Temperature-dependent photoluminescence from nanostructured silicon: role of quantum-confined Bloch states and interfacial defects

The strong visible photoluminescence (PL) in surface-oxidized nanostructured silicon emerges from the interplay between intrinsic Bloch states and oxide-related interfacial defects, making it difficult to isolate their role. Temperature-dependent $\left(5-350K\right)$ PL measurements on nanostructured silicon with varying crystallite sizes manifest three distinct decay mechanisms involving band-to-band, band-to-trap and trap-to-trap transitions to multiple emission bands appearing in the convoluted broad PL spectrum. At lower temperatures $\left(\lesssim 225K\right)$, PL peak energy associated with the quantum-confined Bloch states exhibits a nearly linear blue shift, governed by a strong inverse power law dependence of the temperature coefficient on the effective crystallite size, while this trend reverses at higher temperatures. Conversely, the defect-related peak energies increase monotonically at a nearly constant rate throughout the experimental temperature range. A general analytical model for finite systems with a separable pseudo-potential effectively estimates the contributions from different decay channels to the PL emission. Theoretical results align well with the experimentally obtained values of the power-law exponents, offering a novel way to distinguish between the radiative recombination channels involving quantum-confined Bloch states and interfacial defects/trap states in nanostructured silicon.