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“Antiferroelectric (Pb,Bi)1-xFe1+xO3-y perovskites modulated by crystallographic shear planes”. Abakumov AM, Batuk D, Hadermann J, Rozova MG, Sheptyakov DV, Tsirlin AA, Niermann D, Waschowski F, Hemberger J, Van Tendeloo G, Antipov EV, Chemistry of materials 23, 255 (2011). http://doi.org/10.1021/cm102907h
Abstract: We demonstrate for the first time a possibility to vary the anion content in perovskites over a wide range through a long-range-ordered arrangement of crystallographic shear (CS) planes. Anion-deficient perovskites (Pb,Bi)1−xFe1+xO3−y with incommensurately modulated structures were prepared as single phases in the compositional range from Pb0.857Bi0.094Fe1.049O2.572 to Pb0.409Bi0.567Fe1.025O2.796. Using a combination of electron diffraction and high-resolution scanning transmission electron microscopy, we constructed a superspace model describing a periodic arrangement of the CS planes. The model was verified by refinement of the Pb0.64Bi0.32Fe1.04O2.675 crystal structure from neutron powder diffraction data ((3 + 1)D S.G. X2/m(α0γ), X = [1/2,1/2,1/2,1/2], a = 3.9082(1) Å, b = 3.90333(8) Å, c = 4.0900(1) Å, β = 91.936(2)°, q = 0.05013(4)a* + 0.09170(3)c* at T = 700 K, RP = 0.036, RwP = 0.048). The (Pb,Bi)1−xFe1+xO3−y structures consist of perovskite blocks separated by CS planes confined to nearly the (509)p perovskite plane. Along the CS planes, the perovskite blocks are shifted with respect to each other over the 1/2[110]p vector that transforms the corner-sharing connectivity of the FeO6 octahedra in the perovskite framework to an edge-sharing connectivity of the FeO5 pyramids at the CS plane, thus reducing the oxygen content. Variation of the chemical composition in the (Pb,Bi)1−xFe1+xO3−y series occurs mainly because of a changing thickness of the perovskite block between the interfaces, that can be expressed through the components of the q vector as Pb6γ+2αBi1−7γ−αFe1+γ−αO3−3γ−α. The Pb, Bi, and Fe atoms are subjected to strong displacements occurring in antiparallel directions on both sides of the perovskite blocks, resulting in an antiferroelectric-type structure. This is corroborated by the temperature-, frequency-, and field-dependent complex permittivity measurements. Pb0.64Bi0.32Fe1.04O2.675 demonstrates a remarkably high resistivity >0.1 T Ω cm at room temperature and orders antiferromagnetically below TN = 608(10) K.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 29
DOI: 10.1021/cm102907h
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“Anisotropic cation exchange in PbSe/CdSe core/shell nanocrystals of different geometry”. Casavola M, van Huis MA, Bals S, Lambert K, Hens Z, Vanmaekelbergh D, Chemistry of materials 24, 294 (2012). http://doi.org/10.1021/cm202796s
Abstract: We present a study of Cd2+-for-Pb2+ exchange in PbSe nanocrystals (NCs) with cube, star, and rod shapes. Prolonged temperature-activated cation exchange results in PbSe/CdSe heterostructured nanocrystals (HNCs) that preserve their specific overall shape, whereas the PbSe core is strongly faceted with dominance of {111} facets. Hence, cation exchange proceeds while the Se anion lattice is preserved, and well-defined {111}/{111} PbSe/CdSe interfaces develop. Interestingly, by quenching the reaction at different stages of the cation exchange new structures have been isolated, such as coreshell nanorods, CdSe rods that contain one or two separated PbSe dots and fully zinc blende CdSe nanorods. The crystallographically anisotropic cation exchange has been characterized by a combined HRTEM/HAADF-STEM study of heterointerface evolution over reaction time and temperature. Strikingly, Pb and Cd are only intermixed at the PbSe/CdSe interface. We propose a plausible model for the cation exchange based on a layer-by-layer replacement of Pb2+ by Cd2+ enabled by a vacancy-assisted cation migration mechanism.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 136
DOI: 10.1021/cm202796s
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“Anion rearrangements in fluorinated Nd2CuO3.5”. Corbel G, Attfield JP, Hadermann J, Abakumov AM, Alekseeva AM, Rozova MG, Antipov EV, Chemistry of materials 15, 189 (2003). http://doi.org/10.1021/cm021102m
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 9
DOI: 10.1021/cm021102m
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