Institut Néel, CNRS Grenoble and Université Joseph Fourier, 38042 Grenoble, Cedex 9, France.
J Phys Condens Matter. 2011 Nov 9;23(44):442202. doi: 10.1088/0953-8984/23/44/442202. Epub 2011 Oct 14.
Recent ab initio studies have theoretically predicted room temperature ferromagnetism in several oxide materials of the type AO(2) in which the cation A(4+) is substituted by a non-magnetic element of the 1 A column. Our purpose is to address experimentally the possibility of magnetism in Ti(1-x)K(x)O(2) compounds. The samples have been synthesized via the solid state route method at equilibrium. Our study has shown that Ti(1-x)K(x)O(2) is thermodynamically unstable and leads to a phase separation, in contradiction with the hypothesis of ab initio calculations. In particular, the crystalline TiO(2) grains appear to be surrounded by K-based phase. The oxidization state of the Ti ion is found to be in Ti(4+) as confirmed from the x-ray photoelectron spectra measurement. Nevertheless, K:TiO(2) compounds exhibit weak paramagnetism with the highest magnetic moment of ~0.5 μ(B) K(-1) but no long-range ferromagnetic order. The observed moment in these compounds remains much smaller than the predicted moment of 3 μ(B) by ab initio calculation. The apparent contradictions between our experiments and first-principles studies are discussed.
最近的从头算研究从理论上预测了 A0(2) 型几种氧化物材料在室温下的铁磁性,其中阳离子 A(4+) 被 1 A 列的非磁性元素取代。我们的目的是实验上研究 Ti(1-x)K(x)O(2) 化合物中存在磁性的可能性。样品是通过平衡态的固相法合成的。我们的研究表明 Ti(1-x)K(x)O(2) 在热力学上是不稳定的,并导致相分离,这与从头算计算的假设相矛盾。特别是,TiO(2)晶粒似乎被基于 K 的相所包围。从 X 射线光电子能谱测量中发现 Ti 离子的氧化态为 Ti(4+)。然而,K:TiO(2)化合物表现出弱的顺磁性,最高磁矩约为 0.5 μ(B) K(-1),但没有长程铁磁有序。这些化合物中观察到的磁矩远小于从头算计算预测的 3 μ(B)磁矩。我们的实验与第一性原理研究之间的明显矛盾进行了讨论。