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Register a new user[(Li0.8Fe0.2)OH]FeS and the ferromagnetic superconductors [(Li0.8Fe0.2)OH]Fe(S1-xSex) (0<x<1)
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[(Li0.8Fe0.2)OH]FeS and the series [(Li0.8Fe0.2)OH]Fe(S1-xSex) (0<x<1) were synthesized by hydrothermal methods and characterized by X-ray single crystal and powder diffraction, EDX and chemical analysis. Selenium-rich compounds show the coexistence of magnetic ordering with superconductivity known from the pure selenium compound. Sulphur doping decreases the critical temperature through chemical pressure until superconductivity is completely absent in [(Li0.8Fe0.2)OH]FeS, while the ferromagnetism in the [(Li0.8Fe0.2)OH] layers persists. The Li:Fe ratio in the hydroxide layer, and thus the charge transfer of 0.2 electrons from the hydroxide to the iron chalcogenide layers remains unchanged in [(Li0.8Fe0.2)OH]Fe(S1-xSex), which indicates that the chemical pressure effect of the smaller sulphide ions impedes superconductivity in [(Li0.8Fe0.2)OH]FeS
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We report the phase diagram for the superconducting system (${^{7}}$Li${_{1-x}}$Fe${_{x}}$OD)FeSe and contrast it with that of (Li${_{1-x}}$Fe${_{x}}$OH)FeSe both in single crystal and powder forms. Samples were prepared via hydrothermal methods and characterized with laboratory and synchrotron X-ray diffraction, high-resolution neutron powder diffraction (NPD), and high intensity NPD. We find a correlation between the tetragonality of the unit cell parameters and the critical temperature, $T_{c}$, which is indicative of the effects of charge doping on the lattice and formation of iron vacancies in the FeSe layer. We observe no appreciable isotope effect on the maximum $T_{c}$ in substituting H by by D. The NPD measurements definitively rule out an antiferromagnetic ordering in the non-superconducting (Li${_{1-x}}$Fe${_{x}}$OD)FeSe samples below 120 K, which has been reported in non-superconducting (Li${_{1-x}}$Fe${_{x}}$OH)FeSe.$^{1}$ A likely explanation for the observed antiferromagnetic transition in (Li${_{1-x}}$Fe${_{x}}$OH)FeSe samples is the formation of impurities during their preparation such as Fe${_{3}}$O${_{4}}$ and LixFeO2, which express a charge ordering transition known as the Verwey transition near 120 K. The concentration of these oxide impurities is found to be dependent on the concentration of the lithium hydroxide reagent and the use of H${_{2}}$O vs. D${_{2}}$O as the solvent during synthesis. We also describe the reaction conditions that lead to some of our superconducting samples to exhibit ferromagnetism below $T_{c}$.
Superconducting [(Li(1-x)Fex)OH](Fe(1-y)Liy)Se (x ~ 0.2, y ~ 0.08) was synthesized by hydrothermal methods and structurally characterized by single crystal X-ray diffraction. The crystal structure contains anti-PbO type (Fe(1-y)Liy)Se layers separated by layers of (Li(1-x)Fex)OH. Electrical resistivity and magnetic susceptibility measurements reveal superconductivity at 43 K. An anomaly in the diamagnetic shielding indicates ferromagnetic ordering near 10 K while superconductivity is retained. The ferromagnetism emerges from the iron atoms in the (Li(1-x)Fex)OH layer. Isothermal magnetization measurements confirm the superposition of ferromagnetic with superconducting hysteresis. The internal ferromagnetic field is larger than the lower, but smaller than the upper critical field of the superconductor, which gives evidence for a spontaneous vortex phase where both orders coexist. 57Fe-Mossbauer spectra, 7Li-NMR spectra, and muSR experiments consistently support this rare situation, especially in a bulk material where magnetism emerges from a 3d-element.
FeSe-derived superconductors show some unique behaviors relative to iron-pnictide superconductors, which are very helpful to understand the mechanism of superconductivity in high-Tc iron-based superconductors. The low-energy electronic structure of the heavily electron-doped AxFe2Se2 (A=K, Rb, Cs) demonstrates that interband scattering or Fermi surface nesting is not a necessary ingredient for the unconventional superconductivity in iron-based superconductors. The superconducting transition temperature (Tc) in the one-unit-cell FeSe on SrTiO3 substrate can reach as high as ~65 K, largely transcending the bulk Tc of all known iron-based superconductors. However, in the case of AxFe2Se2, the inter-grown antiferromagnetic insulating phase makes it difficult to study the underlying physics. Superconductors of alkali metal ions and NH3 molecules or organic-molecules intercalated FeSe and single layer or thin film FeSe on SrTiO3 substrate are extremely air-sensitive, which prevents the further investigation of their physical properties. Therefore, it is urgent to find a stable and accessible FeSe-derived superconductor for physical property measurements so as to study the underlying mechanism of superconductivity. Here, we report the air-stable superconductor (Li0.8Fe0.2)OHFeSe with high temperature superconductivity at ~40 K synthesized by a novel hydrothermal method. The crystal structure is unambiguously determined by the combination of X-ray and neutron powder diffraction and nuclear magnetic resonance. It is also found that an antiferromagnetic order coexists with superconductivity in such new FeSe-derived superconductor. This novel synthetic route opens a new avenue for exploring other superconductors in the related systems. The combination of different structure characterization techniques helps to complementarily determine and understand the details of the complicated structures.
We present the results of paramagnetic LDA band structure calculations: band dispersions, densities of states and Fermi surfaces, for the new iron based high-temperature superconductor LiOHFeSe. Main structural motif providing bands in the vicinity of the Fermi level is FeSe layer which is isostructural to the bulk FeSe prototype superconductor. The bands crossing the Fermi level and Fermi surfaces of the new compound are typical for other iron based superconductors. Experimentally it was shown that introduction of Fe ions into LiOH layer gives rise to ferromagnetic ordering of the Fe ions at T$_C$=10K. To study magnetic properties of [Li$_{0.8}$Fe$_{0.2}$OH]FeSe system we have performed LSDA calculations for $sqrt 5 times sqrt 5$ superlattice and found ferromagnetism within the Li$_4$Fe(OH) layer. To estimate the Curie temperature we obtained Fe-Fe exchange interaction parameters for Heisenberg model from our LSDA calculations, leading to theoretical value of Curie temperature 10.4K in close agreement with experiment.
The Fe1+yTe1-xSex series of materials is one of the prototype families of Fe-based superconductors. To provide further insight into these materials we present systematic inelastic neutron scattering measurements of the low energy spin excitations for x=0.27, 0.36, 0.40, 0.49. These measurements show an evolution of incommensurate spin excitations towards the (1/2 1/2 0) wave vector with doping. Concentrations (x=0.40 and 0.49) which exhibit the most robust superconducting properties have spin excitations closest to (1/2 1/2 0) and also exhibit a strong spin resonance in the spin excitation spectrum below Tc. The resonance signal appears to be closer to (1/2 1/2 0) than the underlying spin excitations. We discuss the possible relationship between superconductivity and spin excitations at the (1/2 1/2 0) wave vector and the role that interstitial Fe may play.
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