ABSTRACT
Using Raman spectroscopy to study the correlated 4d-electron metal Sr_{2}RhO_{4}, we observe pronounced excitations at 220 meV and 240 meV with A_{1g} and B_{1g} symmetries, respectively. We identify them as transitions between the spin-orbit multiplets of the Rh ions, in close analogy to the spin-orbit excitons in the Mott insulators Sr_{2}IrO_{4} and α-RuCl_{3}. This observation provides direct evidence for the unquenched spin-orbit coupling in Sr_{2}RhO_{4}. A quantitative analysis of the data reveals that the tetragonal crystal field Δ in Sr_{2}RhO_{4} has a sign opposite to that in insulating Sr_{2}IrO_{4}, which enhances the planar xy orbital character of the effective J=1/2 wave function. This supports a metallic ground state, and suggests that c-axis compression of Sr_{2}RhO_{4} may transform it into a quasi-two-dimensional antiferromagnetic insulator.
ABSTRACT
Topotactic transformations between related crystal structures are a powerful emerging route for the synthesis of novel quantum materials. Whereas most such "soft chemistry" experiments have been carried out on polycrystalline powders or thin films, the topotactic modification of single crystals, the gold standard for physical property measurements on quantum materials, has been studied only sparsely. Here, we report the topotactic reduction of La1−xCaxNiO3 single crystals to La1−xCaxNiO2+δ using CaH2 as the reducing agent. The transformation from the three-dimensional perovskite to the quasitwo-dimensional infinite-layer phase was thoroughly characterized by x-ray diffraction, electron microscopy, Raman spectroscopy, magnetometry, and electrical transport measurements. Our work demonstrates that the infinite-layer structure can be realized as a bulk phase in crystals with micrometer-sized single domains. The electronic properties of these specimens resemble those of epitaxial thin films rather than powders with similar compositions.
