Crystal growth engineering and origin of the weak ferromagnetism in antiferromagnetic matrix of orthochromates from t-e orbital hybridization

We report a combined experimental and theoretical study on intriguing magnetic properties of quasiferroelectric orthochromates. Large single crystals of the family of RECrO₃ (RE = Y, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) compounds were successfully grown. Neutron Laue study indicates a good quality of the obtained single crystals. Applied magnetic field and temperature dependent magnetization measurements reveal their intrinsic magnetic properties, especially the antiferromagnetic (AFM) transition temperatures. Density functional theory studies of the electronic structures were carried out using the Perdew-Burke-Ernzerhof functional plus Hubbard U method. Crystallographic information and magnetism were theoretically optimized systematically. When RE³⁺ cations vary from Y³⁺ and Eu³⁺ to Lu³⁺ ions, the calculated t-e orbital hybridization degree and Néel temperature behave similarly to the experimentally determined AFM transition temperature with variation in cationic radius. We found that the t-e hybridization is anisotropic, causing a magnetic anisotropy of Cr³⁺ sublattices. This was evaluated with the nearest-neighbor J₁-J₂ model. Our research provides a picture of the electronic structures during the t-e hybridization process while changing RE ions and sheds light on the nature of the weak ferromagnetism coexisting with predominated antiferromagnetism. The available large RECrO₃ single crystals build a platform for further studies of orthochromates.