Method for producing a nanoparticle film layer with a periodic patterned distribution, method for producing a multilayer structure and use

Abstract

The application relates to a preparation method of a nanoparticle film layer with a periodic patterned distribution, a preparation method and use of a multilayer structure. The preparation method of the nanoparticle film layer with the patterned distribution comprises the following steps: (1) providing a substrate and a liquid outlet tool; (2) supplying liquid to the liquid outlet tool, heating the substrate, and then moving the liquid outlet tool along a direction A relative to the substrate to form an initial liquid film, and the initial liquid film is self-assembled into thick regions and thin regions periodically and spacedly arranged along the direction A at a first temperature, so that the nanoparticle film layer with the patterned distribution is obtained. The preparation method of the nanoparticle film layer with the patterned distribution provided by the application is simple in operation, easy to control, provides possibility for industrialization, and is high in patterned precision, and can meet the demand of high-precision patterning.

Description

Technical Field

[0001] The present invention belongs to the field of patterning, and in particular relates to a method for preparing a nanoparticle film layer with patterned distribution, a method for preparing a multilayer structure and uses thereof. Background Art

[0002] Nanostructure patterning is the process of creating structures with specific shapes, sizes, and arrangements at the nanoscale. These structures typically range in size from 1 to 1000 nanometers. These nanostructure patterns can impart unique physical, chemical, and optical properties to materials.

[0003] In the existing technology, the methods of nanostructure patterning include traditional photolithography, electron beam exposure process, focused ion beam process, scanning probe processing technology, nanoimprint technology, etc., but these methods have high requirements on equipment and process methods, resulting in high industrialization costs.

[0004] Self-assembly technology relies on interactions between molecules, nanoparticles, or substrates (such as van der Waals forces and hydrogen bonds) to spontaneously assemble molecules or nanoparticles into specific nanostructured patterns. This bottom-up fabrication method offers the advantages of simplicity and low cost. However, existing self-assembly processes suffer from poor controllability, making it difficult to precisely control the shape, size, and consistency of the assembled nanostructured patterns.

[0005] There is a need in the art to develop a method for preparing a nanoparticle film layer with patterned distribution, which is simple to operate, easy to industrialize, and has high patterning accuracy. Summary of the Invention

[0006] In view of the shortcomings of the prior art, one of the objectives of the present invention is to provide a method for preparing a nanoparticle film layer with patterned distribution, characterized in that the preparation method comprises the following steps:

[0007] (1) Providing a substrate and a liquid discharging tool; on the substrate, the liquid discharging tool can uniformly and linearly discharge liquid along a first predetermined direction at the same time; the first predetermined direction is the extension direction of the linear liquid discharge line; the liquid discharged by the liquid discharging tool is a dispersion of nanoparticles; the liquid discharging tool can move along a second predetermined direction;

[0008] (2) supplying liquid to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at a first temperature, and then causing the liquid discharge tool to move relative to the substrate along a direction A to form an initial liquid film, wherein the initial liquid film self-assembles into thick regions and thin regions periodically arranged along the direction A at the first temperature, thereby obtaining a nanoparticle film layer having a patterned distribution; the thickness of the thick region is greater than the thickness of the thin region, and the thick region and the thin region are made of the same material and are continuously distributed; and the thickness of the nanoparticle film layer is at a micro-nano scale;

[0009] The direction A intersects with the first predetermined direction.

[0010] It should be noted that the second predetermined direction is a direction in which the liquid discharge tool can be moved along a certain plane. Typically, the liquid discharge tool can move within a range of 0 to 360 degrees along a certain plane (usually a horizontal plane). Direction A is the specific direction of movement selected by the liquid discharge tool during the operation of step (2).

[0011] The self-assembly described in this application utilizes heat-enhanced capillary flow and three-phase line pinning to cause nanoparticles to continuously and orderly aggregate, forming a number of deposition areas parallel to the first predetermined direction, forming a high-concentration area of ​​nanoparticles; at the same time, due to the continuous aggregation of nanoparticles to obtain a high-concentration area, the concentration of nanoparticles decreases between adjacent high-concentration areas of nanoparticles, forming a low-concentration area of ​​nanoparticles; the solvent evaporates continuously, but due to the existence of the surface tension of the solvent, the liquid film remains intact for a certain period of time, the nanoparticles continue to be transported to the high-concentration area, and the concentration of nanoparticles in the low-concentration area continues to decrease until the liquid film breaks, the high-concentration area of ​​nanoparticles forms a thick area, and the low-concentration area of ​​nanoparticles forms a thin area. The patterning of the nanoparticle film layer obtained in this application has periodicity and presents an orderly patterned structure.

[0012] The micro-nano scale is usually less than 20 μm, and may also be less than 1 μm.

[0013] Preferably, the angle at which the second predetermined direction intersects the second predetermined direction is 5° to 175°, preferably 30° to 150°.

[0014] Preferably, after step (2), step (2') is performed: supplying liquid to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at a second temperature, and then causing the liquid discharge tool to move relative to the surface of the structure obtained in step (2) along a direction B to form another initial liquid film, wherein the another initial liquid film self-assembles into thick regions and thin regions periodically arranged along the direction B at the second temperature to obtain a nanoparticle film layer having a patterned distribution; the thickness of the thick region is greater than the thickness of the thin region, and the thick region and the thin region are made of the same material and are continuously distributed;

[0015] Direction B is the specific movement direction selected by the liquid discharge tool during the operation of step (2'). The nanoparticle film layer with patterned distribution described in this application can be a multilayer structure, and the movement direction of each layer can be independently selected. The selection can be adjusted according to the predetermined direction of the pattern.

[0016] For example, step (2) can be performed first to form a first patterned nanoparticle film layer, and then the direction of the liquid discharge tool can be adjusted (eg, rotated to a specific angle) to perform step (2') to obtain a second patterned nanoparticle film layer.

[0017] Preferably, the brushing speed of the liquid discharge tool on the substrate is 1 to 800 times the evaporation rate of the initial liquid film solvent (for example, 2 times, 10 times, 28 times, 39 times, 48 ​​times, 59 times, 75 times, 88 times, 115 times, 135 times, 158 times, 165 times, 185 times, 193 times, 225 times, 245 times, 283 times, 342 times, 383 times, 450 times, 534 times, 600 times, 620, 685 times, etc.), preferably 5 to 550 times, and more preferably 90 to 550 times.

[0018] The appropriate relationship between the brushing speed of the liquid discharge tool on the substrate and the evaporation speed of the initial liquid film solvent can enable the nanoparticles to have sufficient time to self-assemble in the solvent liquid film. The larger the multiple, the weaker the capillary flow generated by evaporation, which affects the aggregation of nanoparticles to high-concentration areas, while the liquid film in the low-concentration area is not easy to break, and the aggregation of quantum dots is disordered and non-periodic; the smaller the multiple, the solvent has evaporated completely before the nanoparticles have completed aggregation, resulting in unclear patterning, inability to obtain thick and thin areas, and inability to obtain patterned structures.

[0019] Preferably, the brushing speed is 0.2 to 30 μL / s / mm 2 , for example, 0.3 μL / s / mm 2 , 0.5μL / s / mm 2 , 1.3μL / s / mm 2 , 1.8μL / s / mm2 , 2.5μL / s / mm 2 、3.8μL / s / mm 2 , 4.6μL / s / mm 2 , 5.5μL / s / mm 2 、6.8μL / s / mm 2 , 7.4μL / s / mm 2 、8.5μL / s / mm 2 , 9.4μL / s / mm 2 、15.5μL / s / mm 2 、16.4μL / s / mm 2 、18.5μL / s / mm 2 , 20.5μL / s / mm 2 , 22.5μL / s / mm 2 , 26.5μL / s / mm 2 , 28.5μL / s / mm 2 , etc., preferably 2 to 10 μL / s / mm 2 .

[0020] The brushing speed is the brushing volume of the nanoparticle dispersion per unit time and per unit area, which can be understood as the total brushing volume divided by the brushing time divided by the brushing area.

[0021] Preferably, the initial liquid film solvent evaporation rate is 0.05 to 17 μL / s / mm 2 For example, 0.06 μL / s / mm 2 , 0.10μL / s / mm 2 , 0.40μL / s / mm 2 , 1.20μL / s / mm 2 , 2.50μL / s / mm 2 , 4.60μL / s / mm 2 、6.80μL / s / mm 2 , 7.60μL / s / mm 2 、8.50μL / s / mm 2 , 9.80μL / s / mm 2 、10.50μL / s / mm 2 、11.00μL / s / mm 2 、13.00μL / s / mm 2 、14.50μL / s / mm 2 、16.00μL / s / mm 2 、16.60μL / s / mm 2 etc., preferably 1 mg / mL to 15 mg / mL.

[0022] Preferably, the first temperature is 40-230°C, for example, 42°C, 46°C, 55°C, 64°C, 75°C, 85°C, 90°C, 95°C, 100°C, 108°C, 114°C, 119°C, etc.

[0023] The evaporation rate is calculated by high-speed photography to obtain the volume change over time during the evaporation of a predetermined volume of solution, and then converted into the volume change per unit surface area.

[0024] As a specific embodiment, the liquid discharge tool is a brush structure composed of a plurality of conical flexible fibers, the roots of the conical flexible fibers of the brush structure are arranged along a first predetermined direction, and the tips of the conical flexible fibers of the brush structure are arranged in a straight line, or in a curved line, or in a broken line; the brush structure supplies liquid from the roots of the conical fibers and transports it to the conical tip of the conical fibers.

[0025] The brush structure can discharge liquid evenly, and the shape of the brush head can be selected according to the patterned shape. If the tips of the tapered flexible fibers of the brush structure are arranged in a straight line, the shapes of the thick area and the thin area are independently linear; if the tips of the tapered flexible fibers of the brush structure are arranged in a curved line (such as a wavy line), the shapes of the thick area and the thin area are independently curved line (such as a wavy line); if the tips of the tapered flexible fibers of the brush structure are arranged in a zigzag line (such as a sawtooth shape), the shapes of the thick area and the thin area are independently zigzag line (such as a sawtooth shape).

[0026] As another specific embodiment, the liquid discharging tool is a scraper structure capable of evenly supplying liquid. For example, the scraper structure can be configured as a scraper with a slit outlet, and a liquid storage sponge capable of controlling liquid discharge is preferably provided inside the slit.

[0027] Preferably, the substrate includes any one of a rigid substrate and a flexible substrate.

[0028] Preferably, the rigid substrate comprises any one of a metal substrate, a glass substrate, an alumina substrate, a silica substrate and a silicon substrate;

[0029] Preferably, the flexible substrate includes any one of a polyester (PET) substrate, a polycarbonate (PC) substrate, a polyimide (PI) substrate, a polydimethylsiloxane (PDMS) substrate, a polyethylene naphthalate (PEN) substrate, a nanofiber material substrate, a metal oxide composite material substrate, and a poly(3,4-ethylenedioxythiophene:polystyrene sulfonic acid) substrate.

[0030] The nanofiber material substrate includes any one or a combination of at least two of a polyacrylonitrile (PAN) nanofiber material substrate, a nylon nanofiber material substrate, and a zinc oxide nanofiber material substrate, or a nanofiber material substrate of a composite material of the nanofiber material and a metal oxide.

[0031] Preferably, the average roughness Ra of the substrate is in the range of 0.1 nm to 50 nm, for example, 0.2 nm, 1 nm, 4 nm, 8 nm, 12 nm, 18 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, etc.

[0032] The present application does not specifically limit the roughness of the substrate, that is, the preparation method provided in the present application can be adapted to substrates with different average roughnesses in a wide range.

[0033] Preferably, the particle size of the nanoparticles is 3 nm to 1 μm, for example, 4 nm, 6 nm, 9 nm, 15 nm, 20 nm, 40 nm, 60 nm, 90 nm, 130 nm, 150 nm, 180 nm, 250 nm, 300 nm, 380 nm, 420 nm, 480 nm, 550 nm, 580 nm, 650 nm, 700 nm, 770 nm, 850 nm, 900 nm, 950 nm, etc.

[0034] Preferably, the nanoparticles include any one or a combination of at least two of metal nanoparticles, metal oxide nanoparticles, carbon nanoparticles, silicon nanoparticles, semiconductor quantum dots, polymer nanoparticles, and polystyrene nanoparticles; further preferably, the nanoparticles include any one or a combination of at least two of gold nanoparticles, silver nanoparticles, copper nanoparticles, aluminum nanoparticles, platinum nanoparticles, palladium nanoparticles, iron nanoparticles, nickel nanoparticles, titanium oxide nanoparticles, zinc oxide nanoparticles, iron oxide nanoparticles, copper oxide nanoparticles, aluminum oxide nanoparticles, silicon oxide nanoparticles, fullerenes, carbon nanotubes, graphene, carbon nanoparticles, polyvinyl alcohol nanoparticles, polyethylene nanoparticles, polypropylene nanoparticles, and polystyrene nanoparticles.

[0035] Preferably, the solvent of the nanoparticle dispersion includes any one or a combination of at least two of butanol, isopropanol, acetone, chlorobenzene, tetrahydrofuran, heptane, xylene, dichloromethane, ethyl acetate, benzene, n-octane, toluene, n-hexane, chloroform, water, ethanol, dimethyl sulfoxide, dimethylformamide, and polyethylene glycol.

[0036] Preferably, the concentration of the nanoparticle dispersion is 0.01wt% to 60wt%, for example, 0.05wt%, 0.1wt%, 0.5wt%, 0.9wt%, 1wt%, 5wt%, 14wt%, 25wt%, 37wt%, 42wt%, 48wt%, 55wt%, etc.

[0037] Preferably, the second predetermined direction intersects the first predetermined direction perpendicularly, that is, the angle at which the second predetermined direction intersects the first predetermined direction is 90°.

[0038] Preferably, the thickness difference between the thick region and the thin region is 5 nm to 30 μm, for example, 6 nm, 12 nm, 15 nm, 20 nm, 25 nm, 28 nm, etc.

[0039] Generally speaking, the higher the concentration of the nanoparticle dispersion, the faster the evaporation rate of the initial liquid film solvent, the slower the brushing speed, and the greater the thickness difference between the thick area and the thin area.

[0040] Preferably, the width of the thick area is 1 μm to 60 μm, for example, 2 μm, 8 μm, 15 μm, 20 μm, 25 μm, 32 μm, 36 μm, 43 μm, 48 μm, 54 μm, 58 μm, etc.

[0041] Preferably, the width of the thin area is 5nm to 160μm, for example, 7nm, 12nm, 18nm, 20nm, 26nm, 32nm, 38nm, 41nm, 55nm, 64nm, 78nm, 93nm, 2μm, 8μm, 15μm, 25μm, 38μm, 46μm, 58μm, 77μm, 85μm, 105μm, 128μm, 135μm, 142μm, 147μm, etc.

[0042] The second object of this application is to provide a method for preparing a multilayer structure, comprising the following steps:

[0043] (I) preparing a nanoparticle film layer having a patterned distribution according to the preparation method described in one of the purposes;

[0044] (II) coating a covering film material on the nanoparticle film layer described in step (I), wherein the covering material fills the thin regions between the thick regions.

[0045] Preferably, the cover film material fills over the thin regions between the thick regions and covers over the thick regions.

[0046] The present application does not impose any specific limitation on the coating method of the cover film material. Typically but not limited to, it can be any one of spin coating, blade coating, and rod coating, or a combination of at least two of them.

[0047] The present application does not specifically limit the coating thickness of the covering film material. For example, the thickness of the thin area can be filled to the same level as the thick area, or it can be evenly coated above the thick and thin areas, or the thickness of the thin area can be filled to the same level as the thick area and then a flat surface can be coated.

[0048] Preferably, the covering material comprises a curing material, preferably any one of a light curing material, a heat curing material, and a solvent evaporation curing material, or a combination of at least two of them.

[0049] A solidified material refers to a material that can be transformed from a liquid or flowable state to a solid or non-flowable state through a chemical reaction or physical change. Generally, any solidified material that does not destroy the patterned structure can be used as a covering material in this application.

[0050] The third object of this application is to provide a composite multilayer structure, characterized in that the multilayer structure includes at least one nanoparticle film layer with patterned distribution as described in the first object, or at least one multilayer structure as described in the second object.

[0051] The fourth purpose of this application is to provide a method for preparing a nanoparticle film layer with a patterned distribution as described in the first purpose, or the use of the method for preparing a multilayer structure as described in the second purpose, wherein the preparation method is used to prepare any one of sensors, photodetectors, light-emitting devices, flexible photoelectric devices, solar cells, and biological detection devices.

[0052] Compared with the prior art, this application has the following beneficial effects:

[0053] The method for preparing a nanoparticle film layer with patterned distribution provided in the present application is simple to operate and easy to control, providing the possibility for industrialization, and has high patterning accuracy, which can meet the needs of high-precision patterning. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 is a SEM scanning electron microscope image of the silver nanoparticles of Example 1;

[0055] Figure 2 is an optical microscope image of the nanoparticle film layer with patterned distribution in Example 1;

[0056] Figure 3 This is a SEM scanning electron microscope image of the silver cube of Example 3;

[0057] Figure 4 is an optical microscope image of the nanoparticle film layer with patterned distribution of Example 3;

[0058] Figure 5 This is a SEM scanning electron microscope image of the silver nanowires in Example 4;

[0059] Figure 6 This is an optical microscope image of the nanoparticle film layer with patterned distribution in Example 4. DETAILED DESCRIPTION

[0060] The technical solution of the present invention is further explained below in conjunction with specific implementation methods. However, it should be noted that the specific implementation methods are only a specific implementation and explanation of the essence of the technical solution of the present invention and should not be understood as a limitation on the scope of protection of the present invention.

[0061] The reagents and instruments used in the examples can all be purchased from commercial products, and the detection methods are conventional methods well known in the art.

[0062] The liquid storage tool used in Examples 1 to 7 is a brush structure composed of a plurality of conical flexible fibers, the roots of the conical flexible fibers of the brush structure are arranged along a first predetermined direction (recorded as the brush width direction), the brush width is 10 mm, and the tips of the conical flexible fibers of the brush structure are arranged flush along a straight line; the brush structure supplies liquid from the roots of the conical fibers and transports it to the conical tip of the conical fibers.

[0063] The calculation method of the brushing speed described in the embodiment is to divide the flow rate by the brushing area; the method of measuring and calculating the evaporation rate is to use the droplet method to measure the solvent evaporation volume of the corresponding solvent per unit time at the corresponding temperature (recorded as the solvent evaporation volume rate), and then divide the solvent evaporation volume rate by the droplet surface area to obtain the solvent evaporation rate.

[0064] Example 1

[0065] A patterned silver nanoparticle film layer is prepared by the following method:

[0066] (1) Providing a PET substrate (surface roughness 5 nm) and a liquid dispensing tool; preparing an aqueous dispersion of silver nanoparticles (diameter 70 nm) with a concentration of 0.3 wt%;

[0067] (2) supplying liquid (silver nanoparticle aqueous dispersion, flow rate of 100 μL / s) to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at 100° C., and then causing the liquid discharge tool to move relative to the substrate along direction A (perpendicular to the first predetermined direction) (brushing speed of 0.9 mm / s) to form an initial liquid film, at this time, the solvent evaporation rate of the nanoparticle dispersion is 8 μL / min (brushing speed is 550 times the solvent evaporation rate), and the initial liquid film self-assembles on the substrate into linear thick regions and linear thin regions periodically arranged along direction A, thereby obtaining a nanoparticle film layer with a patterned distribution; the width of the thick region is about 5 μm, the thickness of the thin region is about 25 μm, the thick region and the thin region are continuously distributed, and the thickness difference is about 20 nm, and the thickness of the thick region is ≤1 μm;

[0068] The direction A intersects the first predetermined direction at right angles, that is, the liquid discharge tool moves in a direction perpendicular to the width extension direction of the liquid discharge tool.

[0069] Figure 1 The SEM scanning electron microscope image of the silver nanoparticles of Example 1 is given. Figure 2 An optical microscope image of the nanoparticle film layer with patterned distribution of Example 1 is given. Figure 2 It can be seen that the nanoparticle film layer with patterned distribution provided by the present application has thick areas (lines) and thin areas (areas between lines) arranged at intervals along direction A at regular intervals.

[0070] Example 2

[0071] The difference from step (1) is that after step (2), step (2') is performed to continue supplying the same silver nanoparticle aqueous dispersion to the liquid discharge tool (with a flow rate of 100 μL / s) so that the liquid discharge tool can discharge liquid uniformly and linearly along the first predetermined direction, heat the substrate and keep the substrate at 100°C, and then adjust the liquid discharge tool to rotate horizontally by 90° so that the liquid discharge tool moves relative to the surface of the structure obtained in step (2) along direction B (perpendicular to direction A) to form another initial liquid film, and the other initial liquid film self-assembles into linear thick areas and thin areas periodically arranged along direction B at 100°C to obtain another nanoparticle film layer with two layers of patterned distribution; the width of the thick area is about 5 μm, the thickness of the thin area is about 25 μm, the thick area and the thin area are continuously distributed, and the thickness difference is about 20 nm. In the two-layer patterned nanoparticle film, the linear extension direction of the pattern of the nanoparticle film layer close to the substrate and the other nanoparticle film layer far from the substrate is 90°.

[0072] Since the liquid discharge tool is directly rotated, after the rotation, the liquid discharge tool still moves in a direction perpendicular to the width extension direction of the liquid discharge tool.

[0073] Example 3

[0074] A patterned silver cubic particle film layer is prepared by the following method:

[0075] (1) Providing a PET substrate (surface roughness 5 nm) and a liquid dispensing tool; preparing an aqueous dispersion of silver cubic particles (diameter 200 nm) with a concentration of 0.3 wt%;

[0076] (2) supplying liquid (silver cube aqueous dispersion, flow rate of 150 μL / s) to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at 130° C., and then causing the liquid discharge tool to move relative to the substrate along direction A (perpendicular to the first predetermined direction) (brushing speed of 1.0 mm / s) to form an initial liquid film. At this time, the solvent evaporation rate of the nanoparticle dispersion is 19 μL / min (brushing speed is 200 times the solvent evaporation rate), and the initial liquid film self-assembles on the substrate into linear thick regions and linear thin regions periodically arranged along direction A, thereby obtaining a nanoparticle film layer with a patterned distribution; the width of the thick region is about 10 μm, the thickness of the thin region is about 200 μm, the thick region and the thin region are continuously distributed, and the thickness difference is about 30 nm, and the thickness of the thick region is ≤1 μm;

[0077] The direction A intersects the first predetermined direction at right angles, that is, the liquid discharge tool moves in a direction perpendicular to the width extension direction of the liquid discharge tool.

[0078] Figure 3 The SEM scanning electron microscope image of the silver cube of Example 3 is given. Figure 4 An optical microscope image of the nanoparticle film layer with patterned distribution of Example 3 is given. Figure 4 It can be seen that the nanoparticle film layer with patterned distribution provided by the present application has thick areas (lines) and thin areas (areas between lines) arranged at intervals along direction A at regular intervals.

[0079] Example 4

[0080] A patterned silver nanowire film layer is prepared by the following method:

[0081] (1) Providing a PET substrate (surface roughness 5 nm) and a liquid dispensing tool; preparing an isopropanol dispersion of silver nanowires (length 10 μm) with a concentration of 5 wt%;

[0082] (2) supplying liquid (silver nanowire isopropyl alcohol dispersion, flow rate of 150 μL / s) to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at 90° C., and then moving the liquid discharge tool relative to the substrate along direction A (perpendicular to the first predetermined direction) (brushing speed of 1.0 mm / s) to form an initial liquid film. At this time, the solvent evaporation rate of the nanoparticle dispersion is 65 μL / min (brushing speed is 91 times the solvent evaporation rate), and the initial liquid film self-assembles on the substrate into linear thick regions and linear thin regions periodically arranged along direction A, thereby obtaining a nanoparticle film layer with a patterned distribution; the width of the thick region is about 30 μm, the thickness of the thin region is about 600 μm, the thick region and the thin region are continuously distributed, and the thickness difference is about 70 nm, and the thickness of the thick region is ≤1 μm;

[0083] The direction A intersects the first predetermined direction at right angles, that is, the liquid discharge tool moves in a direction perpendicular to the width extension direction of the liquid discharge tool.

[0084] Figure 5 The SEM scanning electron microscope image of the silver nanowires in Example 4 is given. Figure 6 An optical microscope image of a nanoparticle film layer with patterned distribution is given in Example 4. Figure 6 It can be seen that the nanoparticle film layer with patterned distribution provided by the present application has thick areas (lines) and thin areas (areas between lines) arranged at intervals along direction A at regular intervals.

[0085] It can be seen from Examples 1 to 4 that the method provided in this application is adaptable to nanoparticles of different morphologies, such as nanoparticles, nanocubes, nanowires, etc., and can obtain linear thick and thin areas of periodically spaced blankets.

[0086] Example 5

[0087] A patterned carbon sphere film layer is prepared by the following method:

[0088] (1) Providing a PET substrate (surface roughness 5 nm) and a liquid dispensing tool; preparing an aqueous dispersion of carbon spheres (diameter 40 nm) with a concentration of 10 wt%;

[0089] (2) supplying liquid to the liquid outlet tool (water dispersion liquid of carbon spheres, flow rate of 50 μL / s) to make the liquid outlet tool uniformly linearly outlet liquid along a first predetermined direction, heating the substrate and keeping the substrate at 130°C, and then making the liquid outlet tool move relative to the substrate along direction A (perpendicular to the first predetermined direction) (brushing speed of 0.5 mm / s) to form an initial liquid film, at this time, the solvent evaporation speed of the nanoparticle dispersion liquid is 19 μL / min (the brushing speed is 192.4 times the solvent evaporation speed), the initial liquid film is self-assembled on the substrate into linear thick regions and linear thin regions periodically and spaced along direction A, to obtain a nanoparticle film layer with a patterned distribution; the thick region width is about 7 μm, the thin region thickness width is about 380 μm, the thick regions and the thin regions are continuously distributed, and the thickness difference is about 90 nm, and the thick region thickness is ≤1 μm;

[0090] The direction A intersects the first predetermined direction perpendicularly, that is, the liquid outlet tool moves along a direction perpendicular to the extension direction of the liquid outlet tool width.

[0091] Example 6

[0092] A patterned liquid crystal film layer is prepared by the following method:

[0093] (1) providing a PET substrate (surface roughness of 5 nm) and a liquid outlet tool; preparing a n-octane dispersion liquid of C8-BTBT (2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene) with a concentration of 10 wt%;

[0094] (2) supplying liquid to the liquid outlet tool (n-octane dispersion liquid of C8-BTBT, flow rate of 50 μL / s) to make the liquid outlet tool uniformly linearly outlet liquid along a first predetermined direction, heating the substrate and keeping the substrate at 60°C, and then making the liquid outlet tool move relative to the substrate along direction A (perpendicular to the first predetermined direction) (brushing speed of 11 mm / s) to form an initial liquid film, at this time, the solvent evaporation speed of the nanoparticle dispersion liquid is 38 μL / min (the brushing speed is 6.9 times the solvent evaporation speed), the initial liquid film is self-assembled on the substrate into linear thick regions and linear thin regions periodically and spaced along direction A, to obtain a nanoparticle film layer with a patterned distribution; the thick region width is about 5 μm, the thin region thickness width is about 23 μm, the thick regions and the thin regions are continuously distributed, and the thickness difference is about 15 nm, and the thick region thickness is ≤1 μm;

[0095] The direction A intersects the first predetermined direction perpendicularly, that is, the liquid outlet tool moves along a direction perpendicular to the extension direction of the liquid outlet tool width.

[0096] Example 7

[0097] A patterned quantum dot film layer is prepared by the following method:

[0098] (1) Providing a PET substrate (surface roughness 5 nm) and a liquid dispensing tool; preparing a dispersion of CdZnSeS@ZnS quantum dots (diameter 13 nm) in n-octane at a concentration of 1 mg / mL;

[0099] (2) supplying liquid (quantum dot n-octane dispersion, flow rate of 100 μL / s) to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at 100° C., and then causing the liquid discharge tool to move relative to the substrate along direction A (perpendicular to the first predetermined direction) (brushing speed of 4 mm / s) to form an initial liquid film. At this time, the solvent evaporation rate of the nanoparticle dispersion is 61 μL / min (brushing speed is 23.8 times of the solvent evaporation rate), and the initial liquid film self-assembles on the substrate into linear thick regions and linear thin regions periodically arranged along direction A, thereby obtaining a nanoparticle film layer with a patterned distribution; the width of the thick region is 2 μm, the width of the thin region is 25 μm, the thick region and the thin region are continuously distributed, and the thickness difference is about 35 nm, and the thickness of the thick region is ≤1 μm;

[0100] The direction A intersects the first predetermined direction at right angles, that is, the liquid discharge tool moves in a direction perpendicular to the width extension direction of the liquid discharge tool.

[0101] It can be seen from Examples 1 to 7 that the method provided in this application can be adapted to nanoparticles of different materials, such as metal nanoparticles, carbon material examples, liquid crystal molecules, quantum dots, etc., and can obtain linear thick and thin areas of periodically spaced blankets.

[0102] The surface of the nanoparticle film provided in Examples 1 to 7 can also be coated with a curing material as required. For example, Examples 1 to 6 can be coated with a poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid material; and Example 7 can be coated with a polyvinyl chloride material.

[0103] Comparative Example 1

[0104] A patterned silver nanoparticle film layer is prepared by the following method:

[0105] (1) Providing a PET substrate (surface roughness 5 nm) and a liquid dispensing tool; preparing an aqueous dispersion of silver nanoparticles (diameter 70 nm) with a concentration of 0.3 wt%;

[0106] (2) Liquid (silver nanoparticle aqueous dispersion, flow rate of 20 μL / s) is supplied to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, the substrate is heated and maintained at 130°C, and then the liquid discharge tool is moved relative to the substrate along direction A (perpendicular to the first predetermined direction) (the brushing speed is 40 mm / s). At this time, the solvent evaporation rate of the nanoparticle dispersion is 19 μL / min (the brushing speed is 0.96 times the solvent evaporation rate). Since the brushing speed is lower than the evaporation speed, an effective initial film cannot be formed, and periodically spaced linear thick areas and linear thin areas cannot be formed on the substrate.

[0107] 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 above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a nanoparticle film layer having a periodic patterned distribution, characterized in that: The preparation method comprises the following steps: (1) Providing a substrate and a liquid discharging tool; on the substrate, the liquid discharging tool can uniformly and linearly discharge liquid along a first predetermined direction at the same time; the first predetermined direction is the extension direction of the linear liquid discharging line; the liquid discharged by the liquid discharging tool is a dispersion of nanoparticles; the liquid discharging tool can move along a second predetermined direction; (2) supplying liquid to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at a first temperature, and then causing the liquid discharge tool to move relative to the substrate along a direction A to form an initial liquid film, wherein the initial liquid film self-assembles into thick regions and thin regions periodically arranged along the direction A at the first temperature, thereby obtaining a nanoparticle film layer having a patterned distribution; the thickness of the thick region is greater than the thickness of the thin region, and the thick region and the thin region are made of the same material and are continuously distributed; the thickness of the nanoparticle film layer is at a micro-nano scale; The direction A intersects with the first predetermined direction; The brushing speed of the liquid discharge tool on the substrate is 1 to 800 times the evaporation speed of the initial liquid film solvent; The liquid discharge tool is a brush structure composed of a plurality of conical flexible fibers, the roots of the conical flexible fibers of the brush structure are arranged along a first predetermined direction, and the tips of the conical flexible fibers of the brush structure are arranged in a straight line, or in a curved line, or in a broken line; the brush structure supplies liquid from the roots of the conical fibers and transports it to the conical tip of the conical fibers.

2. The preparation method according to claim 1, wherein The brushing speed of the liquid discharge tool on the substrate is 5 to 550 times the evaporation speed of the initial liquid film solvent.

3. The preparation method according to claim 1, wherein The brushing speed is 0.2~30 μL / s / mm 2 .

4. The preparation method according to claim 1, wherein The initial liquid film solvent evaporation rate is 0.05~17μL / s / mm 2 .

5. The preparation method according to claim 1, wherein The first temperature is 40-230°C.

6. The preparation method according to claim 1, wherein After step (2), step (2') is performed: supplying liquid to the liquid discharge tool so that the liquid discharge tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at a second temperature, and then causing the liquid discharge tool to move relative to the surface of the structure obtained in step (2) along direction B to form another initial liquid film, wherein the another initial liquid film self-assembles into linear thick regions and thin regions periodically arranged along direction B at the second temperature to obtain a nanoparticle film layer with a patterned distribution; the thickness of the thick region is greater than the thickness of the thin region, and the thick region and the thin region are made of the same material and are continuously distributed.

7. The preparation method according to claim 1, wherein The substrate includes any one of a rigid substrate and a flexible substrate.

8. The preparation method according to claim 7, wherein The rigid substrate includes any one of a metal substrate, a glass substrate, an aluminum oxide substrate, a silicon dioxide substrate and a silicon substrate.

9. The preparation method according to claim 7, wherein The flexible substrate includes any one of a polyester substrate, a polycarbonate substrate, a polyimide substrate, a polydimethylsiloxane substrate, a polyethylene naphthalate substrate, a nanofiber material substrate, a metal oxide composite material substrate, and a poly (3,4-ethylenedioxythiophene):polystyrene sulfonic acid) substrate.

10. The preparation method according to claim 1, wherein The average roughness Ra of the substrate ranges from 0.1 nm to 50 nm.

11. The preparation method according to claim 1, wherein The particle size of the nanoparticles is 3 nm to 1 μm.

12. The preparation method according to claim 1, wherein The nanoparticles include any one of metal nanoparticles, metal oxide nanoparticles, carbon nanoparticles, silicon nanoparticles, semiconductor quantum dots, polymer nanoparticles, and polystyrene nanoparticles, or a combination of at least two thereof.

13. The preparation method according to claim 12, wherein The nanoparticles include any one or a combination of at least two of gold nanoparticles, silver nanoparticles, copper nanoparticles, aluminum nanoparticles, platinum nanoparticles, palladium nanoparticles, iron nanoparticles, nickel nanoparticles, titanium oxide nanoparticles, zinc oxide nanoparticles, iron oxide nanoparticles, copper oxide nanoparticles, aluminum oxide nanoparticles, silicon oxide nanoparticles, fullerenes, carbon nanotubes, graphene, carbon nanoparticles, polyvinyl alcohol nanoparticles, polyethylene nanoparticles, polypropylene nanoparticles, and polystyrene nanoparticles.

14. The preparation method according to claim 1, wherein The solvent of the nanoparticle dispersion includes any one of butanol, isopropanol, acetone, chlorobenzene, tetrahydrofuran, heptane, xylene, dichloromethane, ethyl acetate, benzene, n-octane, toluene, n-hexane, chloroform, water, ethanol, dimethyl sulfoxide, dimethylformamide, and polyethylene glycol, or a combination of at least two thereof.

15. The preparation method according to claim 1, wherein The concentration of the nanoparticle dispersion is 0.01 wt % to 60 wt %.

16. The preparation method according to claim 1, wherein The second predetermined direction intersects the first predetermined direction perpendicularly.

17. The preparation method according to claim 1, wherein The thickness difference between the thick area and the thin area is 5 nm to 30 μm.

18. The preparation method according to claim 1, wherein The width of the thick area is 1 μm to 60 μm.

19. The preparation method according to claim 1, wherein The width of the thin region is 5 nm to 160 μm.

20. A method for preparing a multilayer structure, characterized in that: (I) preparing a nanoparticle film layer having a patterned distribution according to the preparation method of any one of claims 1 to 7; (II) coating a covering film material on the nanoparticle film layer described in step (I), wherein the covering film material fills the thin regions between the thick regions.

21. The preparation method according to claim 20, characterized in that The cover film material fills over the thin regions between the thick regions and covers over the thick regions.

22. The preparation method according to claim 20, wherein The cover film material includes a solidified material.

23. The preparation method according to claim 20, characterized in that The covering film material includes any one of a light-curing material, a heat-curing material, and a solvent evaporation-curing material, or a combination of at least two of them.

24. A composite multilayer structure, characterized in that: The multilayer structure comprises at least one nanoparticle film layer having a patterned distribution according to any one of claims 1 to 19, or at least one multilayer structure according to claim 8.

25. A use of the method for preparing a nanoparticle film layer with patterned distribution according to any one of claims 1 to 19, or the method for preparing a multilayer structure according to any one of claims 20 to 23, characterized in that: The preparation method is used to prepare any one of a sensor, a photodetector, a light-emitting device, a flexible photoelectric device, a solar cell, and a biological detection device.

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