A preparation method, a preparation system, a product and an application of a selenium-tellurium vanadium material

Abstract

The application discloses a preparation method, a preparation system, a product and application of a selenium-tellurium vanadium material, and belongs to the technical field of material preparation. The application provides a method for preparing a large-area single-layer selenium-tellurium vanadium ternary topological composite material, which comprises the following steps: S1, depositing vanadium oxide on a substrate to obtain a vanadium oxide film; S2, reacting the vanadium oxide film obtained in the step S1 with a selenium source and a tellurium source in an environment containing inert gas and hydrogen, and naturally cooling to obtain a selenium-tellurium vanadium material. The selenium-tellurium vanadium material prepared by the method has the advantages of lower resistivity and higher conductivity, and exhibits unique advantages in the next generation of electronic, energy and quantum devices, so that large-area device manufacturing with high performance and low power consumption can be realized.

Description

Technical Field

[0001] This invention belongs to the field of materials preparation, and relates to a method, system, product and application of vanadium selenide telluride material preparation, specifically to a method, system, product and application of a large-area single-layer vanadium selenide telluride ternary topological composite material. Background Technology

[0002] For understanding the technical content of this invention:

[0003] In recent years, two-dimensional (2D) materials have attracted widespread attention due to their potential applications as high-performance functional nanomaterials. Two-dimensional transition metal dihalides (MTMDs) with ultrathin metallic properties have been extensively studied for their excellent performance in optics, electronics, energy storage, as well as their role as two-dimensional topological insulators and the quantum spin Hall effect. Besides graphene, ultrathin vanadium chalcogenides are a class of half-metallic materials in two-dimensional materials, lacking an electronic gap in their electronic structure. Studies on vanadium disulfide, vanadium diselenide, and vanadium ditelluride have revealed their great potential in a wide range of applications, including supercapacitors, battery materials, electrocatalysis, biosensors, and photoelectric sensors, as well as in condensed matter physics research. Given the excellent properties of vanadium disulfide and vanadium ditelluride, research on vanadium selenide-telluride ternary topological composites is necessary.

[0004] Currently, vanadium selenide is used to prepare ultrathin vanadium selenide ternary topological composite materials. Among them, the main methods for preparing monolayer vanadium selenide are mechanical exfoliation, liquid phase exfoliation, and chemical vapor deposition using inert non-metallic materials (such as silicon dioxide / silicon, aluminum oxide, etc.) as growth substrates.

[0005] Relevant patent documents retrieved:

[0006] This document, published in South Korea (KR102678240B1) on June 20, 2024, discloses a method for preparing layered vanadium diselenide. The first step involves placing vanadium trichloride in heater 1 and a substrate material in heater 2, using an argon-oxygen mixture as the carrier gas. The heated vanadium trichloride, supported by the carrier gas, grows a layer of vanadium pentoxide on the substrate material. The second step involves placing elemental selenium in heater 1 and the substrate material with the vanadium pentoxide layer in heater 2, using hydrogen as the carrier gas. Under heating conditions, hydrogen selenide reacts with elemental selenium to generate hydrogen selenide gas. With the support of excess hydrogen carrier gas, the hydrogen selenide reacts with the vanadium pentoxide on the substrate material to generate layered vanadium diselenide.

[0007] Relevant non-patent literature retrieved:

[0008] The journal *ACS Nano*, the article titled "Two-dimensional Metallic Vanadium ditelluride as a high-performance electrode material" (ACS Nano 2021, 15, 1858-1868), published on January 14, 2021, discloses the synthesis of 1T-phase VTe2 nanosheets using APCVD (Ambient Pressure Chemical Vapor Deposition). Specifically, VCl3 and Te elemental powders were used as precursors, with fluorophlogopite, conductive silicon, alumina, and glass as substrate materials. The reaction was carried out in a three-zone furnace. The Te elemental powder and VCl3 were placed in the first heating zone and heated to 610°C, while the substrate material was placed in the second heating zone at 600-700°C. The carrier gas was a mixture of argon and hydrogen. A growth time of 15 minutes yielded 1T-phase VTe2 nanosheets; a growth time exceeding 15 minutes resulted in hydrogen etching of the nanosheets. The obtained VTe2 nanosheets exhibited a field-effect mobility of 47.5 cm⁻¹. 2 V -1 s -1 It is approximately 6 times larger than that of a single layer of molybdenum disulfide. This VTe2 nanosheet exhibits excellent electrocatalytic activity for the hydrogen evolution reaction (HER).

[0009] Journal title: *Inorganics*, Article title: *Exploring the structure and properties of V* w Se y Te 2-y The paper, "Mixed Crystals in the VTe2-VSe2 System" (Inorganics 2023, 11, 481), was published on December 15, 2023. This document discloses mixed crystals in the VTe2-VSe2 system. w Se y Te 2-y (w=1.10, 1.13; y=0.42, 0.72). The ternary system was prepared by mixing elemental vanadium, elemental selenium, and elemental tellurium in stoichiometric proportions, sealing in quartz ampoules, and heating at 800℃ for 120 h. The crystal structure and space group of the ternary system were confirmed by single-crystal X-ray diffraction, and its chemical composition was obtained by X-ray energy scattering spectroscopy. Magnetic property measurements confirmed that the ternary system possesses antiferromagnetism. Synchronous differential scanning calorimetry / thermogravimetric analysis under nitrogen conditions showed that the ternary system could endothermally decompose into VN.

[0010] The prior art represented by the aforementioned documents has at least the following unresolved technical problems or defects:

[0011] (1) The existing technology has not yet been able to provide a large-area single-layer vanadium selenide ternary topological composite material.

[0012] (2) The prior art has not provided a method for synthesizing large-area single-layer vanadium selenide ternary topological composite materials.

[0013] In solving the above-mentioned problems or overcoming the above-mentioned defects, the present invention encountered the following difficulties and obstacles:

[0014] The inventors previously employed selenization of vanadium ditelluride followed by mechanical and liquid-phase exfoliation to prepare large-area monolayer vanadium selenide ternary topological composite materials. However, these two methods resulted in low yields, low efficiency, and poor reproducibility of the vanadium selenide materials, and failed to successfully produce large-area, monolayer vanadium ditelluride materials. When using traditional chemical vapor deposition to prepare large-area monolayer vanadium selenide ternary topological composite materials, the inventors discovered that due to the van der Waals epitaxial growth mechanism, the number of layers was poorly controlled, resulting in small grain sizes and numerous tellurium vacancies and other structural defects, making it difficult to obtain large-area, uniform monolayer materials. Summary of the Invention

[0015] The purpose of this invention is to provide:

[0016] A method for preparing large-area monolayer vanadium selenide ternary topological composite materials, and related technologies, are provided to address one or more of the technical problems of existing technologies for synthesizing vanadium selenide ternary topological materials, such as low yield, low efficiency, poor repeatability, poor layer number control, small grain size, and many defects, as well as the lack of a method for synthesizing large-area monolayer vanadium selenide ternary topological materials.

[0017] Terminology Explanation:

[0018] Unless otherwise defined, all technical terms in this document have the same meanings as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains. Unless otherwise stated, all patents, patent inventions, and publications cited in this document are incorporated herein by reference in their entirety. If multiple definitions exist for terms in this document, the definitions in this chapter shall prevail.

[0019] It should be understood that the above brief description and the following detailed description are exemplary and for illustrative purposes only, and do not limit the subject matter of the invention in any way. In this invention, the singular is used in conjunction with the plural unless otherwise specifically stated. It should also be noted that, unless otherwise stated, the use of “or” or “or” means “and / or”. Furthermore, the use of the term “comprising” and other forms such as “including,” “containing,” and “contains” are not limiting.

[0020] Available in Lange's handbook of chemistry (McGRAW-HILL, James G. Speight,Ph.D., 16 th The definitions of standard chemical terms can be found in the edition.

[0021] Unless otherwise stated, conventional methods within the scope of the art, such as X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM), shall be used.

[0022] Unless specifically defined herein, the use of various commercially available products herein employs standard techniques. For example, these techniques may be implemented using the instructions for use of the testing instrument, or in accordance with methods known in the art or the description of this invention. The techniques and methods described herein are generally implemented according to conventional methods well known in the art, based on the descriptions in the various general and more specific documents cited and discussed in this specification.

[0023] The term "thermal evaporation" refers to a technique in which a source material is heated and vaporized in a vacuum environment, causing it to deposit onto a substrate surface to form a thin film.

[0024] The term "chemical vapor deposition" refers to a technique that introduces volatile precursor gases into a reaction chamber, causing them to react chemically on a heated substrate surface to generate a solid thin film.

[0025] The term "atomic layer deposition" refers to a technique that uses self-limiting surface chemical reactions to deposit thin films on a substrate surface layer by layer with atomic precision by alternately introducing different gaseous precursors.

[0026] The term "sputtering" refers to a technique in which high-energy particles (usually gas ions) bombard a solid target in a vacuum environment, causing surface atoms to be ejected and deposited onto a substrate to form a thin film.

[0027] To achieve the above-mentioned objectives, the present invention provides a method for preparing vanadium selenide telluride materials, comprising the following steps:

[0028] S1. Vanadium oxide is deposited on the substrate to obtain a vanadium oxide thin film;

[0029] S2. Under an anhydrous and oxygen-free atmosphere, the vanadium oxide film obtained in step S1 is reacted with a gaseous selenium source and a gaseous tellurium source to obtain vanadium selenide telluride material.

[0030] Further, in step S1, the substrate material is selected from silicon, silicon dioxide, silicon / silicon dioxide, aluminum oxide, titanium dioxide, or silicon carbide.

[0031] It should be noted that the substrate material mentioned above, "silicon / silicon dioxide", also known as Si / SiO2 substrate, refers to a material structure in which a layer of silicon dioxide is uniformly covered on the surface of elemental silicon.

[0032] Furthermore, in step S1, the substrate material is selected from silicon dioxide, silicon / silicon dioxide, aluminum oxide, titanium dioxide, or silicon carbide.

[0033] In one embodiment of the present invention, in step S1, the substrate is made of silicon / silicon dioxide.

[0034] In one embodiment of the present invention, in step S1, the substrate is made of titanium dioxide.

[0035] In one embodiment of the present invention, in step S1, the substrate is made of aluminum oxide.

[0036] In one embodiment of the present invention, in step S1, the substrate is made of silicon dioxide.

[0037] In one embodiment of the present invention, in step S1, the substrate is made of silicon carbide.

[0038] Further, in step S1, the size of the substrate is 1-100 cm. 2 .

[0039] The dimensions of the substrate range from 1 to 100 cm. 2 Any value within the range, including but not limited to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 81, 90, 100cm 2 Or any range between the two.

[0040] In some embodiments of the present invention, in step S1, the size of the substrate is 1-81 cm. 2 .

[0041] In one embodiment of the present invention, in step S1, the size of the substrate is 50 cm. 2 .

[0042] In one embodiment of the present invention, in step S1, the size of the substrate is 81 cm. 2 (A circular substrate with a diameter of 4 inches).

[0043] In one embodiment of the present invention, in step S1, the size of the substrate is 4 cm. 2 .

[0044] In one embodiment of the present invention, in step S1, the size of the substrate is 30 cm.2 .

[0045] In one embodiment of the present invention, in step S1, the size of the substrate is 1 cm. 2 .

[0046] Further, in step S1, the deposition method is selected from atomic layer deposition, chemical vapor deposition, thermal evaporation, or sputtering.

[0047] In one embodiment of the present invention, in step S1, the deposition method is atomic layer deposition.

[0048] In one embodiment of the present invention, in step S1, the deposition method is thermal evaporation.

[0049] In one embodiment of the present invention, in step S1, the deposition method is sputtering.

[0050] Further, in step S1, the deposition temperature is 100-550℃, the deposition time is 10min-48h, and the thickness of the vanadium oxide film is 2-100nm.

[0051] The deposition temperature is any value within the range of 100-550℃, including but not limited to 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550℃ or any range between two of these.

[0052] In one embodiment of the present invention, in step S1, the deposition temperature is 550°C.

[0053] In one embodiment of the present invention, in step S1, the deposition temperature is 100°C.

[0054] In one embodiment of the present invention, in step S1, the deposition temperature is 220°C.

[0055] The deposition time is any value within the range of 10 min to 48 h, including but not limited to 10 min, 20 min, 30 min, 40 min, 50 min, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h, 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h, 30 h, 31 h, 32 h, 33 h, 34 h, 35 h, 36 h, 37 h, 38 h, 39 h, 40 h, 41 h, 42 h, 43 h, 44 h, 45 h, 46 h, 47 h, 48 h, or any range between two of these.

[0056] Furthermore, in step S1, the deposition time is 10 min to 24 h.

[0057] The deposition time is any value within the range of 10 min to 24 h, including but not limited to 10 min, 20 min, 30 min, 40 min, 50 min, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h, 20 h, 21 h, 22 h, 23 h, 24 h, or any range between two of these.

[0058] In one embodiment of the present invention, the deposition time in step S1 is 10 min.

[0059] In one embodiment of the present invention, the deposition time in step S1 is 2 hours.

[0060] In one embodiment of the present invention, the deposition time in step S1 is 24 hours.

[0061] The thickness of the vanadium oxide film is any value within the range of 2-100 nm, including but not limited to 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 nm or any range between two of these.

[0062] In one embodiment of the present invention, in step S1, the thickness of the vanadium oxide thin film is 2 nm.

[0063] In one embodiment of the present invention, in step S1, the thickness of the vanadium oxide thin film is 20 nm.

[0064] In one embodiment of the present invention, in step S1, the thickness of the vanadium oxide thin film is 80 nm.

[0065] Further, in step S2, the anhydrous and oxygen-free atmosphere is selected from an argon atmosphere, a hydrogen atmosphere, or a mixture of argon and hydrogen.

[0066] In one embodiment of the present invention, in step S2, the anhydrous and oxygen-free atmosphere is an argon atmosphere.

[0067] In one embodiment of the present invention, in step S2, the anhydrous and oxygen-free atmosphere is a hydrogen atmosphere.

[0068] In one embodiment of the present invention, in step S2, the anhydrous and oxygen-free atmosphere is a mixture of argon and hydrogen.

[0069] Furthermore, in the argon and hydrogen mixture atmosphere, the volume ratio of argon to hydrogen is 99:1 to 1:99.

[0070] The volume ratio of argon to hydrogen is any ratio within the range of 99:1 to 1:99, including but not limited to 99:1, 98:2, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, 5:95, 2:98, 1:99, or any range between two of these.

[0071] In one embodiment of the present invention, the volume ratio of argon to hydrogen is 95:5.

[0072] Further, in step S2, the reaction temperature is 500-900℃, the reaction pressure is 10-800Pa, and the reaction time is 1-90min.

[0073] In step S2, the temperature of the reaction is any value within the range of 500-900℃, including but not limited to 500, 550, 600, 650, 700, 750, 800, 850, 900℃ or any range between two of them.

[0074] Furthermore, in step S2, the reaction temperature is 500-850°C.

[0075] In step S2, the temperature of the reaction is any value within the range of 500-850℃, including but not limited to 500, 550, 600, 650, 700, 750, 800, 850℃ or any range between two of them.

[0076] In one embodiment of the present invention, the reaction temperature in step S2 is 500°C.

[0077] In one embodiment of the present invention, in step S2, the reaction temperature is 600°C.

[0078] In one embodiment of the present invention, the reaction temperature in step S2 is 700°C.

[0079] In one embodiment of the present invention, the reaction temperature in step S2 is 850°C.

[0080] In one embodiment of the present invention, the reaction temperature in step S2 is 750°C.

[0081] In step S2, the gas pressure of the reaction is any value within the range of 10-800 Pa, including but not limited to 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800 Pa or any range between two of these.

[0082] In one embodiment of the present invention, in step S2, the gas pressure of the reaction is 800 Pa.

[0083] In one embodiment of the present invention, the gas pressure of the reaction in step S2 is 500 Pa.

[0084] In one embodiment of the present invention, in step S2, the gas pressure of the reaction is 300 Pa.

[0085] In one embodiment of the present invention, in step S2, the gas pressure of the reaction is 100 Pa.

[0086] In one embodiment of the present invention, in step S2, the gas pressure of the reaction is 10 Pa.

[0087] In step S2, the reaction time is any value within the range of 1-90 min, including but not limited to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90 min or any range between two of these.

[0088] In one embodiment of the present invention, the reaction time in step S2 is 1 minute.

[0089] In one embodiment of the present invention, the reaction time in step S2 is 60 min.

[0090] In one embodiment of the present invention, the reaction time in step S2 is 90 min.

[0091] Further, in step S2, the tellurium source is selected from one or more of elemental tellurium, dialkyl tellurium, and tetraalkoxy tellurium; the selenium source is selected from one or more of dialkyl diselenyl ether and dialkyl selenyl ether.

[0092] Each of the alkyl groups is arbitrarily selected from alkyl groups with the same or different numbers of carbon atoms. For example, in a dialkyl telluride, the two alkyl groups can be alkyl groups with the same number of carbon atoms or alkyl groups with different numbers of carbon atoms.

[0093] Furthermore, in the dialkyl telluride, dialkyl diselenide, and dialkyl selenide, the alkyl group is selected from alkyl groups containing 1-5 carbon atoms, namely methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, or 2,2-dimethylpropyl.

[0094] Furthermore, in the tetraalkoxytellurium, the alkoxy group is a group defined above where an alkyl group is bonded to an oxygen atom.

[0095] More preferably, in step S2, the tellurium source is one or more of elemental tellurium, dimethyl tellurium, diethyl tellurium, di-n-propyl tellurium, diisopropyl tellurium, tetramethoxy tellurium, tetraethoxy tellurium, and tetraisopropoxy tellurium.

[0096] More preferably, in step S2, the selenium source is one or more of dimethyl selenide, diethyl selenide, di-n-propyl selenide, diisopropyl selenide, di-n-butyl selenide, diisobutyl selenide, di-tert-butyl selenide, dimethyl diselenide, diethyl diselenide, di-n-propyl diselenide, diisopropyl diselenide, di-n-butyl diselenide, diisobutyl diselenide, and di-tert-butyl diselenide.

[0097] In one embodiment of the present invention, in step S2, the tellurium source is diethyltellurium.

[0098] In one embodiment of the present invention, in step S2, the tellurium source is diisopropyltellurium.

[0099] In one embodiment of the present invention, in step S2, the selenium source is di-tert-butylselenium.

[0100] In one embodiment of the present invention, in step S2, the selenium source is diethylselenoselenium.

[0101] Furthermore, in step S2, the flow rate of the selenium source is 60-80 sccm.

[0102] In step S2, the flow rate of the selenium source is any value within the range of 60-80 sccm, including but not limited to 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80 sccm or any range between the two.

[0103] In one embodiment of the present invention, in step S2, the flow rate of the selenium source is 60 sccm.

[0104] In one embodiment of the present invention, in step S2, the flow rate of the selenium source is 80 sccm.

[0105] Furthermore, in step S2, the flow rate of the tellurium source is 50-100 sccm.

[0106] In step S2, the flow rate of the tellurium source is any value within the range of 50-100 sccm, including but not limited to 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 sccm or any range between two of these values.

[0107] In one embodiment of the present invention, in step S2, the flow rate of the tellurium source is 100 sccm.

[0108] In one embodiment of the present invention, in step S2, the flow rate of the tellurium source is 80 sccm.

[0109] In one embodiment of the present invention, in step S2, the flow rate of the tellurium source is 50 sccm.

[0110] Furthermore, in step S2, the flow rate ratio of the selenium source and the tellurium source is 0.8-1.2:1.

[0111] In step S2, the flow rate ratio of the selenium source and the tellurium source is any ratio within the range of 0.8-1.2:1, including but not limited to 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1 or any range between the two.

[0112] In one embodiment of the present invention, in step S2, the flow rate ratio of the selenium source and the tellurium source is 0.8:1.

[0113] In one embodiment of the present invention, in step S2, the flow rate ratio of the selenium source and the tellurium source is 1:1.

[0114] In one embodiment of the present invention, in step S2, the flow rate ratio of the selenium source and the tellurium source is 1.2:1.

[0115] On the other hand, the present invention provides a preparation system for vanadium selenide telluride materials, the preparation system being used to perform the above-described preparation method, the preparation system comprising the following parts:

[0116] The reaction chamber, the material carrier device, the carrier gas source, the selenium source, the tellurium source, the vanadium oxide deposition device, and the tail gas treatment device;

[0117] The carrier device is installed inside the reaction chamber. The selenium source is connected to both the carrier gas source and the reaction chamber. The tellurium source is connected to both the carrier gas source and the reaction chamber. The vanadium oxide deposition device is used to deposit vanadium oxide on the substrate surface placed on the carrier device. The exhaust gas treatment device is connected to the reaction chamber.

[0118] Furthermore, the preparation system also includes a cleaning gas source, which is connected to the reaction chamber.

[0119] Furthermore, the reaction chamber is equipped with a temperature control device, a temperature sensor, and a pressure sensor.

[0120] Furthermore, the exhaust gas treatment device includes a gas pump and a gas scrubbing device, and the reaction chamber is sequentially connected to the gas pump and the gas scrubbing device.

[0121] In another aspect, the present invention provides vanadium selenide telluride material prepared by the above-described preparation method.

[0122] Furthermore, the vanadium selenide material is a nano-sized vanadium selenide material.

[0123] Finally, the present invention provides the application of the above-described preparation method or preparation system in material production.

[0124] Furthermore, the material is a nanomaterial.

[0125] Furthermore, the material is selected from optoelectronic materials, aerospace materials, phase change materials, or charge density wave materials.

[0126] Compared with the prior art, the present invention achieves the following technical effects:

[0127] 1. The preparation method provided by this invention is simple and controllable, and can successfully prepare nanomaterials with a few-layer van der Waals layered structure.

[0128] 2. Resistivity characterization experiments show that the vanadium selenide telluride material prepared by the method provided in this invention has lower resistivity and higher conductivity.

[0129] 3. Infrared reflection characterization experiments show that the absorption effect is good in the 10-20μm band, and the reflectivity of this vanadium selenide telluride material in the infrared band can be changed by adjusting the temperature. Attached Figure Description

[0130] Figure 1 This is a transmission electron microscope (TEM) image of the vanadium selenide telluride material prepared in Example 1.

[0131] Figure 2 This is the V2p X-ray photoelectron spectroscopy (XPS) spectrum of the vanadium selenide telluride material prepared in Example 1.

[0132] Figure 3 This is the X-ray photoelectron spectroscopy (XPS) spectrum of Te3d of the vanadium selenide telluride material prepared in Example 1.

[0133] Figure 4 This is the X-ray photoelectron spectroscopy (XPS) spectrum of Se3d of the vanadium selenide telluride material prepared in Example 1.

[0134] Figure 5 This is a schematic diagram of the vanadium selenide telluride material preparation system provided in the apparatus example. Reference numerals: 1 is the reaction chamber, 2 is the material carrier, 3 is the carrier gas source, 3' is the cleaning gas source, 4 is the selenium source, 5 is the tellurium source, 6 is the vanadium oxide deposition device, and 7 is the tail gas treatment device.

[0135] Figure 6 This is the spectrum of reflectance versus temperature in the mid-infrared to far-infrared region for the vanadium selenide material prepared in Example 3.

[0136] Figure 7 The spectrum shows the relationship between the relative reflectance of the vanadium selenide telluride material prepared in Example 4 and temperature in the mid-infrared and far-infrared regions. The upper half of the spectrum represents the spectrum of the amorphous material, and the lower half of the spectrum represents the spectrum of the crystalline material. Detailed Implementation

[0137] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way. The following content is merely an exemplary description of the scope of protection of the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, which should also fall within the scope of protection of the present invention.

[0138] The present invention will be further described below by way of specific embodiments. Unless otherwise specified, all instruments, devices, equipment, reagents, products, etc., used in the embodiments of the present invention are obtained through conventional commercial means.

[0139] Example 1

[0140] A method for preparing vanadium selenide telluride material, comprising the following steps.

[0141] S1. Using thermal evaporation method, in a size of 1cm 2 Vanadium oxide was deposited on a silicon / silicon dioxide substrate at a deposition temperature of 550°C and a deposition time of 10 min to obtain a vanadium oxide film with a thickness of 2 nm.

[0142] S2. Under Ar atmosphere, at a reaction temperature of 500℃ and a reaction pressure of 800Pa, the vanadium oxide film obtained in step S1 was reacted with selenium source di-tert-butylselenium and tellurium source diethyltellurium. The flow rate ratio of the selenium source to the tellurium source was 1:1.25 (80 sccm: 100 sccm), and the reaction time was 1 min. After the reaction, the mixture was allowed to cool naturally to obtain vanadium selenide telluride material.

[0143] The chemical structural formula of di-tert-butylselenide is as follows:

[0144] .

[0145] The chemical structural formula of diethyltellurium is as follows:

[0146] .

[0147] TEM images of vanadium selenide telluride materials prepared by the above method are shown below. Figure 1 As shown. By Figure 1 It is evident that this vanadium selenide telluride material possesses a few-layered van der Waals layered structure.

[0148] The XPS spectrum of the vanadium selenide telluride material prepared by the above method is shown below. Figures 2-4 As shown.

[0149] Depend on Figure 2 The XPS spectrum of V element shows that V 5+ Characteristic peaks (V2p) exist at binding energies of 527-528 eV and 519-521 eV. 4+ The presence of characteristic peaks (V2p) at binding energies of 524-526 eV and 517-518 eV confirms the presence of V in the material and identifies the valence state of V.

[0150] Depend on Figure 3 The XPS spectrum of Te in the material shows characteristic peaks (Te3d) at binding energies of 581-585 eV and 571-574 eV, confirming the presence of Te in the material.

[0151] Depend on Figure 4 The XPS spectrum of Se shows characteristic peaks (Se3d) at binding energies of 53-56 eV and 57-59 eV, confirming the presence of Se in the material.

[0152] Analysis of the XPS spectra of V, Se, and Te confirms the successful synthesis of vanadium selenide telluride materials.

[0153] Example 2

[0154] Compared with Example 1, the only difference is that in step S1, the substrate is changed to 30cm. 2 The titanium dioxide substrate is used. In step S2, the reaction temperature is 600℃ and the reaction pressure is 500Pa. The rest of the synthesis steps are the same.

[0155] Example 3

[0156] S1. Atomic layer deposition (ALD) is used to deposit materials with a size of 4cm. 2 Vanadium oxide was deposited on an alumina substrate at a deposition temperature of 100℃ for 24 hours to obtain a vanadium oxide film with a thickness of 80nm.

[0157] S2. Under a hydrogen atmosphere and at a reaction temperature of 700℃ and a reaction pressure of 300Pa, the vanadium oxide film obtained in step S1 was reacted with a selenium source (diethylselenolene) and a tellurium source (diisopropyltellurium). The flow rate ratio of the selenium source to the tellurium source was 1:1 (80 sccm: 80 sccm), and the reaction time was 60 min. After the reaction, the mixture was allowed to cool naturally to obtain vanadium selenide telluride material.

[0158] The chemical structural formula of diethylselenide is as follows:

[0159] .

[0160] The chemical structural formula of diisopropyltellurium is as follows:

[0161] .

[0162] Example 4

[0163] Compared with Example 3, the only difference is that in step S1, the substrate is changed to a circular silicon dioxide substrate with a diameter of 4 inches; in step S2, the reaction temperature is changed to 850°C and the reaction pressure is 100 Pa, and the rest of the synthesis steps are the same.

[0164] Example 5

[0165] S1. Using the sputtering method, in a 50cm diameter area... 2 Vanadium oxide was deposited on a silicon carbide substrate at a deposition temperature of 220°C for 2 hours to obtain a vanadium oxide film with a thickness of 20 nm.

[0166] S2. Under an Ar / H2 atmosphere, at a reaction temperature of 750℃ and a reaction pressure of 10Pa, the vanadium oxide film obtained in step S1 was reacted with a selenium source (di-tert-butylselenium) and a tellurium source (diethyltellurium). The flow rate ratio of the selenium source to the tellurium source was 1.2:1 (60 sccm:50 sccm), and the reaction time was 90 min. After the reaction, the mixture was allowed to cool naturally to obtain vanadium selenide telluride material.

[0167] Comparative Example 1

[0168] The traditional chemical vapor deposition method was used to synthesize vanadium selenide telluride, and the specific steps are as follows.

[0169] For 1cm 2 Pretreatment of the SiO2 / Si substrate: The substrate is sequentially immersed in fresh acetone and isopropanol solutions, and ultrasonically cleaned for 10-15 minutes each. The substrate surface is carefully dried with a high-purity nitrogen gun. Using a dual-temperature zone tube furnace, the vanadium source (vanadium trioxide) and substrate are placed in the high-temperature zone. In the low-temperature zone: Se / Te sources (elemental Se and elemental Te) are placed. The entire loading sequence is: gas flow direction → Se / Te source → vanadium source + substrate → to the pump and exhaust gas treatment. Growth process: Close the flanges at both ends of the tube furnace to ensure good airtightness. First, close all gas valves, use a mechanical pump to evacuate to a low vacuum (e.g., below 10 Pa), close the pump valve, and observe whether the gas pressure increases significantly in a short time. If it is stable, it indicates good airtightness. Reopen the mechanical pump and evacuate the furnace tube to a low vacuum. Slowly introduce high-purity argon (Ar ≥ 99.999%) to atmospheric pressure. Repeat this process 2-3 times to remove as much oxygen and water vapor as possible from the furnace tube. After evacuation, a carrier gas (Ar / H2) is introduced at a flow rate of 50-200 sccm. The temperature is then raised to the target temperature (700°C for the vanadium source region and 350°C for the Se / Te region). The growth is maintained at this temperature for 10 minutes, followed by natural cooling.

[0170] Device example

[0171] The preparation system for synthesizing vanadium selenide telluride materials in Examples 1-5 above is shown in the schematic diagram below. Figure 5 As shown. Specifically, the preparation system consists of the following parts:

[0172] The reaction chamber, the material carrier, the carrier gas source, the cleaning gas source, the selenium source, the tellurium source, the vanadium oxide deposition device, and the tail gas treatment device;

[0173] The carrier device is installed inside the reaction chamber. The selenium source is connected to both the carrier gas source and the reaction chamber. The tellurium source is connected to both the carrier gas source and the reaction chamber. The vanadium oxide deposition device is used to deposit vanadium oxide on the substrate surface placed on the carrier device. The exhaust gas treatment device is connected to the reaction chamber.

[0174] The reaction chamber is equipped with a temperature control device, a temperature sensor, and a pressure sensor. The temperature control device has a heating function and can control the temperature inside the reaction chamber. The temperature sensor has a temperature detection function and can detect the temperature inside the reaction chamber. The pressure sensor has a pressure detection function and can detect the pressure inside the reaction chamber.

[0175] The carrier device is used to load substrate material.

[0176] The carrier gas source is used to provide an oxygen-free atmosphere for the preparation system during or before the reaction. Different types of carrier gases, such as hydrogen, argon, or a mixture of hydrogen and argon, can be used as needed. The carrier gas source is equipped with a valve to control the on / off state and flow rate of the carrier gas.

[0177] The cleaning gas source is used to remove impurities such as oxygen, air, and water vapor from the preparation system before the reaction. Different types of carrier gases, such as hydrogen, argon, or a mixture of hydrogen and argon, can be used as needed. The cleaning gas source is equipped with a valve to control the on / off state and flow rate of the cleaning gas.

[0178] The selenium source is used to provide selenium-containing gaseous reactants, and a gas valve is installed on the selenium source for switching on and off and controlling the flow rate.

[0179] The tellurium source is used to provide tellurium-containing gaseous reactants, and a gas valve is installed on the tellurium source for switching on and off and controlling the flow rate.

[0180] The vanadium oxide deposition apparatus is used to deposit vanadium oxide on the surface of a substrate material placed on a carrier device. Depending on the method of depositing the vanadium oxide, a corresponding vanadium oxide deposition apparatus from the prior art can be selected. For example, in Example 1, vanadium oxide is deposited on the substrate surface using a thermal evaporation method; therefore, the vanadium oxide deposition apparatus is a thermal evaporation apparatus for the vanadium source.

[0181] The exhaust gas treatment device consists of a gas pump and a gas washing device, and the reaction chamber is connected to the gas pump and the gas washing device in sequence.

[0182] A gas valve is installed between the exhaust gas treatment device and the reaction chamber to control the connection and disconnection between them. The gas pump is controlled by a power switch.

[0183] The gas scrubbing device contains a solution for capturing gases containing selenium and tellurium (such as oxidizing nitric acid aqueous solution, potassium permanganate aqueous solution, sodium hydroxide + hydrogen peroxide mixed aqueous solution, etc.). When the exhaust gas enters the gas scrubbing device through the gas pump, the selenium and tellurium gases react with the oxidizing substances to form selenium and tellurium oxyacids (salts) in solution.

[0184] The operating principle of this preparation system in the preparation of vanadium selenide telluride materials is as follows:

[0185] First, place the substrate on the substrate carrier. Turn off the selenium source, tellurium source, and carrier gas source, and turn on the purge gas source and exhaust gas treatment device to remove impurities such as oxygen and water vapor from the preparation system. Turn off the purge gas source and turn on the gas pump in the exhaust gas treatment device to evacuate the reaction chamber; then turn on the purge gas source again to purge. Repeat the above process twice.

[0186] Then, a vanadium oxide thin film is prepared on the substrate surface. With the selenium source, tellurium source, and carrier gas source turned off, a vanadium oxide thin film is prepared on the substrate surface using a vanadium oxide deposition apparatus under working atmosphere.

[0187] Finally, a selenium and tellurium source are provided to the vanadium oxide thin film for reaction. The purge gas source is shut off, and the valves for the carrier gas source, selenium source, and tellurium source are opened, along with the valve for the exhaust gas treatment device. The flow rates, velocities, and flow ratios of the carrier gas, selenium source, and tellurium source are adjusted by regulating the valves of these sources. The exhaust gas treatment device valve is opened to remove selenium- and tellurium-containing exhaust gases, and the pressure in the reaction chamber is adjusted by regulating the power of the gas pump in the exhaust gas treatment device.

[0188] Effect evaluation

[0189] 1. Evaluation of conductivity and resistivity.

[0190] The specific evaluation process is as follows:

[0191] Electron beam evaporation was used to deposit a 10nm / 30nm Ti / Au layer on the surface of the grown film, which was then covered with a metal mask. The resistivity of the film was measured using a four-probe method, and linearity was verified by forward and reverse scanning (e.g., ±10μA) to eliminate contact nonlinearity. Multiple sets of current and corresponding voltage values ​​were recorded, and the average resistance was calculated. The resistivity and conductivity were then calculated using the average resistance.

[0192] The results are shown in Table 1 below:

[0193] Table 1

[0194]

[0195] The results show that the vanadium selenide telluride materials prepared by the methods in Examples 3-5 have lower resistivity (higher conductivity) and exhibit superior electrical properties compared to the traditional method (Comparative Example 1).

[0196] 2. Infrared band reflection / absorption detection of thin film samples.

[0197] The relationship between infrared absorptivity α and reflectivity ρ, without considering material transmission, is determined by the law of conservation of energy and satisfies the formula α + ρ + τ = 1, where τ is the transmittance. For most opaque solid materials, the transmittance is approximately 0, so absorptivity + reflectivity ≈ 1. Therefore, by detecting the infrared reflectivity of a material, the infrared absorption situation can be reflected; that is, the negative reflectivity peak can be regarded as an absorption peak.

[0198] The detection method is as follows:

[0199] Using the reflectance test mode of a micro Fourier transform infrared spectrometer (Thermo Fisher iN10), the test band range was set to 2.5μm-25μm, the test time was 16s, and the microscopic test area was 150μm×150μm. A hot plate, the sample to be tested, and a gold mirror used as a reflective background were placed on the stage. The stage was moved to the gold mirror to complete surface focusing and background acquisition, and then moved to the test area of ​​the sample on the hot plate to complete focusing. The sample temperature was set to 30℃-115℃ with a temperature interval of 10℃. After the sample temperature stabilized, the sample spectrum was acquired.

[0200] The results are as follows Figure 6 As shown, the grown thin film sample exhibits broad-spectrum reflectance in the infrared band, and its reflectance increases with increasing temperature (i.e., its absorptivity decreases). The reflectance of the thin film sample can be controlled by adjusting the temperature.

[0201] 3. Evaluation of the reflection / absorption effect of the thin film sample in the 10-20μm infrared band.

[0202] The detection method is as follows:

[0203] Using the reflectance test mode of a micro Fourier transform infrared spectrometer (Thermo Fisher iN10), the test band range was set to 2.5μm-25μm, the test time was 16s, and the microscopic test area was 150μm×150μm. A hot plate, the sample to be tested, and a gold mirror used as a reflective background were placed on the stage. The stage was moved to the gold mirror to complete surface focusing and background acquisition, and then moved to the test area of ​​the sample on the hot plate to complete focusing. The sample temperature was set to 25℃, 77℃, and 100℃. After the sample temperature stabilized, the sample spectrum was acquired, and the infrared reflectance spectra of the crystalline and amorphous parts of the sample were obtained respectively.

[0204] The results are as follows Figure 7 As shown, the grown thin film sample exhibits broadband absorption in the 10-20 micrometer infrared band, and the absorption peak bandwidth narrows as the temperature increases. The absorption peak bandwidth can be controlled by adjusting the temperature.

[0205] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution created by the present invention do not depart from the essence and scope of the technical solution created by the present invention.

Claims

1. A method for preparing vanadium selenide telluride material, characterized in that, Includes the following steps: S1. Vanadium oxide is deposited on the substrate to obtain a vanadium oxide thin film; S2. Under an anhydrous and oxygen-free atmosphere, the vanadium oxide film obtained in step S1 is reacted with a gaseous selenium source and a gaseous tellurium source to obtain vanadium selenide telluride material. In step S1, the deposition temperature is 100-550℃, the deposition time is 10min-48h, and the thickness of the vanadium oxide film is 2-100nm. In step S2, the reaction temperature is 750-850℃, the reaction pressure is 10-300Pa, and the reaction time is 60-90min. In step S2, the tellurium source is one or more of dimethyl tellurium, diethyl tellurium, di-n-propyl tellurium, diisopropyl tellurium, tetramethoxy tellurium, tetraethoxy tellurium, and tetraisopropoxy tellurium. The selenium source is one or more of dimethyl selenide, diethyl selenide, di-n-propyl selenide, diisopropyl selenide, di-n-butyl selenide, diisobutyl selenide, di-tert-butyl selenide, dimethyl diselenide, diethyl diselenide, di-n-propyl diselenide, diisopropyl diselenide, di-n-butyl diselenide, diisobutyl diselenide, and di-tert-butyl diselenide. The flow rate of the selenium source is 60-80 sccm, and the flow rate of the tellurium source is 50-100 sccm.

2. The preparation method according to claim 1, characterized in that, In step S1, the substrate material is selected from silicon, silicon dioxide, silicon / silicon dioxide, aluminum oxide, titanium dioxide, or silicon carbide, and the substrate size is 1-100 cm. 2 .

3. The preparation method according to claim 1, characterized in that, In step S1, the deposition method is selected from atomic layer deposition, thermal evaporation, or sputtering.

4. The preparation method according to claim 1, characterized in that, In step S1, the deposition method is chemical vapor deposition.

5. The preparation method according to claim 1, characterized in that, In step S2, the anhydrous and oxygen-free atmosphere is selected from an argon atmosphere, a hydrogen atmosphere, or a mixture of argon and hydrogen.

6. A system for preparing vanadium selenide telluride materials, characterized in that, The preparation system is used to perform the preparation method according to any one of claims 1-5, and the preparation system comprises the following parts: The reaction chamber, the material carrier device, the carrier gas source, the selenium source, the tellurium source, the vanadium oxide deposition device, and the tail gas treatment device; The carrier device is installed inside the reaction chamber. The selenium source is connected to both the carrier gas source and the reaction chamber. The tellurium source is connected to both the carrier gas source and the reaction chamber. The vanadium oxide deposition device is used to deposit vanadium oxide on the substrate surface placed on the carrier device. The exhaust gas treatment device is connected to the reaction chamber.

7. The preparation system according to claim 6, characterized in that, The preparation system also includes a cleaning gas source, which is connected to the reaction chamber; The reaction chamber is equipped with a temperature control device, a temperature sensor, and a pressure sensor. The exhaust gas treatment device includes a gas pump and a gas scrubbing device, and the reaction chamber is connected in sequence to the gas pump and the gas scrubbing device.

8. Vanadium selenide telluride material prepared by the preparation method according to any one of claims 1-5.

9. The application of the preparation method according to any one of claims 1-5 or the preparation system according to any one of claims 5-6 in material production.

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