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Title: Persistent dopants and phase segregation in organolead mixed-halide perovskites

Abstract

Organolead mixed-halide perovskites such as CH 3NH 3PbX 3–aX' a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the true chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskitesmore » at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less

Authors:
 [1];  [2];  [1];  [2];  [2];  [2]
  1. Iowa State Univ., Ames, IA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1321908
Report Number(s):
IS-J-9000
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Name: Chemistry of Materials; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rosales, Bryan A., Men, Long, Cady, Sarah D., Hanrahan, Michael P., Rossini, Aaron J., and Vela, Javier. Persistent dopants and phase segregation in organolead mixed-halide perovskites. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b01874.
Rosales, Bryan A., Men, Long, Cady, Sarah D., Hanrahan, Michael P., Rossini, Aaron J., & Vela, Javier. Persistent dopants and phase segregation in organolead mixed-halide perovskites. United States. doi:10.1021/acs.chemmater.6b01874.
Rosales, Bryan A., Men, Long, Cady, Sarah D., Hanrahan, Michael P., Rossini, Aaron J., and Vela, Javier. Mon . "Persistent dopants and phase segregation in organolead mixed-halide perovskites". United States. doi:10.1021/acs.chemmater.6b01874. https://www.osti.gov/servlets/purl/1321908.
@article{osti_1321908,
title = {Persistent dopants and phase segregation in organolead mixed-halide perovskites},
author = {Rosales, Bryan A. and Men, Long and Cady, Sarah D. and Hanrahan, Michael P. and Rossini, Aaron J. and Vela, Javier},
abstractNote = {Organolead mixed-halide perovskites such as CH3NH3PbX3–aX'a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the true chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.},
doi = {10.1021/acs.chemmater.6b01874},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = ,
volume = ,
place = {United States},
year = {2016},
month = {7}
}

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Works referencing / citing this record:

Lead- and Iodide-Deficient (CH 3 NH 3 )PbI 3 ( d -MAPI): The Bridge between 2D and 3D Hybrid Perovskites
journal, November 2017

  • Leblanc, Antonin; Mercier, Nicolas; Allain, Magali
  • Angewandte Chemie International Edition, Vol. 56, Issue 50
  • DOI: 10.1002/anie.201710021

Lead- and Iodide-Deficient (CH 3 NH 3 )PbI 3 ( d -MAPI): The Bridge between 2D and 3D Hybrid Perovskites
journal, November 2017

  • Leblanc, Antonin; Mercier, Nicolas; Allain, Magali
  • Angewandte Chemie International Edition, Vol. 56, Issue 50
  • DOI: 10.1002/anie.201710021

Lead- and Iodide-Deficient (CH 3 NH 3 )PbI 3 ( d -MAPI): The Bridge between 2D and 3D Hybrid Perovskites
journal, November 2017

  • Leblanc, Antonin; Mercier, Nicolas; Allain, Magali
  • Angewandte Chemie, Vol. 129, Issue 50
  • DOI: 10.1002/ange.201710021