阅读说明：本技术 一种螺旋线形貌硫化钯颗粒的自组装方法 (Self-assembly method of spiral line morphology palladium sulfide particles ) 是由 董孟孟 吕燕飞 赵士超 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种螺旋线形貌硫化钯颗粒的自组装方法,本发明先将硫固体粉末放在石英舟中,再将石英舟放入石英管,将氯化钯盐酸溶液放在基底上,基底放置在石英管中,位置在载气流向下游方向,石英管中输入载气氩氢混合气并加热保温,待冷却到200-250℃后取出并在室温下冷却至室温,获得硫化钯球形颗粒自组装图案；本发明将金属钯盐和硫高温下发生化学反应,该自组装图案是通过化学反应-扩散机制形成。(The invention discloses a self-assembly method of palladium sulfide particles with spiral line morphology, which comprises the steps of firstly placing sulfur solid powder in a quartz boat, then placing the quartz boat in a quartz tube, placing palladium chloride hydrochloric acid solution on a substrate, placing the substrate in the quartz tube, leading the position of the substrate to be in the downstream direction of carrier gas flow, inputting carrier gas argon-hydrogen mixed gas into the quartz tube, heating and preserving heat, taking out the substrate after cooling to 250 ℃ of 200-; the metal palladium salt and the sulfur are subjected to chemical reaction at high temperature, and the self-assembled pattern is formed through a chemical reaction-diffusion mechanism.)

1. A self-assembly method of palladium sulfide particles with spiral line morphology is characterized by comprising the following steps:

taking 1-5 g of sulfur solid powder, putting the sulfur solid powder into a quartz boat, and then putting the quartz boat filled with the sulfur solid powder into a quartz tube in a tubular electric furnace; the quartz boat is placed in the middle of the quartz tube;

step (2) is toCleaning the substrate with deionized water, and drying the substrate with nitrogen for later use; 0.05 to 0.2mol/l of palladium chloride PdCl₂A hydrochloric acid solution is dripped to the surface of the substrate by a pipette; then, placing the substrate in a quartz tube, wherein the position is 20-25 cm away from the quartz boat in the downstream direction of the carrier gas flow;

starting a mechanical pump for vacuumizing, and simultaneously inputting a carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of hydrogen is 5%, and the carrier gas flow is 30-40 sccm; the temperature in the tube is 20-30 ℃ at room temperature, and the vacuum degree in the tube is 300-500 Pa; ventilating for 5-10 min;

step (4), heating the tube furnace to 900-1000 ℃, wherein the heating rate is 20-30 ℃/min; after the temperature is increased to 900-1000 ℃, the temperature is preserved for 60-100 min;

step (5), stopping heating the quartz tube, cooling the tube furnace to 250 ℃ at room temperature, then opening the tube furnace, cooling the quartz tube to room temperature at room temperature, then taking out the substrate, and obtaining a palladium sulfide spherical particle self-assembly pattern on the substrate, wherein the pattern is an Archimedes spiral; the particle size is 50-500 nm.

2. The method for self-assembling spiral-shaped palladium sulfide particles as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the quartz tube is a quartz tube or a corundum tube, and the quartz boat is a quartz boat or a corundum boat.

3. The method for self-assembling spiral-shaped palladium sulfide particles as claimed in claim 1, wherein the method comprises the following steps: the inner diameter of the quartz tube in the step (1) is 1 inch.

4. The method for self-assembling spiral-shaped palladium sulfide particles as claimed in claim 1, wherein the method comprises the following steps: and (2) replacing sulfur solid powder in the step (1) with a sulfur-containing salt capable of evaporating sulfur.

5. The method for self-assembling spiral-shaped palladium sulfide particles as claimed in claim 1, wherein the method comprises the following steps: and (3) the substrate in the step (2) is a silicon wafer with an oxide layer growing on the surface.

6. The method for self-assembling spiral-shaped palladium sulfide particles as claimed in claim 1, wherein the method comprises the following steps: the size of the substrate in the step (2) is 2.5-3.5 cm multiplied by 1.5-2.0 cm.

7. The method for self-assembling spiral-shaped palladium sulfide particles as claimed in claim 4, wherein the method comprises the following steps: the sulfur-containing salt capable of evaporating sulfur is molybdenum sulfide or tungsten sulfide.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a preparation method for self-assembly of palladium sulfide round particles.

Background

The preparation of the nano material is divided into two directions, one is a top-down method (large-size material is used as a starting point and processed into small-size material) represented by photoetching, and the other is a bottom-up method, namely small-size unit substances such as molecules, atoms and the like are aggregated into a large-size nano structure. Self-assembly is particularly interesting in the bottom-up approach. Self-assembly refers to a process of self-assembling basic units such as atoms, molecules, aggregates, etc. to form a specific pattern or structure spontaneously by a certain driving force, and the characteristics of the process make the fabrication of nano materials or devices more material-saving and energy-saving, and may also obtain properties that cannot be obtained by conventional methods, so that the self-assembly technology becomes one of the research hotspots. Self-assembly is generally carried out in a low-temperature, liquid-phase medium, and relatively little is studied for self-assembly in a high-temperature, gas-phase medium, by the interaction of van der waals' force, hydrogen bond, etc. between self-assembled basic units. The method prepares the palladium sulfide self-assembly pattern in a high-temperature and gas-phase environment, and the palladium salt solution is dried in vacuum in a reducing atmosphere, palladium salt crystal particles with coffee ring patterns are left on the surface of a substrate after liquid drops are dried, and then the palladium sulfide crystal particles react with sulfur vapor at high temperature to generate palladium sulfide, and the product palladium sulfide forms the self-assembly pattern through a reaction-diffusion process.

Disclosure of Invention

The invention provides a self-assembly method of palladium sulfide particles with spiral line morphology, aiming at the defects of the prior art.

The invention provides a self-assembly method of spiral line-shaped palladium sulfide particles. The method comprises the following specific steps:

taking 1-5 g of sulfur solid powder, putting the sulfur solid powder into a quartz boat, and then putting the quartz boat filled with the sulfur solid powder into a quartz tube in a tubular electric furnace; the quartz boat is placed in the middle of the quartz tube.

Cleaning the substrate with deionized water, and then blowing nitrogen for later use; 0.05 to 0.2mol/l of palladium chloride PdCl₂Hydrochloric acid solution, and the solution is dripped to the surface of the substrate by a pipette. Then, placing the substrate in a quartz tube, wherein the position is 20-25 cm away from the quartz boat in the downstream direction of the carrier gas flow;

and (3) starting a mechanical pump to pump vacuum, and simultaneously inputting a carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of hydrogen is 5%, and the carrier gas flow is 30-40 sccm. The temperature in the tube is 20-30 ℃ at room temperature, and the vacuum degree in the tube is 300-500 Pa. Ventilating for 5-10 min.

And (4) heating the tube furnace to 900-1000 ℃ at a heating rate of 20-30 ℃/min. And (3) keeping the temperature after the temperature is increased to 900-1000 ℃, wherein the heat preservation time is 60-100 min.

Step (5), stopping heating the quartz tube, cooling the tube furnace to 250 ℃ at room temperature, then opening the tube furnace, cooling the quartz tube to room temperature at room temperature, then taking out the substrate, and obtaining a palladium sulfide spherical particle self-assembly pattern on the substrate, wherein the pattern is an Archimedes spiral; the particle size is 50-500 nm.

In the step (1), the quartz tube is a quartz tube or a corundum tube, and the quartz boat is a quartz boat or a corundum boat.

The inner diameter of the quartz tube in the step (1) is 1 inch.

The sulfur solid powder in step (1) may also be a sulfur-containing salt capable of evaporating sulfur, such as molybdenum sulfide, tungsten sulfide, etc.

And (3) the substrate in the step (2) is a silicon wafer with an oxide layer growing on the surface.

The size of the substrate in the step (2) is 2.5-3.5 cm multiplied by 1.5-2.0 cm.

And (3) ventilating at room temperature, wherein the gas is argon-hydrogen mixed gas to ensure that the liquid drops are dried in a reducing protective atmosphere, and the dried liquid forms a coffee ring pattern on the surface of the substrate.

Has the advantages that: the metal palladium salt and the sulfur are subjected to chemical reaction at high temperature, and the self-assembled pattern is formed through a chemical reaction-diffusion mechanism. The formation of the Archimedes spiral pattern is related to the drying process of palladium chloride solution under reducing protective atmosphere, the formation and diffusion of high-temperature palladium sulfide.

Drawings

FIG. 1 is a scanning electron micrograph of an Archimedes spiral of palladium sulfide.

Detailed Description

Example 1:

a self-assembly method of palladium sulfide particles with spiral line morphology. The method comprises the following specific steps:

step (1), taking 1g of molybdenum sulfide powder, putting the molybdenum sulfide powder into a quartz boat, and then putting the quartz boat filled with sulfur solid powder into a quartz tube in a tubular electric furnace; the quartz boat is placed in the middle of the quartz tube; the inner diameter of the quartz tube is 1 inch;

cleaning the substrate with deionized water, and then blowing nitrogen for later use; 0.2mol/l of palladium chloride PdCl₂Hydrochloric acid solution, and the solution is dripped to the surface of the substrate by a pipette. Then, the substrate is placed in a quartz tube, and the position is 20cm away from the quartz boat in the downstream direction of the carrier gas flow; the substrate is a silicon wafer with an oxide layer growing on the surface; the size of the substrate is 2.5cm multiplied by 1.5 cm;

and (3) starting a mechanical pump to pump vacuum, and simultaneously inputting a carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of the hydrogen is 5%, and the carrier gas flow is 30 sccm. The temperature in the tube was 25 ℃ and the vacuum in the tube was 300 Pa. Aeration was carried out for 6 minutes.

And (4) heating the tubular furnace to 900 ℃, wherein the heating rate is 20 ℃/min. And (4) keeping the temperature after the temperature is increased to 900 ℃, wherein the heat preservation time is 80 min.

Step (5), stopping heating the quartz tube, cooling the tube furnace to 200 ℃ in a room temperature environment, then opening the tube furnace, cooling the quartz tube to room temperature at room temperature, then taking out the substrate, and obtaining a palladium sulfide spherical particle self-assembly pattern on the substrate, wherein the pattern is an Archimedes spiral; the particle size was 120 nm.

As shown in fig. 1, white in the figure is an archimedean spiral formed by self-assembly of palladium sulfide particles.

Example 2:

a self-assembly method of palladium sulfide particles with spiral line morphology. The method comprises the following specific steps:

taking 3g of tungsten sulfide powder, putting the tungsten sulfide powder into a corundum boat, and then putting the corundum boat filled with sulfur solid powder into a corundum tube in a tubular electric furnace; the corundum boat is placed in the middle of the corundum tube; the inner diameter of the corundum tube is 1 inch;

cleaning the substrate with deionized water, and then blowing nitrogen for later use; 0.1mol/l of palladium chloride PdCl₂Hydrochloric acid solution, and the solution is dripped to the surface of the substrate by a pipette. Then, the substrate is placed in a corundum tube and is positioned at a position which is 25cm away from the corundum boat in the downstream direction of the carrier gas flow; the substrate is a silicon wafer with an oxide layer growing on the surface; the size of the substrate is 3.5cm multiplied by 1.5 cm;

and (3) starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas into the corundum tube, wherein the volume content of hydrogen is 5%, and the carrier gas flow is 35 sccm. The temperature in the tube was 20 ℃ and the vacuum in the tube was 400 Pa. Aeration was carried out for 10 minutes.

And (4) heating the tubular furnace to 950 ℃ at a heating rate of 25 ℃/min. And keeping the temperature after the temperature is raised to 950 ℃, wherein the heat preservation time is 95 min.

Step (5), stopping heating the corundum tube, cooling the tubular furnace to 220 ℃ in a room temperature environment, then starting the tubular furnace, cooling the corundum tube to room temperature at room temperature, then taking out the substrate, and obtaining a palladium sulfide spherical particle self-assembly pattern on the substrate, wherein the pattern is an Archimedes spiral; the particle size was 60 nm.

Example 3:

a self-assembly method of palladium sulfide particles with spiral line morphology. The method comprises the following specific steps:

step (1), taking 5g of molybdenum sulfide powder, putting the molybdenum sulfide powder into a quartz boat, and then putting the quartz boat filled with sulfur solid powder into a quartz tube in a tube electric furnace; the quartz boat is placed in the middle of the quartz tube; the inner diameter of the quartz tube is 1 inch;

cleaning the substrate with deionized water, and then blowing nitrogen for later use; 0.05mol/l of palladium chloride PdCl₂Hydrochloric acid solution, and the solution is dripped to the surface of the substrate by a pipette. Then the substrate is placed in a quartz tube, and the position is 22cm away from the quartz boat in the downstream direction of the carrier gas flow; the substrate is a silicon wafer with an oxide layer growing on the surface; the size of the substrate is 2.5cm multiplied by 2 cm;

and (3) starting a mechanical pump to pump vacuum, and simultaneously inputting a carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of the hydrogen is 5%, and the carrier gas flow is 40 sccm. The temperature in the tube was 30 ℃ and the vacuum degree in the tube was 500 Pa. Aeration was carried out for 5 minutes.

And (4) heating the tubular furnace to 1000 ℃ at the heating rate of 30 ℃/min. And (3) keeping the temperature after the temperature is raised to 1000 ℃, wherein the heat preservation time is 60 min.

Step (5), stopping heating the quartz tube, cooling the tube furnace to 250 ℃ in a room temperature environment, then opening the tube furnace, cooling the quartz tube to the room temperature at the room temperature, then taking out the substrate, and obtaining a palladium sulfide spherical particle self-assembly pattern on the substrate, wherein the pattern is an Archimedes spiral; the particle size was 400 nm.

Example 4:

a self-assembly method of palladium sulfide particles with spiral line morphology. The method comprises the following specific steps:

step (1), taking 4g of tungsten sulfide powder, putting the tungsten sulfide powder into a quartz boat, and then putting the quartz boat filled with sulfur solid powder into a quartz tube in a tubular electric furnace; the quartz boat is placed in the middle of the quartz tube; the inner diameter of the quartz tube is 1 inch;

cleaning the substrate with deionized water, and then blowing nitrogen for later use; 0.15mol/l of palladium chloride PdCl₂Hydrochloric acid solution, and the solution is dripped to the surface of the substrate by a pipette. Then, the substrate is placed in a quartz tube, and the position is 20cm away from the quartz boat in the downstream direction of the carrier gas flow; the substrate is a silicon wafer with an oxide layer growing on the surface; the size of the substrate is 3cm multiplied by 1.5 cm;

and (3) starting a mechanical pump to pump vacuum, and simultaneously inputting a carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of the hydrogen is 5%, and the carrier gas flow is 40 sccm. The temperature in the tube was 25 ℃ and the vacuum in the tube was 300 Pa. Aeration was carried out for 8 minutes.

And (4) heating the tubular furnace to 900 ℃, wherein the heating rate is 20 ℃/min. And (4) keeping the temperature after the temperature is increased to 900 ℃, wherein the heat preservation time is 80 min.

Step (5), stopping heating the quartz tube, cooling the tube furnace to 200 ℃ in a room temperature environment, then opening the tube furnace, cooling the quartz tube to room temperature at room temperature, then taking out the substrate, and obtaining a palladium sulfide spherical particle self-assembly pattern on the substrate, wherein the pattern is an Archimedes spiral; the particle size was 300 nm.