The Boundary Between Volume and Surface-Driven Magnetic Properties in Spinel Iron Oxide Nanoparticles

Despite modern preparation techniques offer the opportunity to tailor the composition, size, and shape of magnetic nanoparticles, understanding and hence controlling the magnetic properties of such entities remains a challenging task, due to the complex interplay between the volume-related properties and the phenomena occurring at the particle’s surface. The present work investigates spinel iron oxide nanoparticles as a model system to quantitatively analyze the crossover between the bulk and the surface-dominated magnetic regimes. The magnetic properties of ensembles of nanoparticles with an average size in the range of 5–13 nm are compared. The role of surface anisotropy and the effect of oleic acid, one of the most common and versatile organic coatings, are discussed. The structural and morphological properties are investigated by X-ray diffraction and transmission electron microscopy. The size dependence of the surface contribution to the effective particle anisotropy and the magnetic structure are analyzed by magnetization measurements and in-field Mössbauer spectrometry. The structural data combined with magnetometry and Mössbauer spectrometry analysis are used to shed light on this complex scenario revealing a crossover between volume and surface-driven properties in the range of 5–7 nm. Graphical Abstract: [Figure not available: see fulltext.].