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

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.