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

Journal Article · Wed Jan 01 00:00:00 EST 2014 · Chemistry of Materials

DOI:https://doi.org/10.1021/cm501522v· OSTI ID:1143565

Thompson, Corey ^[1]; Tan, Xiaoyan ^[1]; Kovnir, Kirill ^[1]; Garlea, Vasile O ^[2]; Shatruk, Michael ^[1]

---

1. Florida State University, Tallahassee
2. ORNL

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 structure 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 R1 xBixCo2 As2, with x/ = 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 of 150-200 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.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: DE-AC05-00OR22725
• OSTI ID: 1143565
• Journal Information: Chemistry of Materials, Vol. 26, Issue 12; ISSN 0897--4756
• Country of Publication: United States
• Language: English