Journal of Materials Science, Vol.51, No.16, 7491-7501, 2016
Improved ferromagnetic behavior and novel near-infrared photoluminescence in Mg/Mn-codoped CuCrO2 ceramics
Cu(Cr0.96-xMg0.04Mnx)O2-delta ceramics (0 <= x <= 15 at.%) were prepared by solid-state reaction. The influence of Mg acceptor codoping on microstructure, magnetic, and optical properties was studied. The codoping with Mg acceptors and the resulting lattice expansion are both favorable for the enhancement of hole density. Furthermore, the lower valence of Mg2+ compared with Cr3+ enables the mixed valence state of Mn ions: Mn3+ and Mn4+, and hence induces the hole-mediated double-exchange mechanism not only between Mn3+ and Cr3+ but also between Mn3+ and Mn4+. The coexistence of two ferromagnetic interactions and the high hole density are responsible for the improved saturation magnetization and Curie temperature. For photoluminescence, an unusual near-infrared emission at 1.5 eV is observed in the Mn-contained samples and can be attributed to the internal transition between the e and t(2) states of the Mn3+ impurity band. The emission intensity is primarily affected by two factors: the Mn3+ concentration and the position of the Fermi level. The results show that codoping with Mg acceptors is an effective way to strengthen the hole-mediated ferromagnetic interactions in CuCrO2 delafossite.