Barium di-silicide (BaSi₂) is a very promising absorber material for high-efficiency thin-film solar cells, due to its suitable bandgap, high light absorption coefficient, and long minority-carrier lifetime. In this study, we compare the nanostructure, layer composition, and point defects of BaSi₂ thin films deposited by Radio Frequency (RF) sputtering, Thermal Evaporation (TE), and Molecular Beam Epitaxy (MBE), using Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) depth profiling, Raman spectroscopy, and x-ray diffraction. Our DB-PAS study on thermally annealed RF-sputter deposited and on TE-deposited BaSi₂ layers, in a comparison with high quality BaSi₂ films produced by MBE, points to the presence of vacancy-oxygen complexes and Si or Ba mono-vacancies, respectively, in the (poly)crystalline BaSi₂ films. The degree of near-surface oxidation increases, going from MBE and TE to the industrially applicable RF-sputtered deposition synthesis. The use of a-Si capping layers on the thermally annealed RF-sputtered BaSi₂ films leads to a clear reduction in sub-surface oxidation and improves the quality of the BaSi₂ films, as judged from DB-PAS.