Ultrafast Carrier Dynamics of Silicon Nanowire Ensembles: The Impact of Geometrical Heterogeneity on Charge Carrier Lifetime

Ultrafast carrier dynamics in silicon nanowires with average diameters of 40, 50, 60, and 100 nm were studied with transient absorption spectroscopy. After 388 nm photoexcitation near the direct band gap of silicon, broadband spectra from 400 to 800 nm were collected between 200 fs and 1.3 ns. The transient spectra exhibited both absorptive and bleach features that evolved on multiple time scales, reflecting contributions from carrier thermalization and recombination as well as transient shifts of the ground-state absorption spectrum. The initially formed “hot” carriers relaxed to the band edge within the first ∼300 fs, followed by recombination over several hundreds of picoseconds. The charge carrier lifetime progressively decreased with decreasing diameter, a result consistent with a surface-mediated recombination process. Recombination dynamics were quantitatively modeled using the diameter distribution measured from each sample, and this analysis yielded a consistent surface recombination velocity of ∼2 × 10⁴ cm/s across all samples. The results indicate that transient absorption spectroscopy, which interrogates thousands of individual nanostructures simultaneously, can be an accurate probe of material parameters in inhomogeneous semiconductor samples when geometrical differences within the ensemble are properly analyzed