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Abstract: Strongly correlated electron systems display a complex interplay of structural, magnetic, and electronic degrees of freedom, leading to a variety of emergent phenomena. Utilising neutron and X-ray scattering techniques alongside a group-theoretical framework, I have developed and applied a unified approach to characterise this interplay in a selection of non-model 3d transition metal oxides, with a particular focus on magneto-structural coupling. I first investigate a spin reorientation transition in BiCrO₃, solving its magnetic structures and determining Dzyaloshinskii-Moriya interactions responsible for weak ferromagnetism in each phase. The interactions are demonstrated to couple spin to respective octahedral rotations and antiferroelectric distortions by a phenomenological model. I then present a study on PrMn₇O₁₂, where magneto-elastic coupling and a canted ground state are elucidated by neutron powder diffraction. A mean field model that captures the influence of competing exchange interactions on the complex ferrimagnetic ordering is developed that, together with the results, extends our understanding of magnetism in the A³⁺Mn₇O₁₂ quadruple perovskite manganites. Turning to BiMn₇O₁₂, I determine a highly canted magnetic phase composed of polar E-type antiferromagnetic order superposed on a ferrimagnetic order. Modelling reveals the coupling of the polar antiferromagnetism to ferroelectric distortions, exemplifying a novel category of type I multiferroics with inverse exchange-striction. I then explore the Cu-doped BiMn₇O₁₂ systems in the half-metallic limit, employing a host of complementary experimental techniques to characterise their structural, magnetic order, disorder and transport properties. The study reveals a diverse set of behaviours across the solid solutions, marked by coexisting short and long range magnetic correlations, spin freezing transitions, near zero thermal expansion and magneto-resistance. Lastly, in a resonant X-ray study on CoTi₂O₅, I demonstrate near-complete antiferromagnetic domain switching under uniaxial stress, exploiting the spin Jahn-Teller to relieve its perfectly frustrated exchange topology.

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Abstract: Strontium titanate is a classic quantum paraelectric oxide material that has been widely studied in bulk and thin films. It exhibits a well-known cubic-to-tetragonal antiferrodistortive phase transition at 105 K, characterized by the rotation of oxygen octahedra. A possible second phase transition at lower temperature is suppressed by quantum fluctuations, preventing the onset of ferroelectric order. However, recent studies have shown that ferroelectric order can be established at low temperatures by inducing strain and other means. Here, we used in situ multireflection Bragg coherent x-ray diffraction imaging to measure the strain and rotation tensors for two strontium titanate microcrystals at low temperature. We observe strains induced by dislocations and inclusion-like impurities in the microcrystals. Based on radial magnitude plots, these strains increase in magnitude and spread as the temperature decreases. Pearson's correlation heat maps show a structural transition at 50 K, which could possibly be the formation of a low-temperature ferroelectric phase in the presence of strain. We do not observe any change in local strains associated with the tetragonal phase transition at 105 K.

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Abstract: Surface proton hopping conduction (SPHC) mechanisms is an important proton conduction mechanism in conventional polymer electrolytes, along with the Grotthuss and vehicle mechanisms. Due to the small diffusion coefficient of protons in the SPHC mechanism, few studies have focused on the SPHC mechanism. Recently, it has been found that a dense alignment of SO3− groups significantly lowers the activation energy in the SPHC mechanism, enabling fast proton conduction. In this study, a series of polymerizable amphiphilic-zwitterions is prepared, forming bicontinuous cubic liquid-crystalline assemblies with gyroid symmetry in the presence of suitable amounts of bis(trifluoromethanesulfonyl) imide (HTf2N) and water. In situ polymerization of these compounds yields gyroid-nanostructured polymer films, as confirmed by synchrotron small-angle X-ray scattering experiments. The high proton conductivity of the films on the order of 10−2 S cm−1 at 40 °C and relative humidity of 90% is based solely on the SPHC mechanism.

Open Access

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Abstract: Although the LiCoO2 (LCO) cathode material has been widely used in commercial lithium ion batteries (LIB) and shows high stability, LIB’s improvements have several challenges that still need to be overcome. In this paper, we have studied the in-operando structural properties of LCO within battery cells using Bragg Coherent X-ray Diffraction Imaging to identify ways to optimise the LCO batteries’ cycling. We have successfully reconstructed the X-ray scattering phase variation (a fingerprint of atomic displacement) within a ≈ (1.6 × 1.4 × 1.3) μm3 LCO nanocrystal across a charge/discharge cycle. Reconstructions indicate strained domains forming, expanding, and fragmenting near the surface of the nanocrystal during charging, with a determined maximum relative lattice displacements of 0.467 Å. While discharging, all domains replicate in reverse the effects observed from the charging states, but with a lower maximum relative lattice displacements of 0.226 Å. These findings show the inefficiency-increasing domain dynamics within LCO lattices during cycling.

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Abstract: We have conducted a series of scattering experiments at the uranium 𝑀4 absorption edge on low-symmetry uranium compounds (U2⁢N3 and U3⁢O8) produced as epitaxial films. At weak and forbidden reflections, we find a resonant signal, independent of temperature, with an energy dependence resembling the imaginary part 𝑓″ of the scattering factor. The theory, using the fdmnes code, shows that these results can be reliably reproduced assuming that they originate from aspherical 5⁢𝑓 electron charge distributions around the U nucleus. Such effects arise from the intrinsic anisotropy of the 5⁢𝑓 shell and from the mixing of the 5⁢𝑓 electrons of uranium with the outer 2⁢𝑝 electrons of the anions. The good agreement between theory and experiment includes azimuthal scattering dependences, as well as polarization states of the scattered photons. The methodology reported here opens the way for a deeper understanding of the role the 5⁢𝑓 electrons in the bonding in actinide compounds.