Discrete, Dispersible MnAs Nanocrystals from Solution Methods: Phase Control on the Nanoscale and Magnetic Consequences

Abstract

Nanocrystals of thermodynamically stable alpha-MnAs (hexagonal NiAs-type) and metastable beta-MnAs (orthorhombic MnP-type) have been synthesized by the reaction of triphenylarsine oxide (Ph(3)AsO) and dimanganesedecacarbonyl (Mn(2)CO(10)) at temperatures ranging from 250 to 330 degrees C in the presence of the coordinating solvent trioctylphosphine oxide (TOPO). Morphologically, both alpha- and beta-MnAs nanoparticles adopt a core-shell type structure with a crystalline core and low-contrast noncrystalline shell. In contrast to prior studies on MnAs particles, disks, and films, the present bottom-up synthesis yields discrete, dispersible MnAs nanoparticles without a structural support. Even in the absence of epitaxial strain, the lattice parameters of the nanocrystals are decreased relative to bulk MnAs, resulting in a volume decrease of 0.35% in alpha-MnAs and 0.38% in beta-MnAs nanoparticles. In contrast to bulk MnAs, where the ferromagnetic phase transition upon warming through 313-317 K is concomitant with a structure change from ferromagnetic alpha- to paramagnetic beta-MnAs, powder X-ray diffraction studies suggest there is no conversion of alpha-MnAs to beta over the temperature range 298-343 K. Moreover, magnetic measurements suggest that both alpha- and beta-MnAs are ferromagnetic with T(C) approximately 315 K. Partial phase transformation of beta-MnAs nanoparticles into thermodynamically stable alpha-MnAs occurs slowly over time (i.e., months) at room temperature. However, there is no associated change in magnetization, suggesting the ferromagnetism observed in beta-MnAs is intrinsic and cannot be attributed to alpha-MnAs impurities.