Structural characterization and plasmonic properties of manganese oxide-coated gold nanorods

Abstract

The preparation of metal@(dielectric or semiconductor) core@shell hybrid materials have been shown promising for both SERS and SEF applications due to improved stability in the presence of ions and the adsorbate compared to non-covered metallic nanoparticles. However, fine control over the thickness of the covering layer is essential to maximize the intrinsic trade-off between the plasmonic enhancement and the chemical stability improvement. Here, the preparation of manganese dioxide ultrathin layers covered gold nanorods (AuNR@MnO₂) with varying thicknesses of the MnO₂ layer is reported, and the characterization and evaluation of the resulting materials as SERS and SEF substrate. The MnO₂ layer over the AuNR was prepared by reducing potassium permanganate by sodium oxalate in a basic medium. The AuNR@MnO₂ hybrid material was characterized by UV-Vis spectroscopy, transmission electron microscopy, X-ray powder diffraction, and cyclic voltammetry. It was studied the SEF effect of the cyanine dye IR-820 excited at 785 nm with high performance for several thicknesses of the MnO₂ ultrathin film. The enhancement factor increased for thicker oxide layers. The SERS effect of the IR-820 dye excited at 633 nm showed the most significant enhancement factor for thinner layers. The seemly opposite behavior of the two plasmonic effects may be assigned to the distance dependence of the electromagnetic field generated in the AuNR, which results in decreasing SERS performance. For SEF, the thinner layers resulted in the Au nanoparticles' emission quenching, so a more significant distance was necessary to observe enhancement.

Keywords: AuNR@MnO(2); Gold nanorods; Hybrid plasmonic materials; Manganese oxide; SEF; SERS.