Method for preparing micro-nano material films capable of controlling pattern shapes in real time

Abstract

The present invention provides a method for preparing a micro-nano material film capable of regulating the pattern shape in real time, comprising: preparing a micro-nano material dispersion; using a blocking pattern to block the through holes in a portion of a support film, and then placing the support film with the blocking pattern on the surface of the micro-nano material dispersion, so that the blocking pattern is located above the gas-liquid interface and does not contact the dispersion; heating the dispersion, and self-assembling on the lower surface of the support film to form a micro-nano material patterned self-assembly structure; during the heating process, another one or more blocking patterns can be used to block the support film again, so that the pattern can be controlled in real time to obtain the final desired micro-nano material patterned self-assembly structure; and drying. The present invention uses different patterns to block the through holes of the support film, thereby realizing the preparation of different patterned films; during the heating process, the shape of the blocking pattern can be adjusted in real time by layer-by-layer covering, so that the shape of the prepared patterned film is also adjusted accordingly; the preparation process is more flexible and has high fault tolerance.

Description

Technical Field

[0001] The present invention relates to the technical field of micro-nano material films, and in particular to a method for preparing a micro-nano material film capable of regulating pattern shape in real time. Background Art

[0002] Micro-nano materials refer to a class of materials with particle sizes at the micron and nanometer levels. Materials at the micro-nano scale often have unique properties that are different from those at the macroscopic scale. Therefore, the use of micro-nano materials to prepare high-performance functional materials has become one of the hot topics in scientific research and industrial production. One of the important technologies in this field is to achieve patterned preparation of thin films. According to different needs, various micro-nano processing technologies have emerged and are constantly developing, such as photolithography, electron beam exposure, focused ion beam, scanning probe processing, and nanoimprinting. Various patterned functional materials can be produced by the above-mentioned technical solutions. For example, CN104221168A in the prior art - a method for manufacturing a nano-patterned substrate for high-efficiency nitride light-emitting diodes, discloses a technical solution for manufacturing nano- to micron-sized patterns on a light-emitting diode substrate by nanoimprinting technology.

[0003] However, the above processing technologies have a common problem: if the shape of the micro-nano material pattern is found to be processed incorrectly during the preparation process, it is difficult to adjust it to the correct pattern shape, which makes the entire process inflexible and has a low fault tolerance rate; and once the processing is incorrect, it will cause a large waste of resources and economic losses.

[0004] Therefore, in order to effectively solve the above problems, there is an urgent need for a method for preparing micro-nano material films that can control the pattern shape in real time during the preparation process. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the present invention proposes the following technical solutions:

[0006] In a first aspect, a method for preparing a micro-nano material film capable of controlling the pattern shape in real time is provided, comprising the following steps:

[0007] preparing a micro-nano material dispersion, wherein the dispersion comprises one or more micro-nano material particles;

[0008] Using a blocking pattern to block the through-holes in a portion of the support film, and then placing the support film with the blocking pattern on the surface of the micro-nano material dispersion, so that the blocking pattern is located above the air-liquid interface and does not contact the dispersion;

[0009] The micro-nano material dispersion is heated while the support membrane and the micro-nano material dispersion are in a static state, so that the micro-nano material particles self-assemble on the lower surface of the support membrane to form a micro-nano material patterned self-assembled structure;

[0010] During the heating process, the support film is again masked using another one or more masking patterns to obtain a final patterned self-assembled structure of micro-nano materials;

[0011] The final micro-nano material patterned self-assembled structure is dried to obtain a micro-nano material patterned self-assembled film.

[0012] Furthermore, the micro-nano materials include MXene, carbon nanotubes, polystyrene microspheres, molybdenum disulfide, boron nitride or graphene oxide.

[0013] Furthermore, the concentration of the micro-nano material dispersion is 0.1 g / L to 5 g / L.

[0014] Furthermore, the support membrane includes an organic membrane or an inorganic membrane.

[0015] Furthermore, the organic membrane includes a polyethersulfone membrane or a polypropylene membrane, and the inorganic membrane is an aluminum oxide inorganic membrane.

[0016] Furthermore, the diameter of the through hole is 20 nanometers to 5 micrometers.

[0017] Furthermore, when the support membrane and the micro-nano material dispersion are in a static state, the micro-nano material dispersion is heated in a water bath, the heating temperature is 40 to 85° C., and the heating time is 30 minutes to 12 hours.

[0018] Furthermore, the drying process includes natural air drying or vacuum drying.

[0019] Furthermore, when preparing the micro-nano material dispersion, a polymer material is added.

[0020] It can be seen from the above technical solution that the beneficial technical effects of the present invention are as follows:

[0021] 1. The principle that water molecule evaporation drives micro-nano material particles to form a self-assembled structure on the lower surface of the support membrane is used. Different patterns are used to block the through holes of the support membrane to achieve the preparation of different patterned films.

[0022] 2. The shielding pattern is located above the gas-liquid interface and does not contact the dispersion. During the heating process, the shape of the shielding support film through-hole pattern can be adjusted in real time by covering it layer by layer, so that the shape of the prepared patterned film is also adjusted accordingly; it can be adjusted and used immediately, and the preparation process is more flexible and has high fault tolerance.

[0023] In a second aspect, a micro-nano material patterned film is provided, which is prepared by using the method provided in the first aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly describes the drawings required for the specific embodiments or the description of the prior art. Similar elements or parts are generally identified by similar reference numerals throughout the drawings. Elements or parts in the drawings are not necessarily drawn to scale.

[0025] Figure 1 This is a flow chart of a method for preparing a patterned thin film of micro-nano materials according to an embodiment of the present invention;

[0026] Figure 2 Schematic diagram of the principle of patterned self-assembly of micro-nano materials according to one embodiment of the present invention;

[0027] Figure 3 This is a rendering of a patterned thin film of micro-nano material prepared according to an embodiment of the present invention;

[0028] Reference numerals:

[0029] 1-support film, 2-through hole of support film, 3-micro-nano material dispersion, 4-micro-nano material particles, 5-shielding pattern. DETAILED DESCRIPTION

[0030] The following embodiments of the technical solution of the present invention will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present invention and are therefore only examples and are not intended to limit the scope of protection of the present invention.

[0031] It should be noted that, unless otherwise specified, the technical or scientific terms used in this application should have the common meanings understood by those skilled in the art to which the present invention belongs.

[0032] Example 1

[0033] This embodiment provides a method for preparing a micro-nano material film that can control the pattern shape in real time. Figure 1 As shown, follow these steps:

[0034] The materials required for the thin film preparation method include: micro-nano materials, support films and shielding patterns.

[0035] In a specific embodiment, the micro-nano material includes: MXene, carbon nanotubes (CNTs), polystyrene microspheres (PS microspheres), molybdenum disulfide (MoS2), boron nitride (BN), or graphene oxide (GO). MXene is a two-dimensional inorganic compound composed of transition metal carbides, nitrides, or carbonitrides with a thickness of several atomic layers.

[0036] The support membrane, in a specific embodiment, is a membrane having multiple through-holes, such as a microporous filter membrane. The material, size, and thickness of the support membrane are not limited. In a specific embodiment, the support membrane is selected based on the different micro-nano material dispersions, and can be an organic membrane or an inorganic membrane. The organic membrane is preferably a polyethersulfone membrane or a polypropylene membrane, and the inorganic membrane is preferably an aluminum oxide (Al2O3) inorganic membrane. The support membrane can be in roll form (wrapped into a roll) or sheet form. The pore size of the through-holes in the support membrane is larger than the diameter of the solvent molecules and smaller than the diameter of the micro-nano material particles, and the pore size of the through-holes is preferably 20 nanometers to 5 microns.

[0037] The masking pattern is used to be attached to a local area of ​​the support film. In a specific embodiment, the material of the pattern is not limited. In one embodiment, the pattern can be attached to the support film using transparent adhesive or self-adhesive tape, wherein the transparent adhesive or self-adhesive tape does not contain through holes.

[0038] 1. Prepare a micro-nano material dispersion, which includes one or more micro-nano material particles

[0039] In a specific embodiment, the solvent of the micro-nano material dispersion is not limited, as long as the micro-nano material can be evenly dispersed, such as water or ethanol, with water being preferred. The micro-nano material dispersion can be prepared using any method of the prior art, preferably using ultrasonic dispersion. During ultrasonic dispersion, the equipment used is an ultrasonic cleaning machine, and the time is determined according to the desired degree of dispersion of the micro-nano material dispersion, until uniform dispersion is achieved. In one embodiment, the ultrasonic dispersion time is 30 minutes. In a specific embodiment, the concentration of the micro-nano material dispersion is adjusted by controlling the solute mass, and the concentration is preferably 0.1 g / L to 5 g / L.

[0040] During the ultrasonic dispersion process, the micro-nano material dispersion needs to be cooled to prevent the high temperature caused by ultrasound from damaging the material structure. In a specific embodiment, an ice water bath is used to cool the dispersion for 2 to 3 minutes, and the cooling temperature can be slightly lower than room temperature.

[0041] The prepared dispersion may contain only one type of micro-nano material particles or multiple types of micro-nano material particles, as long as they are evenly dispersed.

[0042] In one embodiment, when preparing the micro-nano material dispersion, one or more polymer materials may be added, preferably polyacrylic acid. The addition of polymer materials can significantly improve the mechanical properties of the micro-nano material film, making it more convenient to prepare large-area films.

[0043] 2. Use a blocking pattern to block the through-holes in a portion of the support film, and then place the support film with the blocking pattern on the surface of the micro-nano material dispersion, so that the blocking pattern is above the air-liquid interface and does not contact the dispersion;

[0044] In a specific embodiment, a polyethersulfone membrane is used as an example to illustrate the support membrane: the polyethersulfone membrane is spread out, and a shielding pattern is attached to the corresponding area of ​​the support membrane using transparent tape to shield the through-holes in this area of ​​the support membrane. Then, the polyethersulfone membrane with the shielding pattern facing upward is gently placed into an open container. The polyethersulfone membrane will automatically float on the liquid surface due to the surface tension of the liquid and spread out at the air-liquid interface of the micro-nano material dispersion; at this time, the shielding pattern is located above the air-liquid interface, in contact with the air but not with the dispersion liquid. Figure 2 shown.

[0045] The size of the open container is not limited and can be selected based on the area of ​​the film to be prepared.

[0046] 3. The micro-nano material dispersion is heated while the support film and the micro-nano material dispersion are in a static state, so that the micro-nano material particles self-assemble on the lower surface of the support film to form a micro-nano material patterned self-assembled structure;

[0047] The micro-nano material dispersion in the open container is heated to a preset temperature and for a preset time. The heating method is not limited. In a specific embodiment, heating is preferably performed in a water bath. The water bath temperature is preset to 40-85°C, preferably 80°C; the preset time is 30 minutes to 12 hours. The specific preset time is related to the preset temperature. When the preset temperature is 50°C, the preset time is 1.5-2 hours; when the preset temperature is 80°C, the preset time is 20-60 minutes.

[0048] like Figure 2 As shown, under heating at a preset temperature, in areas without a masking pattern, water molecules in the micro-nano material dispersion will evaporate and move toward the air-liquid interface. Simultaneously, this upward movement of water molecules will drive the micro-nano material particles toward the support membrane. Because the diameter of water molecules is smaller than the pore size of the support membrane, they will evaporate out of the pores. Meanwhile, the diameter of micro-nano material particles is larger than the pore size of the support membrane and will be blocked by the membrane, thereby adhering to the lower surface of the support membrane and forming a self-assembled structure.

[0049] In areas with a blocking pattern, small, enclosed spaces are formed within some of the through-holes of the support film and between the blocking pattern and the dispersion surface. When heated to a predetermined temperature, these enclosed spaces quickly reach saturated vapor pressure, eliminating evaporation at the blocked areas. Water molecules are unable to evaporate upward from these areas, preventing the formation of self-assembled structures on the lower surface of the support film, in areas with the blocking pattern.

[0050] Different patterned self-assembled structures can be obtained by different blocking patterns.

[0051] 4. During the heating process, use another one or more blocking patterns to block the support film again to obtain the final micro-nano material patterned self-assembly structure

[0052] After the preparation has begun, if it is found that the shape of the patterned film to be prepared needs to be partially adjusted, or it needs to be made into a layered film similar to a gradient step, the support film can be covered layer by layer with another one or more blocking patterns and blocked again to change the shape of the self-assembled structure attached to the lower surface of the support film to form a new patterned self-assembled structure. Specifically, the new blocking pattern can be directly pasted on the support film floating on the liquid surface (not in contact with the liquid surface), or the support film can be removed, the blocking pattern can be readjusted, and then placed back on the liquid surface. If the support film is removed, the time for adjusting the blocking pattern should not exceed 20 minutes to prevent the self-assembled patterned structure from drying out and affecting the second patterning.

[0053] In a specific embodiment, this step is an optional step. If the pattern does not need to be adjusted, the support film may not be covered again.

[0054] 5. Dry the final micro-nano material patterned self-assembled structure to obtain a micro-nano material patterned self-assembled film

[0055] The method for drying the final micro-nano material patterned self-assembled structure is not limited, and can be dried by natural air drying or vacuum drying. In a specific embodiment, the support film with the final micro-nano material patterned self-assembled structure attached thereto is removed from the open container, with the side of the support film with the final micro-nano material patterned self-assembled structure attached thereto facing upward. After drying, a micro-nano material patterned self-assembled thin film is obtained.

[0056] The following examples illustrate the parameters and process for preparing patterned thin films using micro-nano materials:

[0057] (1) Single-component micro-nano material patterned films

[0058] Prepare a uniformly dispersed GO aqueous dispersion and transfer it to a clean, open container. Place a piece of clear tape cut into a masking pattern (e.g., a Tai Chi pattern) on a microporous filter membrane. Place the microporous filter membrane at the air-liquid interface in the open container, with the tape facing up. Heat the filter in an 80°C hot water bath for 30 minutes. Remove the microporous filter membrane from the liquid surface and place it with the GO self-assembled structure facing up to dry.

[0059] (2) Multi-component micro-nano material patterned films

[0060] Prepare a mixed dispersion of micro-nanomaterials: GO and MXene in a 1:1 ratio (blend concentration 1 g / L) to obtain a uniform dispersion. Adhere the cutout pattern to a 0.22 μm PP filter membrane using self-adhesive tape. Place the PP filter membrane at the air-liquid interface in an open container, with the masking pattern facing upward. Heat in an 80°C water bath for 40 minutes. Place the membrane with the GO and MXene self-assembled structure facing upward and allow to dry.

[0061] Using the technical solution of this embodiment, the film obtained after drying is as follows Figure 3 As shown, Figure 3 Examples of patterned films fabricated using graphene oxide as the micro-nanomaterial. The multiple circular patterns on the far right were achieved by repeatedly changing the masking pattern during heating.

[0062] Using the technical solutions provided in the above embodiments, which exploit the principle that water evaporation drives the formation of self-assembled structures of micro-nanomaterial particles on the lower surface of a support film, and using different patterns to block the through-holes of the support film, various patterned films can be prepared. The blocking pattern is located above the gas-liquid interface and does not contact the dispersion. During the heating process, the shape of the blocking pattern of the through-holes of the support film can be adjusted in real time through layer-by-layer covering, and the shape of the resulting patterned film can be adjusted accordingly. This allows for immediate adjustment and use, making the preparation process more flexible and fault-tolerant.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and description of the present invention.

Claims

1. A method for preparing a micro-nano material film capable of real-time control of pattern shape, characterized in that: The following steps are involved: preparing a micro-nano material dispersion, wherein the dispersion comprises one or more micro-nano material particles; Using a blocking pattern to block the through-holes in a portion of the support film, and then placing the support film with the blocking pattern on the surface of the micro-nano material dispersion, so that the blocking pattern is located above the air-liquid interface and does not contact the dispersion; The micro-nano material dispersion is heated while the support membrane and the micro-nano material dispersion are in a static state, so that the micro-nano material particles self-assemble on the lower surface of the support membrane to form a micro-nano material patterned self-assembled structure; During the heating process, the support film is again masked using another one or more masking patterns to obtain a final patterned self-assembled structure of micro-nano materials; The final micro-nano material patterned self-assembled structure is dried to obtain a micro-nano material patterned self-assembled film.

2. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 1, characterized in that: The micro-nano material includes MXene, carbon nanotubes, polystyrene microspheres, molybdenum disulfide, boron nitride or graphene oxide.

3. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 2, characterized in that: The concentration of the micro-nano material dispersion is 0.1 g / L to 5 g / L.

4. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 1, characterized in that: The supporting film includes an organic film or an inorganic film.

5. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 4, characterized in that: The organic membrane includes a polyethersulfone membrane or a polypropylene membrane, and the inorganic membrane is an aluminum oxide inorganic membrane.

6. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 1, characterized in that: The through hole has a pore diameter of 20 nanometers to 5 micrometers.

7. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 1, characterized in that: When the support membrane and the micro-nano material dispersion are in a static state, the micro-nano material dispersion is heated in a water bath, the heating temperature is 40 to 85° C., and the heating time is 30 minutes to 12 hours.

8. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 1, characterized in that: The drying process includes natural air drying or vacuum drying.

9. The method for preparing a micro-nano material film capable of real-time control of pattern shape according to claim 1, characterized in that: When preparing the micro-nano material dispersion, a polymer material is added.

10. A micro-nano material patterned film, characterized in that: It is prepared by using the method according to any one of claims 1 to 9.

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