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Title: Time-Dependent Mechanical Response of APbX 3 (A = Cs, CH 3NH 3; X = I, Br) Single Crystals [The Dynamic Mechanical Properties of Lead-Halide Perovskite Single Crystals are Independent of A-site Cation Chemistry]

Abstract

The ease of processing hybrid organic–inorganic perovskite (HOIPs) films, belonging to a material class with composition ABX 3, from solution and at mild temperatures promises their use in deformable technologies, including flexible photovoltaic devices, sensors, and displays. To successfully apply these materials in deformable devices, knowledge of their mechanical response to dynamic strain is necessary. The authors elucidate the time- and rate-dependent mechanical properties of HOIPs and an inorganic perovskite (IP) single crystal by measuring nanoindentation creep and stress relaxation. The observation of pop-in events and slip bands on the surface of the indented crystals demonstrate dislocation-mediated plastic deformation. The magnitudes of creep and relaxation of both HOIPs and IPs are similar, negating prior hypothesis that the presence of organic A-site cations alters the mechanical response of these materials. Moreover, these samples exhibit a pronounced increase in creep, and stress relaxation as a function of indentation rate whose magnitudes reflect differences in the rates of nucleation and propagation of dislocations within the crystal structures of HOIPs and IP. In conclusion, this contribution provides understanding that is critical for designing perovskite devices capable of withstanding mechanical deformations.

Authors:
 [1];  [2];  [2];  [3];  [2];  [4];  [1]; ORCiD logo [1]
  1. Princeton Univ., Princeton, NJ (United States)
  2. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA), Office of Defense Nuclear Nonproliferation (NA-20)
OSTI Identifier:
1374182
Alternate Identifier(s):
OSTI ID: 1401541
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 24; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dynamic mechanical behavior; hybrid perovskites; single crystals; nanoindentation; viscoplasticity

Citation Formats

Reyes-Martinez, Marcos A., Abdelhady, Ahmed L., Saidaminov, Makhsud I., Chung, Duck Young, Bakr, Osman M., Kanatzidis, Mercouri G., Soboyejo, Wole O., and Loo, Yueh -Lin. Time-Dependent Mechanical Response of APbX3 (A = Cs, CH3NH3; X = I, Br) Single Crystals [The Dynamic Mechanical Properties of Lead-Halide Perovskite Single Crystals are Independent of A-site Cation Chemistry]. United States: N. p., 2017. Web. doi:10.1002/adma.201606556.
Reyes-Martinez, Marcos A., Abdelhady, Ahmed L., Saidaminov, Makhsud I., Chung, Duck Young, Bakr, Osman M., Kanatzidis, Mercouri G., Soboyejo, Wole O., & Loo, Yueh -Lin. Time-Dependent Mechanical Response of APbX3 (A = Cs, CH3NH3; X = I, Br) Single Crystals [The Dynamic Mechanical Properties of Lead-Halide Perovskite Single Crystals are Independent of A-site Cation Chemistry]. United States. doi:10.1002/adma.201606556.
Reyes-Martinez, Marcos A., Abdelhady, Ahmed L., Saidaminov, Makhsud I., Chung, Duck Young, Bakr, Osman M., Kanatzidis, Mercouri G., Soboyejo, Wole O., and Loo, Yueh -Lin. Tue . "Time-Dependent Mechanical Response of APbX3 (A = Cs, CH3NH3; X = I, Br) Single Crystals [The Dynamic Mechanical Properties of Lead-Halide Perovskite Single Crystals are Independent of A-site Cation Chemistry]". United States. doi:10.1002/adma.201606556. https://www.osti.gov/servlets/purl/1374182.
@article{osti_1374182,
title = {Time-Dependent Mechanical Response of APbX3 (A = Cs, CH3NH3; X = I, Br) Single Crystals [The Dynamic Mechanical Properties of Lead-Halide Perovskite Single Crystals are Independent of A-site Cation Chemistry]},
author = {Reyes-Martinez, Marcos A. and Abdelhady, Ahmed L. and Saidaminov, Makhsud I. and Chung, Duck Young and Bakr, Osman M. and Kanatzidis, Mercouri G. and Soboyejo, Wole O. and Loo, Yueh -Lin},
abstractNote = {The ease of processing hybrid organic–inorganic perovskite (HOIPs) films, belonging to a material class with composition ABX3, from solution and at mild temperatures promises their use in deformable technologies, including flexible photovoltaic devices, sensors, and displays. To successfully apply these materials in deformable devices, knowledge of their mechanical response to dynamic strain is necessary. The authors elucidate the time- and rate-dependent mechanical properties of HOIPs and an inorganic perovskite (IP) single crystal by measuring nanoindentation creep and stress relaxation. The observation of pop-in events and slip bands on the surface of the indented crystals demonstrate dislocation-mediated plastic deformation. The magnitudes of creep and relaxation of both HOIPs and IPs are similar, negating prior hypothesis that the presence of organic A-site cations alters the mechanical response of these materials. Moreover, these samples exhibit a pronounced increase in creep, and stress relaxation as a function of indentation rate whose magnitudes reflect differences in the rates of nucleation and propagation of dislocations within the crystal structures of HOIPs and IP. In conclusion, this contribution provides understanding that is critical for designing perovskite devices capable of withstanding mechanical deformations.},
doi = {10.1002/adma.201606556},
journal = {Advanced Materials},
number = 24,
volume = 29,
place = {United States},
year = {Tue May 02 00:00:00 EDT 2017},
month = {Tue May 02 00:00:00 EDT 2017}
}

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  • Cited by 3
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  • We report the synthesis of CH{sub 3}NH{sub 3}Pb(Br{sub 3−y}X{sub y}) (X=Cl and I) single crystals via a stepwise temperature control approach. High-quality CH{sub 3}NH{sub 3}Pb(Br{sub 3−y}X{sub y}) crystals with a tunable bandgap from 1.92 eV to 2.53 eV have been prepared successfully in this way. And further experiments revealed the influence of halogen content and preparation temperature on the structural and optical properties of these crystals. It is observed that chlorine can lower the critical nucleation energy, which results in crystallizing at lower temperature with the chlorine content increasing, while the nucleation energy increases slowly with increasing iodine content. Moreover,more » in contrast to Frank–van der Merwe growth with low heating rate, high heating rate leads to a mass of small size single crystals and Stranski-Krastanov growth. The single crystals with tunable band gap and impressive characteristics enable us to fabricate high performance photodetectors for different wavelengths.« less
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  • The structures of the lead halide perovskites CsPbCl3 and CsPbBr3 have been determined from X-ray powder diffraction data to be orthorhombic with Pnma space group symmetry. Their structures are distorted from the cubic structure of their hybrid analogs, CH3NH3PbX3 (X = Cl, Br), by tilts of the octahedra (Glazer tilt system a–b+a–). Substitution of the smaller Rb+ for Cs+ increases the octahedral tilting distortion and eventually destabilizes the perovskite structure altogether. To understand this behavior, bond valence parameters appropriate for use in chloride and bromide perovskites have been determined for Cs+, Rb+, and Pb2+. As the tolerance factor decreases, themore » band gap increases, by 0.15 eV in Cs1–xRbxPbCl3 and 0.20 eV in Cs1–xRbxPbBr3, upon going from x = 0 to x = 0.6. The band gap shows a linear dependence on tolerance factor, particularly for the Cs1–xRbxPbBr3 system. Comparison with the cubic perovskites CH3NH3PbCl3 and CH3NH3PbBr3 shows that the band gaps of the methylammonium perovskites are anomalously large for APbX3 perovskites with a cubic structure. This comparison suggests that the local symmetry of CH3NH3PbCl3 and CH3NH3PbBr3 deviate significantly from the cubic symmetry of the average structure.« less