CN113718227A - Two-dimensional layered ternary compound and preparation method thereof - Google Patents

Two-dimensional layered ternary compound and preparation method thereof Download PDF

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CN113718227A
CN113718227A CN202010446362.9A CN202010446362A CN113718227A CN 113718227 A CN113718227 A CN 113718227A CN 202010446362 A CN202010446362 A CN 202010446362A CN 113718227 A CN113718227 A CN 113718227A
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dimensional layered
silicon
ternary compound
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substrate
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CN113718227B (en
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任文才
洪艺伦
刘志博
王磊
周天亚
马伟
徐川
陈星秋
成会明
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Institute of Metal Research of CAS
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    • 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
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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
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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
    • C23C16/01—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
    • 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
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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
    • C23C16/22—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
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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
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    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition 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
    • C30B29/10—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

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 groupElements and elements of the fifth main group, growing a single layer or a few layers of MX by CVD at a high temperature not higher than the melting point of copper2Y4Ternary 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 MX2Y4Lays a foundation for research and application in the fields of electronic devices, photoelectronic devices, millet electronic devices, high-strength films, high-light-transmission films, proton/ion exchange membranes, separation membranes and the like.

Description

Two-dimensional layered ternary compound and preparation method thereof
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 MX2Y4(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 MX2Y4Crystals and thin films.
Background art:
the successful exfoliation of graphene opens the door for 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, besides 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 is composed of 7 atomic layers of Y-X-Y-M-Y-X-Y, Van der Waals force bonding is adopted between the layers, the preparation process is simple, the components, the thickness and the size of a product are easy to regulate and control, and the physical properties and the application of a two-dimensional layered material are expanded.
The technical scheme of the invention is as follows:
a two-dimensional layered ternary compound with molecular formula MX2Y4Wherein: m is a transition group metal element including, but not limited to, molybdenum, tungsten, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or chromium; x is a fourth main group 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 growing MX on Cu surface by catalytic reaction at the reaction temp not higher than the smelting point of Cu in the presence of Cu carrier gas, and growing the two-dimensional layered ternary compound by use of Cu as growing substrate and Cu as diffusing channel of transition metal M, introducing X and Y elements in carrier gas atmosphere2Y4Single crystal or thin film, MX being subsequently etched away Cu2Y4Transfer to any substrate.
According to the preparation method of the two-dimensional layered ternary compound, a double-metal-layer growth substrate adopts laminated Cu foil and transition 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.
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 comprises the step of growing the two-dimensional layered MX by chemical vapor deposition2Y4The temperature of the ternary compound is 900-1083 ℃, the growth time is 10-1200 minutes, and MX is increased by prolonging the growth time2Y4The size of the crystal domains, and thus a complete continuous film.
The preparation method of the two-dimensional layered ternary compound, namely the two-dimensional layered MX2Y4The 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 obtained2Y4Single crystal or thin film, increasing the amount of precursor to obtain less or more MXs2Y4。
The preparation method of the two-dimensional layered ternary compound transfers the two-dimensional layered MoSi2N4Firstly, uniformly coating a layer of high molecular polymer on the surface of the substrate to prevent the substrate from being damaged in the subsequent treatment process, and then etching and removing the copper substrate by using a copper etching solution to obtain the high molecular polymer/two-dimensional layered MoSi2N4And finally, placing the composite film on a target substrate, and dissolving and removing the high molecular polymer protective film 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 MX2Y4Can 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, an X-Y double layer is formed by introducing a fourth main group element X, the surface dangling bond of a single-layer transition metal fifth main group element compound MY is passivated, island growth caused by surface energy constraint is changed into layered growth, and a novel two-dimensional layered ternary compound material MX with each layer composed of 7 atomic layers of Y-X-Y-M-Y-X-Y is formed2Y4The 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 substrate grows 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 ensured2Y4And (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 MX2Y4Wherein 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 MX2Y4By chemical vapor deposition ofVitamin-layered MX2Y4The 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 layers2Y4Single 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 used2N4Ternary compound crystals are exemplified. In the figure, 1 gas inlet; 2 a silicon wafer or a 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 substrate2N4The 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 substrates2N4Transfer to SiO2Optical microscopy on/Si substrate. Wherein: a, 15 minutes; b, 30 minutes; c, 1 hour; d, 2 hours; e, 3 hours; f, 3.5 hours.
FIG. 4: a picture is single-layer MoSi2N4The curve is the thickness curve of a single-layer sample measured by an atomic force microscope, and b is a multi-layer MoSi2N4The 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, with Distance on the abscissa representing the measured Distance (μm) and Height on the ordinate representing the measured thickness (nm); d is the thickness variation curve measured by atomic force microscope at the middle upper oblique dashed line of bThe coordinate Distance represents the measured Distance (. mu.m) and the ordinate Height represents the measured thickness (nm).
FIG. 5: a picture is single-layer MoSi2N4A plot b is an electron diffraction pattern of a selected region of the sample plane in plot a, and a plot c is an X-ray Energy dispersion spectrum of the sample in plot a, wherein the copper signal is from a micro grid, the abscissa Energy represents binding Energy (keV) and the ordinate Intensity represents Intensity (a.u.). d is an electron Energy loss spectrum of the sample in the graph a, the abscissa Energy loss represents the electron loss Energy (eV), and the ordinate Intensity represents 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 MoSi2N4Planar high resolution scanning transmission electron microscopy shows that the sample has high crystalline quality. b is a multilayer MoSi2N4High resolution scanning transmission electron micrographs of the cross-section clearly reveal the layered structure with a spacing of approximately 1nm between adjacent layers. c picture is multilayer MoSi2N4And (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 MoSi2N4And (3) high-resolution scanning transmission electron microscopy photographs of the cross section, wherein the h picture and the i picture respectively correspond to the electron energy loss spectrum surface scanning results of the Si element and the N element in the g picture.
FIG. 7: a is MoSi2N4The diagram b is a single-layer MoSi2N4The atomic structure model along the a axis is shown in the figure, and the figure c is a single-layer MoSi2N4Atomic structure model diagram along the c-axis. With MoSi2N4For example, the crystal structures of other novel two-dimensional layered ternary compounds are similar.
FIG. 8: graph a is transferred to SiO2Single layer MoSi on/Si substrate2N4Raman spectra obtained after soaking in ethanol, isopropanol and 1mol/L hydrochloric acid for 24 hr, with Raman shift on abscissa representing Raman shift (cm)-1) The ordinate Intensity represents the Intensity (a.u.),the Raman spectrum signal of the sample has no obvious change before and after soaking, and the sample is proved to have excellent chemical stability. b picture is transferred to SiO2Single layer MoSi on/Si substrate2N4Raman spectra obtained after immersion in water at 80 ℃ for 8 hours, in air for 6 months, and in water for 1 week, respectively, and the abscissa Raman shift represents the Raman shift (cm)-1) The Intensity on the ordinate represents the Intensity (a.u.), and the raman spectrum signal of the sample does not change significantly before and after the treatment, which proves its excellent environmental stability. c picture is single-layer MoSi grown on Cu/Mo substrate2N4Raman spectra after annealing for 3h at different temperatures in an argon atmosphere, with Raman shift on the abscissa representing the Raman shift (cm)-1) With Intensity on the ordinate (a.u.), it can be seen that the raman spectral signal of the sample does not change significantly after annealing up to 300 ℃, indicating its excellent thermal stability.
FIG. 9 is a single layer MoSi2N4Is used for electrical property characterization. a picture is single-layer MoSi2N4Transfer characteristic curve, abscissa V, measured in room temperature airbgRepresenting the grid voltage (V), ordinate-IdsRepresenting the negative number (μ A), V, of the source-drain currentdsRepresents 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 VdsRepresents the source-drain voltage (V), ordinate IdsRepresents the source-drain current (μ A), VgsRepresents the gate voltage (V); c picture is single layer MoSi2N4Transfer characteristic curve, abscissa V, tested in a 77K vacuum environmentbgRepresenting the grid voltage (V), ordinate-IdsRepresents 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 VdsRepresents the source-drain voltage (V), ordinate IdsRepresents the source-drain current (μ A), VgsRepresenting the gate voltage (V).
FIG. 10 is a single layer MoSi2N4The mechanical properties of (1) are characterized. a picture is suspended monolayer MoSi for atomic force microscope nano mechanics test experiment2N4A height profile of the film; b is diagram of suspended monolayer MoSi2N4Mechanical properties of the filmCurves and fitted curves, the abscissa indicating the penetration depth (nm) of the atomic Force probe and the ordinate Force indicating the MoSi applied to the suspended monolayer2N4Force on the membrane (nN); c picture is single layer MoSi2N4The abscissa Young's modulus represents Young's modulus (GPa), the ordinate Counts represents the statistical number of corresponding Young's modulus data, and the upper coordinate E2DRepresents a two-dimensional Young's modulus (N/m) corresponding to the abscissa; d is single-layer MoSi2N4The horizontal coordinate Breaking strength represents the Breaking strength (GPa), the vertical coordinate Counts represents the statistical number of the corresponding Breaking strength data, and the upper coordinate sigma represents the statistical distribution of the Breaking strength2DRepresents the two-dimensional breaking strength (N/m) corresponding to the abscissa.
FIG. 11 is a single layer MoSi2N4And (4) characterizing the optical property of the film. Graph a is a single layer of MoSi transferred onto a quartz plate2N4In the absorption spectrum of the film, the abscissa wavelet represents the Wavelength (nm), the ordinate Absorbance represents the Absorbance (a.u.), and the insets are used for carrying out peak separation on the absorption peak between 450 and 600nm to obtain 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 Photon energy represents Photon energy (eV), and the ordinate (alpha h v)0.5Representing 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, the inset is a single layer of MoSi transferred onto a quartz plate2N4The light Transmittance of the film was measured by a curve in which the abscissa wavelet represents the Wavelength (nm) and the ordinate Transmittance represents the Transmittance (%).
FIG. 12 shows WSi2N4The structural characterization of (1). a diagram is a single-layer WSi2N4The bright field transmission electron microscopy photographs show that the samples have clear crystallographic triangular shapes, and the inset is the corresponding electron diffraction pattern. And b, an X-ray energy dispersion spectrum corresponding to the graph a, and the sample contains W, Si and N elements. The abscissa Energy represents the binding Energy (eV) and the ordinate Intensity represents the Intensity (a.u.). c diagram is a single-layer WSi2N4Planar 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 WSi2N4High 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 at SiO2Multilayer WSi between a substrate and a Pt protective layer2N4And (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 invention2Y4The preparation method comprises adopting a double metal layer composed of an upper Cu layer and a bottom transition metal M layer as a growth substrate, taking Cu as a diffusion channel of M to provide M element, introducing X and Y elements in a carrier gas atmosphere, and growing MX on the Cu surface by catalytic reaction at a reaction temperature not higher than the melting point of copper by CVD technology2Y4Single crystal or thin film, MX being subsequently etched away Cu2Y4Transferring to any substrate by the following specific steps:
(1) two-dimensional layered ternary compound MX2Y4By two-dimensional layered transition group metal silicon nitrogen ternary compound MSi2N4For example, the following steps are carried out: 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 two-dimensional layered MSi2N4；
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: removing 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, 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 MoSi2N4A 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 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 SiO2On 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 structure2N4The 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 MoSi2N4A 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 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 3 ml/min of hydrogen) after the furnace temperature reaches 1080 ℃Gas 200 ml/min), starting to grow the two-dimensional silicon molybdenum nitride, wherein the growth time is 30 min, and rapidly cooling at the speed of 500 ℃/min after the growth is finished to obtain the silicon molybdenum nitride crystal on the surface of the 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 SiO2On 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 structure2N4The 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 MoSi2N4A 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 deg.C in hydrogen atmosphere to melt copper foil (hydrogen flow rate of 200 ml/min, L during heating process)The temperature speed is 20 ℃/min), when the furnace temperature reaches 1090 ℃, the temperature is rapidly reduced to 1080 ℃ within 2 minutes to solidify the copper foil, mixed gas of ammonia and hydrogen is introduced after the furnace temperature reaches 1080 ℃ (the gas flow rates are respectively 3 ml/min of ammonia and 200 ml/min of hydrogen), two-dimensional silicon molybdenum nitride starts to grow, the growth time is 1 hour, after the growth is finished, the rapid cooling is carried out at the speed of 500 ℃/min, and silicon molybdenum nitride crystals are obtained 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 SiO2On 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 structure2N4The 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 figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi2N4A 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 (bimetallic sheet), the silicon wafer is about 3.5 mm away from the bimetallic sheet, and then the copper foil/molybdenum sheet, the silicon wafer and the bimetallic sheet are arrangedThe pyrolytic boron nitride tubes are placed in the central area of a horizontal reaction furnace (the diameter of the furnace tube is 22 mm, and the length of the reaction area 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 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 SiO2On 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 film is a single-layer MoSi film with a hexagonal structure2N4The 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 figure 1, the invention adopts a horizontal reaction furnace to grow a two-dimensional layered transition group metal silicon nitrogen ternary compound MoSi2N4The 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 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 the silicon wafer (14 mm multiplied by 650 microns, the purity is 99.9999 wt%) are placed in the high-temperature area of the horizontal reaction furnacePlacing the tube in the 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 a silicon wafer is placed above a copper foil/molybdenum sheet (a bimetallic strip), the distance between the silicon wafer and the bimetallic strip is about 3.5 mm, and then placing the copper foil/molybdenum sheet, the silicon wafer and the pyrolytic boron nitride tube in the central area of a horizontal reaction furnace (the diameter of a furnace tube is 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 8 ml/min ammonia and 200 ml/min hydrogen respectively) 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 SiO2On 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 multilayer MoSi with a hexagonal structure2N4The 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 MoSi2N4The two ends of the horizontal reaction furnace are respectively provided with a gas inlet 1 and a gas outlet 7, and copper foil/molybdenumPlacing the sheet in a high-temperature area of a horizontal reaction furnace, placing 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 (14 mm multiplied by 650 microns, the purity is 99.9999 wt%) 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 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 pyrolytic boron nitride tube together in the central area of the horizontal reaction furnace (the diameter of the tube is 22 mm, and the length of the reaction area 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 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 SiO2On 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 structure2N4The 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 MoSi2N4A 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 1055 ℃ in 7 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 1055 ℃, 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 SiO2On 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 structure2N4The 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 MoSi2N4A 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 1030 ℃ within 12 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 1030 ℃, 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 SiO2On 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 structure2N4The 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 MoSi2N4A 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, 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 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 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 r/min, the PMMA film is dried at 120 ℃ for 10 min and then placed into 0.2mol/L ammonium persulfate aqueous solution, and the reaction is carried out at 70 DEG CThe PMMA/silicon molybdenum nitride film should be transferred to SiO in 20 minutes to dissolve the copper substrate2On 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 structure2N4The 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 MoSi2N4A 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, the copper foil/molybdenum sheet (the copper foil is 5 mm multiplied by 50 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 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, a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate)4 wt% of methyl acrylate) is dropped on the surface of copper on which the silicon-molybdenum nitride crystal grows, a layer of PMMA film is coated by a spin coater at 5000 r/min, the PMMA film is placed into 0.2mol/L ammonium persulfate aqueous solution after being dried for 10 min at the temperature of 120 ℃, the reaction is carried out for 20 min at the temperature of 70 ℃ to dissolve the copper substrate, and the PMMA/silicon-molybdenum nitride film is transferred to SiO2On 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 structure2N4The 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 MoSi2N4A 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 1080 ℃ in 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, rapidly cooling at the speed of 500 ℃/min after the growth is finished, and obtaining silicon nitridation on the copper surfaceA molybdenum crystal.
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 SiO2On 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 structure2N4The 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
Firstly, as shown in figure 1, the invention adopts a horizontal reaction furnace to grow two-dimensional layered transition group metal silicon nitrogen ternary compound WSi2N4The two ends of the horizontal reaction furnace are respectively provided with a gas inlet 1 and a gas outlet 7, a copper foil/tungsten plate is arranged in a high-temperature zone of the horizontal reaction furnace, a copper foil/tungsten plate (the copper foil is 5 mm multiplied by 12.5 micron, the purity is 99.5 wt%, the tungsten plate 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/tungsten plate (a bimetallic plate), the distance between the silicon wafer and the bimetallic plate is about 3.5 mm, and then the copper foil/tungsten plate, 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 1080 ℃ in 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 ℃, and starting to grow the two-dimensional silicon nitrogenAnd tungsten is grown for 10 hours, and after the growth is finished, the silicon nitride tungsten crystal is rapidly cooled at the speed of 500 ℃/min, so that the silicon nitride tungsten crystal is obtained on the surface of the 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 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 SiO2On 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 using 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 structure2N4The 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 schematic diagram of the experimental apparatus for growing high-quality two-dimensional layered ternary compound by CVD method of the present invention is shown, in which a two-dimensional layered transition group metal silicon nitrogen ternary compound MSi is used2N4For 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 silicon wafers or quartz plates 2 and a metal substrate 3 in the upper and lower parts, and the metal substrate 3 is formed by combining an upper layer copper foil 31 and a lower layer transition group 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. 22N4The geometrical shape of the crystal is not obvious in the initial growth stage, and the crystal gradually grows into a regular triangle with the increase of the growth time and is finally connected together to form a film.
According to the transfer to SiO, as shown in FIG. 32MoSi on a/Si substrate2N4Optical microscope photograph of (1), MoSi with the growth time extended2N4The sample is always connected with SiO in the process from independent single crystal to connected film formation2the/Si substrate maintained consistent optical contrast, indicating MoSi2N4The thickness is uniform and does not change.
As shown in FIG. 4, different growth parameters can regulate MoSi2N4The 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 MoSi2N4The 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 nitrogen2N4. The results of the electron energy spectrum and the electron energy loss spectrum showed that the atomic ratio of Mo atom, Si atom and N atom was 1:2: 4.
As shown in FIG. 6, MoSi2N4The 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, MoSi2N4The 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, a single layer of MoSi2N4Exhibits semiconductor characteristics and maintains good ohmic contact with the metal electrode.
As shown in FIG. 10, a single layer of MoSi2N4Has 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 MoSi2N4The film has certain light absorption characteristics in the visible range, but still has high light transmittance.
As shown in FIG. 12, WSi2N4Is a layered structure, each layer is about 1nm thick.
The results show that the invention uses high-melting point transition group metal M as a growth substrate and a reactant at the same time, uses another low-melting point metal which has catalytic activity and is easy to corrode and remove as a diffusion channel of high-melting point transition group metal M atoms, introduces a fourth main group element X and a fifth main group element Y, and realizes a high-quality novel two-dimensional layered ternary compound MX on the surface of the low-melting point metal with catalytic activity by a simple CVD method at normal pressure and high temperature2Y4Finally removing the low-melting-point metal layer by etching, and MX2Y4Transfer to any substrate. The invention has the characteristics of simple preparation process, easy regulation and control of the thickness and the size of a product and easy preparation of a large-area film. The novel two-dimensional layered ternary compound MX2Y4Each layer of the compound is composed 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 electrical, optical and mechanical properties according to different components. Two-dimensional layered MX obtained by CVD method2Y4The 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 MX2Y4Wherein: m is a transition metal element including, but not limited to, molybdenum, tungsten, titanium, zirconium, hafnium, vanadium, titanium, zirconium, hafnium, zirconium, hafnium, zirconium, hafnium, and mixtures thereof,Niobium, tantalum, or chromium; x is a fourth main group 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.
2. A method for preparing the two-dimensional layered ternary compound as claimed in claim 1, wherein a double metal layer consisting of upper Cu layer/bottom transition metal M 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 catalytic reaction on the surface of Cu at a reaction temperature not higher than the melting point of Cu by chemical vapor deposition2Y4Single crystal or thin film, MX being subsequently etched away Cu2Y4Transfer to any substrate.
3. The method for preparing a two-dimensional layered ternary compound according to claim 2, wherein the double 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 at high temperature to X or Y.
5. The method for preparing a two-dimensional layered ternary compound according to claim 4, wherein X is a group IV element including but not limited to silicon or germanium, a silicon element precursor including but not limited to silicon wafer, quartz wafer or silane, a germanium element precursor including but not limited to germanium wafer 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.
6. The method for preparing a two-dimensional layered ternary compound according to claim 2, wherein the carrier gas is hydrogen gas or a mixed gas 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 deposition2Y4The temperature of the ternary compound is 900-1083 ℃, the growth time is 10-1200 minutes, and MX is increased by prolonging the growth time2Y4The size of the crystal domains, and thus a complete continuous film.
8. The method of preparing a two-dimensional layered ternary compound according to claim 2 wherein the two-dimensional layered MX is2Y4The 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 obtained2Y4Single crystal or thin film, increasing the amount of precursor to obtain less or more MXs2Y4。
9. The method of claim 2, wherein the two-dimensional layered MoSi is transferred in a layered form2N4Firstly, uniformly coating a layer of high molecular polymer on the surface of the substrate to prevent the substrate from being damaged in the subsequent treatment process, and then etching and removing the copper substrate by using a copper etching solution to obtain the high molecular polymer/two-dimensional layered MoSi2N4And finally, placing the composite film on a target substrate, and dissolving and removing the high molecular polymer protective film 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 two or more 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 two or more of ketone, chlorohydrocarbon, halohydrocarbon and aromatic hydrocarbon reagents.
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