Qingdi Zhou

Structures and phase transitions in the ordered double perovskites Ba2BiIIIBiVO6 and Ba2BiIIISbVO6

High-resolution neutron powder diffraction has been used to investigate the structures and phase transitions in the double perovskites Ba(2)Bi(3+)Bi(5+)O(6) (dibarium dibismuth hexaoxide) and Ba(2)BiSbO(6) (dibarium bismuth antimony hexaoxide) in the temperature ranges 4.2-973 and 4.2-625 K, respectively. The charge-ordered bismuthate adopts four structures in the temperature range - monoclinic in P2(1)/n, monoclinic in I2/m, rhombohedral in R3, and finally cubic in Fm3m. The low-temperature monoclinic structure has been determined for the first time. The transitions from P2(1)/n to I2/m, at 132 K, and R3 to Fm3m, at 820 K, are tricritical in nature; the transition from I2/m to R3 at ca 430 K is discontinuous. The behaviour of Ba(2)BiSbO(6) is very similar, except that the transition temperatures are lower - 250 K for I2/m to R3 and 515 K for R3 to Fm3m - and the low-temperature structure is not formed at all. The R3 to Fm3m transition in this compound is closer to second order in nature, although there is evidence for some contribution from higher-order terms.

Structural and spectroscopic studies of BiTa1-xNbxO4

Abstract Polycrystalline samples of type BiTa 1− x Nb x O 4 (0⩽ x ⩽1) in both the orthorhombic and triclinic phases have been characterized by a combination of powder X-ray diffraction, UV-Vis and Raman spectroscopy. The addition of Nb to BiTaO 4 subtly alters the structure and spectroscopic properties of both the orthorhombic and triclinic oxides. The difference in bonding from the Nb 4 d and Ta 5 d electrons results in an unusual variation in the cell parameters in the orthorhombic form. In both structural types the addition of Nb results in a shift of the strong UV-Vis absorption feature towards the visible region. This feature noticeably broadens and shifts towards lower energy in the triclinic structures.

Elastic anomalies associated with transformation sequences in perovskites: II. The strontium zirconate-titanate Sr(Zr,Ti)O 3 solid solution series

The sequence of phase transitions due to octahedral tilting across the Sr(Zr,Ti)O(3) solid solution series has been investigated by resonant ultrasound spectroscopy at high and low temperatures using ceramic samples. The elastic behaviour associated with phase transitions as a function of composition in Sr(Zr,Ti)O(3) at room temperature is proposed to be analogous to that as a function of temperature in SrZrO(3), with the [Formula: see text] transition at SrZr(0.57)Ti(0.43)O(3), [Formula: see text] at SrZr(0.35)Ti(0.65)O(3), and [Formula: see text] at SrZr(0.05)Ti(0.95)O(3). Changes in elastic constants and acoustic dissipation with temperature have been analysed for samples across the compositional range. The intermediate phases, I4/mcm and what is assumed to be Imma, appear to have stability fields across the full compositional range and both show large dissipation effects, most probably due to twin wall mobility. In contrast, the Zr-rich Pnma phase, which should contain transformation twin walls, is an unexpectedly stiff and non-dissipating material, similar to the high temperature and/or Ti-rich [Formula: see text] phase. In the case of Pnma, this is attributed to coupling between the two order parameters, which could impede relaxation responses to an applied stress. The [Formula: see text] structure is a classically stiff cubic perovskite and no transformation-related dissipation processes are expected.

Giant magnetoelastic effect at the opening of a spin-gap in Ba3BiIr2O9.

As compared to 3d (first-row) transition metals, the 4d and 5d transition metals have much more diffuse valence orbitals. Quantum cooperative phenomena that arise due to changes in the way these orbitals overlap and interact, such as magnetoelasticity, are correspondingly rare in 4d and 5d compounds. Here, we show that the 6H-perovskite Ba(3)BiIr(2)O(9), which contains 5d Ir(4+) (S = 1/2) dimerized into isolated face-sharing Ir(2)O(9) bioctahedra, exhibits a giant magnetoelastic effect, the largest of any known 5d compound, associated with the opening of a spin-gap at T* = 74 K. The resulting first-order transition is characterized by a remarkable 4% increase in Ir-Ir distance and 1% negative thermal volume expansion. The transition is driven by a dramatic change in the interactions among Ir 5d orbitals, and represents a crossover between two very different, competing, ground states: one that optimizes direct Ir-Ir bonding (at high temperature), and one that optimizes Ir-O-Ir magnetic superexchange (at low temperature).

Pressure-Induced Intersite BiM (M=Ru, Ir) Valence Transitions in Hexagonal Perovskites†

Pressure-induced charge transfer from Bi to Ir/Ru is observed in the hexagonal perovskites Ba(3+n)BiM(2+n)O(9+3n) (n=0,1; M=Ir,Ru). These compounds show first-order, circa 1% volume contractions at room temperature above 5 GPa, which are due to the large reduction in the effective ionic radius of Bi when the 6s shell is emptied on oxidation, compared to the relatively negligible effect of reduction on the radii of Ir or Ru. They are the first such transitions involving 4d and 5d compounds, and they double the total number of cases known. Ab initio calculations suggest that magnetic interactions through very short (ca. 2.6 Å) M-M bonds contribute to the finely balanced nature of their electronic states.

Key Role of Bismuth in the Magnetoelastic Transitions of Ba3BiIr2O9 and Ba3BiRu2O9 As Revealed by Chemical Doping

The key role played by bismuth in an average intermediate oxidation state in the magnetoelastic spin-gap compounds Ba3BiRu2O9 and Ba3BiIr2O9 has been confirmed by systematically replacing bismuth with La(3+) and Ce(4+). Through a combination of powder diffraction (neutron and synchrotron), X-ray absorption spectroscopy, and magnetic properties measurements, we show that Ru/Ir cations in Ba3BiRu2O9 and Ba3BiIr2O9 have oxidation states between +4 and +4.5, suggesting that Bi cations exist in an unusual average oxidation state intermediate between the conventional +3 and +5 states (which is confirmed by the Bi L3-edge spectrum of Ba3BiRu2O9). Precise measurements of lattice parameters from synchrotron diffraction are consistent with the presence of intermediate oxidation state bismuth cations throughout the doping ranges. We find that relatively small amounts of doping (∼10 at%) on the bismuth site suppress and then completely eliminate the sharp structural and magnetic transitions observed in pure Ba3BiRu2O9 and Ba3BiIr2O9, strongly suggesting that the unstable electronic state of bismuth plays a critical role in the behavior of these materials.

Synchrotron X-Ray Powder Diffraction Studies of Structural Phase Transitions in Perovskite Oxides

The utilization of the high resolution powder diffractometer at the Australian Synchrotron to obtain accurate and precise structures of some perovskite-type oxides is described. The structure of CdTiO3 has been studied from room temperature to 1000°C by high-resolution synchrotron X-ray powder diffraction. It was found that CdTiO3 remains orthorhombic in the Pbnm space group over the entire temperature range, with the expansion in the cell volume well fitted to the expression . The magnitudes of the TiO6 tilts are estimated from the refined structural parameters and these progressively reduce as the temperature is increased. The effect of Sr content on the room temperature structure of the double perovskites Ba2–xSrxInTaO6 is also described. At room temperature Ba2InTaO6 crystallizes in a cubic structure in space group . Doping with Sr results in tilting of the corner sharing octahedra with a concurrent lowering of symmetry with the sequence of structures being

Structural Studies of Five Layer Aurivillius Oxides: A 2 Bi 4 Ti 5 O 18 (A ¼ Ca, Sr, Ba and Pb)

The room temperature structures of the five layer Aurivillius phases A 2Bi4Ti5O18 (A=Ca, Sr, Ba and Pb) have been refined from powder neutron diffraction data using the Rietveld method. The structures consist of [Bi2O2]2+ layers interleaved with perovskite-like [A 2Bi2Ti5O16]2− blocks. The oxides were found to be orthorhombic (space group B2cb) as a consequence of tilting of the TiO6 octahedra coupled with cation displacement. The tilting is a consequence of the mismatch between the Bi2O2 and perovskite-like layers.

Crystal structures and phase transitions in Sr doped Ba{sub 2}InTaO{sub 6} perovskites

The crystal structures of the double perovskites of the type Ba2−xSrxInTaO6 have been studied by synchrotron X-ray and neutron powder diffraction methods. The structures are based on ordered array of the tilted InO6 and TaO6 octahedra, with the Ba/Sr cations being completely disordered. The structure evolves from cubic to monoclinic Fm3¯m→x~0.6I4/m→x~1.2I2/m→x~1.6P21/n. The changes in the symmetry induced by replacing the Ba with Sr have been identified by a symmetry-mode analysis. Variable temperature S-XRD studies of selected examples have shown that heating the samples induces the same sequence of transitions observed in the composition dependent studies.

Valence changes of manganese and structural phase transitions in Sr{sub 1−x}Pr{sub x}MnO₃ (0.1≤x≤0.6)

Abstract Fifteen perovskite manganites Sr 1− x Pr x MnO 3 , x =0.1−0.6 in steps as fine as 0.025, have been synthesized by solid state methods and their crystal structures determined using synchrotron X-ray powder diffraction. At room temperature two first order phase transitions associated with changes in the orbital ordering and the tilting of the corner shared MnO 6 octahedra are evident c u b i c / P m 3 ¯ m ⟹ x ≈ 0.15 t e t r a g o n a l / ( I 4 / m c m ) ⟹ x ≈ 0.45 o r t h o r h o m b i c / I m m a , with two phase regions associated with both transitions. Heating the Pr rich oxide Sr 0.5 Pr 0.5 MnO 3 provides a rare example where chemical pressure and temperature result in a different sequence of transitions Imma – R 3 ¯ c – P m 3 ¯ m , reflecting the importance of the Pr 4 f electrons. X-ray absorption near-edge structure (XANES) measurements at the Mn K and Pr L 3 edges show the valence state of the Mn linearly decreases with increasing Pr content whereas the Pr remains +3 across the entire series. Magnetic susceptibility measurements for selected samples are presented.