CN110863189A - Method for growing single-layer telluride doped structure by pulse type injection of reactant - Google Patents

Abstract

The invention discloses a method for growing a single-layer telluride doped structure by pulse type injection of reactants. The method simultaneously injects a plurality of transition metal organic matters and diethyl tellurium or injects molybdenum hexacarbonyl and a plurality of sulfur group elements to control the flow rate of carrier gas to control the doping amount of telluride, and controls the reaction temperature and the reaction time to control the area and the layer number of the growth of the telluride, thereby obtaining the molybdenum ditelluride with a high-quality doping structure. The invention has the advantages that: the growth condition is accurate and controllable, the operation is simple and convenient, and the stable molybdenum ditelluride with a single-layer doping structure can be prepared. The molybdenum ditelluride with the single-layer doped structure prepared by the invention has wide application prospect in the fields of nano electronic devices, lubricating materials, photocatalysis and the like.

Description

Translated fromChinese

一种脉冲式注入反应物生长单层碲化物掺杂结构的方法A method for growing monolayer telluride doped structures by pulsed implantation of reactants

技术领域technical field

本发明属于材料制备领域，涉及纳米材料制备技术，具体指一种脉冲式注入反应物生长单层碲化物掺杂结构的方法。The invention belongs to the field of material preparation, relates to nanometer material preparation technology, in particular to a method for growing a monolayer telluride doped structure by pulsed injection of reactants.

背景技术Background technique

自从2004年Novoselov和Geim及其合作者成功地使用胶带从石墨上剥离出了石墨烯后，二维材料的研究进入了高速发展的时期，与此同时，石墨烯及类石墨烯材料进一步丰富了二维材料的家族，例如二维过渡金属硫族化合物，其优异的物理化学性质，独特的热电、导电、超导、光学、光伏特性使其在光学材料，存储材料，催化材料以及半导体光电材料等方面有着广泛的应用前景。Since Novoselov and Geim and their collaborators successfully used tape to peel graphene from graphite in 2004, the research on two-dimensional materials has entered a period of rapid development. At the same time, graphene and graphene-like materials have been further enriched. A family of two-dimensional materials, such as two-dimensional transition metal chalcogenides, their excellent physical and chemical properties, unique thermoelectric, conductive, superconducting, optical, and photovoltaic properties make them useful in optical materials, storage materials, catalytic materials, and semiconductor optoelectronic materials. It has broad application prospects.

尽管二维纳米材料展现出诱人的前景，但是制约其发展的瓶颈在于如何能够规模化制备高质量的二维材料。目前常用的二维纳米材料的制备法可以归为两大类：自上而下剥离法和自下而上合成法。前一种是最传统的制备二维材料的方法，制备方法简单，获得的样品缺陷少，但是产量较低，不适合大面积生产。后一种是制备大面积高结晶质量二碲化钼最有效的方法，在尺寸，层数及物理性质控制方面具有优势，但目前制备工艺还不成熟。二维材料由于其层间弱的范德华力使得二维材料层间易于掺杂一些其它的分子、原子或是离子。以过渡金属硫化物为例，随着层间插层组分种类或浓度的变化，其本征电子结构通常会被有效地调控，并引起多种奇特的物理或化学现象，比如电荷密度波、各向异性的输运性能甚至超导电性等多种电子行为。掺杂是一种有效的调控二维材料物理化学性能方法，通过简单易操作控制的方式获得单层碲化物掺杂结构具有重大意义，更是其应用的关键挑战之一。Although two-dimensional nanomaterials show attractive prospects, the bottleneck restricting their development lies in how to prepare high-quality two-dimensional materials on a large scale. The commonly used preparation methods of 2D nanomaterials can be classified into two categories: top-down exfoliation and bottom-up synthesis. The former is the most traditional method for preparing two-dimensional materials. The preparation method is simple, and the obtained samples have few defects, but the yield is low, which is not suitable for large-scale production. The latter is the most effective method for the preparation of large-area, high-crystalline quality molybdenum ditelluride, which has advantages in the control of size, number of layers and physical properties, but the current preparation process is immature. Due to the weak van der Waals force between the two-dimensional materials, it is easy to dope some other molecules, atoms or ions between the two-dimensional material layers. Taking transition metal sulfides as an example, with the change of the types or concentrations of intercalated components, their intrinsic electronic structures are usually effectively regulated, and a variety of peculiar physical or chemical phenomena, such as charge density waves, Anisotropic transport properties and even superconductivity and other electronic behaviors. Doping is an effective method to control the physical and chemical properties of two-dimensional materials. It is of great significance to obtain a single-layer telluride doped structure through a simple and easy-to-operate method, and it is one of the key challenges for its application.

发明内容SUMMARY OF THE INVENTION

本发明的目的是提供一种生长单层碲化物掺杂结构的方法。该方法操作简单方便，可控性好，通过脉冲式注入反应物至反应腔体，精确控制反应物的用量，反应温度和脉冲时间，使反应物脉冲式进入腔体进行沉积反应，从而达到对二碲化钼的掺杂原子量，生长面积和层数的控制，制备出稳定的单层掺杂结构的碲化物。It is an object of the present invention to provide a method for growing a monolayer telluride doped structure. The method is simple and convenient to operate and has good controllability. By injecting the reactants into the reaction chamber in a pulsed manner, the dosage of the reactants, the reaction temperature and the pulse time are precisely controlled, and the reactants are pulsed into the chamber for deposition reaction, so as to achieve the desired The doping atomic weight of molybdenum ditelluride, the growth area and the number of layers are controlled to prepare stable monolayer doped telluride.

本发明所涉及的一种脉冲式注入反应物生长单层碲化物掺杂结构的方法包括如下步骤：A method for growing a single-layer telluride doped structure by pulsed injection of reactants involved in the present invention comprises the following steps:

先将洁净的面积为1-100平方厘米的硅、蓝宝石片、石英片或表面长有三氧化二铝、二氧化硅薄膜的衬底置于反应腔体内，控制反应压力在10-300托；再以惰性气体或氢气为载气脉冲式注入多种过渡金属有机物和二乙基碲或注入六羰基钼和多种硫族元素，控制载气流量在1-500立方厘米/秒，不同的反应物注入的脉冲时间为1秒-5分钟，脉冲式注入共循环1-800次，控制反应温度为600-900℃，在衬底上获得单层掺杂结构的碲化物。First, place clean silicon, sapphire, quartz or substrates with aluminum oxide and silicon dioxide films with an area of 1-100 square centimeters in the reaction chamber, and control the reaction pressure at 10-300 Torr; Pulse injection of various transition metal organic compounds and diethyl tellurium or injection of molybdenum hexacarbonyl and various chalcogen elements with inert gas or hydrogen as carrier gas, control the flow rate of carrier gas at 1-500 cubic centimeters per second, different reactants The implantation pulse time is 1 second to 5 minutes, the pulsed implantation is cycled 1 to 800 times in total, and the reaction temperature is controlled to be 600 to 900° C. to obtain a single-layer doped telluride on the substrate.

所述过渡金属有机物为六羰基钼或六羰基钨。The transition metal organic compound is molybdenum hexacarbonyl or tungsten hexacarbonyl.

所述的硫族元素为二乙基硫，二乙基碲或二乙基二硒醚。The chalcogen is diethyl sulfur, diethyl tellurium or diethyl diselenide.

本发明的优点是：生长条件精确可控，操作简单方便，能实现掺杂结构碲化物的制备。在纳米电子器件、润滑材料、光催化等领域有着广阔的应用前景。The invention has the advantages that the growth conditions are precisely controllable, the operation is simple and convenient, and the preparation of the doped structure telluride can be realized. It has broad application prospects in nanoelectronic devices, lubricating materials, photocatalysis and other fields.

具体实施方式Detailed ways

实施例1Example 1

将100平方厘米洁净的硅衬底置于沉积反应腔体内，控制反应压力在300托，反应温度为900℃；通过载气向腔体脉冲式注入六羰基钼六羰基钨和二乙基碲，设置载气流量为500立方厘米/秒，六羰基钼脉冲注入时间为1分钟，六羰基钨脉冲注入时间为7秒，二乙基碲脉冲注入时间为3分钟，共注入200个循环，沉积获得单层Mo_0.9W_0.1Te₂。A clean silicon substrate of 100 square centimeters was placed in the deposition reaction chamber, the reaction pressure was controlled at 300 Torr, and the reaction temperature was 900 °C; the hexacarbonyl molybdenum hexacarbonyl tungsten and diethyl tellurium were pulsed into the chamber through the carrier gas, Set the carrier gas flow rate to 500 cubic centimeters per second, the pulse injection time of molybdenum hexacarbonyl to be 1 minute, the pulse injection time of tungsten hexacarbonyl to be 7 seconds, and the pulse injection time of diethyl tellurium to be 3 minutes, for a total of 200 cycles of injection. Monolayer Mo_0.9 W_0.1 Te₂ .

实施例2Example 2

将6平方厘米洁净的硅衬底置于沉积反应腔体内，控制反应压力在40托，反应温度为600℃；通过载气向腔体脉冲式注入六羰基钼六羰基钨和二乙基碲，设置载气流量为60立方厘米/秒，六羰基钼脉冲注入时间为30秒，六羰基钨脉冲注入时间为10秒，二乙基碲脉冲注入时间为2分钟，共注入400个循环，沉积获得额单层Mo_0.8W_0.2Te₂。A clean silicon substrate of 6 square centimeters was placed in the deposition reaction chamber, the reaction pressure was controlled at 40 Torr, and the reaction temperature was 600 °C; the hexacarbonyl molybdenum hexacarbonyl tungsten and diethyl tellurium were pulsed into the chamber through the carrier gas, Set the carrier gas flow rate to 60 cm3/s, the pulse injection time of molybdenum hexacarbonyl to be 30 seconds, the pulse injection time of tungsten hexacarbonyl to be 10 seconds, and the pulse injection time of diethyl tellurium to be 2 minutes. A single layer of Mo_0.8 W_0.2 Te₂ .

实施例3Example 3

将54平方厘米洁净的硅衬底置于沉积反应腔体内，控制反应压力在230托，反应温度为710℃；通过载气向腔体脉冲式注入六羰基钼、二乙基硫和二乙基碲，设置载气流量为80立方厘米/秒，六羰基钼脉冲注入时间为1分钟，二乙基硫脉冲注入时间为30秒，二乙基碲脉冲注入时间为4分钟，共注入800个循环，沉积获得单层MoS_0.4Te_1.6。A 54 square centimeter clean silicon substrate was placed in the deposition reaction chamber, the reaction pressure was controlled at 230 Torr, and the reaction temperature was 710 °C; hexacarbonyl molybdenum, diethyl sulfide and diethyl molybdenum were injected into the chamber by pulsed carrier gas. Tellurium, set the carrier gas flow rate to 80 cm3/s, the pulse injection time of molybdenum hexacarbonyl to be 1 minute, the pulse injection time of diethyl sulfide to be 30 seconds, and the pulse injection time of diethyl tellurium to be 4 minutes, for a total of 800 injection cycles , a single layer of MoS_0.4 Te_1.6 was obtained by deposition.

实施例4Example 4

将27平方厘米洁净的硅衬底置于沉积反应腔体内，控制反应压力在170托，反应温度为760℃；通过载气向腔体脉冲式注入六羰基钼、二乙基二硒醚和二乙基碲，设置载气流量为420立方厘米/秒，六羰基钼脉冲注入时间为2分钟，二乙基二硒醚脉冲注入时间为1分钟，二乙基碲脉冲注入时间为5分钟，共注入340个循环，沉积获得单层MoSe_0.3Te_1.6。A 27 square centimeter clean silicon substrate was placed in the deposition reaction chamber, the reaction pressure was controlled at 170 Torr, and the reaction temperature was 760 °C; hexacarbonyl molybdenum, diethyl diselenide, and diethyl molybdenum were injected into the chamber by pulsed carrier gas. Ethyl tellurium, set the carrier gas flow to 420 cubic centimeters per second, the pulse injection time of molybdenum hexacarbonyl is 2 minutes, the pulse injection time of diethyl diselenide is 1 minute, and the pulse injection time of diethyl tellurium is 5 minutes. After 340 cycles of injection, a monolayer of MoSe_0.3 Te_1.6 was obtained by deposition.

Claims (3)

1. A method for growing a single-layer telluride doped structure by injecting reactants in a pulse mode is characterized by comprising the following steps:

firstly, a clean substrate with the area of 1-100 square centimeters, such as a silicon, sapphire sheet, quartz sheet or a substrate with an aluminum oxide and silicon dioxide film growing on the surface is placed in a reaction cavity, and the reaction pressure is controlled to be 10-300 torr; and injecting various transition metal organic matters and diethyl tellurium or injecting molybdenum hexacarbonyl and various chalcogen elements in a pulse mode by taking inert gas or hydrogen as carrier gas, controlling the flow rate of the carrier gas to be 1-500 cubic centimeters per second, controlling the pulse time of injecting different reactants to be 1-5 minutes, performing pulse injection for 1-800 times in a total cycle, controlling the reaction temperature to be 600-900 ℃, and obtaining the telluride with a single-layer doping structure on the substrate.

2. The method of claim 1, wherein the step of growing the single-layer telluride doped structure comprises the steps of: the transition metal organic matter is molybdenum hexacarbonyl or tungsten hexacarbonyl.

3. The method of claim 1, wherein the step of growing the single-layer telluride doped structure comprises the steps of: the chalcogen is diethyl sulfur, diethyl tellurium or diethyl diselenide.