The morphology, structure, composition, and conduction electron properties of quasi-spherical tin nanocrystals (NCs) of 2.5 nm average diameter, with unstrained, bulk-like α-Sn diamond cubic structure, observed in dark cubic boron nitride (cBN) crystallites, were determined by correlated analytical high-resolution scanning transmission electron microscopy and multifrequency electron spin resonance (ESR) investigations. The narrow Lorentzian ESR line with g = 2.0028 is attributed to the conduction ESR of the α-Sn NCs, consistent with the temperature- and frequency-independent small g-shift and intensity reduction under high temperature (950 °C) vacuum annealing when the α-Sn NCs are thermally dissolved in the host cBN crystallites. The ESR linewidth and line intensity vs temperature dependences recorded in the 20 to 295 K range are quantitatively described considering the presence of discrete, quantum confinement-induced conduction electron energy levels with ΔQC/k B = 125 K separation, close to the theoretical value for conductive α-Sn NCs of 2.5 nm in diameter. The observed properties are tentatively explained with the predicted nanosize induced band-gap opening and change of band ordering from bulk α-Sn to small unstrained α-Sn NCs, resulting in a topological phase transition that also explains the predominantly s-like character of the conduction band electron orbitals.
© 2022 The Authors. Published by American Chemical Society.