skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Two new multinary chalcogenides with (Se2)2− dimers: Ba8Hf2Se11(Se2) and Ba9Hf3Se14(Se2)
Two multinary selenides, Ba8Hf2Se11(Se2) and Ba9Hf3Se14(Se2), with unprecedented structure types have been prepared using high-temperature synthesis techniques and represent the first known compounds in the Ba-Hf-Se system. Their structures were determined from single crystal X-ray diffraction (XRD) data. The Ba8Hf2Se11(Se2) compound crystallizes in the monoclinic C2/c space group with a = 12.3962(15) Å, b = 12.8928(15) Å, c = 18.1768(17) Å, and β = 90.685(4)°, while Ba9Hf3Se14(Se2) forms in the rhombohedral R space group with a = b = 19.4907(6) Å and c = 23.6407(11) Å. Both have pseudo-zero-dimensional structures with homoatomic Se–Se bonding in the form of (Se2)2− at distances of 2.400–2.402 Å. The structure of Ba8Hf2Se11(Se2) is comprised of [Hf2Se11]14−, Ba2+, and (Se2)2− dimers. Conversely, the Ba9Hf3Se14(Se2) structure contains a novel perovskite-type cluster constructed from eight octahedrally-coordinated Hf cations, i.e., [Hf8Se36]40−, and isolated [HfSe6]8− units which are separated by (Se2)2− dimers and Ba2+ cations. Polycrystalline Ba8Hf2Se11(Se2) is synthesized at 1073 K using a two-step solid-state synthesis method, with the co-formation of a small amount of a BaSe secondary phase. A direct bandgap of 2.2(2) eV is obtained for the polycrystalline sample of Ba8Hf2Se11(Se2), which is consistent with its yellow color. Density functional theory calculations reveal their bandgap transitions stem from predominantly filled Se-4p to empty Hf-5d at the edges of the valence bands (VB) and conduction bands (CB), respectively. The optical absorption coefficients are calculated to be relatively large, exceeding ∼105 cm−1 at about >2.0 eV with effective masses in the CB varying from ∼0.5 me (Γ → A) in Ba8Hf2Se11(Se2) to ∼1.0 me (Γ → L) in Ba9Hf3Se14(Se2). Thus, their optoelectronic properties are shown to be competitive with existing perovskite-type chalcogenides that have been a focus of recent research efforts.  more » « less
Award ID(s):
2317605
PAR ID:
10469614
Author(s) / Creator(s):
; ;
Publisher / Repository:
ScienceDirect
Date Published:
Journal Name:
Journal of Solid State Chemistry
Volume:
329
Issue:
C
ISSN:
0022-4596
Page Range / eLocation ID:
124376
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Inorganic chemistry)
    Three new NaBa2M3Q3(Q2) (M = Ag, Cu; Q = S, Se) chalcogenides were prepared using solid-state methods and structurally characterized using single-crystal X-ray diffraction. NaBa2Ag3Se3(Se2) and NaBa2Cu3Se3(Se2) crystallize in the monoclinic C2/m space group 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 the C2/m space group 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 eV and 1.9 eV, respectively, which is supported by band structures calculated using density functional theory. Mixed- anion NaBa2Cu3Se5-xSx compositions were prepared to probe for the presence of anion ordering and heteronuclear (S-Se)2- dimers. Structural analyses of the sulfoselenides indicate 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. 
    more » « less
  2. ; ; (, Zeitschrift für Kristallographie - New Crystal Structures)
    null (Ed.)
    Abstract C 42 H 68 Cl 4 Mo 6 N 6 S 12 Se 15 , triclinic, P 1̄ (no. 2), a = 13.0196(19) Å, b = 18.813(3) Å, c = 19.745(3) Å, α = 117.446(2)°, β = 99.775(2)°, γ = 98.233(2)°, V = 4091.7(10) Å 3 , Z = 2, R gt ( F ) = 0.0557, wR ref ( F 2 ) = 0.1618, T = 150 K. 
    more » « less
  3. ; ; ; ; ; ; ; ; (, Journal of Solid State Chemistry)
    Traditional synthetic efforts to prepare Eu(II)-containing oxides have principally involved the use of high temperature reactions starting from EuO or a controlled, highly-reducing, atmosphere. Conversely, chimie douce approaches that are more amenable to the targeted syntheses of new, and potentially metastable, Eu(II)-oxides have yet to be explored. Herein, a cation-exchange route to new Eu(II)-containing oxides, e.g., EuTa4-xO11 (x = 0.04), has been discovered and its structure determined by powder X-ray diffraction (Space group P6322 (#182), a = 6.2539(2) Å; c = 12.3417(2) Å). The compound derives from the cation exchange of Na2Ta4O11, via a reaction with EuBr2 at 1173 K, and replacement by half the number of divalent Eu cations. Rietveld refinements show preferential ordering of the Eu cations over one of the two possible cation sites, i.e., Wyckoff site 2d (~94%; Eu1) versus 2b (~6%; Eu2). Total energy calculations confirm an energetic preference of the Eu cation in the 2d site. Tantalum vacancies of ~1% occur within the layer of Eu cations and TaO6 octahedra, and ~20% partial oxidation of Eu(II) to Eu(III) cations from charge balance considerations. 151Eu M¨ossbauer spectroscopy measured at 78 K found a Eu(II):Eu(III) ratio of 69:31, with a relatively broad line width of the former signal of Γ = 7.6(2) mm s–1. Also, the temperature-dependent magnetic susceptibility could be fitted to a Curie Weiss expression, giving a μeff = 6.2 μB and θCW = 10 K and confirming a mixture of Eu(II)/Eu(III) cations. The optical bandgap of EuTa4-xO11 was found to be ~1.5 eV (indirect), significantly redshifted as compared to ~4.1 eV for Na2Ta4O11. Spin-polarized electronic structure calculations show that this redshift stems from the addition of Eu 4f7 states as a higher-energy valence band. Thus, these results demonstrate a new cation-exchange approach that represents a useful synthetic pathway to new Eu(II)-containing ox- ides for tunable magnetic and optical properties. 
    more » « less
  4. ; (, Materials)
    Halide perovskite solar cells (HPSCs) are promising photovoltaic materials due to their excellent optoelectronic properties, low cost, and high efficiency. Here, we demonstrate atmospheric solution processing and stability of cesium tin-lead triiodide (CsSnPbI3) thin films for solar cell applications. The effect of additives, such as pyrazine and guanidinium thiocyanate (GuaSCN), on bandgap, film morphology, structure, and stability is investigated. Our results indicate the formation of a wide bandgap (>2 eV) structure with a mixed phase of tin oxide (SnO2) and Cs(Sn, Pb)I3. The addition of pyrazine decreases the intensity of SnO2 peaks, but the bandgap does not change much. With the addition of GuaSCN, the bandgap of the films reduces to 1.5 eV, and a dendritic structure of Cs(Sn, Pb)I3 is observed. GuaSCN addition also reduces the oxygen content in the films. To enable uniform film crystallization, cesium chloride (CsCl) and dimethyl sulfoxide (DMSO) additives are used in the precursor. Both CsCl and DMSO suppress dendrite formation with the latter resulting in uniform polycrystalline films with a bandgap of 1.5 eV. Heat and light soaking (HLS) stability tests at 65 °C and 1 sun for 100 h show all film types are stable with temperature but result in phase segregation with light exposure. 
    more » « less
  5. ; ; ; ; ; ; (, Advanced Functional Materials)
    Abstract The dearth of suitable materials significantly restricts the practical development of infrared (IR) laser systems with highly efficient and broadband tuning. Recently, γ‐NaAsSe2is reported, and it exhibits a large nonlinear second‐harmonic generation (SHG) coefficient of 590 pm V−1at 2 µm. However, the crystal growth of γ‐NaAsSe2is challenging because it undergoes a phase transition to centrosymmetric δ‐NaAsSe2. Herein, the stabilization of non‐centrosymmetric γ‐NaAsSe2by doping the As site with Sb, which results in γ‐NaAs0.95Sb0.05Se2is reported. The congruent melting behavior is confirmed by differential thermal analysis with a melting temperature of 450 °C and crystallization temperature of 415 °C. Single crystals with dimensions of 3 mm × 2 mm are successfully obtained via zone refining and the Bridgman method. The purification of the material plays a significant role in crystal growth and results in a bandgap of 1.78 eV and thermal conductivity of 0.79 Wm−1K−1. The single‐crystal SHG coefficient of γ‐NaAs0.95Sb0.05Se2exhibits an enormous value of |d11| = 648 ± 74 pm V−1, which is comparable to that of γ‐NaAsSe2and ≈20× larger than that of AgGaSe2. The bandgap of γ‐NaAs0.95Sb0.05Se2(1.78 eV) is similar to that of AgGaSe2, thus rendering it highly attractive as a high‐performing nonlinear optical material. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email