Preparation method of nano particle film layer with periodic patterning distribution, preparation method of multilayer structure and application

Abstract

The invention relates to a preparation method of a nano particle film layer with periodic patterning distribution, a preparation method of a multilayer structure and application. The preparation method of the nano particle film layer with patterned distribution comprises the following steps: (1) providing a substrate and a liquid outlet tool; and (2) liquid is supplied to a liquid outlet tool, the substrate is heated, then the liquid outlet tool and the substrate move relatively in the direction A to form an initial liquid film, the initial liquid film is self-assembled into thick areas and thin areas which are periodically arranged at intervals in the direction A at the first temperature, and a nanoparticle film layer distributed in a patterned mode is obtained. The preparation method of the nano-particle film layer with the patterned distribution is simple to operate and easy to control, provides possibility for industrialization, is high in patterning precision, and can meet the requirement 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 refers to the technology of constructing structures with specific shapes, sizes and arrangements at the nanoscale, and the size of these structures is usually between 1 and 1000 nanometers. The nanostructure pattern can give materials unique physical, chemical and optical properties.

[0003] In the prior art, methods for patterning nanostructures include traditional photolithography, electron beam exposure technology, focused ion beam technology, scanning probe processing technology, nanoimprinting technology, etc., but these methods have high requirements on equipment and process methods, resulting in high industrialization costs.

[0004] Self-assembly technology relies on the interaction forces between molecules, nanoparticles or substrates (such as van der Waals forces, hydrogen bonds, etc.) to make molecules or nanoparticles spontaneously assemble into specific nanostructure patterns. It is a bottom-up preparation method with the advantages of simple preparation process and low cost. However, the existing self-assembly process has poor controllability and it is difficult to accurately control the shape, size and arrangement consistency of the assembled nanostructure pattern.

[0005] There is a need in the art to develop a method for preparing a nanoparticle film layer with a patterned distribution, wherein the method 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 purposes 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 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;

[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 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; 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 the direction in which the liquid discharge tool can be moved along a certain plane. Generally, the liquid discharge tool can be moved within a range of 0 to 360 degrees along a certain plane (usually a horizontal plane). Direction A is the specific movement direction selected by the liquid discharge tool in the operation of step (2).

[0011] The self-assembly described in the present application utilizes heat-enhanced capillary flow and three-phase line pinning to continuously and orderly aggregate nanoparticles to form 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 to form 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 are continuously 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 the present application is periodic 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 first 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 other initial liquid film self-assembles into thick areas and thin areas periodically arranged along the direction B at the second temperature to obtain a nanoparticle film layer with a patterned distribution; the thickness of the thick area is greater than the thickness of the thin area, and the thick area and the thin area are made of the same material and are continuously distributed;

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

[0016] For example, step (2) may be performed first to form a first patterned nanoparticle film layer, and then the direction of the liquid discharge tool may 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 (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.) of the initial liquid film solvent evaporation rate, 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 allow the nanoparticles to have enough 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 the nanoparticles to the high concentration area, 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 a patterned structure.

[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 dispersion of nanoparticles per unit time and per unit area, that is, it 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 camera method during the evaporation of a predetermined volume of solution, and the volume change obtained is 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. The tips of the tapered flexible fibers of the brush structure are arranged in a straight line, and the shapes of the thick area and the thin area are independently linear; the tips of the tapered flexible fibers of the brush structure are arranged in a curved line (such as a wavy line), and the shapes of the thick area and the thin area are independently arranged in a curved line (such as a wavy line); the tips of the tapered flexible fibers of the brush structure are arranged in a zigzag line (such as a sawtooth shape), and the shapes of the thick area and the thin area are independently arranged in a zigzag line (such as a sawtooth shape).

[0026] As another specific embodiment, the liquid outlet tool is a scraper structure capable of evenly supplying liquid. Exemplarily, the scraper structure can be configured as a scraper with a slit outlet, and a liquid storage sponge capable of controlling liquid outlet is preferably disposed 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 silicon dioxide substrate and a silicon substrate;

[0029] Preferably, the flexible substrate comprises 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 of a polyacrylonitrile (PAN) nanofiber material substrate, a nylon nanofiber material substrate, a zinc oxide nanofiber material substrate or a combination of at least two thereof, 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 by 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 3nm to 1μm, for example 4nm, 6nm, 9nm, 15nm, 20nm, 40nm, 60nm, 90nm, 130nm, 150nm, 180nm, 250nm, 300nm, 380nm, 420nm, 480nm, 550nm, 580nm, 650nm, 700nm, 770nm, 850nm, 900nm, 950nm, etc.

[0034] Preferably, 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; further preferred are 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, or a combination of at least two thereof.

[0035] Preferably, 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.

[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% and the like.

[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 difference in thickness 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 zone 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 covering film material fills over the thin regions between the thick regions and covers over the thick regions at the same time.

[0046] The present application does not specifically limit the coating method of the covering film material, and typically but not restrictively can be any one of spin coating, blade coating, rod coating, or a combination of at least two of them.

[0047] The present application does not make any specific limitation on 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 area and the thin area, or the thickness of the thin area can be filled to the same level as the thick area and then a smooth surface can be coated.

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

[0049] The 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 the present application.

[0050] The third object of the present 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 one of the objects, or at least one multilayer structure as described in the second object.

[0051] The fourth object of the present application is to provide a method for preparing a nanoparticle film layer with a patterned distribution as described in the first object, or a method for preparing a multilayer structure as described in the second object, 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, thus 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 a 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 a nanoparticle film layer with patterned distribution in 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 protection scope 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, wherein 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 parts 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 determination and calculation method of the evaporation rate is to use the droplet method to determine 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 which 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 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 outlet tool moves in a direction perpendicular to the width extension direction of the liquid outlet 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 in 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 width 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 one layer of patterned nanoparticle film close to the substrate and the other layer of patterned nanoparticle film 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 extension direction of the width 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 a water dispersion of silver cubic particles (diameter 200 nm) with a concentration of 0.3 wt %;

[0076] (2) supplying liquid (silver cube water 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 which 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 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 outlet tool moves in a direction perpendicular to the width extension direction of the liquid outlet 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 in 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 isopropanol 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 which the solvent evaporation rate of the nanoparticle dispersion is 65 μL / min (brushing speed is 91 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 patterned distribution; the width of the thick region is about 30 μm, the thickness width 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 outlet tool moves in a direction perpendicular to the width extension direction of the liquid outlet 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 the nanoparticle film layer with patterned distribution in Example 4 is given. Figure 6 It can be seen that the nanoparticle film layer with patterned distribution provided in 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 the present application can be adapted to nanoparticles of different morphologies, such as nanoparticles, nanocubes, nanowires, etc., and can obtain linear thick and thin areas of periodically spaced embryonic cloth.

[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 a water dispersion of carbon spheres (diameter 40 nm) with a concentration of 10 wt%;

[0089] (2) supplying liquid (aqueous dispersion of carbon spheres, with a flow rate of 50 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) (the brushing speed is 0.5 mm / s) to form an initial liquid film. At this time, the solvent evaporation rate of the nanoparticle dispersion is 19 μL / min (the brushing speed is 192.4 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 7 μm, the thickness of the thin region is about 380 μm, the thick region and the thin region are continuously distributed, and the thickness difference is about 90 nm, and the thickness of the thick region is ≤1 μm;

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

[0091] Example 6

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

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

[0094] (2) supplying liquid (n-octane dispersion of C8-BTBT, flow rate of 50 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 60° C., and then moving the liquid discharge tool 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 which the solvent evaporation rate of the nanoparticle dispersion is 38 μL / min (brushing speed is 6.9 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 patterned distribution; the width of the thick region is about 5 μm, the thickness width of the thin region is about 23 μm, the thick region and the thin region are continuously distributed, and the thickness difference is about 15 nm, and the thickness of the thick region is ≤1 μm;

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

[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 a 1 mg / mL n-octane solution of CdZnSeS@ZnS quantum dots (diameter 13 nm);

[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 moving the liquid discharge tool 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 which 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 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 outlet tool moves in a direction perpendicular to the width extension direction of the liquid outlet tool.

[0101] It can be seen from Examples 1 to 7 that the method provided in the present 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 layer provided in Examples 1 to 7 can also be coated with a curing material as required, such as Examples 1 to 6 can be coated with a poly(3,4-ethylenedioxythiophene:polystyrene sulfonic acid) material; 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) supplying liquid (silver nanoparticle aqueous dispersion, flow rate of 20 μL / s) to the liquid discharging tool so that the liquid discharging tool discharges liquid uniformly and linearly along a first predetermined direction, heating the substrate and maintaining the substrate at 130°C, and then moving the liquid discharging tool relative to the substrate along direction A (perpendicular to the first predetermined direction) (brushing speed of 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 aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned 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 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; the thickness of the nanoparticle film layer is at a micro-nano scale; The direction A intersects with the first predetermined direction.

2. The preparation method according to claim 1, characterized in that The brushing speed of the liquid discharge tool on the substrate is 1 to 800 times, preferably 5 to 550 times, the evaporation speed of the initial liquid film solvent; Preferably, the brushing speed is 0.2 to 30 μL / s / mm 2 ; Preferably, the initial liquid film solvent evaporation rate is 0.05 to 17 μL / s / mm 2 ; Preferably, the first temperature is 40-230°C.

3. The preparation method according to claim 1 or 2, characterized in that: After step (2), step (2') is performed, of 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 other 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.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The liquid discharge tool is a brush structure composed of a plurality of tapered flexible fibers, the roots of the tapered flexible fibers of the brush structure are arranged along a first predetermined direction, and the tips of the tapered flexible fibers of the brush structure are arranged in a straight line, or in a curved line, or in a folded line; the brush structure supplies liquid from the roots of the tapered fibers and delivers it to the tapered tip of the tapered fibers; Preferably, the substrate comprises any one of a rigid substrate or a flexible substrate; Preferably, the rigid substrate comprises any one of a metal substrate, a glass substrate, an alumina substrate, a silicon dioxide substrate and a silicon substrate; Preferably, the flexible substrate comprises 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; Preferably, the average roughness Ra of the substrate is in the range of 0.1 nm to 50 nm.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The particle size of the nanoparticles is 3nm to 1μm; Preferably, 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; further preferably, the nanoparticles include any one 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, or a combination of at least two thereof; Preferably, 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, polyethylene glycol, or a combination of at least two thereof; Preferably, the concentration of the nanoparticle dispersion is 0.01 wt% to 60 wt%.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The second predetermined direction intersects the first predetermined direction perpendicularly.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The thickness difference between the thick area and the thin area is 5nm to 30μm; Preferably, the width of the thick region is 1 μm to 60 μm; Preferably, the width of the thin region is 5 nm to 160 μm.

8. 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 material fills above the thin regions between the thick regions; Preferably, the covering film material fills over the thin regions between the thick regions and covers over the thick regions; Preferably, the covering material comprises a curing material, preferably any one of a photocuring material, a heat curing material, and a solvent evaporation curing material, or a combination of at least two of them.

9. A composite multilayer structure, characterized in that: The multilayer structure comprises at least one nanoparticle film layer having a patterned distribution as claimed in any one of claims 1 to 7, or at least one multilayer structure as claimed in claim 8.

10. A method for preparing a nanoparticle film layer with patterned distribution as claimed in any one of claims 1 to 7, or a use of the method for preparing a multilayer structure as claimed in claim 8, characterized in that: The preparation method is used to prepare any one of a sensor, a photoelectric detector, a light-emitting device, a flexible photoelectric device, a solar cell, and a biological detection device.

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