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Title: Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites

Abstract

In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L3 and the Pb M5 edges of the methylammonium lead iodide (MAPbI3) hybrid inorganic-organic perovskite and its binary phase PbI2. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI3 are essentially given by its inorganic component, with negligible influence from the organic groups. Furthermore, the theoretical analysis complementing experimental observations provides the conceptual insights required for a full characterization of this complex material.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3]; ORCiD logo [4];  [2];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Humboldt-Univ. zu Berlin, Berlin (Germany)
  2. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  3. Univ. of Oxford, Oxford (United Kingdom)
  4. Univ. of Oxford, Oxford (United Kingdom); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1432605
Report Number(s):
NREL/JA-5900-71280
Journal ID: ISSN 1948-7185; TRN: US1802527
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 8; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; x-ray absorption; inorganic-organic perovskites

Citation Formats

Vorwerk, Christian, Hartmann, Claudia, Cocchi, Caterina, Sadoughi, Golnaz, Habisreutinger, Severin N., Felix, Roberto, Wilks, Regan G., Snaith, Henry J., Bar, Marcus, and Draxl, Claudia. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b00378.
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Vorwerk, Christian, Hartmann, Claudia, Cocchi, Caterina, Sadoughi, Golnaz, Habisreutinger, Severin N., Felix, Roberto, Wilks, Regan G., Snaith, Henry J., Bar, Marcus, & Draxl, Claudia. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites. United States. https://doi.org/10.1021/acs.jpclett.8b00378
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Vorwerk, Christian, Hartmann, Claudia, Cocchi, Caterina, Sadoughi, Golnaz, Habisreutinger, Severin N., Felix, Roberto, Wilks, Regan G., Snaith, Henry J., Bar, Marcus, and Draxl, Claudia. Fri . "Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites". United States. https://doi.org/10.1021/acs.jpclett.8b00378. https://www.osti.gov/servlets/purl/1432605.
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@article{osti_1432605,
title = {Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites},
author = {Vorwerk, Christian and Hartmann, Claudia and Cocchi, Caterina and Sadoughi, Golnaz and Habisreutinger, Severin N. and Felix, Roberto and Wilks, Regan G. and Snaith, Henry J. and Bar, Marcus and Draxl, Claudia},
abstractNote = {In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L3 and the Pb M5 edges of the methylammonium lead iodide (MAPbI3) hybrid inorganic-organic perovskite and its binary phase PbI2. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI3 are essentially given by its inorganic component, with negligible influence from the organic groups. Furthermore, the theoretical analysis complementing experimental observations provides the conceptual insights required for a full characterization of this complex material.},
doi = {10.1021/acs.jpclett.8b00378},
journal = {Journal of Physical Chemistry Letters},
number = 8,
volume = 9,
place = {United States},
year = {Fri Mar 23 00:00:00 EDT 2018},
month = {Fri Mar 23 00:00:00 EDT 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.8b00378
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Cited by: 16 works
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Figures / Tables:

Figure 1 Figure 1: (a) Calculated X-ray absorption near-edge spectra of the I L3 edge of MAPbI3 (red) and PbI2 (black). A Lorentzian broadening of 0.5 eV is used in the calculations. (b) Experimental XANES from the L3 egde. For a direct comparison, calculated spectra with an increased broadening of 1.5 eVmore » are included. The spectra of MAPbI3 are offset by 0.5 for better readability. In both panels, the difference between the spectra of PbI2 and MAPbI3 is shown in purple. The normalization of the calculated and experimental spectra is described in the Supporting Information.« less
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    Works referencing / citing this record:

    Deprotonation and vacancies at the CH 3 NH 3 PbI 3 /ZnO and CH 3 NH 3 PbI 3 /GaN interfaces, detected in their theoretical XANES
    journal, January 2019

    • Wierzbowska, Małgorzata
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    Bethe–Salpeter equation for absorption and scattering spectroscopy: implementation in the exciting code
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    • Cocchi, Caterina; Mistry, Sonal; Schmeißer, Martin
    • Humboldt-Universität zu Berlin
    • DOI: 10.18452/24111
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