Synthesis of new perovskite-type oxyfluorides, BaInO2F and comparison of the structure among perovskite-type oxyfluorides

Katsumata, Tetsuhiro; Suzuki, Ryo; Satoh, Naoto; Suzuki, Shunpei; Nakashima, Mamoru; Inaguma, Yoshiyuki; Mori, Daisuke; Aimi, Akihisa; Yoneda, Yasutoshi

doi:10.1016/j.jssc.2019.120919

Cited by 12 publications

(15 citation statements)

References 33 publications

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“…The formation of the cubic perovskite structure is also in agreement with the Goldschmidt tolerance factor, provided in eq where r A , r B , r O , and r F are the atomic radii of the A and B cations and O and F, respectively . The calculated value of t for BaScO 2 F is 0.997, corresponding to a cubic structure (0.9 < t < 1.0) …”

Section: Resultssupporting

confidence: 79%

“…These hurdles have motivated researchers to study double perovskites ( A 2 BB′X 6 ) and vacancy ordered double perovskites ( A 2 BX 6 ) as phosphor hosts. , These perovskites perform the down-conversion process as desired; however, these structures contain multiple substitution sites or are only able to incorporate line-emitters such as Eu 3+ or luminescent transition metals such as Bi 3+ or Sb 3+ , limiting their application. , One remaining avenue of the perovskite system to explore is mixed anionic perovskites, with general formula AB O 2 F. There are only a few A 2+ B 3+ O 2 F compositions previously reported that are suitable for rare-earth substitution, including BaScO 2 F, BaFeO 2 F, and BaInO 2 F. Not surprisingly, BaFeO 2 F and BaInO 2 F do not possess a wide bandgap to be a viable phosphor host. , However, beyond a preliminary report, BaScO 2 F has not been widely investigated as a phosphor . This warrants further investigation into the electronic structure of this compound to determine its capability as a potential phosphor host for highly efficient, narrow emission.…”

Section: Introductionmentioning

confidence: 99%

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Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO₂F:Eu²⁺ Perovskite

Hariyani

Brgoch

2020

Chem. Mater.

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Perovskites are a class of materials with applications in photovoltaics, solid-state lighting, and catalysis. Extensive research has gone into modifying the chemical composition of these distortion-prone structures to manipulate and achieve their tremendous physical properties. Here, we report a BaScO2F perovskite that, when doped with Eu2+, produces a highly efficient cyan emission stemming from the structure’s high symmetry and dense connectivity. However, the emission peak is broader than expected and steady-state, temperature-dependent, and time-resolved photoluminescence spectroscopy reveals the presence of two distinct emission peaks despite a single rare-earth substitution site. Ab initio calculations subsequently prove that substituting the smaller Eu2+ induces an unexpected local structure distortion driven by zone-boundary octahedral tilting. This produces two different local coordination environments around Eu2+ that cause the dual emission. This work shows the critical need to analyze local distortions in phosphors upon rare-earth substitution, especially in perovskites on the verge of structural instabilities.

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Section: Resultssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO₂F:Eu²⁺ Perovskite

Hariyani

Brgoch

2020

Chem. Mater.

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“…Besides, due to the similarity of their ionic radii, the replacement of O 2− by F − in flexible structural motifs such as perovskite or rocksalt blocks allows an O 2− /F − random distribution and may accommodate anionic vacancies (v) and subtle metal displacements, as in AM(O,F,v) 3 , BaInO 2 F, or FeO 1−x F x . 7 However, the 1D (chain-based) oxyfluoride topology 8 often induces anionic ordering, especially when surrounded by lone-pair ions with anisotropic electronic density clouds. Such oxyfluoride chains have provided excellent models for low-dimensional magnetism, due to the minimization of electronic delocalization through electronegative F − bridges.…”

Section: ■ Introductionmentioning

confidence: 99%

“…5 Within this frame, the recent discovery of the n=1 Aurivillius oxyfluoride [Bi2O2][CoF4] phase has opened even wider perspectives about novel multiferroics 6 by combining ferroelectric opportunities brought by standard Bi 3+ lone-pair effect, and magnetic ordering brought from the presence of magnetic ions in the [CoF4] perovskite block, mimicking BiFeO3. Besides, due to the similarity on their ionic radii, the replacement of O 2by Fin flexible structural motifs such as perovskite or rocksalt blocks allows the O 2-/Frandom distribution and may accommodate anionic vacancies (v) and subtle metal displacements, as in AM(O,F,v)3, BaInO2F or FeO1-xFx 7 . However, the 1D (chain-based) oxy-fluorides topology 8 often induces anionic ordering, especially when surrounded by lone-pair ions with anisotropic electronic density clouds.…”

mentioning

confidence: 99%

S = 1/2 Chain in BiVO₃F: Spin Dimers versus Photoanodic Properties

et al. 2021

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BiVO3F was prepared, characterized and identified as the unique example of bismuth vanadyl oxyhalide with paramagnetic V 4+ centres. Its crystal structure shows 1D magnetic units with rare alternation of edge sharing O-O and F-F µ2 bridges along the octahedral chains. Structural pairing across the O2 edges induces antiferromagnetic spin dimers(S=0) with J/Kb300K, ⁓15 times greater than the exchange across the F2 bridges, within a non-ordered magnetic ground state. Despite multiple compositional, structural, and electronic analogies with the BiVO4 scheelite compound, one of the most promising photo-anode for solar water splitting, the photo activity of BiVO3F is relatively modest, partially due to this electronic pairing playing for fast electron-hole recombination. Similar to monoclinic-VO2, the V 4+ spin dimerization plays against the singlet → triplet electronic photo-excitation, but brings potential carrier lifetime benefits. The reduction of the bandgap from Eg 2.4 eV to 1.7 eV after incorporation of d 1 cations in BiVO4 makes BiVO3F an inspiring compound for local modifications toward an enhanced photo-active material. The direct d → d transition provides a significant enhancement of the visible light capture section, and opens a prospective route for the chemical design of performant photoanodes with a mixed anionic sublattice.

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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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Synthesis of new perovskite-type oxyfluorides, BaInO2F and comparison of the structure among perovskite-type oxyfluorides

Cited by 12 publications

References 33 publications

Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO₂F:Eu²⁺ Perovskite

Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO₂F:Eu²⁺ Perovskite

S = 1/2 Chain in BiVO₃F: Spin Dimers versus Photoanodic Properties

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

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Synthesis of new perovskite-type oxyfluorides, BaInO2F and comparison of the structure among perovskite-type oxyfluorides

Cited by 12 publications

References 33 publications

Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO2F:Eu2+ Perovskite

Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO2F:Eu2+ Perovskite

S = 1/2 Chain in BiVO3F: Spin Dimers versus Photoanodic Properties

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

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Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO₂F:Eu²⁺ Perovskite

Local Structure Distortion Induced Broad Band Emission in the All-Inorganic BaScO₂F:Eu²⁺ Perovskite

S = 1/2 Chain in BiVO₃F: Spin Dimers versus Photoanodic Properties