Aiming for a more practical route to highly stable visible photoluminescence (PL) from silicon, a novel approach to produce luminescent silicon nanoparticles (Si‐NPs) is developed. Single crystalline Si‐NPs are synthesized by pyrolysis of silane (SiH4) in a microwave plasma reactor at very high production rates (0.1–10 g h−1). The emission wavelength of the Si‐NPs is controlled by etching them in a mixture of hydrofluoric acid and nitric acid. Emission across the entire visible spectrum is obtained by varying the etching time. It is observed that the air oxidation of the etched Si‐NPs profoundly affects their optical properties, and causes their emission to blue‐shift and diminish in intensity with time. Modification of the silicon surface by UV‐induced hydrosilylation also causes a shift in the spectrum. The nature of the shift (red/blue) is dependent on the emission wavelength of the etched Si‐NPs. In addition, the amount of shift depends on the type of organic ligand on the silicon surface and the UV exposure time. The surface modification of Si‐NPs with different alkenes results in highly stable PL and allows their dispersion in a variety of organic solvents. This method of producing macroscopic quantities of Si‐NPs with very high PL stability opens new avenues to applications of silicon quantum dots in optoelectronic and biological fields, and paves the way towards their commercialization.

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We have investigated the role of doping and paramagnetic states on the electronic transport of networks assembled from freestanding Si nanocrystals (Si-NCs). Electrically detected magnetic resonance (EDMR) studies on Si-NCs films, which show a strong increase of conductivity with doping of individual Si-NCs, reveal that P donors and Si dangling bonds contribute to dark conductivity via spin-dependent hopping, whereas in photoconductivity, these states act as spin-dependent recombination centers of photogenerated electrons and holes. Comparison between EDMR and conventional electron paramagnetic resonance shows that different subsets of P-doped nanocrystals contribute to the different transport processes.

When designing nano-Si electrodes for lithium-ion batteries, the detrimental effect of the c-LiSi phase formed upon full lithiation is often a concern. In this study, Si nanoparticles with controlled particle sizes and morphology were synthesized, and parasitic reactions of the metastable c-LiSi phase with the nonaqueous electrolyte was investigated. The use of smaller Si nanoparticles (∼60 nm) and the addition of fluoroethylene carbonate additive played decisive roles in the parasitic reactions such that the c-LiSi phase could disappear at the end of lithiation. This suppression of c-LiSi improved the cycle life of the nano-Si electrodes but with a little loss of specific capacity. In addition, the characteristic c-LiSi peak in the differential capacity (dQ/dV) plots can be used as an early-stage indicator of cell capacity fade during cycling. Our findings can contribute to the design guidelines of Si electrodes and allow us to quantify another factor to the performance of the Si electrodes.