Fabrication of Nano-Pattern Libraries and their Applications in Mode-Selective SERS

Patterned arrays of metallic nanostructures are commonly used in photonics, electronics, as well as functional materials and biotechnology because of their unique electronic and optical properties. Although great effort has been devoted to the development of nano-patterning techniques in the past decades, there are still existing challenges for nano-fabrication to achieve fine resolution and complex features over macroscopic areas in a reasonable time period. Herein, we devise two versatile patterning strategies, namely indentation colloidal lithography (ICL) and oblique colloidal lithography (OCL), for the stepwise patterning of planar substrates with numerous complex and unique designs. Those strategies combine colloidal self-assembly, imprint molding in conjunction with capillary force lithography and reactive ion etching, all of which are simple and straightforward.

Hexagonal arrays of symmetric and nonconcentric gold features are fabricated on glass substrates with highly controllable geometric parameters. The width, size and asymmetry of each surface structure could be tuned down to the ~10 nm level while the scale of the patterned area could exceed 1 cm^(2). Moreover, our technique also leads to the ability to develop an enormous variety of patterns through stepwise amplification of feature types. In particular, some of the features are fabricated for the first time, including target-triangle, hexagram, hexagram-dot and triangle-dot. Distinctive surface plasmon resonance (SPR) properties, such as higher order surface plasmon modes and Fano resonances are both observed from our patterns, which would be highly desired forthe study of plasmonic coupling. In addition, we have demonstrated a surface orientation dependent Raman selectivity on two nano-structures for the first time. Molecular vibrations with opposite symmetries can be selectively enhanced on different substrates. As a demonstration, this property is applied to the odd-even effect of n-alkanethiol self-assembly monolayers (SAMs) on the gold surface. The alternative alternation of the intensity ratios of two vibration pairs have been shown by surface enhanced Raman spectroscopy (SERS) as a function of the number of carbon atoms. The results obtained exhibit high sensitivity and excellent agreement with previous publications.