Crystal structure and magnetic properties of the Ba<sub>3</sub>TeCo<sub>3</sub>P<sub>2</sub>O1<sub>4</sub>, Pb<sub>3</sub>TeCo<sub>3</sub>P<sub>2</sub>O<sub>14</sub>, and Pb<sub>3</sub>TeCo<sub>3</sub>V<sub>2</sub>O<sub>14</sub> langasites
Krizan, J.W.2; de la Cruz, C.4; Andersen, Niels Hessel1; Cava, R.J.2
1 Department of Physics, Technical University of Denmark2 Princeton University3 Oak Ridge National Laboratory4 Oak Ridge National Laboratory
We report the structural and magnetic characterizations of Ba3TeCo3P2O14, Pb3TeCo3P2O14, and Pb3TeCo3V2O14, compounds that are based on the mineral dugganite, which is isostructural to langasites. The magnetic part of the structure consists of layers of Co2+ triangles. Nuclear and magnetic structures were determined through a co-refinement of synchrotron and neutron powder diffraction data. In contrast to the undistorted P321 langasite structure of Ba3TeCo3P2O14, a complex structural distortion yielding a large supercell is found for both Pb3TeCo3P2O14 and Pb3TeCo3V2O14. Comparison of the three compounds studied along with the zinc analog Pb3TeZn3P2O14, also characterized here, suggests that the distortion is driven by Pb2+ lone pairs; as such, the Pb compounds crystallize in a pyroelectric space group, P2. Magnetic susceptibility, magnetization, and heat capacity measurements were performed to characterize the magnetic behavior. All three compounds become antiferromagnetic with Néel temperatures TN≈21K (Ba3TeCo3P2O14), ≈13K (Pb3TeCo3P2O14), and ≈8K (Pb3TeCo3V2O14), and they exhibit magnetic transitions at high applied magnetic fields, suggesting intrinsically complex magnetic behavior for tetrahedrally coordinated d7 Co2+ in this structure type.
Journal of Solid State Chemistry, 2013, Vol 203, p. 310-320
Langasite; Dugganite; Frustrated magnetism; Neutron diffraction; Magnetic structure; Rietveld co-refinement