CN102508409A - Ultraviolet-light-assisted thermocuring nanoimprint lithography technology and material - Google Patents
Ultraviolet-light-assisted thermocuring nanoimprint lithography technology and material Download PDFInfo
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- CN102508409A CN102508409A CN2011103312533A CN201110331253A CN102508409A CN 102508409 A CN102508409 A CN 102508409A CN 2011103312533 A CN2011103312533 A CN 2011103312533A CN 201110331253 A CN201110331253 A CN 201110331253A CN 102508409 A CN102508409 A CN 102508409A
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- nano impression
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Abstract
The invention provides an ultraviolet-light-assisted thermocuring nanoimprint lithography technology and material, belonging to the technical field of micro-nanometer processing. A cationic photoinitiator is adopted to replace thermal initiator; based on the characteristics that the cation polymerization rate of an epoxy group is slow under the normal temperature, the conversation rate is only below 10%, and the conversation rate can be improved to 80% at the temperature above 60DEG C, cationic photoinitiator is photolyzed by the ultraviolet light at the normal temperature to generate cations; then the steps of lithography and heating for curing are carried out to realize quick thermocuring nanoimprint lithography; and the problems of high thermocuring nanoimprint lithography temperature and long time are solved and the limitation that the ultraviolet light curing nanoimprint lithography needs a transparent lithography template or substrate material is overcome.
Description
Technical field
The invention belongs to the micro-nano manufacture field, be specifically related to a kind of ultraviolet light auxiliary heat curing nano stamping technique, and the nano impression material that in moulding process, uses.
Background technology
Nanometer embossing (openly U.S. Pat 6180239) is Stephen Y. professor Chou of middle nineteen nineties in the last century U.S. Princeton Nanostructure Lab of university receives exposure wavelength to traditional photoetching process restriction; Reached the preparation micro-structure the limit (~ 30nm); Can't further obtain littler size; And proposed to be similar to a kind of technology of macromolecule mold pressing, and successfully proof can obtain the structural unit of size less than 10nm through this technology on semi-conductor silicon chip.Nano impression is divided into hot padding and ultraviolet light polymerization impresses two types; The nano impression material is to be the basis with thermoplastics type's macromolecular material such as polymethylmethacrylate (PMMA); Make macromolecular material softening through heating, fusion, and pass through impressed pressure; Be printed on the nanostructured on the template on the polymeric membrane of fusion cooling forming.Owing to need adopt higher pressure (several 10 atmospheric pressure) when carrying out nano impression, destroy the nanostructured on the template easily, be unfavorable for the repetition of template, repeatedly use.Simultaneously; Print the process need heating and make that macromolecular material is softening, fusion; Because the thermal expansivity of template, macromolecular material and substrate is different, the stress that produces in heating and the cooling procedure also can cause the defective of nanostructured, and destroys the nanostructured on the template.U.S. Pat 6334960 discloses a kind of ultraviolet light curing nano stamping technique; Employing viscosity is low, and the uV curable prepolymer system of good fluidity is as the nano impression material, and is spin-coated on the uV curable material on the substrate; When template with after the uV curable prepolymer contacts; Do not need ambient pressure, utilize the distinctive capillarity of liquid, ultraviolet photocureable material is injected in the nanostructured of template at an easy rate; And make its quick curing, thereby the process of nano impression can be accomplished under room temperature, very low pressure rapidly through ultraviolet light.But it is the material of ultraviolet light that the ultraviolet light curing nano impression needs impression block or substrate to have at least a kind of, has limited the ultraviolet light curing nano stamping technique and has been applied to lighttight material.In order to remedy the deficiency of ultraviolet light polymerization, the heat-setting acrylic ester of employing (Malaquin, L. are arranged also; Carcenac, F., Vieu, C.; Mauzac, M.
Microelectron. Eng. 2002,61 – 62,379.) epoxy (Liao, W.; Hsu S. L.
Nanotechnology 2007, 18,065303) and prepolymer, carry out the heat curing nano impression.But the solidification temperature of these thermosetting materials is generally more than 150 ℃, and more needs dozens of minutes set time.
Summary of the invention
The objective of the invention is to remedy the deficiency of prior art; Solve as current heat curing nano impression needs that solidification temperature is high, set time problem and the ultraviolet light curing nano impression need the restriction of transparent impression block or backing material, provide a kind of can be under mild temperature, the Rapid Thermal nanometer embossing and the heat curing nano impression glue material that solidify.
For realizing above-mentioned purpose, the technical scheme that nanometer embossing of the present invention is taked is:
A kind of ultraviolet light auxiliary heat curing nano stamping technique is characterized in that, utilizes ultraviolet light that the nano impression glue material is made public at first at normal temperatures, carries out nano impression step and thermal cure step then; The heating-up temperature of said thermal cure step between 80 ℃ ~ 130 ℃, preferred 90 ℃ ~ 110 ℃.
The technical scheme that the nano impression glue material that uses in a kind of ultraviolet light auxiliary heat curing nano stamping technique of the present invention is taked is: the nano impression glue material comprises multiple functionality epoxide resin prepolymer, cationic photoinitiator and solvent, can also comprise that other adjuvants such as plastifier, curing accelerator, photosensitizer, levelling agent, release agent optimize performance.
General thermosetting material comprises the higher temperature of its curing of epoxy resin or needs as more than 180 degree, or very long set time, more than the dozens of minutes.The light-initiated cationic polymerization of epoxy resin has following two characteristics on the other hand: 1. cation light initiator is caused back generation proton kation by ultraviolet light; This cationoid is insensitive to oxygen; Therefore under aerobic environment, also can keep reactivity for a long time, even at dark state; 2. initiation ring-opening polymerization of the kation of epoxide group and polymerization temperature are closely related, and below room temperature, the polymerization speed of epoxide group is slow; And conversion ratio is more below 10%; When temperature was higher than more than 60 ℃, conversion ratio significantly increased, when temperature is higher than after 100 ℃; Can in 1 minute, reach more than 80% by conversion ratio, make the epoxy resin full solidification.Based on these two characteristics; The method for stamping that has adopted the ultraviolet light auxiliary heat to solidify in the present invention; With ultraviolet light light trigger is decomposed, with a large amount of proton kation of interior generation, and traditional heat causes in the several seconds; Need at 150 ℃, even 180 ℃ of above heating and decomposition thermal initiators of temperature.Because the reaction rate of epoxide group is slow under the room temperature, conversion ratio is low, so nano impression glue does not almost solidify behind the uv-exposure, but the proton kation that produces still keeps reactivity.Then impress with impression block again; Because epoxy prepolymer still is in liquid condition; When template with after prepolymer contacts, do not need external pressure, utilize the distinctive capillarity of liquid; Ultraviolet photocureable material is injected in the nanostructured of template at an easy rate, and impression can even not have under the press strip spare and accomplish in low pressure.Impression heats in moderate moisture after accomplishing, and can accomplish curing rapidly in one minute.Impression block can be the template of being made by transparent material, also is the template that opaque materials such as silicon, metal are made.
Among the present invention ultraviolet light auxiliary heat curing nano impression glue material mainly by epoxy prepolymer, light trigger, the solvent composition of polyfunctionality.The epoxy prepolymer of polyfunctionality at room temperature presents low viscous liquid condition, room temperature or with 25 ℃ be standard, the viscosity of prepolymer is at 10 centipoises～10000 centipoises, preferred 25 ℃ of following viscosity are at the prepolymer of 100 centipoises～2000; But the epoxy prepolymer of polyfunctionality comprises the epoxide group of two or more ring-opening polymerizations; Epoxide group can be an oxirane, 1,2-epoxypropane, 1,2-epoxide ring butane, 1,2-cyclopentane epoxide or 1,2-7-oxa-bicyclo[4.1.0 etc.; Epoxy prepolymer accounts for 1%～40% of nano impression glue total amount.
In the nano impression glue, solvent can the reactive solvent of right and wrong also can be a reactive monomeric.Non-reactive solvent is glycol monoethyl ether, chlorobenzene, toluene, and xylene, acetone, MEK, methyl isobutyl ketone, formic ether, ethyl acetate or dimethyl formamide etc. also can be their potpourris.For after preventing spin-coating, residual solvent preferentially selects for use reactive monomer or their potpourri as thinning agent to the harmful effect that the impression glue that solidifies produces among the present invention.Reactive monomer comprises oxirane, epoxypropane, epichlorokydrin, 1,2-7-oxa-bicyclo[4.1.0 etc.
Among the present invention, the curing mechanismization of epoxy prepolymer mainly causes the mechanism of ring-opening polymerization based on kation.Cationic initiator is preferably used triaryl sulphur or diaryl iodide ion type optical acid generating agent; The water of trace reaction in sulphur, iodide ion salt and the environment under UV-irradiation; Produce hydrogen ion, hydrogen ion further causes the epoxide group ring-opening polymerization under heating, liquid film is solidified.The consumption of cationic initiator is 0.5% ~ 5% of an amount of epoxy, preferred 1% ~ 3%.
Nano impression material and nanometer embossing that the present invention adopts; Some restrictions have been solved in traditional hot curing nano impression and the ultraviolet light curing nano stamping technique to temperature and material; Can realize the Rapid Thermal solidified imprinting, be with a wide range of applications in the process of nano impression.
Description of drawings
Fig. 1 is the process schematic representation of a kind of ultraviolet light auxiliary heat curing nano stamping technique of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is explained further details.
Ultraviolet light auxiliary heat curing nano method for stamping of the present invention, with the multiple functionality epoxide resin prepolymer as heat curing nano impression glue material, with the initiating agent of cationic photoinitiator as the epoxy resin ring-opening polymerization.At first will be coated on the substrate by the nano impression glue material that epoxy prepolymer and cationic photoinitiator are formed; Then with ultraviolet light under the room temperature it being made public, after exposure is accomplished, be pressed into nano-imprint stamp and impress in the glue film with nanostructured; Under moderate moisture, be heating and curing then; After the impression glue material solidifying and setting, remove nano-imprint stamp, the nanostructured on the template promptly is replicated on the substrate.
Nano impression glue material in the present embodiment is: the organosilicon epoxy resin of mass percent 1%; Eight functionality epoxy resin cross-linking agent Epon SU-8 (Shell Chemical company) of mass percent 4%; The diaryl iodide ion borofluoride of mass percent 0.2%; 1 of mass percent 94.8%, the 2-7-oxa-bicyclo[4.1.0.
For nano-imprint process; Duplicate vertically/laterally to prepare the big structure plan of aspect ratio than little structure plan easy; Therefore it is aforesaid curable epoxide resin prepolymer liquid film that nano impression colloid of the present invention system has adopted double membrane structure, upper strata, thickness < 100 nm; And between epoxy prepolymer liquid film layer and substrate, introduced one deck polymeric membrane transfer layer, thickness>200 nm.The duplicature system can the aspect ratio that on ultraviolet curing resin film, forms is little structure plan; Method through the selectivity plasma etching is enlarged into the big structure plan of aspect ratio on macromolecule membranous layer, structure plan can be copied on the substrate more reliably.In the common macromolecular material of forming by carbon, hydrogen, oxygen, add the ability that the material that contains element silicon can effectively improve material antioxygen gas plasma etching.
Add organosilicon material in the epoxy prepolymer in the present embodiment; The macromolecule membranous layer of lower floor is the macromolecular material of carbon, hydrogen, oxygen composition; Solidify back upper layer of material and subsurface material the oxygen plasma etching is had selectivity, the speed of upper layer film etching is less than the speed of lower membrane etching, so the structure plan that forms in the upper layer film can be used as mask; Transfer on the lower membrane through the oxygen plasma etching, the aspect ratio of patterning is exaggerated simultaneously.The organosilicon material that adds in the epoxy resin can be to have reactive functional groups, as has the epoxide group organosilicon material; Also can the reactive organosilicon material of right and wrong.The organosilicon material that preferably has reactive epoxy groups can form cross-linked network with other epoxide resin material simultaneously when solidifying, what present embodiment adopted is that U.S. Gelest company article number is the polyfunctionality organosilicon epoxy resin of ECMS-924.Lower floor's macromolecular material among the present invention can be the macromolecule membranous layer behind the curing cross-linked, through copying on the substrate as etch mask bar structure pattern; Also can be soluble thermoplastics type's macromolecule membranous layer, lift the method that leaves through metal and copy to patterning on the substrate.
Claims (10)
1. a ultraviolet light auxiliary heat curing nano stamping technique is characterized in that, utilizes ultraviolet light that the nano impression glue material is made public at first at normal temperatures, carries out nano impression step and thermal cure step then; The heating-up temperature of said thermal cure step between 80 ℃ ~ 130 ℃, preferred 90 ℃ ~ 110 ℃.
2. the nano impression glue material that in a kind of ultraviolet light auxiliary heat curing nano stamping technique as claimed in claim 1, uses; It is characterized in that; Said nano impression glue material comprises multiple functionality epoxide resin prepolymer, cationic photoinitiator and solvent, can also comprise other adjuvants such as plastifier, curing accelerator, photosensitizer, levelling agent, release agent.
3. nano impression glue material according to claim 2 is characterized in that, said multiple functionality epoxide resin prepolymer is the thin fluid body, and under 25 ℃, its viscosity is at 10 centipoises ~ 10000 centipoises, and preferred viscosities is at the prepolymer of 100 ~ 2000 centipoises.
4. nano impression glue material according to claim 2 is characterized in that said multiple functionality epoxide resin prepolymer comprises the epoxide group of plural ring-opening polymerization at least.
5. nano impression glue material according to claim 4 is characterized in that, the epoxide group of said multiple functionality epoxide resin prepolymer is an oxirane, 1,2-epoxypropane, 1,2-epoxide ring butane, 1,2-cyclopentane epoxide or 1,2-7-oxa-bicyclo[4.1.0.
6. nano impression glue material according to claim 2 is characterized in that, said cationic photoinitiator is triaryl sulphur or diaryl iodide ion type optical acid generating agent.
7. nano impression glue material according to claim 2; It is characterized in that; Said solvent can be non-reactive solvent such as glycol monoethyl ether, chlorobenzene, toluene, xylene, acetone, MEK, methyl isobutyl ketone, formic ether, ethyl acetate or dimethyl formamide etc., or their potpourri; Also can be reactive monomer, like oxirane, epoxypropane, epichlorokydrin or 1,2-7-oxa-bicyclo[4.1.0 etc.
8. nano impression glue material according to claim 2; It is characterized in that said multiple functionality epoxide resin prepolymer accounts for the mass ratio 1% ~ 40% of impression sol solution, preferred 3 ~ 10%; The consumption of said cationic photoinitiator is 0.5% ~ 5% of an epoxy prepolymer mass ratio, preferred 1% ~ 3%.
9. the duplicature impression colloid system that forms by the described nano impression glue material of one of claim 2 to 8; It is characterized in that; The upper strata of said duplicature impression glue is the nano impression glued membrane of being made up of multiple functionality epoxide resin prepolymer and cationic photoinitiator that spin-coating forms, and lower floor is thermoplastics type or the thermosetting macromolecule material membrane that spin-coating forms.
10. duplicature impression colloid according to claim 9 is; It is characterized in that; Adding in the said nano impression glued membrane has the organosilicon material of epoxide group or non-reactive organic silicone material to improve the etch resistance of this layer material to oxygen plasma, the preferred reactive organosilicon material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103091983A (en) * | 2013-01-29 | 2013-05-08 | 南京丰强纳米科技有限公司 | Preparation method of surface-enhanced Raman scattering substrate |
| CN103578353A (en) * | 2013-11-13 | 2014-02-12 | 无锡英普林纳米科技有限公司 | Method for manufacturing gradient-gradual-change double-layer-system material and application in anti-counterfeiting identification |
| CN103926789A (en) * | 2014-02-07 | 2014-07-16 | 南方科技大学 | Nano-imprinting template, system thereof and imprinting method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101706638A (en) * | 2009-10-23 | 2010-05-12 | 上海市纳米科技与产业发展促进中心 | Ultraviolet nanoimprint resist and components thereof |
| CN101848915A (en) * | 2007-11-07 | 2010-09-29 | 昭和电工株式会社 | Epoxy group-containing organosiloxane compound, curable composition for transfer material, and fine pattern forming method using the composition |
| JP2011073444A (en) * | 2009-09-29 | 2011-04-14 | Asml Netherlands Bv | Imprint lithography |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101848915A (en) * | 2007-11-07 | 2010-09-29 | 昭和电工株式会社 | Epoxy group-containing organosiloxane compound, curable composition for transfer material, and fine pattern forming method using the composition |
| JP2011073444A (en) * | 2009-09-29 | 2011-04-14 | Asml Netherlands Bv | Imprint lithography |
| CN101706638A (en) * | 2009-10-23 | 2010-05-12 | 上海市纳米科技与产业发展促进中心 | Ultraviolet nanoimprint resist and components thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103091983A (en) * | 2013-01-29 | 2013-05-08 | 南京丰强纳米科技有限公司 | Preparation method of surface-enhanced Raman scattering substrate |
| CN103578353A (en) * | 2013-11-13 | 2014-02-12 | 无锡英普林纳米科技有限公司 | Method for manufacturing gradient-gradual-change double-layer-system material and application in anti-counterfeiting identification |
| CN103926789A (en) * | 2014-02-07 | 2014-07-16 | 南方科技大学 | Nano-imprinting template, system thereof and imprinting method |
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