Electronic, spin-state, and magnetic transitions inBa2Co9O14investigated by x-ray spectroscopies and neutron diffraction

Abstract

The mixed $\mathrm{B}{\mathrm{a}}_{2}\mathrm{C}{\mathrm{o}}_{9}{\mathrm{O}}_{14}\phantom{\rule{4pt}{0ex}}\mathrm{C}{\mathrm{o}}^{2+}/\mathrm{C}{\mathrm{o}}^{3+}$ system undergoes an insulator-insulator transition at ${T}_{\mathrm{SS}}\ensuremath{\sim}567\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ that arises from a spin-state transition at trivalent cobalt sites. Below this temperature, Co1, Co2, and Co4 are nonmagnetic ($S=0$, low spin). Ferromagnetically aligned Co5 spins are sandwiched between antiparallel planes of Co3 spins below ${T}_{\mathrm{N}}\ensuremath{\approx}41\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. The successive antiferromagnetic trilayers are inverted along the $c$ axis (compatible with ${C}_{c}2/c,\phantom{\rule{0.28em}{0ex}}{C}_{c}2/m$, or ${P}_{S}\text{\ensuremath{-}}1$ magnetic space groups, depending on the moment orientation in the $ab$ plane). The origin of the resistivity drop on warming was investigated by means of neutron and x-ray diffraction, x-ray absorption and emission spectroscopies, and x-ray magnetic circular dichroism. Charge-transfer multiplet calculations confirm that the divalent Co sites are both in an $S=3/2$ high spin state. Independently, the analysis of measured Co K\ensuremath{\beta} x-ray emission spectroscopy spectra agrees with this model. The magnetic moment from divalent Co5 ions is not fully ordered, likely due to the competition between magnetic anisotropy and weak supersuperexchange interactions, but not to covalency effects. Results agree with the spin blockade of electronic transport being partially removed at the octahedral trimers and also at the $\mathrm{Co}4{\mathrm{O}}_{6}$ units within the $\mathrm{Cd}{\mathrm{I}}_{2}$-type layer.