Advanced transmission electron microscopy on nanostructured magnetic materials

This doctoral work is focused on the study of nanostructured magnetic materials by advanced transmission electron microscopy (TEM) techniques, with emphasis on Ni2MnGa shape memory alloy thin films and magnetite nanoparticles for biomedical applications. The combination of high-resolution transmission electron microscopy and electron diffraction to characterize morphology and crystalline structure, with Lorentz microscopy and Electron Holography, permits to achieve a deep insight in the structural and magnetic nano-characterization of magnetic nanostructured materials. The work, carried out at the CNR-IMEM institute of Parma and partially at the LMA-INA institute of Zaragoza in the framework of the Erasmus Placement, produced remarkable results concerning the correlation between the microstructure of these systems and their magnetic/functional properties, from nano-to micro-to macro scale. In detail, the main topics treated are: 1) The use of Lorentz microscopy to investigate the role of dipolar interaction on hyperthermia of magnetic nanoparticles. Magnetic nanoparticles (NPs) in the superparamagnetic state are suitable for both diagnostic and therapeutic approaches. In particular, the magnetic hyperthermia, performed applying radiofrequency magnetic fields, can be effectively employed to locally induce cancer cell death. In real systems, clusters of magnetic nanoparticles with different size can form and the dipolar interactions that arise among nanoparticles can strongly influence the heating ability of the colloidal suspension. The role of the dipolar interactions in the hyperthermic behaviour of the system, however, is still not completely understood. About this topic, an investigation about magnetite nanoparticles with different degrees of interaction was carried out by Lorentz microscopy in a TEM. With this technique, it was possible to visualize and map the inter-particle interactions and to develop reliable models on the power losses mechanisms for different nanoparticles aggregates. As a result, a deeper understanding of the interactions effects on the performance of different nanoparticles suspensions as hyperthermic mediators was obtained. All the TEM results were supported and complemented by conventional o macroscopic (?) magnetic characterization. 2) Employment of advanced TEM techniques to study the effect of epitaxial strain and film thickness in the twin variants formation in Ni2MnGa martensitic thin films In martensitic thin films, the martensitic phase transition gives rise to a poly-twinned system characterized by a complex microstructure in which two families of twin variants can be displayed, with different magnetic anisotropies. Both the use of different substrates and film thickness can significantly modify the twin variants formation and consequently alter their functional properties. High-resolution TEM (HRTEM), Selected Area Electron Diffraction (SAED) and Electron Holography was employed to fully characterize Ni2MnGa thin films in plan and cross section geometries, by variyng film thicknesses in the range 50-100 nm and substrate type (MgO, MgO/Cr buffer layer). The structural and magnetic properties at the nano-micro scale were obtained by comparing TEM analysis with the morphological, structural and magnetic properties on a larger scale (by atomic force microscopy(AFM) , X-ray diffraction (XRD) and magnetic force microscopy (MFM)). A model for the twin variants selective formation, based on the stress states induced by the different substrates and film thicknesses, is moreover proposed. The model represents a powerful tool to selectively control the twin variants formation in martensitic films with low thicknesses and to tailor their magnetic domains structure. 3) An in depth TEM characterization to study the role of microstructure on magnetically induced reorientation of twin variants in Ni2MnGa 200 nm thin films In Ni2MnGa alloys, giant strains, one order of magnitude higher than the typical magnetostriction and state-of-the-art piezoelectric values, can be obtained by a magnetomechanical effect based on twin variants reorientation induced by magnetic field (MIR). Therefore, the possibility of exploiting the martensitic distortions to create tiny machines while keeping simple design, and high actuation frequencies makes these materials particularly appealing for the integration in active microsystems. However, very limited MIR effects were found in thin films and a full comprehension and exploitation of the effect is still lacking. An in-depth TEM characterization to correlate the crystal structure to the twin variants configurations and the magnetism inside each domain of the Ni2MnGa alloys is proposed by the combination of different advanced TEM techniques such as High Angle Annular Dark Field (HAADF) imaging, HRTEM with the comparison of the experimental images to the simulated ones, SAED, Electron Holography and magnetic domain analysis by in-situ observation. A model based on TEM results, compared with the findings obtained by XRD, AFM, MFM and magnetization curves, has been finally suggested to explain the anisotropic microstructure formation in a 200 nm thick Ni2MnGa film grown on MgO/Cr, displaying a huge anisotropic MIR. The proposed model is crucial for the engineering of the martensitic microstructure and for achieving substantial values of MIR in constrained films. 4) TEM study of the reduction of dimensionality in martensitic Ni2MnGa systems: from thin films to sub-micrometric disks After gaining a good understanding of the microstructure of two-dimensional NiMnGa martensitic films with relation to their application properties, the last chapter is devoted to test the possibility to obtain new functional properties by scaling down the dimensionality of these systems. To this aim, the in-depth TEM characterization was extended to a novel class of nanostructures, Ni2MnGa nano-disks, to investigate the structural and magnetic properties of the disks and the effect of the lateral confinement on the martensitic phase. By employing HRTEM, Lorentz microscopy and electron diffraction analysis as a function of temperature with heating holder, the actuation mechanisms, which remain active with the dimensionality reduction, can be studied.