Exchange Interactions Mediated by Nonmagnetic Cations in Double Perovskites.

Establishing the physical mechanism governing exchange interactions is fundamental for exploring exotic phases such as quantum spin liquids in real materials. In this Letter, we address exchange interactions in Sr_{2}CuTe_{x}W_{1-x}O_{6}, a series of double perovskites that realize a spin-1/2 square lattice and are suggested to harbor a quantum spin liquid ground state arising from the random distribution of nonmagnetic ions. Our ab initio multireference configuration interaction calculations show that replacing Te atoms with W atoms changes the dominant couplings from nearest to next-nearest neighbor due to the crucial role of unoccupied states of the nonmagnetic ions in the super-superexchange mechanism. Combined with spin-wave theory simulations, our calculated exchange couplings provide an excellent description of the inelastic neutron scattering spectra of the parent compounds, as well as explaining that the magnetic excitations in Sr_{2}CuTe_{0.5}W_{0.5}O_{6} emerge from bond-disordered exchange couplings. Our results demonstrate the crucial role of the nonmagnetic cations in exchange interactions paving the way to further explore quantum spin liquid phases in bond-disordered materials.

Spin-liquid-like state in a spin-1/2 square-lattice antiferromagnet perovskite induced by d10-d0 cation mixing.

A quantum spin liquid state has long been predicted to arise in spin-1/2 Heisenberg square-lattice antiferromagnets at the boundary region between Néel (nearest-neighbor interaction dominates) and columnar (next-nearest-neighbor interaction dominates) antiferromagnetic order. However, there are no known compounds in this region. Here we use d10-d0 cation mixing to tune the magnetic interactions on the square lattice while simultaneously introducing disorder. We find spin-liquid-like behavior in the double perovskite Sr2Cu(Te0.5W0.5)O6, where the isostructural end phases Sr2CuTeO6 and Sr2CuWO6 are Néel and columnar type antiferromagnets, respectively. We show that magnetism in Sr2Cu(Te0.5W0.5)O6 is entirely dynamic down to 19 mK. Additionally, we observe at low temperatures for Sr2Cu(Te0.5W0.5)O6-similar to several spin liquid candidates-a plateau in muon spin relaxation rate and a strong T-linear dependence in specific heat. Our observations for Sr2Cu(Te0.5W0.5)O6 highlight the role of disorder in addition to magnetic frustration in spin liquid physics.

Isovalent Ca and Ba substitutions in thermoelectric layer-structured oxyselenide Sr2CoO2Cu2Se2.

Multilayered compounds typically present exotic functionalities, and some of them have been suggested as potential materials for thermoelectric conversion owing to their unique capability to decouple electronic and heat transport. Here we report new [CoO2] and [Cu2Se2] layered A2CoO2Cu2Se2 compounds in which Sr at the intervening alkaline-earth A site is partially replaced with Ca or Ba. The parent Sr2CoO2Cu2Se2 phase is a direct gap p-type semiconductor, and density functional theory (DFT) calculations indicate its topmost valence band consists of Cu 3d-Se 4p states. Upon the isovalent cation substitution the lattice modification in the ab plane is constrained by the stiff [CoO2] layer such that the lattice shrinkage/expansion mainly happens along the c axis. Substitution of Sr with the heavier and larger Ba significantly enhances the thermopower but more hole states would be required to optimize the thermoelectric performance. Thermal stability is related to the inter-oxide-selenide-layer interaction, and our thermogravimetric measurement data reveal that the A2CoO2Cu2Se2 materials could operate in the intermediate temperature region.