Specific features of synthesis and luminescence for lithium–aluminum spinels doped with manganese ions

Ceramic samples of lithium aluminates doped with manganese ions have been synthesized by a solid-state reaction method. The ceramics sintered at temperatures of 1000, 1100, 1200 or 1300 °C for 4 h in air are identified as LiAl5O8 compounds belonging to a spinel-like crystal structure with the P4132 space group. Nonetheless, ceramic compositions obtained by annealing at temperatures 1000, 1100 or 1200 °C have larger lattice parameters than that of a LiAl5O8 single crystal and are considered as metastable LiAl5O8 phases having partial disorder for the occupation of two inequivalent octahedral sites by Li+ and Al3+ ions, i.e. possessing Li - Al inversion. Such Mn doped disordered compositions show typical Mn4+ red luminescence with an emission peak at ∼662 nm. The charge compensation of Mn4+ replacing Al3+ ions in octahedral sites is achieved by Li+ ions entering some adjacent Al3+ sites due to inversion. On the other hand, annealing at a higher temperature (1300 °C) or prolonged (170 h) annealing at a lower temperature (1100 °C) leads to complete ordering of Li+ and Al3+ in ratio 1:3 at different octahedral sites in the LiAl5O8 structure in which Mn4+ luminescence is not observed due to the lack of a charge compensation mechanism. Doping Mn ions in such an ordered structure are realized in di- and trivalent states causing green and far-red luminescence, respectively. Additional annealing of the mixtures of the Mn-doped ordered LiAl5O8 composition and Li2CO3 at 1300 °C in air results in the production of phosphors which again show intense Mn4+ red luminescence and have the spinel-like crystal structure with the Fd3‾m space group due to random occupation of cationic sites by Li+ and Al3+ ions. •Partially disordered LiAl5O8 structure (P4132) is formed due to Li–Al inversion.•Completely ordered LiAl5O8 structure (P4132) is formed under prolonged annealing.•Random cation distribution creates fully disordered LiAl5O8 spinel structure (Fd3‾m).•Red luminescence of doping Mn4+ ions is observed only in disordered LiAl5O8 hosts.•Mn doped completely ordered LiAl5O8 is characterized by Mn2+ and Mn3+ luminescence.