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Additive-assisted synthesis and optoelectronic properties of (CH3NH3)4Bi6I22

Journal Article · · Inorganic Chemistry Frontiers (Online)
DOI:https://doi.org/10.1039/C9QI01574D· OSTI ID:2570511
 [1];  [1];  [2];  [2];  [3];  [4];  [3];  [1]
  1. Univ. of Oklahoma, Norman, OK (United States)
  2. Univ. Paris-Saclay, Versailles (France); Centre National de la Recherche Scientifique (CNRS), Versailles (France). Groupe d’Étude de la Matière Condensée (GEMaC); Univ. of Versailles Saint-Quentin-en-Yvelines (France)
  3. Idaho National Laboratory (INL), Idaho Falls, ID (United States)
  4. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
Hybrid organic-inorganic halides containing Bi and Sb generally exhibit higher stability and lower toxicity compared to Pb analogues. Here, in this work, synthesis, crystal and electronic structures and optical properties of a brand-new methylammonium bismuth iodide, (MA)4Bi6I22 (MA+ = CH3NH3+), are reported. Interestingly, we find that the presence of the HgI2 is necessary for the targeted preparation of (MA)4Bi6I22. (MA)4Bi6I22 contains isolated [Bi6I22]4- clusters made of six edge-sharing octahedral BiI6 units, which are separated by MA+ cations in its 0D crystal structure. A relatively low optical band gap of 1.9 eV was estimated for (MA)4Bi6I22 based on diffuse reflectance measurements. An intense photoluminescence peak emerges at 636 nm at low temperatures that supports the assigned band gap value. Electronic structure calculations show the presence of flat bands in the valence and conduction bands, consistent with the low-dimensional structure of (MA)4Bi6I22, and slightly indirect nature of the bandgap. Our findings suggest that the use of facilitator moieties such as HgI2 may provide a pathway to obtaining alternative methylammonium bismuth iodides to (MA)3Bi2I9.
Research Organization:
Idaho National Laboratory (INL), Idaho Falls, ID (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
National Science Foundation (NSF); Oklahoma Center for the Advancement of Science and Technology (OCAST); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)
Grant/Contract Number:
AC05-00OR22725; AC07-05ID14517
OSTI ID:
2570511
Alternate ID(s):
OSTI ID: 1602328
OSTI ID: 1631242
Report Number(s):
INL/JOU--19-56801-Rev000
Journal Information:
Inorganic Chemistry Frontiers (Online), Journal Name: Inorganic Chemistry Frontiers (Online) Journal Issue: 7 Vol. 7; ISSN 2052-1553
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hybrid organic-inorganic halides