsenic.
In the preparation method of the two-dimensional layered ternary compound, in the chemical vapor deposition reaction process, the carrier gas is hydrogen or the mixed gas of hydrogen and inert gas.
The preparation method of the two-dimensional layered ternary compound is chemical vapor deposition growth of two-dimensional layered MX 2 Y 4 Temperature of ternary CompoundThe temperature is 900-1083 ℃, the growth time is 10-1200 minutes, and MX is increased by prolonging the growth time 2 Y 4 The size of the crystal domains, and thus the complete continuous film.
The preparation method of the two-dimensional layered ternary compound is two-dimensional layered MX 2 Y 4 The number of layers of the ternary compound is regulated by changing the amount of X, Y element precursors in the chemical vapor deposition process: in the case of small precursor amounts, a complete monolayer of MX is obtained 2 Y 4 Single crystal or thin film, increasing the amount of precursor to obtain less or more MX layers 2 Y 4 。
The preparation method of the two-dimensional layered ternary compound transfers the two-dimensional layered MoSi 2 N 4 When in use, firstly, a layer of high molecular polymer is uniformly coated on the surface of the substrate to prevent the substrate from being damaged in the subsequent treatment process, and then the copper substrate is etched and removed by using copper etching solution to obtain the high molecular polymer/two-dimensional layered MoSi 2 N 4 And finally, placing the composite membrane on a target substrate, and dissolving and removing the high-molecular polymer protective membrane by adopting an organic solvent.
The preparation method of the two-dimensional layered ternary compound adopts one or more than two of polymethyl methacrylate, polyethylene, polystyrene and polypropylene as high molecular polymer, adopts ammonium persulfate aqueous solution, stannic chloride aqueous solution, ferric chloride aqueous solution, concentrated ammonia water or dilute hydrochloric acid as copper etching solution, and adopts one or more than two of ketone, chlorohydrocarbon, halohydrocarbon and aromatic hydrocarbon reagents as organic solvent for removing a high molecular polymer protective layer.
The design idea of the invention is as follows:
structurally, single-layer ternary compound MX 2 Y 4 Can be seen as a sandwich structure two-dimensional material consisting of a double layer of a fourth main group element X-Y and a fifth main group element X-Y, a single layer of a transition group metal, a fifth main group element compound MY, a fourth main group element X-Y and a fifth main group element X-Y. Transition metal fifth main group element compound is a non-layered material, and a fourth main group element X is introduced to form an X-Y double layer to passivate single-layer transition metalBelongs to a surface dangling bond of a fifth main group element compound MY, changes island growth caused by surface energy constraint into layered growth, and forms a novel two-dimensional layered ternary compound material MX with each layer consisting of 7 atomic layers of Y-X-Y-M-Y-X-Y 2 Y 4 The layers are bonded through Van der Waals force; in addition, a double metal layer formed by an upper Cu layer and a bottom transition metal M layer is used as a growth substrate, and when the growth is carried out at a reaction temperature not higher than the melting point of copper, the diffusion of the bottom transition metal M is greatly limited by the solid copper layer, so that a uniform single-layer MX is ensured 2 Y 4 And (5) growing the thin film.
The invention has the advantages and beneficial effects that:
1. the invention provides a novel two-dimensional layered ternary compound material with a molecular formula of MX 2 Y 4 Wherein M is a transition group metal element, X is a fourth main group element, Y is a fifth main group element, each layer of the compound is composed of 7 atomic layers of Y-X-Y-M-Y-X-Y, the layers are combined through Van der Waals force, the compound shows different properties of electricity, optics, mechanics and the like according to different components, and can be semiconductors or magnetic semimetals with different band gaps.
2. The invention provides a method for preparing two-dimensional layered MX 2 Y 4 The obtained two-dimensional layered MX is obtained by the chemical vapor deposition method 2 Y 4 The structure is uniform, and the material has high crystallization quality, excellent environmental, chemical, thermal stability and mechanical properties, and lays a foundation for research and application in the fields of electronic devices, optoelectronic devices, millet electronic devices, high-strength films, high-light-transmission films, proton/ion exchange membranes, separation membranes and the like.
3. The CVD method provided by the invention can be carried out under normal pressure, has the characteristics of convenient operation, easy regulation and control, easy large-area preparation and the like, and can obtain MX with different layers 2 Y 4 Single crystal or large area films, the size of which depends on the size of the substrate used in the growth process.
Description of the drawings:
FIG. 1 is a schematic diagram of an experimental device for growing a high-quality two-dimensional layered ternary compound by a CVD method, in which two-dimensional layered MoSi is used 2 N 4 Ternary compound crystals are exemplified. In the figure, 1 gas inlet; 2 silicon wafer or quartz wafer; 3 a metal substrate; 31 a copper foil; 32 transition group metal flakes; 4, heating the furnace; 5 pyrolyzing the boron nitride tube; 6, a quartz tube; 7 gas outlet.
FIG. 2 shows single-layer MoSi obtained at different growth times on a Cu/Mo substrate 2 N 4 The optical microscope photograph of (1). Wherein: a, 15 minutes; b, 30 minutes; c, 1 hour; d, 2 hours; e, 3 hours; f, 3.5 hours.
FIG. 3 shows single-layer MoSi obtained at different growth times on Cu/Mo substrates 2 N 4 Transfer to SiO 2 Optical microscope pictures on Si substrates. Wherein: a, 15 minutes; b, 30 minutes; c, 1 hour; d, 2 hours; e, 3 hours; f, 3.5 hours.
FIG. 4: a is single-layer MoSi 2 N 4 The curve is the thickness curve of a single-layer sample measured by an atomic force microscope, and b is a multi-layer MoSi 2 N 4 The atomic force microscope photograph of (1); c is a thickness variation curve measured by an atomic force microscope at a horizontal dotted line at the upper left of the b graph, the abscissa represents the measured distance (μm), and the ordinate represents the measured thickness (nm); d is a thickness variation curve measured by an atomic force microscope at the middle upper oblique dotted line of the b graph, the abscissa represents the measured distance (μm), and the ordinate represents the measured thickness (nm).
FIG. 5: a picture is single-layer MoSi 2 N 4 B is a selected area electron diffraction pattern of the sample plane in panel a, c is an X-ray energy dispersion spectrum of the sample in panel a, wherein the copper signal is from a micro grid, the abscissa represents binding energy (keV) and the ordinate represents intensity (a.u.). d is the electron energy loss spectrum of the sample in graph a, with the abscissa representing the electron loss energy (eV) and the ordinate representing the intensity (a.u.). The data of panels c and d show that the atomic ratio of Mo atoms, Si atoms and N atoms in the sample is approximately 1:2: 4.
FIG. 6: a picture is single-layer MoSi 2 N 4 Planar high resolution scanning transmission electron microscopy shows that the sample has high crystalline quality. b is a multilayer MoSi 2 N 4 Height of cross sectionThe layered structure is clearly seen in the resolution of the scanning transmission electron micrograph, with a spacing of about 1nm between adjacent layers. c picture is multilayer MoSi 2 N 4 And (3) a high-resolution scanning transmission electron microscopy surface scanning photograph of the cross section, wherein d-f images respectively correspond to X-ray energy dispersion spectrum surface scanning results of Mo element, Si element and Mo + Si element in the c image. g picture is multilayer MoSi 2 N 4 High resolution scanning transmission electron microscopy photographs of the cross sections, and the h-picture and the i-picture correspond to the electron energy loss spectrum surface scanning results of the Si element and the N element in the g-picture, respectively.
FIG. 7 is a schematic view of: a is MoSi 2 N 4 The 3D atomic structure model diagram in (b) is a single-layer MoSi 2 N 4 The model of the atomic structure along the a axis, and the c diagram is a single-layer MoSi 2 N 4 Atomic structure model diagram along the c-axis. With MoSi 2 N 4 For example, the crystal structures of other novel two-dimensional layered ternary compounds are similar.
FIG. 8: graph a is transferred to SiO 2 Single layer MoSi on a/Si substrate 2 N 4 Raman spectra obtained after 24 hours of immersion in ethanol, isopropanol and 1mol/L hydrochloric acid, respectively, the abscissa represents the Raman shift (cm) -1 ) And the ordinate represents the intensity (a.u.), and the Raman spectrum signal of the sample has no obvious change before and after soaking, which proves that the sample has excellent chemical stability. b picture is transferred to SiO 2 Single layer MoSi on a/Si substrate 2 N 4 Raman spectra after being respectively placed in air for 6 months, soaked in water for 1 week and soaked in water at 80 ℃ for 8 hours, the abscissa represents Raman shift (cm) -1 ) The ordinate represents intensity (a.u.) and the raman spectrum signal of the sample did not change significantly before and after treatment, demonstrating excellent environmental stability. c picture is single layer MoSi grown on Cu/Mo substrate 2 N 4 Raman spectra after annealing for 3h at different temperatures in an argon atmosphere, with the abscissa representing the Raman shift (cm) -1 ) The ordinate represents intensity (a.u.) and it can be seen that the raman spectral signal of the sample after annealing up to 300 ℃ has no significant change, indicating its excellent thermal stability.
FIG. 9 is a single layer MoSi 2 N 4 Is measured. a diagramIs a single layer of MoSi 2 N 4 Transfer characteristic curve, abscissa V, measured in room temperature air bg Representing the grid voltage (V), ordinate-I ds Representing the negative number (μ A), V, of the source-drain current ds Represents the source-drain voltage (V); b is the output characteristic curve of the sample tested in the room temperature air in the graph a, and the abscissa V ds Represents the source-drain voltage (V), ordinate I ds Represents the source-drain current (μ A), V gs Represents the gate voltage (V); c picture is single layer MoSi 2 N 4 Transfer characteristic curve, abscissa V, tested in a 77K vacuum environment bg Representing the grid voltage (V), ordinate-I ds Represents the negative number (μ a) of the source-drain current; d is the output characteristic curve of the sample tested in the 77K vacuum environment in the c picture, and the abscissa V ds Represents source-drain voltage (V), ordinate I ds Represents the source-drain current (μ A), V gs Representing the gate voltage (V).
FIG. 10 is a single layer MoSi 2 N 4 The mechanical properties of (1) are characterized. a picture is suspended monolayer MoSi used for an atomic force microscope nano mechanics test experiment 2 N 4 A height profile of the film; b is diagram of suspended monolayer MoSi 2 N 4 The abscissa represents the penetration depth (nm) of the atomic force probe, and the ordinate represents MoSi applied to the suspended monolayer 2 N 4 Force on the membrane (nN); c picture is single layer MoSi 2 N 4 The abscissa represents the Young's modulus (GPa), the ordinate represents the statistical number of the corresponding Young's modulus data, and the upper coordinate E 2D Represents a two-dimensional Young's modulus (N/m) corresponding to the abscissa; d is single-layer MoSi 2 N 4 The abscissa represents the fracture strength (GPa), the ordinate represents the statistical number of the corresponding fracture strength data, and the upper coordinate sigma 2D Represents the two-dimensional breaking strength (N/m) corresponding to the abscissa.
FIG. 11 is a single layer MoSi 2 N 4 And (4) characterizing the optical property of the film. a picture is a single layer of MoSi transferred onto a quartz plate 2 N 4 The absorption spectrum of the film has a wavelength (nm) on the abscissa and an absorbance (a.u) on the ordinate, and the inset is for wavelengths between 450 and 600nmThe absorption peaks were separated to give an A exciton absorption peak at 560nm (2.21eV) and a B exciton absorption peak at 527nm (2.35 eV). The b picture is a Tauc picture obtained by converting the absorption spectrum of the a picture, the abscissa represents photon energy (eV), and the ordinate (alpha h v) 0.5 Representing the absorption coefficient-related variable (a.u), the intersection of the line extending from the linear segment of the curve with the abscissa represents the indirect bandgap value of the material, and the inset is a single layer of MoSi transferred onto a quartz plate 2 N 4 The transmittance of the film was measured by a curve, the abscissa represents the wavelength (nm) and the ordinate represents the transmittance (%).
FIG. 12 shows WSi 2 N 4 The structural characterization of (2). a diagram is a single-layer WSi 2 N 4 The bright field transmission electron microscopy shows that the sample has a clear crystallographic triangular shape, and the inset is the corresponding electron diffraction pattern. And b, a graph is an X-ray energy dispersion spectrum corresponding to the graph a, and shows that the sample contains W, Si and N elements. The abscissa represents binding energy (eV) and the ordinate represents intensity (a.u.). c is a single layer WSi 2 N 4 Planar high resolution scanning transmission electron microscopy photographs show that the samples have high crystalline quality, indicating the position of the W, Si, N atoms and the image intensity information of the W and Si atoms. d diagram is a multilayer WSi 2 N 4 High resolution scanning transmission electron micrographs of the cross-section clearly show the layered structure with a layer spacing of about 1 nm. e diagram is in SiO 2 Multilayer WSi between a substrate and a Pt protective layer 2 N 4 And (3) a high-resolution scanning transmission electron microscopy surface scanning photograph of the cross section, wherein the f-j diagram corresponds to the X-ray energy dispersion spectrum surface scanning result of the W element, the Si element, the N element, the O element and the Pt element in the e diagram respectively.
The specific implementation mode is as follows:
in the specific implementation process, the two-dimensional layered ternary compound MX provided by the invention 2 Y 4 The preparation method adopts a double metal layer formed by an upper Cu layer/a bottom layer transition metal M as a growth substrate, Cu is used as a diffusion channel of the M to provide an M element, X and Y elements are introduced in a carrier gas atmosphere, and MX is grown on the Cu surface through a catalytic reaction at a reaction temperature not higher than the melting point of the copper by a CVD (chemical vapor deposition) technology 2 Y 4 A single crystal or a thin film of,MX by subsequent Cu etching 2 Y 4 Transferring to any substrate by the following specific steps:
(1) two-dimensional layered ternary compound MX 2 Y 4 By two-dimensional layered transition group metal silicon nitrogen ternary compound MSi 2 N 4 For example: a double metal layer formed by copper (upper layer)/transition metal M (bottom layer) is used as a growth substrate, a silicon wafer or a quartz wafer is placed above or in front of the growth substrate to be used as a silicon source, and ammonia gas is used as a nitrogen source. The double metal layer substrate may be a bi-metal laminate composed of a copper foil/transition metal foil, or may be obtained by plating a transition metal M film and a copper film on a copper foil and a transition metal M foil, respectively. In the high-temperature CVD process, the transition metal layer provides M atoms of transition metals, the solid copper layer is used as a diffusion channel of the M atoms of transition metals, and a small amount of M atoms of transition metals diffused to the surface of the solid copper react with Si atoms and N atoms cracked at high temperature to form a two-dimensional layered MSi 2 N 4 ；
In the bimetal lamination growth substrate, the transition metal foil adopted by the bottom layer is a titanium sheet, a zirconium sheet, a hafnium sheet, a vanadium sheet, a niobium sheet, a tantalum sheet, a chromium sheet, a molybdenum sheet or a tungsten sheet and the like, and the copper foil adopted by the upper layer has the thickness of 100 nm-100 μm, and the preferred range is 1 μm-25 μm; the purity is 98 wt% -99.9999 wt%, and the preferred range is 99.5 wt% -99.9999 wt%. The nitrogen source used in the CVD growth process is ammonia gas, and the silicon source is silicon wafer, quartz wafer or silane. When other two-dimensional layered ternary compound crystals grow, the germanium source is a germanium sheet or germane, the phosphorus source is simple substance phosphorus, and the arsenic source is simple substance arsenic. The carrier gas used for CVD growth is hydrogen or a mixed gas of hydrogen and inert gas (the carrier gas flow is 20 ml/min-1000 ml/min). The CVD growth temperature is 900-1083 ℃, and the preferable range is 1050-1080 ℃; the growth time is 10 minutes to 1200 minutes, preferably 15 minutes to 240 minutes; the cooling rate after the reaction is 10 to 600 ℃/min, preferably 200 to 600 ℃/min.
(2) Coating of high molecular polymer protective layer: uniformly coating a layer of high molecular polymer on the surface of the two-dimensional layered ternary compound to prevent the surface of the two-dimensional layered ternary compound from being damaged in the subsequent treatment process; the high molecular polymer is one or more than two of polymethyl methacrylate, polyethylene, polystyrene and polypropylene.
(3) Dissolution of copper substrate: dissolving the copper substrate by using a copper etching solution to obtain a high molecular polymer/two-dimensional layered ternary compound crystal composite film; the dissolving solution for removing the copper substrate is a tin tetrachloride aqueous solution, an ammonium persulfate aqueous solution, a ferric chloride aqueous solution or dilute hydrochloric acid and the like, the molar concentration of the dissolving solution is 0.05-2 mol/L, and concentrated ammonia water can also be used as a copper etching solution.
(4) Removing the high-molecular polymer protective layer: and placing the obtained high molecular polymer/two-dimensional layered ternary compound crystal composite membrane on a target substrate, and dissolving and removing the high molecular polymer protective membrane covered on the surface of the two-dimensional layered ternary compound by using an organic solvent.
The organic solvent is used for removing the high molecular polymer protective layer, and the organic solvent is one or more than two of acetone, ethyl lactate, dichloroethane, trichloroethylene, chloroform and other ketones, chlorohydrocarbons, halogenated hydrocarbons and aromatic hydrocarbon reagents.
The novel two-dimensional layered ternary compound crystal or film obtained by the invention is of a layered structure, Van der Waals force is combined between layers, the growth thickness of the novel two-dimensional layered ternary compound crystal or film is controllable, a uniform single-layer large-area polycrystalline film can be grown, the grain size can reach 100 mu m to the maximum extent, the single-layer thickness is about 1nm, and the plane size of the film depends on the size of a used substrate; few layers of crystals can also be grown with a thickness of 2-10 nm. The material has uniform components and high crystallization quality.
The present invention will be described in more detail below with reference to examples and the accompanying drawings.
Example 1
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 The two ends of the horizontal reaction furnace are respectively provided with a gas inlet 1 and a gas outlet 7, the copper foil/molybdenum sheet is arranged in a high-temperature area of the horizontal reaction furnace, and the copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm) is used as the material for preparing the catalyst100 microns with a purity of 99.95 wt%) and a silicon wafer (14 mm x 650 micron with a purity of 99.9999 wt%) were placed in the central region of a pyrolytic boron nitride tube (tube inner diameter 16 mm, length 20 cm), wherein the silicon wafer was placed above a copper foil/molybdenum sheet (bimetallic sheet), the silicon wafer and bimetallic sheet were spaced approximately 3.5 mm apart, and then the copper foil/molybdenum sheet, silicon wafer and pyrolytic boron nitride tube were placed together in the central region of a horizontal reactor (furnace tube diameter 22 mm, reaction zone length 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), rapidly cooling to 1080 ℃ within 2 min when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 15 min, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the copper surface.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) is dripped on the surface of copper on which a silicon-nitrogen molybdenum nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 rpm, the PMMA film is dried at 120 ℃ for 10 minutes and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 minutes to dissolve the copper substrate, and the PMMA/silicon-molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of silicon-molybdenum nitride crystals is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the obtained silicon molybdenum nitride is single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 10 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 2
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/molybdenum sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the tube inner diameter is 16 mm, the length is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the tube has a diameter of 22 mm, and the length of a reaction zone is 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), rapidly cooling to 1080 ℃ within 2 min when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature reaches 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 30 min, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the copper surface.
Then, an ethyl lactate solution (4 wt% of polymethyl methacrylate) of polymethyl methacrylate (PMMA) is dripped on the copper surface where the molybdenum silicon nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 r/min, the PMMA film is dried at 120 ℃ for 10 min and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 min to dissolve the copper substrate, the PMMA/silicon molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of the silicon-molybdenum nitride crystal is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the obtained silicon molybdenum nitride is single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 15 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 3
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/molybdenum sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the inner diameter of the tube is 16 mm, the length of the tube is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the diameter of the tube is 22 mm, and the length of the reaction zone is 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, and the heating rate is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature reaches 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 1 hour, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the copper surface.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) is dripped on the surface of copper on which a silicon-nitrogen molybdenum nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 rpm, the PMMA film is dried at 120 ℃ for 10 minutes and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 minutes to dissolve the copper substrate, and the PMMA/silicon-molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of silicon-molybdenum nitride crystals is realized.
The composition, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are measured by using an optical microscope, a transmission electron microscope and an atomic force microscopeThe obtained molybdenum silicon nitride is represented by single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 25 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 4
Firstly, as shown in FIG. 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/molybdenum sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the tube inner diameter is 16 mm, the length is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the tube has a diameter of 22 mm, and the length of a reaction zone is 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), rapidly cooling to 1080 ℃ within 2 min when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature reaches 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 3.5 hours, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride film on the copper surface.
Then, an ethyl lactate solution (4 wt% of polymethyl methacrylate) of polymethyl methacrylate (PMMA) is dripped on the copper surface where the molybdenum silicon nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 r/min, the PMMA film is dried at 120 ℃ for 10 min and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 min to dissolve the copper substrate, the PMMA/silicon molybdenum nitride film is transferred to SiO 2 On a Si substrate, PMMA is dissolved off by acetone at a temperature of 55 ℃,finally realizing the successful transfer of the silicon-molybdenum nitride crystal.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the obtained silicon molybdenum nitride film is a single-layer MoSi film with a hexagonal structure 2 N 4 The polycrystalline thin film had an average size of 40 μm and a thickness of about 1nm, was free from defects, vacancies, and had semiconductor characteristics.
Example 5
Firstly, as shown in FIG. 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/molybdenum sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the tube inner diameter is 16 mm, the length is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the tube has a diameter of 22 mm, and the length of a reaction zone is 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, and the heating rate is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 8 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature reaches 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 1 hour, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the copper surface.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) was dropped on the copper surface on which the molybdenum silicon nitride crystal was grown, a PMMA film was formed by a spin coater at 5000 rpm, and the film was baked at 120 ℃ for 10 minutesPutting the mixture into 0.2mol/L ammonium persulfate aqueous solution after the reaction for 20 minutes at the temperature of 70 ℃ to dissolve the copper substrate, and transferring the PMMA/silicon molybdenum nitride film to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of the silicon-molybdenum nitride crystal is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the obtained silicon molybdenum nitride is multilayer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 20 μm, a thickness of about 2 to 10nm, a high crystalline quality, and semiconductor characteristics.
Example 6
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/molybdenum sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the inner diameter of the tube is 16 mm, the length of the tube is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the diameter of the tube is 22 mm, and the length of the reaction zone is 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), rapidly cooling to 1070 ℃ within 4 min when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature reaches 1070 ℃, starting to grow two-dimensional silicon molybdenum nitride, wherein the growth time is 1.5 hours, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain silicon molybdenum nitride crystals on the copper surface.
Then, an ethyl lactate solution (4 wt% of polymethyl methacrylate) of polymethyl methacrylate (PMMA) is dripped on the copper surface where the molybdenum silicon nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 r/min, the PMMA film is dried at 120 ℃ for 10 min and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 min to dissolve the copper substrate, the PMMA/silicon molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of the silicon-molybdenum nitride crystal is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the obtained silicon molybdenum nitride is single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 40 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 7
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/molybdenum sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the inner diameter of the tube is 16 mm, the length of the tube is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the diameter of the tube is 22 mm, and the length of the reaction zone is 20 mm); heating to 1090 ℃ in hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), rapidly cooling to 1055 ℃ within 7 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ammonia for ammonia gas) when the furnace temperature is reduced to 1055 ℃Milliliter per minute and 200 milliliters per minute of hydrogen gas) to start to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 1.5 hours, and after the growth is finished, the two-dimensional silicon molybdenum nitride is rapidly cooled at the speed of 500 ℃/minute to obtain a silicon molybdenum nitride crystal on the surface of copper.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) is dripped on the surface of copper on which a silicon-nitrogen molybdenum nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 rpm, the PMMA film is dried at 120 ℃ for 10 minutes and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 minutes to dissolve the copper substrate, and the PMMA/silicon-molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of silicon-molybdenum nitride crystals is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained silicon molybdenum nitride is a single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 15 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 8
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/molybdenum sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the tube inner diameter is 16 mm, the length is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the tube has a diameter of 22 mm, and the length of a reaction zone is 20 mm); heating to 1090 deg.C in hydrogen atmosphere to melt copper foil (hydrogen flow rate of 20 during heating process)0 ml/min, the heating rate is 20 ℃/min), when the furnace temperature reaches 1090 ℃, the temperature is rapidly reduced to 1030 ℃ within 12 minutes to solidify the copper foil, mixed gas of ammonia and hydrogen is introduced after the furnace temperature reaches 1030 ℃, the growth of two-dimensional silicon molybdenum nitride is started, the growth time is 1.5 hours, and after the growth is finished, the rapid cooling is carried out at the speed of 500 ℃/min, so that silicon molybdenum nitride crystals are obtained on the surface of the copper.
Then, an ethyl lactate solution (4 wt% of polymethyl methacrylate) of polymethyl methacrylate (PMMA) is dripped on the copper surface where the molybdenum silicon nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 r/min, the PMMA film is dried at 120 ℃ for 10 min and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 min to dissolve the copper substrate, the PMMA/silicon molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of the silicon-molybdenum nitride crystal is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained silicon molybdenum nitride is a single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 3 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 9
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 The two ends of the horizontal reaction furnace are respectively provided with a gas inlet 1 and a gas outlet 7, a copper foil/molybdenum sheet is arranged in a high-temperature area of the horizontal reaction furnace, the copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 25 micron, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the tube inner diameter is 16 mm, the length is 20 cm), wherein the silicon wafer is arranged above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil is arrangedPutting a molybdenum sheet, a silicon wafer and a pyrolytic boron nitride tube together in the central area of a horizontal reaction furnace (the diameter of the furnace tube is 22 mm, and the length of the reaction zone is 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), rapidly cooling to 1080 ℃ within 2 min when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature reaches 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 1.5 hours, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the copper surface.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) is dripped on the surface of copper on which a silicon-nitrogen molybdenum nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 rpm, the PMMA film is dried at 120 ℃ for 10 minutes and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 minutes to dissolve the copper substrate, and the PMMA/silicon-molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of silicon-molybdenum nitride crystals is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained silicon molybdenum nitride is a single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 25 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 10
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 The two ends of the horizontal reaction furnace are respectively provided with a gas inlet 1 and a gas outlet 7, the copper foil/molybdenum sheet is arranged in a high-temperature area of the horizontal reaction furnace, and the copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 50 microns, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 microns, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 microns, pure99.9999 wt%) was placed in the central region of a pyrolytic boron nitride tube (tube inner diameter 16 mm, length 20 cm), wherein a silicon wafer was placed above a copper foil/molybdenum sheet (bimetallic sheet), the silicon wafer was spaced from the bimetallic sheet by about 3.5 mm, and then the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube were placed together in the central region of a horizontal reactor (tube diameter 22 mm, reaction zone length 20 mm); heating to 1090 ℃ in a hydrogen atmosphere to melt the copper foil (the hydrogen flow is 200 ml/min in the heating process, and the heating rate is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil, introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature reaches 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 1.5 hours, and rapidly cooling at the rate of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the copper surface.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) is dripped on the surface of copper on which a silicon-nitrogen molybdenum nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 rpm, the PMMA film is dried at 120 ℃ for 10 minutes and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 minutes to dissolve the copper substrate, and the PMMA/silicon-molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of silicon-molybdenum nitride crystals is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained silicon molybdenum nitride is a single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 10 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 11
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi 2 N 4 The two ends of the horizontal reaction furnace are respectively provided with a gas inlet 1 and a gas outlet 7, and copper foilPlacing a copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 12.5 microns, the purity is 99.5 wt%, the molybdenum sheet is 5 mm multiplied by 7 mm multiplied by 100 microns, the purity is 99.95 wt%) and a silicon wafer (the silicon wafer is 14 mm multiplied by 650 microns, the purity is 99.9999 wt%) in a central area of a pyrolysis boron nitride tube (the tube inner diameter is 16 mm, the length is 20 cm), wherein the silicon wafer is placed above the copper foil/molybdenum sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then placing the copper foil/molybdenum sheet, the silicon wafer and the pyrolysis boron nitride tube together in a central area of a horizontal reaction furnace (the tube diameter is 22 mm, and the length of a reaction zone is 20 mm); heating to 1080 ℃ in a hydrogen atmosphere (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen) after the furnace temperature is raised to 1080 ℃, starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 10 hours, and rapidly cooling at the speed of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the copper surface.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) is dripped on the surface of copper on which a silicon-nitrogen molybdenum nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 rpm, the PMMA film is dried at 120 ℃ for 10 minutes and then placed into 0.2mol/L ammonium persulfate aqueous solution, the reaction is carried out at 70 ℃ for 20 minutes to dissolve the copper substrate, and the PMMA/silicon-molybdenum nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of silicon-molybdenum nitride crystals is realized.
The components, the crystal structure, the appearance and the thickness of the silicon molybdenum nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained silicon molybdenum nitride is a single-layer MoSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 10 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
Example 12
First, as shown in FIG. 1, the present invention employs a horizontal reactor to grow two-dimensional layered transition group metal-silicon-nitrogenTernary compound WSi 2 N 4 A gas inlet 1 and a gas outlet 7 are respectively arranged at two ends of a horizontal reaction furnace, a copper foil/tungsten sheet is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/tungsten sheet (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the tungsten sheet is 5 mm multiplied by 7 mm multiplied by 100 micron, the purity is 99.95 wt%) and a silicon wafer (14 mm multiplied by 650 micron, the purity is 99.9999 wt%) are arranged in a central area of a pyrolytic boron nitride tube (the tube inner diameter is 16 mm, the length is 20 cm), wherein the silicon wafer is arranged above the copper foil/tungsten sheet (a bimetallic sheet), the distance between the silicon wafer and the bimetallic sheet is about 3.5 mm, and then the copper foil/tungsten sheet, the silicon wafer and the pyrolytic boron nitride tube are arranged in the central area of the horizontal reaction furnace (the tube has a diameter of 22 mm, and the length of a reaction zone is 20 mm); heating to 1080 ℃ in a hydrogen atmosphere (the hydrogen flow is 200 ml/min in the heating process, the heating rate is 20 ℃/min), introducing mixed gas of ammonia and hydrogen (the gas flow rates are respectively 3 ml/min for ammonia and 200 ml/min for hydrogen) after the furnace temperature is raised to 1080 ℃, starting to grow the two-dimensional tungsten silicon nitride, wherein the growth time is 10 hours, and rapidly cooling at the speed of 500 ℃/min after the growth is finished to obtain the tungsten silicon nitride crystal on the copper surface.
Then, an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%) is dripped on the surface of copper on which the tungsten silicon nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 rpm, the PMMA film is placed into 0.2mol/L ammonium persulfate aqueous solution after being dried for 10 minutes at the temperature of 120 ℃, the reaction is carried out for 20 minutes at the temperature of 70 ℃ to dissolve the copper substrate, and the PMMA/tungsten silicon nitride film is transferred to SiO 2 On a/Si substrate, PMMA is dissolved away by acetone at the temperature of 55 ℃, and finally the successful transfer of the tungsten silicon nitride crystal is realized.
The components, the crystal structure, the appearance and the thickness of the tungsten silicon nitride crystal are characterized by an optical microscope, a transmission electron microscope and an atomic force microscope, and the obtained tungsten silicon nitride is a single-layer WSi with a hexagonal structure 2 N 4 The crystal has a triangular shape, an average size of 10 μm, a thickness of about 1nm, a high crystalline quality, and semiconductor characteristics.
As shown in FIG. 1, the present inventionSchematic diagram of experimental device for growing high-quality two-dimensional layered ternary compound by CVD method, and two-dimensional layered transition group metal silicon nitrogen ternary compound MSi 2 N 4 For example, the method mainly comprises the following steps: the device comprises a gas inlet 1, a silicon wafer or quartz wafer 2, a metal substrate 3, a heating furnace 4, a pyrolytic boron nitride tube 5, a quartz tube 6, a gas outlet 7 and the like, and has the following specific structure:
the quartz tube 6 is horizontally arranged in the heating furnace 4, the two ends of the quartz tube are respectively provided with a gas inlet 1 and a gas outlet 7, the pyrolytic boron nitride tube 5 is horizontally arranged in the quartz tube 6, the pyrolytic boron nitride tube 5 is provided with a silicon wafer or a quartz plate 2 and a metal substrate 3 from top to bottom, and the metal substrate 3 is formed by combining an upper copper foil 31 and a lower transition metal plate 32 (such as a Mo plate). Ammonia gas and hydrogen gas enter a quartz tube 6 of a heating furnace 4 from a gas inlet 1 and are discharged from a gas outlet 7, a silicon source (such as a silicon wafer or a quartz wafer 2) is arranged above a metal substrate 3, the silicon source and the metal substrate 3 are both arranged in the center of a pyrolytic boron nitride tube 5, and the silicon source, the metal substrate 3 and the pyrolytic boron nitride tube 5 are jointly arranged in a heating zone of the heating furnace 4.
MoSi obtained by the CVD method, as shown in FIG. 2 2 N 4 The geometric shape of the crystal is not obvious in the initial growth stage, and the crystal gradually grows into a regular triangle along with the extension of the growth time and is finally connected together to form a film.
According to the transfer to SiO, as shown in FIG. 3 2 MoSi on a/Si substrate 2 N 4 Optical microscope photograph of (1), MoSi with the growth time extended 2 N 4 The sample is always connected with SiO in the process from independent single crystal to connected film formation 2 the/Si substrate maintains consistent optical contrast, indicating MoSi 2 N 4 The thickness is uniform and does not change.
As shown in FIG. 4, different growth parameters can regulate MoSi 2 N 4 The thickness (number of layers) of the crystal and the atomic force microscope picture show that the material has smooth and flat surface and complete structure, and each layer of MoSi 2 N 4 The thickness of (a) is kept around 1 nm.
As shown in FIG. 5, the transmission electron microscope characterization result shows that the crystal obtained by the CVD method is MoSi consisting of molybdenum, silicon and nitrogen 2 N 4 . Electronic energy spectrum andthe results of the electron energy loss spectrum showed that the atomic ratio of Mo atoms, Si atoms and N atoms was 1:2: 4.
As shown in FIG. 6, MoSi 2 N 4 The layer structure is a laminated structure, each layer is about 1nm thick and consists of 7 atomic layers of N-Si-N-Mo-N-Si-N.
As shown in FIG. 7, MoSi 2 N 4 The crystal structure model of (1).
As shown in fig. 8, the raman spectra of the samples before and after the long-term soaking in different chemical agents did not change significantly, and the raman spectra of the samples before and after the long-term soaking in air and water oxygen environments did not change significantly, indicating that they have excellent environmental stability and chemical stability. The Raman spectrum of the sample does not obviously change before and after long-time annealing at high temperature, and the sample has excellent thermal stability.
As shown in fig. 9, single layer MoSi 2 N 4 Exhibits semiconductor characteristics and maintains good ohmic contact with the metal electrode.
As shown in FIG. 10, a single layer of MoSi 2 N 4 Has excellent mechanical property, the average Young modulus is 491.4 +/-139.1 GPa, and the average breaking strength is 65.8 +/-18.3 GPa.
As shown in FIG. 11, a single layer of MoSi 2 N 4 The film has certain light absorption characteristics in the visible range, but still has high light transmittance.
As shown in FIG. 12, WSi 2 N 4 Is a layered structure, each layer is about 1nm thick.
The results show that the invention takes the high melting point transition metal M as a growth substrate and a reactant at the same time, takes the other low melting point metal which has catalytic activity and is easy to corrode and remove as a diffusion channel of the high melting point transition metal M atom, and realizes the high-quality novel two-dimensional layered ternary compound MX on the surface of the low melting point metal with catalytic activity by introducing the fourth main group element X and the fifth main group element Y and adopting a simple CVD method at normal pressure and high temperature 2 Y 4 Finally removing the low-melting-point metal layer by etching, and MX 2 Y 4 Transfer to any substrate. The invention has simple preparation processThe thickness and the size of the product are easy to regulate and control, and the large-area film is easy to prepare. The novel two-dimensional layered ternary compound MX 2 Y 4 Each layer of the compound consists of 7 atomic layers of Y-X-Y-M-Y-X-Y, and the layers are combined through Van der Waals force and show different properties of electricity, optics, mechanics and the like according to different components. Two-dimensional layered MX obtained by CVD method 2 Y 4 The structure is uniform, and the material has high crystallization quality, excellent environmental, chemical, thermal stability and mechanical properties, and lays a foundation for research and application in the fields of electronic devices, optoelectronic devices, millet electronic devices, high-strength films, high-light-transmission films, proton/ion exchange membranes, separation membranes and the like.
Claims (10)
1. A two-dimensional layered ternary compound is characterized in that the molecular formula of the ternary compound is MX 2 Y 4 Wherein: m is a transition metal element selected from one of molybdenum, tungsten, titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium; x is a fourth main group element selected from one of silicon and germanium; y is a fifth main group element selected from nitrogen, phosphorus or arsenic; each layer of the compound consists of 7 atomic layers of Y-X-Y-M-Y-X-Y, which are bonded to each other by van der waals forces.
2. A method for preparing the two-dimensional layered ternary compound as claimed in claim 1, wherein a double metal layer consisting of an upper Cu layer/a bottom transition metal M layer is used as a growth substrate, Cu is used as a diffusion channel of the transition metal M to provide M element, X and Y elements are introduced in a carrier gas atmosphere, and MX is grown by a chemical vapor deposition technique at a reaction temperature not higher than the melting point of copper through a catalytic reaction on the Cu surface 2 Y 4 Single crystal or thin film, MX being subsequently etched away Cu 2 Y 4 Transfer to any substrate.
3. The method for preparing a two-dimensional layered ternary compound according to claim 2, wherein the two-metal layer growth substrate is a laminated Cu foil and a transition group metal M foil; or the coating is obtained by adopting a coating method of magnetron sputtering or thermal evaporation; the thickness of the upper layer copper is 100 nm-100 μm.
4. The method for preparing a two-dimensional layered ternary compound according to claim 2, wherein the X, Y element is introduced by using X, Y-containing precursor which is solid, powder, liquid or gas that volatilizes or decomposes X or Y at high temperature.
5. The method for preparing a two-dimensional layered ternary compound according to claim 4, wherein X is a fourth main group element selected from silicon or germanium, the precursor of the silicon element is a silicon wafer, a quartz plate or silane, and the precursor of the germanium element is a germanium plate or germane; y is a fifth main group element, one of nitrogen, phosphorus and arsenic is selected, the precursor of the nitrogen element is ammonia gas, the precursor of the phosphorus element is white phosphorus or red phosphorus, and the precursor of the arsenic element is simple substance arsenic.
6. The method for preparing a two-dimensional layered ternary compound according to claim 2, wherein the carrier gas is hydrogen gas or a mixture of hydrogen gas and an inert gas during the chemical vapor deposition reaction.
7. The method of claim 2, wherein the two-dimensional layered MX is grown by chemical vapor deposition 2 Y 4 The temperature of the ternary compound is 900-1083 ℃, the growth time is 10-1200 minutes, and MX is increased by prolonging the growth time 2 Y 4 The size of the crystal domains, and thus the complete continuous film.
8. The method of preparing a two-dimensional layered ternary compound according to claim 2 wherein the two-dimensional layered MX is 2 Y 4 The number of layers of the ternary compound is regulated by changing the amount of X, Y element precursors in the chemical vapor deposition process: in the case of small precursor amounts, a complete monolayer of MX is obtained 2 Y 4 Single crystals or films, increasing the amount of precursor to obtain fewer or more layersLayer MX 2 Y 4 。
9. The method of claim 2, wherein the two-dimensional layered MoSi is transferred in a layered form 2 N 4 When in use, firstly, a layer of high molecular polymer is uniformly coated on the surface of the substrate to prevent the substrate from being damaged in the subsequent treatment process, and then the copper substrate is etched and removed by using copper etching solution to obtain the high molecular polymer/two-dimensional layered MoSi 2 N 4 And finally, placing the composite membrane on a target substrate, and dissolving and removing the high-molecular polymer protective membrane by adopting an organic solvent.
10. The method for preparing a two-dimensional layered ternary compound according to claim 9, wherein the adopted high molecular polymer is one or a mixture of more than two of polymethyl methacrylate, polyethylene, polystyrene and polypropylene, the etching solution of copper is an ammonium persulfate aqueous solution, a tin tetrachloride aqueous solution, a ferric chloride aqueous solution, concentrated ammonia water or dilute hydrochloric acid, and the organic solvent adopted for removing the high molecular polymer protective layer is one or a mixture of more than two of ketone, halohydrocarbon and aromatic hydrocarbon reagents.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762660A (en) * | 2015-04-13 | 2015-07-08 | 中国科学院宁波材料技术与工程研究所 | Carbide crystal material with two-dimensional lamellar structure and preparation method thereof |
| JP2016211038A (en) * | 2015-05-08 | 2016-12-15 | 国立研究開発法人産業技術総合研究所 | Transition metal silicide film, manufacturing method and manufacturing device therefor, and semiconductor device |
| CN106319628A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院金属研究所 | High-quality ultrathin two-dimensional transition-group metal carbide crystal and preparation method thereof |
| CN106567055A (en) * | 2015-10-08 | 2017-04-19 | 中国科学院金属研究所 | A method of preparing large-area high-quality completely single-layered tungsten disulfide |
| WO2019092521A1 (en) * | 2017-11-07 | 2019-05-16 | King Abdullah University Of Science And Technology | Method for growing a transition metal dichalcogenide layer, transition metal dichalcogenide growth device, and method for forming a semiconductor device |
-
2020
- 2020-05-25 CN CN202010446362.9A patent/CN113718227B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762660A (en) * | 2015-04-13 | 2015-07-08 | 中国科学院宁波材料技术与工程研究所 | Carbide crystal material with two-dimensional lamellar structure and preparation method thereof |
| JP2016211038A (en) * | 2015-05-08 | 2016-12-15 | 国立研究開発法人産業技術総合研究所 | Transition metal silicide film, manufacturing method and manufacturing device therefor, and semiconductor device |
| CN106319628A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院金属研究所 | High-quality ultrathin two-dimensional transition-group metal carbide crystal and preparation method thereof |
| CN106567055A (en) * | 2015-10-08 | 2017-04-19 | 中国科学院金属研究所 | A method of preparing large-area high-quality completely single-layered tungsten disulfide |
| WO2019092521A1 (en) * | 2017-11-07 | 2019-05-16 | King Abdullah University Of Science And Technology | Method for growing a transition metal dichalcogenide layer, transition metal dichalcogenide growth device, and method for forming a semiconductor device |
Non-Patent Citations (1)
| Title |
|---|
| "Large-area high-quality 2D ultrathin Mo2C superconducting crystals";Chuan Xu等;《Nature Materials》;20150817;第14卷(第11期);全文 * |
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