Method for preparing multiple transition metal chalcogenide nanobelts with assistance of gold catalyst particles

Abstract

The invention provides a method for realizing the controllable growth of the transition metal chalcogenide nanobelt by a chemical vapor deposition method assisted by gold catalyst particles, and through magnetron sputtering of a gold nano film and high-temperature annealing treatment, a diameter-adjustable silicon wafer modified by uniformly distributed gold nano particles can be obtained, and the silicon wafer is used as a growth substrate. In the chemical vapor deposition high-temperature reaction process, the proportion and evaporation rate of transition metal oxide powder, sulfur powder and selenium powder are further finely regulated and controlled through a single / double-temperature-zone high-temperature furnace, the flow and proportion of hydrogen and argon are regulated and controlled, and finally controllable growth of the transition metal chalcogenide nanobelt with high crystal quality can be achieved. The growth process of the transition metal chalcogenide nanobelts can be obviously influenced by regulating and controlling the temperature of the growth substrate, the types of the evaporation precursors and the evaporation rate, the transition metal chalcogenide nanobelts with different structures such as components and chirality are obtained, and controllable growth and directional regulation and control of physical properties of the transition metal chalcogenide nanobelts are achieved.

Description

Technical Field

[0001] The invention relates to a method for preparing a transition metal sulfide compound nanobelt, and realizes controllable growth of the transition metal sulfide compound nanobelt through a chemical vapor deposition method catalyzed by gold nanoparticles. Background Art

[0002] With the continuous development of the preparation and structural regulation of two-dimensional transition metal chalcogenides (TMD) materials, the types of transition metal chalcogenides are becoming increasingly rich, further stimulating in-depth exploration of their novel physical properties and device applications. In this context, breaking through the traditional structural construction methods and regulation strategies of transition metal chalcogenides and seeking new research ideas have become the key to expanding their research and applications.

[0003] Transition metal chalcogenide nanoribbon structures can be viewed as one-dimensional ribbon structures formed by two-dimensional transition metal chalcogenides in a specific direction. Compared with their two-dimensional and three-dimensional structures, nanoribbons exhibit unique properties such as enhanced photoelectric effect, excellent conductivity and catalytic performance, becoming an emerging field of research and application.

[0004] As early as 2005, researchers first reported the preparation of transition metal chalcogenide nanobelts, using chemical vapor deposition (CVD) to successfully prepare nanobelts of tungsten sulfide and tungsten selenide. Although this method has made some progress in achieving large-scale preparation of nanobelts, it still has limitations in the preparation of a variety of transition metal chalcogenides, especially the lack of control over the size, shape and chirality of the nanobelts. These problems have led to relatively slow research progress in transition metal chalcogenide nanobelts.

[0005] In recent years, researchers have tried to solve these challenges by improving chemical vapor deposition technology and solution methods, exploring different precursors and reaction conditions, in order to achieve efficient growth and chiral control of transition metal chalcogenide nanoribbons. However, these methods still face many challenges in adaptability and repeatability, which limits the widespread application of nanoribbons.

[0006] Therefore, developing simple and effective growth methods and control strategies to enhance the understanding and application potential of transition metal chalcogenide nanoribbons is a key research direction. This will open up new paths for promoting the basic research and practical application of transition metal chalcogenides. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide a method for preparing a variety of transition metal sulfide nanobelts assisted by gold catalyst particles, so as to achieve the preparation of transition metal sulfide nanobelts with high yield. The preparation method is a chemical vapor deposition method assisted by gold catalyst particles. A gold nanoparticle catalyst is obtained after annealing a gold film on a silicon substrate by magnetron sputtering, and the gold nanoparticle catalyst is used as a growth substrate to achieve the growth of transition metal sulfide nanobelts in an inert atmosphere and at a certain temperature. A transition metal sulfide nanobelt with uniform width, controllable length and adjustable number of layers is obtained, which meets the requirements of high crystal quality and high yield of transition metal sulfide nanobelts.

[0008] In order to solve the above technical problems, the technical solution adopted by the present invention is: The present invention provides a gold catalyst particle-assisted preparation method for realizing controllable growth of various transition metal chalcogenide nanotube heterojunctions, wherein the catalyst is composed of gold particles, and by controlling the magnetron sputtering coating thickness and the annealing temperature and time, gold nanoparticle catalysts with different diameters and high catalytic activity can be formed after annealing. The preparation steps are as follows: S1: Using high-purity gold as the sputtering target and silicon wafer as the sputtering substrate, sputtering for 35 seconds at 100°C and 50W DC power to obtain a gold film with a uniform thickness of 10nm; S2: The gold film obtained by magnetron sputtering is placed in a high-temperature tube furnace for annealing. The temperature is raised from 25°C to 750°C in 40 minutes during the heating stage, maintained at 750°C for 10 minutes during the constant temperature stage, and cooled to 25°C in 10 minutes during the cooling stage, thereby obtaining a gold nanoparticle catalyst with high catalytic activity and uniform particle diameter; the prepared silicon wafer with gold nanoparticles is placed on a rectangular sample table; S3: Weigh the transition metal oxide and chalcogenide powder respectively with a quartz boat, spread the transition metal oxide evenly on the quartz boat, and place the chalcogenide powder on the feeding device; a small amount of chalcogenide powder is placed on one side of the feeding device, and the remaining sulfur powder is placed on the other side of the feeding device, with a certain distance between the two; S4: placing the sample stage, the quartz boat and the feeding device into specific areas of the high-temperature tube furnace, respectively, and setting specific heating intervals and heating temperatures; S5: When the temperature reaches a certain temperature, a certain amount of hydrogen and argon mixed gas is introduced, and then the feeding device is controlled to move; S6: When the heat preservation time is over, stop heat preservation, cool naturally to 25°C, take out the sample table, and obtain the finished product.

[0009] Furthermore, the feeding device includes a magnetic base and a magnet. The chalcogenide powder is placed on the magnetic base. The magnet is located outside the high-temperature tube furnace. By moving the magnet, the magnetic base inside the high-temperature tube furnace is driven to move.

[0010] Furthermore, the metal oxide is MoO3, and the chalcogen element powder is one of S and Se.

[0011] Compared with the prior art, this application has the following beneficial effects: The gold catalyst particle-assisted preparation method for controllable growth of transition metal chalcogenide nanobelts prepares highly active gold nanoparticle catalysts through magnetron sputtering and annealing processes, and has excellent high-temperature stability. The preparation method is simple to prepare, realizes controllable growth of transition metal chalcogenide nanobelts, obtains relatively uniform transition metal chalcogenide nanobelts, and can control the temperature of the growth substrate to achieve controllable adjustment of the width and number of layers of the transition metal chalcogenide nanobelts. The new transition metal chalcogenide nanobelts have great scientific research and application potential in electronic devices and optoelectronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is a SEM image of gold nanoparticles formed on a silicon wafer provided by the present invention; Figure 2 The SEM image of the transition metal chalcogenide nanoribbon provided by the present invention; Figure 3 Schematic diagram of the tungsten sulfide nanoribbon growth device; Figure 4 Schematic diagram of the MoSe nanoribbon growth device. DETAILED DESCRIPTION

[0013] The present invention is further described in detail below by combining implementation examples, but the specific implementation scope is not limited to the examples given. Example 1

[0014] A method for preparing tungsten sulfide nanobelts is provided. The method comprises two parts: preparation of gold nanoparticle catalyst and chemical vapor deposition growth. The preparation steps are as follows: S1: Using high-purity gold as the sputtering target and silicon wafer as the sputtering substrate, sputtering for 35 seconds at 100°C and 50W DC power to obtain a gold film with a uniform thickness of 10nm; S2: The gold film obtained by magnetron sputtering is placed in a high-temperature tube furnace for annealing. The temperature is first raised from 25°C to 750°C in 40 minutes, then kept at 750°C for 10 minutes, and finally dropped to 25°C in 10 minutes, thereby obtaining a gold nanoparticle catalyst with high catalytic activity and uniform particle diameter on the silicon wafer; Figure 1As shown; the prepared silicon wafer with gold nanoparticles is placed on the rectangular sample stage; S3: Use a quartz boat (15*100) to weigh 0.45g of nano tungsten trioxide (Nanopower<200nm, 99.9% metal-based) and 0.55g of sublimated sulfur (>99.5%), spread the tungsten trioxide evenly on the quartz boat, and place the sulfur powder on the feeding device; a small amount of sulfur powder is placed on one side of the feeding device, and the remaining sulfur powder is placed on the other side of the feeding device, with a certain distance between the two; In this embodiment, the mass of the small amount of sulfur powder is 0.05 g, and the mass of the remaining larger amount of sulfur powder is 0.5 g.

[0015] S4: Place the quartz boat filled with tungsten trioxide in the center of the single-temperature zone high-temperature tube furnace, place the sample table in the heating zone of the tube furnace, and place the feeding device in the non-heating zone on the left side of the high-temperature tube furnace; S5: Heat the high-temperature tube furnace, raise the temperature from 25°C to 900°C within 40 minutes, when the temperature reaches 900°C, introduce 10sccm of hydrogen and 150sccm of argon from the left side of the high-temperature tube furnace, and adjust the gas pressure of the high-temperature tube furnace to maintain a constant low pressure; then continue to heat up, raise the temperature to 985°C within 4 minutes, and keep it at 985°C for 15 minutes, when the temperature reaches 900°C, use the sulfur powder feeding device to slowly feed the sulfur powder into the left side of the heating zone to make it reach the initial melting state, when the temperature reaches 985°C, start to slowly push 0.05g of sulfur powder on the feeding device into the heating zone within 0-3 minutes, so that the contact surface between the gold particles and the silicon wafer forms a block WO 3-x , quickly move the feeding device within 3-15min to push all the remaining sulfur powder into the heating zone. Under the catalysis of gold particles, the sulfur powder and block WO 3-x Rapid reaction, epitaxial growth of tungsten sulfide nanoribbons; S6: When the heat preservation time is over, stop heat preservation, cool naturally to 25°C, take out the sample table, and obtain the finished product. Example 2

[0016] Provided is a method for preparing a molybdenum selenide nanobelt, the method comprising two parts: preparation of a gold nanoparticle catalyst and chemical vapor deposition growth, and the preparation steps are as follows: S1: Using high-purity gold as the sputtering target and silicon wafer as the sputtering substrate, sputtering for 35 seconds at 100°C and 50W DC power to obtain a gold film with a uniform thickness of 10nm; S2: The gold film obtained by magnetron sputtering is placed in a high-temperature tube furnace for annealing. The temperature is first raised from 25°C to 750°C in 40 minutes, then kept at 750°C for 10 minutes, and finally dropped to 25°C in 10 minutes, thereby obtaining a gold nanoparticle catalyst with high catalytic activity and uniform particle diameter on the silicon wafer; Figure 1 As shown; the prepared silicon wafer with gold nanoparticles is placed on the rectangular sample stage; S3: Use a quartz boat (15*100) to weigh 0.5g of nano molybdenum trioxide (Nanopower<200nm, 99.9% metal base) and 0.82g of selenium powder (>99.5%), spread the molybdenum trioxide evenly on the quartz boat, and place the selenium powder on the feeding device; a small amount of selenium powder is placed on one side of the feeding device, and the remaining more selenium powder is placed on the other side of the feeding device, with a certain distance between the two; In this embodiment, the mass of the small amount of selenium powder is 0.1 g, and the mass of the remaining larger amount of selenium powder is 0.72 g.

[0017] S4: Place the quartz boat filled with molybdenum trioxide in the center of the left temperature zone of the high-temperature tube furnace, place the sample table in the right temperature zone of the tube furnace, and place the feeding device in the non-heating zone on the right side of the high-temperature tube furnace; S5: First, heat the right temperature zone of the high-temperature tube furnace, and raise the temperature of the right temperature zone from 25°C to 900°C within 40 minutes. When the right temperature zone starts to heat for 20 minutes, start heating the left temperature zone, and raise the temperature of the center of the left temperature zone of the high-temperature tube furnace from 25°C to 510°C within 20 minutes. When the temperature of the left temperature zone rises to 510°C and the temperature of the right temperature zone rises to 900°C, introduce 13sccm of hydrogen and 150sccm of argon from the left side of the high-temperature tube furnace, and adjust the gas pressure of the high-temperature tube furnace to maintain a constant low pressure; then continue to heat the left temperature zone and In the right temperature zone, the left temperature zone is heated to 580℃ within 4 minutes and maintained at 580℃ for 15 minutes. While the left temperature zone is heated, the right temperature zone is heated to 985℃ within 5 minutes and maintained at 985℃ for 15 minutes. When the temperature of the right temperature zone reaches 900℃, the selenium powder is slowly fed into the right side of the right temperature zone by the feeding device to make it reach the initial melting state. When the temperature reaches 985℃, 0.1g of selenium powder on the feeding device is slowly pushed into the right temperature zone within 0-3 minutes to form a block MoO on the contact surface between the gold particles and the silicon wafer. 3-x , the feeding device is quickly moved within 3-15min to push all the remaining selenium powder into the right temperature zone; under the catalysis of gold particles, selenium powder and bulk MoO 3-x Rapid reaction, epitaxy of MoSe nanoribbons; S6: When the insulation time of the left temperature zone is over, stop insulation and let the temperature drop naturally to 25°C. When the insulation time of the right temperature zone is over, stop insulation and let the temperature drop naturally to 25°C. Take out the sample table to obtain the finished product.

[0018] The finished products were taken out, and the SEM and TEM test results showed that the grown nanobelts had uniform width and controllable number of layers, meeting the requirements of high-quality and large-scale growth.

Claims

1. A method for preparing multiple transition metal chalcogenide nanobelts assisted by gold catalyst particles, characterized in that: The steps include: S1: Using high-purity gold as the sputtering target and silicon wafer as the sputtering substrate, sputtering for 35 seconds at 100°C and 50W DC power to obtain a gold film with a uniform thickness of 10nm; S2: The gold film obtained by magnetron sputtering is placed in a high-temperature tube furnace for annealing. The temperature is raised from 25°C to 750°C in 40 minutes during the heating stage, maintained at 750°C for 10 minutes during the constant temperature stage, and cooled to 25°C in 10 minutes during the cooling stage, thereby obtaining a gold nanoparticle catalyst with high catalytic activity and uniform particle diameter; the prepared silicon wafer with gold nanoparticles is placed on a rectangular sample table; S3: Weigh the transition metal oxide and chalcogenide powder respectively with a quartz boat, spread the transition metal oxide evenly on the quartz boat, and place the chalcogenide powder on the feeding device; a small amount of chalcogenide powder is placed on one side of the feeding device, and the remaining sulfur powder is placed on the other side of the feeding device, with a certain distance between the two; S4: placing the sample stage, the quartz boat and the feeding device into specific areas of the high-temperature tube furnace, respectively, and setting specific heating intervals and heating temperatures; S5: When the temperature reaches a certain temperature, a certain amount of hydrogen and argon mixed gas is introduced, and then the feeding device is controlled to move; S6: When the heat preservation time is over, stop heat preservation, cool naturally to 25°C, take out the sample table, and obtain the finished product.

2. The method according to claim 1, characterized in that The feeding device includes a magnetic base and a magnet. Chalcogenide powder is placed on the magnetic base. The magnet is located outside the high-temperature tube furnace. By moving the magnet, the magnetic base in the high-temperature tube furnace is driven to move.

3. The method according to claim 1, characterized in that The metal oxide is MoO3, and the chalcogen element powder is one of S and Se.

Images