CN109809372B - Method for preparing single-layer tungsten diselenide nanobelt based on space confinement strategy - Google Patents
Method for preparing single-layer tungsten diselenide nanobelt based on space confinement strategy Download PDFInfo
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Abstract
The invention discloses a method for preparing a single-layer tungsten diselenide nanobelt based on a space confinement strategy. The invention can realize effective regulation and control of the width and the thickness of the nanobelt by changing the flow and the growth time of the hydrogen, and comprises the following steps: the tungsten trioxide powder is evenly sprinkled on a substrate, and then the other substrate is covered with a bottom cover to form a micro reaction space with a sandwich-like structure. Growing the tungsten diselenide nanobelt by using a normal-pressure chemical vapor deposition method; the physicochemical properties of one-dimensional transition metal chalcogenides strongly depend on their type of edge dangling bonds, with ultra-narrow bands exhibiting metallic properties, while wider bands exhibiting a transition from metallic to semiconducting properties from their edges to their centers; the special property enables the tungsten diselenide nanoribbon to be widely applied to micro-nano photoelectric devices; and the industrial production of the tungsten diselenide nanobelt can be realized according to the experimental method of the invention.
Description
Technical Field
The invention relates to materials and microelectronic technology, in particular to a method for preparing a single-layer tungsten diselenide nanobelt based on a space confinement strategy.
Background
One-dimensional nanostructures, such as nanorods, nanowires, nanobelts and the like, have been widely studied in the last two decades, have a special electronic band structure due to quantum confinement effect, exhibit peculiar physical properties, and have important basic research value and scientific significance. In recent years, researchers have successfully synthesized graphene nanoribbons with atomic-scale thickness, and researches show that the graphene nanoribbons with the width of less than 10 nanometers show semiconductor properties, and field effect transistors prepared by the graphene nanoribbons have the on-off ratio of 107. The novel one-dimensional carbon nano material has wide application prospect in future nano electronic devices.
The semimetal characteristic of the graphene nanoribbon opens up a new round of research hot tide of the spin electron device. As a p-type direct band gap semiconductor material, single-layer tungsten diselenide attracts extensive attention of researchers due to its excellent optical and electrical properties and its potential applications. Tungsten diselenide having a layered structure is stacked by three atomic layers (Se-W-Se) by van der waals force, and belongs to the hexagonal system. The calculation result of the first principle based on the density functional theory shows that the armchair tungsten diselenide nanoribbon presents a semiconductor characteristic, while the zigzag nanoribbon presents a metallic characteristic, and presents a potential application value in the fields of photoelectrons, light-emitting devices, energy sources and the like. Meanwhile, when the tungsten diselenide material is reduced from two dimensions to one dimension, the thermoelectric property of the tungsten diselenide material is greatly improved, and for the armchair-type nanobelt, the thermoelectric property index at room temperature is as high as 2.2, which is mainly caused by disorder introduced by a suspension bond existing at the edge of the nanobelt. Meanwhile, the tungsten diselenide nanoribbon has abundant edge nanostructures, so that the tungsten diselenide nanoribbon also has wide application prospects in the fields of novel supercapacitors, lithium ion batteries, electrocatalytic hydrogen evolution reaction and the like.
The precondition for realizing the physical property research and the application exploration is to prepare the single-layer tungsten diselenide nanobelt with high quality and high length-width ratio. The methods for preparing the nanobelt material reported at present mainly comprise a template method and a solvent method, and although the two methods can obtain the narrow nanobelt, the preparation method has complex operation and high preparation cost, and cannot realize industrial application. The common chemical vapor deposition method usually needs to add salt to prepare the tungsten diselenide nanobelt, but the method inevitably introduces impurities into the material due to the use of the salt, so that the quality of a sample is reduced, and the subsequent device preparation process and the device performance are finally influenced.
China invention CN201810078755 provides a method for preparing large-area single-layer tungsten diselenide single crystal, and reports that CVD method is adopted and WO is used3Preparation of Single layer WSe for precursors2The method is representative in two-dimensional materials, in the adopted process, only argon is used as carrier gas, NaCl solution is dripped on a growth substrate by a liquid-transferring gun for pretreatment, but the method can only grow a single-layer WSe2The one-dimensional nano material cannot be obtained by the triangular nanosheets, so that the application of devices of the material is limited, meanwhile, impurity ions are inevitably introduced by adding NaCl salt to influence the purity of the product, and salt appears on a growth substrate after the salt is addedThe product can affect the subsequent device preparation process and device performance.
Disclosure of Invention
The invention aims to provide a method for preparing a single-layer tungsten diselenide nanobelt based on a space confinement strategy, wherein the one-dimensional tungsten diselenide nanobelt with adjustable width and thickness can be controllably prepared by utilizing a normal-pressure chemical vapor deposition method under the space confinement strategy. The tungsten diselenide nanoribbon has excellent performance in the fields of hydrodesulfurization reaction, hydrogen evolution reaction, spintronics and the like, has stable properties in air, and provides a nano-scale experimental platform for researching the optical, electrical and magnetic properties of the one-dimensional semiconductor transition metal chalcogenide material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing a single-layer tungsten diselenide nanobelt based on a space confinement strategy comprises the following steps:
(1) cleaning the substrate;
(2) placing the treated substrate in a heating center of a high-temperature tube furnace, placing an alumina boat containing selenium powder at the upstream (close to a pipe orifice) and placing the boat containing tungsten trioxide and the substrate in a downstream heating center in the sequence of air flow from the upstream to the downstream;
(3) introducing argon and hydrogen into a reaction cavity of the high-temperature tubular furnace, and cleaning the reaction cavity;
(4) raising the temperature of the tubular furnace to 800-850 ℃, so that the temperature of the selenium powder is controlled to be 400-450 ℃, the temperature of the tungsten trioxide is controlled to be 800-850 ℃, and the growth of the tungsten diselenide is carried out;
(5) and after the growth of the tungsten diselenide is finished, cooling the temperature to room temperature, and simultaneously closing argon and hydrogen to obtain the single-layer tungsten diselenide nanobelt.
Preferably, in the step (1), the substrate is one or two of a silicon dioxide substrate, a sapphire substrate, a graphene substrate, a mica substrate, a glass substrate and a monocrystalline silicon substrate.
Preferably, in the step (1), the mass ratio of the selenium powder to the tungsten trioxide is 430-500: 15 to 30.
Preferably, in step (2), the boat containing tungsten trioxide and the substrate is arranged according to the following method: placing a substrate sheet on an alumina boat with the smooth surface facing upwards, spraying tungsten trioxide powder on the substrate sheet, and covering the tungsten trioxide powder with another substrate sheet with the smooth surface facing downwards to form a micro-reaction chamber with a sandwich-like structure.
Preferably, in the step (2), before the substrate is used, the substrate is sequentially cleaned in acetone, isopropanol, ethanol and deionized water, and then dried by blowing with nitrogen gas, so that the cleaning of the substrate is completed.
Preferably, in the step (3), argon accounts for 6-9% of the total volume of argon and hydrogen.
Preferably, in the step (3), the flow rate of argon is 60-80 sccm, and the flow rate of hydrogen is 7-15 sccm.
Preferably, in step (4), the growth time is 8 to 30 minutes.
Compared with the prior art, the invention has the following advantages:
(1) the method realizes the successful preparation of the single-layer tungsten diselenide nanoribbon by a space confinement strategy and a chemical vapor deposition method, the width of the obtained tungsten diselenide nanoribbon is 0.17-1.62 microns, and the thickness of the single-layer nanoribbon is about 0.7 nm.
(2) The carrier gas is mixed gas, and trace hydrogen is used as one of reactants, so that the carrier gas can react with tungsten trioxide to obtain trace W, and can also react with selenium powder to generate trace H2Se, experiments show that trace hydrogen just can obviously promote the reaction and improve the yield.
(3) The method of the invention does not need to add extra salt, avoids introducing impurity ions into the product, does not corrode the tube furnace and the quartz tube at high temperature, does not have salt products on the growth substrate, and does not influence the preparation process and performance of subsequent devices, thereby not only having better quality, but also being more beneficial to application.
(4) The tubular furnace used as the main device of the invention is a common tubular furnace, the temperature does not need to be controlled in different areas, the reaction requirement can be met only by properly adjusting the placing position, and the requirement on equipment is low.
(5) The atmospheric pressure chemical vapor deposition method has good reproducibility, and can realize the batch preparation of the tungsten diselenide nanobelt with high uniformity and high quality.
(6) The material obtained by the invention is a tungsten diselenide nanobelt, namely a one-dimensional nanomaterial, and can be directly characterized by an atomic force microscope, a Kelvin probe microscope, a scanning electron microscope, a transmission electron microscope and the like, so that the exploration of the microstructure and the electronic structure of the material can be realized;
(7) the invention can realize the regulation and control of the growth of the tungsten diselenide nanobelt by the chemical vapor deposition method through the design of the precursor.
Drawings
Fig. 1 is an optical microscope characterization result of a single-layer tungsten diselenide nanobelt prepared based on a spatial confinement strategy, which corresponds to example 1;
fig. 2 is a raman characterization result of a single-layer tungsten diselenide nanobelt prepared based on a spatial confinement strategy corresponding to example 3;
fig. 3 is an atomic force microscope characterization result of a single-layer tungsten diselenide nanobelt prepared based on a spatial confinement strategy, which corresponds to example 2.
Fig. 4 is a scanning electron microscope characterization result of a single-layer tungsten diselenide nanoribbon prepared based on a spatial confinement strategy, which corresponds to example 2.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the following detailed description, but the present invention is not limited thereto.
Example 1
The purchased silica pieces were washed in ethanol and deionized water in sequence and then blown dry with nitrogen. The silicon dioxide piece after cleaning treatment is placed in the heating center of a high-temperature tube furnace, selenium powder (close to the upstream of a tube opening), tungsten trioxide and the silicon dioxide piece (the heating center of the downstream) are sequentially placed in the order from the upstream to the downstream of the airflow, and the tungsten trioxide powder is sprinkled between two silicon pieces. The mass of the selenium powder and the mass of the tungsten trioxide are respectively 430-500 mg and 15-30 mg, and the distance between the selenium powder and the tungsten trioxide is 24 cm. Then argon gas (500sccm) is introduced into the reaction chamber, the reaction chamber is cleaned, and residual air in the chamber is discharged, wherein the cleaning time is 30 minutes. And then, controlling the temperature of the tubular furnace to be 800-850 ℃ by program heating, so that the temperatures of the selenium powder and the tungsten trioxide powder are respectively controlled to be 400-450 ℃ and 800-850 ℃. Argon (80sccm) and hydrogen (7-15 sccm) are used as carrier gases, reactive species of the tungsten diselenide are conveyed to the silicon dioxide substrate to realize the growth of the tungsten diselenide, and the growth time of the tungsten diselenide is adjustable within 8-30 minutes. After the growth is finished, the temperature of the tube furnace is reduced to the room temperature, the argon and the hydrogen are closed at the same time, and the sample is taken out after the cavity is opened.
And (3) performing characterization on the obtained tungsten diselenide nanobelt sample by using an optical microscope, a Raman microscope, an atomic force microscope and a scanning electron microscope, wherein the result is shown in figures 1-4. The characterization data of an optical microscope show that on a single-layer tungsten diselenide film, a tungsten diselenide nanobelt grows on the single-layer tungsten diselenide film according to a certain rule and grows spirally from the periphery to the middle. As can be seen from the Raman characterization data, the sample is 250cm-1And 260cm-1The tungsten diselenide E actually appears as a peak nearby by comparison with the literature2g 1And A1gPeak(s). As can be seen from the characterization data of the atomic force microscope and the scanning electron microscope, the average height of the single nanobelt is 0.7nm, the average width is 300nm, and the distribution is uniform.
Examples 2 to 36
The silicon dioxide-silicon dioxide substrate in the embodiment 1 is replaced by a sapphire substrate, a graphene-graphene substrate, a mica-mica substrate, a glass-glass substrate, a monocrystalline silicon-monocrystalline silicon substrate, or any two of the substrates, and other preparation conditions are not changed, so that the tungsten diselenide nanobelt with better quality can be obtained.
Examples 37 to 72
The substrates of various combinations of two sheets in examples 2 to 36 were vertically stacked, and the tungsten diselenide nanobelts with good quality could be obtained without changing other preparation conditions.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A method for preparing a single-layer tungsten diselenide nanobelt based on a space confinement strategy is characterized by comprising the following steps of:
(1) cleaning the substrate;
(2) placing the treated substrate in a heating center of a high-temperature tube furnace, placing an alumina boat filled with selenium powder at the upstream and placing the boat filled with tungsten trioxide and the substrate in a heating center at the downstream according to the sequence of air flow from the upstream to the downstream;
the boat containing tungsten trioxide and substrate was set up as follows: placing a substrate sheet on an alumina boat with a smooth surface facing upwards, spraying tungsten trioxide powder on the substrate sheet, and covering the tungsten trioxide powder with another substrate sheet with a smooth surface facing downwards to form a micro-reaction chamber with a sandwich-like structure;
(3) introducing argon and hydrogen into a reaction cavity of the high-temperature tubular furnace, and cleaning the reaction cavity;
(4) raising the temperature of the tubular furnace to 800-850 ℃, so that the temperature of the selenium powder is controlled to be 400-450 ℃, the temperature of the tungsten trioxide is controlled to be 800-850 ℃, and the growth of the tungsten diselenide is carried out;
(5) and after the growth of the tungsten diselenide is finished, cooling the temperature to room temperature, and simultaneously closing argon and hydrogen to obtain the single-layer tungsten diselenide nanobelt.
2. The method for preparing single-layer tungsten diselenide nanobelts based on the spatial confinement strategy of claim 1, wherein in the step (1), the substrate is one or two of a silicon dioxide substrate, a sapphire substrate, a graphene substrate, a mica substrate, a glass substrate and a monocrystalline silicon substrate.
3. The method for preparing the single-layer tungsten diselenide nanobelt based on the space-limited strategy of claim 1, wherein in the step (1), the mass ratio of the selenium powder to the tungsten trioxide is 430-500: 15 to 30.
4. The method for preparing the single-layer tungsten diselenide nanobelt based on the space-limited domain strategy of claim 1, wherein in the step (2), the substrate is sequentially cleaned in acetone, isopropanol, ethanol and deionized water before being used, and then is dried by nitrogen to complete cleaning of the substrate.
5. The method for preparing the single-layer tungsten diselenide nanobelt based on the space-limited strategy of claim 1, wherein in the step (3), the argon gas accounts for 6-9% of the total volume of the argon gas and the hydrogen gas.
6. The method for preparing the single-layer tungsten diselenide nanobelt based on the spatial confinement strategy as claimed in claim 1, wherein in the step (3), the flow rate of argon gas is 60-80 sccm, and the flow rate of hydrogen gas is 7-15 sccm.
7. The method for preparing single-layer tungsten diselenide nanoribbons based on the spatial confinement strategy as claimed in claim 1, wherein in the step (4), the growth time is 8 to 30 minutes.
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| CN113511681B (en) * | 2020-04-09 | 2022-06-03 | 北京大学 | Method for locally growing transition metal chalcogenide with assistance of chalcogenide wafer |
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| CN113173562B (en) * | 2021-05-17 | 2022-10-21 | 福州大学 | Preparation method of metallic ditelluride |
| CN115246631A (en) * | 2021-12-22 | 2022-10-28 | 青岛大学 | Preparation method and application of concentric triangular structure tungsten selenide nanosheet |
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