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ABSTRACT: The monoclinic perovskite BiCo(1-x) Fe(x) O(3) (x≈0.7) undergoes a second-order structural transition from tetragonal to monoclinic, which is accompanied by a rotation of the polarization vector from the [001] to [111] directions of a pseudo cubic cell. The crystal structure, determined by electron diffraction and powder synchrotron X-ray diffraction, was the same as that of Pb(Ti(1-x) Zr(x) )O(3) at the morphotropic phase boundary.
Angewandte Chemie International Edition 08/2012; 51(32):7977-80. · 13.45 Impact Factor
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ABSTRACT: The crystal structure of the layered cobalt oxyfluoride Sr(2)CoO(3)F synthesized under high-pressure and high-temperature conditions has been determined from neutron powder diffraction and synchrotron powder diffraction data collected at temperatures ranging from 320 to 3 K. This material adopts the tetragonal space group I4/mmm over the measured temperature range and the crystal structure is analogous to n = 1 Ruddlesden-Popper type layered perovskite. In contrast to related oxyhalide compounds, the present material exhibits the unique coordination environment around the Co metal center: coexistence of square pyramidal coordination around Co and anion disorder between O and F at the apical sites. Magnetic susceptibility and electrical resistivity measurements reveal that Sr(2)CoO(3)F is an antiferromagnetic insulator with the Néel temperature T(N) = 323(2) K. The magnetic structure that has been determined by neutron diffraction adopts a G-type antiferromagnetic order with the propagation vector k = (1/2 1/2 0) with an ordered cobalt moment μ = 3.18(5) μ(B) at 3 K, consistent with the high spin electron configuration for the Co(3+) ions. The antiferromagnetic and electrically insulating states remain robust even against 15%-O substation for F at the apical sites. However, applying pressure exhibits the onset of the metallic state, probably coming from change in the electronic state of square-pyramidal coordinated cobalt.
Inorganic Chemistry 04/2012; 51(8):4802-9. · 4.60 Impact Factor
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Masaki Azuma,
Wei-tin Chen,
Hayato Seki,
Michal Czapski,
Smirnova Olga, Kengo Oka,
Masaichiro Mizumaki,
Tetsu Watanuki,
Naoki Ishimatsu,
Naomi Kawamura,
Shintaro Ishiwata,
Matthew G Tucker,
Yuichi Shimakawa,
J Paul Attfield
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ABSTRACT: The unusual property of negative thermal expansion is of fundamental interest and may be used to fabricate composites with zero or other controlled thermal expansion values. Here we report that colossal negative thermal expansion (defined as linear expansion <-10(-4) K(-1) over a temperature range ~100 K) is accessible in perovskite oxides showing charge-transfer transitions. BiNiO(3) shows a 2.6% volume reduction under pressure due to a Bi/Ni charge transfer that is shifted to ambient pressure through lanthanum substitution for Bi. Changing proportions of coexisting low- and high-temperature phases leads to smooth volume shrinkage on heating. The crystallographic linear expansion coefficient for Bi(0.95)La(0.05)NiO(3) is -137×10(-6) K(-1) and a value of -82×10(-6) K(-1) is observed between 320 and 380 K from a dilatometric measurement on a ceramic pellet. Colossal negative thermal expansion materials operating at ambient conditions may also be accessible through metal-insulator transitions driven by other phenomena such as ferroelectric orders.
Nature Communications 01/2011; 2:347. · 7.40 Impact Factor
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Kengo Oka,
Masaki Azuma,
Wei-tin Chen,
Hitoshi Yusa,
Alexei A Belik,
Eiji Takayama-Muromachi,
Masaichiro Mizumaki,
Naoki Ishimatsu,
Nozomu Hiraoka,
Masahiko Tsujimoto,
Matthew G Tucker,
J Paul Attfield,
Yuichi Shimakawa
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ABSTRACT: The structural and electronic properties of BiCoO(3) under high pressure have been investigated. Synchrotron X-ray and neutron powder diffraction studies show that the structure changes from a polar PbTiO(3) type to a centrosymmetric GdFeO(3) type above 3 GPa with a large volume decrease of 13% at room temperature revealing a spin-state change. The first-order transition is accompanied by a drop of electrical resistivity. Structural results show that Co(3+) is present in the low spin state at high pressures, but X-ray emission spectra suggest that the intermediate spin state is present. The pressure-temperature phase diagram of BiCoO(3) has been constructed enabling the transition temperature at ambient pressure to be estimated as 800-900 K.
Journal of the American Chemical Society 07/2010; 132(27):9438-43. · 9.91 Impact Factor
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ABSTRACT: An A-site-ordered double perovskite BiCu(3)Fe(4)O(12) was synthesized at high-pressure and high-temperature conditions. Similar to the isostructural LaCu(3)Fe(4)O(12), the temperature-induced intermetallic charge transfer between the A'-site Cu and the B-site Fe ions occurs but at higher temperature (428 K) than LaCu(3)Fe(4)O(12) (393 K) does. This charge transfer causes an isostructural phase transition with volume contraction by 0.6% as well as semiconductor-to-metal and antiferromagnetism-to-paramagnetism transitions. Although the Bi cation at the A site does not take part in the charge transfer, it appears to enhance the charge-transfer temperature by stabilizing the square-planar coordinated Cu(3+).
Inorganic Chemistry 09/2009; 48(17):8489-92. · 4.60 Impact Factor
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ABSTRACT: A tetragonal perovskite PbMnO(3) was obtained by treating the 6H hexagonal perovskite phase at 15 GPa and 1273 K. Structural analysis using synchrotron X-ray diffraction suggested that PbMnO(3) crystallizes in the centrosymmetric space group P4/mmm, unlike PbTiO(3) and PbVO(3) which have a polar structure in space group P4mm. Iodometric titration revealed the presence of the oxygen deficiency of x = 0.06 for PbMnO(3-x). The hexagonal 6H and the 3C perovskite phases exhibited antiferromagnetic ordering at 155 and 20 K, respectively.
Inorganic Chemistry 04/2009; 48(5):2285-8. · 4.60 Impact Factor
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ABSTRACT: The magnetic properties of PbVO 3, a PbTiO 3-type perovskite with a large tetragonal distortion ( c/a = 1.229), were investigated. The temperature dependence of the measured magnetization of multidomain single-crystal samples showed a broad maximum centered around 180 K, indicating a two-dimensional antiferromagnetism. muSR measurement revealed the presence of a long-range order below 43 K. The two-dimensional magnetism is due to the ordering of d xy orbitals, which is thought to also be related to the large tetragonal distortion of PbVO 3.
Inorganic Chemistry 08/2008; 47(16):7355-9. · 4.60 Impact Factor
