Ultrahigh porosity photoluminescent silicon aerocrystals with greater than 50% nanocrystal ensemble quantum yields

Abstract

Three types of mesoporous silicon flakes were fabricated by anodization in methanoic hydrofluoric acid from the same substrates (heavily doped p-type). Even though anodization current density, rinsing, drying method, and storage condition were the same for all three wafers, the resulting porous silicon (PSi) structures had very different properties. They had very different colors. Two of them showed quite high luminescence quantum yields (QYs), confirmed by very long luminescence lifetimes. The highest QY exceeded 50% for a peak photoluminescence wavelength of ∼750 nm. To date, this QY is the highest obtained for PSi and very importantly for silicon with large mesopores, which is typically not highly efficient (as opposed to silicon with small mesopores and microporous silicon). Large mesopores (>15 nm diameter) facilitate impregnation of various substances into luminescent material, such as metals for plasmonics and drugs for theranostics. The differing luminescent properties were correlated to electrolyte temperature during anodization, and evolution of the electrolyte batch (lowering of active fluoride content and buildup of hexafluorosilicate) used to anodize several wafers, whose effects are often overlooked when mass-producing PSi. Supercritical drying and completion of the slow growth of native oxide passivation in the dark leading to different final partially oxidized PSi structures are also important factors for the high QYs obtained. The highest QY was obtained with the structure having the most isolated Si nanocrystals in an amorphous Si oxide tissue.