Segregation Engineering in MgO Nanoparticle-Derived Ceramics: The Impact of Calcium and Barium Admixtures on the Microstructure and Light Emission Properties

[Image: see text] Nanostructured segregates of alkaline earth oxides exhibit bright photoluminescence emission and great potential as components of earth-abundant inorganic phosphors. We evaluated segregation engineering of Ca(2+)- and Ba(2+)-admixtures in sintered MgO nanocube-derived compacts. Compaction and sintering transform the nanoparticle agglomerates into ceramics with residual porosities of Φ = 24–28%. Size mismatch drives admixture segregation into the intergranular region, where they form thin metal oxide films and inclusions decorating grain boundaries and pores. An important trend in the median grain size evolution of the sintered bodies with d(Ca(10 at. %)) = 90 nm < d(Ba(1 at. %)) = 160 nm < d(MgO) = 250 nm ∼ d(Ca(1 at. %)) = 280 nm < d(Ba(10 at. %)) = 870 nm is rationalized by segregation and interface energies, barriers for ion diffusion, admixture concentration, and the increasing surface basicity of the grains during processing. We outline the potential of admixtures on interface engineering in MgO nanocrystal-derived ceramics and demonstrate that in the sintered compacts, the photoluminescence emission originating from the grain surfaces is retained. Interior parts of the ceramic, which are accessible to molecules from the gas phase, contribute with oxygen partial pressure-dependent intensities to light emission.