Origin of Wasp-Waisted Shape of Magnetization Hysteresis Loops in Co_xFe_3–xO₄ Nanoassemblies for Magnetic Hyperthermia

High Resolution Image Download MS PowerPoint Slide The origin of double-step magnetization reversal processes, so-called wasp-waist magnetization hysteresis loops, in single magnetic phase 3D cobalt ferrite nanoassemblies is still poorly understood. So far, this behavior has been mainly attributed to the coexistence of hard–soft magnetic phases and spin canting in nanoparticles. Here, we demonstrate the wasp-waisted magnetization loops in single-phase flower-like Co 0.83 Fe 2.17 O 4 nanoassemblies that were synthesized by modifying the ligand chemistry. Combining magnetization hysteresis loops at different concentrations, degrees of dipolar interactions, and temperatures, energy-dispersive X-ray and in-field Mössbauer spectroscopy, and small-angle neutron scattering, we propose that a combination of a strong dipolar field and spin-disordered nanobuilding blocks, leading to a soft magnetic phase at the grain boundaries, accounts for this anomalous and abrupt drop in magnetization in nanoassemblies. The nanoassemblies have a porous nanostructure with nanogaps between their nanobuilding blocks, as revealed from electron microscopy investigations. Small-angle neutron-scattering studies reveal spin disorder at the surfaces and interfaces of the nanobuilding blocks. The strong dipolar field at the ensemble level is achieved only when particle colloidal suspensions are dried from high particle concentrations, indicating the concentration-dependent nature of this behavior. Single-core nanoparticles with comparable chemical composition, effective size, coercive field, and magnetization, but with a coherent crystal structure, do not reveal this peculiar behavior even at the highest concentrations. Our study introduces organic capping ligands as a means to tune magnetization processes in nanoparticles for applications in magnetic hyperthermia, an unexplored role for organic ligands beyond giving nanoparticles colloidal stability.