α-Bi2O3 microcrystals and microrods: Thermal synthesis, structural and luminescence properties

► Synthesis and growth mechanism of α-Bi2O3 microstructures with different shapes. ► Influence of annealing time and temperature on the obtained morphology. ► Phase purity assessment of Bi2O3 microrods by confocal micro-Raman spectroscopy. ► Luminescence of α-Bi2O3 microrods investigated by spatially-resolved techniques. ► Correlation between luminescence and X-ray photoelectron spectroscopy measurements.