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Title: Coupling of organic cation and inorganic lattice in methylammonium lead halide perovskites: Insights into a pressure-induced isostructural phase transition

Abstract

Organic-inorganic hybrid metal-halide perovskite (OIHP) materials provide a tunable platform for engineering their optoelectronic properties. Although several high-pressure studies have been conducted from the OIHP family of single crystals and films, the exact nature of the dynamic coupling of the CH3NH3 (MA) cation with the octahedral lattice framework and the mechanisms responsible for the structural phase transformation under pressure are not well captured. By combined photoluminescence (PL), synchrotron-based x-ray diffraction, and Raman-scattering studies as a function of pressure from methylammonium lead bromide (MAPbBr3), we shed light on an isostructural phase transition due to the coupling of the MA cation and the PbBr6 lattice through hydrogen bonding. The sharp discontinuities at ~ 1 GPa and ~ 3 GPa in the PL peak positions correlate with the structural changes observed in high-pressure XRD and Raman-scattering studies. The electronic band edge as a function of pressure is calculated within density-functional theory. The PL peak position, intensity and width of the excitonic peak show significant changes at 2 GPa, which corroborate the changes observed in high-pressure Raman-scattering studies. The frequencies of the lattice modes and the C-H/N-H bending and stretching modes of the MA cation show anomalous changes and other nuances at 2 GPa. The suppression of rotational and orientational disorder of the organic moiety is initiated at 2 GPa and the ordering is completed by 3.0 GPa, leading to an order-disorder type cubic II (Im$$\overline{3}$$) to orthorhombic (Pnma) phase transition. Along with the revelation of an isostructural transformation at 2 GPa, this paper highlights the impact of molecular vibrations on the electronic properties of MAPbBr3 under pressure.

Authors:
 [1];  [1];  [2];  [3];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Missouri, Columbia, MO (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  3. Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1776843
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 4; Journal Issue: 10; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Yesudhas, Sorb, Burns, Randy, Lavina, Barbara, Tkachev, Sergey N., Sun, Jiuyu, Ullrich, Carsten A., and Guha, Suchismita. Coupling of organic cation and inorganic lattice in methylammonium lead halide perovskites: Insights into a pressure-induced isostructural phase transition. United States: N. p., 2020. Web. doi:10.1103/physrevmaterials.4.105403.
Yesudhas, Sorb, Burns, Randy, Lavina, Barbara, Tkachev, Sergey N., Sun, Jiuyu, Ullrich, Carsten A., & Guha, Suchismita. Coupling of organic cation and inorganic lattice in methylammonium lead halide perovskites: Insights into a pressure-induced isostructural phase transition. United States. https://doi.org/10.1103/physrevmaterials.4.105403
Yesudhas, Sorb, Burns, Randy, Lavina, Barbara, Tkachev, Sergey N., Sun, Jiuyu, Ullrich, Carsten A., and Guha, Suchismita. Fri . "Coupling of organic cation and inorganic lattice in methylammonium lead halide perovskites: Insights into a pressure-induced isostructural phase transition". United States. https://doi.org/10.1103/physrevmaterials.4.105403. https://www.osti.gov/servlets/purl/1776843.
@article{osti_1776843,
title = {Coupling of organic cation and inorganic lattice in methylammonium lead halide perovskites: Insights into a pressure-induced isostructural phase transition},
author = {Yesudhas, Sorb and Burns, Randy and Lavina, Barbara and Tkachev, Sergey N. and Sun, Jiuyu and Ullrich, Carsten A. and Guha, Suchismita},
abstractNote = {Organic-inorganic hybrid metal-halide perovskite (OIHP) materials provide a tunable platform for engineering their optoelectronic properties. Although several high-pressure studies have been conducted from the OIHP family of single crystals and films, the exact nature of the dynamic coupling of the CH3NH3 (MA) cation with the octahedral lattice framework and the mechanisms responsible for the structural phase transformation under pressure are not well captured. By combined photoluminescence (PL), synchrotron-based x-ray diffraction, and Raman-scattering studies as a function of pressure from methylammonium lead bromide (MAPbBr3), we shed light on an isostructural phase transition due to the coupling of the MA cation and the PbBr6 lattice through hydrogen bonding. The sharp discontinuities at ~ 1 GPa and ~ 3 GPa in the PL peak positions correlate with the structural changes observed in high-pressure XRD and Raman-scattering studies. The electronic band edge as a function of pressure is calculated within density-functional theory. The PL peak position, intensity and width of the excitonic peak show significant changes at 2 GPa, which corroborate the changes observed in high-pressure Raman-scattering studies. The frequencies of the lattice modes and the C-H/N-H bending and stretching modes of the MA cation show anomalous changes and other nuances at 2 GPa. The suppression of rotational and orientational disorder of the organic moiety is initiated at 2 GPa and the ordering is completed by 3.0 GPa, leading to an order-disorder type cubic II (Im$\overline{3}$) to orthorhombic (Pnma) phase transition. Along with the revelation of an isostructural transformation at 2 GPa, this paper highlights the impact of molecular vibrations on the electronic properties of MAPbBr3 under pressure.},
doi = {10.1103/physrevmaterials.4.105403},
journal = {Physical Review Materials},
number = 10,
volume = 4,
place = {United States},
year = {Fri Oct 16 00:00:00 EDT 2020},
month = {Fri Oct 16 00:00:00 EDT 2020}
}

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