Where is the unpaired transition metal in substoichiometric diboride line compounds

Abstract The atomic structure and local composition of high quality epitaxial substoichiometric titanium diboride (TiB1.9) thin film, deposited by unbalanced magnetron sputtering, were studied using analytical high-resolution scanning transmission electron microscopy, density functional theory and image simulations. The unpaired Ti is pinpointed to inclusion of Ti-based stacking faults within a few atomic layers, which terminates the { 1 1 ¯ 00 } prismatic plans of the crystal structure and attributed to the absence of B between Ti planes that locally relaxes the structure. This mechanism allows the line compound to accommodate the off-stoichiometry and remain a line compound between defects. The planar defects are embedded in otherwise stoichiometric TiB2 and are delineated by insertion of dislocations. An accompanied decrease in Ti-Ti bond lengths along and across the faults is observed.