[(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
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 separate
d 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.
The solid solution of antimonide-oxides Ba1-xKxTi2Sb2O (0 < x < 1) has been synthesized by solid-state reactions and characterized by X-ray powder diffraction (CeCr2Si2C-type structure; P4/mmm, Z = 1). The crystal structure consists of Ti2Sb2O-layers
that are stacked with layers of barium atoms along the c-axis. BaTi2Sb2O is a known superconductor with a critical temperature (Tc) of 1.2 K. Substitution of barium through potassium raises Tc up to 6.1 K at 12 % potassium, while no superconductivity emerges with concentrations higher than 20 %. Anomalies in electrical transport and magnetic susceptibility indicate charge density wave (CDW) instabilities. The CDW transition temperatures (Ta) decrease from 50 K in the parent compound to 28 K at 10 % potassium substitution. No CDW transition was detected at higher concentrations, and no evidence for a reduction of the lattice symmetry below Ta was found. The lattice parameters vary linearly while the unit cell volume increases with higher potassium concentrations. The phase diagrams Tc(x) and Ta(x) of Ba1-xKxTi2Sb2O are remarkably similar to the known series Ba1-xNaxTi2Sb2O (0 < x < 0.33) in spite of the reverse volume effect. From this we conclude that the charge and not the volume determines the phase diagrams of these superconducting antimony oxides.
