Defect clusters and precipitation/oxidation of MgO-Co1−xO solid solution

MgO and Co_1−xO powders in 9:1 and 1:9 molar ratio (denoted as M₉C₁ and M₁C₉, respectively) were sintered and homogenized at 1600°C followed by annealing at 850°C and 800°C, respectively to form defect clusters and precipitates. Analytical electron microscopic observations indicated the protoxide remained as rock salt structure with complicated planar diffraction contrast for M₉C₁ sample, however with spinel paracrystal precipitated from the M₁C₉ sample due to the assembly of charge- and volume-compensating defects of the 4:1 type, i.e., four octahedral vacant sites surrounding one Co³⁺-filled tetrahedral interstitial site. The spacing of such defect clusters is 4.5 times the lattice spacing of the average spinel structure of Mg-doped Co_3−δO₄, indicating a higher defect cluster concentration than undoped Co_3−δO₄. The {111} faulting of Mg-doped Co_3−δO₄/Co_1−xO in the annealed M₁C₉ sample implies the possible presence of zinc blend-type defect clusters with cation vacancies assembled along oxygen close packed (111) plane.