Record Details

Title:
Controlling Magnetic Ordering in Ca$_{1–x}$Eu$_x$Co$_2$As$_2$ by Chemical Compression
Affiliation(s):
EuXFEL staff
Author group:
Instrument SCS
Topic:
Scientific area:
Abstract:
To investigate the interplay between electronic structure and itinerant magnetism, Ca$_{1–x}$Eu$_x$Co$_2$As$_2$ solid solutions (x = 0, 0.1, 0.3, 0.4, 0.5, 0.6, 0.65, 0.7, 0.9, 1.0) were prepared by reactions between constituent elements in molten Bi. All of the samples crystallize in the ThCr$_2$Si$_2$ structure type. The crystal structure refinement revealed the formation of Co vacancies, the concentration of which decreases as the Eu content increases. The Eu site exhibits mixed valence in all samples. X-ray absorption near-edge structure spectroscopy revealed that the average Eu oxidation state decreases from +2.17 at 0 &lt; x ≤ 0.6 to +2.14 at x ≥ 0.65. The same borderline behavior is observed in magnetic properties. The substitution of Eu for Ca causes the transition from the antiferromagnetic (AFM) ordering of Co moments in CaCo$_2$As$_2$ to ferromagnetic (FM) ordering of Co moments in Ca1–xEuxCo$_2$As$_2$ with 0.1 ≤ x ≤ 0.6. At higher Eu content, AFM ordering of Eu moments is observed, whereas the Co sublattice exhibits only paramagnetic behavior. Single-crystal neutron diffraction studies revealed that both Co and Eu sublattices order FM in Ca$_{0.5}$Eu$_{0.5}$Co$_2$As$_2$ with the magnetic moments aligned along the tetragonal c axis. In the AFM phases with x ≥ 0.65, only Eu moments are ordered in a helical spin structure defined by an incommensurate propagation vector k = [00q], with the moment lying in the ab plane. The changes in magnetic behavior are well-justified by the analysis of the electronic density of states and crystal orbital Hamilton population.
Imprint:
2016
Journal Information:
Chemistry of Materials, 28 (20), 7459–7469 (2016)
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Language(s):
English
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