RESUMO
Connections between crystal chemistry and critical temperature Tc have been in the focus of superconductivity, one of the most widely studied phenomena in physics, chemistry, and materials science alike. In most Fe-based superconductors, materials chemistry and physics conspire so that Tc correlates with the average anion height above the Fe plane, i.e., with the geometry of the FeAs4 or FeCh4 (Ch = Te, Se, or S) tetrahedron. By synthesizing Fe1-ySe1-xSx (0 ≤ x ≤ 1; y ≤ 0.1), we find that in alloyed crystals Tc is not correlated with the anion height like it is for most other Fe superconductors. Instead, changes in Tc(x) and tetragonal-to-orthorhombic (nematic) transition Ts(x) upon cooling are correlated with disorder in Fe vibrations in the direction orthogonal to Fe planes, along the crystallographic c-axis. The disorder stems from the random nature of S substitution, causing deformed Fe(Se,S)4 tetrahedra with different Fe-Se and Fe-S bond distances. Our results provide evidence of Tc and Ts suppression by disorder in anion height. The connection to local crystal chemistry may be exploited in computational prediction of new superconducting materials with FeSe/S building blocks.
RESUMO
Four distinct tungsten suboxide (WO3-x) nanomaterials were synthesized via chemical vapour transport reaction and the role of their crystal structures on the optical properties was studied. These materials grow either as thin, quasi-2D crystals with the WnO3n-1formula (in shape of platelets or nanotiles), or as nanowires (W5O14, W18O49). For the quasi-2D materials, the appearance of defect states gives rise to two indirect absorption edges. One is assigned to the regular bandgap occurring between the valence and the conduction band, while the second is a defect-induced band. While the bandgap values of platelets and nanotiles are in the upper range of the reported values for the suboxides, the nanowires' bandgaps are lower due to the higher number of free charge carriers. Both types of nanowires sustain localized surface plasmon resonances, as evidenced from the extinction measurements, whereas the quasi-2D materials exhibit excitonic transitions. All four materials have photoluminescence emission peaks in the UV region. The interplay of the crystal structure, oxygen vacancies and shape can result in changes in optical behaviour, and the understanding of these effects could enable intentional tuning of selected properties.
RESUMO
We present a detailed investigation of the crystal structure of VI3, a two-dimensional van der Waals material of interest for studies of low-dimensional magnetism. As opposed to the average crystal structure that features R3Ì symmetry of the unit cell, our Raman scattering and X-ray atomic pair distribution function analysis supported by density functional theory calculations point to the coexistence of short-range ordered P3Ì 1c and long-range ordered R3Ì phases. The highest-intensity peak, A1g3, exhibits a moderate asymmetry that might be traced back to the spin-phonon interactions, as in the case of CrI3.
