Preparation method of gas-liquid interface self-assembled film, gas-liquid interface self-assembled film, substrate and preparation method thereof

Abstract

The invention discloses a method for preparing a gas-liquid interface self-assembled film, the gas-liquid interface self-assembled film, a substrate containing the gas-liquid interface self-assembled film, and a method for preparing the substrate. The method for preparing the gas-liquid interface self-assembled film comprises the following steps: S1, placing solid particles and a solvent in a container, subjecting the container to ultrasonic stirring to obtain a suspension, and allowing the suspension to stand; S2, taking another film-making container and filling it with water; S3, taking out a precipitate at the bottom of the suspension and placing it in a release container, placing the release container containing the precipitate in the film-making container, so that the precipitate is at the air / water interface, until the solid particles in the precipitate diffuse under the action of the solvent and cover the water surface to obtain the gas-liquid interface self-assembled film. Compared with the prior art, the present invention has the following advantages: the particle release and film-forming process is carried out at the gas-liquid interface, the interference factor of gravitational potential energy is small, so that large-sized metal particles such as 10-500 microns can also be applied to the method.

Description

Technical Field

[0001] The present invention relates to the technical field of thin film preparation, in particular to a method for preparing a gas-liquid interface self-assembled film, a gas-liquid interface self-assembled film, a substrate and a preparation method thereof. Background Art

[0002] Various modified LB-based self-assembly methods are important approaches for preparing ordered thin films and have found widespread application in fields such as photonic crystals and flexible electronics. To achieve high-quality films and improve film formation efficiency, conventional methods are primarily suitable for nanoparticles, such as metal nanoparticles, silica microspheres, and graphene. These materials are relatively stable at interfaces and are generally less susceptible to sinking due to disturbances. However, larger metal particles (diameter > 5 μm) exhibit poor stability at the gas-liquid interface and are easily sunk by even the slightest disturbance, making film assembly at this interface difficult. Large-diameter metal particles have important applications in various fields. For example, large-diameter liquid metal particles can be used to fabricate flexible circuits capable of handling high currents, and large-diameter magnetic metal particles can be used to prepare microwave-absorbing coatings. Therefore, there is an urgent need to optimize existing methods for preparing self-assembled thin films at gas-liquid interfaces to adapt them to larger, denser particles.

[0003] Existing methods for preparing self-assembled membranes at gas-liquid interfaces require uniformly dispersing nanoparticles in an organic solution, then adding the dispersion dropwise to water, allowing it to diffuse freely on the water surface to form a membrane. When the particle density and size are large (e.g., metal particles), it is difficult to form a stable dispersion in the organic solution, and the subsequent dropwise addition to water makes it difficult to stabilize and quickly sink into the water. Therefore, traditional methods for preparing self-assembled particle membranes limit the application of large-sized metal particles. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for preparing a gas-liquid interface self-assembled film, in which the particle release and film formation process is carried out at the gas-liquid interface, the interference factor of gravitational potential energy is small, and large-sized metal particles can also be applied to the method.

[0005] To achieve the above object, the present invention provides a method for preparing a gas-liquid interface self-assembled film, the preparation method comprising the following steps:

[0006] S1. placing solid particles and a solvent in a container, subjecting them to ultrasonic stirring to obtain a suspension, and allowing the suspension to stand;

[0007] S2, take another film-making container and fill it with water;

[0008] S3. Take the precipitate at the bottom of the suspension into a release container, place the release container containing the precipitate into a film-forming container, and place the precipitate at the air / water interface until the particles in the precipitate diffuse under the action of the solvent and cover the water surface to obtain a self-assembled film at the air-liquid interface.

[0009] Preferably, in step S1, the diameter of the solid particles ranges from 1 nm to 1 mm. If the solid particles are larger than 1 mm, they tend to sink and are difficult to form a film.

[0010] Preferably, the solid particles are selected from one or more of metal element particles, metal compound particles and organic particles.

[0011] Preferably, the metal element particles are selected from one or more of copper, iron, silver, and gallium; the metal compound particles are selected from one or more of zinc sulfide, gallium oxide, and aluminum oxide; and the organic particles are selected from one or more of PI, PU, ​​PDMS, PET, and PVC.

[0012] Preferably, in step S1, the solvent is a water-soluble solvent.

[0013] The second aspect of the present invention is to provide a gas-liquid interface self-assembled film prepared by the preparation method.

[0014] The third aspect of the present invention is to provide a substrate, comprising a base material and the gas-liquid interface self-assembled film, wherein the gas-liquid interface self-assembled film is attached to the surface of the base material.

[0015] The fourth aspect of the present invention is to provide a method for preparing a substrate, which is characterized in that the preparation method specifically includes the following steps: contacting the substrate with a gas-liquid interface self-assembled film located at the air / water interface, driving the gas-liquid interface self-assembled film to detach from the air / water interface and attach to the substrate to obtain a substrate.

[0016] Preferably, the material of the substrate is selected from one of glass, silicon wafer, paper, silicone rubber, PI, PET, PVC, human skin, leaves, petals, and gloves.

[0017] Preferably, the shape of the substrate is selected from a plane, a curved surface, a sphere, a cylinder, and a cone.

[0018] The method for preparing self-assembled films at a gas-liquid interface provided by the present invention releases particles at the gas-liquid interface, avoiding the high-rise and low-rise processes found in traditional methods. This reduces interference factors during film formation and makes this method suitable for metal particles as small as 100 microns. Compared with existing methods for preparing self-assembled films at a gas-liquid interface, this method has the following advantages:

[0019] First, the present invention does not need to obtain a uniform particle dispersion and directly uses the precipitate, thereby eliminating the process of modifying the particle surface.

[0020] Secondly, the particle release and film formation process takes place at the gas-liquid interface, where the interference factor of gravitational potential energy is relatively small, making large-sized (10-500 microns) metal particles also applicable to this method. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of the preparation process of the gas-liquid interface self-assembled film according to Example 1 of the present invention;

[0022] Figure 2 Schematic diagram of the preparation process of the substrate according to Example 2 of the present invention;

[0023] Figure 3 This is an optical image of the substrate prepared in Example 2 of the present invention;

[0024] Figure 4 This is an optical image of the substrate prepared in Example 3 of the present invention;

[0025] Figure 5 This is an optical image of the substrate prepared in Example 4 of the present invention;

[0026] Figure 6 This is an optical image of the substrate prepared in Example 5 of the present invention. DETAILED DESCRIPTION

[0027] To make the above-mentioned objects, features, and advantages of the present invention more clearly understood, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings. It should be noted that the following embodiments are only intended to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter ranges described in the present invention. Reasonable variations derived therefrom are still within the scope of protection of the claims of the present invention.

[0028] It should be noted that the endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0029] An embodiment of the present invention discloses a method for preparing a gas-liquid interface self-assembled film, comprising the following steps:

[0030] S1. placing solid particles and a solvent in a container, subjecting them to ultrasonic stirring to obtain a suspension, and allowing the suspension to stand;

[0031] S2, take another film-making container and fill it with water;

[0032] S3. Take the precipitate at the bottom of the suspension into a release container, place the release container containing the precipitate into a film-forming container, and place the precipitate at the air / water interface until the particles in the precipitate diffuse under the action of the solvent and cover the water surface to obtain a self-assembled film at the air-liquid interface.

[0033] In the preparation process of this embodiment, during the diffusion process in step S3 , the height of the medicine spoon can be adjusted at any time to keep the solid particles in the medicine spoon always at the gas-liquid interface.

[0034] According to a preferred embodiment of the present invention, in step S1, the diameter of the solid particles is in the range of 1 nm to 1 mm.

[0035] According to a preferred embodiment of the present invention, the solid particles are selected from one or more of metal element particles, metal compound particles and organic particles.

[0036] According to a preferred embodiment of the present invention, the metal element particles are selected from one or more of copper, iron, silver, and gallium; the metal compound particles are selected from one or more of zinc sulfide, gallium oxide, and aluminum oxide; and the organic particles are selected from one or more of PI, PU, ​​PDMS, PET, and PVC.

[0037] According to a preferred embodiment of the present invention, in step S1, the solvent is a water-soluble solvent.

[0038] Another embodiment of the present invention discloses a substrate, comprising a base material and the above-mentioned gas-liquid interface self-assembled film, wherein the above-mentioned gas-liquid interface self-assembled film is attached to the surface of the base material.

[0039] Another embodiment of the present invention discloses a method for preparing the above-mentioned substrate, which specifically includes the following steps: contacting the substrate with a gas-liquid interface self-assembled film located at the air / water interface, driving the gas-liquid interface self-assembled film to detach from the air / water interface and attach to the substrate to obtain a substrate.

[0040] According to a preferred embodiment of the present invention, the material of the substrate is selected from one of glass, silicon wafer, paper, silicone rubber, PI, PET, PVC, human skin, leaves, and petals.

[0041] According to a preferred embodiment of the present invention, the shape of the substrate is selected from a plane, a curved surface, a sphere, a cylinder, and a cone.

[0042] Example 1

[0043] A gas-liquid interface self-assembled film is prepared by the following method:

[0044] S1, such as Figure 1As shown: Weigh 0.5 g of solid particles and 10 ml of solvent and place them in a beaker, turn on the ultrasonic wand, select the ultrasonic wand horn model as Ф5, select the working mode as on for 1 second and off for 1 second, and the working time is 3 minutes to obtain a solid particle alcohol suspension, and let the suspension stand;

[0045] S2: Take another beaker and add water;

[0046] S3: Use a medicine spoon to take out the precipitate obtained in step S1, and place the medicine spoon into the beaker in step S2, so that the precipitate in the medicine spoon is placed at the water / air interface. The particles in the precipitate will diffuse into the water surface as the alcohol diffuses into the water, thereby obtaining a gas-liquid interface self-assembled film.

[0047] In this embodiment, the solid particles are composed of gallium and indium, the diameter of the solid particles is 10 μm, and the solvent is ethanol.

[0048] Example 2

[0049] A substrate comprising a substrate and the gas-liquid interface self-assembled film prepared in Example 1, wherein the preparation method is as follows Figure 2 As shown: Place the substrate into the water from one side of the beaker until it is placed under the air-liquid interface self-assembled film, and then slowly lift the substrate from the water to transfer the air-liquid interface self-assembled film at the air-liquid interface to the substrate surface. The optical image obtained is as follows Figure 3 shown.

[0050] In this embodiment, the substrate is made of a silicon wafer and has a flat shape.

[0051] Example 3

[0052] A substrate comprises a substrate and the gas-liquid interface self-assembled film prepared in Example 1. The substrate is made of silica gel and has a hemispherical shape. The preparation method is as follows: the substrate is placed in water from one side of a beaker until it is located below the gas-liquid interface self-assembled film, and the substrate is slowly lifted from the water to transfer the gas-liquid interface self-assembled film at the gas-liquid interface to the surface of the substrate. The optical image of the obtained substrate is as follows: Figure 4 shown.

[0053] Example 4

[0054] A substrate comprises a substrate and the gas-liquid interface self-assembled membrane prepared in Example 1. The substrate is made of a glove and has a hemispherical shape. The preparation method is as follows: the substrate is placed in water from one side of a beaker until it is located below the gas-liquid interface self-assembled membrane, and the substrate is slowly lifted from the water to transfer the gas-liquid interface self-assembled membrane at the gas-liquid interface to the surface of the substrate. The optical image of the obtained substrate is as follows: Figure 5 shown.

[0055] Example 5

[0056] A substrate comprises a substrate and the gas-liquid interface self-assembled film prepared in Example 1. The material of the substrate is a leaf and the shape of the substrate is hemispherical. The preparation method is as follows: the substrate is placed in water from one side of a beaker until it is located below the gas-liquid interface self-assembled film, and the substrate is slowly lifted from the water to transfer the gas-liquid interface self-assembled film at the gas-liquid interface to the surface of the substrate. The optical image of the obtained substrate is as follows: Figure 6 shown.

[0057] In other embodiments, the substrate may be brought into contact with the air-liquid interface self-assembled film at the air / water interface from the air side, and the air-liquid interface self-assembled film may be driven to detach from the air / water interface and adhere to the substrate to obtain a base.

[0058] The method for preparing self-assembled films at a gas-liquid interface provided by the present invention releases particles at the gas-liquid interface, avoiding the high-rise and low-rise processes found in traditional methods. This reduces interference factors during film formation and makes this method suitable for metal particles as small as 100 microns. Compared with existing methods for preparing self-assembled films at a gas-liquid interface, this method has the following advantages:

[0059] First, the present invention does not need to obtain a uniform particle dispersion and directly uses the precipitate, thereby eliminating the process of modifying the particle surface.

[0060] Secondly, the particle release and film formation process takes place at the gas-liquid interface, where the interference factor of gravitational potential energy is relatively small, making large-sized (10-500 microns) metal particles also applicable to this method.

[0061] Although the present disclosure is disclosed as above, the protection scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. A method for preparing a gas-liquid interface self-assembled film, characterized in that: The preparation method comprises the following steps: S1. placing solid particles and a solvent in a container, subjecting them to ultrasonic stirring to obtain a suspension, and allowing the suspension to stand, wherein the solid particles are selected from one or more of metal elemental particles, metal compound particles, and organic particles, and the solvent is a water-soluble solvent; S2, take another film-making container and fill it with water; S3. Remove the precipitate at the bottom of the suspension into a release container, and place the release container containing the precipitate into the film-forming container so that the precipitate is at the air / water interface until the particles in the precipitate diffuse under the action of the solvent and cover the water surface to form a self-assembled film at the air-liquid interface; In step S1, the diameter of the solid particles ranges from 1 nm to 1 mm.

2. The method for preparing a gas-liquid interface self-assembled film according to claim 1, wherein The metal element particles are selected from one or more of copper, iron, silver, and gallium; the metal compound particles are selected from one or more of zinc sulfide, gallium oxide, and aluminum oxide; and the organic particles are selected from one or more of PI, PU, ​​PDMS, PET, and PVC.

3. A gas-liquid interface self-assembled film, characterized in that Prepared by any preparation method of claims 1-2.

4. A substrate, characterized in that The method comprises a substrate and the gas-liquid interface self-assembled film as claimed in claim 3, wherein the gas-liquid interface self-assembled film is attached to the surface of the substrate.

5. A method for preparing a substrate as claimed in claim 4, characterized in that: The preparation method specifically includes the following steps: contacting a substrate with a gas-liquid interface self-assembled film located at the air / water interface, and driving the gas-liquid interface self-assembled film to separate from the air / water interface and attach to the substrate to obtain a base.

6. The method for preparing a substrate according to claim 5, wherein: The material of the substrate is selected from one of glass, silicon wafer, paper, silicone rubber, PI, PET, PVC, human skin, leaves, petals, and gloves.

7. The method for preparing a substrate according to claim 5, wherein: The shape of the substrate is selected from a plane, a curved surface, a sphere, a cylinder, and a cone.

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