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Surface Energy-Controlled SERS Substrates for Molecular Concentration at Plasmonic Nanogaps

机译：表面能控制的SERS基质在等离子纳米间隙处的分子浓度

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摘要

Positioning probe molecules at electromagnetic hot spots with nanometer precision is required to achieve highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) analysis. In this article, molecular positioning at plasmonic nanogaps is reported using a high aspect ratio (HAR) plasmonic nanopillar array with a controlled surface energy. A large-area HAR plasmonic nanopillar array is generated using a nanolithography-free simple process involving Ar plasma treatment applied to a smooth polymer surface and the subsequent evaporation of metal onto the polymer nanopillars. The surface energy can be precisely controlled through the selective removal of an adsorbed self-assembled monolayer of low surface-energy molecules prepared on the plasmonic nanopillars. This process can be used to tune the surface energy and provide a superhydrophobic surface with a water contact angle of 165.8 degrees on the one hand or a hydrophilic surface with a water contact angle of 40.0 degrees on the other. The highly tunable surface wettability is employed to systematically investigate the effects of the surface energy on the capillary-force-induced clustering among the HAR plasmonic nanopillars as well as on molecular concentration at the collapsed nanogaps present at the tops of the clustered nanopillars.
机译：需要将探针分子以纳米精度定位在电磁热点上，以实现高度灵敏且可重现的表面增强拉曼光谱（SERS）分析。在本文中，使用高纵横比（HAR）等离子体纳米柱阵列并控制了表面能，报道了等离子体在纳米间隙处的分子定位。使用无纳米光刻技术的简单过程生成大面积的HAR等离子体纳米柱阵列，该简单过程包括将Ar等离子体处理应用于光滑的聚合物表面，然后将金属蒸发到聚合物纳米柱上。通过选择性去除在等离激元纳米柱上制备的低表面能分子的吸附自组装单层，可以精确控制表面能。此过程可用于调整表面能，一方面提供具有165.8度水接触角的超疏水表面，另一方面提供具有40.0度水接触角的亲水性表面。高度可调节的表面润湿性用于系统研究表面能对毛细作用力诱导的HAR等离子体纳米柱之间的毛细作用诱导的聚集以及聚集纳米柱顶部出现的塌陷纳米间隙处的分子浓度的影响。

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