CN102053489B - Mercaptan-alkene based high-precision ultraviolet imprinting method of continuous embossment micro optical elements - Google Patents
Mercaptan-alkene based high-precision ultraviolet imprinting method of continuous embossment micro optical elements Download PDFInfo
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- CN102053489B CN102053489B CN 201010533159 CN201010533159A CN102053489B CN 102053489 B CN102053489 B CN 102053489B CN 201010533159 CN201010533159 CN 201010533159 CN 201010533159 A CN201010533159 A CN 201010533159A CN 102053489 B CN102053489 B CN 102053489B
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Abstract
The invention discloses a mercaptan-alkene based high-precision ultraviolet imprinting method of continuous embossment micro optical elements, belonging to the field of manufacturing micro optical elements. The method provided by the invention is characterized in that based on the traditional ultraviolet imprinting process of continuous embossment micro optical elements, a mercaptan-alkene class ultraviolet light initiated high polymer material is utilized as etchant resist; shrinkage stress generated by etchant resist solidification is relaxed in a fluid flow mode by utilizing a method of adjusting the imprinting pressure and controlling the adhesive residue thickness; the shrinkage error of the continuous embossment micro optical element is lowered to below 3%; and the adhesive residue thickness is 500-1000nm. The method has the characteristics of small copying shrinkage error, good etching selectivity and the like, and can be used for realizing graph transmission to a quartz glass substrate by the continuous embossment micro optical element.
Description
Technical field
The invention belongs to the micro optical element manufacturing approach, relate to the method for application of a kind of ultraviolet stamping based on mercaptan-alkene class superpolymer with anticorrosive additive material.
Background technology
The development of micro-optic makes optical system produce deep change.The hyperfine structure diffraction optical element is to realize optical system microminiaturization, array, integrated important component part.The process technology of this type of diffraction optical element is one of gordian technique of micro-optic.
Existing Microstructure Optics element process technology mainly contains multilayer cover lithography, gray scale mask technology, direct electronic beam writing technology, laser direct-writing technology, reproduction technology etc.Wherein, nanometer embossing is a kind of high resolution, low cost, high efficiency Microstructure Optics element processing reproduction technology.
Nanometer embossing mainly is divided into two kinds of hot press printing technology and ultraviolet stamping technology, Comparatively speaking, has more wide application prospect but the ultraviolet stamping technology has advantages such as the simple rapid batch of equipment duplicates.
The volumetric contraction of ultraviolet stamping resist in solidification process will produce very big influence to the accuracy of repetition of continuous relief structure micro-optical element; And mainly show as the contraction of Z direction, the bigger contraction of Z direction will produce very big influence for the diffraction efficiency of micro optical element.Traditional ultraviolet stamping technology mainly adopts the light-initiated macromolecular material of esters of acrylic acid to use (US 2005/0160934 A1) as resist, and the volumetric shrinkage of this type of material in solidification process can be up to 15%.Using the vinyl ethers material to make resist can make cure shrinkage obtain very big reduction (E.K.Kim; M.D.Stewart; K.Wu; Et al.Vinyl ether formulations for step and flash imprint lithography.Journal of Vacuum Science & Technology is (6) B.2005.23: 2967-2971.), but there are problems such as big knockout press and higher monomer vapours pressure in such glue, thereby application receives very big restriction.In resist, introduce epoxies ring-opening polymerization monomer and can compensate (J.J.Hao effectively contraction; M.W.Lin; F.Palmieri; Et al.Photocurable silicon-based materials for imprint lithography-art.no.651729.in Emerging Lithographic Technologies XI; But still can not solve the influence of cure shrinkage completely Pts 1 and 2.M.J.Lercel.Editor.2007.Spie-Int Soc Optical Engineering:Bellingham.51729-51729), to the ultraviolet stamping accuracy of repetition.
Mercaptan-alkene class material is the novel high polymer material that receives extensive concern and application in recent years; Said material has advantages such as gel point hysteresis, differential contraction stress, extremely low oxygen resistance inhibitor action, quick solidifying, good mechanical property, is widely used in fields such as profile of tooth patching material, flexible display, LED.
The people such as Erik C.Hagberg in American I BM company Ao Ermadeng research centre have proposed the ultraviolet stamping technology based on the mercaptan-alkene material in 2007.(Hagberg; E.C., et al., Effects of modulus and surface chemistry of thiol-enephotopolymers in nanoimprinting.Nano Letters; 2007.7 (2): p.233-237.); This technology can realize nanoscale lines stripe shape graphic structure, and the oxygen resistance inhibitor action of this technology is very little, but this technology is not done further discussion to shrinkage; And the processing that this technology is not used for continuous relief structure is duplicated, and the anti-etching performance of resist is not studied.
People such as the Khire of Univ Colorado-Boulder USA have proposed to use the surface treatment and the nanostructured processing technology of mercaptan-alkene material and ultraviolet stamping technology in 2008.(V.S.Khire; Y.Yi; N.A.Clark and C.N.Bowman.Formation and surface modification of nanopatterned thiol-ene substrates using Step and Flash Imprint Lithography.Advanced Materials.2008.20 (17): 3308-+.); But the surface grafting characteristic of this process application mercaptan has realized the further refinement of nanostructured, but its anti-shrinkage character is not done further discussion.
Summary of the invention
The objective of the invention is to overcome the influence that the resist contraction produces in the ultraviolet stamping micro optical element technology; But the present invention introduces the anticorrosive additive material that a kind of relaxation is shunk in traditional micro optical element ultraviolet stamping technology; Reduce and shrink the influence that brings; Improve impression micro optical element machining precision, increase the diffraction efficiency of micro optical element.
Concrete solution of the present invention is; A kind of continuous relief micro optical element high precision ultraviolet stamping method based on mercaptan-alkene; In traditional continuous relief structure micro-optical element ultraviolet stamping technology; Using mercaptan-alkene class ultraviolet light to cause macromolecular material uses as resist; Method through regulating impression pressure, control cull layer thickness makes the differential contraction stress that resist solidifies generation be able to relaxation through the mode that fluid flows, and the deflation error of continuous relief structure micro-optical element is reduced to below 3%, and the cull layer thickness is 500-1000nm.
Used mercaptan-alkene class ultraviolet light causes macromolecular material and has the volumetric shrinkage less than 15%.
Used mercaptan-alkene class ultraviolet light causes the reactive ion etching process that macromolecular material can be used for mixed gas, realizes the figure transmission of continuous relief structure.
Innovation part of the present invention is, in ultraviolet stamping technology, uses a kind of mercaptan-alkene class material as resist.The polymerization methods of mercaptan-alkene class material is a step-growth polymerization, has the characteristic that curing gel point lags behind, the mode relaxation that the differential contraction stress that resist was produced before gel point flows through fluid.Impress pressure through regulating, can control the cull layer thickness, suitable cull layer thickness can compensate shrinking the volume minimizing that produces, thereby can make the error of shrinking generation be superior to 3%.Simultaneously, said material also has anti-etching preferably performance, can realize the figure crimping and transfer processes of continuous relief structure.
Description of drawings
Fig. 1 is the schematic diagram that passes through fluid-flow mode relaxation internal stress in the ultraviolet stamping technology
Fig. 2 impresses the microphotograph of the imprint result that obtains for the mercaptan-alkene class material of using the present invention's proposition
Fig. 3 is for carrying out imprint result that the continuous relief structure micro-optical element ultraviolet stamping obtains, passing through result and the contour curve of used pressing mold behind the reactive ion etching process again with embodiment one described mercaptan-alkene material.
Fig. 4 carries out the imprint result that the continuous relief structure micro-optical element ultraviolet stamping obtains and the contour curve of used pressing mold for embodiment two, three described mercaptan-alkene materials.
Fig. 5 carries out the imprint result that the continuous relief structure micro-optical element ultraviolet stamping obtains and the contour curve of used pressing mold for embodiment one, four described mercaptan-alkene materials.
The practical implementation method
Embodiment 1
The mercaptan-alkene class ultraviolet light of using cyanacrylate (TATATO), four (3-mercaptopropionic acid) pentaerythritol ester (PETMP), light trigger Darocur 1173 preparations causes macromolecular material and carries out ultraviolet stamping technology as resist; Make continuous relief structure micro-optical element, base material is a quartz glass.Its concrete steps are:
A) anticorrosive additive material of being prepared is filled between pressing mold and the substrate, exerting pressure compresses substrate and pressing mold, regulates pressure, makes the cull layer thickness be about 500-1000nm.
B) use the UV-LED light source with populated resist exposure, implement the demoulding then, the structure that obtains is as shown in Figure 2, and the stamper architecture profile is as shown in Figure 2, and the deflation error of continuous relief structure micro-optical element is lower than 3%.
C) application response ion etching technology structure that impression is obtained is delivered in the quartz glass substrate, and structure is as shown in Figure 3.
Embodiment 2
The mercaptan-alkene class ultraviolet light of using ethylene glycol dimethacrylate (EGDMA), PETMP, light trigger Darocur 1173 preparations causes macromolecular material and carries out ultraviolet stamping technology, makes continuous relief structure micro-optical element, and base material is a quartz glass.Its concrete steps are:
A) anticorrosive additive material of being prepared is filled between pressing mold and the substrate, exerting pressure compresses substrate and pressing mold, regulates pressure, makes the cull layer thickness be about 500-1000nm;
B) use the UV-LED light source with populated resist exposure, implement the demoulding then, the structure that obtains is as shown in Figure 4, and stamper architecture is as shown in Figure 4, and the deflation error of continuous relief structure micro-optical element is lower than 3%
Embodiment 3
The mercaptan-alkene class ultraviolet light of using cyanuric acid triallyl ester (TTT), PETMP, light trigger Darocur 1173 preparations causes macromolecular material and carries out ultraviolet stamping technology, makes continuous relief structure micro-optical element, and base material is a quartz glass.Its concrete steps are:
A) anticorrosive additive material of being prepared is filled between pressing mold and the substrate, exerting pressure compresses substrate and pressing mold, regulates pressure, makes the cull layer thickness be about 500-1000nm;
B) use the UV-LED light source with populated resist exposure, implement the demoulding then, the structure that obtains is as shown in Figure 4, and stamper architecture is as shown in Figure 4, and the deflation error of continuous relief structure micro-optical element is lower than 3%
Embodiment 4
The mercaptan-alkene class ultraviolet light of using TATATO, PETMP, EGDMA, light trigger Darocur 1173 preparations causes macromolecular material and carries out ultraviolet stamping technology, makes continuous relief structure micro-optical element, and base material is a quartz glass.Its concrete steps are:
A) anticorrosive additive material of being prepared is filled between pressing mold and the substrate, exerting pressure compresses substrate and pressing mold, regulates pressure, makes the cull layer thickness be about 500-1000nm;
B) use the UV-LED light source with populated resist exposure, implement the demoulding then, the structure that obtains is as shown in Figure 5, and stamper architecture is as shown in Figure 5, and the deflation error of continuous relief structure micro-optical element is lower than 3%
Claims (1)
1. continuous relief micro optical element high precision ultraviolet stamping method based on mercaptan-alkene; In traditional continuous relief structure micro-optical element ultraviolet stamping technology; Use mercaptan-alkene class ultraviolet light to cause macromolecular material, it is characterized in that, comprising as resist:
At first said resist is filled between pressing mold and the substrate,
Next is exerted pressure substrate and pressing mold is compressed,
And then regulate impression pressure, and the residual layer thickness strictness is controlled between the 500nm-1000nm, make the differential contraction stress that resist solidifies generation be able to relaxation through the mode that fluid flows,
Exposure at last, the demoulding is reduced to below 3% the deflation error of continuous relief structure micro-optical element;
Wherein employed mercaptan-alkene class ultraviolet light causes macromolecular material and has the volumetric shrinkage less than 15%.
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| CN 201010533159 CN102053489B (en) | 2010-11-05 | 2010-11-05 | Mercaptan-alkene based high-precision ultraviolet imprinting method of continuous embossment micro optical elements |
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| CN102053489B true CN102053489B (en) | 2012-12-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7691275B2 (en) * | 2005-02-28 | 2010-04-06 | Board Of Regents, The University Of Texas System | Use of step and flash imprint lithography for direct imprinting of dielectric materials for dual damascene processing |
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Non-Patent Citations (2)
| Title |
|---|
| Isaac W. Moran, et al..Device Fabrication by Easy Soft Imprint Nano-Lithography.《Chemistry of Materials》.2008,第20卷4595-4601. * |
| Vaibhav S. Khire, et al..Formation and Surface Modification of Nanopatterned Thiol-ene Substrates using Step and Flash Imprint Lithography.《Advanced Materials》.2008,第20卷3308-3313. * |
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