Hongjun Niu

Interstitial oxide ion conductivity in the layered tetrahedral network melilite structure

High-conductivity oxide ion electrolytes are needed to reduce the operating temperature of solid-oxide fuel cells. Oxide mobility in solids is associated with defects. Although anion vacancies are the charge carriers in most cases, excess (interstitial) oxide anions give high conductivities in isolated polyhedral anion structures such as the apatites. The development of new families of interstitial oxide conductors with less restrictive structural constraints requires an understanding of the mechanisms enabling both incorporation and mobility of the excess oxide. Here, we show how the two-dimensionally connected tetrahedral gallium oxide network in the melilite structure La(1.54)Sr(0.46)Ga(3)O(7.27) stabilizes oxygen interstitials by local relaxation around them, affording an oxide ion conductivity of 0.02-0.1 S cm(-1) over the 600-900 degrees C temperature range. Polyhedral frameworks with central elements exhibiting variable coordination number can have the flexibility needed to accommodate mobile interstitial oxide ions if non-bridging oxides are present to favour cooperative network distortions.

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.

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.

A Polar Corundum Oxide Displaying Weak Ferromagnetism at Room Temperature

Combining long-range magnetic order with polarity in the same structure is a prerequisite for the design of (magnetoelectric) multiferroic materials. There are now several demonstrated strategies to achieve this goal, but retaining magnetic order above room temperature remains a difficult target. Iron oxides in the +3 oxidation state have high magnetic ordering temperatures due to the size of the coupled moments. Here we prepare and characterize ScFeO3 (SFO), which under pressure and in strain-stabilized thin films adopts a polar variant of the corundum structure, one of the archetypal binary oxide structures. Polar corundum ScFeO3 has a weak ferromagnetic ground state below 356 K—this is in contrast to the purely antiferromagnetic ground state adopted by the well-studied ferroelectric BiFeO3.

Interstitial Oxide Ion Order and Conductivity in La1.64Ca0.36Ga3O7.32 Melilite

Solid oxide fuel cells (SOFCs) are a major candidate technology for clean energy conversion because of their high efficiency and fuel flexibility.1 The development of intermediate-temperature (500–750 °C) SOFCs requires electrolytes with high oxide ion conductivity (exceeding 10−2 S cm−1 assuming an electrolyte thickness of 15 μm1). This conductivity, in turn, necessitates enhanced understanding of the mechanisms of oxide ion charge carrier creation and mobility at an atomic level. The charge carriers are most commonly oxygen vacancies in fluorites2, 3 and perovskites.3, 4 There are fewer examples of interstitial-oxygen-based conductors such as the apatites5, 6 and La2Mo2O9-based materials,7–9 so information on how these excess anion defects are accommodated and the factors controlling their mobility is important.

Frustration of Magnetic and Ferroelectric Long-Range Order in Bi2Mn4/3Ni2/3O6

The slight incommensurate modulation of the structure of Bi(2)Mn(4/3)Ni(2/3)O(6) is sufficient to suppress the electrical polarization which arises in commensurate treatments of the structure, due to antiferroelectric coupling of local polar units of over 900 A(3). The incommensurate structure is produced by the competition between ferroelectric Bi lone pair-driven A site displacement, chemical order of Mn and Ni on the B site, and both charge and orbital order at these transition metals. The interplay between the frustrated polar Bi displacements and the frustrated spin order at the B site, induced by positional disorder, produces magnetodielectric coupling between the incommensurately modulated lattice and the spin-glass-like ground state with an unusual relationship between the magnetocapacitance and the applied field.

Crystal structure, microwave dielectric properties and AC conductivity of B-cation deficient hexagonal perovskites La5MxTi4−xO15 (x = 0.5, 1; M = Zn, Mg, Ga, Al)

Three new n = 5 members of the B-cation deficient hexagonal perovskite AnBn−1O3n family, La5Zn0.5Ti3.5O15, La5GaTi3O15 and La5AlTi3O15, have been synthesised and their crystal structures determined. Their microwave dielectric properties and AC conductivities, as well as those of a known material, La5Mg0.5Ti3.5O15, were characterized. These four analogues adopt a 10H structure with an AO3 stacking sequence of (hhccc)2 with empty octahedral sites between two hexagonal layers. Zn, Mg, Ga and Al atoms prefer the octahedral sites between two cubic layers to those between cubic and hexagonal layers. The Mg phase exhibits more extensive B-cation order than the Zn, Ga and Al phases. These three new materials exhibit relatively high dielectric permittivity e, 28–37, modest Q × f values, 23 000–30 000 GHz and a negative temperature coefficient of resonant frequency τf from −37 ppm/°C to −55 ppm/°C. τf of these four members and other n = 5 La-based and Ba-based members of B-cation hexagonal deficient perovskites are compared and the correlations between their τf and tolerance factors are discussed. Based on the comparison of these four materials with BaLa4Ti4O15, correlations between the defects, conductivity and microwave dielectric loss are also addressed.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Cation ordering within the perovskite block of a six-layer Ruddlesden-Popper oxide from layer-by-layer growth – artificial interfaces in complex unit cells

The (AO)(ABO3)n Ruddlesden-Popper structure is an archetypal complex oxide consisting of two distinct structural units, an (AO) rock salt layer separating an n-octahedra thick perovskite block. Conventional high-temperature oxide synthesis methods cannot access members with n > 3, but low-temperature layer-by-layer thin film methods allow the preparation of materials with thicker perovskite blocks, exploiting high surface mobility and lattice matching with the substrate. This paper describes the growth of an n = 6 member CaO[(CSMO)2(LCMO)2 (CSMO)2] in which the six unit cell perovskite block is sub-divided into two central La0.67Ca0.33MnO3 (LCMO) and two terminal Ca0.85Sm0.15MnO3 (CSMO) layers to allow stabilization of the rock salt layer and variation of the transition metal charge.

Fabrication of nanocrystalline and amorphous Chevrel phase PbMo6S8 powder by ball milling

Abstract Chevrel phase PbMo 6 S 8 (PMS) superconducting powder ball-milled from 5 to 200 h has been investigated using X-ray diffraction (XRD) and scanning and transmission electron microscopy. Ball milling produced particles with crystallites of PMS in the range 10–100 nm and amorphous phase. From XRD data, it was found that the crystallite size decreased and lattice strain increased with increasing milling time until by 200 h the material was predominantly amorphous. The powder ball-milled for 100 h was subsequently annealed at temperatures from 400 to 1000 °C for 8 h. Annealing at 600 °C and above released the lattice strain. At 800 °C and above the amorphous phase crystallised and grains coarsened with sizes in the range 50–100 nm.