Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Quantum Otto heat engine based on a multiferroic chain working substance

We study a quantum Otto engine operating on the basis of a helical spin-1/2 multiferroic chain with strongly coupled magnetic and ferroelectric order parameters. The presence of a finite spin chirality in the working substance enables steering of the cycle by an external electric field that couples to the electric polarization. We observe a direct connection between the chirality, the entanglement and the efficiency of the engine. An electric-field dependent threshold temperature is identified, above which the pair correlations in the system, as quantified by the thermal entanglement, diminish. In contrast to the pair correlations, the collective many-body thermal entanglement is less sensitive to the electric field, and in the high temperature limit converges to a constant value. We also discuss the correlations between the threshold temperature of the pair entanglement, the spin chirality and the minimum of the fidelities in relation to the electric and magnetic fields. The efficiency of the quantum Otto cycle shows a saturation plateau with increasing electric field amplitude.

Dielectric studies of Liquid Crystal Nanocomposites and Nanomaterial systems.

Liquid crystals (LCs) have revolutionized the display and communication technologies. Doping of LCs with inorganic nanoparticles such as carbon nanotubes, gold nanoparticles and ferroelectric nanoparticles have garnered the interest of research community as they aid in improving the electro-optic performance. In this thesis, we examine a hybrid nanocomposite comprising of 5CB liquid crystal and block copolymer functionalized barium titanate ferroelectric nanoparticles. This hybrid system exhibits a giant soft-memory effect. Here, spontaneous polarization of ferroelectric nanoparticles couples synergistically with the radially aligned BCP chains to create nanoscopic domains that can be rotated electromechanically and locked in space even after the removal of the applied electric field. The resulting non-volatile memory is several times larger than the non-functionalized sample and provides an insight into the role of non-covalent polymer functionalization. We also present the latest results from the dielectric and spectroscopic study of field assisted alignment of gold nanorods.

DIFFUSE-INTERFACE FIELD APPROACH TO MODELING SELF-ASSEMBLY OF HETEROGENEOUS COLLOIDAL SYSTEMS AND RELATED DIPOLE-DIPOLE INTERACTION PHENOMENA

Colloid self-assembly under external control is a new route to fabrication of advanced materials with novel microstructures and appealing functionalities. The kinetic processes of colloidal self-assembly have attracted great interests also because they are similar to many atomic level kinetic processes of materials. In the past decades, rapid technological progresses have been achieved on producing shape-anisotropic, patchy, core-shell structured particles and particles with electric/magnetic charges/dipoles, which greatly enriched the self-assembled structures. Multi-phase carrier liquids offer new route to controlling colloidal self-assembly. Therefore, heterogeneity is the essential characteristics of colloid system, while so far there still lacks a model that is able to efficiently incorporate these possible heterogeneities. This thesis is mainly devoted to development of a model and computational study on the complex colloid system through a diffuse-interface field approach (DIFA), recently developed by Wang et al. This meso-scale model is able to describe arbitrary particle shape and arbitrary charge/dipole distribution on the surface or body of particles. Within the framework of DIFA, a Gibbs-Duhem-type formula is introduced to treat Laplace pressure in multi-liquid-phase colloidal system and it obeys Young-Laplace equation. The model is thus capable to quantitatively study important capillarity related phenomena. Extensive computer simulations are performed to study the fundamental behavior of heterogeneous colloidal system. The role of Laplace pressure is revealed in determining the mechanical equilibrium of shape-anisotropic particles at fluid interfaces. In particular, it is found that the Laplace pressure plays a critical role in maintaining the stability of capillary bridges between close particles, which sheds light on a novel route to in situ firming compact but fragile colloidal microstructures via capillary bridges. Simulation results also show that competition between like-charge repulsion, dipole-dipole interaction and Brownian motion dictates the degree of aggregation of heterogeneously charged particles. Assembly and alignment of particles with magnetic dipoles under external field is studied. Finally, extended studies on the role of dipole-dipole interaction are performed for ferromagnetic and ferroelectric domain phenomena. The results reveal that the internal field generated by dipoles competes with external field to determine the dipole-domain evolution in ferroic materials.

Direct visualization of magnetic-field-induced magnetoelectric switching in multiferroic Aurivillius phase thin films

Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi6Ti2.8Fe1.52Mn0.68O18, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here, we demonstrate the growth of a similar composition, Bi6Ti2.99Fe1.46Mn0.55O18, via the liquid injection chemical vapor deposition technique. High-resolution magnetic measurements reveal a considerably higher in-plane ferromagnetic signature than CSD grown films (MS = 24.25 emu/g (215 emu/cm3), MR = 9.916 emu/g (81.5 emu/cm3), HC = 170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95%. In addition, we report the direct piezoresponse force microscopy visualization of ferroelectric switching while going through a full in-plane magnetic field cycle, where increased volumes (8.6 to 14% compared with 4 to 7% for the CSD-grown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching.

Radiation characteristics enhancement of planar structures using metasurfaces

In this thesis, the focus is on utilizing metasurfaces to improve radiation characteristics of planar structures. The study encompasses various aspects of metasurface applications, including enhancing antenna radiation characteristics and manipulating electromagnetic (EM) waves, such as polarization conversion and anomalous reflection. The thesis introduces the design of a single-port antenna with dual-mode operation, integrating metasurfaces. This antenna serves as the front-end for a next-generation tag, functioning as a position sensor with identification and energy harvesting capabilities. It operates in the lower European Ultra-Wideband (UWB) frequency range for communication/localization and the UHF band for wireless energy reception. The design aims for a low-profile stack-up that remains unaffected by background materials. Researchers worldwide are drawn to metasurfaces due to their EM wave manipulation capabilities. The thesis also demonstrates how a High-Impedance Surface (HIS) can enhance the antenna's versatility through metasurface application, including conformal design using 3D-printing technology, ensuring adaptability for various deformation and tracking/powering scenarios. Additionally, the thesis explores two distinct metasurface applications. One involves designing an angularly stable super-wideband Circular Polarization Converter (CPC) operating from 11 to 35GHz with an impressive relative impedance bandwidth of 104.3%. The CPC shows a stable response even at oblique incidences up to 40 degrees, with a Peak Cross-Polarization Ratio (PCR) exceeding 62% across the entire band. The second application focuses on an Intelligent Reflective Surface (IRS) capable of redirecting incoming waves in unconventional directions. Tunability is achieved through an artificially developed ferroelectric material (HfZrO) and distributed capacitive elements (IDC) to fine-tune impedance and phase responses at the meta-atom level. The IRS demonstrates anomalous reflection for normal incident waves. These innovative applications of metasurfaces offer promising advancements in antenna design, EM wave manipulation, and versatile wireless communication systems.