Synthesis of the novel perovskite-type oxyfluoride PbScO2F under high pressure and high temperature

Katsumata, Tetsuhiro; Nakashima, Mamoru; Umemoto, Hiroshi; Inaguma, Yoshiyuki

doi:10.1016/j.jssc.2008.06.048

Cited by 39 publications

(23 citation statements)

References 10 publications

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“…However, although O 2− and F − are neighboring anions in the periodic table, the oxyfluorides exhibit an anionic ordering depending on the structure. While simple cubic perovskites (SrFeO 2 F [9], BaFeO 2 F [10], PbScO 2 F [11], BaScO 2 F [12], AgFeOF 2 [13], BaInO 2 F [14], and AgTiO 2 F [15]) adopt disordered configurations, a variety of Ruddlesden-Popper type layered perovskites (Sr 2 CuO 2 F 2 [16], Sr 2 FeO 3 F [17,18], Ba 2 InO 3 F [19], Ba 2 ScO 3 F [20], Sr 2 MnO 3 F [21], Sr 3 Fe 2 O 5−x F y [17,22]) exhibit ordered configurations of F − [23]. In layered perovskites, multiple distinct anion sites are present and support anion order.…”

Section: Introductionmentioning

confidence: 99%

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

Oka,

Ichibha,

Kato

et al. 2021

Preprint

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Understanding the mechanisms of anionic ordering in mixed anion compounds is a crucial factor for designing their structural and functional properties. Some oxyfluorides are known to exhibit the F − ordering. The ordering is accompanied by a tetragonal distortion, which is believed to be originated by the 6s 2 lone pairs of Bi and Pb. To elucidate the role played by the lone pair, we studied isostructural Bi 2 Ti 4 O 11 and Pb 2 Ti 4 O 9 F 2 with a combination of synchrotron X-ray diffraction techniques and ab initio calculations. Bi 2 Ti 4 O 11 undergoes antiferroelectric-paraelectric transitions from C2/c to C2/m. Meanwhile, Pb 2 Ti 4 O 9 F 2 does not, because F − selectively occupies the closest anion site to Bi/Pb and reduces the distortion. The question on why a particular site is selectively occupied by F − in Pb 2 Ti 4 O 9 F 2 becomes important to understand the role of 6s 2 lone pair electrons for stabilizing the anion order. Our DFT ab initio calculations reproduced the same anionic arrangement in terms of the total energy. However, this energy gain cannot be fully explained by the electrostatic (Madelung) potential alone, being an exception of the Pauling's second rule. We explain the reason focusing on the steric effects of 6s lone pairs. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the US Department of Energy (DOE). The US Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US Government purposes. Ichibha provided a large part of the calculation results. Ichibha and Fernando wrote the paper coworking with the other authors. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).

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Section: Introductionmentioning

confidence: 99%

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

Oka,

Ichibha,

Kato

et al. 2021

Preprint

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“…Some studies described fluorine containing compounds as superconductors, dielectrics, and piezoelectrics [1][2][3][4][5][6]. Materials with high magnetic resistance and catalytic and photocata lytic properties are known [7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, hydration, and electrical properties of oxyfluoride Ba2InO3F

Tarasova

Анимица

2015

Russ J Electrochem

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“…In fact, some of mixed anionic compounds based on transition metals exhibit exotic properties beyond oxides, such as photocatalytic activity or strong magnetoresistance in oxynitride, 11,12 induced antiferromagnetic order, electrical conduction and even superconductivity in oxyhydrides, 13,14 and wide gap p-type semiconductivity in oxychalcogenides. 15 As compared with the preparation of simple oxides, the preparation of mixed anion materials requires rather sophisticated techniques (and care), for example, high-temperature reactions under a controlled atmosphere (e.g., under NH 3 flow for preparing oxynitrides), high-pressure techniques, 16,17 and hydrothermal reactions. 18 The presence of different anions with distinct valence states (O 2− , N 3− , Cl − , etc.…”

Section: Introductionmentioning

confidence: 99%

Substrate-induced anion rearrangement in epitaxial thin films of LaSrCoO_4−xH_x

et al. 2014

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The hydride reduction of a tetragonal layered perovskite LaSrCoO 4 is known to yield orthorhombic LaSrCoO 3 H 0.7 with a complete hydride/oxide order within the ab plane. In this study, epitaxial thin films of LaSrCoO 4 with a-axis and c-axis orientations have been deposited on ( 100) and ( 001) LaSrAlO 4 (LSAO) substrates, respectively, and allowed to react with hydride to convert into oxyhydrides. X-ray diffraction, secondary ion mass spectroscopy and thermal desorption spectroscopy experiments indicate that both films are topochemically reduced and can integrate hydride ions with a chemical composition close to that obtained for the powder. A significant reduction in the a-axis was observed for the a-axis oriented LaSrCoO 3 H 0.7 film, indicating hydride/oxide order, as previously reported. In contrast, the c-axis oriented LaSrCoO 3 H 0.7 film remains tetragonal, suggesting hydride/oxide disorder. These results demonstrate that strain engineering can lead to new materials with designed anion arrangement in mixed anion materials.

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Synthesis of the novel perovskite-type oxyfluoride PbScO2F under high pressure and high temperature

Cited by 39 publications

References 10 publications

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

Synthesis, hydration, and electrical properties of oxyfluoride Ba2InO3F

Substrate-induced anion rearrangement in epitaxial thin films of LaSrCoO_4−xH_x

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Synthesis of the novel perovskite-type oxyfluoride PbScO2F under high pressure and high temperature

Cited by 39 publications

References 10 publications

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

O/F anion order in Pb$_2$Ti$_4$O$_9$F$_2$ stabilized by the 6$s^2$ lone pair electrons of Pb$^{2+}$

Synthesis, hydration, and electrical properties of oxyfluoride Ba2InO3F

Substrate-induced anion rearrangement in epitaxial thin films of LaSrCoO4−xHx

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Substrate-induced anion rearrangement in epitaxial thin films of LaSrCoO_4−xH_x