Materials Science (cond-mat.mtrl-sci)

Abstract: A potential application of two-dimensional (2D) MXenes, such as Ti2CTx and Ti3C2Tx, is energy storage devices, such as supercapacitors, batteries, and hydride electrochemical cells, where intercalation of ions between the 2D layers is considered as a charge carrier. Electrochemical cycling investigations in combination with Ti 1s X-ray absorption spectroscopy (XAS) have therefore been performed with the objective to study oxidation state changes during potential variations. In some of these studies Ti3C2Tx has shown main edge shifts in the Ti 1s X-ray absorption near-edge structure (XANES). Here we show that these main edge shifts originate from the Ti 4p orbital involvement in the bonding between the surface Ti and the termination species at the fcc-sites. The study further shows that the t2g-eg crystal field splitting (10Dq) observed in the pre-edge absorption region indicate weaker Ti-C bonds in Ti2CTx and Ti3C2Tx compared to TiC and the corresponding MAX phases. The results from this study provide information necessary for improved electronic modeling and subsequently a better description of the materials properties of the MXenes. In general, potential applications, where surface interactions with intercalation elements are important processes, will benefit from the new knowledge presented.

Abstract: Many thermal measurements in high magnetic fields require thermometers that are sensitive over a wide temperature range, are low mass, have a rapid thermal response, and have a minimal, easily correctable magnetoresistance. Here we report the development of a new granular-metal oxide ceramic composite (cermet) for this purpose formed by co-sputtering of the metallic alloy nichrome Ni$_{0.8}$Cr$_{0.2}$ and the insulator silcon dioxide SiO$_2$. The resulting thin films are sensitive enough to be used from room temperature down to below 100 mK in magnetic fields up to at least 35 tesla.

Abstract: Morphology plays a crucial role in deciding the chemical and optical properties of nanomaterials due to confinement effects. We report the morphology transition of colloidal molybdenum disulfide (MoS2) nanostructures, synthesized by one pot heat-up method, from mix of quantum dots (QDs) and nanosheets to predominantly nanorods by varying the synthesis reaction temperature from 90 to 160 degree C. The stoichiometry and composition of the synthesized QDs, nanosheets and nanorods have been quantified to be MoS2 using energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analysis. Nanostructure morphology transition due to variation in reaction temperature has resulted in photoluminescence quantum yield enhancement from zero to 4.4% on increase in temperature from 90 to 120 degree C. On further increase in temperature to 160 degree C, a decrease in quantum yield to 2.63% is observed. A red shift of 18 nm and 140 nm in the emission maxima and absorption edge respectively is observed for the synthesized nanostructures with increase in reaction temperature from 90 to 160 degree C. The change in the quantum yield is attributed to the change in shape and hence confinement of charge carriers. To the best of our knowledge, first-time microscopic analysis of colloidal MoS2 nanostructures shape and optical property variation with temperature explained by non-classical growth mechanism is presented.

Abstract: Manipulating the interlayer twist angle is a powerful tool to tailor the properties of layered two-dimensional crystals. The twist angle has a determinant impact on these systems' atomistic structure and electronic properties. This includes the corrugation of individual layers, formation of stacking domains and other structural elements, and electronic structure changes due to the atomic reconstruction and superlattice effects. However, how these properties change with the twist angle (ta) is not yet well understood. Here, we monitor the change of twisted bilayer MoS2 characteristics as function of ta. We identify distinct structural regimes, with particular structural and electronic properties. We employ a hierarchical approach ranging from a reactive force field through the density-functional-based tight-binding approach and density-functional theory. To obtain a comprehensive overview, we analyzed a large number of twisted bilayers with twist angles in the range 0.2-59.6deg. Some systems include up to half a million atoms, making structure optimization and electronic property calculation challenging. For 13<ta<47, the structure is well-described by a moir\'e regime composed of two rigidly twisted monolayers. At small ta (ta<3 and 57<ta), a domain-soliton regime evolves, where the structure contains large triangular stacking domains, separated by a network of strain solitons and short-ranged high-energy nodes. The corrugation of the layers and the emerging superlattice of solitons and stacking domains affects the electronic structure. Emerging predominant characteristic features are Dirac cones at K and kagome bands. These features flatten for ta approaching 0 and 60deg. Our results show at which ta range the characteristic features of the reconstruction emerge and give rise to exciting electronics. We expect our findings also to be relevant for other twisted bilayer systems.

Abstract: Hybrid or organic plastic crystals have the potential as lead-free alternatives to conventional inorganic ferroelectrics. These materials are gaining attention for their multiaxial ferroelectricity, above-room-temperature Curie temperatures, and low-temperature synthesis. Here, we report a screening study of the Cambridge Structural Database (CSD) resulting in 55 new candidate plastic and plastic ionic ferroelectric molecular crystals, along with 16 previously reported ferroelectrics. With over 1.2 million entries in the CSD, the screening procedure involved many steps, including considerations of molecular geometry and size, space group, and hydrogen bonding pattern. The spontaneous polarization and electronic band gaps were predicted using density functional theory. 21 of the candidate ferroelectrics have a polarization greater than 10 {\mu}C/cm2, out of which nine are reported at room temperature.

Abstract: We report on the chemical structure and spin Hall magnetoresistance (SMR) in epitaxial {\alpha}-Fe2O3(hematite)(0001)/Pt(111) bilayers with hematite thicknesses of 6 nm and 15 nm grown by molecular beam epitaxy on a MgO(111) substrate. Unlike previous studies that involved Pt overlayers on hematite, the present hematite films were grown on a stable Pt buffer layer and displayed structural changes as a function of thickness. These structural differences (the presence of a ferrimagnetic phase in the thinner film) significantly affected the magnetotransport properties of the bilayers. We observed a sign change of the SMR from positive to negative when the thickness of hematite increased from 6 nm to 15 nm. For {\alpha}-Fe2O3(15 nm)/Pt, we demonstrated room-temperature switching of the N\'eel order with rectangular, nondecaying switching characteristics. Such structures open the way to extending magnetotransport studies to more complex systems with double asymmetric metal/hematite/Pt interfaces.

Abstract: A spin Hamiltonian, which characterizes interatomic interactions between spin moments, is highly valuable in predicting and comprehending the magnetic properties of materials. A deeper understanding of the microscopic origin of magnetic interactions can open new pathways toward realizing nanometer-scale systems for future spintronic devices. Here, we explore a method for explicitly calculating interatomic exchange interactions in non-collinear configurations of magnetic materials considering only a bilinear spin Hamiltonian in a local scenario. Based on density-functional theory (DFT) calculations of dimers adsorbed on metallic surfaces, and with a focus on the Dzyaloshinskii-Moriya interaction (DMI) which is essential for stabilizing chiral non-collinear magnetic states, we discuss the interpretation of the DMI when decomposed into microscopic electron and spin densities and currents. We clarify the distinct origins of spin currents induced in the system and their connection to the DMI. In addition, we reveal how non-collinearity affects the usual DMI, which is solely induced by spin-orbit coupling, and DMI-like interactions brought about by non-collinearity. We explain how the dependence of the DMI on the magnetic configuration establishes a connection between high-order magnetic interactions, enabling the transition from a local to a global spin Hamiltonian.