[show abstract][hide abstract] ABSTRACT: DOI: 10.1021/cm301486v
The series Sr2MnO2Cu1.5(S1–xSex)2 (0 ≤ x ≤ 1) contains mixed-valent Mn ions (Mn2+/Mn3+) in MnO2 sheets which are separated by copper-deficient antifluorite-type Cu2−δCh2 layers with δ 0.5. The compounds crystallize in the structure type first described for Sr2Mn3Sb2O2 and are described in the I4/mmm space group at ambient temperatures. Below about 250 K, ordering between Cu+ ions and tetrahedral vacancies occurs which is long-range and close to complete in the sulfide-containing end member of the series Sr2MnO2Cu1.5S2 but which occurs over shorter length scales as the selenide content increases. The superstructure is an orthorhombic 2√2a × √2a × c expansion in Ibam of the room temperature cell. For x > 0.3 there are no superstructure reflections evident in the X-ray or neutron diffraction patterns, and the I4/mmm description is valid for the average structure at all temperatures. However, in the pure selenide end member, Sr2MnO2Cu1.5Se2, diffuse scattering in electron diffractograms and modulation in high resolution lattice image profiles may arise from short-range Cu/vacancy order. All members of the series exhibit long-range magnetic order. In the sulfide-rich end member and in compounds with x < 0.1 in the formula Sr2MnO2Cu1.5(S1–xSex)2, which show well developed superstructures due to long-range Cu/vacancy order, the magnetic structure has a (1/41/4 0) propagation vector in which ferromagnetic zigzag chains of Mn moments in the MnO2 sheets are coupled antiferromagnetically in an arrangement described as the CE-type magnetic structure and found in many mixed-valent perovskite and Ruddlesden–Popper type oxide manganites. In these cases the magnetic cell is an a × 2b × c expansion of the low temperature Ibam structural cell. For x ≥ 0.2 in the formula Sr2MnO2Cu1.5(S1–xSex)2 the magnetic structure has a (0 0 0) propagation vector and is similar to the A-type structure, also commonly adopted by some perovskite-related manganites, in which the Mn moments in the MnO2 sheets are coupled ferromagnetically and long-range antiferromagnetic order results from antiferromagnetic coupling between planes. In the region of the transition between the two different structural and magnetic long-range ordering schemes (0.1 < x < 0.2) the two magnetic structures coexist in the same sample. The evolution of the competition between magnetic ordering schemes and the length scale of the structural order with composition in Sr2MnO2Cu1.5(S1–xSex)2 suggest that the changes in magnetic and structural order are related consequences of the introduction of chemical disorder.
Chemistry of Materials 01/2012; 24(14):2802. · 8.24 Impact Factor
[show abstract][hide abstract] ABSTRACT: On the application of hydrostatic pressures of up to 1.3 GPa, the superconducting transition temperatures (T(c)) of samples of LiFeAs are lowered approximately monotonically at approximately -2 K GPa(-1). Measurements of the X-ray powder diffraction pattern at hydrostatic pressures of up to 17 GPa applied by a He gas pressure medium in a diamond anvil cell reveal a bulk modulus for LiFeAs of 57.3(6) GPa which is much smaller than that of other layered arsenide and oxyarsenide superconductors. LiFeAs also exhibits much more isotropic compression than other layered iron arsenide superconductors. The higher and more isotropic compressibility is presumably a consequence of the small size of the lithium ion. At ambient pressure the FeAs(4) tetrahedra are the most compressed in the basal plane of those in any of the superconducting iron arsenides. On increasing the pressure the Fe-Fe distance contracts more rapidly than the Fe-As distance so that the FeAs(4) tetrahedra become even more distorted from the ideal tetrahedral shape. The decrease in T(c) with applied pressure is therefore consistent with the observations that in the iron arsenides and related materials investigated thus far, T(c) is maximized for a particular electron count when the FeAs(4) tetrahedra are close to regular.
Journal of the American Chemical Society 03/2009; 131(8):2986-92. · 10.68 Impact Factor
[show abstract][hide abstract] ABSTRACT: Transverse-field muon-spin rotation measurements performed on two samples of LiFeAs demonstrate that the superfluid stiffness of the superconducting condensate in relation to its superconducting transition temperature is enhanced compared to other pnictide superconductors. Evidence is seen for a field-induced magnetic state in a sample with a significantly suppressed superconducting transition temperature. The results in this system highlight the role of direct Fe-Fe interactions in frustrating pairing mediated by antiferromagnetic fluctuations and indicate that, in common with other pnictide superconductors, the system is close to a magnetic instability.
[show abstract][hide abstract] ABSTRACT: Lithium iron arsenide phases with compositions close to LiFeAs exhibit superconductivity at temperatures at least as high as 16 K, demonstrating that superconducting [FeAs](-) anionic layers with the anti-PbO structure type occur in at least three different structure types and with a wide range of As-Fe-As bond angles.
Chemical Communications 01/2009; · 6.38 Impact Factor
[show abstract][hide abstract] ABSTRACT: A series of layered oxychalcogenide and oxypnictide solids is described that contain oxide layers separated by distinct layers, which contain the softer chalcogenide (S, Se, Te) or pnictide (P, As, Sb, Bi) anions. The relationships between the crystal structures adopted by these compounds are described, and the physical and chemical properties of these materials are related to the structures and the properties of the elements. The properties exhibited by the oxychalcogenide materials include semiconductor properties, for example, in LaOCuCh (Ch = chalcogenide) and derivatives, unusual magnetic properties exhibited by the class Sr 2MO 2Cu 2-deltaS 2 (M = Mn, Co, Ni), and redox properties exhibited by the materials Sr 2MnO 2Cu 2 m-0.5 S m+1 ( m = 1-3) and Sr 4Mn 3O 7.5Cu 2Ch 2 (Ch = S, Se). Recent results in the oxychalcogenide area are reviewed, and some new results on the intriguing series of compounds Sr 2MO 2Cu 2-deltaS 2 (M = Mn, Co, Ni) are reported. Oxypnictides have received less recent attention, but this is changing: a new frenzy of research is underway following the discovery of high-temperature superconductivity (>40 K) in derivatives of the layered oxyarsenide LaOFeAs. The early results in this exciting new area will be reviewed.
[show abstract][hide abstract] ABSTRACT: The structures of the new oxysulfide Ruddlesden-Popper phases La2LnMS2O5 (Ln=La, Y; M=Nb, Ta) are reported together with an iodide-containing variant: La3-xNb1+xS2O5I2x (0<or=x<0.11). Structures were refined against powder-neutron or single-crystal X-ray diffraction data. All of these compounds exhibit an intergrowth structure with NaCl-type slabs [La2S2] alternating regularly with perovskite-type oxide slabs [LnMO5] or [La1-xNb1+xO5I2x]. In the oxide slabs, the trivalent and pentavalent cations are disordered on the long-length scale probed by diffraction methods, but bond length considerations suggest that they must be ordered at least on the length scale of the unit cell. The [LnMO5] block of the iodide-free compounds derive from the ideal [Ti2O5] blocks found in Ln2Ti2S2O5 (Ln=Nd-Er; Y) by the formal substitution of two Ti4+ ions with one Ln3+ and one M5+ion. The unusual partial insertion of iodide in the perovskite voids of the [LaNbO5] block in La3NbS2O5 was found to be coupled to a La/Nb substitution, maintaining the charge balance within the [La1-xNb1+xO5I2x]2- block. The Nb5+ ions were found to be too resistant to reduction to undergo the intercalation of alkali metals observed in the Ln2Ti2S2O5 series.