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.

Silicon nanocrystals are an extensively studied light-emitting material due to their inherent biocompatibility and compatibility with silicon-based technology. Although they might seem to fall behind their rival, namely, direct band gap based semiconductor nanocrystals, when it comes to the emission of light, room for improvement still lies in the exploitation of various surface passivations. In this paper, we report on an original way, taking place at room temperature and ambient pressure, to replace the silicon oxide shell of luminescent Si nanocrystals with capping involving organic residues. The modification of surface passivation is evidenced by both Fourier transform infrared spectroscopy and nuclear magnetic resonance measurements. In addition, single-nanocrystal spectroscopy reveals the occurrence of a systematic fine structure in the emission single spectra, which is connected with an intrinsic property of small nanocrystals since a very similar structure has recently been observed in specially passivated semiconductor CdZnSe nanoparticles. The organic capping also dramatically changes optical properties of Si nanocrystals (resulting ensemble photoluminescence quantum efficiency 20%, does not deteriorate, radiative lifetime 10 ns at 550 nm at room temperature). Optically clear colloidal dispersion of these nanocrystals thus exhibits properties fully comparable with direct band gap semiconductor nanoparticles.

We introduce a general method which allows reconstruction of electronic band structure of nanocrystals from ordinary real-space electronic structure calculations. A comprehensive study of band structure of a realistic nanocrystal is given including full geometric and electronic relaxation with the surface passivating groups. In particular, we combine this method with large scale density functional theory calculations to obtain insight into the luminescence properties of silicon nanocrystals of up to 3 nm in size depending on the surface passivation and geometric distortion.We conclude that the band structure concept is applicable to silicon nanocrystals with diameter larger than ≈ 2 nm with certain limitations. We also show how perturbations due to polarized surface groups or geometric distortion can lead to considerable moderation of momentum space selection rules.

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.