Evolution mechanism of mesoporous silicon nanopillars grown by metal-assisted chemical etching and nanosphere lithography: correlation of Raman spectra and red photoluminescence

Abstract

We have fabricated highly ordered, vertically aligned, high aspect ratio silicon nanopillars (SiNPLs) of diameter ~80 nm by combining metal-assisted chemical etching and nanosphere lithography. The evolution of surface morphology of porous silicon nanopillars has been explained, and the presence of mesoporous structures was detected on the top of silicon nanopillars using field emission scanning electron microscopy. The mesoporosity of the SiNPLs is confirmed by Brunauer–Emmett–Teller measurements. The peak shift and the splitting of optical phonon modes into LO and TO modes in the micro-Raman spectra of mesoporous SiNPLs manifest the presence of 2–3 nm porous Si nanocrystallites (P-SiNCs) on the top of SiNPLs and the size of crystallites was calculated using bond polarizability model for spherical phonon confinement. The origin of red luminescence is explained using quantum confinement (QC) and QC luminescent center models for the P-SiNCs, which is correlated with the micro-Raman spectra. Finally, we confirmed the origin of the red luminescence is from the P-SiNCs formed on surface of SiNPLs, highly desired for LED devices by suitably tailoring the substrate.