LaMn3Ni2Mn2O12: An A- and B‑Site Ordered Quadruple Perovskite with A‑Site Tuning Orthogonal Spin Ordering

• Published in: Chemistry of materials 2016-12, Vol.28 (24), p.8988-8996
• Main Authors: Yin, Yun-Yu, Liu, Min, Dai, Jian-Hong, Wang, Xiao, Zhou, Long, Cao, Huibo, dela Cruz, Clarina, Chen, Chien-Te, Xu, Yuanji, Shen, Xi, Yu, Richeng, Alonso, José Antonio, Muñoz, Angel, Yang, Yi-Feng, Jin, Changqing, Hu, Zhiwei, Long, Youwen
• Format: Article
• Language: English
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.6b03785

A new oxide, LaMn3Ni2Mn2O12, was prepared by high-pressure and high-temperature synthesis methods. The compound crystallizes in an AA′3B2B′2O12-type A-site and B-site ordered quadruple perovskite structure. The charge combination is confirmed to be LaMn3+ 3Ni2+ 2Mn4+ 2O12, where La and Mn3+ are 1:3 ordered at the A and A′ sites and the Ni2+ and Mn4+ are also distributed at the B and B′ sites in an orderly fashion in a rocksalt-type manner, respectively. A G-type antiferromagnetic ordering originating from the A′-site Mn3+ sublattice is found to occur at T N ≈ 46 K. Subsequently, the spin coupling between the B-site Ni2+ and B′-site Mn4+ sublattices leads to an orthogonally ordered spin alignment with a net ferromagnetic component near T C ≈ 34 K. First-principles calculations demonstrate that the A′-site Mn3+ spins play a crucial role in determining the spin structure of the B and B′ sites. This LaMn3Ni2Mn2O12 provides a rare example that shows orthogonal spin ordering in the B and B′ sites assisted by ordered A-site magnetic ions in perovskite systems.