CN103676473B - The method that nano impression prepares metal pattern in conjunction with wet etching on curved surface - Google Patents
The method that nano impression prepares metal pattern in conjunction with wet etching on curved surface Download PDFInfo
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- CN103676473B CN103676473B CN201310551957.0A CN201310551957A CN103676473B CN 103676473 B CN103676473 B CN 103676473B CN 201310551957 A CN201310551957 A CN 201310551957A CN 103676473 B CN103676473 B CN 103676473B
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Abstract
The invention discloses a kind of method that nano impression prepares metal pattern in conjunction with wet etching on curved surface.First the method is deposited with layer of metal on curved surface, then by the method imprinted pattern of transfer on metal, carved after removing remnant layer by the method for reactive ion etching, for mask, metal is performed etching to substrate imprinting glue, remove the impressing glue on metal pattern upper strata again by reactive ion etching, obtain metal pattern.The present invention is simple, both can substitute in the plane and lift off technique and prepare metal pattern, than the conventional technique that lifts off be less susceptible to destroy the integrity of figure and reduce the generation of defect；On curved surface, preparation can prepare metal pattern again, and on curved surface, prepare pattern lift off technique and cannot realize.The present invention has broad application prospects in manufacture bragg grating, folding/field such as mixed optical element, nano electromechanical systems of spreading out.
Description
Technical field
The present invention relates to a kind of method utilizing nanometer embossing to prepare metal pattern on curved surface in conjunction with wet etching.
Background technology
Preparing nanostructured at curved surface and complex topography surface increasingly receives the concern of people recently, and the application particularly in fields such as artificial compound eye, hemispherical electronic eye camera, photovoltaic device, image sensor array, micro-executive component and Fibre Optical Sensors is more and more extensive.Nineteen ninety-five, after StevenY.Chou et al. invention nanometer embossing, nanometer embossing makes field by advantages such as its high efficiency, high-resolution and low costs in micro structure, has attracted the concern of many scientific research personnel and engineers and technicians.Although current many micro-nano technology technology can both prepare patterned nanostructure on planar substrate surface, but these technology are unsuitable for greatly preparing nano-pattern at nonplanar substrate surface.Therefore the curved surface nano-pattern preparation method of a kind of with low cost, reliable in quality of exploitation is needed badly.Various nano-pattern can be imprinted out on curved surface by elastomer soft template at present, but so far, no matter be which kind of photoetching or stamping technique, all metal pattern can not be transferred to curved surface up.
The preparation technology of existing frequently-used metal pattern realizes by lifting off technique.This technique is to adopt thermoplastic polymer for lifting off layer, on thermoplastic-polymer solution spin coating and substrate, then directly hot padding, or the thermosetting impressing glue that spin coating is siliceous more above, remnant layer is removed by reactive ion etching, after evaporation metal, the dissolubility of thermoplastic polymer is utilized to remove the metal on residual polymer in organic solvent, thus obtaining suprabasil metal pattern.Lifting off technique needs acquisition to lift off layer uniformly, and is impossible utilize the technique of spin coating to obtain uniform film on curved surface；And utilize soft template to carry out curved surface impressing, can only imprint glue with ultra-violet curing imprints, and imprints and define cross-linked network after glue solidifies under ultraviolet lighting, thus cannot be re-dissolved among organic solvent, it is impossible to realize lifting off.
Summary of the invention
For deficiency of the prior art, the purpose of the present invention is to propose to a kind of method preparing metal structure on curved surface.
The method preparing metal structure on curved surface that the present invention proposes, is based on ultraviolet nanometer and imprints in conjunction with wet etching method.It is characterized in first being deposited with on curved surface layer of metal film, then on metal film, soft impression block stamping structure and ultra-violet curing are adopted by double; two transfer methods, etching removes remnant layer, after exposing metal, again using remaining polymer as etch mask, wet etching metal, obtains final metal structure after removing polymer mask again through reactive ion etching.
The concrete technical scheme of the present invention is as follows:
The method that nano impression prepares metal pattern in conjunction with wet etching on curved surface, specifically comprises the following steps that
1) first being cleaned up by curved-surface materials surface deionized water, the dried method by electron beam evaporation plating or magnetron sputtering is deposited with layer of metal thin film on curved-surface materials, and metal can be gold, silver, copper, aluminum or chromium, and thickness is 1～100 nanometer；
2) at one layer of ultra-violet curing of clean silicon wafer surface spin coating impressing glue, this ultraviolet solidified nano impressing glue is the performed polymer containing (methyl) acrylate group, monomer containing (methyl) acrylate group or the above two mixture dissolved with in ultraviolet initiator high boiling solvent solution；
3) flexible nano impression block is covered on the impressing glue that spin coating is good, is covered on the curved surface being coated with metal prepared by step 1) after spending 1-5 minute, and ultra-violet curing；
4) after impressing adhesive curing, the impressing soft template on surface is removed, then obtain the polymer stamping structure on curved surface, under stamping structure, have one layer of uniform metallic film；
5) adopt oxygen plasma to react ion etching, remove impressing glue；
6) in corrosive liquid, wet etching is carried out for mask solidifying polymer；
7) reacting ion etching with oxygen plasma, removing the polymer solidified, thus obtaining metallic pattern on curved surface.
When evaporation metal be golden or silver-colored time, the aqueous solution consisting of Fe(NO3)39H2O and thiourea of wet etching liquid, its pH value dilute hydrochloric acid is adjusted to as 1-5；When evaporation metal is copper, the aqueous solution consisting of iron chloride of wet etching liquid；When evaporation metal is chromium, the glacial acetic acid solution consisting of ammonium ceric nitrate of wet etching liquid.
The present invention is simple, both can substitute in the plane and lift off technique and prepare metal pattern, than the conventional technique that lifts off be less susceptible to destroy the integrity of figure and reduce the generation of defect；On curved surface, preparation can prepare metal pattern again, and on curved surface, prepare pattern lift off technique and cannot realize.The method of the present invention both make use of the LJV curable of existing impressing glue, high-resolution nano-pattern can not be obtained on curved surface again by the technique that lifts off, thus laying the first stone for the preparation of various novel micro nanometer components, manufacturing bragg grating (fiberBragggrating), roll over/spread out mixed optical element (HybridOptics), nano electromechanical systems (NEMS) field has broad application prospects.Up to now, not yet there is any report of this method.
Accompanying drawing explanation
Fig. 1 is the method flow diagram of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, this method is further described.
The present invention proposes a kind of method prepared by novel metallic pattern, the method passes through metal evaporation, curved surface plates layer of metal thin film equably, then on curved surface, on metallic film, the micro structure of polymer is prepared by the method for double; two transfer impressings, afterwards, remove remnant layer again through reactive ion etching and expose substrate, and carry out wet etching with remaining polymer for mask, the Metallic film corrosion of lower floor is gone out required figure.Concrete operation step is as follows:
(1) evaporation metal on curved surface
First adopting plating layer of metal on curved surface, this metal can be gold, silver, copper, aluminum, chromium.The method that can adopt electron beam evaporation plating, it would however also be possible to employ the method for magnetron sputtering, the thickness of evaporation metal is 1～100 nanometer.
(2) double; two transfer methods imprinted pattern on curved surface
First one layer of ultra-violet curing impressing glue of spin coating on silicon chip, this impressing glue can use conventional various not siliceous liquid UV curable monomer or performed polymer, includes but are not limited to CN975, CN996 etc..Then the soft template prepared by polydimethylsiloxane is covered thereon, opened after 1～5 minute, and be covered on the curved surface being coated with metal, and under high voltage mercury lamp, irradiate solidification when nitrogen protection.After impressing adhesive curing, template is taken off, namely obtain the structure of polymer.
(3) wet etching prepares metal structure on curved surface
Adopting oxygen plasma etch, is removed by the remnant layer of polymer architecture, after exposing lower metal, placed by metal with corrosive liquid, corrosion is to after exposing substrate, then removes polymer with oxygen plasma etch, namely obtains the metal pattern on curved surface.
The present embodiment prepares gold optical grating construction in conjunction with wet etching at curved surface with nano impression.
The substrate with curved surface can be the plastics such as silicon, silicon dioxide, silicon nitride and polyethylene, polypropylene, polymethyl methacrylate, polyimides.First 30 nanometer gold are plated on curved surface with electron beam evaporation plating, standby.
The additionally spin coating 80 nanometers CN975(Sartomer containing 3% light trigger on silicon chip), polydimethylsiloxane soft template is covered thereon, its structure is optical grating construction, and the cycle is 550 nanometers, and gash depth is 110 nanometers.After 3 minutes, soft template being thrown off, then soft template be covered on the curved surface being coated with gold, 100 watts of high voltage mercury lamp ultra-violet curings are after 15 minutes under nitrogen protection, throw off soft template, namely obtain the structure of impressing glue.
Impressing above being had curved surface dry etching 15 seconds in oxygen plasma of structure, removes the remnant layer of stamping structure, wet etching 5 minutes in etching liquid, etching liquid is the Fe (NO containing 50mmol/L3)3.9H2The aqueous solution of O and 30mmol/L thiourea.
Claims (5)
1. the method that nano impression prepares metal pattern in conjunction with wet etching on curved surface, it is characterised in that specifically comprise the following steps that
1) first being cleaned up by curved-surface materials surface deionized water, the dried method by electron beam evaporation plating or magnetron sputtering forms layer of metal thin film on curved-surface materials；
2) at one layer of ultra-violet curing impressing glue of clean silicon wafer surface spin coating；
3) flexible nano impression block is covered on the impressing glue that spin coating is good, crosses after 1-5 minute and it is opened from silicon chip surface, and be covered in step 1) on the curved surface with metal prepared, and ultra-violet curing；
4) after impressing adhesive curing, the impressing soft template on surface is removed, then obtain the impressing glue with structure on curved surface, under impressing glue, have one layer of uniform metallic film；
5) adopt oxygen plasma to react ion etching, remove the remnant layer of impressing glue, expose the metal of lower floor；
6) in corrosive liquid, wet etching is carried out for mask imprinting glue；
7) reacting ion etching with oxygen plasma, removing impressing glue, thus obtaining metallic pattern on curved surface.
2. the method that nano impression according to claim 1 prepares metal pattern in conjunction with wet etching on curved surface, it is characterized in that, step 2) ultraviolet solidified nano of spin coating impressing glue is the performed polymer containing acrylate group, monomer containing acrylate group or both mixture be dissolved with the solution in the high boiling solvent of ultraviolet initiator.
3. the method that nano impression according to claim 1 prepares metal pattern in conjunction with wet etching on curved surface, it is characterised in that step 1) material of metallic film is gold, silver, copper, aluminum or chromium.
4. the method that nano impression according to claim 3 prepares metal pattern in conjunction with wet etching on curved surface, it is characterised in that the thickness of metallic film is 1～100 nanometer.
5. the method that the nano impression according to claim 3 or 4 prepares metal pattern in conjunction with wet etching on curved surface, it is characterized in that, when the material of metallic film be golden or silver-colored time, the aqueous solution consisting of Fe(NO3)39H2O and thiourea of wet etching liquid, its pH value dilute hydrochloric acid is adjusted to as 1-5；When evaporation metal is copper, the aqueous solution consisting of iron chloride of wet etching liquid；When the material of metallic film is chromium, the glacial acetic acid solution consisting of ammonium ceric nitrate of wet etching liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105448799A (en) * | 2015-11-25 | 2016-03-30 | 东莞同济大学研究院 | Curved surface film circuit manufacture method based on laser projection technology |
| CN105448800B (en) * | 2015-11-25 | 2018-11-30 | 东莞同济大学研究院 | A kind of production method of the curved surface thin film circuit based on 3D printing technique |
| CN105858591B (en) * | 2016-03-29 | 2017-07-28 | 中国科学院高能物理研究所 | A kind of metal micro structure and preparation method thereof |
| CN107572834A (en) * | 2016-07-04 | 2018-01-12 | 正达国际光电股份有限公司 | A kind of bend glass processing technology |
| CN106185791B (en) * | 2016-07-14 | 2017-11-21 | 重庆大学 | A kind of manufacturing processing technic of local hydrophobic material |
| CN107561857A (en) * | 2017-09-20 | 2018-01-09 | 南方科技大学 | A kind of method that the super structure surface of optics is prepared based on nano impression |
| CN108008599B (en) * | 2017-12-27 | 2024-01-26 | 青岛天仁微纳科技有限责任公司 | Method and device for three-dimensional curved surface nanoscale imprinting and mold preparation method |
| CN109256477B (en) * | 2018-09-20 | 2020-05-26 | 合肥鑫晟光电科技有限公司 | Manufacturing method of hole injection layer for QLED and QLED display device |
| CN114016025B (en) * | 2021-10-29 | 2024-04-19 | 株洲中车时代半导体有限公司 | Metal film transfer method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388388A (en) * | 1981-06-04 | 1983-06-14 | General Dynamics Electronics Division | Method of forming metallic patterns on curved surfaces |
| CN101692151A (en) * | 2009-09-17 | 2010-04-07 | 复旦大学 | Method for manufacturing silicon nano-wire based on soft template nano-imprinting technique |
| CN101834407A (en) * | 2009-03-11 | 2010-09-15 | 中国科学院半导体研究所 | Method for preparing surface-emitting surface plasma laser by utilizing nanoimprint technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8163188B2 (en) * | 2007-04-03 | 2012-04-24 | The University Of Massachusetts | Article with PHEMA lift-off layer and method therefor |
| US20100279228A1 (en) * | 2007-12-21 | 2010-11-04 | The Regents Of The University Of California | Organo-metallic hybrid materials for micro- and nanofabrication |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388388A (en) * | 1981-06-04 | 1983-06-14 | General Dynamics Electronics Division | Method of forming metallic patterns on curved surfaces |
| CN101834407A (en) * | 2009-03-11 | 2010-09-15 | 中国科学院半导体研究所 | Method for preparing surface-emitting surface plasma laser by utilizing nanoimprint technology |
| CN101692151A (en) * | 2009-09-17 | 2010-04-07 | 复旦大学 | Method for manufacturing silicon nano-wire based on soft template nano-imprinting technique |
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