Institute of Materials Research and Engineering, A STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore 117602, Republic of Singapore.
ACS Nano. 2012 Feb 28;6(2):1494-502. doi: 10.1021/nn204405k. Epub 2012 Jan 17.
Although step-and-flash imprint lithography, or S-FIL, has brought about tremendous advancement in wafer-scale fabrication of sub-100 nm features of photopolymerizable organic and organo-silicon-based resists, it has not been successful in direct patterning of inorganic materials such as oxides because of the difficulties associated with resist formulation and its dispensing. In this paper, we demonstrate the proof-of-concept S-FIL of titanium dioxide (TiO(2)) carried by an acrylate-based formulation containing an allyl-functionalized titanium complex. The prepolymer formulation contains 48 wt % metal precursor, but it exhibits low enough viscosity (∼5 mPa·s) to be dispensed by an automatic dispensing system, adheres and spreads well on the substrate, is insensitive to pattern density variations, and rapidly polymerizes when exposed to broadband UV radiation to give a yield close to 95%. Five fields, each measuring 1 cm × 1 cm, consisting of 100 nm gratings were successively imprinted. Heat-treatment of the patterned structures at 450 °C resulted in the loss of organics and their subsequent shrinkage without the loss of integrity or aspect ratio and converted them to TiO(2) anatase nanostructures as small as 30 nm wide. With this approach, wafer-scale direct patterning of functional oxides on a sub-100 nm scale using S-FIL can become a distinct possibility.
虽然步进式闪光压印光刻(step-and-flash imprint lithography,或 S-FIL)在晶圆级制造亚 100nm 尺寸的光聚合有机和有机硅基抗蚀剂方面取得了巨大进展,但由于抗蚀剂配方及其分配的困难,它未能成功地直接对无机材料(如氧化物)进行图案化。在本文中,我们展示了基于丙烯酸酯的配方中携带的二氧化钛(TiO(2))的 S-FIL 概念验证,该配方含有烯丙基官能化钛配合物。预聚物配方含有 48wt%的金属前体,但它的粘度足够低(约 5mPa·s),可以通过自动分配系统分配,在基底上附着和扩展良好,对图案密度变化不敏感,并且在暴露于宽带紫外辐射时迅速聚合,产率接近 95%。成功地压印了五个尺寸均为 1cm×1cm 的区域,每个区域包含 100nm 的光栅。对图案结构在 450°C 下进行热处理,导致有机物的损失及其随后的收缩,而不会损失完整性或纵横比,并将其转化为 TiO(2)锐钛矿纳米结构,最小宽度可达 30nm。通过这种方法,使用 S-FIL 可以在亚 100nm 尺度上对功能氧化物进行晶圆级的直接图案化,这成为一种可能。