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Title: High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties

Abstract

Here, we report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX 3 (MA = CH 3NH 3 +, X = Br or I ) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI 3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(Br xI 1–x) 3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain themore » low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.« less

Authors:
;  [1];  [2];  [3];  [1];
  1. Photon Science and Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
  2. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  3. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1245682
Alternate Identifier(s):
OSTI ID: 1249096
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515; DMR-1351538
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Name: ACS Central Science Journal Volume: 2 Journal Issue: 4; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Jaffe, Adam, Lin, Yu, Beavers, Christine M., Voss, Johannes, Mao, Wendy L., and Karunadasa, Hemamala I. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties. United States: N. p., 2016. Web. doi:10.1021/acscentsci.6b00055.
Jaffe, Adam, Lin, Yu, Beavers, Christine M., Voss, Johannes, Mao, Wendy L., & Karunadasa, Hemamala I. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties. United States. doi:10.1021/acscentsci.6b00055.
Jaffe, Adam, Lin, Yu, Beavers, Christine M., Voss, Johannes, Mao, Wendy L., and Karunadasa, Hemamala I. Wed . "High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties". United States. doi:10.1021/acscentsci.6b00055.
@article{osti_1245682,
title = {High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties},
author = {Jaffe, Adam and Lin, Yu and Beavers, Christine M. and Voss, Johannes and Mao, Wendy L. and Karunadasa, Hemamala I.},
abstractNote = {Here, we report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3+, X = Br– or I–) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(BrxI1–x)3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.},
doi = {10.1021/acscentsci.6b00055},
journal = {ACS Central Science},
issn = {2374-7943},
number = 4,
volume = 2,
place = {United States},
year = {2016},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acscentsci.6b00055

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Cited by: 48 works
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Works referencing / citing this record:

CCDC 1446529: Experimental Crystal Structure Determination: AVAPUK : catena-[methylammonium tris(μ-bromo)-lead]
dataset, January 2016


CCDC 1446530: Experimental Crystal Structure Determination: AVAQAR : catena-[methylammonium tris(μ-bromo)-lead]
dataset, January 2016


CCDC 1446531: Experimental Crystal Structure Determination: MAPBTI08 : catena-[methylammonium tris(μ-iodo)-lead]
dataset, January 2016


CCDC 1446532: Experimental Crystal Structure Determination: MAPBTI09 : catena-[methylammonium tris(μ-iodo)-lead]
dataset, January 2016


Piezofluorochromism in Charge-Transfer Inclusion Crystals: The Influence of High Pressure versus Mechanical Grinding
journal, March 2018


Factors Influencing the Mechanical Properties of Formamidinium Lead Halides and Related Hybrid Perovskites
journal, July 2017


Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach
journal, January 2016

  • Deng, Zeyu; Wei, Fengxia; Sun, Shijing
  • Journal of Materials Chemistry A, Vol. 4, Issue 31
  • DOI: 10.1039/c6ta05817e

Structural origins of broadband emission from layered Pb–Br hybrid perovskites
journal, January 2017

  • Smith, Matthew D.; Jaffe, Adam; Dohner, Emma R.
  • Chemical Science, Vol. 8, Issue 6
  • DOI: 10.1039/c7sc01590a

Mechanical properties of the ferroelectric metal-free perovskite [MDABCO](NH 4 )I 3
journal, January 2019

  • Ehrenreich, Michael G.; Zeng, Zhixin; Burger, Stefan
  • Chemical Communications, Vol. 55, Issue 27
  • DOI: 10.1039/c9cc00580c

Metal halide perovskites under compression
journal, January 2019

  • Li, Qian; Zhang, Liming; Chen, Zhongwei
  • Journal of Materials Chemistry A, Vol. 7, Issue 27
  • DOI: 10.1039/c9ta04930d

Hydrogen-bond-mediated structural variation of metal guanidinium formate hybrid perovskites under pressure
journal, May 2019

  • Yang, Zhengqiang; Cai, Guanqun; Bull, Craig L.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2149
  • DOI: 10.1098/rsta.2018.0227

Chemically diverse and multifunctional hybrid organic–inorganic perovskites
journal, February 2017


Ultrafast carrier dynamics in all-inorganic CsPbBr 3 perovskite across the pressure-induced phase transition
journal, January 2019


Piezofluorochromism in Charge-Transfer Inclusion Crystals: The Influence of High Pressure versus Mechanical Grinding
journal, April 2018


Factors Influencing the Mechanical Properties of Formamidinium Lead Halides and Related Hybrid Perovskites
journal, July 2017


Chemically diverse and multifunctional hybrid organic–inorganic perovskites
journal, February 2017


Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach
journal, January 2016

  • Deng, Zeyu; Wei, Fengxia; Sun, Shijing
  • Journal of Materials Chemistry A, Vol. 4, Issue 31
  • DOI: 10.1039/c6ta05817e

Structural origins of broadband emission from layered Pb–Br hybrid perovskites
journal, January 2017

  • Smith, Matthew D.; Jaffe, Adam; Dohner, Emma R.
  • Chemical Science, Vol. 8, Issue 6
  • DOI: 10.1039/c7sc01590a

Mechanical properties of the ferroelectric metal-free perovskite [MDABCO](NH 4 )I 3
journal, January 2019

  • Ehrenreich, Michael G.; Zeng, Zhixin; Burger, Stefan
  • Chemical Communications, Vol. 55, Issue 27
  • DOI: 10.1039/c9cc00580c

Metal halide perovskites under compression
journal, January 2019

  • Li, Qian; Zhang, Liming; Chen, Zhongwei
  • Journal of Materials Chemistry A, Vol. 7, Issue 27
  • DOI: 10.1039/c9ta04930d

Hydrogen-bond-mediated structural variation of metal guanidinium formate hybrid perovskites under pressure
journal, May 2019

  • Yang, Zhengqiang; Cai, Guanqun; Bull, Craig L.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2149
  • DOI: 10.1098/rsta.2018.0227

Ultrafast carrier dynamics in all-inorganic CsPbBr 3 perovskite across the pressure-induced phase transition
journal, January 2019


Exploring the Stability of Novel Wide Bandgap Perovskites by a Robot Based High Throughput Approach
journal, October 2017