CN100514185C - Method for making polymer self-supporting nano-micron-line - Google Patents

Abstract

The invention relates to a method for making polymer self-supporting nanometer wires, belonging to the technical field of polymer microstructure materials. First, make a master plate with a micro-patterned surface of undulating stripes; mix the silicone prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly, pour it on the surface of the above master plate, remove the master plate after curing, and obtain a polymer Soft stamp; the polymer is dissolved in a solvent as an ink solution, the soft stamp is immersed in the ink solution, and then the soft stamp is imprinted on the substrate, the soft stamp is lifted, and the polymer cured by the ink solution is obtained on the substrate The micropattern of undulating stripes; the substrate was etched with hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires. Using the method of the invention to replace the conventional process to produce polymer self-supporting nano-micro wires (including polymer micro wires) has the advantages of simple process, low cost, high efficiency and controllability, and wide application.

Description

A method of making polymer self-supporting nanometer wires

technical field

The invention relates to a method for making polymer self-supporting nanometer wires, belonging to the technical field of polymer microstructure materials.

Background technique

One-dimensional nano-microstructured materials, including nano-microscale wires, tubes, rods, ribbons, etc., have attracted great attention due to their special optical, electrical, thermal and mechanical properties. Nano-micro-wire is the most typical structure among one-dimensional nano-micro materials, and has broad application prospects in many fields such as scientific research, production, and life, such as sensors, micromachines, microwires, and microelectronic devices.

Existing methods for making nano-micro wires generally only target one or several specific materials, and are not universally applicable. Moreover, the reported nano-micro wires are mainly limited to materials such as metals, metal oxides, semiconductor materials, and inorganic materials, and only a few conductive polymers are involved in the polymer materials. The general-purpose polymer (including conductive polymer, azo polymer material, and other commercial polymers, etc.) self-supporting nano-micro wire fabrication method has not been reported yet.

At present, a kind of nano-micro wire production method that has been studied is the micro-contact printing method (Chinese patent, publication number CN1672100): by transferring a small molecule containing an adsorbable functional group to the target surface through a stamping template, an adsorbed self-printing method is formed. Assembling monolayer stripe patterns, monolayer nanowires with lateral dimensions in the range of 1-100 nanometers can be fabricated. The disadvantage of this method is that only specific adsorbable small molecules can be used, and three-dimensional nano-micro-wires cannot be obtained, and this method cannot obtain self-supporting nano-micro-structures, only nano-micro-wires fixed on the substrate can be obtained.

Soft printing technology is a new method of making three-dimensional microstructures developed in recent years. It uses elastic soft stamps (commonly polydimethylsiloxane) to prepare microstructures, and its core uses soft stamps as the transfer of micropatterns. Intermediary: For example, the undulating structure on the surface of the mother board can be copied to the soft stamp by replica molding, and then the soft stamp can absorb the polymer solution for imprinting, so as to realize the molecular transfer or the construction of the nano-micron structure.

Contents of the invention

The purpose of the present invention is to propose a method for making polymer self-supporting nano-micro wires, using the existing soft printing technology and wet chemical etching to make polymer self-supporting nano-micro wires, so that the preparation process is simple and the preparation cost is low. The structure of the nanometer wire is controllable and the production efficiency is high.

The method for making polymer self-supporting nanometer wires proposed by the present invention comprises the following steps:

(1) making a master plate with a micro-patterned surface of undulating stripes;

(2) Making soft stamps: Mix the silicone prepolymer of polydimethylsiloxane and the silicone crosslinking agent in a mass ratio of 3:1 to 20:1, pour it on the surface of the above-mentioned motherboard, and let it stand for 4 to 10 minutes. After 10 minutes, heat to 20°C-80°C, react for 1-8 hours, remove the mother board after curing, and obtain a soft seal;

(3) Embossing ink solution: immerse the above-mentioned soft seal in the ink solution, then emboss the soft seal on the substrate, lift the soft seal, and obtain the undulating stripe micropattern of the polymer solidified by the ink solution on the substrate ;

(4) Etching the substrate: Etching the substrate with hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

The method for making polymer self-supporting nano-micron wires proposed by the present invention uses a polymer elastomer to replicate a micro-patterned surface of undulating stripes (such as azo polymer surface undulating gratings, a patterned surface prepared by photolithography, and a friction method. Micro-grooved surface, etc.) as a soft stamp, dissolved in polymer materials (such as polyimide, epoxy resin, polymethacrylate, azo polymer, conductive polymer and other general polymers, etc.) As an "ink" solution in a solvent, and then use a soft stamp to imprint the "ink" solution on a substrate (such as glass, silicon wafer, quartz, etc.) to obtain a nano-micron-scale stripe micropattern of the polymer, and then pass through the etchant (such as hydrofluoric acid) etch to remove the substrate and peel off the self-supporting nano-micron wires of the polymer. It replaces conventional methods for making polymer self-supporting nano-micro wires (including polymer micro-wires), and has the advantages of simple process, low cost, high efficiency and controllability, and wide application.

Description of drawings

Fig. 1 is the schematic diagram of the process of the method for making polymer self-supporting nano-micro wires proposed by the present invention, wherein (a) is the mother board made in step (1) of the method, wherein 1 represents the mother board; (b) is the polymer Pouring onto the motherboard for curing, where 2 represents the cured soft stamp; (c) is the soft stamp obtained after peeling off the motherboard; (d) is the soft stamp immersed in the ink solution, where 3 represents the ink solution; (e) It is to emboss the soft stamp on the substrate, wherein 4 represents the substrate; (f) is to remove the soft stamp and obtain a polymer micropattern on the substrate, wherein 5 represents the polymer after the ink solution is cured; (g) is to pass hydrogen After etching the substrate with hydrofluoric acid, the obtained polymer self-supporting nanometer wire.

Detailed ways

The process of the method for making polymer self-supporting nano-micro wires proposed by the present invention is shown in Figure 1. First, a master plate with a micro-patterned surface of undulating stripes is produced, as shown in Figure 1(a).

The manufacturing method of above-mentioned mother board can have following multiple:

a. Dissolve 0.05-2 grams of epoxy resin-based azo polymer in 1 ml of N, N-dimethylformamide, filter the solution with a 0.2 micron needle filter, and then spin-coat the filtered solution on a glass slide Form a film and dry at 40-80°C for 2-48 hours to obtain an epoxy resin-based azo polymer film with a smooth surface; irradiate the azo polymer film with two beams of P-polarized interference 488nm Ar ⁺ laser for 5-60 minutes, an epoxy resin-based azo polymer film with surface relief gratings is obtained, which can be used as a master plate with surface relief micro-nano patterns. The structural formula of the above-mentioned epoxy resin-based azo polymer is:

b. Dissolve 0.05-1 g of photosensitive polymer in 1 ml of N, N-dimethylformamide, filter the solution with a 0.2-micron needle filter, and spin-coat the filtered solution on a glass slide to form a film, 40-80 ℃ dry 2 ~ 48h. Then put the chrome-plated patterned photomask close on the spin-coated film, and expose it under ultraviolet light for 5-40 minutes. After exposure, the spin-coated film is soaked in acetone (or tetrahydrofuran) for 10-60s, and finally dried at 40-80°C for 2-48 hours to obtain a master plate with surface relief micro-patterns. The above-mentioned photosensitive polymer can be photopolymerized by the following structural formula Material (graft rate is 30%):

c, commercial photoresist: HPR photoresist No. 15 (polyvinyl alcohol cinnamate No. 15) or photoresist No. 16 (polyvinyl alcohol oxyacetaldehyde cinnamate No. 16) or photoresist BP218 ( 300), after steps such as gluing, exposure, development, fixing, drying, etc., the finally obtained surface relief micro-pattern is used as a master. The specific equipment, process conditions and parameters adopted in the method can be realized by conventional techniques in the field of photolithography;

d. Chromium-plated patterned template (usually used as a UV mask in photolithography technology), which can be purchased directly.

Then make the female mold soft stamp of the above-mentioned undulating stripe micro-pattern: the silica gel prepolymer of polydimethylsiloxane (sylgard 184, purchased from Dow Corning company) and silica gel crosslinking agent are in mass ratio 3:1～20: 1 Mix evenly, pour it on the surface of the mother board with the micro-pattern of undulating stripes, let it stand for 4 to 10 minutes, and then heat and solidify, as shown in Figure 1(b), the curing reaction temperature is 40°C to 80°C, and the reaction time is 1 ~ 8 hours; or stand at room temperature for 8 hours after pouring to let it solidify naturally. The soft stamp can be obtained by peeling off the mother board after curing, as shown in Figure 1(c).

The polymer is dissolved in a solvent, and this solution is used as an ink solution for soft stamps. The above-mentioned soft stamp is immersed in the ink solution, after the soft stamp absorbs the ink solution, as shown in Figure 1 (d), then the soft stamp is embossed on the substrate, as shown in Figure 1 (e), keeping the soft stamp and the substrate The surface is in close contact, and the soft stamp is lifted after a few seconds, and the undulating stripe micropattern of the polymer cured by the ink solution is obtained on the substrate, as shown in Figure 1(f), where the substrate is glass, silicon or quartz Any of the tablets; the ink solution therein is any of the following soluble polymer solutions:

a, tetrahydrofuran solution of epoxy resin-based azo polymer, concentration 0.05～20 g/liter;

b. Tetrahydrofuran solution of polystyrene, concentration 0.1-25 g/L;

c. Toluene solution of polystyrene, concentration 0.1-25 g/L;

d, poly(3-hexylthiophene) toluene solution, concentration 0.05～25 g/liter;

E, the chloroform solution of poly(3-hexylthiophene), concentration 0.1～15 grams/liter;

f. Dichloromethane solution of polyaniline, concentration 0.3-20 g/L;

G, the chloroform solution of polyaniline, concentration 0.2～25 grams/liter;

h, tetrahydrofuran solution of polyethylene, concentration 0.1～15 g/liter;

i, tetrahydrofuran solution of bisphenol A type epoxy resin, concentration 0.2～10 g/liter;

j, N,N-dimethylformamide solution of polyimide, concentration 0.2～15 g/liter;

k, toluene solution of polymethyl methacrylate, concentration 0.2～10 g/liter;

1. N,N-dimethylformamide solution of polyimide containing isosorbide structural unit, concentration 0.05～30 g/liter;

m, ethanol solution of polyacrylic acid random polymer substituted by chalcone, concentration 0.1～20 g/liter;

n, ethanol solution of polyacrylic acid random polymer substituted by chalcone, concentration 0.1～20 g/liter;

o. An ethanol solution of polyacrylic acid random polymer substituted by cinnamic acid, with a concentration of 0.1-20 g/L.

Finally, the substrate is etched with an aqueous solution of hydrofluoric acid to obtain polymer self-supporting nanometer wires, as shown in Figure 1(g). Etching can be done in either of two ways:

a. Put the substrate in a plastic container, with the polymer microstripe side facing up, slowly add hydrofluoric acid with a concentration of 0.05-30% to exceed the upper surface of the quartz substrate, and wait until the polymer microstripe structure is peeled off from the substrate out, that is, to obtain the corresponding self-supporting nano-micron wire of the polymer. Adding hydrofluoric acid to the side of the micro-stripe structure to make the etching proceed along the side direction of the surface micro-stripe structure (that is, the direction of etching entering is perpendicular to the extension direction of the nano-micro-stripe structure) is a more favorable way, and better results can be obtained. Nanowire stripping results. After the etching is completed, the polymer self-supporting nano-micron wires can be transferred to other target substrates or liquid surfaces as needed;

b. Add hydrofluoric acid with a concentration of 0.1 to 30% into a plastic container, and slowly immerse the inclined substrate (the side with the polymer pattern facing up) into the hydrofluoric acid to peel off the microstripe structure of the polymer from the substrate , so as to obtain self-supporting nano-micron wires of polymers. Immersing in hydrofluoric acid along the direction perpendicular to the extending direction of the microstripes, so that the etching is carried out along the side direction of the microstripes structure is a more favorable way, which can obtain better nano-micro-line stripping results. After the etching is completed, the polymer self-supporting nano-micron wires can be transferred to other target substrates or liquid surfaces as required.

Introduce the embodiment of the present invention below:

Example 1

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to get a soft seal;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of a kind of epoxy resin base azo polymer that concentration is 5 grams/liter, then this soft seal is embossed on the glass substrate, keeps After the soft seal is in close contact with the surface of the substrate for a few seconds, the soft seal is lifted, and a micro-pattern of polymer stripes is obtained on the substrate; the structural formula of the epoxy resin-based azo polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 2

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, remove the mother board after curing to get a soft seal;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of a kind of epoxy resin base azo polymer that concentration is 0.5 g/liter, then this soft seal is embossed on the glass substrate, keeps After the soft seal is in close contact with the surface of the substrate for a few seconds, the soft seal is lifted, and a micro-pattern of polymer stripes is obtained on the substrate; the structural formula of the epoxy resin-based azo polymer is:

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 3

(1) Using the process (c) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, remove the mother board after curing to get a soft seal;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of a kind of epoxy resin base azo polymer that concentration is 15 grams per liter, then this soft seal is embossed on the glass substrate, keeps After the soft seal is in close contact with the surface of the substrate for a few seconds, the soft seal is lifted, and a micro-pattern of polymer stripes is obtained on the substrate; the structural formula of the epoxy resin-based azo polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 4

(1) using the process (d) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 80°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of polystyrene (purchased in Alfa AESAR company, molecular weight 100000) that concentration is 5 g/liter, then this soft seal is embossed on glass substrate Keep the soft stamp in close contact with the surface of the substrate for a few seconds and then lift the soft stamp to obtain a micropattern of polymer undulating stripes on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 5

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of polystyrene (purchased in Alfa AESAR company, molecular weight 100000) that concentration is 0.5 g/liter, then this soft seal is embossed on glass substrate Keep the soft stamp in close contact with the surface of the substrate for a few seconds and then lift the soft stamp to obtain a micropattern of polymer undulating stripes on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 6

(1) Using the process (c) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of polystyrene (purchased in Alfa AESAR company, molecular weight 100 000) that concentration is 15 grams per liter, then this soft seal is embossed on glass On the substrate, keep the soft stamp in close contact with the surface of the substrate for a few seconds and then lift the soft stamp to obtain a polymer undulating stripe micropattern on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 7

(1) using the process (d) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of polystyrene (purchased in Alfa AESAR company, molecular weight 100000) that concentration is 5 grams per liter, then this soft seal is embossed on glass substrate Keep the soft stamp in close contact with the surface of the substrate for a few seconds and then lift the soft stamp to obtain a micropattern of polymer undulating stripes on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 8

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of polystyrene (purchased in Alfa AESAR company, molecular weight 100000) that concentration is 0.5 g/liter, then this soft seal is embossed on glass substrate Keep the soft stamp in close contact with the surface of the substrate for a few seconds and then lift the soft stamp to obtain a micropattern of polymer undulating stripes on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 9

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of polystyrene (purchased in Alfa AESAR company, molecular weight 100000) that concentration is 15 grams per liter, then this soft seal is embossed on glass substrate Keep the soft stamp in close contact with the surface of the substrate for a few seconds and then lift the soft stamp to obtain a micropattern of polymer undulating stripes on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 10

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(Method 3 of etching the substrate with the above-mentioned hydrofluoric acid aqueous solution) The above-mentioned soft stamp is immersed in an ink solution, which is chloroform of poly(3-hexylthiophene) with a concentration of 5 g/liter, and then the soft stamp is The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 11

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the chloroform of poly(3-hexylthiophene) that concentration is 0.5 g/liter, then this soft seal is embossed on the glass substrate, keeps soft seal After being in close contact with the surface of the substrate for a few seconds, the soft stamp is lifted, and a micro pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 12

(1) Using the process (c) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the trichloromethane that concentration is the poly(3-hexylthiophene) of 15 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal After being in close contact with the surface of the substrate for a few seconds, the soft stamp is lifted, and a micro pattern of polymer undulating stripes is obtained on the substrate;

(4) process (a) in the method for etching substrate with above-mentioned hydrofluoric acid aqueous solution, obtain polymerized Supports nanometer wires.

Example 13

(1) using the process (d) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of poly(3-hexylthiophene) that concentration is 5 grams/liter, then this soft seal is embossed on the glass substrate, keeps soft seal and After a few seconds of close contact with the surface of the substrate, the soft seal is lifted, and a micro-pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 14

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of poly(3-hexylthiophene) that concentration is 0.5 g/liter, then this soft seal is embossed on the glass substrate, keeps soft seal and After a few seconds of close contact with the surface of the substrate, the soft seal is lifted, and a micro-pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 15

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of poly(3-hexylthiophene) that concentration is 15 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal and After a few seconds of close contact with the surface of the substrate, the soft seal is lifted, and a micro-pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 16

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the trichloromethane solution that concentration is the polyaniline of 5 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate surface closely After a few seconds of contact, the soft stamp is lifted to obtain a micropattern of undulating stripes of polymer on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 17

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the trichloromethane solution that concentration is the polyaniline of 0.5 g/liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate surface closely After a few seconds of contact, the soft stamp is lifted to obtain a micropattern of undulating stripes of polymer on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 18

(1) Using the process (c) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the chloroform solution that concentration is the polyaniline of 15 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate surface closely After a few seconds of contact, the soft stamp is lifted to obtain a micropattern of undulating stripes of polymer on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 19

(1) using the process (d) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the dichloromethane solution that concentration is the polyaniline of 5 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate surface closely After a few seconds of contact, the soft stamp is lifted to obtain a micropattern of undulating stripes of polymer on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 20

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the dichloromethane solution that concentration is the polyaniline of 0.5 g/liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate surface closely After a few seconds of contact, the soft stamp is lifted to obtain a micropattern of undulating stripes of polymer on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 21

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the dichloromethane solution that concentration is the polyaniline of 15 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate surface closely After a few seconds of contact, the soft stamp is lifted to obtain a micropattern of undulating stripes of polymer on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 22

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) Dip the above-mentioned soft stamp into the ink solution, which is a tetrahydrofuran solution of polyethylene with a concentration of 15 grams per liter, and then emboss the soft stamp on the glass substrate, keeping the soft stamp in close contact with the surface of the substrate for a few seconds After a few minutes, the soft stamp was lifted to obtain a micro-pattern of undulating stripes of the polymer on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 23

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) Dip the above-mentioned soft stamp into the ink solution, which is a tetrahydrofuran solution of polyethylene with a concentration of 0.5 g/L, and then emboss the soft stamp on the glass substrate, keeping the soft stamp in close contact with the surface of the substrate for a few seconds After a few minutes, the soft stamp was lifted to obtain a micro-pattern of undulating stripes of the polymer on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 24

(1) Using the process (c) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of the bisphenol A type epoxy resin that concentration is 15 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal and After a few seconds of close contact with the surface of the substrate, the soft seal is lifted, and a micro-pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 25

(1) using the process (d) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the tetrahydrofuran solution of the bisphenol A type epoxy resin that concentration is 0.5 g/liter, then this soft seal is embossed on the glass substrate, keeps soft seal and After a few seconds of close contact with the surface of the substrate, the soft seal is lifted, and a micro-pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 26

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the N, N-dimethylformamide solution of polyimide that concentration is 0.5 g/liter, then this soft seal is embossed on the glass substrate , keeping the soft stamp in close contact with the surface of the substrate for a few seconds and then lifting the soft stamp to obtain a polymer undulating stripe micropattern on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 27

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the N, N-dimethylformamide solution of polyimide that concentration is 15 grams per liter, then this soft seal is embossed on the glass substrate , keeping the soft stamp in close contact with the surface of the substrate for a few seconds and then lifting the soft stamp to obtain a polymer undulating stripe micropattern on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 28

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of the polymethyl methacrylate that concentration is 15 grams per liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate After the surface is in close contact for a few seconds, the soft stamp is lifted, and a micro-pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 29

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the toluene solution of the polymethyl methacrylate that concentration is 0.5 g/liter, then this soft seal is embossed on the glass substrate, keeps soft seal and substrate After the surface is in close contact for a few seconds, the soft stamp is lifted, and a micro-pattern of polymer undulating stripes is obtained on the substrate;

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 30

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the N, N-dimethylformamide solution of the polyimide containing isosorbide structural unit that concentration is 15 grams per liter, then this soft seal The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate; the structural formula of the polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 31

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the N, N-dimethylformamide solution of the polyimide that contains isosorbide structural unit that concentration is 0.5 g/liter, then this soft seal The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate; the structural formula of the polymer is:

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 32

(1) Using the process (c) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the N, N-dimethylformamide solution of the polyimide containing isosorbide structural unit that concentration is 5 grams/liter, then this soft seal The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate; the structural formula of the polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 33

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the ethanol solution of the chalcone-substituted polyacrylic acid random polymer (graft rate 30%) that concentration is 15 g/liter, then this soft seal The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate; the structural formula of the polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 34

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) the above-mentioned soft seal is immersed in the ink solution, and this ink solution is the ethanol solution of the chalcone-substituted polyacrylic acid random polymer (graft rate 30%) whose concentration is 0.5 g/liter, and then the soft seal The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate; the structural formula of the polymer is:

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 35

(1) Using the process (c) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) above-mentioned soft seal is immersed in the ink solution, and this ink solution is the ethanol solution of the chalcone-substituted polyacrylic acid random polymer (graft rate 30%) that concentration is 15 g/liter, then this soft seal The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate; the structural formula of the polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 36

(1) using the process (d) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 5:1, pour it on the surface of the above-mentioned motherboard, let it stand for 5 minutes, heat it to 60°C, and react After 1 hour, remove the mother board after curing to obtain a polymer soft stamp;

(3) the above-mentioned soft seal is immersed in the ink solution, and this ink solution is the ethanol solution of the chalcone-substituted polyacrylic acid random polymer (graft rate 30%) whose concentration is 0.5 g/liter, and then the soft seal The stamp is imprinted on the glass substrate, and the soft stamp is kept in close contact with the surface of the substrate for a few seconds, then the soft stamp is lifted, and a polymer undulating stripe micro-pattern is obtained on the substrate; the structural formula of the polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 37

(1) Using the process (a) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel crosslinking agent evenly at a mass ratio of 10:1, pour it on the surface of the above-mentioned mother board, let it stand for 8 minutes, heat it to 50°C, and react After 2 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) The above-mentioned soft seal is immersed in the ink solution, and this ink solution is the ethanol solution of the polyacrylic acid random polymer (graft rate 30%) that the cinnamic acid replaces with concentration of 0.5 g/liter, then the soft seal Embossed on the glass substrate, keep the soft seal in close contact with the surface of the substrate for a few seconds, then lift the soft seal, and obtain a micro-pattern of polymer stripes on the substrate; the structural formula of the polymer is:

(4) Process (b) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Example 38

(1) Using the process (b) in the above-mentioned method for making a master plate to make a master plate with a micro-patterned surface of undulating stripes;

(2) Mix the silica gel prepolymer of polydimethylsiloxane and the silica gel cross-linking agent evenly at a mass ratio of 15:1, pour it on the surface of the above-mentioned motherboard, let it stand for 10 minutes, heat it to 40°C, and react After 4 hours, the mother board is removed after curing to obtain a polymer soft stamp;

(3) The above-mentioned soft seal is immersed in the ink solution, and this ink solution is the ethanol solution of the polyacrylic acid random polymer (grafting rate 30%) that the cinnamic acid replaces with concentration of 15 grams per liter, then the soft seal Embossed on the glass substrate, keep the soft seal in close contact with the surface of the substrate for a few seconds, then lift the soft seal, and obtain a micro-pattern of polymer stripes on the substrate; the structural formula of the polymer is:

(4) Process (a) in the method of etching the substrate with the above hydrofluoric acid aqueous solution to obtain polymer self-supporting nanometer wires.

Transfer the polymer self-supporting nano-micron wires produced in the above-mentioned embodiments to a glass plate, observe under a polarizing microscope, or use a scanning electron microscope, transmission electron microscope and atomic force microscope to observe, and you can observe that the polymer self-supporting nano-micron wires Wire. The above results show that this is an effective new method for rapidly fabricating polymer self-supporting nanowires.

Claims (3)

1, a kind of method of making polymer self-supporting nano-micron-line is characterized in that, this method may further comprise the steps:

(1) make the motherboard with the little patterned surfaces of fluctuating striped, the method for making of motherboard is:

Epoxy resin-matrix azobenzene polymer 0.05～2 gram is dissolved in 1 milliliter of N, in the dinethylformamide, solution filters with 0.2 micron syringe filters, the solution spin-coating film on glass sheet after will filtering then, 40～80 ℃ of dryings 2～48 hours obtain the azobenzene polymer film; 488 nanometer Ar with two bundle P polarization interferences ⁺Laser radiation azobenzene polymer film, 5～60 minutes time, obtain having the azobenzene polymer film motherboard of surface relief grating, wherein the structural formula of epoxy resin-matrix azobenzene polymer is:

Or: photopolymer 0.05～1 gram is dissolved in 1 milliliter of N, in the dinethylformamide, solution filters with 0.2 micron syringe filters, with the solution spin-coating film on glass sheet after filtering, 40～80 ℃ of dryings 2～48 hours, patterning photomask with chromium plating is placed on the spin-coating film then, under ultraviolet lamp, exposed 5～40 minutes, spin-coating film after the exposure soaked in acetone or tetrahydrofuran 10～60 seconds, last 40～80 ℃ of dryings 2～48 hours, obtain having the motherboard of the little pattern of surface undulation, photopolymer wherein has following structural formula, and percent grafting is 30%:

(2) make soft seal: the silica gel performed polymer and the silica gel agent of dimethyl silicone polymer are mixed by mass ratio 3:1～20:1, are poured on the above-mentioned motherboard surface, leave standstill 4～10 minutes after, be heated to 40 ℃～80 ℃, reacted 1～8 hour, and threw off motherboard after the curing, obtain soft seal;

(3) impression ink solution: above-mentioned soft seal is immersed in the ink solution, should be stamped on the substrate by soft seal then, uncover soft seal, at the little pattern of fluctuating striped that obtains on the substrate by the polymkeric substance after the ink solution curing, wherein said substrate is any one in glass sheet, silicon chip or the piezoid;

(4) etch substrate: use the hydrofluoric acid aqueous solution etch substrate, obtain polymer self-supporting nano-micron-line.

2, the method for claim 1 is characterized in that wherein said ink solution is any one in the following polymer solution:

The tetrahydrofuran solution of a, epoxy resin-matrix azobenzene polymer, concentration 0.05～20 grams per liter;

The tetrahydrofuran solution of b, polystyrene, concentration 0.1～25 grams per liter;

The toluene solution of c, polystyrene, concentration 0.1～25 grams per liter;

The toluene solution of d, poly-(3-hexyl thiophene), concentration 0.05～25 grams per liter;

The chloroform soln of e, poly-(3-hexyl thiophene), concentration 0.1～15 grams per liter;

The dichloromethane solution of f, polyaniline, concentration 0.3～20 grams per liter;

The chloroform soln of g, polyaniline, concentration 0.2～25 grams per liter;

H, poly tetrahydrofuran solution, concentration 0.1～15 grams per liter;

The tetrahydrofuran solution of i, bisphenol A type epoxy resin, concentration 0.2～10 grams per liter;

The N of j, polyimide, dinethylformamide solution, concentration 0.2～15 grams per liter;

The toluene solution of k, polymethylmethacrylate, concentration 0.2～10 grams per liter;

L, contain the N of the polyimide of isobide structural unit, dinethylformamide solution, concentration 0.05～30 grams per liter;

The ethanolic solution of the polyacrylic acid atactic polymers that m, chalcone replace, concentration 0.1～20 grams per liter;

The ethanolic solution of the polyacrylic acid atactic polymers that n, chalcone replace, concentration 0.1～20 grams per liter;

The ethanolic solution of the polyacrylic acid atactic polymers that o, cinnamic acid replace, concentration 0.1～20 grams per liter.

3, the method for claim 1 is characterized in that wherein said method with the hydrofluoric acid aqueous solution etch substrate is:

Substrate is placed in the vessel, has one of micro polymer striped to face up, slowly add concentration and be 0.05～30% hydrofluorite, treat that little striated structure of polymkeric substance is peeled off from substrate, promptly obtain polymer self-supporting nano-micron-line to surpassing upper surface of base plate;

Or: with concentration is that 0.1～30% hydrofluorite adds in the vessel, and the inclination substrate faces up one of polymer pattern, immerses slowly in the hydrofluorite, and little striated structure of polymkeric substance is peeled off from substrate, obtains polymer self-supporting nano-micron-line.

Images