Ba8Zr2Se11(Se2): The first polychalcogenide of the ternary Ba–Zr–Q (Q = S/Se/Te) system

Srivastava, Komal; Shahid, Omair; Ray, Akshay K.; Deepa, Melepurath; Niranjan, Manish K.; Prakash, Jai

doi:10.1016/j.jssc.2023.124344

Cited by 5 publications

(2 citation statements)

References 59 publications

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“…As a result, a relatively short Zr···Zr distance occurs across the shared octahedral face at 3.488(1)Å, as found similarly for the Hf···Hf distance in the structure of 1 . In the structure of 2 , the Zr–Se distances of Zr(1)Se 6 octahedra range from 2.621(1) to 2.758(1) Å, consistent with previously reported distances in the structures of Ba 8 Zr 2 Se 11 (Se 2 ) (2.6337(7)–2.7940(7) Å) and Ba 15 Zr 14 Se 42 (2.612(4)–2.769(4) Å) …”

Section: Resultssupporting

confidence: 89%

“…Beyond the perovskite-type chalcogenides, recent investigations have shown that group-IV chalcogenides forming in alternative structures can possess similar favorable optoelectronic properties. In metal selenides where the perovskite-type structure has yet to be obtained, synthetic attempts have instead yielded the Ba 8 M 2 Se 11 (Se 2 ) (M = Zr, Hf) and Ba 9 Hf 3 Se 14 (Se 2 ) structures. , These have also shown promising properties for solar energy applications, including optical band gaps of less than ∼2.2 eV, strong optical absorption coefficients, and small carrier effective masses. Motivated initially by subsequent synthetic attempts to prepare a mixed B-site solid-solution “Ba(M 0.5 Sn 0.5 )Se 3 ” analogue, reactions instead resulted in the discovery of two new quaternary metal chalcogenides that have been characterized by single-crystal X-ray diffraction.…”

Section: Introductionmentioning

confidence: 99%

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Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors

Jana,

Gabilondo,

McGuigan

et al. 2024

Inorg. Chem.

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Early transition-metal chalcogenides have garnered recent attention for their optoelectronic properties for solar energy conversion. Herein, the first Zr-/Hf-chalcogenides with a main group cation, Ba9Hf3Sn2Se19 (1) and Ba8Zr2SnSe13(Se2) (2), have been synthesized. The structure of 1 is formed from isolated SnSe4 4– tetrahedra and distorted HfSe6 octahedra. The latter condense via face-sharing trimeric motifs that are further vertex-bridged into chains of 1 ∞[Hf(1)2Hf(2)Se11]10–. The structure of 2 is comprised of SnSe4 4– tetrahedra, Se2 2– dimers, and face-sharing dimers of distorted ZrSe6 octahedra. These represent the first reported examples of Hf-/Zr-chalcogenides exhibiting face-sharing octahedra with relatively short Hf–Hf and Zr–Zr distances. Their preparation in high purity is inhibited by their low thermodynamic stability, with calculations showing small calculated ΔU dec values of +7 and +9 meV atom–1 for 1 and 2, respectively. Diffuse reflectance measurements confirm the semiconducting nature of 1 with an indirect band gap of ∼1.4(1) eV. Electronic structure calculations show that the band gap absorptions arise from transitions between predominantly Se-4p valence bands and mixed Hf-5d/Sn-5p or Zr-4d/Sn-5p conduction bands. Optical absorption coefficients were calculated to be more than ∼105 cm–1 at greater than 1.8 eV. Thus, promising optical properties are demonstrated for solar energy conversion within these synthetically challenging chemical systems.

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Section: Resultssupporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors

Jana,

Gabilondo,

McGuigan

et al. 2024

Inorg. Chem.

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Thermoelectric and photovoltaic properties of 12-BaBi2S4

Srivastava,

Shahid,

Ray

et al. 2024

Journal of Physics and Chemistry of Solids

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Layered NaBa₂M₃Q₃(Q₂) (M = Cu or Ag; Q = S or Se) Chalcogenides and Local Ordering in Their Mixed-Anion Compositions

Tassanov,

Lee,

Xia

et al. 2024

Inorg. Chem.

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Three new NaBa2M3Q3(Q2) (M = Ag or Cu; Q = S or Se) chalcogenides were prepared by using solid-state methods and structurally characterized by using single-crystal X-ray diffraction. NaBa2Ag3Se3(Se2) and NaBa2Cu3Se3(Se2) crystallize in monoclinic space group C2/m and have a two-dimensional structure composed of edge-sharing MSe4/4 tetrahedra separated by Na+ and Ba2+ cations, along with (Se2)2– dimers at the center of the spacings between [M3Se3]3– slabs. NaBa2Ag3S3(S2) adopts a related structure with space group C2/m but has additional, crystallographically distinct Ag atoms in the [Ag3S3]3– layer that are linearly coordinated. NaBa2Ag3Se3(Se2) and NaBa2Ag3S3(S2) have indirect band gaps measured to be 1.2 and 1.9 eV, respectively, which is supported by band structures calculated using density functional theory. Mixed-anion NaBa2Cu3Se5–x S x compositions were prepared to probe the presence of anion ordering and heteronuclear (S–Se)2– dimers. Structural analyses of the sulfoselenides indicate that selenium preferentially occupies the Q–Q dimer sites, while Raman spectroscopy reveals a mixture of (S2), (Se2), and heteronuclear (S–Se) units in the sulfur-rich products. The local ordering of the chalcogens is rationalized using simple bonding concepts and adds to a growing framework for understanding ordering phenomena in mixed-anion systems.

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Ba8Zr2Se11(Se2): The first polychalcogenide of the ternary Ba–Zr–Q (Q = S/Se/Te) system

Cited by 5 publications

References 59 publications

Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors

Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors

Thermoelectric and photovoltaic properties of 12-BaBi2S4

Layered NaBa₂M₃Q₃(Q₂) (M = Cu or Ag; Q = S or Se) Chalcogenides and Local Ordering in Their Mixed-Anion Compositions

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Ba8Zr2Se11(Se2): The first polychalcogenide of the ternary Ba–Zr–Q (Q = S/Se/Te) system

Cited by 5 publications

References 59 publications

Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors

Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors

Thermoelectric and photovoltaic properties of 12-BaBi2S4

Layered NaBa2M3Q3(Q2) (M = Cu or Ag; Q = S or Se) Chalcogenides and Local Ordering in Their Mixed-Anion Compositions

Contact Info

Product

Resources

About

Layered NaBa₂M₃Q₃(Q₂) (M = Cu or Ag; Q = S or Se) Chalcogenides and Local Ordering in Their Mixed-Anion Compositions