Soft-Chemical Synthetic Route to Superparamagnetic FeAs@C Core–Shell Nanoparticles Exhibiting High Blocking Temperature

Abstract

Superparamagnetic FeAs nanoparticles with a fairly high blocking temperature (TB) have been synthesized through a hot injection precipitation technique. The synthesis involved usage of triphenylarsine (TPA) as the As precursor, which reacts with Fe(CO)5 by ligand displacement at moderate temperatures (300 °C). Addition of a surfactant, hexadecylamine (HDA), assists in the formation of the nanoparticles, due to its coordinating ability and low melting point which provides a molten flux like condition making this synthesis a solventless method. Decomposition of the carbonaceous precursors, HDA, TPA and Fe(CO)5, also produces the carbonaceous shell coating the FeAs nanoparticles. Magnetic characterization of these nanoparticles revealed the superparamagnetic nature of these nanoparticles with a perfect anhysteretic nature of the isothermal magnetization above TB. The TB observed in this system was indeed high (240 K) when compared with other superparamagnetic systems conventionally utilized for magnetic storage devices. It could be further increased by decreasing the strength of the applied magnetic field. The narrow hysteresis with low magnitude of coercivity at 5 K suggested soft ferromagnetic ordering in these nanoparticle ensembles. Mössbauer and XPS studies indicated that the Fe was present in +3 oxidation state and there was no signature of Fe(0) that could have been responsible for the increased magnetic moment and superparamagnetism. Typically for superparamagnetic nanoparticle ensemble, the need for isolation of the superparamagnetic domains (thereby inhibiting particle aggregation and enhancing the TB) has been in constant limelight. Carbonaceous coating on these as-synthesized nanoparticles formed in situ provided the physical nonmagnetic barrier needed for such isolation. The high TB and room temperature magnetic moment of these FeAs@C nanoparticles also make them potentially useful for applications in ferrofluids and magnetic refrigeration. In principle this method can be used as a general route toward synthesis of other arsenide nanostructures including the transition metal arsenide which show interesting magnetic and electronic properties (e.g., CoAs, MnAs) with finer control over morphology, composition and structure.