ABSTRACT
Layered van der Waals (vdW) chalcogenides of 3d transition metals are a rich source of two-dimensional (2D) nanomaterials, in which atomically thin layers with the terminating chalcogen atoms exhibit promising functionality for novel spintronic devices. Here, we report on the synthesis, crystal growth, and magnetic properties of FeAl2Se4, MnAl2S4, and MnAl2Se4 ternary chalcogenides. Crystal structures are probed by powder X-ray diffraction, Mössbauer spectroscopy, and high-resolution transmission electron microscopy. We improve the structural models of FeAl2Se4 and MnAl2S4 and show that isostructural MnAl2S4 and MnAl2Se4 crystallize in the centrosymmetric R3Ì Ì m space group. In the crystal structure, transition metal and Al atoms mutually occupy the octahedral and tetrahedral voids of four close-packing chalcogen layers terminated by vdW gaps. The transition-metal atoms form a triangular arrangement inside the close-packing layers. As a result, FeAl2Se4 and MnAl2S4 show no long-range magnetic order in the studied temperature range. In the paramagnetic state, Fe and Mn possess effective magnetic moments of 4.99(2) and 5.405(6) µB, respectively. Furthermore, FeAl2Se4 enters a frozen spin-disordered state below 12 K.
ABSTRACT
Transition metal-based layered compounds with van der Waals gaps between the adjacent layers are a source of two-dimensional (2D) nanomaterials with nontrivial transport and magnetic properties. 2D ferromagnets, both metals and semiconductors, can be leveraged to produce spin-polarized current in spintronic devices with tailored functionalities. Here, we report on the synthesis, crystal growth, crystal and electronic structure, and magnetic properties of the Fe-based FeAl2S4 layered sulfide. In the crystal structure, Fe and Al atoms mix on octahedral and tetrahedral sites between hexagonal layers of S atoms, which are terminated by the van der Waals gaps. Band structure calculations reveal strong electronic correlations within the semiconducting ground state, which induce ferromagnetism with the magnetic moment of 0.12µB per formula unit for a Hubbard interaction U = 5 eV and Hund's rule coupling J = 0.8 eV. Crystal growth employing chemical vapor transport reactions results in bulk cleavable crystals, which show paramagnetic Curie-Weiss behavior at high temperatures with the Fe2+ magnetic centers. At low temperatures, an anomaly is observed on the magnetic susceptibility curve, below which the magnetization shows ferromagnetic hysteresis, indicating the presence of ferromagnetic correlations in FeAl2S4.
