Interplay of valence states and magnetic interactions in the perovskite system LaNi1–xRhxO3

We report on the structural, magnetic and electronic properties of Rh substituted LaNiO3, LaNi1–xRhxO3 (0 ​≤ ​x ​≤ ​1). Increased Rh contents are associated with increased structural distortion, and we observe a phase transformation and an immiscibility gap between 0.15 ​≤ ​x ​≤ ​0.25, separating the R-3c and Pnma perovskite structure regimes. Structural evaluation by synchrotron X-ray diffraction, X-ray absorption spectroscopy and DC magnetic measurements suggest variations in oxidation state for the B-site cations, with Ni(II)/Rh(IV), in addition to Rh(III), dominating for high Rh-contents. Although ordering of Ni(II)/Rh(IV) is possible, no B-site ordering between Ni and Rh is observed for any composition. A metal-to-insulator transition occurs upon Rh-substitution, correlating with the structural transition. DC- and AC magnetic measurements reveal that several of the compositions are magnetically frustrated with both antiferro- and ferromagnetic behaviour at low temperatures. The antiferromagnetic interactions are dominating, while the ferromagnetic interactions increase with increasing Rh-content, to a maximum at x ​= ​0.80 and x ​= ​0.90 in LaNi1–xRhxO3. The mixed valence states are assumed to contribute with a ferromagnetic super-exchange interaction between Ni(II) and Rh(IV). [Display omitted] •A phase transformation from R-3c to Pnma correlate with a MIT for 0.10 ​ ​0.60) samples show weak ferromagnetism, correlating with mixed valence.•Conduction mechanisms strongly depend on Rh-content (x) and temperature.