We report that a layered iron-based compound LaOFeAs undergoes superconducting transition under doping with F- ions at the O2- site. The transition temperature (Tc) exhibits a trapezoid shape dependence on the F- content, with the highest Tc of ∼26 K at ∼11 atom %.

Iron-Based Layered Superconductor La[O1-xFx]FeAs (x = 0.05−0.12) with Tc = 26 K

The recent discovery of superconductivity with relatively high transition temperature (Tc) in the layered iron-based quaternary oxypnictides La[O1−xFx] FeAs by Kamihara et al. [Kamihara Y, Watanabe T, Hirano M, Hosono H (2008) Iron-based layered superconductor La[O1-xFx] FeAs (x = 0.05–0.12) with Tc = 26 K. J Am Chem Soc 130:3296–3297.] was a real surprise and has generated tremendous interest. Although superconductivity exists in alloy that contains the element Fe, LaOMPn (with M = Fe, Ni; and Pn = P and As) is the first system where Fe plays the key role to the occurrence of superconductivity. LaOMPn has a layered crystal structure with an Fe-based plane. It is quite natural to search whether there exists other Fe based planar compounds that exhibit superconductivity. Here, we report the observation of superconductivity with zero-resistance transition temperature at 8 K in the PbO-type α-FeSe compound. A key observation is that the clean superconducting phase exists only in those samples prepared with intentional Se deficiency. FeSe, compared with LaOFeAs, is less toxic and much easier to handle. What is truly striking is that this compound has the same, perhaps simpler, planar crystal sublattice as the layered oxypnictides. Therefore, this result provides an opportunity to better understand the underlying mechanism of superconductivity in this class of unconventional superconductors.

/pdf/superconductivity-in-the-pbo-type-structure-a-fese-1iqsdyi568.pdf

Superconductivity in the PbO-type structure α-FeSe

The ternary iron arsenide ${\mathrm{BaFe}}_{2}{\mathrm{As}}_{2}$ becomes superconducting by hole doping, which was achieved by partial substitution of the barium site with potassium. We have discovered bulk superconductivity at ${T}_{c}=38\text{ }\text{ }\mathrm{K}$ in $({\mathrm{Ba}}_{1\ensuremath{-}x}{\mathrm{K}}_{x}){\mathrm{Fe}}_{2}{\mathrm{As}}_{2}$ with $x\ensuremath{\approx}0.4$. The parent compound ${\mathrm{BaFe}}_{2}{\mathrm{As}}_{2}$ crystallizes in the tetragonal ${\mathrm{ThCr}}_{2}{\mathrm{Si}}_{2}$-type structure, which consists of $(\mathrm{FeAs}{)}^{\ensuremath{\delta}\ensuremath{-}}$ iron arsenide layers separated by ${\mathrm{Ba}}^{2+}$ ions. ${\mathrm{BaFe}}_{2}{\mathrm{As}}_{2}$ is a poor metal and exhibits a spin density wave anomaly at 140 K. By substituting ${\mathrm{Ba}}^{2+}$ for ${\mathrm{K}}^{+}$ ions we have introduced holes in the $(\mathrm{FeAs}{)}^{\ensuremath{-}}$ layers, which suppress the anomaly and induce superconductivity. The ${T}_{c}$ of 38 K in $({\mathrm{Ba}}_{0.6}{\mathrm{K}}_{0.4}){\mathrm{Fe}}_{2}{\mathrm{As}}_{2}$ is the highest in hole doped iron arsenide superconductors so far. Therefore, we were able to expand this class of superconductors by oxygen-free compounds with the ${\mathrm{ThCr}}_{2}{\mathrm{Si}}_{2}$-type structure.

Superconductivity at 38 K in the iron arsenide (Ba1-xKx)Fe2As2.

We report the superconductivity in iron-based oxyarsenide Sm[O1-xFx]FeAs, with the onset resistivity transition temperature at 55.0K and Meissner transition at 54.6 K. This compound has the same crystal structure as LaOFeAs with shrunk crystal lattices, and becomes the superconductor with the highest critical temperature among all materials besides copper oxides up to now.

https://iopscience.iop.org/article/10.1088/0256-307X/25/6/080/pdf

Superconductivity at 55 K in Iron-Based F-Doped Layered Quaternary Compound Sm[O1-xFx] FeAs

Following the discovery of long-range antiferromagnetic order in the parent compounds of high-transition-temperature (high-T(c)) copper oxides, there have been efforts to understand the role of magnetism in the superconductivity that occurs when mobile 'electrons' or 'holes' are doped into the antiferromagnetic parent compounds. Superconductivity in the newly discovered rare-earth iron-based oxide systems ROFeAs (R, rare-earth metal) also arises from either electron or hole doping of their non-superconducting parent compounds. The parent material LaOFeAs is metallic but shows anomalies near 150 K in both resistivity and d.c. magnetic susceptibility. Although optical conductivity and theoretical calculations suggest that LaOFeAs exhibits a spin-density-wave (SDW) instability that is suppressed by doping with electrons to induce superconductivity, there has been no direct evidence of SDW order. Here we report neutron-scattering experiments that demonstrate that LaOFeAs undergoes an abrupt structural distortion below 155 K, changing the symmetry from tetragonal (space group P4/nmm) to monoclinic (space group P112/n) at low temperatures, and then, at approximately 137 K, develops long-range SDW-type antiferromagnetic order with a small moment but simple magnetic structure. Doping the system with fluorine suppresses both the magnetic order and the structural distortion in favour of superconductivity. Therefore, like high-T(c) copper oxides, the superconducting regime in these iron-based materials occurs in close proximity to a long-range-ordered antiferromagnetic ground state.

Magnetic order close to superconductivity in the iron-based layered LaO1-xFxFeAs systems

Iron-Based Layered Superconductor La[O1-xFx]FeAs (x = 0.05—0.12) with Tc = 26 K.

A layered oxyphosphide, LaNiOP, was synthesized by solid-state reactions. This crystal was confirmed to have a layered structure composed of an alternating stack of (La3+O2-)+ and (Ni2+P3-)-. We found that the resulting LaNiOP shows a superconducting transition at ∼3 K. This material exhibited metallic conduction and Pauli paramagnetism in the temperature range of 4−300 K. The resistivity sharply dropped to zero and the magnetic susceptibility became negative at <4 K, indicating that a superconducting transition occurs. The volume fraction of the superconducting phase estimated from the diamagnetic susceptibility reached ∼40 vol % at 1.8 K, substantiating that LaNiOP is a bulk superconductor.

Nickel-based oxyphosphide superconductor with a layered crystal structure, LaNiOP.

Nickel-based layered superconductor, LaNiOAs

Electronic and magnetic properties of a layered compound LaMnPO are examined in relation to a newly discovered iso-structural superconductor LaFeAs(P)O. Neutron diffraction measurements, together with temperature dependent magnetic susceptibility, clarify that LaMnPO is an antiferromagnet at least up to 375 K. The spin moment of a Mn ion is determined to be 2.26 μB at room temperature, and the spin configuration is antiparallel in the Mn–P plane and parallel between the Mn–P planes, which is rather different from that of LaFeAsO. Optical absorption spectra, photoemission spectra, and temperature dependent electrical conductivity indicate that LaMnPO is a semiconductor. Furthermore, nominally undoped LaMnPO exhibits n-type conduction while the conduction type is changed by doping of Cu or Ca to the La sites, indicating that LaMnPO is a bipolar conductor. Density functional calculation using the GGA+U approximation supports the above conclusions; the electronic band structure has an open band gap and the antiferromagnetic spin configuration is more stable than the ferromagnetic one.

/pdf/antiferromagnetic-bipolar-semiconductor-lamnpo-with-zrcusias-5go60xgg2w.pdf

Takumi Watanabe

Papers

Iron-Based Layered Superconductor La[O1-xFx]FeAs (x = 0.05−0.12) with Tc = 26 K

Iron-Based Layered Superconductor La[O1-xFx]FeAs (x = 0.05—0.12) with Tc = 26 K.

Nickel-based oxyphosphide superconductor with a layered crystal structure, LaNiOP.

Nickel-based layered superconductor, LaNiOAs

Antiferromagnetic bipolar semiconductor LaMnPO with ZrCuSiAs-type structure