Local Valence and Hole-Doping Effect on Magnetic Properties in Double Perovskite La2NiMnO6

Local valence and Ca-doping effect in polycrystalline La₂NiMnO₆ have been investigated by using X-ray diffraction, X-ray absorption spectroscopy, Raman spectrum, and magnetometry. The refinement of X-ray diffraction data shows that all the samples are crystallized in pure double perovskite phase. The refined Ni(Mn)–O bond lengths and X-ray absorption spectroscopy provide evidences that the oxidation state of Ni and Mn ions in bulk La₂NiMnO₆ has the Ni²⁺ and Mn⁴⁺ configuration and the decrease of average A-site valence caused by Ca doping is compensated by the increase of Ni valence, while Mn keeps unchanged. As the Ca-doping content increases, the peak shapes of Raman spectroscopy exhibit an increase in the linewidth and decrease in the intensity, respectively, which reveals the increase the disorder of Ni–O bond length and the decrease of Ni/Mn ordering degree. Both the paramagnetic–ferromagnetic transition temperature and the saturation magnetization exhibit decrease with the increase of Ca-doping content, which are attributed to the decrease of Ni–O–Mn bond angle and the increase of Ni/Mn antisite disorder, respectively. All those behaviors can be ascribed to the valence state change of Ni ion caused by hole doping.