Additive-assisted synthesis and optoelectronic properties of (CH3NH3)4Bi6I22
Abstract
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.
- Authors:
-
[1];
[1];
[5];
[4];
[1]
- 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
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1631242
- Alternate Identifier(s):
- OSTI ID: 1602328
- Grant/Contract Number:
- AC05-00OR22725; 19P43-013FP
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry Frontiers (Online)
- Additional Journal Information:
- Journal Name: Inorganic Chemistry Frontiers (Online); Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2052-1553
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sharma, Manila, Yangui, Aymen, Lusson, Alain, Boukheddaden, Kamel, Ding, Xiaxin, Du, Mao-Hua, Gofryk, Krzysztof, and Saparov, Bayrammurad. Additive-assisted synthesis and optoelectronic properties of (CH3NH3)4Bi6I22. United States: N. p., 2020.
Web. doi:10.1039/c9qi01574d.
Sharma, Manila, Yangui, Aymen, Lusson, Alain, Boukheddaden, Kamel, Ding, Xiaxin, Du, Mao-Hua, Gofryk, Krzysztof, & Saparov, Bayrammurad. Additive-assisted synthesis and optoelectronic properties of (CH3NH3)4Bi6I22. United States. https://doi.org/10.1039/c9qi01574d
Sharma, Manila, Yangui, Aymen, Lusson, Alain, Boukheddaden, Kamel, Ding, Xiaxin, Du, Mao-Hua, Gofryk, Krzysztof, and Saparov, Bayrammurad. Wed .
"Additive-assisted synthesis and optoelectronic properties of (CH3NH3)4Bi6I22". United States. https://doi.org/10.1039/c9qi01574d. https://www.osti.gov/servlets/purl/1631242.
@article{osti_1631242,
title = {Additive-assisted synthesis and optoelectronic properties of (CH3NH3)4Bi6I22},
author = {Sharma, Manila and Yangui, Aymen and Lusson, Alain and Boukheddaden, Kamel and Ding, Xiaxin and Du, Mao-Hua and Gofryk, Krzysztof and Saparov, Bayrammurad},
abstractNote = {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.},
doi = {10.1039/c9qi01574d},
journal = {Inorganic Chemistry Frontiers (Online)},
number = 7,
volume = 7,
place = {United States},
year = {Wed Jan 01 00:00:00 EST 2020},
month = {Wed Jan 01 00:00:00 EST 2020}
}
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