CN103676473B - Method for preparing metal pattern on curved surface by combining nano-imprinting with wet etching - Google Patents
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Abstract
Description
技术领域 technical field
本发明涉及一种利用纳米压印技术结合湿法刻蚀在曲面上制备金属图案的方法。 The invention relates to a method for preparing a metal pattern on a curved surface by using nanoimprint technology combined with wet etching.
背景技术 Background technique
最近在曲面和复杂形貌表面制备纳米结构越来越受到人们的关注,尤其是在人造复眼、半球形电子眼相机、光伏器件、图像传感器阵列、微执行元件和光纤传感器等领域的应用越来越广泛。1995年,自从StevenY.Chou等人发明纳米压印技术之后,纳米压印技术在微结构制作领域凭借其高效率、高分辨率以及低成本等优势,吸引了许多科研人员与工程技术人员的关注。虽然目前许多微纳加工技术都能够在平面衬底表面制备图案化纳米结构,但是这些技术大都不适合在非平面的衬底表面制备纳米图案。因此亟需开发一种成本低廉、质量可靠的曲面纳米图案制备方法。目前通过弹性体软模板可以在曲面上压印出各种纳米图案,但是目前为止,无论是哪种光刻或压印技术,都不能将金属图案转移到曲面上去。 Recently, the preparation of nanostructures on curved and complex surfaces has attracted more and more attention, especially in the fields of artificial compound eyes, hemispherical electronic eye cameras, photovoltaic devices, image sensor arrays, micro actuators and fiber optic sensors. widely. In 1995, since Steven Y. Chou and others invented nanoimprint technology, nanoimprint technology has attracted the attention of many researchers and engineers in the field of microstructure production due to its advantages of high efficiency, high resolution and low cost. . Although many micro-nanofabrication techniques can fabricate patterned nanostructures on planar substrate surfaces, most of these techniques are not suitable for fabricating nanopatterns on non-planar substrate surfaces. Therefore, it is urgent to develop a low-cost and reliable method for preparing curved surface nanopatterns. At present, various nano-patterns can be imprinted on curved surfaces through elastomeric soft templates, but so far, no matter what kind of lithography or imprinting technology is used, metal patterns cannot be transferred to curved surfaces.
现在常用的金属图案的制备工艺是通过举离工艺实现的。该工艺是采用热塑性聚合物为举离层,将热塑性聚合物溶液旋涂与基底之上,然后直接热压印,或者在其之上再旋涂含硅的热固性压印胶,通过反应离子刻蚀除去残余层,蒸镀金属之后,在有机溶剂中利用热塑性聚合物的溶解性而除去剩余聚合物之上的金属,从而得到基底上的金属图案。举离工艺需要获得均匀的举离层,而在曲面上是不可能利用旋涂的工艺得到均匀的膜;而利用软模板进行曲面压印,只能用紫外固化压印胶进行压印,而压印胶在紫外光照之下固化后形成了交联网络,从而无法再溶解于有机溶剂之中,无法实现举离。 The commonly used metal pattern preparation process is realized by lift-off process. The process is to use thermoplastic polymer as the lift-off layer, spin-coat the thermoplastic polymer solution on the substrate, and then directly heat emboss, or spin-coat silicon-containing thermosetting embossing glue on it, through reactive ion etching After removing the residual layer by etching and evaporating the metal, the metal on the remaining polymer is removed by using the solubility of the thermoplastic polymer in an organic solvent, so as to obtain a metal pattern on the substrate. The lift-off process needs to obtain a uniform lift-off layer, and it is impossible to use the spin-coating process to obtain a uniform film on the curved surface; while using a soft template for curved surface imprinting, only UV-curable imprinting glue can be used for embossing, and After the imprinting glue is cured under ultraviolet light, a cross-linked network is formed, so that it can no longer be dissolved in organic solvents and cannot be lifted off.
发明内容 Contents of the invention
针对现有技术中的不足,本发明的目的是提出一种在曲面上制备金属结构的方法。 Aiming at the deficiencies in the prior art, the object of the present invention is to propose a method for preparing a metal structure on a curved surface.
本发明提出的在曲面上制备金属结构的方法,是基于紫外纳米压印结合湿法腐蚀方法。其特点是首先在曲面上蒸镀一层金属膜,然后在金属膜上通过双转移法采用软压印模板压印结构并紫外固化,刻蚀除去残余层,暴露出金属后,再以剩余的聚合物作为刻蚀掩膜,湿法刻蚀金属,再通过反应离子刻蚀除去聚合物掩膜后获得最终的金属结构。 The method for preparing a metal structure on a curved surface proposed by the present invention is based on an ultraviolet nanoimprint combined with a wet etching method. It is characterized in that first a layer of metal film is vapor-deposited on the curved surface, and then the structure is imprinted on the metal film by a double transfer method using a soft imprint template and cured by ultraviolet light. The residual layer is removed by etching, and after the metal is exposed, the remaining The polymer is used as an etching mask, the metal is wet etched, and the final metal structure is obtained after removing the polymer mask by reactive ion etching.
本发明具体技术方案如下: Concrete technical scheme of the present invention is as follows:
纳米压印结合湿法刻蚀在曲面上制备金属图案的方法,具体步骤如下: The method for preparing a metal pattern on a curved surface by combining nanoimprinting with wet etching, the specific steps are as follows:
1)首先将曲面材料表面用去离子水清洗干净,干燥后通过电子束蒸镀或磁控溅射的方法在曲面材料上蒸镀一层金属薄膜,金属可为金、银、铜、铝或铬,厚度为1~100纳米; 1) First, clean the surface of the curved surface material with deionized water, and after drying, evaporate a layer of metal film on the curved surface material by electron beam evaporation or magnetron sputtering. The metal can be gold, silver, copper, aluminum or Chromium, with a thickness of 1 to 100 nanometers;
2)在洁净硅片表面旋涂一层紫外固化压印胶,该紫外固化纳米压印胶为含(甲基)丙烯酸酯基团的预聚体、含(甲基)丙烯酸酯基团的单体或前两者的混合物在溶有紫外光引发剂高沸点溶剂中的的溶液; 2) Spin-coat a layer of UV-curable imprinting glue on the surface of the clean silicon wafer. The UV-curing nano-imprinting glue is a prepolymer containing (meth)acrylate groups, The solution of the body or the mixture of the former two in the high boiling point solvent of the ultraviolet photoinitiator;
3)将柔性纳米压印模板覆盖于旋涂好的压印胶上,过1-5分钟后将其覆盖于步骤1)制备的镀有金属的曲面上,并紫外固化; 3) Cover the flexible nano-imprint template on the spin-coated imprint glue, and cover it on the metal-coated curved surface prepared in step 1) after 1-5 minutes, and UV-cure;
4)压印胶固化后将表面的压印软模板移去,则获得曲面上的聚合物压印结构,在压印结构之下有一层均匀的金属薄膜; 4) After the embossing glue is cured, remove the embossed soft template on the surface to obtain a polymer imprinted structure on the curved surface, and there is a uniform metal film under the imprinted structure;
5)采用氧等离子体进行反应离子刻蚀,除去压印胶; 5) Use oxygen plasma for reactive ion etching to remove the imprinting glue;
6)在腐蚀液中以固化聚合物为掩膜进行湿法刻蚀; 6) Wet etching is carried out in the etching solution with the cured polymer as a mask;
7)以氧等离子进行反应离子刻蚀,除去固化的聚合物,从而在曲面上得到金属图形。 7) Reactive ion etching is performed with oxygen plasma to remove the solidified polymer, thereby obtaining a metal pattern on the curved surface.
当蒸镀金属为金或银时,湿法刻蚀液的组成为九水合硝酸铁与硫脲的水溶液,其pH值用稀盐酸调至为1-5;当蒸镀金属为铜时,湿法刻蚀液的组成为氯化铁的水溶液;当蒸镀金属为铬时,湿法刻蚀液的组成为硝酸铈铵的冰醋酸溶液。 When the evaporated metal is gold or silver, the composition of the wet etching solution is an aqueous solution of ferric nitrate nonahydrate and thiourea, and its pH value is adjusted to 1-5 with dilute hydrochloric acid; when the evaporated metal is copper, wet The composition of the wet etching solution is an aqueous solution of ferric chloride; when the evaporated metal is chromium, the composition of the wet etching solution is a glacial acetic acid solution of ammonium cerium nitrate.
本发明简单易行,既可以在平面上替代举离工艺制备金属图案,比之常用的举离工艺更不易破坏图形的完整性并减少缺陷的发生;又可以在曲面上制备制备金属图案,而在曲面上制备图案是举离工艺无法实现的。本发明的方法既利用了现有的压印胶的紫外固化性,又可以不通过举离的工艺而在曲面上获得高分辨率的纳米图案,从而为各种新型微纳器件元件的制备打下基础,在制造布拉格光纤光栅(fiberBragggrating)、折/衍混合光学元件(HybridOptics)、纳机电系统(NEMS)领域具有广阔的应用前景。迄今为止,尚未有这种方法的任何报道。 The invention is simple and easy, and can replace the lift-off process to prepare metal patterns on a plane, which is less likely to damage the integrity of the graphics and reduce the occurrence of defects than the commonly used lift-off process; it can also prepare and prepare metal patterns on curved surfaces, and Patterning on curved surfaces is not possible with lift-off processes. The method of the present invention not only utilizes the ultraviolet curability of the existing embossing glue, but also can obtain high-resolution nano-patterns on the curved surface without lifting off the process, thereby laying a solid foundation for the preparation of various new micro-nano device components. It has broad application prospects in the manufacture of fiber Bragg gratings (fiberBragggrating), hybrid optical elements (HybridOptics) and nanoelectromechanical systems (NEMS). So far, there have not been any reports of this method.
附图说明 Description of drawings
图1是本发明的方法流程图。 Fig. 1 is a flow chart of the method of the present invention.
具体实施方式 detailed description
下面结合附图对本方法进行进一步说明。 The method will be further described below in conjunction with the accompanying drawings.
本发明提出了一种新型的金属图形制备的方法,该方法通过金属蒸镀,在曲面上均匀地镀一层金属薄膜,然后在曲面上通过双转移压印的方法在金属薄膜上制备聚合物的微结构,之后,再通过反应离子刻蚀去除残余层暴露出基底,并以剩余的聚合物为掩膜进行湿法腐蚀,将下层的金属膜腐蚀出所需的图形。具体操作步骤如下: The present invention proposes a novel metal pattern preparation method, which uses metal vapor deposition to evenly coat a layer of metal film on the curved surface, and then prepares a polymer on the metal film by double transfer embossing method on the curved surface. Afterwards, the residual layer is removed by reactive ion etching to expose the substrate, and the remaining polymer is used as a mask for wet etching to etch the underlying metal film to form the desired pattern. The specific operation steps are as follows:
(1)曲面上蒸镀金属 (1) Evaporation of metal on the curved surface
首先在曲面上采用镀一层金属,该金属可为金、银、铜、铝、铬。可以采用电子束蒸镀的方法,也可以采用磁控溅射的方法,蒸镀金属的厚度为1~100纳米。 First, a layer of metal is plated on the curved surface, and the metal can be gold, silver, copper, aluminum, or chrome. The method of electron beam evaporation can be adopted, and the method of magnetron sputtering can also be adopted, and the thickness of the evaporated metal is 1-100 nanometers.
(2)双转移法在曲面上压印图案 (2) Double transfer method imprints patterns on curved surfaces
首先在硅片上旋涂一层紫外固化压印胶,该压印胶可以用常规的各种不含硅的液体紫外固化单体或预聚体,包括但不仅限于CN975、CN996等。然后将由聚二甲基硅氧烷制得的软模板覆盖于其上,1~5分钟后将其揭开,并覆盖于镀有金属的曲面上,并在氮气保护的条件下于高压汞灯下照射固化。压印胶固化后将模板揭下,即获得聚合物的结构。 First, spin-coat a layer of UV-curable embossing glue on the silicon wafer. The embossing glue can use various conventional silicon-free liquid UV-curable monomers or prepolymers, including but not limited to CN975, CN996, etc. Then cover it with a soft template made of polydimethylsiloxane, uncover it after 1 to 5 minutes, and cover it on a metal-coated curved surface, and put it under the condition of nitrogen protection under a high-pressure mercury lamp Curing under irradiation. After the imprint glue is cured, the template is peeled off to obtain the polymer structure.
(3)湿法刻蚀在曲面上制备金属结构 (3) Wet etching prepares metal structures on curved surfaces
采用氧等离子体刻蚀,将聚合物结构的残余层去除,暴露出下层金属后,将金属放置与腐蚀液中,腐蚀至暴露出基底后,再用氧等离子体刻蚀除去聚合物,即得到曲面上的金属图案。 Oxygen plasma etching is used to remove the residual layer of the polymer structure, and after exposing the underlying metal, the metal is placed in the etching solution, etched until the substrate is exposed, and then the polymer is removed by oxygen plasma etching to obtain Metal pattern on the surface.
本实施例以纳米压印结合湿法刻蚀在曲面制备金光栅结构。 In this embodiment, a gold grating structure is prepared on a curved surface by combining nanoimprinting with wet etching.
具有曲面的基底可以是硅、二氧化硅、氮化硅及聚乙烯、聚丙烯、聚甲基丙烯酸甲酯、聚酰亚胺等塑料。首先用电子束蒸镀镀30纳米金于曲面上,备用。 The substrate with a curved surface can be silicon, silicon dioxide, silicon nitride, and plastics such as polyethylene, polypropylene, polymethyl methacrylate, and polyimide. Firstly, 30 nanometer gold is deposited on the curved surface by electron beam evaporation, and it is set aside.
另外在硅片上旋涂80纳米含有3%光引发剂的CN975(沙多玛公司),将聚二甲基硅氧烷软模板覆盖于其上,其结构为光栅结构,周期为550纳米,沟槽深度为110纳米。3分钟后,将软模板揭去,再将软模板覆盖于镀有金的曲面之上,在氮气保护下100瓦高压汞灯紫外固化15分钟后,揭去软模板,即得到压印胶的结构。 In addition, 80 nanometers of CN975 (Sartomer Company) containing 3% photoinitiator were spin-coated on the silicon wafer, and the polydimethylsiloxane soft template was covered on it. The structure was a grating structure with a period of 550 nanometers. The groove depth is 110 nm. After 3 minutes, the soft template was removed, and then the soft template was covered on the gold-plated curved surface. After 15 minutes of UV curing under the protection of nitrogen, a 100-watt high-pressure mercury lamp was used, and the soft template was removed to obtain the imprinting adhesive. structure.
将以上压印有结构的曲面于氧等离子中干法刻蚀15秒,除去压印结构的残余层,在刻蚀液中湿法刻蚀5分钟,刻蚀液为含有50mmol/L的Fe(NO3)3.9H2O和30mmol/L硫脲的水溶液。 The above curved surface imprinted with the structure was dry-etched in oxygen plasma for 15 seconds, the residual layer of the imprinted structure was removed, and wet-etched in the etching solution for 5 minutes. The etching solution was Fe( Aqueous solution of NO 3 ) 3 .9H 2 O and 30mmol/L thiourea.
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CN105858591B (en) * | 2016-03-29 | 2017-07-28 | 中国科学院高能物理研究所 | A kind of metal microstructure and its manufacturing method |
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CN107561857A (en) * | 2017-09-20 | 2018-01-09 | 南方科技大学 | Method for preparing optical super-structure surface based on nano-imprinting |
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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 |
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