KR20130055419A - Method for micro polymer patterns on different substrates - Google Patents

Abstract

PURPOSE: A manufacturing method of a micropolymer pattern is provided to control polymer patterns according to the moderate ratio of solvent and non-solvent, based on solubility parameter of the polymer. CONSTITUTION: A manufacturing method of a micropolymer pattern on a substrate comprises a step of manufacturing a mixed solvent by diluting solvent by nonsolvent; a step of manufacturing a polymer solution by dissolving the polymer resin into the mixed liquid; and a step of coating a substrate with the polymer solution and drying the coated substrate. The solvent is acetone, acetic acid, aniline, arylamine, benzene, bromobenzene, chloroform, chloroethane, chlrorobenzene, chlorohexanol, ethylbenzene, ethoxyethane, hexane, methyl acetate, N-methyl-2-pyrrolidone, 2- pyrrolidone, pyridine, p-dioxane, tetrahydrofuran, or toluene.

Description

Methods for manufacturing micropolymer patterns on various substrates {Method for micro polymer patterns on different substrates}

The present invention relates to a method of manufacturing a micropolymer pattern on various substrates.

Patterned and functionalized polymer surface fabrication is of increasing interest due to the potential for microfluidics, microelectromechanical systems, polymer electronics, multifunctional coatings and biotechnology. Patterned polymer surfaces can be easily processed to provide a method of manufacturing that reduces the cost used to pattern other types of surfaces, such as metals or ceramics.

Micro patterning, which is essential for the manufacture of typical semiconductors and displays, is usually micropatterned by photolithography. However, because photolithography is expensive and consumes a large amount of energy and materials, non-photolithographic techniques such as micro contact printing (μCP), inkjet printing, and screen printing methods have been described for manufacturing micro patterns. Inkjet printing or screen printing methods are not suitable for producing micropatterns of 10 μm or less. Micro-contact printing (μCP) is a technique that can directly obtain micropatterns with a minimum of 10 μm or less without etching. Microcontact printing (μCP) technology is mainly applied to patterning for self-assembled monolayers (SAMs).

Imprint lithography techniques disclosed in many publications and patents include the formation of layer-embossed patterns possible with polymers and transferring the pattern corresponding to the embossed pattern on a base substrate. The substrate may be coupled to a substrate chuck and a motion step to obtain a position that enables the patterning process.

Block copolymers (BCPs) consist of two or more chemically different polymer chains at the end of a polymer. The unfavorable action between pieces in a block creates a periodic array of spherical, cylindrical or layered microdomains of several tens of nanometers in size depending on the volume ratio of the blocks in the microphase separation of the BCP. BCP templates are used in polarizers, templates for microelectronic integrated circuits, magnetic media and optical waveguides. The key to using block copolymers (BCPs) is to control the lattice order and orientation of the microdomains on thin films. Recent external fields, shear, temperature gradients, graphoepitaxy, chemically patterned materials, limited interfacial interactions, zone casting, optical alignment, or Many approaches have been developed by enhanced process of lattice ordering and process control of microdomains applied to solvent fields, but most methods are time consuming and expensive.

U.S.A. Patent No. 2004-0065976

Accordingly, the inventors have invented a method of manufacturing micropatterns on various substrates in a short time by using a solvent and a nonsolvent system.

The present invention relates to a method for producing a micropolymer pattern on a different substrate in a single step, and more specifically, (a) diluting the solvent in a non-solvent to prepare a mixed solvent; (b) dissolving a polymer resin in the mixed solution to prepare a polymer solution; And (c) coating the polymer solution on a substrate and then drying it;

It relates to a method for producing a micropolymer pattern on a substrate comprising a.

The polymer pattern of the present invention can be adjusted according to an appropriate ratio of solvent and non-solvent based on the solubility parameter of the polymer, and can be manufactured at low cost.

In addition, the present invention can be applied to the manufacture of semiconductors and displays, it is possible to prepare a biocompatible material interface.

1 shows a scanning electron microscope (SEM) image of a substrate on which a micropolymer is patterned.

The present invention relates to a simple method for producing a micropolymer pattern on a variety of substrates in a single step. More specifically,

(a) diluting the solvent in a non-solvent to produce a mixed solvent; (b) dissolving a polymer resin in the mixed solution to prepare a polymer solution; And (c) coating the polymer solution on a substrate and then drying it;

It relates to a method for producing a micropolymer pattern on a substrate comprising a.

Examples of the solvent include, but are not limited to, acetone, acetic acid, aniline, allylamine, benzene, bromobenzene, chloroform, and chloroethane. (chloroethane), chlorobenzene, chlorohexanol, ethylbenzene, ethoxyethane, hexane, methyl acetate, N-methyl-2-pyrroli N-methyl-2-pyrrolidone, 2-pyrrolidone, pyridine, p-dioxane, tetrahydrofuran or toluene have.

The non-solvent is not limited to this, butanol (butanol), 1-butoxybutane (1-butoxybutane), 1,3-butanediol (1,3-butanediol), cyclohexanol, ethanol (ethanol) , Ethylene glycol, formamide, 1-pentanol, 2-isopropoxypropane, isopropyl alcohol, methanol or water Can be.

In the step (a), it may include preparing 1 to 100 vol% mixed solvent by diluting 1 to 10 solvents with 1 to 10 non-solvents, wherein the volume ratio of the solvent and the non-solvent is 1 To 100: 1 to 100.

The solvent and nonsolvent can be prepared in an appropriate ratio of solvent and nonsolvent using solubility parameters as indicators. The solubility constant value in the present invention is the solubility constant is hildeo brand (Hidebrand) define, when the absolute value of the separated solvent and non-solvent ^{5 J 1/2 / cm 3} /2 may not be the permanent application, Depending on Hansen's three-dimensional solubility constants, the relative energy difference between the solvent and the polymer solute is calculated and this is a solvent if it falls within the interaction radius, and if it is beyond that range, it is a nonsolvent. Can be defined.

The solvent may be used as a solvent or a non-solvent, depending on the type of polymer resin. If the absolute value of the solubility constant value difference of the solubility constant of the selected polymer resins of the selected solvent is difficult to dissolve the polymeric resin selected exceeding ^{5 J 1/2 / cm 3} /2 , the said selected solvent is used as a non-solvent, On the contrary, when the absolute value of the difference between the solubility constant of the selected solvent and the solubility constant of the selected polymer resin is 5 J ^1/2 / cm ^3/2 or less, it can be used as a solvent when the selected polymer resin is easily dissolved. As an example, when the solubility constant of the polymer resin 15 J of ^{1/2 /} cm ^3/2, the solubility constant value of ^{17 J 1/2 / cm 3} /2 in the solvent is the absolute of the difference between the polymer resin and the solubility constant value is ^{5 J 1/2 / cm 3} /2 or less because it can be used as a solvent, the solubility constant value of 21 J ^1/2 / cm ^3/2 of the case of the solvent, the polymer resin and the solubility of the absolute value of the difference of a constant value Since it exceeds 5 J ^1/2 / cm ^3/2 , it can be used as a non-solvent.

The polymer resin is not limited thereto, but polystyrene (PS), polypropylene (PP), polyethylene (PE, PE), polymethyl methacrylate (PMMA), polylactic acid (PLA) ), Polyethylene terephthalate (PET), polyvinyl chloride (PVC), polycarbonate (PC), or polyvinylidene fluoride (PVDF).

Dissolving the polymer resin in the mixed solution in step (b) may include preparing a 0.01 to 50 wt% polymer solution.

The substrate is not limited thereto, but may include aluminum sheets, ceramics, common glass, copper, polymer sheets, FTO glass, and silicon wafers. ), Silver sheet or zinc sheet.

When the polymer pattern is manufactured as the coating and drying processes are sequentially performed in the step (c), the coating method may include a doctor blade, a bar coating, a dip coating, or a spin coating. (spin coating).

When using the doctor blade coating method, it can be coated at a rate of 0.5 to 200 mm / sec, in the case of bar coating is shown in Table 1 the relationship between the thickness of the coating layer and the coating bar. The immersion coating may include coating for 1 second to 30 minutes at a speed of 0.1 μm / sec to 200 mm / sec. In addition, the spin coating may be coated at a speed of 50 to 5000 rpm.

The depth and size of the micropolymer pattern well according to the present invention may be deeper and larger from the top layer to the bottom layer, and the thickness of the polymer resin may be thicker as the coating bar number increases.

NO . ㎛ NO . ㎛ 3 # 6.86 12 # 27.4 4# 9.14 14 # 32.0 5 # 11.4 16 # 36.6 6 # 13.7 18 # 41.1 7 # 16.0 20 # 45.7 8# 18.3 22 # 50.3 9 # 20.6 24 # 54.8 10 # 22.9 26 # 59.4

Drying in the step (c) may be dried for 1 to 48 hours at 0 to 100 ℃.

The micropolymer pattern according to the present invention can be easily formed and controlled on a substrate when compared to other kinds of templates, in which the polymer pattern is based on the solubility parameter of the polymer. As it is prepared in the proper ratio of solvent and non-solvent, it can be easily adjusted to produce a hexagonal or round pattern of polymer.

The micro-patterned surface according to the present invention does not provide simple unique properties but is an intelligent surface that can selectively affect various functions applied to biocompatible materials, surface engineering, photonics and sensor systems. Can serve as

1 shows a runner electron microscope (SEM) image of a substrate on which a micropolymer is patterned. The topmost polymer pattern was determined by the type of polymer, the concentration between the solvent and the nonsolvent, and the polymer concentration. With the right conditions of the solvent / non-solvent mixture and the right polymer, it is possible to make the desired polymer pattern.

In one embodiment of the present invention, the micropolymer pattern may be a large area micropolymer pattern. The large area may be a large area of 1 mm ² to several m ² .

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are intended to illustrate the contents of the present invention, but the scope of the present invention is not limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

< Example >

Example 1

In the process of producing a micro PS pattern on a copper foil, more specifically, three solvents were diluted with two non-solvents to prepare a 20 wt% mixed solvent. PS resin was dissolved in the mixed solution to prepare a 20 wt% PS solution. The mixed solvent was spin coated on a copper foil at 3000 rpm and then dried at 70 ° C. for 24 hours.

At this time, pyridine, benzene and toluene were used as solvents, and ethanol and formamide were used as nonsolvents. The volume ratio of the solvent was 1: 4: 5 and the volume ratio of the nonsolvent was 2: 3.

Example 2

In the process of producing a micro PMMA pattern on the silicon wafer, more specifically, four solvents were diluted with ethanol to prepare a 50 vol% mixed solvent. PMMA resin was dissolved in the mixed solution to prepare a 5 wt% PMMA solution. The silicon wafer was immersed in the PMMA solution vertically for 10 minutes. The silicon wafer was removed at a rate of 50 mm / sec and dried at 50 ° C. for 9 hours.

At this time, benzene, p-dioxene, tetrahydrofuran and toluene were used as the solvent, where the volume ratio of the solvent was 1: 5: 2: 7.

Example 3

In the process of producing a micro PVDF pattern on the FTO glass, more specifically, five solvents were diluted with three non-solvents to prepare an 80 vol% mixed solvent. PVDF resin was dissolved in the mixed solution to prepare a 25 wt% PVDF solution. The PVDF solution was coated with 10 # bar on FTO glass and dried at 100 ° C. for 24 hours.

At this time, 2-pyrrolidine, pyridine, p-dioxene, tetrahydrofuran and toluene were used as solvents, and 2-isopropoxypropane, water and ethanol were used as nonsolvents. Here, the volume ratio of the solvent was 1: 7: 3: 5: 2, and the volume ratio of the nonsolvent was 4: 6: 5.

Example 4

In the process of preparing a micro PLA pattern on silver, more specifically, three solvents were diluted with four non-solvents to prepare a 15 vol% mixed solvent. PLA resin was dissolved in the mixture to prepare a 4 wt% PLA solution. PLA solution was coated on silver at a rate of 5 mm / sec with doctor blade and then dried at 65 ° C. for 5 hours.

At this time, tetrahydrofuran, bromobenzene and chloroform were used as solvents, and cyclohexanol, methanol, ethanol and water were used as nonsolvents. The volume ratio of the solvent was 5: 2: 3 and the volume ratio of the nonsolvent was 2: 1: 3: 5.

Example 5

In the process of producing a micro PS pattern on the PET plate, more specifically, two solvents were diluted with two non-solvents to prepare a 35 vol% mixed solvent. PS resin was dissolved in the mixture to prepare a 23 wt% PS solution. The PS solution was coated with 7 # bars on PET and dried at 55 ° C. for 10 hours.

At this time, tetrahydrofuran and toluene were used as solvents, and water and ethanol were used as nonsolvents. The volume ratio of the solvent was 1: 7 and the volume ratio of the nonsolvent was 4: 6.

Example 6

In the process of producing a micro PLA pattern on the copper foil, more specifically, chloroform and methanol to prepare a mixed solvent using a magnetic bar in a volume ratio of 17: 3. PLA resin was dissolved in the mixture to prepare a 1 wt% PLA solution. PLA-coated copper foil was vertically immersed in the mixed solvent for 10 seconds. The copper foil was removed at a rate of 30 mm / sec and then dried at 25 ° C. for 1 hour.

The results of this example are shown in FIG. The polymer was patterned into polygons. Such a pattern may be usefully used for structural control and synthesis of various electrode materials through additional deposition, sputtering, or plating processes.

Claims (10)

(a) diluting the solvent in a non-solvent to produce a mixed solvent; (b) dissolving a polymer resin in the mixed solution to prepare a polymer solution; And (c) coating the polymer solution on a substrate and then drying it;
Method of producing a micropolymer pattern on a substrate comprising a. The method of claim 1, wherein the solvent is acetone, acetic acid, aniline, allylamine, benzene, bromobenzene, chloroform, chloroethane, chlorobenzene, chlorohexanol, ethylbenzene, ethoxyethane, hexane, methyl acetate, N- Methyl-2-pyrrolidone, 2-pyrrolidone, pyridine, p-dioxene, tetrahydrofuran or toluene. The method of claim 1, wherein the non-solvent is butanol, 1-butoxybutane, 1,3-butanediol, cyclohexanol, ethanol, ethylene glycol, formamide, 1-pentanol, 2-isopropoxypropane, isopropyl alcohol Method for producing a micropolymer pattern on a substrate, characterized in that, methanol or water. The method of claim 1, wherein in step (a), 1 to 10 solvents are diluted with 1 to 10 non-solvents to prepare 1 to 100 vol% mixed solvent. How to make. The method of claim 1, wherein the volume ratio of the solvent and the non-solvent is 1 to 100: 1 to 100. The substrate of claim 1, wherein the polymer resin is polystyrene, polypropylene, polyethylene, polymethyl methacrylate, polylactic acid, polyethylene terephthalate, polyvinyl chloride, polycarbonate, or polyvinylidene fluoride. A method of making a micropolymer pattern thereon. The method of claim 1, wherein in step (b), the polymer resin is dissolved in a mixed solution to prepare a 0.01-50 wt% polymer solution. The method of claim 1, wherein the substrate is an aluminum substrate, ceramic, glass, copper, polymer substrate, FTO glass, silicon wafer, silver or zinc substrate. The method of claim 1, wherein the coating of step (C) is a doctor blade, a bar coating, a dip coating or a spin coating. A method of making a polymer pattern. The method of claim 1, wherein the drying in step (C) is from 1 to 48 hours at 0 to 100 ° C. 6.

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