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Title: Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites

Abstract

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(NH2)2CsPb-halide (FACsPb-) and CH3NH3Pb-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. 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 aremore » 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

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5]; ORCiD logo [5]; ORCiD logo [6];  [2];  [7]; ORCiD logo [8]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division. Materials Sciences Division
  2. Univ. of California, Berkeley, CA (United States). Electrical Engineering and Computer Sciences; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of Trieste (Italy). Dept. of Physics. Graduate School of Nanotechnology
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division. Joint Center for Artificial Photosynthesis
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Technical Univ. of Munich (Germany). Walter Schottky Inst. Physics Dept.
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); LBNL Laboratory Directed Research and Development (LDRD) Program; Swiss National Science Foundation (SNSF)
OSTI Identifier:
1439237
Grant/Contract Number:  
AC02-05CH11231; SC0004993; P2EZP2_155586; P300P2_171420
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 18; Journal Issue: 6; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cation variation; halide demixing; in situ characterization; metal halide perovskite; photoluminescence

Citation Formats

Sutter-Fella, Carolin M., Ngo, Quynh P., Cefarin, Nicola, Gardner, Kira L., Tamura, Nobumichi, Stan, Camelia V., Drisdell, Walter S., Javey, Ali, Toma, Francesca M., and Sharp, Ian D. Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites. United States: N. p., 2018. Web. doi:10.1021/acs.nanolett.8b00541.
Sutter-Fella, Carolin M., Ngo, Quynh P., Cefarin, Nicola, Gardner, Kira L., Tamura, Nobumichi, Stan, Camelia V., Drisdell, Walter S., Javey, Ali, Toma, Francesca M., & Sharp, Ian D. Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites. United States. https://doi.org/10.1021/acs.nanolett.8b00541
Sutter-Fella, Carolin M., Ngo, Quynh P., Cefarin, Nicola, Gardner, Kira L., Tamura, Nobumichi, Stan, Camelia V., Drisdell, Walter S., Javey, Ali, Toma, Francesca M., and Sharp, Ian D. Mon . "Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites". United States. https://doi.org/10.1021/acs.nanolett.8b00541. https://www.osti.gov/servlets/purl/1439237.
@article{osti_1439237,
title = {Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites},
author = {Sutter-Fella, Carolin M. and Ngo, Quynh P. and Cefarin, Nicola and Gardner, Kira L. and Tamura, Nobumichi and Stan, Camelia V. and Drisdell, Walter S. and Javey, Ali and Toma, Francesca M. and Sharp, Ian D.},
abstractNote = {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(NH2)2CsPb-halide (FACsPb-) and CH3NH3Pb-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. 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.},
doi = {10.1021/acs.nanolett.8b00541},
journal = {Nano Letters},
number = 6,
volume = 18,
place = {United States},
year = {Mon Apr 30 00:00:00 EDT 2018},
month = {Mon Apr 30 00:00:00 EDT 2018}
}

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