Synthesis, Structures, and Magnetic Properties of Rare-Earth Cobalt Arsenides, RCo2As2 (R = La, Ce, Pr, Nd)

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• 作者：Corey M. Thompson ; Xiaoyan Tan ; Kirill Kovnir ; V. Ovidiu Garlea ; Andrei A. Gippius ; Alexander A. Yaroslavtsev ; Alexey P. Menushenkov ; Roman V. Chernikov ; Norbert B眉ttgen ; Wolfgang Kr盲tschmer ; Yan V. Zubavichus ; Michael Shatruk
• 刊名：Chemistry of Materials
• 出版年：2014
• 出版时间：June 24, 2014
• 年：2014
• 卷：26
• 期：12
• 页码：3825-3837
• 全文大小：666K
• ISSN：1520-5002

文摘

Four rare-earth cobalt arsenides, RCo₂As₂ (R = La, Ce, Pr, Nd), were obtained by reactions of constituent elements in molten Bi. The use of Bi flux also allowed the growth of representative single crystals. All compounds are isostructural and belong to the ThCr₂Si₂ type (space group I4/mmm). The formation of Co vacancies is observed in all structures, while the structures of La- and Ce-containing compounds also show incorporation of minor Bi defects next to the R crystallographic site. Correspondingly, the general formula of these materials can be written as R_1鈥?i>xBi_xCo_{2鈭捨?/sub>As2, with x/未 = 0.03/0.1, 0.05/0.15, 0/0.2, and 0/0.3 for R = La, Ce, Pr, and Nd, respectively. All compounds exhibit high-temperature ferromagnetic ordering of Co magnetic moments in the range 60鈥?00 K. Electronic band structure calculations revealed a high peak in the density of states at the Fermi level, thus supporting the itinerant nature of magnetism in the Co sublattice. The magnetic ordering in the lanthanide sublattice takes place at lower temperatures, with the R moments aligning antiparallel to the Co moments to give a ferrimagnetic ground state. The measurements on oriented single crystals demonstrated significant magnetic anisotropy in the ferrimagnetic state, with the preferred moment alignment along the c axis of the tetragonal lattice. Neutron powder diffraction failed to reveal the structure of magnetically ordered states but confirmed the presence of Co vacancies. X-ray absorption near-edge structure spectroscopy on Ce1.95Bi0.05Co1.85As2 showed the average oxidation state of Ce to be +3.06. Solid state NMR spectroscopy revealed a substantially reduced hyperfine field on the Co atoms in the vicinity of Bi defects.}