We investigate the effect of controlled annealing on the structural and electronic phase evolution of Tin dioxide from Tin (II) oxyhydroxide prepared by simple precipitation method. Thermogravimetric analysis suggests a complex weight loss-gain process involved, passing through an intermediate phase of tin oxide nanoparticles. The probable structural and electronic phase evolution is discussed using detailed X-ray diffraction and X-ray photoelectron spectroscopy investigations.
SnSe monolayers experience a temperature induced two-dimensional Pnm2$_1 to$ P4/nmm structural transformation precipitated by the softening of vibrational modes. The standard theoretical treatment of thermoelectricity---which relies on a zero temperature phonon dispersion and on a zero temperature electronic structure---is incapable of describing thermoelectric phenomena induced by structural transformations. Relying on structural data obtained from {em ab initio} molecular dynamics calculations that is utilized in a non-standard way to inform of electronic and vibrational transport coefficients, the present work establishes a general route to understand thermoelectricity across phase transitions. Similar to recent experimental observations pointing to an overestimated thermoelectric figure of merit $ZT$ past the transition temperature, our work indicates a smaller $ZT$ when compared to its value predicted by the standard paradigm. Its decrease is related to the dramatic changes in the electrical conductivity and lattice thermal conductivity as the structural transformation ensues. Though exemplified on a SnSe monolayer, the method does not have any built-in assumptions concerning dimensionality, and thus applicable to arbitrary thermoelectric materials in one, two, and three dimensions.
The wealth of properties of titanium dioxide relies on its various polymorphs and on their mixtures coupled with a sensitivity to crystallographic orientations. It is therefore pivotal to set out methods that allow surface structural identification. We demonstrate herein the ability of photoemission spectroscopy to provide Ti LMV (V = valence) Auger templates to quantitatively analyze TiO$_2$ polymorphs. The Ti LMV decay reflects Ti 4sp-O 2p hybridizations that are intrinsic properties of TiO$_2$ phases and orientations. Ti LMV templates collected on rutile (110), anatase (101), and (100) single crystals allow for the quantitative analysis of mixed nanosized powders, which bridges the gap between surfaces of reference and complex materials. As a test bed, the anatase/rutile P25 is studied both as received and during the anatase-to-rutile transformation upon annealing. The agreement with X-ray diffraction measurements proves the reliability of the Auger analysis and highlights its ability to detect surface orientations.
We investigate the electronic and structural changes at the nanoscale in vanadium dioxide (VO2) in the vicinity of its thermally driven phase transition. Both electronic and structural changes exhibit phase coexistence leading to percolation. In addition, we observe a dichotomy between the local electronic and structural transitions. Nanoscale x-ray diffraction reveals local, non-monotonic switching of the lattice structure, a phenomenon that is not seen in the electronic insulator-to-metal transition mapped by near-field infrared microscopy.
The complexity of strongly correlated electron physics in vanadium dioxide is exemplified as its rich phase diagrams of all kinds, which in turn shed light on the mechanisms behind its various phase transitions. In this work, we map out the hydrostatic pressure - temperature phase diagram of vanadium dioxide nanobeams by independently varying pressure and temperature with a diamond anvil cell. In addition to the well-known insulating M1 (monoclinic) and metallic R (tetragonal) phases, the diagram identifies the existence at high pressures of the insulating M1 (monoclinic, more conductive than M1) phase, and two metallic phases of X (monoclinic) and O (orthorhombic, at high temperature only). Systematic optical and electrical measurements combined with density functional calculations allow us to delineate their phase boundaries as well as reveal some basic features of the transitions.
Vanadium dioxide, an archetypal correlated-electron material, undergoes an insulator-metal transition near room temperature that exhibits electron-correlation-driven and structurally-driven physics. Using ultrafast optical spectroscopy and x-ray scattering we show that these processes can be disentangled in the time domain. Specifically, following intense sub-picosecond electric-field excitation, a partial collapse of the insulating gap occurs within the first ps. Subsequently, this electronic reconfiguration initiates a change in lattice symmetry taking place on a slower timescale. We identify the kinetic energy increase of electrons tunneling in the strong electric field as the driving force, illustrating a novel method to control electronic interactions in correlated materials on an ultrafast timescale.