Michael J. Pitcher

Structures, Physical Properties, and Chemistry of Layered Oxychalcogenides and Oxypnictides

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.

Tilt engineering of spontaneous polarization and magnetization above 300 K in a bulk layered perovskite

Tilting toward two properties Opposing electronic and symmetry constraints can make it difficult to combine some pairs of material properties in a single crystalline material. Magnetization and electrical polarization are such a pair, but their combination could be useful for applications such as magnetoelectric information storage. Pitcher et al. now show that careful design of chemical substitutions in a layered perovskite are both electrically polar and weakly ferromagnetic at temperatures up to 330 K. Science, this issue p. 420 Chemical substitutions produce atomic displacements in a crystal that lead to both electrical polarization and magnetization. Crystalline materials that combine electrical polarization and magnetization could be advantageous in applications such as information storage, but these properties are usually considered to have incompatible chemical bonding and electronic requirements. Recent theoretical work on perovskite materials suggested a route for combining both properties. We used crystal chemistry to engineer specific atomic displacements in a layered perovskite, (CaySr1–y)1.15Tb1.85Fe2O7, that change its symmetry and simultaneously generate electrical polarization and magnetization above room temperature. The two resulting properties are magnetoelectrically coupled as they arise from the same displacements.

Control of the competition between a magnetic phase and a superconducting phase in cobalt-doped and nickel-doped NaFeAs using electron count.

Dinah R. Parker, Matthew J. P. Smith, Tom Lancaster, Andrew J. Steele, Isabel Franke, Peter J. Baker, Francis L. Pratt, Michael J. Pitcher, Stephen J. Blundell, ∗ and Simon J. Clarke † Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, United Kingdom Clarendon Laboratory, University of Oxford, Parks Road, Oxford OX1 3PU, United Kingdom ISIS Facility, STFC-Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, OX11 0QX, United Kingdom (Dated: September 16, 2010)

Designing switchable polarization and magnetization at room temperature in an oxide

Ferroelectric and ferromagnetic materials exhibit long-range order of atomic-scale electric or magnetic dipoles that can be switched by applying an appropriate electric or magnetic field, respectively. Both switching phenomena form the basis of non-volatile random access memory, but in the ferroelectric case, this involves destructive electrical reading and in the magnetic case, a high writing energy is required. In principle, low-power and high-density information storage that combines fast electrical writing and magnetic reading can be realized with magnetoelectric multiferroic materials. These materials not only simultaneously display ferroelectricity and ferromagnetism, but also enable magnetic moments to be induced by an external electric field, or electric polarization by a magnetic field. However, synthesizing bulk materials with both long-range orders at room temperature in a single crystalline structure is challenging because conventional ferroelectricity requires closed-shell d0 or s2 cations, whereas ferromagnetic order requires open-shell dn configurations with unpaired electrons. These opposing requirements pose considerable difficulties for atomic-scale design strategies such as magnetic ion substitution into ferroelectrics. One material that exhibits both ferroelectric and magnetic order is BiFeO3, but its cycloidal magnetic structure precludes bulk magnetization and linear magnetoelectric coupling. A solid solution of a ferroelectric and a spin-glass perovskite combines switchable polarization with glassy magnetization, although it lacks long-range magnetic order. Crystal engineering of a layered perovskite has recently resulted in room-temperature polar ferromagnets, but the electrical polarization has not been switchable. Here we combine ferroelectricity and ferromagnetism at room temperature in a bulk perovskite oxide, by constructing a percolating network of magnetic ions with strong superexchange interactions within a structural scaffold exhibiting polar lattice symmetries at a morphotropic phase boundary (the compositional boundary between two polar phases with different polarization directions, exemplified by the PbZrO3–PbTiO3 system) that both enhances polarization switching and permits canting of the ordered magnetic moments. We expect this strategy to allow the generation of a range of tunable multiferroic materials.

Response of Superconductivity and Crystal Structure of LiFeAs to Hydrostatic Pressure

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.

Antiferromagnetic spin fluctuations in LiFeAs observed by neutron scattering

We report neutron inelastic scattering measurements on the stoichiometric iron-based superconductor LiFeAs. We find evidence for (i) magnetic scattering consistent with strong antiferromagnetic fluctuations, and (ii) an increase in intensity in the superconducting state at low energies, similar to the resonant magnetic excitation observed in other iron-based superconductors. The results do not support a recent theoretical prediction of spin-triplet p-wave superconductivity in LiFeAs, and instead suggest that the mechanism of superconductivity is similar to that in the other iron-based superconductors.

Compositional Control of the Superconducting Properties of LiFeAs

The response of the superconducting state and crystal structure of LiFeAs to chemical substitutions on both the Li and the Fe sites has been probed using high-resolution X-ray and neutron diffraction measurements, magnetometry, and muon-spin rotation spectroscopy. The superconductivity is extremely sensitive to composition: Li-deficient materials (Li(1-y)Fe(1+y)As with Fe substituting for Li) show a very rapid suppression of the superconducting state, which is destroyed when y exceeds 0.02, echoing the behavior of the Fe(1+y)Se system. Substitution of Fe by small amounts of Co or Ni results in monotonic lowering of the superconducting transition temperature, T(c), and the superfluid stiffness, rho(s), as the electron count increases. T(c) is lowered monotonically at a rate of 10 K per 0.1 electrons added per formula unit irrespective of whether the dopant is Co and Ni, and at higher doping levels superconductivity is completely suppressed. These results and the demonstration that the superfluid stiffness in these LiFeAs-derived compounds is higher than in all of the iron pnictide materials underlines the unique position that LiFeAs occupies in this class.

High-energy spin excitations in BaFe 2 As 2 observed by inelastic neutron scattering

We report neutron-scattering measurements of cooperative spin excitations in antiferromagnetically ordered

Heat capacity measurements on FeAs-based compounds: a thermodynamic probe of electronic and magnetic states

{\text{BaFe}}_{2}{\text{As}}_{2}

Gradual destruction of magnetism in the superconducting family NaFe1−xCoxAs

, the parent phase of an iron pnictide superconductor. The data extend up to