A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and the quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6-12.6 nm) are isostructural with a body centred tetragonal (bct) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.

No abstract

We report about the magnetic properties of antiferromagnetic (AF) MnO nanoparticles (NPs) with different sizes (6-19 nm). Using a combination of polarized neutron scattering and magnetometry we were able to resolve previously observed peculiarities. Magnetometry, on the one hand, reveals a peak in the zero field cooled (ZFC) magnetization curves at low temperatures (∼25 K) but no feature around the Néel temperature at 118 K. On the other hand, polarized neutron scattering shows the expected behavior of the AF order parameter vanishing around 118 K. Moreover, hysteresis curves measured at various temperatures reveal an exchange bias effect indicating a coupling of an AF core to a ferromagnetic (FM)-like shell. ZFC data measured at various fields exclude a purely superparamagnetic (SPM) scenario. We conclude that the magnetic behavior of MnO particles can be explained by a superposition of SPM-like thermal fluctuations of the AF-Néel vector inside the AF core and a strong magnetic coupling to a ferrimagnetic Mn2O3 or Mn3O4 shell. In addition, we have studied heterodimer ('Janus') particles, where a FM FePt particle is attached to the AF MnO particle. Via the exchange bias effect, the magnetic moment of the FePt subunit is stabilized by the MnO.