Method for inducing ordered arrangement of ZnS nanospheres and application thereof

Abstract

A method for inducing the ordered arrangement of ZnS nanospheres includes the following steps: S1, Preparation of ZnS nanospheres: ZnS nanospheres of 60-120 nm are prepared using a hydrothermal method. After multiple washings and centrifugation, pure ZnS nanospheres are obtained. S2, Preparation of a ZnS mixed solution: The ZnS nanospheres prepared in step S1 are dispersed in a mixed solution of water, ethanol, and a surfactant, and the solution is ultrasonically vibrated to obtain a ZnS mixed solution. S3, Dropping the film: The heating platform is heated to 30-60°C and maintained at a constant temperature. A pipette is used to draw 50-200 μL of the ZnS mixed solution from step S2 and drop it onto a clean silicon wafer. After the solvent evaporates, the sample is removed to obtain an ordered pattern. This invention provides a simple and widely applicable method for inducing the ordered arrangement of nanospheres.

Description

Technical Field

[0001] This invention relates to a method for inducing the ordered arrangement of ZnS nanospheres through the evaporation of a mixed solution and its application, belonging to the field of nanomaterials technology. Background Technology

[0002] Nanomaterials have been widely used due to their unique structure and excellent properties. Researchers not only want to control the morphology of nanomaterials, but also their ordered arrangement. Nanospheres, as a typical structure of nanomaterials, have wide applications in optics and other fields due to their ordered structure. There are many methods to achieve ordered arrangement of nanospheres, currently mainly using self-assembly, gas-liquid interface assembly, and template methods. For example, Jiang Chunxiao et al. used styrene / acrylate nanospheres prepared by soap-free emulsion polymerization as an example, and used the self-assembly method to obtain single-layer or multi-layer ordered nanosphere structures (Self-assembly method for obtaining ordered structures of St / AA nanospheres, Jiang Chunxiao et al., Chemical World, 2012, Vol. 53, pp. 44-45). However, these methods still have their own drawbacks. For example, the self-assembly method relies on electrostatic interactions and hydrogen bonding, resulting in slightly lower stability and a longer processing time. The template method requires template removal, which is a cumbersome process. Therefore, researchers in this field are still trying new methods to order nanospheres. Summary of the Invention

[0003] To overcome the shortcomings of existing technologies, this invention provides a method for inducing the ordered arrangement of ZnS nanospheres and its application. The method induces the ordered arrangement of ZnS nanospheres by evaporating a mixed solution, using a mixture of water, ethanol, and surfactant as a dispersant. The ordered pattern of ZnS is induced by solvent evaporation. This method is simple to operate, widely applicable, and time-saving.

[0004] The technical solution adopted by this invention to solve its technical problem is:

[0005] A method for inducing the ordered arrangement of ZnS nanospheres, the method being a mixed solution evaporation-induced method, comprising the following steps:

[0006] Preparation of S1 and ZnS nanospheres: ZnS nanospheres with a particle size of 60~120 nm were prepared by hydrothermal method. After washing 2-3 times, pure ZnS nanospheres were obtained by centrifugation.

[0007] S2. Preparation of ZnS mixed solution: The ZnS nanospheres prepared in step S1 are dispersed in a mixed solution of water, ethanol and surfactant, and then ultrasonically vibrated to obtain the ZnS mixed solution.

[0008] S3, Film Dropping: Heat the heating platform to 30~60℃ and maintain a constant temperature. Use a pipette to draw up the ZnS mixed solution from step S2, and then drop 50~200μL of the mixed solution onto the cleaned silicon wafer. After the solvent evaporates, remove the sample to obtain an ordered pattern.

[0009] The method for inducing the ordered arrangement of ZnS nanospheres described above, wherein the preparation method of ZnS nanospheres in step S1 includes the following steps:

[0010] a. Weigh out zinc acetate dihydrate (Zn(AC)2·2H2O) and thiourea, dissolve them in 10~25mL of deionized water solution, stir in a water bath at 30~80℃ for 20min, and record it as solution A;

[0011] b. Weigh a certain amount of polyvinylpyrrolidone K30 (PVP) and add it to solution A. Stir in a water bath at 30~80℃ for 20 minutes. This solution is called solution B.

[0012] c. Place solution B into a reaction vessel and heat in an oven at 100-200℃ for 5-15 hours. After the reaction is complete, centrifuge and wash to obtain pure ZnS nanospheres of 60-120 nm.

[0013] In the above method for inducing the ordered arrangement of ZnS nanospheres, in step a, the mass ratio of zinc acetate dihydrate (Zn(AC)2·2H2O) to thiourea is 1:8~16.

[0014] In the above method for inducing the ordered arrangement of ZnS nanospheres, the mass concentration of polyvinylpyrrolidone K30 (PVP) in step b is 0.1~5wt%.

[0015] In the above method for inducing the ordered arrangement of ZnS nanospheres, in step S2, the volume ratio of water to ethanol in the mixed solution of water, ethanol and surfactant is 1:0.5~3, and the mass concentration of surfactant is 0.1~5wt%.

[0016] In the above method for inducing the ordered arrangement of ZnS nanospheres, the surfactant is at least one of polyvinylpyrrolidone, polyethylene glycol 400 (PEG-400) or sodium hexadecylbenzenesulfonate, preferably polyvinylpyrrolidone.

[0017] In the above method for inducing the ordered arrangement of ZnS nanospheres, in step S2, the mass concentration of ZnS in the ZnS mixed solution is 0.5~3wt%, preferably 0.8~2wt%.

[0018] In the above method for inducing the ordered arrangement of ZnS nanospheres, in step S3, the heating temperature is preferably 30~50℃, and 50~150μL of mixed solution is added dropwise.

[0019] An application of a method for inducing the ordered arrangement of ZnS nanospheres: The above-mentioned method for inducing the ordered arrangement of ZnS nanospheres by evaporation of mixed solution is used in drop casting coating process.

[0020] The beneficial effects of this invention are:

[0021] 1. The method for inducing the ordered arrangement of ZnS nanospheres by evaporation of mixed solutions proposed in this invention is highly operable, widely applicable, and reproducible. During the preparation process, the movement of ZnS nanospheres can be directly observed under a microscope, providing a theoretical basis for studying the mechanism of the ordered arrangement of the nanospheres.

[0022] 2. The ordered ZnS structure prepared by this invention has a certain regular structure in its microstructure and can be applied to the drop casting coating process. Attached Figure Description

[0023] Figure 1 These are scanning electron microscope images of ZnS nanospheres obtained in Example 1 of this invention;

[0024] Figure 2 Images (a)-(d) are scanning electron microscope images of different regions and magnification ratios of the ordered pattern obtained in Embodiment 1 of the present invention;

[0025] Figure 3 These are scanning electron microscope images of the ordered pattern obtained in Embodiment 2 of the present invention;

[0026] Figure 4 These are scanning electron microscope images of the ordered pattern obtained in Embodiment 3 of the present invention;

[0027] Figure 5 These are scanning electron microscope images of the ordered pattern obtained in Embodiment 4 of the present invention. Detailed Implementation

[0028] This invention relates to a mixed solution evaporation-induced dispersion method using ZnS microspheres as the dispersion phase and a mixture of water, ethanol, and a surfactant as the dispersant. After the dispersion phase and dispersant are uniformly mixed, the mixture is dropped onto a silicon wafer, where the solvent evaporates to form an ordered pattern. The dispersant consists of water, ethanol, and a surfactant. The surfactant plays two main roles: first, it adjusts the viscosity of the dispersant to control the movement speed of the ZnS nanospheres; second, it adjusts the drying time of the solution in the dispersant, thereby controlling the final arrangement pattern of the ZnS microspheres.

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Example 1

[0030] The method of inducing the ordered arrangement of ZnS nanospheres by evaporation of a mixed solution specifically includes the following steps:

[0031] S1. Preparation of ZnS nanospheres: Add 25 mL of deionized water to a 100 mL Erlenmeyer flask, then weigh 0.2 g of zinc acetate dihydrate (Zn(AC)2·2H2O) and 2.8 g of thiourea and dissolve them in the deionized water solution. Place the Erlenmeyer flask in a 30 °C water bath and stir for 20 min. This solution is labeled as solution A. Weigh 0.75 g of polyvinylpyrrolidone K30 (PVP) and add it to solution A. Stir in a 30 °C water bath for 20 min. This solution is labeled as solution B. Then, pour solution B into a reaction vessel and heat it in an oven at 140 °C for 5 h. After the reaction is complete, centrifuge and wash to obtain pure ZnS nanospheres with a size of approximately 120 nm.

[0032] S2. Preparation of ZnS mixed solution: Disperse the pure ZnS nanospheres obtained in step S1 in a mixed solution of 5 mL deionized water and 15 mL ethanol, then add 0.1 g PVP, stir evenly to obtain a mixed solution of ZnS nanoparticles with a ZnS concentration of 2 wt%.

[0033] S3, Film Dropping: Heat the heating platform to 40℃ and maintain a constant temperature. Use a pipette to draw up the mixed solution from step S2, and then drop 50 μL of the mixture onto the cleaned silicon wafer. After the solvent has evaporated, remove the sample to obtain an ordered pattern.

[0034] Figure 1 This is a scanning electron microscope image of the ZnS nanospheres obtained in Example 1 of the present invention. It can be seen that the size of the ZnS nanospheres is approximately 120 nm.

[0035] Figure 2 Images (a)-(d) are scanning electron microscope images of different regions and at different magnifications of the ordered pattern obtained in Example 1 of this invention. It can be seen that an ordered pattern can be obtained through drop casting of a ZnS mixed solution. Example 2

[0036] The method of inducing the ordered arrangement of ZnS nanospheres by evaporation of a mixed solution is described in Example 1, except that the volumes of anhydrous ethanol and deionized water in step S2 are both 10 mL.

[0037] Figure 3These are scanning electron microscope images of the ordered patterns obtained in Embodiment 2 of the present invention. It can be seen that by changing the ratio of water to ethanol in the dispersion, patterns of different shapes can be obtained. Example 3

[0038] The method of inducing the ordered arrangement of ZnS nanospheres by evaporation of mixed solution is as described in Example 1, except that the surfactant added in step S2 is 0.1g of polyethylene glycol 400 (PEG-400).

[0039] Figure 4 These are scanning electron microscope images of the ordered pattern obtained in Embodiment 3 of the present invention. It can be seen that changing the added surfactant significantly alters the pattern. Example 4

[0040] The method for inducing the ordered arrangement of ZnS nanospheres by evaporation of mixed solution according to the present invention is as described in Example 1, except that the surfactant added in step S2 is 0.5g of polyethylene glycol 400 (PEG-400).

[0041] Figure 5 These are scanning electron microscope images of the ordered pattern obtained in Example 4 of this invention. It can be seen that changing the amount of surfactant added significantly alters the pattern.

[0042] The induced ZnS ordered structure of this invention has a certain regular structure arranged in the microstructure and can be applied to the drop casting coating process.

[0043] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A method for inducing the ordered arrangement of ZnS nanospheres, characterized in that: The method is a mixed solution evaporation-induced method, which includes the following steps: Preparation of S1 and ZnS nanospheres: ZnS nanospheres of 60-120 nm were prepared by hydrothermal method. After washing 2-3 times, pure ZnS nanospheres were obtained by centrifugation. S2. Preparation of ZnS mixed solution: The ZnS nanospheres prepared in step S1 are dispersed in a mixed solution of water, ethanol and surfactant, and then ultrasonically vibrated to obtain the ZnS mixed solution. S3, Dropping film: Heat the heating platform to 30~60℃ and keep it constant. Use a pipette to draw up the ZnS mixed solution from step S2, and then drop 50~200μL of the mixed solution onto the cleaned silicon wafer. After the solvent evaporates, remove the sample to obtain an ordered pattern. In step S2, the volume ratio of water to ethanol in the mixed solution of water, ethanol, and surfactant is 1:0.5~3, and the mass concentration of surfactant is 0.1~5wt%. The surfactant is polyvinylpyrrolidone.

2. The method for inducing ordered arrangement of ZnS nanospheres according to claim 1, characterized in that: The preparation method of ZnS nanospheres in step S1 includes the following steps: a. Weigh out zinc acetate dihydrate and thiourea and dissolve them in 10-25 mL of deionized water solution. Stir in a water bath at 30-80℃ for 20 min and record this as solution A. b. Weigh a certain amount of polyvinylpyrrolidone K30 and add it to solution A. Stir in a water bath at 30~80℃ for 20 minutes. This solution is called solution B. c. Place solution B into a reaction vessel and heat in an oven at 100-200℃ for 5-15 hours. After the reaction is complete, centrifuge and wash to obtain pure ZnS nanospheres of 60-120 nm.

3. The method for inducing ordered arrangement of ZnS nanospheres according to claim 2, characterized in that: In step a, the mass ratio of zinc acetate dihydrate to thiourea is 1:8~16.

4. The method for inducing ordered arrangement of ZnS nanospheres according to claim 2, characterized in that: In step b, the mass concentration of polyvinylpyrrolidone K30 is 0.1~5wt%.

5. The method for inducing ordered arrangement of ZnS nanospheres according to claim 1, characterized in that: In step S2, the mass concentration of ZnS in the ZnS mixed solution is 0.5~3wt%.

6. An application of the method for inducing ordered arrangement of ZnS nanospheres as described in any one of claims 1-5, characterized in that: The method described above, which induces the ordered arrangement of ZnS nanospheres through the evaporation of the mixed solution, can be used in drop casting deposition processes.

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