1D to 2D Na+ ion diffusion inherently linked to structural transitions in Na0.7CoO2.

We report the observation of a stepwise "melting" of the low-temperature Na-vacancy order in the layered transition-metal oxide Na0.7CoO2. High-resolution neutron powder diffraction analysis indicates the existence of two first-order structural transitions, one at T1≈290 K followed by a second at T2≈400 K. Detailed analysis strongly suggests that both transitions are linked to changes in the Na mobility. Our data are consistent with a two-step disappearance of Na-vacancy order through the successive opening of first quasi-1D (T1>T>T2) and then 2D (T>T2) Na diffusion paths. These results shed new light on previous, seemingly incompatible, experimental interpretations regarding the relationship between Na-vacancy order and Na dynamics in this material. They also represent an important step towards the tuning of physical properties and the design of tailored functional materials through an improved control and understanding of ionic diffusion.

Synthesis of a new alkali metal-organic solvent intercalated iron selenide superconductor with Tc ≈ 45 K.

We report on a new iron selenide superconductor with a T(c) onset of 45 K and the nominal composition Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2), synthesized via intercalation of dissolved alkaline metal in anhydrous pyridine at room temperature. This superconductor exhibits a broad transition, reaching zero resistance at 10 K. Magnetization measurements reveal a superconducting shielding fraction of approximately 30%. Analogous phases intercalated with Na, K and Rb were also synthesized and characterized. The superconducting transition temperature of Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2) is clearly enhanced in comparison to those of the known superconductors FeSe(0.98) (T(c) ~ 8 K) and A(x)Fe(2-y)Se(2) (T(c) ~ 27-32 K) and is in close agreement with critical temperatures recently reported for Li(x)(NH(3))(y)Fe(2-z)Se(2). Post-annealing of intercalated material (Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2)) at elevated temperatures drastically enlarges the c-parameter of the unit cell (~44%) and increases the superconducting shielding fraction to nearly 100%. Our findings indicate a new synthesis route leading to possibly even higher critical temperatures for materials in this class: by intercalation of organic compounds between Fe-Se layers.

Room temperature antiferromagnetic order in superconducting X(y)Fe(2-x)Se2 (X = Rb, K): a neutron powder diffraction study.

Magnetic and crystal structures of superconducting X(y)Fe(2-x)Se2 (X = Rb and K with T(c) = 31.5 and 29.5 K) have been studied by neutron powder diffraction at room temperature. Both crystals show an ordered iron vacancy pattern and the crystal structure is well described by the I4/m space group with the lattice constants a = 8.799, c = 14.576 and a = 8.730, c = 14.115 Å and the refined stoichiometry x = 0.30(1), y = 0.83(2) and x = 0.34(1), y = 0.83(1) for Rb and K crystals, respectively. The structure contains one fully occupied iron position and one almost empty vacancy position. Assuming that the iron moment is ordered only on the fully occupied site we have sorted out all eight irreducible representations (irreps) for the propagation vector k = 0 and have found that irreps τ2 and τ7 fit the experimental data well with the moments along the c axis. The moment amplitudes amounted to 2.15(3) µ(B), 2.55(3) µ(B) for τ2 and 2.08(6) µ(B), 2.57(3) µ(B) for τ7 for Rb and K crystals, respectively. Irrep τ2 corresponds to the Shubnikov group I4/m' and gives a constant moment antiferromagnetic configuration, whereas τ7 does not have a Shubnikov counterpart and allows two different magnetic moments in the structure.

Evidence for the strong effect of quenched correlated disorder on phase separation and magnetism in (La(1-y)Pr(y))0.7Ca0.3MnO3.

High resolution neutron diffraction shows that the mesoscopic separation into ferromagnetic (FM) and antiferromagnetic (AFM) phases and the FM transition temperature T(C) in the perovskite manganite (La(1-y)Pr(y))(0.7)Ca(0.3)MnO(3) strongly depend on the quenched correlated disorder. The different disorder strengths are achieved by different procedures of the sample synthesis and are quantitatively characterized by the microstrain-type diffraction peak broadening. The system shifts to predominantly a one-phase state with smaller T(C) as the correlated disorder strength is decreased, supporting the viewpoint that the origin of phase separation in the indicated manganite system is the correlated quenched disorder. The ground state of an ultimately chemically homogeneous sample is FM-like containing about 20% of the AFM minority phase. This FM-like state can be readily transformed to the AFM-like one having < 20% of the FM phase by the decrease of the effective charge carrier bandwidth via oxygen isotope substitution.