WO2018098801A1 - Method for patterning thermoplastic polymer by using room-temperature transfer imprinting technology - Google Patents

Abstract

Provided is a method for patterning a thermoplastic polymer by using a room-temperature transfer imprinting technology. The method comprises the following steps: firstly, dissolving a thermoplastic polymer solid in a solvent; then spin-coating or spraying the thermoplastic polymer solution onto a surface of a soft template; then making the surface of the thermoplastic polymer on the soft template hydrophilic; and finally, contacting the soft template obtained in the previous step with a hydrophilic substrate in a room-temperature environment, and transferring the polymer on the surface of the soft template to the surface of the substrate. The room-temperature transfer imprinting technology involved in the present invention can quickly pattern a thermoplastic polymer at normal temperature under normal pressure, and can achieve imprinting on surfaces of various substrates.

Description

 Method for patterning thermoplastic polymer by using room temperature transfer imprinting technology

 [0001] The present invention relates to the field of material micro/nano processing techniques, and more particularly to a method of patterning a thermoplastic polymer using room temperature transfer imprinting techniques.

 Background technique

 [0002] Patterned functional materials are increasingly used in electronics, optics, bionics, energy, etc. So far, there are a variety of techniques for patterning materials, such as lithography, nanoimprinting, Scanning probe technology, interface assembly technology, etc.

[0003] The patterning of thermoplastic polymers is typically achieved by nanoimprinting methods. The traditional nanoimprinting is hot stamping. It is a layer of thermoplastic polymer material, such as polymethyl methacrylate or polystyrene, which is heated onto the glass transition temperature (T _g ). The polymer is filled into the template cavity by mechanical pressurization; and then cooled to a pressure below _{Tg to} release the patterned material. CN105487151A reports a method for preparing a grating based on nanoimprinting pattern transfer; CN105619774A reports a method for preparing a superhydrophobic material based on hot stamping. However, these methods are only applicable to thermoplastic materials, high temperature and high pressure, high energy consumption, long inter-turn cycle, which is not conducive to mass production; and high temperature environment limits the patterning of thermoplastic materials on the surface of polymer substrates; Since the thermoplastic material is attached to the planar substrate by spin coating, the process is difficult to achieve on a non-flat substrate such as a curved surface, which affects subsequent imprinting.

 technical problem

 [0004] The object of the present invention is to overcome the shortcomings of high temperature and high pressure, long power consumption and expensive equipment in the conventional thermoplastic polymer patterning process, and to provide a method for efficiently patterning a thermoplastic polymer at room temperature. It realizes the normal temperature, normal pressure and rapid patterning of thermoplastic polymers, and is suitable for soft substrates, hard substrates, flat substrates and curved substrates, which is beneficial to the popularization of this method.

 Problem solution

 Technical solution

According to the technical solution provided by the present invention, the one is patterned by using room temperature transfer imprint technology. The method of polymer, characterized in that it comprises the following steps:

 [0006] (1) First, the thermoplastic polymer solid is dissolved into a solvent by ultrasonication and heating, and the solvent is selected according to a similarly compatible polarity principle to obtain a thermoplastic polymer solution;

[0007] (2) then spin coating or spraying a thermoplastic polymer solution on the surface of the soft template of the convex-concave structure, after the solvent is evaporated, to obtain a soft template with a thermoplastic polymer attached to the surface;

[0008] (3) then treating with a peroxygen plasma or ultraviolet ozone to produce a large amount of hydroxyl groups on the surface of the thermoplastic polymer on the soft template in the step (2), thereby achieving a hydrophilic effect;

[0009] (4) Finally, the soft template coated with the thermoplastic polymer on the surface treated by the step (3) is brought into contact with the hydrophilic substrate at room temperature, and the hydroxyl group on the surface of the thermoplastic polymer hydrogen bonds with the hydroxyl group on the surface of the substrate. After 5 to 600 s, the soft template is separated from the surface of the substrate, and the thermoplastic polymer on the surface of the soft template is transferred to the surface of the substrate.

 [0010] Further, the thermoplastic polymer in the step (1) includes polymethyl methacrylate, polystyrene, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polydibutylene, polyvinyl alcohol, polyphenylene. Ethylene-butadiene copolymer, poly-p-styrene-polyethylene oxide copolymer, ABS resin, polyacrylamide, polyethylene oxide

[0011] Further, the soft template in the steps (2), (3) and (4) comprises a polydimethylsiloxane template, an ethylene propylene diene rubber template, a perfluoropolyether template, and a urethane acrylate template.

 [0012] Further, the substrate in the step (4) comprises a planar and curved silicon wafer, a silicon oxide wafer, a gallium arsenide wafer, a quartz wafer, a conductive glass sheet, and a polymer sheet.

 [0013] Further, the hydrophilic substrate in the step (4) is obtained by treating the substrate with oxygen plasma, ultraviolet ozone or a hydrophilic aqueous solution.

 [0014] Further, the hydrophilic method of the solution treatment in the step (4) is to place the substrate in a mixed aqueous solution of ammonia water and hydrogen peroxide, or to place the substrate in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and heat at 50 to 90 ° C. Processing under conditions.

 [0015] Further, the room temperature in the step (4) is 0 to 40 °C.

 Advantageous effects of the invention

 Beneficial effect

[0016] The present invention has the following advantages: [0017] (1) The thermoplastic polymer is patterned at normal temperature and pressure to avoid the process of high temperature and high pressure energy consumption; [0018] (2) The thermoplastic polymer is not required to be expensive in the patterning process, and the power consumption is short. Improve the efficiency of patterning;

 (3) Patterning of the thermoplastic polymer on the surfaces of the planar substrate, the curved substrate, the hard substrate, and the soft substrate can be achieved.

 Brief description of the drawing

 DRAWINGS

 1 is a schematic view of a process for patterning a thermoplastic polymer using a room temperature transfer imprint technique;

 2 is an atomic force microscope photograph of a polymethyl methacrylate strip obtained in Example 1;

 3 is a micrograph of a polymethyl methacrylate strip obtained on the outer wall surface of the capillary tube in Example 2, wherein the inset is an enlarged view.

Embodiments of the invention

Embodiment 1

 [0024] Step 1: Dissolution of the thermoplastic polymer

 [0025] Polymethyl methacrylate (PMMA) solid was ultrasonically dissolved in an acetone solution to prepare a PMMA solution having a mass concentration of 2.5%.

Step 2: Preparation of soft template

 [0027] Weighing the prepolymer of polydimethylsiloxane (PDMS) and the initiator, the mass ratio is 10: 1, stirring and mixing

Then cast on a silicon template with a strip width of 3 μηι and a pitch of Ι μηι, cured at 60 °C

After curing, the PDMS is separated from the silicon template to obtain a PDMS soft template.

[0028] Step 3: Spin coating thermoplastic polymer on the surface of the soft template

[0029] at a rotation speed of 4000 rpm and a rotation time of 30

 Under the condition of s, the PMMA solution was spin-coated on the surface of the PDMS soft template to obtain PD with PMMA on the surface.

MS soft template.

 [0030] Step 4: The hydrophilicity of the thermoplastic polymer on the surface of the soft template

[0031] The PMMA on the surface of the PDMS is treated with oxygen plasma to ensure that the surface of the PMMA is hydrophilic, with the following conditions: The oxygen flow rate is 100 m! Jmin, the power is 45 W, and the daytime is 30 s. [0032] Step 5: Hydrophilic treatment of the substrate

 [0033] The silicon substrate is hydrolyzed by a solution method, specifically, a silicon wafer is placed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3, and heated at 90 ° C for 2 h. After taking out, rinse with distilled water and blow dry with nitrogen.

[0034] Step 6: Transfer of the polymer to the surface of the substrate

 [0035] The PDMS soft template with the hydrophilic PMMA attached to the surface obtained in the fourth step is contacted with the hydrophilic silicon substrate obtained in the step 5 at room temperature, after passing through 60

 After s, the PDMS is separated from the surface of the wafer substrate, and the PMMA on the PDMS surface is transferred to the surface of the substrate.

Embodiment 2

 [0037] Step 1: Dissolution of the thermoplastic polymer

 [0038] Polymethyl methacrylate (PMMA) solid was ultrasonically dissolved in an acetone solution to prepare a PMMA solution having a mass concentration of 2.5%.

[0039] Step 2: Preparation of soft template

 [0040] Weighing the prepolymer of polydimethylsiloxane (PDMS) and the initiator, the mass ratio is 10: 1, stirring and mixing

Then cast on a silicon template with a strip width of 3 μηι and a pitch of Ι μηι, cured at 60 °C

After curing, the PDMS is separated from the silicon template to obtain a PDMS soft template.

[0041] Step 3: Spin coating thermoplastic polymer on the surface of the soft template

[0042] at a rotation speed of 4000 rpm and a rotation time of 30

 Under the condition of s, the PMMA solution was spin-coated on the surface of the PDMS soft template to obtain PD with PMMA on the surface.

MS soft template.

 Step 4: The hydrophilicity of the thermoplastic polymer on the surface of the soft template

 [0044] The PMMA on the surface of the PDMS is treated with oxygen plasma to ensure the hydrophilicity of the PMMA surface under the following conditions: The oxygen flow rate is lOO m! Jmin, the power is 45 W, and the daytime is 30 s.

[0045] Step 5: Hydrophilic treatment of the substrate

 [0046] The outer wall of the capillary having a diameter of 10 mm was hydrolyzed by a solution method, specifically, a capillary solution was placed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3, and heated at 90 ° C for 2 h. After taking out, rinse with distilled water and blow dry with nitrogen.

 [0047] Step 6: Transfer of the polymer to the surface of the substrate

[0048] at room temperature, the surface obtained in step four is attached with a hydrophilic PMMA PDMS soft template and step 5 The resulting hydrophilic capillary is in contact with the outer wall, after passing through 200

 After s, the PDMS is separated from the surface of the outer wall of the capillary, and the PMMA on the surface of the PDMS is transferred to the surface of the outer wall of the capillary.

Example 3

 [0050] Step 1: Dissolution of the thermoplastic polymer

 [0051] The polystyrene (PS) solid was ultrasonically dissolved in an acetone solution to prepare a Ps solution having a mass concentration of 2%.

 [0052] Step 2: Preparation of Soft Template

 [0053] Weighing the prepolymer of polydimethylsiloxane (PDMS) and the initiator, the mass ratio is 10:1, stirring and mixing; then casting the silicon template with a strip width of 1 μηι and a pitch of Ι μηι Above, curing at 60 ° C; after curing, the PDMS is separated from the silicon template to obtain a PDMS soft template.

 [0054] Step 3: Spin coating thermoplastic polymer on the surface of the soft template

 [0055] Under the conditions of a rotation speed of 6000 rpm and a rotation of 60 s, the PS solution was spin-coated on the surface of the PDMS soft template to obtain a PDMS soft template with PS attached to the surface.

Step 4: Hydrophilic surface of the thermoplastic polymer on the soft template

 [0057] The PS of the surface of the PDMS is treated with oxygen plasma to ensure the hydrophilicity of the PMMA surface under the following conditions: the oxygen flow is 100 m! Jmin, the power is 45 W, and the daytime is 30 s.

[0058] Step 5: Hydrophilic treatment of the substrate

 [0059] The silicon substrate is hydrolyzed by a solution method, specifically, a silicon wafer is placed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3, and heated at 90 ° C for 2 h. After taking out, rinse with distilled water and blow dry with nitrogen.

[0060] Step 6: Transfer of the polymer to the surface of the substrate

 [0061] The PDMS soft template with the hydrophilic PS attached to the surface obtained in the step 4 is contacted with the hydrophilic silicon substrate obtained in the step 5 at room temperature, and after 30 s, the PDMS is separated from the surface of the silicon substrate. The PS of the PDMS surface is transferred to the surface of the substrate.

 Example 4

 [0063] Step 1: Dissolution of the thermoplastic polymer

[0064] The polymethyl methacrylate (PMMA) solid was ultrasonically dissolved in an acetone solution to prepare a PMMA solution having a mass concentration of 3%. Step 2: Preparation of Soft Template

 [0066] Weighing the prepolymer of polydimethylsiloxane (PDMS) and the initiator, the mass ratio is 10: 1, stirring and mixing

Then cast on a silicon template with a grid width of 1 μηι and a pitch of Ι μηι, cured at 60 °C

After curing, the PDMS is separated from the silicon template to obtain a PDMS soft template.

[0067] Step 3: Spin coating thermoplastic polymer on the surface of the soft template

[0068] at a rotation speed of 3000 rpm and a rotation time of 60

 Under the condition of s, the PMMA solution was spin-coated on the surface of the PDMS soft template to obtain PD with PMMA on the surface.

MS soft template.

 Step 4: Hydrophilic surface of the thermoplastic polymer

 [0070] The PMMA on the surface of the PDMS is treated with oxygen plasma to ensure the hydrophilicity of the PMMA surface under the following conditions: The oxygen flow rate is 100 m! Jmin, the power is 45 W, and the daytime is 30 s.

[0071] Step 5: Hydrophilic treatment of the substrate

 [0072] The conductive glass substrate is hydrophilic by a solution method, specifically, a conductive glass substrate is placed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3, and heated at 90 ° C for 2 h. After taking out, rinse with distilled water and blow dry with nitrogen.

 [0073] Step 6: Transfer of the polymer to the surface of the substrate

 [0074] The PDMS soft template with the hydrophilic PMMA attached to the surface obtained in the step 4 is contacted with the hydrophilic conductive glass substrate obtained in the step 5 at room temperature, and after 5 s, the PDMS is separated from the surface of the conductive glass substrate. The PMMA on the PDMS surface is transferred to the surface of the substrate.

 The above is a further detailed description of the present invention in connection with the specific preferred embodiments, and it is not intended that the specific embodiments of the invention are limited to the description. Many simple deductions or substitutions may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims

 Claim

A method of patterning a thermoplastic polymer using room temperature transfer imprinting techniques, comprising the steps of:

 (1) First, the thermoplastic polymer solid is dissolved into a solvent by ultrasonication and heating;

(2) then spin coating or spraying the thermoplastic polymer solution on the surface of the soft template having a convex-concave structure;

 (3) then hydrophilically treating the thermoplastic polymer on the surface of the soft template in step (2) by oxygen plasma or ultraviolet ozone;

 (4) Finally, the soft template with the thermoplastic polymer on the surface obtained in the step (3) is contacted with the hydrophilic substrate at room temperature, and after 5 to 600 s, the soft template is separated from the surface of the substrate, and the polymer on the surface of the soft template Transfer to the surface of the substrate.

The method for patterning a thermoplastic polymer by a room temperature transfer imprinting technique according to claim 1, wherein: the thermoplastic polymer in the step (1) comprises polymethyl methacrylate, polystyrene, polyurethane, polyethylene. , polypropylene, polyvinyl chloride, polydibutylene, polyvinyl alcohol, polystyrene-butadiene copolymer, poly-p-styrene-polyethylene oxide copolymer, ABS resin, polyacrylamide, polyethylene oxide .

A method of patterning a thermoplastic polymer using a room temperature transfer imprinting technique according to claim 1, wherein: the soft template in steps (2), (3) and (4) comprises a polydimethylsiloxane template , EPDM rubber template, perfluoropolyether template, urethane acrylate template.

The method for patterning a thermoplastic polymer by using a room temperature transfer imprinting technique according to claim 1, wherein: the substrate in the step (4) comprises a planar and curved silicon wafer, a silicon oxide wafer, a gallium arsenide wafer, and a quartz. Sheet, conductive glass, polymer sheet.

The method for patterning a thermoplastic polymer by a room temperature transfer imprinting technique according to claim 1, wherein: the hydrophilic substrate in the step (4) is obtained by treating the substrate with oxygen plasma, ultraviolet ozone or a hydrophilic aqueous solution. .

The hydrophilic aqueous solution treatment substrate according to claim 5, wherein: the substrate is placed in a mixed aqueous solution of ammonia water and hydrogen peroxide, or the substrate is placed in a mixture of concentrated sulfuric acid and hydrogen peroxide. In the solution, heat it at 50 ~ 90 °C.

[Claim 7] A method of patterning a thermoplastic polymer using a room temperature transfer imprinting technique according to claim 1, wherein: the room temperature in the step (4) is 0 to 40 °C.