Magnetic MoS2 pizzas and sandwiches with Mnn (n=1-4) cluster toppings and fillings: A first-principles investigation

The inorganic layered crystal (ILC) MoS2 in low dimensions is considered as one of the most promising and efficient semiconductors. To enable the magnetism and keep intrinsic crystal structures, we carried out a first-principles study of the magnetic and semiconductive monolayer MoS2 adsorbed with the Mn-n (n = 1-4) clusters, and bilayer MoS2 intercalated with the same clusters. Geometric optimizations of the Mn-n@MoS2 systems show the complexes prefer to have Mn-n@MoS2(M) pizza and Mn-n@MoS2(B) sandwich forms in the mono-and bi-layered cases, respectively. Introductions of the clusters will enhance complex stabilities, while bonds and charge transfers are found between external Mn clusters and the S atoms in the hosts. The pizzas have medium magnetic moments of 3, 6, 9, 4 mu(B) and sandwiches of 3, 2, 3, 2 mu(B) following the manganese numbers. The pizzas and sandwiches are semiconductors, but with narrower bandgaps compared to their corresponding pristine hosts. Direct bandgaps were found in the Mn-n@MoS2(M) (n = 1,4) pizzas, and excitingly in the Mn-1@MoS2(B) sandwich. Combining functional clusters to the layered hosts, the present work shows a novel material manipulation strategy to boost semiconductive ILCs applications in magnetics.