RESUMO
A combination of phenomenological analysis and Mössbauer spectroscopy experiments on the tetragonal Fe(1+y)Te system indicates that the magnetic ordering transition in compounds with higher Fe excess, y≥0.11, is unconventional. Experimentally, a liquidlike magnetic precursor with quasistatic spin order is found from significantly broadened Mössbauer spectra at temperatures above the antiferromagnetic transition. The incommensurate spin-density wave order in Fe(1+y)Te is described by a magnetic free energy that violates the weak Lifshitz condition in the Landau theory of second-order transitions. The presence of multiple Lifshitz invariants provides the mechanism to create multidimensional, twisted, and modulated solitonic phases.
RESUMO
Room-temperature precipitation from aqueous solutions yields the hitherto unknown metastable stoichiometric iron selenide (ms-FeSe) with tetragonal anti-PbO type structure. Samples with improved crystallinity are obtained by diffusion-controlled precipitation or hydrothermal recrystallization. The relations of ms-FeSe to superconducting ß-FeSe(1-x) and other neighbor phases of the iron-selenium system are established by high-temperature X-ray diffraction, DSC/TG/MS (differential scanning calorimetry/thermogravimetry/mass spectroscopy), (57)Fe Mössbauer spectroscopy, magnetization measurements, and transmission electron microscopy. Above 300 °C, ms-FeSe decomposes irreversibly to ß-FeSe(1-x) and Fe(7)Se(8). The structural parameters of ms-FeSe (P4/nmm, a = 377.90(1) pm, c = 551.11(3) pm, Z = 2), obtained by Rietveld refinement, differ significantly from literature data for ß-FeSe(1-x). The Mössbauer spectrum rules out interstitial iron atoms or additional phases. Magnetization data suggest canted antiferromagnetism below T(N) = 50 K. Stoichiometric non-superconducting ms-FeSe can be regarded as the true "parent" compound for the "11" iron-chalcogenide superconductors and may serve as starting point for new chemical modifications.