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Title: Determining Atomic-Scale Structure and Composition of Organo-Lead Halide Perovskites by Combining High-Resolution X-ray Absorption Spectroscopy and First-Principles Calculations

Abstract

In this paper, we combine high-energy resolution fluorescence detection (HERFD) X-ray absorption spectroscopy (XAS) measurements with first-principles density functional theory (DFT) calculations to provide a molecular-scale understanding of local structure, and its role in defining optoelectronic properties, in CH3NH3Pb(I1–xBrx)3 perovskites. The spectra probe a ligand field splitting in the unoccupied d states of the material, which lie well above the conduction band minimum and display high sensitivity to halide identity, Pb-halide bond length, and Pb-halide octahedral tilting, especially for apical halide sites. The spectra are also sensitive to the organic cation. We find that the halides in these mixed compositions are randomly distributed, rather than having preferred octahedral sites, and that thermal tilting motions dominate over any preferred structural distortions as a function of halide composition. Finally, these findings demonstrate the utility of the combined HERFD XAS and DFT approach for determining structural details in these materials and connecting them to optoelectronic properties observed by other characterization methods.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [1]; ORCiD logo [1];  [3];  [1];  [1];  [4];  [4];  [5]; ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1379834
Alternate Identifier(s):
OSTI ID: 1368759
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 2; Journal Issue: 5; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Drisdell, Walter S., Leppert, Linn, Sutter-Fella, Carolin M., Liang, Yufeng, Li, Yanbo, Ngo, Quynh P., Wan, Liwen F., Gul, Sheraz, Kroll, Thomas, Sokaras, Dimosthenis, Javey, Ali, Yano, Junko, Neaton, Jeffrey B., Toma, Francesca M., Prendergast, David, and Sharp, Ian D. Determining Atomic-Scale Structure and Composition of Organo-Lead Halide Perovskites by Combining High-Resolution X-ray Absorption Spectroscopy and First-Principles Calculations. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.7b00182.
Drisdell, Walter S., Leppert, Linn, Sutter-Fella, Carolin M., Liang, Yufeng, Li, Yanbo, Ngo, Quynh P., Wan, Liwen F., Gul, Sheraz, Kroll, Thomas, Sokaras, Dimosthenis, Javey, Ali, Yano, Junko, Neaton, Jeffrey B., Toma, Francesca M., Prendergast, David, & Sharp, Ian D. Determining Atomic-Scale Structure and Composition of Organo-Lead Halide Perovskites by Combining High-Resolution X-ray Absorption Spectroscopy and First-Principles Calculations. United States. doi:10.1021/acsenergylett.7b00182.
Drisdell, Walter S., Leppert, Linn, Sutter-Fella, Carolin M., Liang, Yufeng, Li, Yanbo, Ngo, Quynh P., Wan, Liwen F., Gul, Sheraz, Kroll, Thomas, Sokaras, Dimosthenis, Javey, Ali, Yano, Junko, Neaton, Jeffrey B., Toma, Francesca M., Prendergast, David, and Sharp, Ian D. Thu . "Determining Atomic-Scale Structure and Composition of Organo-Lead Halide Perovskites by Combining High-Resolution X-ray Absorption Spectroscopy and First-Principles Calculations". United States. doi:10.1021/acsenergylett.7b00182. https://www.osti.gov/servlets/purl/1379834.
@article{osti_1379834,
title = {Determining Atomic-Scale Structure and Composition of Organo-Lead Halide Perovskites by Combining High-Resolution X-ray Absorption Spectroscopy and First-Principles Calculations},
author = {Drisdell, Walter S. and Leppert, Linn and Sutter-Fella, Carolin M. and Liang, Yufeng and Li, Yanbo and Ngo, Quynh P. and Wan, Liwen F. and Gul, Sheraz and Kroll, Thomas and Sokaras, Dimosthenis and Javey, Ali and Yano, Junko and Neaton, Jeffrey B. and Toma, Francesca M. and Prendergast, David and Sharp, Ian D.},
abstractNote = {In this paper, we combine high-energy resolution fluorescence detection (HERFD) X-ray absorption spectroscopy (XAS) measurements with first-principles density functional theory (DFT) calculations to provide a molecular-scale understanding of local structure, and its role in defining optoelectronic properties, in CH3NH3Pb(I1–xBrx)3 perovskites. The spectra probe a ligand field splitting in the unoccupied d states of the material, which lie well above the conduction band minimum and display high sensitivity to halide identity, Pb-halide bond length, and Pb-halide octahedral tilting, especially for apical halide sites. The spectra are also sensitive to the organic cation. We find that the halides in these mixed compositions are randomly distributed, rather than having preferred octahedral sites, and that thermal tilting motions dominate over any preferred structural distortions as a function of halide composition. Finally, these findings demonstrate the utility of the combined HERFD XAS and DFT approach for determining structural details in these materials and connecting them to optoelectronic properties observed by other characterization methods.},
doi = {10.1021/acsenergylett.7b00182},
journal = {ACS Energy Letters},
number = 5,
volume = 2,
place = {United States},
year = {2017},
month = {4}
}

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Works referencing / citing this record:

Heteroleptic samarium( iii ) halide complexes probed by fluorescence-detected L 3 -edge X-ray absorption spectroscopy
journal, January 2018

  • Goodwin, Conrad A. P.; Réant, Benjamin L. L.; Kragskow, Jon G. C.
  • Dalton Transactions, Vol. 47, Issue 31
  • DOI: 10.1039/c8dt01452c

Heteroleptic samarium( iii ) halide complexes probed by fluorescence-detected L 3 -edge X-ray absorption spectroscopy
journal, January 2018

  • Goodwin, Conrad A. P.; Réant, Benjamin L. L.; Kragskow, Jon G. C.
  • Dalton Transactions, Vol. 47, Issue 31
  • DOI: 10.1039/c8dt01452c