Discovery of a series of silicon-based ferrimagnets in CrMnSi (n = 4-20) clusters.

Herein, the structural evolution, electronic and magnetic properties of silicon clusters with two different dopants, CrMnSi (n = 4-20) clusters were investigated at density functional theory (DFT) level. Small-sized CrMnSi (n = 4-9) clusters tend to adopt bipyramid-based geometries, while clusters with sizes n = 10 and 11 prefer to opening cage-like structures. For sizes n = 12 to 14, the half-encapsulated structures gradually transform into closed-cage Cr@Si structures, with the Mn atom exposed outside. Starting from size 15, both the Cr and Mn atoms are completely encapsulated by silicon atoms. Meanwhile, the Cr and Mn atoms in smaller-sized CrMnSi (n = 4-7) clusters tend to be separated, while they prefer to stay together for larger sizes. Cr atom always acts as electron donor, but not for Mn atom. From the average binding energies, one can conclude that it is easier to form larger size clusters. Smaller and larger sized CrMnSi (n = 4-9 and 19-20) clusters prefer to exhibit ferromagnetic Cr-Mn coupling, while sizes n = 10-18 always exhibit ferrimagnetic state. To our knowledge, the CrMnSi clusters is the first kind of neutral transition-metal doped semiconductor clusters that show ferrimagnetic state within a wide size range.