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Electronic Structure and Chemical Bonding in Methylammonium Lead Triiodide and Its Precursor Methylammonium Iodide
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0001-9518-9405
Stockholm University, Faculty of Science, Department of Physics. Raja Ramanna Centre for Advanced Technology, India; Homi Bhabha National Institute, India.ORCID iD: 0000-0002-4546-8219
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Number of Authors: 102022 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 126, no 47, p. 20143-20154Article in journal (Refereed) Published
Abstract [en]

A detailed examination of the electronic structures of methylammonium lead triiodide (MAPI) and methylammonium iodide (MAI) is performed with ab initio molecular dynamics (AIMD) simulations based on density functional theory, and the theoretical results are compared to experimental probes. The occupied valence bands of a MAPI single crystal and MAI powder are probed with X-ray photoelectron spectroscopy, and the conduction bands are probed from the perspective of nitrogen K-edge X-ray absorption spectroscopy. Combined, the theoretical simulations and the two experimental techniques allow for a dissection of the electronic structure unveiling the nature of chemical bonding in MAPI and MAI. Here, we show that the difference in band gap between MAPI and MAI is caused chiefly by interactions between iodine and lead but also weaker interactions with the MA+ counterions. Spatial decomposition of the iodine p levels allows for analysis of Pb–I σ bonds and π interactions, which contribute to this effect with the involvement of the Pb 6p levels. Differences in hydrogen bonding between the two materials, seen in the AIMD simulations, are reflected in nitrogen valence orbital composition and in nitrogen K-edge X-ray absorption spectra.

Place, publisher, year, edition, pages
2022. Vol. 126, no 47, p. 20143-20154
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:su:diva-211925DOI: 10.1021/acs.jpcc.2c06782ISI: 000888147500001Scopus ID: 2-s2.0-85142648869OAI: oai:DiVA.org:su-211925DiVA, id: diva2:1714331
Funder
Swedish Research Council Formas, 2019-02496Swedish Research Council, 2018- 05973Swedish Research Council, 2018-04125Swedish Research Council, 2018-04330Swedish Research Council, 2018-05525Swedish Research Council, 2018-06465Swedish Research Council, 2018-07152Swedish Energy Agency, 2017-006797Swedish Energy Agency, STEM P50626-1Göran Gustafsson Foundation for Research in Natural Sciences and MedicineVinnova, 2018-04969Available from: 2022-11-29 Created: 2022-11-29 Last updated: 2023-01-10Bibliographically approved
In thesis
1. Modeling hybrid halide perovskites for solar cell applications: Simulations of electronic structure and X-ray spectroscopy
Open this publication in new window or tab >>Modeling hybrid halide perovskites for solar cell applications: Simulations of electronic structure and X-ray spectroscopy
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Over the past 13 years, perovskites have become a very promising candidate in the search for cheap and effective photovoltaic materials for solar cells.  Perovskite solar cell power conversion efficiency has increased from 3.8% in 2009 to over 25% by late 2022, rivaling that of crystalline silicon cells, and there are a variety of potential chemical compositions that provide a range of materials to investigate.  However, there are still questions about the specific role of all the different chemical components in the material and how they influence its efficiency.  This thesis aims to investigate the effect of material composition and structure through electronic structure calculations and theoretical X-ray absorption and X-ray photoelectron spectroscopy, with comparison to experimental spectra.  Herein, studies on the prototypical hybrid halide perovskite methylammonium lead triiodide (CH3NH3PbI3) are presented and compared among materials with various differences: structural/elemental changes in the case of its precursor methylammonium iodide (CH3NH3I), halide substitution in the case of methylammonium lead tribromide (CH3NH3PbBr3), or organic cation substitution in the case of formamidinium lead triiodide (CH(NH2)2PbI3).

Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm University, 2022. p. 54
Keywords
Solar cells, perovskites, computational chemistry, simulations, electronic structure, density functional theory, X-ray spectroscopy
National Category
Atom and Molecular Physics and Optics
Research subject
Chemical Physics
Identifiers
urn:nbn:se:su:diva-211949 (URN)978-91-8014-114-7 (ISBN)978-91-8014-115-4 (ISBN)
Public defence
2023-01-13, Lärosal 14, Albano Hus 2, Albanovägen 18, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Energy Agency, 2017-006797
Available from: 2022-12-20 Created: 2022-11-29 Last updated: 2022-12-12Bibliographically approved

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