Show Abstract ▼

Abstract: Recent progress in the growth and characterization of thin-film VO 2 has shown its electronic properties can be significantly modulated by epitaxial matching. To throw new light on the concept of “Mott engineering,” we develop a symmetry-consistent approach to treat structural distortions and electronic correlations in epitaxial VO 2 films under strain, and compare our design with direct experimental probes. We find strong evidence for the emergence of correlation-driven charge order deep in the metallic phase, and our results indicate that exotic phases of VO 2 can be controlled with epitaxial stabilization.

Show Abstract ▼

Abstract: Rutile-type RuO2 likely supports a simple antiferromagnetic structure which can be verified by x-ray Bragg diffraction. Three magnetic motifs that do not break translation symmetry are explored in calculations of amplitudes suitable for diffraction enhanced by tuning the primary x-ray energy to a ruthenium atomic resonance. Coupling to x-ray helicity through a charge-magnetic interference is common to all motifs, together with magnetic and charge intensities in quadrature in the rotated channel of polarization. Necessary conditions for these diffraction phenomena are a centrosymmetric crystal structure, null magnetic propagation vector, and absence of a linear magnetoelectric effect. Published x-ray diffraction data for RuO2 were analyzed by the authors against a magnetic motif that does not satisfy the conditions. A polarized neutron study of antiferromagnetic domains can be achieved with a sample that meets the stated crystal and magnetic symmetries.

Show Abstract ▼

Abstract: We investigate electron-phonon coupling (EPC) in the charge density wave (CDW) phase of V Se 2 by Raman spectroscopy, angle-resolved photoemission spectroscopy (ARPES), and ab initio calculations. Zone folding induced by the 4 × 4 in-plane CDW phase promotes the appearance of a Raman peak at ∼ 170 cm − 1 . The suppression of ARPES intensity in parts of the Fermi surface is also a result of CDW-induced zone folding and anticrossing of the electron energy bands. The appearance of the new Raman peak is in line with the ARPES observation of a kink feature in the spectral function at the same energy. A self-energy analysis yields an EPC constant of λ = 0.3 . Our calculations of the EPC are in excellent agreement and reveal that the kink is caused by several optical phonon branches close in energy. Our paper highlights the CDW phase as a means of inducing EPC pathways to optical phonons that directly affect its Raman spectrum.

Open Access

Show Abstract ▼

Abstract: Demonstrating both the intrinsic and extrinsic nature of the giant piezoelectric effect (GPE) in complex solid solutions, near the morphotropic phase boundary, has been extremely challenging until now, because such materials exhibit multiple phases on the order of tens of microns across, meaning important information is lost due to averaging when using established high resolution diffraction techniques to extract three dimensional structural information. We have used a different approach proposed by Nisbet et al. [Acta Crystallogr. Sect. A 71, 20 (2015)], which has been adapted to differentiate between spatially adjacent phases and simultaneously track the evolution of those phases in response to electric fields. As a result, we have identified three environment specific GPEs. The first of these is a GPE which is an order of magnitude greater than previously reported for a given change in field. This is observed during a tetragonal-monoclinic transition in a multiphasic environment. A secondary, large GPE is observed in the neighboring, nontransitioning, monoclinic phase due to stress biasing, and a more typical GPE is observed when the system becomes monophasic. Our results demonstrate the simultaneous and complex interplay of intrinsic and extrinsic factors contributing to the GPE which is likely to have implications for device manufacture and miniaturization.

Show Abstract ▼

Abstract: X-ray powder diffraction experiments at high pressures combining conventional sources and synchrotron radiation, together with theoretical simulations have allowed us to study the anomalous compression of the entire α- R E 2 ( WO 4 ) 3 ( RE = La-Ho) family with modulated scheelite structure (α phase). The investigated class of materials is of great interest due to their peculiar structural behavior with temperature and pressure, which is highly sought after for specialized high-tech applications. Experimental data were analyzed using full-profile refinements and were complemented with computational methods based on density functional theory (DFT) total energy calculations for a subset of the samples investigated. An unusual change in the compression curves of the lattice parameters a , c , and β was observed in both the experiments and theoretical simulations. In particular, in all the studied compounds the lattice parameter a decreased with pressure to a minimum value and then increased upon further compression. Pressure evolution of the experimental x-ray diffraction (XRD) patterns and cell parameters is correlated with the ionic radius of the rare earth element: (1) the lighter La-Nd tungstates underwent two phase transitions, and both transition pressures decreased as the rare earth's ionic radius increased. The XRD patterns of the first high pressure phase could be indexed with propagation vectors parallel to the a axis (tripling the unit cell). At higher pressures, the lattice parameters for the second phase (referred to as the preamorphous phase) showed little variation with pressure. (2) The heavier tungstates, from Sm to Dy, undergo a transition to the preamorphous phase without any intermediate phase. The reversibility of both phase transitions was investigated. DFT calculations support this unusual response of the crystal structures under pressure and shed light on the structural mechanism of negative linear compressibility (NLC) and the resulting softening. The pressure dependence of the structural modifications is related to tilting, along with small elongation and alignment, of the WO 2 − 4 tetrahedrons. These changes correlate with those in the alternating RE…RE…RE chains and blocks of cationic vacancies arranged along the a axis. Possible stacking defects, which emerge between them, helped to explain this anomalous compression and the pressure induced amorphization. Such mechanisms were compared with other ferroelastic families of molybdates, niobates, vanadates, and other compounds with similar structural motifs classified as having “hinge frames.”