A promising route to discover exotic electronic states in correlated electron systems is to vary the hole or electron doping away from a Mott insulating state. Important examples include quantum criticality and high-temperature superconductivity in cuprates. Here, we report the surprising discovery of a quantum insulating state upon electron doping the Mott insulator CeMnAsO, which emerges below a distinct critical transition temperature, T II . The insulator-insulator transition is accompanied by a significant reduction in electron mobility as well as a colossal Seebeck effect and slow dynamics due to decoupling of the electrons from the lattice phonons. The origin of the transition is tentatively interpreted in terms of many-body localization, which has not been observed previously in a solid-state material.

Significant oxide ion conductivity has previously been reported for the Ba3M′M″O8.5 family (M′ = Nb5+, V5+; M″ = Mo6+, W6+) of cation-deficient hexagonal perovskite derivatives. These systems exhibit considerable structural disorder and competitive occupation of two distinct oxygen positions (O3 site and O2 site), enabling two-dimensional (2D) ionic conductivity within the ab plane of the structure; higher occupation of the tetrahedral O3 site vs the octahedral O2 site is known to be a major factor that promotes oxide ion conductivity. Previous chemical doping studies have shown that substitution of small amounts of the M′ or M″ ions can result in significant changes to both the structure and ionic conductivity. Here, we report on the electrical and structural properties of the Ba3Nb1–xTaxMoO8.5 series (x = 0.00, 0.025, 0.050, 0.100). AC impedance measurements show that substitution of Nb5+ with Ta5+ leads to a significant increase in low-temperature (<500 °C) conductivity for x = 0.1. Analysis of neutron and X-ray diffraction (XRD) data confirms that there is a decrease in the M1O4/M1O6 ratio upon increasing x from 0 to 0.1 in Ba3Nb1–xTaxMoO8.5, which would usually coincide with a lowering in the conductivity. However, neutron diffraction results show that Ta doping causes an increase in the oxide ion conductivity as a result of longer M1–O3 bonds and increased polyhedral distortion.

The pressure response of Ba3MoNbO8.5 reveals a structural transformation, which acts to increase the energy barriers to migration along all available transport pathways, and an exceptionally low bulk modulus.

Several different mechanisms of magnetoresistance (MR) have been observed in 1111 LnMnAsO1-xFx oxypnictides (Ln = lanthanide) as a result of magnetic coupling between the Mn and Ln. Such phases also exhibit interesting magnetic phase transitions upon cooling. Sr2Mn2CrAs2O2 has been synthesized to investigate if it is possible to observe MR and/or magnetic phase transitions as a result of magnetic coupling between the Mn and Cr. Sr2Mn2CrAs2O2 crystallizes in the tetragonal space group I4/mmm containing alternating MO22- and M'2As22- layers, and neutron diffraction results demonstrate that the actual stoichiometry is Sr2Mn2.23Cr0.77As2O2. Cation order is present between Mn and Cr, with Cr predominantly occupying the square planar MO22- site. Below 410 K, the magnetic moments of the Mn/Cr ions in the M'2As22- sublattice exhibit G-type antiferromagnetic order. The Mn/Cr moments within the MO22- layer order below 167 K with a K2NiF4-type antiferromagnetic structure that simultaneously induces a spin flip of the magnetic moments in the M'2As22- layers from a G-type to a C-type antiferromagnetic arrangement. The results demonstrate that the superexchange interactions are finely balanced in Sr2Mn2.23Cr0.77As2O2. Sr2Mn2.23Cr0.77As2O2 is semiconducting, and there is no evidence of MR.

Oxide ion and proton conductors, which exhibit high conductivity at intermediate temperature, are necessary to improve the performance of ceramic fuel cells. The crystal structure plays a pivotal role in defining the ionic conduction properties, and the discovery of new materials is a challenging research focus. Here, we show that the undoped hexagonal perovskite Ba7Nb4MoO20 supports pure ionic conduction with high proton and oxide ion conductivity at 510 °C (the bulk conductivity is 4.0 mS cm−1), and hence is an exceptional candidate for application as a dual-ion solid electrolyte in a ceramic fuel cell that will combine the advantages of both oxide ion and proton-conducting electrolytes. Ba7Nb4MoO20 also showcases excellent chemical and electrical stability. Hexagonal perovskites form an important new family of materials for obtaining novel ionic conductors with potential applications in a range of energy-related technologies. Fast oxide ion and proton conductors at intermediate temperature are required to improve the performance of ceramic fuel cells. An undoped hexagonal perovskite Ba7Nb4MoO20 electrolyte with high proton and oxide ion conductivity (4.0 mS cm−1) at 510 °C is now reported.

Various structural families have been reported to support oxide ion conductivity; among these, perovskite conductors have received particular attention. The perovskite structure is generally composed of a framework of corner-sharing octahedral units. When the octahedral units share their faces, hexagonal perovskites are formed. Mixed combinations of corner-sharing and face-sharing octahedral units can give rise to a variety of hexagonal perovskite derivatives. However, the ionic conducting properties of these materials have not been well explored. In this feature article, we review the conducting properties of the most significant hexagonal perovskite derivatives, with special focus on Ba3MMO8.5. Ba3MMO8.5 is the first hexagonal perovskite derivative to exhibit substantial oxide ion conductivity, and here we outline the structural features that are key for the oxide ion conduction within this system. The results demonstrate that further investigation of hexagonal perovskite derivatives could open up new directions in the design of oxide ion conductors.

The oxide ionic conductor Ba3W1.2Nb0.8O8.6 has been synthesized as part of an investigation into the new class of Ba3M'M''O8.5 (M' = W, Mo; M'' = Nb) oxide-ion conducting hexagonal perovskite derivatives. The substitution of W6+ for Nb5+ in Ba3W1+ xNb1- xO8.5+ x/2 leads to an increase in the oxygen content, which enhances the low-temperature ionic conductivity. However, at 400 °C, the ionic conductivity of Ba3W1.2Nb0.8O8.6 is still significantly lower than the molybdenum compound Ba3MoNbO8.5. Remarkably, at 600 °C the bulk oxide ionic conductivities of Ba3MoNbO8.5, Ba3WNbO8.5, and Ba3W1.2Nb0.8O8.6 are very similar (σb = 0.0022, 0.0017, and 0.0016 S cm-1, respectively). The variable-temperature neutron diffraction results reported here demonstrate that Ba3W1.2Nb0.8O8.6 undergoes a similar structural rearrangement to Ba3MoNbO8.5 above 300 °C, but the ratio of (W/Nb)O4 tetrahedra to (W/Nb)O6 octahedra rises at a faster rate upon heating between 300 and 600 °C. There is a clear relationship between the ionic conductivity of Ba3M'1+ xM''1- xO8.5+ x/2 (M' = W, Mo; M'' = Nb) phases and the number of tetrahedrally coordinated M' and M ″ cations present within the crystal structure.

The colossal magnetoresistance (CMR) observed in the oxypnictide NdMnAsO1-xFx has been further investigated. The magnetotransport is dominated by magnetopolarons. Magnetoresistance measurements of the series Nd(Mn1-xCox)AsO0.95F0.05 show that doping with cobalt on the manganese site pins the magnetopolarons and suppresses the CMR, which is completely destroyed by x = 0.047. The chemical doping results in non-stoichiometric samples, with both As and O vacancies. The relationship between the non-stoichiometry, magnetic order, electron doping and CMR is explored. The Nd antiferromagnetic transition and simultaneous reorientation of the Mn spins into the basal plane at 23 K (TSR) is not effected by Co doping. However, there is a significant decrease in TN(Mn) as the antiferromagnetic transition is suppressed from 360 K to 300 K as x increases from 0-0.047. The manganese moment at 10 K is also reduced from 3.86(2)μB to 3.21(2)μB over the same doping range. This reduction in the in-plane Mn moment decreases the electron-electron correlations below TSR and acts to further diminish the magnetoresistance.

The crystal structure of the novel oxide ion conductor Ba3WNbO8.5.

The electrical and structural properties of the series Ba3Mo1-xNb1+xO8.5-x/2 (x = 0.0, 0.1, 0.2, 0.3) have been determined. Ba3Mo1-xNb1+xO8.5-x/2 crystallizes in a hybrid of the 9R hexagonal perovskite and palmierite structures, in which (Mo/Nb)O4 and (Mo/Nb)O6 units coexist within the structure. Nb substitutes preferentially at the octahedral site so that the ratio of (Mo/Nb)O4 tetrahedra to (Mo/Nb)O6 octahedra decreases with increasing x resulting in a reduction in the magnitude of the ionic conductivity from 1.3 × 10-6 S cm-1 for x = 0.0 to 1.1 × 10-7 S cm-1 for x = 0.3 at 300 °C. However, upon heating the conductivities of the solid solution converge, which suggests that the unusual thermal structural rearrangement previously reported for Ba3MoNbO8 preserves the high temperature conductivity. The results demonstrate that the presence of (Mo/Nb)O4 tetrahedra with nonbridging apical oxygen atoms is an important prerequisite for the ionic conduction observed in the Ba3MoNbO8.5 system.

A variable temperature neutron diffraction study of the novel oxide ion conductor Ba3MoNbO8.5 has been performed between 25 and 600 degrees C. Nonmonotonic behavior of the cell parameters, bond lengths, and angles are observed indicating a structural rearrangement above 300 degrees C. The oxygen/vacancy distribution changes as the temperature increases so that the ratio of (Mo/Nb)O-4 tetrahedra to (Mo/Nb)O-6 octahedra increases upon heating above 300 degrees C. A strong correlation between the oxide ionic conductivity and the number of (Mo/Nb)O-4 tetrahedra within the average structure of Ba3MoNbO8.5 is observed. The increase in the number of (Mo/Nb)O-4 tetrahedra upon heating from 300-600 degrees C most likely offers more low energy transition paths for transport of the O2- ions enhancing the conductivity. The unusual structural rearrangement also results in relaxation of Mo(1)/Nb(1) and Ba(2) away from the mobile oxygen, increasing the ionic conductivity. The second order Jahn Teller effect most likely further enhances the distortion of the MO4/MO6 polyhedra as distortions created by both electronic and structural effects are mutually supportive.

The structural, magnetic and electronic properties of the Ruddlesden-Popper material Sr3CoRuO7 have been investigated. Examination of the dc and ac magnetic susceptibility demonstrates that Sr3CoRuO7 exhibits a spin glass transition at 40K and a magnetic transition at 140K. Variable-temperature neutron powder diffraction experiments showed no evidence of magnetic diffraction peaks down to 5K. This suggests the transition at 140K is a result of short range magnetic order or magnetic clustering of the Co/Ru spins. Sr3CoRuO7 is semiconducting and Mott variable range hopping behaviour is observed below 240K.

The structure of Ba3Nb2O8 has been investigated using high resolution neutron powder diffraction. Our results show that, while the structure has some features in common with the 9R perovskite and palmierite structures, it is a new and distinct structure. It is shown to follow a (chh)(hhc)(chh) sequence with BaO3-δ packing layers and is a cation- and anion-deficient 9H perovskite polytype. Nb atoms occupy octahedral sites with vacancies between hexagonal close-packed layers. Isolated, corner-sharing and face-sharing Nb-O octahedra all occur within the unit cell. The identification of purely octahedral Nb is supported by solid-state 93Nb wideline NMR measurements. A two-component line shape was detected: a narrow featureless resonance with an isotropic chemical shift of δiso -928 ± 5 ppm consistent with regular Nb octahedra, and a much broader featureless resonance with an approximate isotropic chemical shift in the range δiso ∼ -944 to -937 ± 10 ppm consistent with Nb octahedra influenced by O vacancies. These are both characteristic of 6-fold oxo-coordinated Nb environments. The highly distorted octahedral environments in Ba3Nb2O8 make it a potential candidate for dielectric and photocatalytic applications.

Oxide ion conductors are important materials with a range of technological applications and are currently used as electrolytes for solid oxide fuel cells and solid oxide electrolyzer cells. Here we report the crystal structure and electrical properties of the hexagonal perovskite derivative Ba3MoNbO8.5. Ba3MoNbO8.5 crystallizes in a hybrid of the 9R hexagonal perovskite and palmierite structures. This is a new and so far unique crystal structure that contains a disordered distribution of (Mo/Nb)O-6 octahedra and (Mo/Nb)O-4. tetrahedra. Ba3MoNbO8.5 shows a wide stability range and exhibits predominantly oxide ion conduction over a pO(2) range from 10(-20) to 1 atm with a bulk conductivity of 2.2 X 10(-3) S cm(-1) at 600 degrees C. The high level of conductivity in a new structure family suggests that further study of hexagonal perovskite derivatives containing mixed tetrahedral and octahedral geometry could open up new horizons in the design of oxygen conducting electrolytes.

The recent discovery of high temperature superconductivity in Fe arsenides has invigorated research into transition metal pnictides. Colossal magnetoresistance (CMR) has recently been reported for NdMnAsO1-xFx for x = 0.05–0.08, with a maximum magnetoresistance achieved at low temperature (MR 9T (3 K)) = −95%). This appears to be a novel mechanism of CMR, which is as a result of a second order phase transition in field from an insulating antiferromagnet to a semiconducting paramagnet. Here we report a variable temperature synchrotron X-ray powder diffraction study of the CMR oxypnictide NdMnAsO 0.95 F 0.05 between 4 K–290 K. An excellent fit to the tetragonal unit cell with space group P4/ nmm is obtained over the entire temperature range, with no change in crystal structure detected down to 4 K. A coupling of the lattice and magnetic order is observed, where subtle discontinuities in the temperature variation of a and the c/a ratio are apparent as the Nd spins order antiferromagnetically and the Mn moments reorient into the basal plane at T SR . The results suggest that very small changes in lattice parameters effect the coupling between lattice, electronic and magnetic degrees of freedom.

A high pressure neutron diffraction study of the oxypnictide NdMnAsO0.95F0.05 has been performed at temperatures of 290 K - 383 K and pressures up to 8.59 GPa. The results demonstrate that the antiferromagnetic order of the Mn spins is robust to pressures of up to 8.59 GPa. TN is enhanced from 360 K to 383 K upon applying an external pressure of 4.97 GPa, a rate of 4.63 K/GPa. NdMnAsO0.95F0.05 is shown to violate Bloch's rule which would suggest that NdMnAsO0.95F0.05 is on the verge of a localised to itinerant transition. There is no evidence of a structural transition but applied pressure tends to result in more regular As-Mn-As and Nd-O-Nd tetrahedra. The unit cell is significantly more compressible along the c-axis than the a-axis, as the inter-layer coupling is weaker than the intrinsic bonds contained within NdO and MnAs slabs.

We have recently reported a new mechanism of colossal magnetoresistance (CMR) in electron doped manganese oxypnictides NdMnAsO1-xFx. Magnetoresistances of up to -95% at 3 K have been observed. Here we show that upon replacing Nd for Pr, the CMR is surprisingly no longer present. Instead a sizable negative magnetoresistance is observed for PrMnAsO0.95F0.05 below 35 K (MR7T (12 K) = -13.4% for PrMnAsO0.95F0.05). A detailed neutron and synchrotron X-ray diffraction study of PrMnAsO0.95F0.05 has been performed, which shows that a structural transition, Ts, occurs at 35 K from tetragonal P4/nmm to orthorhombic Pmmn symmetry. The structural transition is driven by the Pr 4f electrons degrees of freedom. The sizable -MR observed below the transition most likely arises due to a reduction in magnetic and/or multipolar scattering upon application of a magnetic field.

The oxypnictides Nd1-xSrxMnAsO have been successfully synthesised with x up to 0.1. A synchrotron X-ray diffraction study demonstrates that there is no change in crystal symmetry upon doping with Sr. An expansion of the inter-layer distance between Nd-O-Nd and As-Mn-As blocks is observed with increasing x. Results from variable temperature neutron diffraction and resistivity measurements show that the local moment antiferromagnetic order of the Mn spins is preserved as the [MnAs]- layers are hole doped and the materials are driven metallic for x > 0.05. A sizeable positive magnetoresistance is observed at low temperature which demonstrates that multiple MR mechanisms are possible in LnMnAsO oxypnictides.