Defects and Dopants in CaFeSi2O6: classical and DFT simulations

Calcium (Ca)-bearing minerals are of interest for the design of electrode materials required for rechargeable Ca-ion batteries. Here we use classical simulations to examine defect, dopant and transport properties of CaFeSi2O6. The formation of Ca-iron (Fe) anti-site defects is found to be the lowest energy process (0.42 eV/defect). The Oxygen and Calcium Frenkel energies are 2.87 eV/defect and 4.96 eV/defect respectively suggesting that these defects are not significant especially the Ca Frenkel. Reaction energy for the loss of CaO via CaO Schottky is 2.97 eV/defect suggesting that this process requires moderate temperature. Calculated activation energy of Ca-ion migration in this material is high (>4 eV), inferring very slow ionic conductivity. However, we suggest a strategy to introduce additional Ca2+ ions in the lattice by doping trivalent dopants on the Si site in order to enhance the capacity and ion diffusion and it is calculated that Al3+ is the favourable dopant for this process. Formation of Ca vacancies required for the CaO Schottky can be facilitated by doping of gallium (Ga) on the Fe site. The electronic structures of favourable dopants were calculated using density functional theory (DFT)

Determination of the Bending Rigidity of Graphene via Electrostatic Actuation of Buckled Membranes

The small mass and atomic-scale thickness of graphene membranes make them highly suitable for nanoelectromechanical devices such as e.g. mass sensors, high frequency resonators or memory elements. Although only atomically thick, many of the mechanical properties of graphene membranes can be described by classical continuum mechanics. An important parameter for predicting the performance and linearity of graphene nanoelectromechanical devices as well as for describing ripple formation and other properties such as electron scattering mechanisms, is the bending rigidity, {\kappa}. In spite of the importance of this parameter it has so far only been estimated indirectly for monolayer graphene from the phonon spectrum of graphite, estimated from AFM measurements or predicted from ab initio calculations or bond-order potential models. Here, we employ a new approach to the experimental determination of {\kappa} by exploiting the snap-through instability in pre-buckled graphene membranes. We demonstrate the reproducible fabrication of convex buckled graphene membranes by controlling the thermal stress during the fabrication procedure and show the abrupt switching from convex to concave geometry that occurs when electrostatic pressure is applied via an underlying gate electrode. The bending rigidity of bilayer graphene membranes under ambient conditions was determined to be $35.5^{+20}_{-15}$ eV. Monolayers have significantly lower {\kappa} than bilayers

Lithium Storage in Nanoporous Complex Oxide 12CaO•7Al2O3 (C12A7)

Porous materials have generated a great deal of interest for use in energy storage technologies, as their architectures have high surface areas due to their porous nature. They are promising candidates for use in many fields such as gas storage, metal storage, gas separation, sensing and magnetism. Novel porous materials which are non-toxic, cheap and have high storage capacities are actively considered for the storage of Li ions in Li-ion batteries. In this study, we employed density functional theory simulations to examine the encapsulation of lithium in both stoichiometric and electride forms of C12A7. This study shows that in both forms of C12A7, Li atoms are thermodynamically stable when compared with isolated gas-phase atoms. Lithium encapsulation through the stoichiometric form (C12A7:O2−) turns its insulating nature metallic and introduces Li+ ions in the lattice. The resulting compound may be of interest as an electrode material for use in Li-ion batteries, as it possesses a metallic character and consists of Li+ ions. The electride form (C12A7:e−) retains its metallic character upon encapsulation, but the concentration of electrons increases in the lattice along with the formation of Li+ ions. The promising features of this material can be tested by performing intercalation experiments in order to determine its applicability in Li-ion batteries

Semi-Empirical Model for Nano-Scale Device Simulations

We present a new semi-empirical model for calculating electron transport in atomic-scale devices. The model is an extension of the Extended H\"uckel method with a self-consistent Hartree potential. This potential models the effect of an external bias and corresponding charge re-arrangements in the device. It is also possible to include the effect of external gate potentials and continuum dielectric regions in the device. The model is used to study the electron transport through an organic molecule between gold surfaces, and it is demonstrated that the results are in closer agreement with experiments than ab initio approaches provide. In another example, we study the transition from tunneling to thermionic emission in a transistor structure based on graphene nanoribbons.Comment: 8 pages, 8 figures. Submitted to PR

A perspective on using experiment and theory to identify design principles in dye-sensitized solar cells

Dye-sensitized solar cells (DSCs) have been the subject of wide-ranging studies for many years because of their potential for large-scale manufacturing using roll-to-roll processing allied to their use of earth abundant raw materials. Two main challenges exist for DSC devices to achieve this goal; uplifting device efficiency from the 12 to 14% currently achieved for laboratory-scale ‘hero’ cells and replacement of the widely-used liquid electrolytes which can limit device lifetimes. To increase device efficiency requires optimized dye injection and regeneration, most likely from multiple dyes while replacement of liquid electrolytes requires solid charge transporters (most likely hole transport materials – HTMs). While theoretical and experimental work have both been widely applied to different aspects of DSC research, these approaches are most effective when working in tandem. In this context, this perspective paper considers the key parameters which influence electron transfer processes in DSC devices using one or more dye molecules and how modelling and experimental approaches can work together to optimize electron injection and dye regeneration. This paper provides a perspective that theory and experiment are best used in tandem to study DSC device

Probing Quantum Confinement and Electronic Structure at Polar Oxide Interfaces

Polar discontinuities occurring at interfaces between two different materials constitute both a challenge and an opportunity in the study and application of a variety of devices. In order to cure the large electric field occurring in such structures, a reconfiguration of the charge landscape sets in at the interface via chemical modifications, adsorbates or charge transfer. In the latter case, one may expect a local electronic doping of one material: one sparkling example is the two-dimensional electron liquid (2DEL) appearing in SrTiO$_3$ once covered by a polar LaAlO$_3$ layer. Here we show that tuning the formal polarisation of a (La,Al)$_{1-x}$(Sr,Ti)$_x$O$_3$ (LASTO:$x$) overlayer through chemical composition modifies the quantum confinement of the 2DEL in SrTiO$_3$ and its electronic band structure. The analysis of the behaviour in magnetic field of superconducting field-effect devices reveals, in agreement with $ab\ initio$ calculations and self-consistent Poisson-Schr\"odinger modelling, that quantum confinement and energy splitting between electronic bands of different symmetries strongly depend on interface charge densities. These results not only strongly support the polar discontinuity mechanisms with a full charge transfer to explain the origin of the 2DEL at the celebrated LaAlO$_3$/SrTiO$_3$ interface, but also demonstrate an effective tool for tailoring the electronic structure at oxide interfaces.Comment: 18 pages, 4 figures, 1 ancillary file (Supporting Information