Manipulating the Curie point in γ-Fe filled carbon nano-onions: The role of Mn and Gd for enhanced magnetic functionalities

Recent works have proposed the stabilization of γ-Fe nanocrystals inside carbon nano-onions (CNOs) and nanotubes (CNTs) as active ferromagnetic phases for possible applications in hyperthermic dissipative systems. Stabilization of the γ-phase of iron is of particular interest due to the unit-cell dependent ferromagnetic properties and controllable Curie point. Here we investigate a modification of the chemical vapor synthesis (CVS) method for the in-situ manipulation of γ-Fe nanocrystals within CNOs, in presence of bis(isopropyl-cyclopentadienyl)manganese or tris(tetramethyl-cyclopentadienyl)gadolinium(III) as additional growth-precursors. In the presented experiments ferrocene, dichlorobenzene and sulfur mixtures were employed with a fixed ratio. Interestingly, when employing bis(isopropyl-cyclopentadienyl)manganese we demonstrate the stabilization of a modified FCC γ-Fe phase inside the CNOs, identifiable as a γ-Fe₂₃C₆ through X-ray diffraction and refinement of the structural model (obtained by employing the Rietveld method), with unit cell parameters a=b=c= 10.5569 Å and space group Fm-3m. The relative amount of Mn content was found to vary from 0.2% to 0.5%. Differently, comparative experiments performed in presence of great excess of tris(tetramethylcyclo-pentadienyl)gadolinium(III) reveal a significant variation of the sample's morphology, with the nucleation of Gd nanoparticles around γ-Fe filled CNOs. Magnetic characterization with field-dependent zero field cooled (ZFC) and field cooled (FC) acquisitions revealed for the first batch of experiments (method 1) a ferromagnetic behavior comparable to that of γ-Fe, with a T₁ Curie point located in proximity of T∼ 400 K and a T₂ Curie point in proximity of T∼90 K. Differently, for method-2, an important interplay of ferromagnetic and paramagnetic components was found in the Gd-decorated γ-Fe filled CNOs, with a reduction of the Curie point down to T∼350 K. The presented findings highlight the important role of 1) the γ-Fe₂₃C₆ phase in enhancing the saturation magnetization Ms of the filled CNOs and 2) the crystallinity of the Gd-component in allowing for an enhancement of the paramagnetic response in the filled CNOs.