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ZnAl2O4∶Cr3+ hollow spheres composed of secondary nanoparticles with single spinel phase were fabricated using carbon templets.Monitoring the emission of 687 nm,two wide excitation bands attributed to the electrons of Cr3+ transiting from 4A2g (4F) → 4T1g (4F) and 4A2g (4F) → 4T2g (4F) were observed.The broad excitation band at about 397 nm was asymmetric and consisted of two peaks,indicating that there was a trigonal distortion existing in the lattices.The intensity of all emitting peaks revealed sharp increasing trend with the sintering temperature increase,and the intensity of emission at 698 nm assigned to inversion defects was more intense than that of emission at 687 nm assigned to octahedral Cr3+ ions in the undistorted spinel lattice.The samples with higher synthesized temperature revealed longer decay time,and the relative weightage of shorter decay time component decreased with the increase of sintering temperature,indicating that the surface defects decreased.