Doping of silicon nanostructures is crucial to understand their properties and to enhance their potential in various fields of application. Herein, SiO$_{2}$-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

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... lculate the 1s (K shell) electron binding energies of B in 11 different, thermodynamically stable configurations of the Si/SiO$_{x}$/SiO$_{2}$ 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$_{2}$ matrix and near the Si-nanocrystal/SiO$_{2}$ 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.