CN1314544C - Thermal moulding method for making pattern on high-molecular film - Google Patents
Thermal moulding method for making pattern on high-molecular film Download PDFInfo
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- CN1314544C CN1314544C CNB021290156A CN02129015A CN1314544C CN 1314544 C CN1314544 C CN 1314544C CN B021290156 A CNB021290156 A CN B021290156A CN 02129015 A CN02129015 A CN 02129015A CN 1314544 C CN1314544 C CN 1314544C
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Abstract
The present invention relates to a method for making micropatterns on a macromolecular film by hot molding, which comprises the following steps that step 1, silicon rubber prepolymers and crosslinking agents thereof are used for pouring on the surface of an original hard template for hot-molding micropattern, and a soft stamp whose patterns are opposite to the patterns of the surface of the original hard template; step 2, the mixed solution of the epoxy resin prepolymers and the crosslinking agents are moved to the surface of the soft silicon rubber stamp, the soft stamp with the uncured epoxy resin solution inosculates with the surface of a substrate, and patterns complementary to the patterns on the soft stamp are obtained by curing at room temperature; step 3, the macromolecular hard template inosculates with the surface of a macromolecular film prepared by spin coating, put into a stamping device, heated, pressurized and cooled, the hard epoxy resin template is stripped, and the patterns opposite to the patterns on the surface of the hard epoxy resin template are obtained on the surface of the macromolecular film. The thickness of the macromolecular film is from 0.5 to 2 micrometers, and the macromolecular solution can be polymethylmethacrylate or poly methyl-butyl methyl acrylate.
Description
Technical field
Present technique belongs to a kind of hot-moulded patterning techniques, relates in particular to a kind of preparation method of hot-moulded macromolecule membrane micro-patterning.
Background technology
Along with the develop rapidly of art such as information technology, biotechnology, material science in recent years, people press for the technology of the inexpensive fast little pattern of making.Micro-patterning is the utilization photoetching technique on the traditional means, but photoetching technique has many shortcomings that can't overcome itself, as: precision is subjected to the influence of light scattering and can not breaks through the 100nm limit; Need complex apparatus and technology, complex process, thus cause the cost height; Be unsuitable for non-planar surfaces is carried out patterning, can only directly be used in (as photoresist) on the light-sensitive material, and can not the control surface chemical property etc.Therefore there is the researcher to propose the technology of hot-moulded micro-patterning.
Hot-moulded micro-patterning lithographic technique is a kind of simple, quick, high-precision macromolecule membrane micro-patterning technology.The work of the Stephen Y.Chou that reported among the Science in 1996 etc., and the work of the R.W.Jaszewski that reports among United States Patent (USP) 5772905 in 1998 and the Microelectronic Engineering etc., all introduced the technology that the method that adopts hot-moulded is made nanometer and micron pattern.The impression that adopts in above work about the hot-moulded micro-patterning all is to adopt monocrystalline silicon or allied substances with hard template, as silica or silicon nitride making material as hard template, and by the final hard template with micron and nano-scale figure that forms of processing methods such as electron beam lithography.Though the hard template durability that above method is made is strong, but its processing cost is quite expensive, and hard template is running stores, the access times of each hard template are limited, generally can only reach tens times, so the use of inorganic hard template has increased cost of processing undoubtedly, also limited the application in practice of this technology.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of hot-moulded macromolecule membrane micro-patterning.
For achieving the above object, the preparation method of hot-moulded macromolecule membrane micro-patterning provided by the invention, its key step is as follows:
1, the making of the soft seal of silicon rubber: after the performed polymer that the soft seal of silicon rubber adopts silicon rubber and its crosslinking agent mix according to 8: 1～15: 1 mass ratio and stir, at original hot-moulded micro-patterning hard template surface casting, under 50～65 ℃ of conditions, solidified 4～10 hours, to the complete crosslinking curing of silicon rubber, peel off, obtain the soft seal opposite with original hard template surfacial pattern.
2, the making of epoxy resin template: is after 2: 1～3: 1 ratio is mixed and stirred, mixed liquid to be transferred to the soft seal of silicon rubber surface with the solution of epoxy prepolymer and its crosslinking agent according to volume ratio, removes surperficial excess liquid.The soft seal and the substrate surface that will have uncured epoxy resin solution coincide, and at room temperature solidify 8～24 hours, and then soft seal is peeled off from patterned surface, obtains the figure with soft seal graphics complementation.The epoxy resin that is cured was further being solidified 1～12 hour under 120～180 ℃ of conditions, the figure of material is finalized the design fully and improving its mechanical performance.With the patterned surface evaporation layer of aluminum modification that is cured,, be convenient to hot-moulded patterning rear pattern plate and peel off to reduce even to eliminate the cementation on template surface patterned layer surface in the moulding process.
3, the making of patterning macromolecule membrane: the macromolecule membrane surface that at first macromolecule hard template and spin coating is made coincide and places autogram instrument, be warming up to 30～55 ℃ of the temperature of raising again after the macromolecule membrane vitrification point, kept 5～15 minutes, make the temperature stable homogeneous of each several part, on the macromolecule hard template, add the pressure of 1～6MPa again, keep after 10～20 minutes, stop heating and be cooled to rapidly under the macromolecule membrane vitrification point after 20～30 ℃, take out epoxy resin hard template and patterning macromolecule membrane, the epoxy resin hard template is peeled off, obtained having on the macromolecule membrane surface and the opposite figure of epoxy resin hard template surfacial pattern.
The method that macromolecule membrane can adopt Polymer Solution to pass through spin-coating film on planar substrates is made, and film thickness is at 0.5～2 micron.Polymer Solution can be polymethyl methacrylate or poly-methyl-butylacrylic acid methyl esters.
Because the present invention has adopted the patterning techniques that shifts little molding and common epoxy resin as raw material, make the processing technology of macromolecule hard template simple, the equipment that does not need complexity, costliness, easy to operate, the processing conditions gentleness, selectable wide ranges, the processing cost that this greatly reduces undoubtedly.
Description of drawings
Fig. 1 is the process schematic diagram of epoxy resin hard template of the present invention, and wherein: 1 is epoxy resin, and 2 is the soft seal of silicon rubber, and 3 are substrate.
Fig. 2 is for adopt shifting the soft seal of original hard template, silicon rubber that obtains in little molding methods process and the electron micrograph of epoxy resin hard template, and wherein 4 is original hard template, and 5 is the soft seal of silicon rubber, and 6 is the epoxy resin hard template.
The epoxy resin hard template behind the hot-moulded patterning that Fig. 3 obtains for the embodiment of the invention and the optical photograph of macromolecule membrane, wherein:
The epoxy resin hard template behind the 7 hot-moulded patternings that obtain for embodiment 1 and the optical photograph of PMMA film, the left side are the epoxy resin hard template, and the right is the PMMA film.
The epoxy resin hard template behind the 8 hot-moulded patternings that obtain for embodiment 2 and the optical photograph of PMMA film, the left side are the epoxy resin hard template, and the right is the PMMA film.
The epoxy resin hard template behind the 9 hot-moulded patternings that obtain for embodiment 3 and the optical photograph of PMMA film, the left side are the epoxy resin hard template, and the right is the PMMA film.
The optical photograph of epoxy resin hard template behind the 10 hot-moulded patternings that obtain for embodiment 4 and poly-methyl-butylacrylic acid methyl esters film, the left side are the epoxy resin hard template, and the right is poly-methyl-butylacrylic acid methyl film.
The specific embodiment
The silicon rubber that uses among following each embodiment be Sylgard 184 type silicon rubber produced in USA and and its supporting crosslinking agent, epoxy resin is the aliphatic chain epoxy resin that Nanjing, Shenyang fine chemicals company produces, epoxide number 0.47.
Embodiment 1:
See also Fig. 1, be the process schematic diagram of epoxy resin hard template of the present invention.After silicon rubber prepolymer and crosslinking agent thereof mixed according to 8: 1 mass ratio and stirring, after solidifying 10 hours under 50 ℃ of conditions, peel off, standby.Be to be applied to the soft seal of silicon rubber surface after 3: 1 the ratio mixing and stirring with this epoxy resin and its curing agent according to volume ratio.The soft seal and the monocrystal silicon substrate surface that will have uncured epoxy resin solution coincide, and room temperature condition solidifies after 8 hours down peels off soft seal, the epoxy resin figure after obtaining solidifying.Epoxy resin after solidifying is deepened to solidify 12 hours under 120 ℃ of environment, then carry out surface modification in surface vacuum evaporation layer of aluminum.Epoxy resin hard template of having handled well and the glass sheet surface that is loaded with polymethyl methacrylate film are coincide, together be positioned in the autogram instrument, kept after being warming up to 140 ℃ 5 minutes, and then added the pressure of 6MPa and kept 20 minutes, stop heating afterwards and be cooled to 80 ℃ rapidly.Take out epoxy resin hard template and PMMA film, the epoxy resin hard template is peeled off, obtain having and the opposite figure of epoxy resin hard template surfacial pattern at the PMMA film surface.7 for adopting the epoxy resin hard template behind the hot-moulded patterning that above condition processing obtains and the optical photograph of PMMA film among Fig. 3, and the left side is the epoxy resin hard template, and the right is the PMMA film.
Embodiment 2: after silicon rubber prepolymer and crosslinking agent thereof are mixed according to 10: 1 mass ratio and stirring, after solidifying 6 hours under 60 ℃ of conditions, peels off, and standby.Be to be applied to the soft seal of silicon rubber surface after 3: 1 the ratio mixing and stirring with this epoxy resin and its curing agent according to volume ratio.The soft seal and the monocrystal silicon substrate surface that will have uncured epoxy resin solution coincide, and room temperature condition solidifies after 12 hours down peels off soft seal, the epoxy resin figure after obtaining solidifying.Epoxy resin after solidifying is deepened to solidify 3 hours under 150 ℃ of environment, then carry out surface modification in surface vacuum evaporation layer of aluminum.The epoxy resin hard template of having handled well is coincide with being loaded with the sheet glass table of PMMA film, together be positioned in the autogram instrument, kept after being warming up to 150 ℃ 10 minutes, and then added the pressure of 3MPa and kept 15 minutes, stop heating afterwards and be cooled to 80 ℃ rapidly.Take out epoxy resin hard template and PMMA film, the epoxy resin hard template is peeled off, obtain having and the opposite figure of epoxy resin hard template surfacial pattern at the PMMA film surface.8 for adopting the epoxy resin hard template behind the hot-moulded patterning that above condition processing obtains and the optical photograph of PMMA film among Fig. 3, and the left side is the epoxy resin hard template, and the right is the PMMA film.
Embodiment 3: after silicon rubber prepolymer and crosslinking agent thereof are mixed according to 12: 1 mass ratio and stirring, after solidifying 4 hours under 65 ℃ of conditions, peels off, and standby.Be to be applied to the soft seal of silicon rubber surface after 2: 1 the ratio mixing and stirring with this epoxy resin and its curing agent according to volume ratio.The soft seal and the monocrystal silicon substrate surface that will have uncured epoxy resin solution coincide, and room temperature condition solidifies after 18 hours down peels off soft seal, the epoxy resin figure after obtaining solidifying.Epoxy resin after solidifying is deepened to solidify 2 hours under 160 ℃ of environment, then carry out surface modification in surface vacuum evaporation layer of aluminum.Epoxy resin hard template of having handled well and the glass sheet surface that is loaded with the PMMA film are coincide, together be positioned in the autogram instrument, kept after being warming up to 160 ℃ 10 minutes, and then added the pressure of 1MPa and kept 10 minutes, stop heating afterwards and be cooled to 85 ℃ rapidly.Take out epoxy resin hard template and PMMA film, the epoxy resin hard template is peeled off, obtain having and the opposite figure of epoxy resin hard template surfacial pattern at the PMMA film surface.9 for adopting the epoxy resin hard template behind the hot-moulded patterning that above condition processing obtains and the optical photograph of PMMA film among Fig. 3, and the left side is the epoxy resin hard template, and the right is the PMMA film.
Embodiment 4: after silicon rubber prepolymer and crosslinking agent thereof are mixed according to 15: 1 mass ratio and stirring, after solidifying 4 hours under 65 ℃ of conditions, peels off, and standby.Be to be applied to the soft seal of silicon rubber surface after 2: 1 the ratio mixing and stirring with this epoxy resin and its curing agent according to volume ratio.The soft seal and the monocrystal silicon substrate surface that will have uncured epoxy resin solution coincide, and room temperature condition solidifies after 24 hours down peels off soft seal, the epoxy resin figure after obtaining solidifying.Epoxy resin after solidifying is deepened to solidify 1 hour under 180 ℃ of environment, then carry out surface modification in surface vacuum evaporation layer of aluminum.Epoxy resin hard template of having handled well and the glass sheet surface that is loaded with poly-methyl-butylacrylic acid methyl esters film are coincide, together be positioned in the autogram instrument, kept after being warming up to 82 ℃ 10 minutes, and then added the pressure of 3MPa and kept 10 minutes, stop heating afterwards and be cooled to 32 ℃ rapidly.Take out epoxy resin hard template and poly-methyl-butylacrylic acid methyl esters film, the epoxy resin hard template is peeled off, obtain having and the opposite figure of epoxy resin hard template surfacial pattern at poly-methyl-butylacrylic acid methyl esters film surface.10 for adopting the epoxy resin hard template behind the hot-moulded patterning that above condition processing obtains and the optical photograph of poly-methyl-butylacrylic acid methyl esters film among Fig. 3, and the left side is the epoxy resin hard template, and the right is poly-methyl-butylacrylic acid methyl esters film.
Claims (5)
1, a kind of preparation method of hot-moulded macromolecule membrane micro-patterning, its key step is as follows:
The making of A, the soft seal of silicon rubber: after the performed polymer that the soft seal of silicon rubber adopts silicon rubber and its crosslinking agent mix according to 8: 1～15: 1 mass ratio and stir, at original hot-moulded micro-patterning hard template surface casting, under 50～65 ℃ of conditions, solidified 4～10 hours, to the complete crosslinking curing of silicon rubber, peel off, obtain the soft seal opposite with original hard template surfacial pattern;
The making of B, epoxy resin template: is after 2: 1～3: 1 ratio is mixed and stirred, mixed liquid to be transferred to the soft seal of silicon rubber surface with the solution of epoxy prepolymer and its crosslinking agent according to volume ratio; To have the soft seal of uncured epoxy resin solution and substrate surface and coincide, solidify under the room temperature 8～24 hours, soft seal will be peeled off from patterned surface, obtain having macromolecule hard template with soft seal graphics complementation;
C, the making of patterning macromolecule membrane: macromolecule hard template and the macromolecule membrane surface that is made by the Polymer Solution spin coating are coincide and place autogram instrument, be warming up to 30～50 ℃ of the temperature of raising again after the macromolecule membrane vitrification point, kept 5～15 minutes, make the temperature stable homogeneous of each several part, on the macromolecule hard template, add the pressure of 1～6MPa again, keep after 10～20 minutes, stop heating and be cooled to rapidly under the macromolecule membrane vitrification point after 20～30 ℃, take out epoxy resin hard template and patterning macromolecule membrane, the epoxy resin hard template is peeled off, obtained having on the macromolecule membrane surface and the opposite figure of epoxy resin hard template surfacial pattern.
2, preparation method as claimed in claim 1 is characterized in that, the epoxy resin that is cured among the step B further solidified 1～12 hour under 120～180 ℃ of conditions, the figure of material is finalized the design fully and improves its mechanical performance.
3, preparation method as claimed in claim 1 or 2, it is characterized in that, the patterned surface evaporation layer of aluminum of described macromolecule hard template, modification is carried out on its surface, to reduce even to eliminate the cementation of template surface and patterned layer surface in the moulding process, be convenient to hot-moulded patterning rear pattern plate and peel off.
4, preparation method as claimed in claim 1 is characterized in that, Polymer Solution described in the step C is polymethyl methacrylate or poly-methyl-butylacrylic acid methyl esters.
As claim 1 or 4 described preparation methods, it is characterized in that 5, described macromolecule membrane is Polymer Solution spin-coating film on planar substrates, film thickness is 0.5～2 micron.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021290156A CN1314544C (en) | 2002-08-28 | 2002-08-28 | Thermal moulding method for making pattern on high-molecular film |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021290156A CN1314544C (en) | 2002-08-28 | 2002-08-28 | Thermal moulding method for making pattern on high-molecular film |
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| CN1397432A CN1397432A (en) | 2003-02-19 |
| CN1314544C true CN1314544C (en) | 2007-05-09 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100444027C (en) * | 2006-07-07 | 2008-12-17 | 中国科学院长春应用化学研究所 | Method for making reverse ladder structure by using architecture-complementary micro-patterning technique |
| CN1888978B (en) * | 2006-07-20 | 2011-03-30 | 中国科学院长春应用化学研究所 | Photoetching patterning method with micro-transfer patterned graph as mask plate |
| TWI596404B (en) * | 2013-02-06 | 2017-08-21 | 財團法人工業技術研究院 | Film structure and manufacturing method for organic light-emitting diode display |
| CN109270696B (en) * | 2018-11-08 | 2021-02-09 | 宁波维真显示科技股份有限公司 | Preparation method of 3D film |
| CN111823697A (en) * | 2020-07-28 | 2020-10-27 | 李强 | Epoxy resin seal cutting art seal copying process |
| CN112175221B (en) * | 2020-09-18 | 2022-12-02 | 郑州大学 | Preparation method of surface-patterned piezoresistive electronic skin |
| CN117341370B (en) * | 2023-09-21 | 2024-04-05 | 浙江大学 | Preparation method of soft lithography seal attached to curved object without external force, product and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4606788A (en) * | 1984-04-12 | 1986-08-19 | Moran Peter L | Methods of and apparatus for forming conductive patterns on a substrate |
| US4731155A (en) * | 1987-04-15 | 1988-03-15 | General Electric Company | Process for forming a lithographic mask |
| JPH01196749A (en) * | 1988-01-30 | 1989-08-08 | Hoya Corp | Manufacture of substrate for optical information recording medium |
| US5277749A (en) * | 1991-10-17 | 1994-01-11 | International Business Machines Corporation | Methods and apparatus for relieving stress and resisting stencil delamination when performing lift-off processes that utilize high stress metals and/or multiple evaporation steps |
| US5772905A (en) * | 1995-11-15 | 1998-06-30 | Regents Of The University Of Minnesota | Nanoimprint lithography |
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2002
- 2002-08-28 CN CNB021290156A patent/CN1314544C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4606788A (en) * | 1984-04-12 | 1986-08-19 | Moran Peter L | Methods of and apparatus for forming conductive patterns on a substrate |
| US4731155A (en) * | 1987-04-15 | 1988-03-15 | General Electric Company | Process for forming a lithographic mask |
| JPH01196749A (en) * | 1988-01-30 | 1989-08-08 | Hoya Corp | Manufacture of substrate for optical information recording medium |
| US5277749A (en) * | 1991-10-17 | 1994-01-11 | International Business Machines Corporation | Methods and apparatus for relieving stress and resisting stencil delamination when performing lift-off processes that utilize high stress metals and/or multiple evaporation steps |
| US5772905A (en) * | 1995-11-15 | 1998-06-30 | Regents Of The University Of Minnesota | Nanoimprint lithography |
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