CN110065925B - Micro-nano material self-assembly method, substrate and application - Google Patents
Micro-nano material self-assembly method, substrate and application Download PDFInfo
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- CN110065925B CN110065925B CN201910223533.9A CN201910223533A CN110065925B CN 110065925 B CN110065925 B CN 110065925B CN 201910223533 A CN201910223533 A CN 201910223533A CN 110065925 B CN110065925 B CN 110065925B
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Abstract
The invention relates to the field of self-assembly of micro-nano materials, and discloses a method for self-assembling micro-nano materials, a substrate and application. A method for self-assembling micro-nano materials comprises the following steps: (A) printing ink containing a polymer on the surface of a substrate with hydrophilicity, wherein the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate to obtain the substrate with the patterned structural units; (B) dripping the assembly liquid containing the micro-nano material on the surface of the substrate with the patterned structure unit to obtain the substrate containing the assembly liquid; (C) covering the substrate containing the assembly liquid with a cover plate with hydrophobicity, volatilizing or evaporating a solvent in the assembly liquid, and carrying out self-assembly on the micro-nano material at the edge of the patterning structure unit; and then peeling the cover plate to obtain the substrate with the patterned micro-nano material. The method has the advantages of simplicity, rapidness, strong controllability, good uniformity, low preparation cost and convenience for large-scale production.
Description
Technical Field
The invention relates to the field of self-assembly of micro-nano materials, in particular to a method for self-assembling micro-nano materials, a substrate and application.
Background
In recent years, nanotechnology has developed rapidly, and synthesis, assembly and application of multi-dimensional nanoparticles based on micro and/or nano materials (micro-nano materials) have attracted attention and research in various fields such as flexible devices, raman sensing, photonic crystals and the like. The realization of ordered assembly of particles and controllable patterning of different micro-nano materials is to explore the physicochemical properties of materials and prepare bridges and ties of high-performance photoelectric devices.
With the miniaturization of electronic devices and the continuous improvement of requirements of people on the sensitivity and the multifunctionality of the devices, the development of high-precision micro-nano devices has great significance on scientific progress and social development. Wherein, the application of the photoetching method, the electron beam etching method and the micro-contact printing method which take the top-down micro-processing technology as the core is limited in the aspect of large-area patterning because the preparation process is complex and the cost is higher; although the printing technology can realize large-area pattern direct writing, is simple and convenient to prepare and low in cost, the patterns obtained by the methods can reach the nanometer size, but the morphology controllability is poor, and large-area preparation is difficult to realize. Therefore, how to utilize a simple, efficient and universal method to realize controllable patterning preparation of the micro-nano material is of far-reaching significance in promoting scientific development and social progress.
Disclosure of Invention
The invention aims to solve the problem that the patterned micro-nano material is difficult to prepare simply, controllably, efficiently and in a large area in the prior art, and provides a preparation method for self-assembling the micro-nano material, a substrate and application.
In order to achieve the above object, a first aspect of the present invention provides a method for self-assembling a micro-nano material, including:
(A) printing ink containing a polymer on the surface of a substrate with hydrophilicity, wherein the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate to obtain the substrate with the patterned structural units;
(B) dripping the assembly liquid containing the micro-nano material on the surface of the substrate with the patterned structure unit to obtain the substrate containing the assembly liquid;
(C) covering the substrate containing the assembly liquid with a cover plate with hydrophobicity, volatilizing or evaporating a solvent in the assembly liquid, and carrying out self-assembly on the micro-nano material at the edge of the patterning structure unit; then peeling the cover plate to obtain a substrate with the patterned micro-nano material;
alternatively, the first and second electrodes may be,
(A) printing ink containing a polymer on the surface of a substrate with hydrophilicity, wherein the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate to obtain the substrate with the patterned structural units;
(B) dripping the assembly liquid containing the micro-nano material on the surface of the substrate with the patterned structure unit to obtain the substrate containing the assembly liquid;
(C) covering the substrate containing the assembly liquid with a cover plate with hydrophobicity, volatilizing or evaporating a solvent in the assembly liquid, and carrying out self-assembly on the micro-nano material at the edge of the patterning structure unit; then peeling the cover plate to obtain a substrate with the patterned micro-nano material;
(D) and removing the patterned structural unit.
The invention provides a substrate containing a micro-nano material prepared by the method, and the substrate comprises a substrate, a protruded polymer structure unit pattern formed on the surface of the substrate and a patterned micro-nano material formed at the edge of the polymer structure unit pattern, or the substrate comprises a substrate and a patterned micro-nano material formed on the surface of the substrate.
The third aspect of the invention provides an application of the substrate containing the micro-nano material in a laser, a solar cell, a flexible sensing device or a light emitting diode.
The method comprises the steps of printing ink containing polymers on the surface of a substrate with hydrophilicity by using a printing method, forming a plurality of raised patterned structural units (patterned templates) by using the polymers in the ink after a solvent in the ink is volatilized, dropping an assembly liquid containing micro-nano materials on the surface of the substrate with the patterned structural units by using the raised patterned structural units as the templates, covering (covering and pressing) a cover plate with hydrophobicity on the surface of the substrate with the assembly liquid to form a limited domain assembly system consisting of the hydrophobic cover plate, the assembly liquid containing the micro-nano materials and the patterned substrate, so that the self-assembly of the micro-nano materials (micro-nano materials) is induced, and the in-situ fine self-assembly of the micro-nano materials on the edges of the raised patterned structural units is realized. The substrate containing the micro-nano material is prepared, the preparation method is simple and rapid, the controllability is strong, the uniformity is good, the preparation cost is low, large-scale production is facilitated, and the substrate containing the high-precision micro-nano material can be prepared.
Drawings
Fig. 1 is an optical microscope picture of a substrate having patterned structural units according to example 1 or example 2 of the present invention;
fig. 2 is a scanning electron microscope picture of a substrate with patterned micro-nano material of example 1 of the invention;
fig. 3 is a scanning electron microscope picture of a substrate with patterned micro-nano material of example 2 of the invention;
fig. 4 is a scanning electron microscope picture of a substrate with patterned micro-nano material of example 3 of the invention;
fig. 5 is a scanning electron microscope picture of a substrate of a patterned micro-nano material of example 4 of the invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for self-assembling a micro-nano material in a first aspect, which comprises the following steps:
(A) printing ink containing a polymer on the surface of a substrate with hydrophilicity, wherein the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate to obtain the substrate with the patterned structural units;
(B) dripping the assembly liquid containing the micro-nano material on the surface of the substrate with the patterned structure unit to obtain the substrate containing the assembly liquid;
(C) covering the substrate containing the assembly liquid with a cover plate with hydrophobicity, volatilizing or evaporating a solvent in the assembly liquid, and carrying out self-assembly on the micro-nano material at the edge of the patterning structure unit; then peeling the cover plate to obtain a substrate with the patterned micro-nano material;
alternatively, the first and second electrodes may be,
(A) printing ink containing a polymer on the surface of a substrate with hydrophilicity, wherein the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate to obtain the substrate with the patterned structural units;
(B) dripping the assembly liquid containing the micro-nano material on the surface of the substrate with the patterned structure unit to obtain the substrate containing the assembly liquid;
(C) covering the substrate containing the assembly liquid with a cover plate with hydrophobicity, volatilizing or evaporating a solvent in the assembly liquid, and carrying out self-assembly on the micro-nano material at the edge of the patterning structure unit; then peeling the cover plate to obtain a substrate with the patterned micro-nano material;
(D) and removing the patterned structural unit.
In the invention, the micro-nano material refers to a material with one dimension of length, width and height and with the size of micron and/or nanometer.
According to the method of the present invention, the method of printing may be an inkjet printing method, a direct printing method, or the like. For example, an ink containing a polymer is printed on a substrate surface having hydrophilicity by a direct write printing method with parameters set according to a target pattern. The accuracy of the printing depends on the requirements of the target product.
According to the method, the ink containing the polymer is printed on the surface of the substrate with hydrophilicity, and is naturally dried or dried, so that the solvent in the ink is volatilized, and the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate, so that the substrate with the patterned structural units is obtained.
According to the method of the present invention, the ink may contain a polymer and a solvent; preferably, the polymer is present in an amount of 10 to 80 vol% and the solvent is present in an amount of 20 to 90 vol%, based on the total volume of the ink.
According to the method of the present invention, the polymer may be a thermosetting resin and/or a photocurable resin. Specifically, the polymer may be one or more of polyvinyl alcohol, polystyrene, polycarbonate, photoresist, polymethyl methacrylate, and epoxy resin. The photoresist mainly comprises resin, photosensitizer, solvent and additive, wherein the resin is adhesive, the photosensitizer is a compound with extremely strong photoactivity, the content of the photosensitizer in the photoresist is equivalent to that of the resin, and the photosensitizer and the resin are dissolved in the solvent at the same time and stored in a liquid state for convenient use. The photoresist is conventional in the art, such as AZ1560 of the AZ series of photoresists, GM1070 of the SU8 series of photoresists. The photoresist may be a commercially available product.
According to the method of the present invention, the solvent in the ink is intended to be capable of dissolving the polymer, and may be, for example, one or more of ethanol, acetone, toluene, benzene, and chloroform.
According to the method, the assembly liquid can comprise a micro-nano material, a solvent and a surfactant. Preferably, the size of the micro-nano material is 1 nm-100 mu m, wherein the size refers to the size with one dimension of length, width and height being 1 nm-100 mu m.
According to the method, the content of the micro-nano material can be 0.1-3 wt%, the content of the solvent can be 96-99 wt%, and the content of the surfactant can be 0.01-1 wt% based on the total weight of the assembly liquid.
According to the method, the micro-nano material can be one or more of metal micro-nano particles, inorganic micro-nano particles, composite micro-nano particles of inorganic materials and metals, organic dye small molecules, polymer micro-nano particles, metal micro-nano lines and high polymer micro-nano materials. Further preferably, the material is one or more of silver micro-nano particles, platinum micro-nano particles, gold micro-nano particles, copper micro-nano particles, palladium micro-nano particles, cobalt micro-nano particles, nickel micro-nano particles, silver copper micro-nano particles, silver palladium micro-nano particles, silica micro-nano particles, composite micro-nano particles of silica and gold, InP/ZnS quantum dots, CdSe/ZnS quantum dots, rhodamine B, fluorescein sodium, fluorescent polystyrene spheres, silver micro-nano wires, copper micro-nano wires, platinum micro-nano wires, nickel micro-nano wires, gold platinum micro-nano wires, polythiophene, PEDOT (poly (3, 4-ethylenedioxythiophene)), polyaniline and polyphenylacetylene. Wherein, the polythiophene, the PEDOT, the polyaniline and the polyphenylacetylene only need to have the length, the width and the height with one dimension of micron and/or nanometer.
According to the method of the present invention, the solvent in the assembly liquid is used for dissolving the micro-nano material, and may be one or more of water, ethanol, acetone, anisole, chlorobenzene and petroleum ether.
According to the method of the present invention, the surfactant may be an anionic surfactant, a cationic surfactant, a zwitterionic surfactant or a nonionic surfactant, which are conventional in the art. Specifically, for example, the anionic surfactant may be one or more of sodium dodecylbenzene sulfonate, Sodium Dodecyl Sulfate (SDS), and stearic acid; the cationic surfactant may be a quaternary ammonium compound; the zwitterionic surfactant can be one or more of amino acid type zwitterionic surfactant, betaine type zwitterionic surfactant, polyacrylamide and lecithin; the non-ionic surfactant may be one or more of sorbitan fatty acid, glycerol fatty acid ester, polysorbate and tween.
According to the method of the invention, the substrate can be made of silicon wafer, glass sheet, quartz sheet, PET (polyethylene terephthalate) film, PS (polystyrene) film, PU (polyurethane) film, aluminum sheet, aluminum oxide sheet or PDMS (polydimethylsiloxane) film. Substrates having hydrophilicity the substrates may be subjected to a hydrophilic treatment resulting in a substrate having a contact angle of less than 90 °. The hydrophilic treatment method may be a treatment method conventional in the art, and may be, for example, oxygen plasma treatment, air plasma treatment, ultraviolet radiation treatment, piranha solution boiling treatment, or the like.
According to the method of the present invention, the shape of the structural unit may be one or more of a point, a straight line and a curved line. The plurality of structural units may be arranged in an array or in a non-array, depending on the requirements of the target pattern. The shape and height of the print is determined by the needs of the target product. For example, the height of each structural unit may be 100nm to 100 μm.
According to the method, the cover plate can be made of a silicon wafer, a glass sheet, a quartz sheet, a PET film, a PS film, a PU film, an aluminum sheet, an aluminum oxide sheet or a PDMS film. Specifically hydrophobic coverslips the coverslip may be subjected to a hydrophobic treatment, for example a chemical grafting hydrophobic treatment, to give a coverslip with a contact angle of greater than 90 °. Specifically, the hydrophobic treatment method may be performed by using a silane coupling agent, and the silane coupling agent may be one of 1H, 2H-perfluorodecyltrimethoxysilane, γ - (methacryloyloxy) propyltrimethoxysilane (GPTS), 3-Aminopropyltrimethoxysilane (APTS), n-octyltriethoxysilane (ots), and n-Decyltrichlorosilane (DTCS).
According to the method of the present invention, the removing of the patterned structural unit may include removing using a detergent. The detergent may be one or more of ethanol, acetone, ethylene glycol, isopropanol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, diacetone alcohol, tridecanol, tetradecanol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, xylene, dicyclohexyl, n-butanol, methyl ethyl ketone, dimethyl phthalate, and sorbitol.
The invention provides a substrate containing a micro-nano material prepared by the method, wherein the substrate comprises a substrate, a protruded polymer structure unit pattern formed on the surface of the substrate and a patterned micro-nano material formed at the edge of the polymer structure unit pattern, or the substrate comprises a substrate and a patterned micro-nano material formed on the surface of the substrate.
In the invention, the precision of the patterned micro-nano material can be 30 nm-100 μm. Wherein, the precision refers to the diameter or the line width, for example, when the shape of the structural unit is a point, the precision is the diameter; when the shape of the structural unit is a straight line and/or a curve, the accuracy is the line width. The precision of the patterned micro-nano material obtained by printing is related to the size and the concentration of the micro-nano material in the assembly liquid. The size of the micro-nano material, wherein the size refers to the diameter and/or the line width, for example, when the micro-nano material is a spherical material, for example, particles, the diameter is related; for example, when the micro-nano material is a linear material, for example, a metal micro-nano wire, the diameter is related.
The third aspect of the invention provides an application of the substrate containing the micro-nano material in a laser, a solar cell, a flexible sensing device or a light emitting diode.
For example, a substrate containing a micro-nano material obtained by using a silicon wafer as a substrate, GM1070 and acetone in SU8 as inks containing polymers and a fluorescent polystyrene bead aqueous solution added with SDS (sodium dodecyl sulfate) as an assembly liquid can be used as a laser;
for example, the substrate containing the micro-nano material obtained by using quartz glass as a substrate, GM1070 and acetone in SU8 as polymer-containing ink and SDS-added fluorescent polystyrene bead aqueous solution as an assembly liquid can be used as a laser.
The present invention will be described in detail below by way of examples.
AZ1560 photoresists were purchased from Wenchang chip technologies, Inc., Shanghai;
SU8-GM1070 from Shanxi information corporation;
PMMA is purchased from national medicine, the mark is CAS number 9011-14-7, and the weight-average molecular weight is 35000;
optical microscopes available from Nikon, Japan, under the model ECLIPSE Ti;
scanning Electron Microscope (SEM) from JEOL, JSM-7500F;
example 1
(A) A silicon wafer having a length of 5cm, a width of 5cm and a thickness of 1cm was treated with oxygen plasma at a power of 60W using a plasma cleaning machine (model YS-DT02S, obtained from Ompus plasma technology Co., Ltd., Suzhou) for 60 seconds to obtain a silicon wafer having hydrophilicity (contact angle of the silicon wafer: 30 ℃). Carrying out ultrasonic treatment on ink containing a polymer AZ1560 (the content of the AZ1560 polymer is 50 volume percent, and the content of an ethanol solvent is 50 volume percent), uniformly mixing the ink, and then dripping the ink into a sucking disc; setting array pattern parameters (structural units are straight lines) of 20 straight lines on a printer according to a target pattern, setting an array with the center-to-center distance of every two adjacent straight lines being 22 mu m, then enabling a capillary needle point to be close to a sucker dropping ink, sucking the ink into the needle point by using capillary action, directly printing polymer ink on a silicon wafer with hydrophilicity by using a direct-writing printing method, drying at 80 ℃, volatilizing solvent in the ink, forming a plurality of raised patterning straight lines on the surface of the substrate by using the polymer in the ink to obtain the substrate with the patterning straight lines, and observing the substrate through an optical microscope, wherein the deep lines in the image 1 are raised patterning structural units (formed by the polymer) as shown in the image 1;
(B) sucking 10 mu L of assembly liquid (the micro-nano material is silicon dioxide micro-nano particles, the average particle size is 200nm, the particle size range is 195 nm-205 nm, the content is 2 weight percent, the solvent is deionized water, the content is 97.9 weight percent, the surfactant is sodium dodecyl benzene sulfonate, the content is 0.1 weight percent) by using a micro-syringe to the surface of the substrate to obtain the substrate containing the assembly liquid;
(C) covering a substrate containing an assembly liquid with a hydrophobic glass sheet with a contact angle of 120 degrees to form a limited domain assembly system consisting of a hydrophobic cover sheet, the assembly liquid containing the micro-nano material and a patterned substrate, and carrying out self-assembly on the micro-nano material and a surfactant at the edge of the patterned structure unit along with the evaporation of a solvent (deionized water) in the assembly liquid; after the deionized water is completely evaporated, peeling off the cover plate to obtain a substrate with the patterned micro-nano material, wherein the line width of each line formed by the micro-nano material is 1 micrometer;
(D) and washing and removing the patterned straight line by using ethylene glycol ethyl ether, and observing the substrate with the patterned micro-nano material through a scanning electron microscope, wherein a white line in fig. 2 is the patterned micro-nano material, as shown in fig. 2.
Example 2
(A) A silicon wafer having a length of 5cm, a width of 5cm and a thickness of 1cm was treated with oxygen plasma at a power of 60W using a plasma cleaning machine (model YS-DT02S, obtained from Ompus plasma technology Co., Ltd., Suzhou) for 60 seconds to obtain a silicon wafer having hydrophilicity (contact angle of the silicon wafer: 30 ℃). Carrying out ultrasonic treatment on ink containing a polymer AZ1560 (the content of the AZ1560 polymer is 50 volume percent, and the content of an ethanol solvent is 50 volume percent), uniformly mixing the ink, and then dripping the ink into a sucking disc; setting array pattern parameters (structural units are straight lines) of 20 straight lines on a printer according to a target pattern, setting the center-to-center distance between every two adjacent straight lines to be an array of 20 micrometers, then enabling a capillary needle point to be close to a sucker dropping ink, sucking the ink into the needle point by using capillary action, directly printing polymer ink on a silicon wafer with hydrophilicity by using a direct writing printing method, drying at 80 ℃, volatilizing solvent in the ink, forming a plurality of raised patterning straight lines on the surface of the substrate by using the polymer in the ink to obtain the substrate with the patterning straight lines, and observing the substrate through an optical microscope, wherein the deep lines in the image 1 are raised patterning structural units (formed by the polymer) as shown in the image 1;
(B) sucking 10 mu L of assembly liquid (the micro-nano material is silicon dioxide micro-nano particles, the average particle size is 200nm, the particle size range is 195 nm-205 nm, the content is 2 weight percent, the solvent is deionized water, the content is 97.9 weight percent, the surfactant is sodium dodecyl benzene sulfonate, the content is 0.1 weight percent) by using a micro-syringe to the surface of the substrate to obtain the substrate containing the assembly liquid;
(C) covering a substrate containing an assembly liquid with a hydrophobic glass sheet with a contact angle of 120 degrees to form a limited domain assembly system consisting of a hydrophobic cover sheet, the assembly liquid containing the micro-nano material and a patterned substrate, and carrying out self-assembly on the micro-nano material and a surfactant at the edge of the patterned structure unit along with the evaporation of a solvent (deionized water) in the assembly liquid; after the deionized water is completely evaporated, peeling off the cover plate to obtain a substrate with the patterned micro-nano material, wherein the line width of each line formed by the micro-nano material is 1 micrometer; and observing the substrate with the patterned micro-nano material through a scanning electron microscope, as shown in fig. 3, wherein the white line in fig. 3 is the patterned micro-nano material.
Example 3
(A) A silicon wafer 5cm long by 5cm wide by 1cm thick was treated with oxygen plasma at a power of 300W for 300 seconds to obtain a hydrophilic silicon wafer (contact angle of silicon wafer 5 ℃ C.). Carrying out ultrasonic treatment on ink containing polymers SU8-GM1070 (the content of the SU8-GM1070 polymer is 80 volume percent, and the content of an acetone solvent is 20 volume percent) to uniformly mix the ink, and then dripping the ink into a sucking disc; setting array pattern parameters of 12 dots (structural units are dots, 3 dots are arranged in each line and 4 lines are arranged) on a printer according to a target pattern, setting the center-to-center distance between every two adjacent dots to be an array of 30 mu m, then enabling a capillary needle point to be close to a sucker dropping ink, sucking the ink into the needle point by using capillary action, directly printing polymer ink on a hydrophilic silicon wafer by using a direct writing printing method, naturally drying, volatilizing a solvent in the ink, and forming a plurality of raised patterned dots on the surface of a substrate by using a polymer in the ink to obtain the substrate with the patterned dots;
(B) sucking 10 mu L of assembly liquid (the micro-nano material is silver micro-nano particles, the average particle size of the particles is 200nm, the particle size range is 195 nm-205 nm, the content is 0.1 weight percent, the solvent is ethanol, the content is 98.9 weight percent, the surfactant is lecithin, and the content is 1 weight percent) by using a micro-injector on the surface of the substrate to obtain the substrate containing the assembly liquid;
(C) covering a substrate containing an assembly liquid with a hydrophobic glass sheet with a contact angle of 120 degrees to form a limited domain assembly system consisting of a hydrophobic cover sheet, the assembly liquid containing the micro-nano material and a patterned substrate, wherein the micro-nano material and a surfactant are self-assembled at the edge of the patterned structure unit along with volatilization of a solvent (ethanol) in the assembly liquid; stripping the cover plate after the ethanol is completely volatilized to obtain a substrate with the patterned micro-nano material,
(D) the patterned spots are washed and removed by using ethylene glycol ethyl ether, and a substrate with the patterned micro-nano material is observed by a scanning electron microscope, an electron microscope image of the patterned micro-nano material formed by one spot (structural unit) is shown in fig. 4, each white circle in fig. 4 is one micro-nano material, a circle consisting of 17 circles is 1 spot (structural unit, 1 spot in 12 spots) induced to form the patterned micro-nano material, and the diameter of each circle formed by the micro-nano material is 1 μm.
Example 4
(A) A silicon wafer 5cm long by 5cm wide by 1cm thick was treated with oxygen plasma at a power of 300W for 300 seconds to obtain a hydrophilic silicon wafer (contact angle of silicon wafer 5 ℃ C.). Carrying out ultrasonic treatment on ink containing polymers SU8-GM1070 (the content of the SU8-GM1070 polymer is 80 volume percent, and the content of an acetone solvent is 20 volume percent) to uniformly mix the ink, and then dripping the ink into a sucking disc; setting array pattern parameters of 12 dots (structural units are dots, 3 dots are arranged in each line and 4 lines are arranged) on a printer according to a target pattern, setting the center-to-center distance between every two adjacent dots to be an array of 30 mu m, then enabling a capillary needle point to be close to a sucker dropping ink, sucking the ink into the needle point by using capillary action, directly printing polymer ink on a hydrophilic silicon wafer by using a direct writing printing method, naturally drying, volatilizing a solvent in the ink, and forming a plurality of raised patterned dots on the surface of a substrate by using a polymer in the ink to obtain the substrate with the patterned dots;
(B) sucking 10 mu L of assembly liquid (the micro-nano material is silver micro-nano particles, the average particle size of the particles is 200nm, the particle size range is 195 nm-205 nm, the content is 3 wt%; the solvent is ethanol, the content is 96 wt%; the surfactant is lecithin, the content is 1 wt%) on the surface of the substrate by using a micro-injector to obtain the substrate containing the assembly liquid;
(C) covering a substrate containing an assembly liquid with a hydrophobic glass sheet with a contact angle of 120 degrees to form a limited domain assembly system consisting of a hydrophobic cover sheet, the assembly liquid containing the micro-nano material and a patterned substrate, wherein the micro-nano material and a surfactant are self-assembled at the edge of the patterned structure unit along with volatilization of a solvent (ethanol) in the assembly liquid; and after the ethanol is completely volatilized, peeling off the cover plate to obtain a substrate with the patterned micro-nano material, observing the substrate with the patterned micro-nano material through a scanning electron microscope, wherein an electron microscope image of the patterned micro-nano material formed by one point (structural unit) is shown in fig. 5, each white circle in fig. 5 is the micro-nano material, a circle consisting of 20 circles is the patterned micro-nano material formed by inducing 1 point (structural unit, 1 point in 12 points), the inside of the circle consisting of 20 circles is 1 structural unit (a raised patterned point formed on the surface of the substrate by a polymer in ink), and the diameter of each circle formed by the micro-nano material is 1 mu m.
Example 5
(A) Boiling a PS film with the length of cm, the width of 5cm and the thickness of 1cm for 2 hours by using a piranha solution (concentrated sulfuric acid with the mass fraction of 98 percent and hydrogen peroxide with the mass fraction of 30 percent in a volume ratio of 3:7) to obtain a silicon wafer with hydrophilicity (the contact angle of the silicon wafer is 8 degrees). Carrying out ultrasonic treatment on ink containing polymer PMMA (the content of PMMA polymer is 10 volume percent, and the content of acetone solvent is 90 volume percent), uniformly mixing the ink, and then dripping the ink into a sucker; setting pattern parameters (structural units are curves) of 10 curves on a printer according to a target pattern, directly printing polymer ink on a hydrophilic silicon wafer by using a direct-writing printing method, naturally drying, volatilizing a solvent in the ink, and forming a plurality of raised patterning curves on the surface of a substrate by using the polymer in the ink to obtain the substrate with the patterning curves;
(B) sucking 5 mu L of assembly liquid (the micro-nano material is silver micro-nano particles, the average particle size of the particles is 100 mu m, the particle size range is 95-105 mu m, the content is 2 wt%, the solvent is acetone, the content is 97.7 wt%, the surfactant is polysorbate, the content is 0.3 wt%) on the surface of the substrate by using a micro-injector to obtain the substrate containing the assembly liquid;
(C) covering a substrate containing an assembly liquid with a hydrophobic glass sheet with a contact angle of 120 degrees to form a limited domain assembly system consisting of a hydrophobic cover sheet, the assembly liquid containing the micro-nano material and a patterned substrate, wherein the micro-nano material and a surfactant are self-assembled at the edge of the patterned structure unit along with volatilization of a solvent (acetone) in the assembly liquid; after acetone is completely volatilized, peeling the cover plate to obtain a substrate with a patterned micro-nano material, wherein the line width of each curve formed by the micro-nano material is 100 micrometers;
(D) the patterned curve was washed away using ethanol.
Example 6
(A) Boiling a PS film with the length of cm, the width of 5cm and the thickness of 1cm for 2 hours by using a piranha solution (concentrated sulfuric acid with the mass fraction of 98 percent and hydrogen peroxide with the mass fraction of 30 percent in a volume ratio of 3:7) to obtain a silicon wafer with hydrophilicity (the contact angle of the silicon wafer is 8 degrees). Carrying out ultrasonic treatment on ink containing polymer PMMA (the content of PMMA polymer is 10 volume percent, and the content of acetone solvent is 90 volume percent), uniformly mixing the ink, and then dripping the ink into a sucker; setting pattern parameters (structural units are curves) of 10 curves on a printer according to a target pattern, directly printing polymer ink on a hydrophilic silicon wafer by using a direct-writing printing method, naturally drying, volatilizing a solvent in the ink, and forming a plurality of raised patterning curves on the surface of a substrate by using the polymer in the ink to obtain the substrate with the patterning curves;
(B) sucking 5 mu L of assembly liquid (the micro-nano material is silver micro-nano particles, the average particle size of the particles is 100 mu m, the particle size range is 95-105 mu m, the content is 2 wt%, the solvent is acetone, the content is 97.7 wt%, the surfactant is polysorbate, the content is 0.3 wt%) on the surface of the substrate by using a micro-injector to obtain the substrate containing the assembly liquid;
(C) covering a substrate containing an assembly liquid with a hydrophobic glass sheet with a contact angle of 120 degrees to form a limited domain assembly system consisting of a hydrophobic cover sheet, the assembly liquid containing the micro-nano material and a patterned substrate, wherein the micro-nano material and a surfactant are self-assembled at the edge of the patterned structure unit along with volatilization of a solvent (acetone) in the assembly liquid; after acetone is completely volatilized, peeling the cover plate to obtain a substrate with a patterned micro-nano material, wherein the line width of each curve formed by the micro-nano material is 100 micrometers;
(D) the patterned curve was washed away using ethanol.
Comparative example 1
According to the method of the embodiment 1, except that the substrate is not subjected to hydrophilic treatment, the prepared micro-nano structure is difficult to form a continuous and regular pattern, and large-area preparation is difficult to realize.
Comparative example 2
Following the procedure of example 1, except that the coverslip was not hydrophobically treated, the assembly fluid failed to shrink regularly on the substrate and a random structure formed on the coverslip.
The results of the embodiment and the comparative example show that the patterned micro-nano material can be controllably and efficiently prepared by adopting the method. The preparation method has the advantages of simplicity, rapidness, strong controllability, good uniformity, low preparation cost and convenience for large-scale production.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A method for self-assembling micro-nano materials comprises the following steps:
(A) printing ink containing a polymer on the surface of a substrate with hydrophilicity, wherein the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate to obtain the substrate with the patterned structural units;
(B) dripping the assembly liquid containing the micro-nano material on the surface of the substrate with the patterned structure unit to obtain the substrate containing the assembly liquid;
(C) covering the substrate containing the assembly liquid with a cover plate with hydrophobicity, volatilizing or evaporating a solvent in the assembly liquid, and carrying out self-assembly on the micro-nano material at the edge of the patterning structure unit; then peeling the cover plate to obtain a substrate with the patterned micro-nano material;
alternatively, the first and second electrodes may be,
(A) printing ink containing a polymer on the surface of a substrate with hydrophilicity, wherein the polymer in the ink forms a plurality of raised patterned structural units on the surface of the substrate to obtain the substrate with the patterned structural units;
(B) dripping the assembly liquid containing the micro-nano material on the surface of the substrate with the patterned structure unit to obtain the substrate containing the assembly liquid;
(C) covering the substrate containing the assembly liquid with a cover plate with hydrophobicity, volatilizing or evaporating a solvent in the assembly liquid, and carrying out self-assembly on the micro-nano material at the edge of the patterning structure unit; then peeling the cover plate to obtain a substrate with the patterned micro-nano material;
(D) removing the patterned structural unit;
wherein the ink contains a polymer and a solvent; based on the total volume of the ink, the content of the polymer is 10-80 vol%, and the content of the solvent is 20-90 vol%;
the polymer is a thermosetting resin and/or a light-curing resin;
the solvent is one or more of ethanol, acetone, toluene, benzene and chloroform.
2. The method of claim 1, the polymer being one or more of polyvinyl alcohol, polystyrene, polycarbonate, polymethyl methacrylate, and epoxy.
3. The method according to claim 1 or 2, wherein the assembly liquid comprises a micro-nano material, a solvent and a surfactant;
and/or the size of the micro-nano material is 1 nm-100 mu m;
and/or based on the total weight of the assembly liquid, the content of the micro-nano material is 0.1-3 wt%, the content of the solvent is 96-99 wt%, and the content of the surfactant is 0.01-1 wt%.
4. The method according to claim 3, wherein the micro-nano material is one or more of a metal micro-nano particle, an inorganic micro-nano particle, a composite micro-nano particle of an inorganic material and a metal, an organic dye small molecule, a metal micro-nano wire and a polymer micro-nano material;
and/or the solvent is one or more of water, ethanol, acetone, anisole, chlorobenzene and petroleum ether;
and/or the surfactant is an anionic surfactant, a cationic surfactant, a zwitterionic surfactant or a nonionic surfactant.
5. The method according to claim 4, wherein the micro-nano material is one or more of silver micro-nano particles, platinum micro-nano particles, gold micro-nano particles, copper micro-nano particles, palladium micro-nano particles, cobalt micro-nano particles, nickel micro-nano particles, silver copper micro-nano particles, silver palladium micro-nano particles, silica micro-nano particles, composite micro-nano particles of silica and gold, InP/ZnS quantum dots, CdSe/ZnS quantum dots, rhodamine B, fluorescein sodium, fluorescent polystyrene spheres, silver micro-nano wires, copper micro-nano wires, platinum micro-nano wires, nickel micro-nano wires, gold platinum micro-nano wires, polythiophene, PEDOT, polyaniline and polyphenylacetylene.
6. The method of claim 1 or 2, wherein the substrate is made of silicon wafer, glass sheet, quartz sheet, PET film, PS film, PU film, aluminum sheet, aluminum oxide sheet or PDMS film.
7. The method of claim 1 or 2, wherein the shape of the structural unit is one or more of a point, a straight line and a curved line.
8. The method of claim 1 or 2, wherein the cover sheet is made of silicon wafer, glass sheet, quartz sheet, PET film, PS film, PU film, aluminum sheet, aluminum oxide sheet or PDMS film.
9. The method of claim 1 or 2, wherein removing the patterned structural units comprises removing with a detergent.
10. The method of claim 9, wherein the detergent is one or more of ethanol, acetone, ethylene glycol, isopropanol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, diacetone alcohol, tridecanol, tetradecanol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, xylene, dicyclohexyl, n-butanol, methyl ethyl ketone, dimethyl phthalate, and sorbitol.
11. The substrate containing the micro-nano material prepared by the method of any one of claims 1 to 10, wherein the substrate comprises a substrate, a projected polymer structure unit pattern formed on the surface of the substrate and a patterned micro-nano material formed at the edge of the polymer structure unit pattern, or,
the substrate comprises a substrate and a patterned micro-nano material formed on the surface of the substrate.
12. The use of the substrate comprising micro-nano material according to claim 11 in a laser, a solar cell, a flexible sensing device or a light emitting diode.
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