Structural and electronic properties of nanosize semiconductor HfSin0/-/2- (n=6-16) material: a double-hybrid density functional theory investigation

Equilibrium geometries, thermodynamic stabilities, chemical reactivities, and electronic properties of neutral, mono-, and di-anionic Hf-doped silicon nanoclusters HfSin0/-2- (n = 6-16) are calculated by employing an ABCluster global search technique combined with mPW2PLYP scheme. Based on the concordance between simulated and experimental PES, the true global minima are confirmed for n = 6, 9, and 12-16. Optimized geometries for neutral HfSin nanoclusters can be divided into three stages: first, Hf atom prefers locating on the surface site of the cluster for n = 6-9, which can be obtained by adding one, two, three, and four Si atoms to HfSi5 tetragonal bipyramid, respectively (denoted as additive type); then, Hf atom is surrounded by Si atoms with half-cage configuration for n = 10-13; finally, Hf atom is encapsulated into Si cage pattern for n = 14-16. For mono-anions, it is from additive type (n = 6-11) to the cagelike configuration with Hf atom resided in silicon clusters (n = 12-16). For di-anions, it is additive type (n = 6-9) to the Hf-linked configuration (n = 10-11), and in the end to the Hf-encapsulated cagelike motif (n = 12-16). The thorough analysis of stability and chemical bonding revealed that the neutral HfSi16 and di-anionic HfSi152- are magic nanoclusters with good thermodynamic and chemical stability, which may make them as the most suitable building block for new functional materials. We suggest that the experimental PES of HfSin- with n = 7, 8, 10, and 11 should be further examined due to the lack of comparably low electron binding energy peaks.