Three-Dimensional Au-Coated Electrosprayed Nanostructured BODIPY Films on Aluminum Foil as Surface-Enhanced Raman Scattering Platforms and Their Catalytic Applications.

Abstract

The design and development of three-dimensional (3D) nanostructures with high surface-enhanced Raman scattering (SERS) performances have attracted considerable attention in the fields of chemistry, biology, and materials science. Nevertheless, electrospraying of organic small molecules on low-cost flexible substrates has never been studied to realize large-scale SERS-active platforms. Here, we report the facile, efficient, and low-cost fabrication of stable and reproducible Au-coated electrosprayed organic semiconductor films (Au@BDY-4T-BDY) on flexible regular aluminum foil at a large scale (5 cm × 5 cm) for practical SERS and catalytic applications. To this end, a well-designed acceptor-donor-acceptor-type solution-processable molecular semiconductor, BDY-4T-BDY, developed by our group, is used because of its advantageous structural and electrical properties. The morphology of the electrosprayed organic film changes by solution concentration, and two different 3D morphologies with out-of-plane features are obtained. Highly uniform dendritic nanoribbons with sharp needle-like tips and vertically oriented nanoplates (∼50 nm thickness) are achieved when electrospraying solution concentrations of 240 and 253% w/v (mg/mL) are, respectively, used. When these electrosprayed organic films are coated with a nanoscopic thin (30 nm) Au layer, the resulting Au@BDY-4T-BDY platforms demonstrate remarkable SERS enhancement factors up to 1.7 × 106 with excellent Raman signal reproducibility (relative standard deviation ≤ 0.13) for methylene blue over the entire film. Finally, Au@BDY-4T-BDY films showed good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with rate constants of 1.3 × 10-2 and 9.2 × 10-3 min-1. Our results suggest that electrospraying of rationally designed organic semiconductor molecules on flexible substrates holds great promise to enable low-cost, solution-processed, SERS-active platforms.