Direct bandgap silicon quantum dots achieved via electronegative capping

We propose a novel concept of achieving silicon quantum dots with radiative rates enhanced by more than two orders of magnitude up to the values characteristic for direct band gap semiconductors. Our tight-binding simulations show how the surface engineering can dramatically change the density of confined electrons in real- and $k$-space and give rise to the new conduction band levels in $\Gamma$-valley, thus promoting the direct radiative transitions. The effect may be realized by covering the silicon dots with covalently bonded electronegative ligands, such as alkyl or teflon chains and/or by embedding in highly electronegative medium.Comment: 5 pages, 3 figures+ Supplementary Material

Fluorescent Silicon Clusters and Nanoparticles

The fluorescence of silicon clusters is reviewed. Atomic clusters of silicon have been at the focus of research for several decades because of the relevance of size effects for material properties, the importance of silicon in electronics and the potential applications in bio-medicine. To date numerous examples of nanostructured forms of fluorescent silicon have been reported. This article introduces the principles and underlying concepts relevant for fluorescence of nanostructured silicon such as excitation, energy relaxation, radiative and non-radiative decay pathways and surface passivation. Experimental methods for the production of silicon clusters are presented. The geometric and electronic properties are reviewed and the implications for the ability to emit fluorescence are discussed. Free and pure silicon clusters produced in molecular beams appear to have properties that are unfavourable for light emission. However, when passivated or embedded in a suitable host, they may emit fluorescence. The current available data show that both quantum confinement and localised transitions, often at the surface, are responsible for fluorescence. By building silicon clusters atom by atom, and by embedding them in shells atom by atom, new insights into the microscopic origins of fluorescence from nanoscale silicon can be expected.Comment: 5 figures, chapter in "Silicon Nanomaterials Sourcebook", editor Klaus D. Sattler, CRC Press, August 201