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Nanolithography on non-planar surfaces and self-assembly of metal salt-polymer nanomaterials

机译:金属盐聚合物纳米材料在非平面表面上的纳米光刻及其自组装

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摘要

This thesis is focused on fabrication of high aspect ratio nanostructures on non-planar surfaces using evaporated electron beam resist (Part I), and a novel fabrication methods of high resolutionhigh-resolution surface nanostructures using metal salt: polymer nanocomposites self-assembly (Part II).Various top-down and bottom-up nanopatterning techniques are currently available with the rapid progress in instrumentation and material engineering. However, patterning on non-planar surfaces of various materials still remains an overwhelming challenge because the conventional resist coating method, spin-coating, works well for only planar surfaces such as a flat wafer. On the other hand, the ability to pattern any given surface at the nanoscale, in particular surfaces with high inherent roughness or with pre-patterned micro-scale features, opens new perspectives in various fields from multi-scale biomimetics to optoelectronics. Part I (Chapter 1-4) of the present thesis aims to address this issue using evaporated electron beam resist. Electron beam lithography (EBL) is a versatile technique for creating arbitrary patterns on substrates with sub-10 nm resolution. Contrary to conventional lithography techniques, EBL was previously shown to be able to pattern non-planar surfaces using modified lithography system to adjust the beam position along z-axis, spray coating of the resist, and evaporation of the resist. Among them, evaporation of the resist is more favorable as it can be done on any irregular surfacesurfaces using commonly available thermal evaporation equipment. Yet, previous evaporated resist materials suffer from low resolution and sensitivity, as well as poor dry etching resists for subsequent pattern transfer to the sub-layer. Here, evaporation of polystyrene electron beam resist is studied which was used to pattern on irregular surfaces such as the cantilever of atomic force microscope and side surface of an optical fiber. Furthermore, in order to drastically increase the resist’s dry etching resistance, chromium that is a hard etching mask material was successfully incorporated into the resist by co-evaporating or Cr and polystyrene. This nanocomposite resist enabled the fabrication of very high aspect ratio structures by electron beam lithography followed by dry plasma etching. As this material can be evaporated on any substrate, including non-planar surfaces, it can open new era to spectroscopy and bio-sensing techniques.Part II (Chapter 5-6) presents a low-cost bottom-up fabrication techniques for creatingto create dense surface nanostructures without long-range ordering. Recently, micro- and nano-structured surfaces have become a hot topic in nanotechnology where performance of devices is enhanced due to such surface nanostructuring. Such structures are often called as a “smart” coating on the surfaces where they could provide wetting/de-wetting, adhesion, thermal and/or electrical conductivity, super-hydrophobicity, self-cleaning, anti-icing, anti-reflectivity, etc. Bottom-up techniques, such as self-assembly lithography, areis undoubtedly much more cost-effective than top down lithography techniques for applications that do not need long range ordering. Block co-polymer lithography, colloidal lithography, sol-gel processing, wet/dry etching are some commonly used techniques of bottom-up fabrication. However, fabrication of those structures with low costslow-cost as well as high performance is still challenging. Here a novel fabrication method is introduced, which involves spin-coating of metal salt : polymer composite followed by its phase-separation upon thermal annealing. Both spin-coating and thermal annealing are very low- cost processes. With this method, after pattern transfer to the substrate using the self-formed metal salt islands as mask, dense and high resolutionhigh-resolution nanostructures over large area without long-range ordering is achieved, which offered greatly enhanced super-hydrophobic and anti-reflective properties.
机译:本论文的重点是利用蒸发的电子束抗蚀剂在非平面表面上制备高纵横比纳米结构(第一部分),以及利用金属盐制备高分辨率高分辨率表面纳米结构的新方法:聚合物纳米复合材料自组装(第二部分) )。随着仪器和材料工程的飞速发展,目前可以使用各种自上而下和自下而上的纳米图案技术。然而,在各种材料的非平面表面上构图仍然是一个巨大的挑战,因为常规的抗蚀剂涂覆方法,旋涂,仅对平坦表面如平坦晶片有效。另一方面,能够在纳米级上对任何给定的表面进行图案化的能力,特别是具有高固有粗糙度或具有预先图案化的微米级特征的表面,为从多尺度仿生到光电学的各个领域打开了新的视野。本论文的第一部分(第1-4章)旨在利用蒸发的电子束抗蚀剂解决这一问题。电子束光刻(EBL)是一种通用技术,可在分辨率低于10 nm的基板上创建任意图案。与传统的光刻技术相反,以前已证明EBL能够使用改进的光刻系统来调整非平面表面的图案,以调整沿z轴的光束位置,抗蚀剂的喷涂和抗蚀剂的蒸发。其中,抗蚀剂的蒸发是更有利的,因为可以使用常规的热蒸发设备在任何不规则的表面上进行抗蚀剂的蒸发。然而,先前蒸发的抗蚀剂材料具有较低的分辨率和灵敏度,以及较差的干法蚀刻抗蚀剂,以用于随后的图案转移至子层。在此,研究了聚苯乙烯电子束抗蚀剂的蒸发,该蒸发用于在不规则表面(例如原子力显微镜的悬臂和光纤的侧面)上进行图案化。此外,为了显着提高抗蚀剂的抗干蚀刻性,通过共蒸发或Cr和聚苯乙烯成功地将铬(一种硬质蚀刻掩模材料)成功地掺入了抗蚀剂中。这种纳米复合抗蚀剂使得能够通过电子束光刻接着干法等离子体蚀刻来制造非常高的纵横比结构。由于这种材料可以在包括非平面表面在内的任何基材上蒸发,因此可以为光谱学和生物传感技术开辟新纪元。第二部分(第5-6章)介绍了一种低成本的自下而上的制造技术,用于创造创造没有长程有序的致密表面纳米结构。近来,微结构和纳米结构的表面已经成为纳米技术中的热门话题,其中由于这种表面纳米结构而增强了器件的性能。此类结构通常在表面上被称为“智能”涂层,可在这些表面上提供润湿/去润湿,附着力,导热和/或导电性,超疏水性,自清洁,防冰,抗反射性等自下而上的技术(例如自组装光刻)无疑比自上而下的光刻技术在不需要长期订购的应用中更具成本效益。嵌段共聚物光刻,胶体光刻,溶胶-凝胶处理,湿法/干法蚀刻是自下而上制造的一些常用技术。然而,以低成本,低成本以及高性能来制造那些结构仍然是挑战。在此介绍一种新颖的制造方法,该方法包括旋涂金属盐:聚合物复合材料,然后在热退火时进行相分离。旋涂和热退火都是非常低成本的过程。用这种方法,在将图形形成的图案以自形成的金属盐岛作为掩模转移到基板上之后,实现了大面积的致密,高分辨率,高分辨率的纳米结构,并且没有长程有序排列,从而大大增强了超疏水性和抗反射性属性。

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