[(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.
We report the successful substitution of cobalt, nickel, and copper for iron in the 1038 phase parent compound Ca$_{10}$(FeAs)$_{10}$(Pt$_3$As$_8$) yielding Ca$_{10}$(Fe$_{1-x}$Co$_x$As)$_{10}$(Pt$_3$As$_8$), Ca$_{10}$(Fe$_{1-x}$Ni$_x$As)$_{10}$(Pt$_
3$As$_8$), and Ca$_{10}$(Fe$_{1-x}$Cu$_x$As)$_{10}$(Pt$_3$As$_8$), respectively. Superconductivity is induced in Co and Ni doped compounds reaching critical temperatures up to 15 K, similar to known Pt substituted Ca$_{10}$(Fe$_{1-x}$Pt$_x$As)$_{10}$(Pt$_3$As$_8$), whereas no superconductivity was detected in Ca$_{10}$(Fe$_{1-x}$Cu$_x$As)$_{10}$(Pt$_3$As$_8$). The obtained Tc(x) phase diagrams are very similar to those of other iron arsenide superconductors indicating rather universal behavior despite the more complex structures of the 1038-type compounds, where the physics is primarily determined by the FeAs layer.
We report superconductivity in polycrystalline samples of the 1038-type compounds (Ca$_{1-x}$RE$_x$)$_{10}$(FeAs)$_{10}$(Pt$_3$As$_8$) up to T$_c$ = 35 K with RE = Y, La-Nd, Sm, Gd-Lu. The critical temperatures are independent of the trivalent rare e
arth element used, yielding an universal T$_c$($x$) phase diagram for electron doping in all these systems. The absence of superconductivity in Eu$^{2+}$ doped samples, as well as the close resemblance of (Ca$_{1-x}$RE$_x$)$_{10}$(FeAs)$_{10}$(Pt$_3$As$_8$) to the 1048 compound substantiate that the electron doping scenario in the RE-1038 and 1048 phases is completely analogous to other iron-based superconductors with simpler crystal structures.
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.
The palladium-iron-arsenides Ca10(Fe1-xPdxAs)10(Pd3As8) were synthesized by solid state methods and characterized by X-ray powder and single crystal diffraction. The triclinic crystal structure (space group P-1) is isotypic to the homologue platinum
1038 type superconductors with alternating FeAs4/4- and Pd3As8-layers, each separated by layers of calcium atoms. Iron is tetrahedral and palladium is planar coordinated by four arsenic atoms. As2-dimers (dAs-As = 250 pm) are present in the Pd3As8-layer. Even though each layer itself has a fourfold rotational symmetry, the shifted layer stacking causes the triclinic space group. Resistivity measurements of La-doped samples show the onset of superconductivity at 17 K and zero resistivity below 10 K. The magnetic shielding fraction is about 20 % at 3.5 K. 57Fe-Mossbauer spectra exhibit one absorption line and show no hint to magnetic ordering. The electronic structure is very similar to the known iron-arsenides with cylinder-like Fermi surfaces and partial nesting between hole- and electron-like sheets. Our results show that superconductivity in the palladium-iron-compounds is present but complicated by too high substitution of iron by palladium in the active FeAs-layers. Since the electronic preconditions are satisfied, we expect higher critical temperatures in Pd1038-compounds with lower or even without Pd-doping in the FeAs-layer.
The compounds Ca(Fe1-xNix)2As2 with the tetragonal ThCr2Si2-type structure (space group I4/mmm) show a continuous transition of the interlayer As-As distances from a non-bonding state in CaFe2As2 (dAs-As = 313 pm) to single-bonded As2-dimers in CaNi2
As2 (dAs-As = 260 pm). Magnetic measurements reveal weak ferromagnetism which develops near the composition Ca(Fe0.5Ni0.5)2As2, while the compounds with lower and higher nickel concentrations both are Pauli-paramagnetic. DFT band structure calculations reveal that the As2-dimer formation is a consequence of weaker metal-metal in MAs4-layers (M = Fe1-xNix) of Ni-richer compounds, and depends not on depopulation or shift of As-As antibonding states as suggested earlier. Our results also indicate that the ferromagnetism of Ca(Fe0.5Ni0.5)2As2 and related compounds like SrCo2(Ge0.5P0.5)2 is probably not induced by dimer breaking as recently suggested, but arises from the high density of states generated by the transition metal 3d bands near the Fermi level without contribution of the dimers.
SrRh2As2 exhibits structural phase transitions reminiscent to those of BaFe2As2, but crystallizes with three polymorphs derived from the tetragonal ThCr2Si2-type structure. The structure of alpha-SrRh2As2 is monoclinic with a = 421.2(1) pm, b = 1105.
6(2) pm, c = 843.0(1) pm and beta = 95{deg} and was refined as a partially pseudo meroedric twin in the space group P21/c with R1 = 0.0928. beta-SrRh2As2 crystallizes with a modulated structure in the (3+1) dimensional superspace group Fmmm(10gamma)sigma 00 with the unit cell parameters a = 1114.4(3) pm, b = 574.4(2) pm and c = 611.5(2) pm and an incommensurable modulation vector q = (1, 0, 0.3311(4)). High temperature single crystal diffraction experiments confirm the tetragonal ThCr2Si2-type structure for gamma-SrRh2As2 above 350{deg}C. Electronic band structure calculations indicate that the structural distortion in alpha-SrRh2As2 is caused by strong Rh-Rh bonding interactions and has no magnetic origin as suggested for isotypic BaFe2As2.
