On the Location of Boron in SiO<inf>2</inf>-Embedded Si Nanocrystals - An X-ray Absorption Spectroscopy and Density Functional Theory Study

Abstract

Doping of silicon nanostructures is crucial to understand their properties and to enhance their potential in various fields of application. Herein, SiO -embedded Si nanocrystals (quantum dots) ≈3–6 nm in diameter are used as a model system to study the incorporation of B dopants by X-ray absorption near-edge spectroscopy (XANES). Such samples represent a model system for ultimately scaled, 3D-confined Si nanovolumes. The analysis is complemented by real-space density functional theory to calculate the 1s (K shell) electron binding energies of B in 11 different, thermodynamically stable configurations of the Si/SiO /SiO system. Although no indications for a substitutional B-acceptor configuration are found, the predominant O coordination of B indicates the preferred B incorporation into the SiO matrix and near the Si-nanocrystal/SiO interface, which is inherently incompatible with charge carrier generation by dopants. It is concluded that B doping of ultrasmall Si nanostructures fails due to a lack of B incorporation onto Si lattice sites that cannot be overcome by increasing the B concentration. The inability to efficiently insert B into Si nanovolumes appears to be a boron-specific fundamental obstacle for electronic doping (e.g., not observed for phosphorus) that adds to the established nanosize effects, namely, increased dopant activation and ionization energies.