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Title: Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites

Abstract

Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. Here, this work shows the important role of light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5];  [5];  [3]; ORCiD logo [3];  [6];  [7];  [3];  [3];  [3];  [3];  [8];  [1];  [8];  [3]; ORCiD logo [5];  [7] more »;  [2]; ORCiD logo [9] « less
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States). Makineni Theoretical Lab., Dept. of Chemistry
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
  5. Columbia Univ., New York, NY (United States). Dept. of Chemistry
  6. Carnegie Inst. for Science, Washington, DC (United States). Extreme Materials Initiative, Geophysical Lab.
  7. Weizmann Inst. of Science, Rehovoth (Israel). Dept. of Materials and Interfaces
  8. Stanford Univ., CA (United States). Dept. of Chemistry
  9. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Austrian Science Fund (FWF)
OSTI Identifier:
1380107
Grant/Contract Number:
AC02-76SF00515; ER46980; N00014-17-1-2574; DGE-114747; ECCS-1542152
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 7; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Wu, Xiaoxi, Tan, Liang Z., Shen, Xiaozhe, Hu, Te, Miyata, Kiyoshi, Trinh, M. Tuan, Li, Renkai, Coffee, Ryan, Liu, Shi, Egger, David A., Makasyuk, Igor, Zheng, Qiang, Fry, Alan, Robinson, Joseph S., Smith, Matthew D., Guzelturk, Burak, Karunadasa, Hemamala I., Wang, Xijie, Zhu, Xiaoyang, Kronik, Leeor, Rappe, Andrew M., and Lindenberg, Aaron M. Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites. United States: N. p., 2017. Web. doi:10.1126/sciadv.1602388.
Wu, Xiaoxi, Tan, Liang Z., Shen, Xiaozhe, Hu, Te, Miyata, Kiyoshi, Trinh, M. Tuan, Li, Renkai, Coffee, Ryan, Liu, Shi, Egger, David A., Makasyuk, Igor, Zheng, Qiang, Fry, Alan, Robinson, Joseph S., Smith, Matthew D., Guzelturk, Burak, Karunadasa, Hemamala I., Wang, Xijie, Zhu, Xiaoyang, Kronik, Leeor, Rappe, Andrew M., & Lindenberg, Aaron M. Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites. United States. doi:10.1126/sciadv.1602388.
Wu, Xiaoxi, Tan, Liang Z., Shen, Xiaozhe, Hu, Te, Miyata, Kiyoshi, Trinh, M. Tuan, Li, Renkai, Coffee, Ryan, Liu, Shi, Egger, David A., Makasyuk, Igor, Zheng, Qiang, Fry, Alan, Robinson, Joseph S., Smith, Matthew D., Guzelturk, Burak, Karunadasa, Hemamala I., Wang, Xijie, Zhu, Xiaoyang, Kronik, Leeor, Rappe, Andrew M., and Lindenberg, Aaron M. Wed . "Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites". United States. doi:10.1126/sciadv.1602388. https://www.osti.gov/servlets/purl/1380107.
@article{osti_1380107,
title = {Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites},
author = {Wu, Xiaoxi and Tan, Liang Z. and Shen, Xiaozhe and Hu, Te and Miyata, Kiyoshi and Trinh, M. Tuan and Li, Renkai and Coffee, Ryan and Liu, Shi and Egger, David A. and Makasyuk, Igor and Zheng, Qiang and Fry, Alan and Robinson, Joseph S. and Smith, Matthew D. and Guzelturk, Burak and Karunadasa, Hemamala I. and Wang, Xijie and Zhu, Xiaoyang and Kronik, Leeor and Rappe, Andrew M. and Lindenberg, Aaron M.},
abstractNote = {Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. Here, this work shows the important role of light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.},
doi = {10.1126/sciadv.1602388},
journal = {Science Advances},
number = 7,
volume = 3,
place = {United States},
year = {Wed Jul 26 00:00:00 EDT 2017},
month = {Wed Jul 26 00:00:00 EDT 2017}
}

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Cited by: 4works
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  • Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. In this paper, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2) 2CsPb-halide (FACsPb-) and CH 3NH 3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials.more » However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Finally, because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.« less
  • No abstract prepared.
  • Mixed halide hybrid perovskites, CH 3NH 3Pb(I 1-xBrx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionallymore » explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.« less