Silicon quantum dots (SiQDs) hold great promise for many future technologies. Silicon is already at the core of photovoltaics and microelectronics, and SiQDs are capable of efficient light emission and amplification. This is crucial for the development of the next technological frontiers-silicon photonics and optoelectronics. Unlike any other quantum dots (QDs), SiQDs are made of non-toxic and abundant material, offering one of the spectrally broadest emission tunabilities accessible with semiconductor QDs and allowing for tailored radiative rates over many orders of magnitude. This extraordinary flexibility of optical properties is achieved via a combination of the spatial confinement of carriers and the strong influence of surface chemistry. The complex physics of this material, which is still being unraveled, leads to new effects, opening up new opportunities for applications. In this review we summarize the latest progress in this fascinating research field, with special attention given to surface-induced effects, such as the emergence of direct bandgap transitions, and collective effects in densely packed QDs, such as space separated quantum cutting.

Small oxidized silicon nanocrystals of average sizes below 3.5 nm are prepared using modified electrochemical etching of a silicon wafer. Modifications introduced in the etching procedure together with postetching treatment in H2O2 lead to a decrease in the nanocrystalline core size and also, to some extent, to changes in the surface oxide. The interplay between these two factors allows us to blueshift the photoluminescence (PL) spectrum from 680 down to 590 nm, which is accompanied by changes in PL dynamics. This continual development, however, stops at about 590 nm, below which abrupt switching to fast decaying blue emission band at about 430 nm was observed. Discontinuity of the spectral shift and possible relation between both bands are discussed.

We collect a large number of experimental data from various sources to demonstrate that free-standing (FS) oxide-passivated silicon nanocrystals (SiNCs) exhibit considerably blueshifted emission, by 200 meV on average, compared to those prepared as matrix-embedded (ME) ones of the same size. This is suggested to arise from compressive strain, exerted on the nanocrystals by their matrix, which plays an important role in the light-emission process; this strain has been neglected up to now as opposed to the impact of quantum confinement or surface passivation. Our conclusion is also supported by the comparison of low-temperature behavior of photoluminescence of matrix-embedded and free-standing silicon nanocrystals.