Magnetic ordering of a van der Waals material combining vastly different magnetic anisotropies

Abstract

Among magnetic van der Waals materials, the vanadium trihalide family exhibits unique features. In particular, VI3 contains V atoms of two different types, as two energetically close electronic occupations can coexist in real samples. These types show strikingly different magnetic anisotropy, predicted to differ by more than an order of magnitude. The combination forms a distinctive magnetic system. VI3 also displays an unusual thickness dependence: the monolayer Curie temperature (TC) is higher than that of the bulk, contrary to the expectation that interlayer coupling reinforces magnetic order. Using atomistic spin-dynamics simulations informed by first-principles calculations, we investigate the critical temperature behavior from the combined perspective of single-ion anisotropy and exchange interactions. The strong anisotropy contrast significantly affects thermal stability: increasing the fraction of high-anisotropy sites raises the energy cost of transverse spin fluctuations and increases the ordering temperature. Furthermore, V-atom inhomogeneity makes the interlayer super-superexchange network spatially nonuniform, creating competing exchange pathways. This weakens coherent interlayer order while preserving robust intralayer ferromagnetic correlations, thus modifying the bulk-monolayer TC relation. Our model reproduces experimental TC values when the ratio of the two V types is close to 1:1, in agreement with two experimental methods. This supports the coexistence of two V configurations in VI3. The monolayer TC is reproduced with a slightly modified ratio, possibly linked to polaron concentration. The sensitivity of TC to this ratio suggests that the ordering temperature of VI3 can in principle be tuned over a broad range by controlling the relative occupation of the two vanadium configurations.