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

Sharma, Manila; Yangui, Aymen; Lusson, Alain; Boukheddaden, Kamel; Ding, Xiaxin; Du, Mao-Hua; Gofryk, Krzysztof; Saparov, Bayrammurad

doi:10.1039/c9qi01574d

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

Journal Article · Wed Jan 01 00:00:00 EST 2020 · Inorganic Chemistry Frontiers (Online)

DOI:https://doi.org/10.1039/c9qi01574d· OSTI ID:1631242

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^[1]; Lusson, Alain ^[2]; Boukheddaden, Kamel ^[3]; Ding, Xiaxin ^[4];

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Univ. of Oklahoma, Norman, OK (United States)
Univ. Paris-Saclay, Gif-sur-Yvette (France); National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France); Univ. of Versailles Saint-Quentin-en-Yvelines (France)
National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France); Univ. of Versailles Saint-Quentin-en-Yvelines (France); Univ. Paris-Saclay, Gif-sur-Yvette (France)
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division

Hybrid organic-inorganic halides containing Bi and Sb generally exhibit higher stability and lower toxicity compared to Pb analogues. 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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; 19P43-013FP

OSTI ID:: 1631242

Alternate ID(s):: OSTI ID: 1602328

Journal Information:: Inorganic Chemistry Frontiers (Online), Vol. 7, Issue 7; ISSN 2052-1553

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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