Method for gold catalyst particle assisted preparation of various transition metal chalcogenide nanoribbons

Abstract

The application provides a gold catalyst particle assisted chemical vapor deposition method for realizing controllable growth of transition metal chalcogenide nanobelt, gold nanometer particle modified silicon wafers with adjustable and uniform distribution of diameters can be obtained through magnetron sputtering of gold nanometer film and high temperature annealing treatment, and the silicon wafers are used as growth substrates. In the high temperature reaction process of the chemical vapor deposition, the ratio and evaporation rate of transition metal oxide powder, sulfur powder and selenium powder and the flow rate and ratio of hydrogen and argon are further fine controlled through a single / two-temperature zone high temperature furnace, and finally controllable growth of high crystal quality transition metal chalcogenide nanobelt can be realized. By controlling the temperature of the growth substrate, the type of the evaporation precursor and the evaporation rate, the growth process of the transition metal chalcogenide nanobelt can be significantly affected, transition metal chalcogenide nanobelts with different structures such as composition and chirality are obtained, and controllable growth and directional regulation of the physical properties of the transition metal chalcogenide nanobelt are realized.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for preparing transition metal chalcogenide nanoribbons. The controllable growth of transition metal chalcogenide nanoribbons is achieved by chemical vapor deposition catalyzed by gold nanoparticles. BACKGROUND

[0002] With the continuous development of preparation and structure regulation of two-dimensional transition metal chalcogenide (TMD) materials, the types of transition metal chalcogenides are increasingly rich, which further stimulates the in-depth exploration of their novel properties and device applications. Under this background, breaking through the traditional structure construction method and regulation strategy of transition metal chalcogenides, and seeking new research ideas, have become the key to expanding their research and application.

[0003] The structure of transition metal chalcogenide nanoribbons can be regarded as a one-dimensional ribbon structure formed in a specific direction by two-dimensional transition metal chalcogenides. Compared with its two-dimensional and three-dimensional structures, nanoribbons exhibit unique properties, such as enhanced photoelectric effect, excellent electrical conductivity and catalytic performance, becoming a new field of research and application.

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

[0005] In recent years, researchers have tried to solve these challenges through improved chemical vapor deposition techniques and solution methods, exploring different precursors and reaction conditions in order to achieve efficient growth and chirality regulation of transition metal chalcogenide nanoribbons. However, these methods still face many challenges in adaptability and repeatability, limiting the wide application of nanoribbons.

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

[0007] The technical problem solved by the present application is to provide a gold catalyst particle assisted preparation method of various transition metal chalcogenide nanobelts, and to realize high-yield preparation of transition metal chalcogenide nanobelts.

[0008] To solve the above technical problems, the technical solution adopted by the present application is:

[0009] The present application 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 gold nanoparticle catalysts with different diameters and high catalytic activity can be formed after annealing by controlling the magnetron sputtering film thickness and the annealing temperature and time.

[0010] S1: using high-purity gold as a sputtering target and a silicon wafer as a sputtering substrate, sputtering 35S under the sputtering conditions of 100℃ and a direct current power of 50W to obtain a 10nm-thick gold film;

[0011] S2: placing the gold film obtained by magnetron sputtering into a high-temperature tube furnace for annealing, raising the temperature from 25℃ to 750℃ in 40 minutes, keeping the temperature at 750℃ for 10 minutes, and then lowering the temperature to 25℃ in 10 minutes to obtain a gold nanoparticle catalyst with high catalytic activity and uniform particle diameter; and placing the prepared silicon wafer with gold nanoparticles on a cuboid sample stage;

[0012] S3: weighing transition metal oxides and chalcogen element powders in a quartz boat respectively, uniformly spreading the transition metal oxides on the quartz boat, and placing the chalcogen element powders on a feeding device; wherein a small amount of chalcogen element powders is placed on one side of the feeding device, and the remaining chalcogen powders are placed on the other side of the feeding device, and the two are separated by a certain distance;

[0013] S4: placing the sample stage, the quartz boat and the feeding device into specific areas of a high-temperature tube furnace respectively, and setting specific heating intervals and heating temperatures;

[0014] S5: when the temperature reaches a certain specific temperature, start to pass a certain amount of hydrogen and argon mixed gas, and then control the feeding device to move;

[0015] S6: when the holding time is over, stop holding and naturally cool down to 25℃, take out the sample stage, and obtain the finished product.

[0016] Further, the feeding device comprises a magnetic base and a magnet, the chalcogen element powder is placed on the magnetic base, and the magnet is located outside the high-temperature tube furnace, and the magnetic base in the high-temperature tube furnace is moved by moving the magnet.

[0017] Further, the metal oxide is MoO3, and the chalcogen element powder is one of S and Se.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] The gold catalyst particle assisted preparation method for controllable growth of transition metal chalcogenide nanobelt has high activity gold nanoparticle catalyst prepared through magnetron sputtering and annealing process, and has excellent high-temperature stability. The preparation method is simple in preparation, realizes controllable growth of the transition metal chalcogenide nanobelt, obtains relatively uniform transition metal chalcogenide nanobelt, and can control the temperature of the growth substrate to realize controllable adjustment of the width and the number of layers of the transition metal chalcogenide nanobelt. The new transition metal chalcogenide nanobelt has great scientific research and application potential in electronic devices and optoelectronic devices. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The SEM image of the gold nanoparticles formed on the silicon wafer provided by the application is shown in the figure;

[0021] Figure 2 The SEM image of the transition metal chalcogenide nanobelt provided by the application is shown in the figure;

[0022] Figure 3 The schematic diagram of the tungsten sulfide nanobelt growth device is shown in the figure;

[0023] Figure 4 The schematic diagram of the molybdenum selenide nanobelt growth device is shown in the figure. DETAILED DESCRIPTION

[0024] The application will be further described in detail below by combining with the examples. However, the specific implementation range is not limited to the examples. Example 1

[0025] A preparation method of tungsten sulfide nanobelt is provided, which consists of preparation of gold nanoparticle catalyst and chemical vapor deposition growth, and the preparation steps are as follows:

[0026] S1: under the sputtering conditions of 100 DEG C and direct current power 50 W, 35S is sputtered by taking high-purity gold as a sputtering target and a silicon wafer as a sputtering substrate, and a gold film with a uniform thickness of 10 nm is obtained;

[0027] S2: Put the gold film obtained by magnetron sputtering into a high-temperature tube furnace for annealing, first raise the temperature from 25℃ to 750℃ in 40 minutes, then keep the temperature at 750℃ for 10 minutes, and finally reduce the temperature to 25℃ in 10 minutes, to obtain a gold nanoparticle catalyst with high catalytic activity and uniform particle diameter on the silicon wafer; as shown in Figure 1 The prepared silicon wafer with gold nanoparticles is placed on the cuboid sample table;

[0028] S3: Use a quartz boat (15*100) to weigh Nanopower <200nm, 99.9% metal base) 0.45g and sublimed sulfur (>99.5%) 0.55g respectively, evenly spread the tungsten trioxide 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 more sulfur powder is placed on the other side of the feeding device, with a certain distance between the two;

[0029] In this embodiment, the mass of the small amount of sulfur powder is 0.05g, and the mass of the remaining more sulfur powder is 0.5g.

[0030] S4: Place the quartz boat containing 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;

[0031] S5: Heat the high-temperature tube furnace, raise the temperature from 25℃ to 900℃ in 40 minutes, when the temperature rises to 900℃, introduce 10sccm of hydrogen and 150sccm of argon from the left side of the high-temperature tube furnace, adjust the pressure of the high-temperature tube furnace to maintain a constant low pressure; then continue to raise the temperature, raise the temperature to 985℃ in 4 minutes, and keep the temperature at 985℃ for 15 minutes, when the temperature reaches 900℃, slowly push the sulfur powder into the heating area on the left side using the sulfur powder feeding device, so that it reaches the initial melting state, when the temperature reaches 985℃, start, push the 0.05g sulfur powder on the feeding device into the heating area slowly within 0-3 minutes, so that the gold particles and the silicon wafer contact surface form a block-shaped WO 3-x , within 3-15 minutes, move the feeding device quickly, push all the remaining sulfur powder into the heating area, under the catalysis of gold particles, the sulfur powder and the block-shaped WO 3-x react quickly, and epitaxially grow tungsten sulfide nanobands;

[0032] S6: When the holding time is over, stop holding, naturally cool to 25℃, take out the sample table, and obtain the finished product. Example 2

[0033] A preparation method of molybdenum selenide nanobands is provided, which consists of the preparation of a gold nanoparticle catalyst and chemical vapor deposition growth, and the preparation steps are as follows:

[0034] S1: Using high-purity gold as the sputtering target and silicon wafer as the sputtering substrate, sputtering was performed for 35 seconds at 100°C and DC power of 50W to obtain a gold film with a uniform thickness of 10nm.

[0035] S2: The gold film obtained by magnetron sputtering is annealed in a high-temperature tube furnace. The temperature is first increased from 25°C to 750°C over 40 minutes, then held at 750°C for 10 minutes, and finally reduced to 25°C over 10 minutes. This yields gold nanoparticle catalysts with high catalytic activity and uniform particle diameter on a silicon wafer. Figure 1 As shown, the prepared silicon wafer with gold nanoparticles is placed on a cuboid sample stage.

[0036] S3: Weigh 0.5g of nano molybdenum trioxide (Nanopower<200nm, 99.9% metal-based) and 0.82g of selenium powder (>99.5%) using a quartz boat (15*100). 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 larger amount of selenium powder is placed on the other side of the feeding device, with a certain distance between them.

[0037] In this embodiment, the mass of a small amount of selenium powder is 0.1g, and the mass of the remaining larger amount of selenium powder is 0.72g.

[0038] S4: Place the quartz boat containing molybdenum trioxide in the center of the left temperature zone of the high-temperature tube furnace, place the sample stage 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.

[0039] S5: First, heat the right temperature zone of the high-temperature tubular furnace from 25°C to 900°C within 40 minutes. After 20 minutes of heating in the right zone, start heating the left temperature zone, raising the center temperature of the left zone from 25°C to 510°C within 20 minutes. When the left zone reaches 510°C and the right zone reaches 900°C, introduce 13 sccm of hydrogen and 150 sccm of argon gas from the left side of the furnace, adjusting the furnace pressure to maintain a constant low pressure. Then continue heating the left and right zones. In the right temperature zone, the temperature of the left temperature zone is raised to 580℃ within 4 minutes and maintained at 580℃ for 15 minutes. Simultaneously, the right temperature zone is raised to 985℃ within 5 minutes and maintained at 985℃ for 15 minutes. When the right temperature zone reaches 900℃, selenium powder is slowly fed into the right side of the right temperature zone using a feeding device to achieve initial melting. Starting at 985℃, 0.1g of selenium powder is slowly pushed into the right temperature zone within 0-3 minutes using the feeding device, causing the gold particles to form blocky MoO at the contact surface with the silicon wafer. 3-xIn 3-15 min, the feeding device is moved quickly to push the remaining selenium powder into the right temperature zone; under the catalysis of gold particles, the selenium powder and the block MoO 3-x Fast reaction, epitaxial growth of molybdenum selenide nanobelt;

[0040] S6: When the left temperature zone reaches the end of the holding time, stop holding and naturally cool to 25°C. When the right temperature zone reaches the end of the holding time, stop holding and naturally cool to 25°C. Take out the sample platform to obtain the finished product.

[0041] The finished product is taken out. The SEM and TEM test results show that the grown nanobelt is uniform in width and controllable in layer number, meeting the requirements of high quality and large batch growth.

Claims

1. A method for preparing tungsten sulfide nanoribbons, comprising two parts: preparation of a gold nanoparticle catalyst and chemical vapor deposition growth, characterized in that... The preparation steps are as follows: S1: Using high-purity gold as the sputtering target and silicon wafer as the sputtering substrate, sputtering was performed for 35 seconds at 100°C and DC power of 50W 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 over 40 minutes, then held at 750°C for 10 minutes, and finally lowered to 25°C over 10 minutes to obtain gold nanoparticle catalysts with high catalytic activity and uniform particle diameter on the silicon wafer. The silicon wafer with gold nanoparticles is then placed on a cuboid sample stage. S3: Weigh 0.45g of nano tungsten trioxide and 0.55g of sublimed sulfur separately using a quartz boat. 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 larger amount of sulfur powder is placed on the other side of the feeding device, with a certain distance between them. The mass of the small amount of sulfur powder is 0.05g, and the mass of the remaining larger amount of sulfur powder is 0.5g. S4: Place the quartz boat containing tungsten trioxide in the center of the single-temperature zone high-temperature tube furnace, place the sample stage 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 tubular furnace, increasing the temperature from 25℃ to 900℃ within 40 minutes. When the temperature reaches 900℃, introduce 10 sccm of hydrogen and 150 sccm of argon gas from the left side of the furnace, adjusting the furnace pressure to maintain a constant low pressure. Continue heating, increasing the temperature to 985℃ within 4 minutes and maintaining this temperature for 15 minutes. When the temperature reaches 900℃, slowly feed sulfur powder into the left side of the heating zone using a sulfur powder feeding device to achieve initial melting. Starting at 985℃, slowly push 0.05g of sulfur powder from the feeding device into the heating zone within 0-3 minutes, causing the gold particles to form a blocky WO3 at the silicon wafer contact surface. 3-x Within 3-15 minutes, a rapid moving feeding device pushes all the remaining sulfur powder into the heating zone. Under the catalysis of gold particles, the sulfur powder and lumpy WO3... 3-x Rapid reaction, epitaxial growth of tungsten sulfide nanoribbons; S6: After the heat preservation time is over, stop the heat preservation and allow it to cool naturally to 25°C. Remove the sample stage to obtain the finished product.

2. A method for preparing molybdenum selenide nanoribbons, comprising two parts: preparation of gold nanoparticle catalyst and chemical vapor deposition growth, characterized in that... The preparation steps are as follows: S1: Using high-purity gold as the sputtering target and silicon wafer as the sputtering substrate, sputtering was performed for 35 seconds at 100°C and DC power of 50W 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 over 40 minutes, then held at 750°C for 10 minutes, and finally lowered to 25°C over 10 minutes to obtain gold nanoparticle catalysts with high catalytic activity and uniform particle diameter on the silicon wafer. The silicon wafer with gold nanoparticles is then placed on a cuboid sample stage. S3: Weigh 0.5g of nano molybdenum trioxide and 0.82g of selenium powder separately using a quartz boat. 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 larger amount of selenium powder is placed on the other side of the feeding device, with a certain distance between them. The mass of the small amount of selenium powder is 0.1g, and the mass of the remaining larger amount of selenium powder is 0.72g. S4: Place the quartz boat containing molybdenum trioxide in the center of the left temperature zone of the high-temperature tube furnace, place the sample stage 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 tubular furnace from 25°C to 900°C within 40 minutes. After 20 minutes of heating in the right zone, start heating the left temperature zone, raising the center temperature of the left zone from 25°C to 510°C within 20 minutes. When the left zone reaches 510°C and the right zone reaches 900°C, introduce 13 sccm of hydrogen and 150 sccm of argon gas from the left side of the furnace, adjusting the furnace pressure to maintain a constant low pressure. Then continue heating the left and right zones. In the right temperature zone, the temperature of the left temperature zone is raised to 580℃ within 4 minutes and maintained at 580℃ for 15 minutes. Simultaneously, the right temperature zone is raised to 985℃ within 5 minutes and maintained at 985℃ for 15 minutes. When the right temperature zone reaches 900℃, selenium powder is slowly fed into the right side of the right temperature zone using a feeding device to achieve initial melting. Starting at 985℃, 0.1g of selenium powder is slowly pushed into the right temperature zone within 0-3 minutes using the feeding device, causing the gold particles to form blocky MoO at the contact surface with the silicon wafer. 3-x Within 3-15 minutes, the rapid moving feeding device pushes all the remaining selenium powder into the right-side heating zone; under the catalysis of gold particles, the selenium powder and lumpy MoO... 3-x Rapid reaction, epitaxially producing molybdenum selenide nanoribbons; S6: After the left temperature zone's heat preservation time ends, stop the heat preservation and allow it to cool naturally to 25℃. After the right temperature zone's heat preservation time ends, stop the heat preservation and allow it to cool naturally to 25℃. Remove the sample stage to obtain the finished product.

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