A High-Efficiency Patterned Confined Printing Method

Abstract

This invention relates to a highly efficient patterned confined printing method, comprising the following steps: 1) preparing a polymer soft stencil with patterned microstructures; 2) performing superhydrophilic treatment on all surfaces of the polymer soft stencil using a vacuum phase grafting method; 3) immersing a polymer film in a hydrophobic solution, then covering the surface of the polymer soft stencil with the immersed polymer film, performing hydrophobic modification on the top surface of the polymer soft stencil through contact, and then separating the polymer film from the polymer soft stencil; 4) printing a liquid containing functional materials onto the patterned microstructures on the polymer soft stencil, thereby obtaining a patterned array of functional materials. This invention combines high-resolution photolithography stencils, self-assembly of functional materials, and printing technology. It not only overcomes the limitations of single technologies, achieving refined, high-throughput, and high-efficiency fabrication of functional material patterns, but also broadens the applicability of the materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of patterning of functional materials, in particular to a high-efficiency patterning method of confined printing. BACKGROUND

[0002] In recent years, with the development of electronic devices towards lightweight, miniaturization and integration, the patterning of functional layers has become a key step. Through the design of fine patterning structure, the device surface and internal space can be effectively utilized, realizing high-density arrangement of electronic components, and thus improving the overall performance and reliability of the device. Micro-nano processing manufacturing technology promotes the preparation of various functional material patterned structures. One type is based on the "top-down" subtractive manufacturing strategy, such as photolithography, electron beam lithography, ion beam lithography, etc. Another type is based on the "bottom-up" additive manufacturing strategy, mainly including inkjet printing, direct writing technology, screen printing, 3D printing, gravure printing, transfer printing technology and electrohydrodynamic jet printing, etc. The pattern structure prepared by subtractive strategy has high resolution, but has the disadvantages of complicated processing steps, high cost, low scalability and limited material applicability, and is usually used for processing rigid materials. The additive manufacturing strategy can be applied to the large-area preparation of functional patterns of different materials, especially the solution-processed patterning method.

[0003] Due to the poor controllability of the solution, the prepared microstructure has obvious defects, and faces the problems of low resolution and low integration. Therefore, the current research focuses include improving the resolution and controllability of additive manufacturing strategy, and improving the scalability and material applicability of subtractive manufacturing strategy. This will help to overcome the challenges in the patterning process and promote the further development and application of electronic devices.

[0004] Based on photolithography technology, the silicon-based semiconductor industry has realized the etching preparation of silicon material micro- to nanometer resolution patterns. However, for most functional materials, it is not suitable to directly pattern them by photolithography, and the solvents used in the etching process will also affect the functional materials. The solvent may interact with the material, causing changes in the chemical or physical properties of the material, thereby affecting the quality and precision of the patterned structure.

[0005] A printing preparation method of super-high-precision organic functional material patterning based on bubble template array is disclosed in patent document 1. The method first designs and synthesizes the required printing molecules according to the "two-stage" organic functional molecule structure design principle; then prepares a lower substrate with suitable wettability and a patterned structure on the surface and an upper substrate with suitable wettability and a smooth surface, assembles the lower substrate and the upper substrate to form a "sandwich" structure bubble generating system; then fills the assembly liquid containing microbubbles and printing molecules in the bubble generating system, and forms a two-dimensional bubble array with a preset pattern through bubble fusion; after the solvent in the assembly liquid evaporates, the upper and lower substrates are separated, and a super-high-precision printing molecule pattern printing body with a preset pattern is obtained on the surface of the smooth upper substrate.

[0006] CITED DOCUMENTS:

[0007] Patent document 1: CN114454634A. SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] The patterning printing method in the prior art still has room for improvement in resolution, pattern quality, material adaptability and production efficiency.

[0010] Therefore, the technical problem to be solved by the present application is to provide a patterning printing scheme with high resolution, good pattern quality, wide material adaptability and high production efficiency.

[0011] SOLUTIONS FOR SOLVING THE PROBLEMS

[0012] The present inventors have conducted in-depth research on the above problems and proposed a solution processing limited pattern strategy, including the design and preparation of a microstructure template, the modification of a patterned substrate and the printing of a functional material on the substrate.

[0013] Specifically, the present application solves the problems of the present application by the following solutions.

[0014] [1] A limited pattern printing method, comprising the following steps:

[0015] 1) preparing a polymer soft template with patterned microstructures;

[0016] 2) performing super-hydrophilic treatment on all surfaces of the polymer soft template by vacuum air phase grafting method;

[0017] 3) immersing the polymer film in a hydrophobic solution, then covering the immersed polymer film on the surface of the polymer soft template, and modifying the top surface of the polymer soft template by contact, and separating the polymer film from the polymer soft template after modification;

[0018] 4) printing a liquid containing a functional material in the patterned microstructure on the polymer soft template, thereby obtaining a patterned array of the functional material.

[0019] [2] The confined patterned printing method according to [1], wherein the patterned microstructure is a zero-dimensional dot array pattern, a one-dimensional linear / nonlinear array pattern, a two-dimensional grid pattern, or a three-dimensional pattern.

[0020] Preferably, the polymer soft template with patterned microstructure is prepared by the following method (i) or (ii):

[0021] (i) preparing a patterned hard template by a patterning process, and then preparing a polymer soft template by a replication process using the patterned hard template and a solution containing a polymer material constituting the polymer soft template;

[0022] (ii) patterning the surface of a polymer material constituting the polymer soft template by a patterning process, thereby obtaining a polymer soft template with patterned microstructure.

[0023] [3] The confined patterned printing method according to [2], wherein,

[0024] the patterning process is an etching technique, preferably photolithography, electron beam lithography, laser lithography, ion beam lithography, and solvent soft lithography;

[0025] the replication process is one selected from thermal curing, photocuring, and imprinting.

[0026] [4] The confined patterned printing method according to [2], wherein the hard material constituting the hard template is one or more selected from metal, ceramic, glass, hard plastic, or composite material; preferably one or more selected from titanium, nickel, copper, molybdenum, aluminum, silicon, silicon nitride, zirconium oxide, soda-lime glass, quartz glass, borosilicate glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyimide, carbon fiber reinforced plastic, glass fiber reinforced plastic, and metal matrix composite.

[0027] [5] The confined pattern printing method according to any one of [1] to [4], wherein the material constituting the polymeric soft template is a soluble polymer, preferably a water-soluble polymer or a polymer soluble in an organic solvent; preferably, the polymeric material is one or more selected from polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, sodium polystyrene sulfonate, polyethyleneimine, cellulose, styrene-ethylene-butadiene-styrene block copolymer, polyvinylidene fluoride and derivatives thereof, thermoplastic polyester elastomer, polyimide, polyetherimide, polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, polytetrafluoroethylene, polypropylene, silicone rubber, natural rubber, styrene-butadiene rubber, nitrile-butadiene rubber, or a photoresist.

[0028] [6] The confined pattern printing method according to any one of [1] to [4], wherein the functional material is one or more selected from semiconductor materials, dielectric materials, conductive materials, magnetic materials, optical materials, sensing materials, smart materials, biomedical materials, and energy materials.

[0029] Preferably, the functional material is one or more selected from silicon, germanium, gallium arsenide, indium antimonide, silicon carbide, gallium nitride, zinc oxide, diamond, aluminum nitride, zinc selenide, porphyrin conjugated small molecules, naphthalimide conjugated small molecules, conjugated oligomer small molecules based on heteroatom five-membered ring and its fused ring compounds, 2,7-diocty[1]benzothiopheno[3,2-B]benzothiophene, perylene imide and derivatives thereof, poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(diformylimine)-2,6-diyl]-alt-5,5'-(2,29-bithiophene)}, porphyrin and derivatives thereof, indenodithiophene co-benzothiadiazole, carbazole and derivatives thereof, 6,13-bis(triisopropylsilylacetylene)pentacene, naphthalimide and derivatives thereof, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), polyacetylene, polyaniline and derivatives thereof, polypyridine and derivatives thereof, polythiophene and derivatives thereof, poly(9,9-di-n-octylfluorenyl-2,7-diyl), hydrogel, ionic liquid, gold nanoparticles, silver nanoparticles, silver nanoplatelets, silver nanowires, silicon nanowires, platinum nanoparticles, copper nanoparticles, germanium nanoparticles, nickel nanoparticles, titanium nanoparticles, aluminum nanoparticles, MOFs materials, carbon quantum dots, graphene, graphyne, carbon nanotubes, Mxene materials, perovskite, silicon dioxide, zirconium dioxide, aluminum oxide, magnesium oxide, barium titanate, barium strontium titanate, lead zirconium titanate, molybdenum disulfide, boron nitride, tungsten oxide.

[0030] [7] The confined patterning printing method according to any one of [1] to [4], wherein the printing method in step 4) is one or more selected from the group consisting of doctor blading, bar coating, spin coating, inkjet printing, screen printing, 3D printing, direct writing printing, transfer printing, and electroblotting.

[0031] [8] The confined patterning printing method according to any one of [1] to [4], wherein in step 2), the vacuum vapor phase grafting method is performed by plasma treatment, and the contact angle of the polymer soft template after the plasma treatment is < 20°; preferably, the plasma treatment is performed under the conditions of a time of 10 to 300 s and a power of 10 to 100 W; further preferably, the plasma treatment is performed under the conditions of a time of 20 to 60 s and a power of 20 to 50 W.

[0032] The hydrophobic solution in step 3) comprises a silane coupling agent and an organic solvent, the silane coupling agent is preferably one or more selected from the group consisting of perfluorosiloxane, dichlorosiloxane, vinylsiloxane, phenyltrichlorosilane, and aminopropylsiloxane; the organic solvent is preferably one or more selected from the group consisting of ethylene glycol, ethanol, methanol, isopropanol, n-hexane, and cyclohexane; and the contact angle of the top surface of the polymer soft template after the hydrophobic treatment is greater than 45°.

[0033] [9] A patterned array of functional materials obtained by the confined patterning printing method according to any one of [1] to [8].

[0034]

[10] Use of the patterned array of functional materials according to [9] in flexible wearable devices, optoelectronic devices, sensors, electronic skin, energy storage devices, supercapacitors, energy harvesting devices, biochips, field effect transistors, electrochemical transistors, light emitting diodes, optical gratings, waveguides, electrochemical cells, solar cells, memories, memristors, radio frequency microwave devices, lasers, and photodetectors.

[0035] Effects of the application

[0036] The application is a printing-based method for preparing a functional pattern on a template with microstructures, and the deposition of different functional materials can be achieved by heterogeneity treatment of the wettability of the patterned template interface. The confined effect of etching microstructures avoids the problem of solution diffusion, and can effectively improve the resolution and integration density of the printed lines. The patterning method has the advantages of high efficiency and high throughput.

[0037] The method of the application has high flexibility, and can prepare patterned arrays of different dimensions and precision according to the structure of the template. The material has wide applicability, high regularity, and good uniformity, and can significantly improve the efficiency of functional material patterning. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1is a partially enlarged scanning electron microscope picture of the patterned array of BaTi03 Nps obtained in Example 1;

[0039] Figure 2 is a partially enlarged scanning electron microscope picture of the patterned array of BN Ns obtained in Example 2;

[0040] Figure 3 is a partially enlarged scanning electron microscope picture of the patterned array of IDT-BT obtained in Example 3;

[0041] Figure 4 is a partially enlarged scanning electron microscope picture of the patterned array of C8-BTBT obtained in Example 4. DETAILED DESCRIPTION

[0042] Hereinafter, the content of the present application will be described in detail. The description of the technical features described below is based on representative embodiments, specific examples of the present application, but the present application is not limited to these embodiments, specific examples.

[0043] <TERMS AND DEFINITIONS>

[0044] In the present specification, "room temperature" means a temperature range of 20 to 30°C, for example, 25°C.

[0045] In the present specification, a numerical range indicated using "numerical value A to numerical value B" means a range including the end point numerical values A, B.

[0046] In the present specification, a numerical range indicated using "above" or "below" means a numerical range including the present number.

[0047] In the present specification, the meaning indicated using "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0048] In the present specification, "optionally" or "optional" indicates that a certain substance, component, execution step, applied condition, and the like are used or not used.

[0049] In the present specification, the unit names used are international standard unit names, and if not specifically stated, "%" used indicates a percentage by weight or mass.

[0050] In the present specification, "preferred embodiments", "embodiments", and the like referred to mean that the specific elements (for example, features, structures, properties, and / or characteristics) described in relation to the embodiments are included in at least one of the embodiments described herein, and can or can not be present in other embodiments. In addition, it should be understood that the elements can be combined in various embodiments in any suitable manner.

[0051] An object of the present application is to provide a confined patterning printing method, which comprises the following steps:

[0052] 1) preparing a polymer soft template with a patterned microstructure;

[0053] 2) performing superhydrophilic treatment on all surfaces of the polymer soft template by a vacuum air phase grafting method;

[0054] 3) immersing the polymer film in a hydrophobic solution, then covering the immersed polymer film on the surface of the polymer soft template, performing hydrophobic modification on the top surface of the polymer soft template by contact, and separating the polymer film from the polymer soft template after modification;

[0055] 4) printing a liquid containing a functional material in the patterned microstructure on the polymer soft template, thereby obtaining a patterned array of the functional material.

[0056] The method of the present application combines photolithography and printing technology, uses photolithography as the basis, provides a high-resolution patterned template, and lays the foundation for subsequent patterning process; the solution processable manner broadens the application range of materials; and the printing technology can rapidly deposit the functional material on the substrate in a large area, achieving efficient preparation. The method of the present application not only can overcome the limitations of a single technology, but also can exert the respective advantages, realize fine and high-throughput preparation of functional material patterns, provide more possibilities for the design and manufacture of electronic devices, and is expected to promote the further application and development of micro-nano processing technology in the electronic field.

[0057] The following describes each step of the confined patterning printing method of the present application in detail.

[0058] Step 1)

[0059] The method of the present application is a patterned template assisted rapid printing method of functional materials. First, in step 1), a polymer soft template with a patterned microstructure is prepared.

[0060] The patterned microstructure of the polymer soft template of the present application is not particularly limited and can be selected as needed. Specifically, the patterned microstructure in the present application is a specific and particular pattern of concave-convex structure formed on the surface of the polymer soft template.

[0061] In one embodiment, the patterned microstructure has a zero-dimensional point array pattern, a one-dimensional linear / non-linear array pattern, a two-dimensional grid pattern, or a three-dimensional pattern. The present application is not limited to the shape of the microstructure array unit and the constituent of each unit, and can be designed according to the needs. In one embodiment, the microstructure array unit is selected from one of linear micro-wall / micro-column structure, non-linear micro-wall / micro-column structure, and arbitrary polygonal microstructure.

[0062] In a specific embodiment, the polymer soft stamp with patterned microstructure is prepared by the following method (i) or (ii):

[0063] (i) preparing a patterned hard stamp by a patterning process, and then preparing a polymer soft stamp by a replication process using the patterned hard stamp and a solution comprising the polymer material constituting the polymer soft stamp;

[0064] (ii) patterning the surface of the polymer material constituting the polymer soft stamp by a patterning process, thereby obtaining a polymer soft stamp with patterned microstructure.

[0065] More specifically, the patterning process is an etching technique, preferably photolithography, electron beam lithography, laser lithography, ion beam lithography, and solvent soft lithography;

[0066] More specifically, the replication process is one selected from thermal curing, photo-curing, and imprinting.

[0067] The present application is not particularly limited to the hard material constituting the hard stamp, and can be any known suitable material. In one embodiment, the hard material constituting the hard stamp is one or more selected from metal, ceramic, glass, hard plastic, or composite material; preferably one or more selected from titanium, nickel, copper, molybdenum, aluminum, silicon, silicon nitride, zirconium oxide, soda-lime glass, quartz glass, borosilicate glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyimide, carbon fiber reinforced plastic, glass fiber reinforced plastic, and metal matrix composite.

[0068] The polymer material constituting the polymer soft mold is not particularly limited and can be any known suitable material. In one embodiment, the polymer material constituting the polymer soft mold is a soluble polymer material, preferably a water-soluble polymer or a polymer capable of being dissolved in an organic solvent. Preferably, the polymer material is one or more selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, sodium polystyrene sulfonate, polyethyleneimine, cellulose, styrene-ethylene-butadiene-styrene block copolymer, thermoplastic polyester elastomer, polyvinylidene fluoride and derivatives thereof, polyimide, polyetherimide, polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, polytetrafluoroethylene, polypropylene, silicone rubber, natural rubber, styrene butadiene rubber, and nitrile rubber. Alternatively, the polymer material is a photoresist.

[0069] In one embodiment of the use method (i), the replication process is: coating a solution containing a polymer material constituting the polymer soft mold on a patterned hard mold, then removing the solvent, and then peeling the formed layer of the polymer material from the patterned hard mold to obtain the polymer soft mold.

[0070] Specifically, the solution contains a polymer material constituting the polymer soft mold and a solvent, wherein the mass fraction of the polymer material constituting the polymer soft mold is 5-30%.

[0071] Preferably, after coating the solution, the patterned hard mold is placed in a vacuum for defoaming to remove bubbles in the solution.

[0072] Preferably, the solvent is removed by heating, and the heating temperature can be selected according to the solvent used, preferably 50-100°C, and more preferably 60-80°C. The heating time is preferably 7-10h.

[0073] The solvent in the solution can be specifically selected according to the polymer material used, and is preferably methanol, ethanol, isopropanol, tetrahydrofuran, toluene, xylene, o-dichlorobenzene, pentane, hexane, octane, cyclohexanone, cyclohexane, dichloromethane, trichloromethane, monochlorobenzene, N,N-dimethylformamide, N,N-diethylformamide, N-methylpyrrolidone, and water, etc. The above-mentioned solvents can be used alone or in combination of 2 or 3.

[0074] The solution can be coated on the patterned hard mold by a conventional coating method, such as doctor blade coating, bar coating, spin coating, etc.

[0075] In method (ii), the surface of the polymeric material constituting the polymeric soft template is directly patterned by a conventional patterning process, thereby forming a patterned microstructure on the surface thereof. The polymeric material used in method (ii) can have any suitable shape, typically a sheet shape. The polymeric material used in method (ii) is preferably a photoresist as described in method (i).

[0076] Step 2)

[0077] Step 2) is a hydrophilization treatment step, in which the hydrophilization treatment is performed to make all the surfaces of the patterned microstructure of the polymeric soft template (super) hydrophilic. Specifically, the contact angle of the polymeric soft template after the hydrophilization treatment is < 20°.

[0078] In one embodiment, the vacuum vapor grafting method is performed by plasma treatment. Preferably, the conditions of the plasma treatment are: time of 10-300 s, power of 10-100 W; further preferably, time of 20-60 s, power of 20-50 W.

[0079] Step 3)

[0080] In step 3), the top surface of the polymeric soft template after the hydrophilization treatment is subjected to a hydrophobization treatment, so as to make the top surface thereof hydrophobic, thereby preventing the functional material from being attached to the top surface in the subsequent printing process, and causing adverse effects on the clarity and resolution of the pattern.

[0081] In step 3), the polymeric film is first immersed in a hydrophobic solution, and then the immersed polymeric film is covered on the surface of the polymeric soft template, so as to perform the hydrophobic modification on the top surface of the polymeric soft template by contact, and the polymeric film is separated from the polymeric soft template after the modification.

[0082] Preferably, the contact angle of the top surface of the polymeric soft template after the hydrophobization treatment is greater than 45°.

[0083] The polymeric film material used in step 3) is not particularly limited, and can be a soft material selected from plastic or rubber. Specifically, the soft material is one or more selected from polyurethane, styrene-ethylene-butadiene-styrene block copolymer, polyvinyl alcohol, polydimethylsiloxane, silicone rubber, natural rubber, styrene-butadiene rubber, and nitrile rubber.

[0084] In one embodiment, the hydrophobic solution comprises a silane coupling agent and an organic solvent. The silane coupling agent is preferably selected from one or more of perfluorosiloxanes, dichlorosiloxanes, vinylsiloxanes, phenyltrichlorosilanes, and aminopropylsiloxanes. The organic solvent is preferably selected from one or more of ethylene glycol, ethanol, methanol, isopropanol, n-hexane, and cyclohexane.

[0085] Preferably, the polymer film is immersed in the hydrophobic solution for 10 to 20 seconds.

[0086] Preferably, the time for the impregnated polymer film to cover the surface of the polymer soft template is 30 to 100 seconds, more preferably 40 to 80 seconds.

[0087] Preferably, the polymer is dried after impregnation, preferably by blowing it with nitrogen gas.

[0088] Step 4)

[0089] In step 4), the liquid containing the functional material is printed onto the patterned microstructure on the polymer soft stencil to obtain a patterned array of the functional material.

[0090] In this invention, "functional material" refers to the material to be printed. Specifically, functional material refers to material that possesses specific functions after being subjected to light, electricity, magnetism, heat, chemical, biochemical, or other influences. Based on the material's characteristics and applications, functional material can also be defined as: material possessing electrical, magnetic, optical, thermal, acoustic, mechanical, chemical, and biological functions, and the ability to transform into each other, used for non-structural purposes.

[0091] This invention does not impose any particular limitation on the type of functional material, which can be selected as needed. In one embodiment, the functional material is one or more selected from semiconductor materials, dielectric materials, conductive materials, magnetic materials, optical materials, sensing materials, smart materials, biomedical materials, and energy materials.

[0092] The present invention does not have a special limitation on the morphology of the functional material. In one embodiment, it can be nanoparticles, nanosheets or nanowires.

[0093] Preferably, the functional material is one or more selected from silicon, germanium, gallium arsenide, indium antimonide, silicon carbide, gallium nitride, zinc oxide, diamond, aluminum nitride, zinc selenide, porphyrin conjugated small molecules, naphthalimide conjugated small molecules, conjugated oligomer small molecules based on heteroatom five-membered ring and its fused ring compounds, 2,7-diocty[1]benzothiopheno[3,2-B]benzothiophene, perylene imide and its derivatives, poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,29-bithiophene)}, porphyrin and its derivatives, indenodithiophene co-benzothiadiazole, carbazole and its derivatives, 6,13-bis(triisopropylsilylethynyl)pentacene, naphthalimide and its derivatives poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), polyacetylene, polyaniline and its derivatives, polypyridine and its derivatives, polythiophene and its derivatives, poly(9,9-di-n-octylfluorenyl-2,7-diyl), hydrogel, ionic liquid, gold nanoparticle, silver nanoparticle, silver nanosheet, silver nanowire, silicon nanowire, platinum nanoparticle, copper nanoparticle, germanium nanoparticle, nickel nanoparticle, titanium nanoparticle, aluminum nanoparticle, MOFs material, carbon quantum dot, graphene, graphyne, carbon nanotube, Mxene material, perovskite, silicon dioxide, zirconium dioxide, aluminum oxide, magnesium oxide, barium titanate, barium strontium titanate, lead zirconium titanate, molybdenum disulfide, boron nitride, tungsten oxide.

[0094] Preferably, the content of the functional material in the liquid containing the functional material is 10-30 mg / ml.

[0095] Preferably, the liquid containing the functional material further contains a solvent, which is preferably one or more selected from water and organic solvents, and the organic solvents are preferably alcohols, ethers, ketones, esters and halogenated hydrocarbons, and more preferably halogenated aromatic hydrocarbons such as o-dichlorobenzene and the like.

[0096] The printing method of the present application is not particularly limited and can be any known suitable printing method. In one embodiment, the printing method is one or more selected from doctor blading, bar coating, spin coating, inkjet printing, screen printing, 3D printing, direct writing printing, transfer printing, electroblotting.

[0097] Preferably, the speed of the doctor blading is 0.5-2.5 mm / min.

[0098] The present application also correspondingly relates to a patterned array of functional materials obtained by the confined patterned printing method of the present application.

[0099] The patterned array of the functional material of the present application has a wide range of uses, and can be used in flexible wearable devices, optoelectronic devices, sensors, electronic skin, energy storage devices, supercapacitors, energy harvesting devices, biochips, field effect transistors, electrochemical transistors, light emitting diodes, optical gratings, waveguides, electrochemical cells, solar cells, memories, memristors, radio frequency microwave devices, lasers and photodetectors. The present application also correspondingly relates to the above uses of the patterned array of the functional material of the present application.

[0100] Embodiments

[0101] The present application is further described in the following non-limiting examples. It should be understood that these examples are intended to illustrate the present application and are not intended to limit the scope of the present application. Moreover, it should be understood that upon reading the disclosure of the present application, those skilled in the art will be able to affect various modifications and variations of the present application, which are also within the scope of the present application.

[0102] Unless otherwise indicated, the starting materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0103] The plasma treatment instrument used in the following examples is a plasma treatment instrument of SAT-9D type from Satispec Technology Co., Ltd.

[0104] Example 1

[0105] (1) Preparation of polymer soft template

[0106] 25 g of polyvinylidene fluoride (PVDF) powder was dissolved in N,N-dimethylformamide (DMF) solvent to prepare a solution with a concentration of 15%. Then, the solution was spread on a silicon hard template with microstructure by bar coating, and was subjected to a degassing treatment in a vacuum oven for 30 min, and then was heated at 70°C for about 8 h to completely remove the solvent. After complete drying, the formed PVDF film was slowly removed from the silicon hard template to obtain a replicated PVDF soft template.

[0107] (2) Microstructure wettability hetero-treatment

[0108] The surface of the PVDF soft template was treated using a plasma treatment instrument to obtain super-hydrophilic properties of all interfaces of the microstructure. The modification power of the plasma treatment instrument was 20 W, and the time was 30 s.

[0109] The PDMS film was cut into a square piece, immersed in a solvent of perfluorodecyltrimethoxysilane / n-hexane for hydrophobic treatment (immersion time 15 s), and dried with nitrogen. Then the hydrophobic PDMS film was covered on the PVDF soft template for 60 s to obtain a PVDF soft template with heterogeneous wettability.

[0110] (3) Preparation of barium titanate nanoparticle patterned array

[0111] First, 3 g of barium titanate nanoparticles (BaTiO3 Nps) were dispersed in water to prepare a suspension with a concentration of 20 mg / ml. Then 7 μl of the suspension was added to one side of the PVDF soft template, and slowly coated by a doctor blade at a speed of 1 mm / min. Then the prepared sample with embedded BaTiO3 Nps patterned array was placed on a hot stage for heating to remove the solvent.

[0112] Example 2

[0113] (1) Preparation of polymer soft template

[0114] 25 g of polyvinylidene fluoride (PVDF) powder was dissolved in N, N-dimethylformamide (DMF) solvent to prepare a solution with a concentration of 15%. Then it was spread on a silicon hard template with a concave-convex pattern structure by bar coating, and then placed in a vacuum oven for 30 min of debubbling treatment, and then heated at 70°C for about 7 h to completely remove the solvent. After complete drying, the formed PVDF film was slowly removed from the silicon hard template to obtain a replicated PVDF soft template.

[0115] (2) Microstructure wettability heterogeneity treatment

[0116] The surface of the PVDF soft template was treated using a plasma treatment instrument to obtain superhydrophilic properties of all interfaces of the microstructure. The modification power of the plasma treatment instrument was 20 W, and the time was 30 s.

[0117] The PDMS film was cut into a square piece, immersed in a solvent of perfluorodecyltrimethoxysilane / n-hexane for hydrophobic treatment (immersion time 15 s), and dried with nitrogen. Then the hydrophobic PDMS film was covered on the PVDF soft template for 60 s to obtain a PVDF soft template with heterogeneous wettability.

[0118] (3) Preparation of boron nitride nanoplate patterned array

[0119] First, 3 g of boron nitride nanosheets (BN Ns) were dispersed in water to prepare a suspension with a concentration of 20 mg / ml. Then, 7 μl of the suspension was dropped on one side of the PVDF soft template, and slowly coated by a doctor blade at a speed of 1 mm / min. Then, the prepared sample with embedded BN Ns patterned array was placed on a hot stage for heating to remove the solvent.

[0120] Example 3

[0121] (1) Preparation of polymer soft template

[0122] 25 g of polyurethane (TPU, BASF, 1180A) masterbatch was dissolved in N, N-dimethylformamide (DMF) solvent to prepare a solution with a concentration of 20%. Then, it was spread on a silicon hard template with a pattern structure by bar coating, and then placed in a vacuum oven for 30 min of debubbling treatment, and then heated at 70°C for about 8 h to completely remove the solvent. After complete drying, the formed TPU film was slowly removed from the silicon hard template to obtain a replicated TPU soft template.

[0123] (2) Microstructure wettability heterogeneity treatment

[0124] The surface of the TPU soft template was treated using a plasma treatment instrument to obtain superhydrophilic properties of all interfaces of the microstructure. The modification power of the plasma treatment instrument was 20 W, and the time was 30 s.

[0125] The PDMS film was cut into a square piece, immersed in a perfluorodecyltrimethoxysilane / n-hexane solvent for hydrophobic treatment (immersion time 15 s), and dried with nitrogen. Then, the hydrophobic PDMS was covered on the TPU soft template, and the covering time was 60 s, and finally a TPU soft template with heterogeneity wettability was obtained.

[0126] (3) Preparation of semiconductor polymer patterned array

[0127] First, the polymer indenodithiophene co-benzothiadiazole (IDT-BT) was dissolved in o-dichlorobenzene with a concentration of 30 mg / ml. Then, 7 μl of the solution was dropped on one side of the TPU soft template, and slowly coated by a doctor blade at a speed of 1 mm / min. When the semiconductor polymer solution passes through the hydrophilic region, IDT-BT is easily deposited, while when it passes through the hydrophobic region, it will flow to the other end of the soft template under the action of shear force, and finally form an embedded IDT-BT patterned array. Finally, the prepared sample was placed on a hot stage for heating to remove the solvent.

[0128] Example 4

[0129] (1) Preparation of polymer soft template

[0130] Take 25g polyurethane (TPU, BASF, 1180A) master batch dissolved in N, N-dimethylformamide (DMF) solvent, and prepare a solution with a concentration of 20%. Then spread it on a silicon hard template with a pattern structure by rod coating, and place it in a vacuum oven for 30min of debubbling treatment, then heat it at 70℃ for about 7h to completely remove the solvent. After complete drying, slowly remove it from the silicon template to obtain a replica TPU soft template.

[0131] (2) Microstructure wettability heterogeneity treatment

[0132] The surface of the TPU soft template is treated using a plasma treatment instrument to make all the interfaces of the microstructure super-hydrophilic. The modification power of the plasma treatment instrument is 20W, and the time is 30s.

[0133] Cut the PDMS film into squares, immerse it in a solvent of perfluorodecyltrimethoxysilane / n-hexane for hydrophobic treatment (immersion time 15s), and dry it with nitrogen. Then cover the hydrophobic PDMS on the TPU soft template, and the covering time is 60s. Finally, a TPU soft template with heterogeneity wettability is obtained.

[0134] (3) Preparation of semiconductor small molecule patterned array

[0135] First, dissolve 2,7-dioctyl[1]benzothieno[3,2-B]benzothiophene (C8-BTBT) in o-dichlorobenzene to prepare a solution with a concentration of 30mg / ml. Then take 5μl of the solution and drop it on one side of the TPU soft template, and slowly spread it by scraper at a speed of 0.5mm / min. When the small molecule solution passes through the hydrophilic area, C8-BTBT is easily deposited, while when it passes through the hydrophobic area, it flows to the other end of the soft template under the action of shear force, finally forming an embedded C8-BTBT patterned array. Finally, place the prepared sample on a hot stage to remove the solvent.

[0136] Industrial applicability

[0137] The preparation method and the patterned array obtained by the method can be widely used in the fields of electronics, optics, biomedicine, batteries, etc.

Claims

1. A confined pattern printing method, characterized by, The method comprises the following steps: 1) preparing a polymer soft template with patterned microstructure; 2) performing super-hydrophilic treatment on all surfaces of the polymer soft template by vacuum vapor phase grafting method, which is performed by plasma treatment, and the contact angle of the polymer soft template after plasma treatment is <20°; 3) immersing the polymer film in a hydrophobic solution, then covering the immersed polymer film on the surface of the polymer soft template, performing hydrophobic modification on the top surface of the polymer soft template by contact, separating the polymer film from the polymer soft template after modification, the hydrophobic solution comprising silane coupling agent and organic solvent, and the contact angle of the top surface of the polymer soft template after hydrophobic treatment is >45°; 4) printing a liquid containing functional materials in the patterned microstructure on the polymer soft template, thereby obtaining a patterned array of functional materials.

2. The confined pattern printing method according to claim 1, wherein The patterned microstructure is a zero-dimensional dot array pattern, a one-dimensional linear / non-linear array pattern, a two-dimensional grid pattern, or a three-dimensional pattern.

3. The confined pattern printing method according to claim 1, wherein The polymer soft template with patterned microstructure is prepared by the following method (i) or (ii): (i) preparing a patterned hard template by a patterning process, then using the patterned hard template and a solution containing polymer material constituting the polymer soft template to prepare the polymer soft template by a replication process; (ii) patterning the surface of the polymer material constituting the polymer soft template by a patterning process, thereby obtaining a polymer soft template with patterned microstructure.

4. The confined patterned printing method according to claim 3, wherein The patterning process is an etching technique. The replication process is one selected from thermal curing, photocuring, and imprinting.

5. The confined pattern printing method according to claim 4, wherein The etching technique is photolithography, electron beam etching, laser etching, ion beam etching, or solvent soft etching.

6. The confined pattern printing method according to claim 3, wherein The hard material constituting the hard template is one or more selected from metal, ceramic, glass, hard plastic, or composite material.

7. The confined pattern printing method according to claim 3, wherein The hard material constituting the hard template is one or more selected from titanium, nickel, copper, molybdenum, aluminum, silicon, silicon nitride, zirconium oxide, soda-lime glass, quartz glass, borosilicate glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyimide, carbon fiber reinforced plastic, glass fiber reinforced plastic, and metal matrix composite material.

8. The confined pattern printing method according to any one of claims 1 to 7, wherein The polymer material constituting the polymer soft template is a soluble polymer, or the polymer material is a photoresist.

9. The confined pattern printing method according to claim 8, wherein The soluble polymer is a water-soluble polymer or a polymer that can be dissolved in an organic solvent.

10. The confined pattern printing method according to claim 8, wherein The polymer material is one or more selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, sodium polystyrene sulfonate, polyethyleneimine, cellulose, styrene-ethylene-butadiene-styrene block copolymer, polyvinylidene fluoride and its derivatives, thermoplastic polyester elastomer, polyimide, polyetherimide, polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, polytetrafluoroethylene, polypropylene, silicone rubber, natural rubber, styrene-butadiene rubber, and nitrile rubber.

11. The confined pattern printing method according to any one of claims 1 to 7, wherein The functional material is one or more selected from semiconductor materials, dielectric materials, conductive materials, magnetic materials, optical materials, sensing materials, smart materials, biomedical materials, and energy materials.

12. The confined pattern printing method according to any one of claims 1 to 7, wherein The functional material is one or more selected from silicon, germanium, gallium arsenide, indium antimonide, silicon carbide, gallium nitride, zinc oxide, diamond, aluminum nitride, zinc selenide, porphyrin conjugated small molecules, naphthalimide conjugated small molecules, conjugated oligomer small molecules based on heteroatom five-membered ring and its fused ring compounds, 2,7-dioctyl[1]benzothieno[3,2-B]benzothiophene, perylene imide and its derivatives, poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(diformylimine)-2,6-diyl]-alt-5,5'- (2,29-bithiophene)}, porphyrin and its derivatives, indenodithiophene co-benzothiadiazole, carbazole and its derivatives, 6,13-bis(triisopropylsilyl ethynyl) pentacene, naphthalimide and its derivatives poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate), polyacetylene, polyaniline and its derivatives, polypyridine and its derivatives, polythiophene and its derivatives, poly(9,9-di-n-octylfluorenyl-2,7-diyl), hydrogel, ionic liquid, gold nanoparticles, silver nanoparticles, silver nanosheet, silver nanowire, silicon nanowire, platinum nanoparticles, copper nanoparticles, germanium nanoparticles, nickel nanoparticles, titanium nanoparticles, aluminum nanoparticles, MOFs material, carbon quantum dots, graphene, graphyne, carbon nanotube, Mxene material, perovskite, silicon dioxide, zirconium dioxide, aluminum oxide, magnesium oxide, barium titanate, barium strontium titanate, lead zirconium titanate, molybdenum disulfide, boron nitride, tungsten oxide.

13. The confined pattern printing method according to any one of claims 1 to 7, wherein The printing method in step 4) is one or more selected from doctor blade coating, bar coating, spin coating, inkjet printing, screen printing, 3D printing, direct writing printing, transfer printing, and electroblotting.

14. The confined pattern printing method according to any one of claims 1 to 7, wherein In step 2), the conditions of the plasma treatment are: time of 10-300 s, power of 10-100 W. The silane coupling agent is one or more selected from perfluorosiloxane, dichlorosiloxane, vinyl siloxane, phenyltrichlorosilane, and aminopropyl siloxane; and the organic solvent is one or more selected from ethylene glycol, ethanol, methanol, isopropanol, n-hexane, and cyclohexane.

15. The confined pattern printing method according to any one of claim 14, wherein, The conditions of the plasma treatment are: time of 20-60 s, power of 20-50 W.

16. A patterned array of functional material obtained by the confined patterned printing method according to any one of claims 1-15.

17. Use of the patterned array of functional material according to claim 16 in flexible wearable devices, optoelectronic devices, sensors, energy storage devices, biochips, field effect transistors, electrochemical transistors, optical gratings, waveguides, memories, and radio frequency microwave devices.

18. Use of the patterned array of functional material according to claim 16 in electronic skin, supercapacitors, light emitting diodes, electrochemical cells, solar cells, memristors, lasers, and photodetectors.

19. Use of a patterned array of functional materials according to claim 16 in an energy harvesting device.

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