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Title: Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals

Abstract

Significant interest exists in lead trihalides that present the perovskite structure owing to their demonstrated potential in photovoltaic, lasing, and display applications. These materials are also notable for their unusual phase behavior often displaying easily accessible phase transitions. In this work, time-resolved X-ray diffraction, performed on perovskite cesium lead bromide nanocrystals, maps the lattice response to controlled excitation fluence. These nanocrystals undergo a reversible, photoinduced orthorhombic-to-cubic phase transition which is discernible at fluences greater than 0.34 mJ cm-2 through the loss of orthorhombic features and shifting of high-symmetry peaks. This transition recovers on the timescale of 510 ± 100 ps. A reversible crystalline-to-amorphous transition, observable through loss of Bragg diffraction intensity, occurs at higher fluences (greater than 2.5 mJ cm-2). These results demonstrate that light-driven phase transitions occur in perovskite materials, which will impact optoelectronic applications and enable the manipulation of non-equilibrium phase characteristics of the broad perovskite material class.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [3];  [1];  [1]; ORCiD logo [1];  [4];  [3]; ORCiD logo [5]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Science and Engineering
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  5. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1494798
Grant/Contract Number:  
AC02-06CH11357; FG02-99ER14999; DGE-1324585; DMR-1720139; ECCS-1542205; 0960140
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nanoparticles; semiconductors

Citation Formats

Kirschner, Matthew S., Diroll, Benjamin T., Guo, Peijun, Harvey, Samantha M., Helweh, Waleed, Flanders, Nathan C., Brumberg, Alexandra, Watkins, Nicolas E., Leonard, Ariel A., Evans, Austin M., Wasielewski, Michael R., Dichtel, William R., Zhang, Xiaoyi, Chen, Lin X., and Schaller, Richard D. Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals. United States: N. p., 2019. Web. doi:10.1038/s41467-019-08362-3.
Kirschner, Matthew S., Diroll, Benjamin T., Guo, Peijun, Harvey, Samantha M., Helweh, Waleed, Flanders, Nathan C., Brumberg, Alexandra, Watkins, Nicolas E., Leonard, Ariel A., Evans, Austin M., Wasielewski, Michael R., Dichtel, William R., Zhang, Xiaoyi, Chen, Lin X., & Schaller, Richard D. Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals. United States. doi:10.1038/s41467-019-08362-3.
Kirschner, Matthew S., Diroll, Benjamin T., Guo, Peijun, Harvey, Samantha M., Helweh, Waleed, Flanders, Nathan C., Brumberg, Alexandra, Watkins, Nicolas E., Leonard, Ariel A., Evans, Austin M., Wasielewski, Michael R., Dichtel, William R., Zhang, Xiaoyi, Chen, Lin X., and Schaller, Richard D. Wed . "Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals". United States. doi:10.1038/s41467-019-08362-3. https://www.osti.gov/servlets/purl/1494798.
@article{osti_1494798,
title = {Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals},
author = {Kirschner, Matthew S. and Diroll, Benjamin T. and Guo, Peijun and Harvey, Samantha M. and Helweh, Waleed and Flanders, Nathan C. and Brumberg, Alexandra and Watkins, Nicolas E. and Leonard, Ariel A. and Evans, Austin M. and Wasielewski, Michael R. and Dichtel, William R. and Zhang, Xiaoyi and Chen, Lin X. and Schaller, Richard D.},
abstractNote = {Significant interest exists in lead trihalides that present the perovskite structure owing to their demonstrated potential in photovoltaic, lasing, and display applications. These materials are also notable for their unusual phase behavior often displaying easily accessible phase transitions. In this work, time-resolved X-ray diffraction, performed on perovskite cesium lead bromide nanocrystals, maps the lattice response to controlled excitation fluence. These nanocrystals undergo a reversible, photoinduced orthorhombic-to-cubic phase transition which is discernible at fluences greater than 0.34 mJ cm-2 through the loss of orthorhombic features and shifting of high-symmetry peaks. This transition recovers on the timescale of 510 ± 100 ps. A reversible crystalline-to-amorphous transition, observable through loss of Bragg diffraction intensity, occurs at higher fluences (greater than 2.5 mJ cm-2). These results demonstrate that light-driven phase transitions occur in perovskite materials, which will impact optoelectronic applications and enable the manipulation of non-equilibrium phase characteristics of the broad perovskite material class.},
doi = {10.1038/s41467-019-08362-3},
journal = {Nature Communications},
number = ,
volume = 10,
place = {United States},
year = {2019},
month = {1}
}

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Figures / Tables:

Figure 1 Figure 1: Comparison of orthorhombic and cubic phases. a Schematic of CsPbBr3 in the orthorhombic (top) and cubic phases (bottom). b XRD patterns for the orthorhombic (blue) and cubic phases (red) as generated with VESTA along with the experimental NC XRD pattern (black). The bulk crystal structures are based onmore » a CIF data from Stoumpos et al.22 which were adapted with permission. Copyright 2013 American Chemical Society« less

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.