CN111020526A

CN111020526A - Method for preparing single-layer and multi-layer vanadium diselenide materials through alternative reaction

Info

Publication number: CN111020526A
Application number: CN201911093518.3A
Authority: CN
Inventors: 杨万丽; 陈鑫; 孙艳; 刘从峰; 戴宁
Original assignee: Shanghai Institute of Technical Physics of CAS
Current assignee: Shanghai Institute of Technical Physics of CAS
Priority date: 2019-11-11
Filing date: 2019-11-11
Publication date: 2020-04-17

Abstract

The invention discloses a method for preparing single-layer and multi-layer vanadium diselenide materials through alternative reaction. The method comprises the steps of alternately injecting one or more vanadium metal compounds and one or more selenium-containing compounds for deposition reaction, and controlling the number of layers and the area of the growth of the vanadium diselenide material by adjusting the reaction temperature and time to obtain the high-quality layered vanadium diselenide material. The invention has the advantages that: the operation is simple and convenient, the growth conditions are accurate and controllable, and the large-area preparation of the vanadium diselenide material can be realized. The vanadium diselenide material has unique chemical, electronic, magnetic and mechanical properties, and has wide application prospects in the scientific and technical fields of optoelectronics, spintronics, catalysts, sensors, energy collection and storage and the like.

Description

Method for preparing single-layer and multi-layer vanadium diselenide materials through alternative reaction

Technical Field

The invention belongs to the technical field of materials, relates to a nano material preparation technology, and particularly relates to a method for preparing single-layer and multi-layer vanadium diselenide materials by alternately injecting reactants.

Background

Since the graphene was successfully stripped in 2004, the two-dimensional material has excellent electrical and optical propertiesAnd mechanical properties have become a focus of research. Graphene has been widely used in batteries, sensors, memories, etc., and exhibits excellent performance. Graphene, vanadium diselenide, and the like are all metal transition metal bis-haloalkanes, and the metal transition metal bis-haloalkanes (MTMDCs) show many interesting properties in their volume states, such as magnetism, charge density waves, and superconductivity, and have attracted wide attention of physicists. Recently, there has been new research interest in these MTMDCs as they have proven to be ideal systems for exploring collective electronic states at the two-dimensional (2D) limit. More interestingly, the lack of good conductivity and band gap of these layered materials also suggests that if they can be refined to the nanometer scale, they will have a wide range of potential applications, such as transparent electrodes and energy conversion/storage, etc. The basic chemical formula of the vanadium diselenide material is MX₂Wherein M is a group V element or other transition metal element (V, Nb, Ta), and X is a group selenium element (S, Se, Te), wherein VSe is₂And NbSe₂Is typically represented by VSe₂For example, macro VSe₂Has a layered structure, each layer has a structure of Se-V-Se (X-M-X), and comprises 2 layers of selenium atoms and one layer of vanadium atoms which are arranged in a hexagonal way, and Van der Waals force is bonded between the layers. At present, the two-dimensional vanadium diselenide material is mainly prepared by a mechanical stripping method and a chemical vapor deposition method. The mechanical stripping method is simple in preparation method, and the obtained sample has few defects, but the yield is low, so that the mechanical stripping method is not beneficial to large-area production. The chemical vapor deposition method is mainly characterized in that VSe is generated on a substrate by reacting a vanadium source and a selenium source at high temperature₂The film, the present preparation technology of the method is not mature, and the method is not widely applied. The biggest current problem limiting the practical application of ultra-thin two-dimensional layered materials is the preparation of high quality wafer-level materials. Obtaining high-quality wafer-level vanadium diselenide material by a simple and easy-to-operate and control mode has great significance, and is one of the key challenges of the application.

Disclosure of Invention

The invention provides a method for growing single-layer and multi-layer vanadium diselenide materials by alternately injecting reactants into a reaction cavity, which is simple to operate and controllable in process. According to the method, the reactant pulses alternately enter the reaction cavity to perform deposition reaction by accurately controlling the dosage and the reaction time of the reactant pulses, so that the number of layers and the area of the grown vanadium diselenide material are controlled, and the high-quality layered vanadium diselenide material is obtained.

The method is characterized in that the method of the deposition process is as follows:

placing a clean silicon substrate with an area of 1-100 square centimeters, quartz, sapphire or a silicon substrate with a silicon dioxide film in a reaction chamber, controlling the reaction temperature at 100-700 ℃ and the reaction pressure at 100-2000 Pa; one or more than one vanadium metal compound and one or more than one selenium-containing compound are injected alternately by controlling the flow rate of carrier gas at 1-500 cubic centimeters per second, the number of times of the alternate injection is 1-1000, and the interval time of the injection of different reactants is 1 second-10 minutes, so that single-layer and multi-layer vanadium diselenide materials are obtained on the substrate.

The metal vanadium compound refers to vanadium isopropoxide, tetramethylethylaminovanadium, tetradiethylaminovanadium and tetradimethylaminodovanadium.

The selenium-containing compound refers to selenourea, dimethyl selenoether, diethyl diselenide and diphenyl diselenide.

The invention has the advantages that: the growth condition is accurate and controllable, the operation is simple and convenient, and the large-area preparation of the vanadium diselenide material can be realized. The method has wide application prospect in the scientific and technical fields of spinning electronics, optoelectronics, sensors, catalysts, energy collection and storage and the like.

Detailed Description

Example 1

Placing a 100 square centimeter clean silicon substrate in a deposition reaction chamber under the conditions that the reaction temperature is 700 ℃ and the reaction pressure is 100 Pa; setting the flow rate of carrier gas as 1 cubic centimeter per second, circularly and alternately injecting triisopropoxytriantivaquo and diphenyl diselenide into the reaction cavity through the carrier gas, wherein the interval time between the triisopropoxytriantivaquo and the diphenyl diselenide is 3 minutes, the interval time between the diphenyl diselenide and the triisopropoxytriantivaquo is 1 second, and injecting 1000 cycles together to deposit on the substrate to obtain the single-layer vanadium diselenide.

Example 2

Placing a 1 square centimeter clean silicon wafer with a silicon dioxide film in a deposition reaction chamber at the reaction temperature of 100 ℃ and the reaction pressure of 2000 Pa; the flow rate of the carrier gas is 500 cubic centimeters per second, tetramethylethylaminovanadium and dimethyl selenide are circularly and alternately injected into the reaction cavity through the carrier gas, the interval time between the tetramethylethylaminovanadium and the dimethyl selenide is 10 minutes, the interval time between the dimethyl selenide and the tetramethylethylaminovanadium is 10 minutes, 1 cycle is totally injected, and the multilayer vanadium diselenide is obtained through deposition.

Example 3

Placing 21.3 square centimeters of clean quartz into a deposition reaction chamber at the reaction temperature of 300 ℃ and the reaction pressure of 500 Pa; setting the flow rate of carrier gas at 150 cubic centimeters per second, circularly and alternately injecting tetradiethylaminovanadium, selenourea, tetramethylethylaminovanadium and diphenyl diselenide into the reaction cavity through the carrier gas, wherein the interval time between the tetradiethylaminovanadium and the selenourea is 1.5 minutes, the interval time between the selenourea and the tetramethylethylaminovanadium is 1 minute, the interval time between the tetramethylethylaminovanadium and the diphenyl diselenide is 10 seconds, the interval time between the diphenyl diselenide and the tetradiethylaminovanadium is 44 seconds, and co-injecting for 1 cycle to obtain single-layer and multi-layer vanadium diselenide through deposition.

Example 4

Placing clean sapphire with the thickness of 4 square centimeters in a deposition reaction chamber under the conditions that the reaction temperature is 500 ℃ and the reaction pressure is 1000 Pa; setting the flow rate of carrier gas at 10 cubic centimeters per second, circularly and alternately injecting tetradimethylaminodovanadium and diethylselenide into the reaction cavity through the carrier gas, wherein the interval time between the tetradimethylaminodovanadium and the diethylselenide is 3 seconds, the interval time between the diethylselenide and the tetradimethylaminodovanadium is 8 minutes, totally injecting 600 cycles, and depositing to obtain single-layer and multi-layer vanadium diselenide.

Claims

1. A method for preparing single-layer and multi-layer vanadium diselenide materials through alternative reaction is characterized by comprising the following steps:

placing clean silicon, quartz, sapphire or a silicon substrate with a silicon dioxide film in a reaction chamber, controlling the reaction temperature at 100-700 ℃ and the reaction pressure at 100-2000 Pa; one or more than one vanadium metal compound and one or more than one selenium-containing compound are injected alternately by controlling the flow rate of carrier gas at 1-500 cubic centimeters per second, the number of times of the alternate injection is 1-1000, and the interval time of the injection of different reactants is 1 second-10 minutes, so that single-layer and multi-layer vanadium diselenide materials are obtained on the substrate.

2. The method of claim 1, wherein the vanadium metal compound is tetradimethylaminodovanadium, vanadium triisopropoxide, vanadium tetradiethylaminoselenide or vanadium tetramethylethylaminovanadium.

3. The method for preparing single-layer and multilayer vanadium diselenide materials through alternating reaction according to claim 1, wherein the selenium-containing compound is dimethyl selenide, selenourea, diphenyl diselenide or diethyl diselenide.