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Title: Making and Breaking of Lead Halide Perovskites

Abstract

A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into themore » lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH3NH3PbI3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH3NH3PbI3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.« less

Authors:
;  [1]; ;  [1];
  1. Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1235976
Alternate Identifier(s):
OSTI ID: 1438191
Grant/Contract Number:  
FC02-04ER15533
Resource Type:
Published Article
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Name: Accounts of Chemical Research Journal Volume: 49 Journal Issue: 2; Journal ID: ISSN 0001-4842
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Manser, Joseph S., Saidaminov, Makhsud I., Christians, Jeffrey A., Bakr, Osman M., and Kamat, Prashant V. Making and Breaking of Lead Halide Perovskites. United States: N. p., 2016. Web. doi:10.1021/acs.accounts.5b00455.
Manser, Joseph S., Saidaminov, Makhsud I., Christians, Jeffrey A., Bakr, Osman M., & Kamat, Prashant V. Making and Breaking of Lead Halide Perovskites. United States. doi:10.1021/acs.accounts.5b00455.
Manser, Joseph S., Saidaminov, Makhsud I., Christians, Jeffrey A., Bakr, Osman M., and Kamat, Prashant V. Tue . "Making and Breaking of Lead Halide Perovskites". United States. doi:10.1021/acs.accounts.5b00455.
@article{osti_1235976,
title = {Making and Breaking of Lead Halide Perovskites},
author = {Manser, Joseph S. and Saidaminov, Makhsud I. and Christians, Jeffrey A. and Bakr, Osman M. and Kamat, Prashant V.},
abstractNote = {A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH3NH3PbI3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH3NH3PbI3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.},
doi = {10.1021/acs.accounts.5b00455},
journal = {Accounts of Chemical Research},
number = 2,
volume = 49,
place = {United States},
year = {2016},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1021/acs.accounts.5b00455

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Works referencing / citing this record:

Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation
journal, July 2017

  • Zhou, Chenkun; Tian, Yu; Wang, Mingchao
  • Angewandte Chemie International Edition, Vol. 56, Issue 31
  • DOI: 10.1002/anie.201702825

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

Reversible solid-state thermochromism of a 2D organic–inorganic hybrid perovskite structure based on iodoplumbate and 2-aminomethyl-pyridine
journal, January 2017

  • Yu, Hui; Wei, ZhenHong; Hao, YanHuan
  • New Journal of Chemistry, Vol. 41, Issue 18
  • DOI: 10.1039/c7nj02229h

Two new oxyiodoplumbates: the unique 3-D hybrid oxyiodoplumbate based on neutral 2-D [Pb 2 I 4 ] n layers
journal, January 2018

  • Xiao, Hong; Zhou, Jian; Hu, Feilong
  • Dalton Transactions, Vol. 47, Issue 25
  • DOI: 10.1039/c8dt01927d

Surprising discoveries on the way to an old compound: four transient iodido antimonates
journal, January 2019

  • Dehnhardt, Natalie; Böth, André; Heine, Johanna
  • Dalton Transactions, Vol. 48, Issue 16
  • DOI: 10.1039/c9dt00575g

Encapsulation of methylammonium lead bromide perovskite in nanoporous GaN
journal, February 2019

  • Lim, Kevin T. P.; Deakin, Callum; Ding, Boning
  • APL Materials, Vol. 7, Issue 2
  • DOI: 10.1063/1.5083037

A mixed solvent for rapid fabrication of large-area methylammonium lead iodide layers by one-step coating at room temperature
journal, January 2019

  • Liu, Qiuju; Zhao, Yanan; Ma, Yinxing
  • Journal of Materials Chemistry A, Vol. 7, Issue 31
  • DOI: 10.1039/c9ta06084g

A Redox-Based Resistive Switching Memory Device Consisting of Organic-Inorganic Hybrid Perovskite/Polymer Composite Thin Film
journal, October 2017

  • Ercan, Ender; Chen, Jung-Yao; Tsai, Ping-Chun
  • Advanced Electronic Materials, Vol. 3, Issue 12
  • DOI: 10.1002/aelm.201700344

Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation
journal, July 2017

  • Zhou, Chenkun; Tian, Yu; Wang, Mingchao
  • Angewandte Chemie International Edition, Vol. 56, Issue 31
  • DOI: 10.1002/anie.201702825

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

Influence of mobile ions on the electroluminescence characteristics of methylammonium lead iodide perovskite diodes
journal, January 2016

  • Bandiello, Enrico; Ávila, Jorge; Gil-Escrig, Lidón
  • Journal of Materials Chemistry A, Vol. 4, Issue 47
  • DOI: 10.1039/c6ta06854e

Impact of H 2 O on organic–inorganic hybrid perovskite solar cells
journal, January 2017

  • Huang, Jianbing; Tan, Shunquan; Lund, Peter D.
  • Energy & Environmental Science, Vol. 10, Issue 11
  • DOI: 10.1039/c7ee01674c

Reversible solid-state thermochromism of a 2D organic–inorganic hybrid perovskite structure based on iodoplumbate and 2-aminomethyl-pyridine
journal, January 2017

  • Yu, Hui; Wei, ZhenHong; Hao, YanHuan
  • New Journal of Chemistry, Vol. 41, Issue 18
  • DOI: 10.1039/c7nj02229h

Two new oxyiodoplumbates: the unique 3-D hybrid oxyiodoplumbate based on neutral 2-D [Pb 2 I 4 ] n layers
journal, January 2018

  • Xiao, Hong; Zhou, Jian; Hu, Feilong
  • Dalton Transactions, Vol. 47, Issue 25
  • DOI: 10.1039/c8dt01927d

Surprising discoveries on the way to an old compound: four transient iodido antimonates
journal, January 2019

  • Dehnhardt, Natalie; Böth, André; Heine, Johanna
  • Dalton Transactions, Vol. 48, Issue 16
  • DOI: 10.1039/c9dt00575g

A mixed solvent for rapid fabrication of large-area methylammonium lead iodide layers by one-step coating at room temperature
journal, January 2019

  • Liu, Qiuju; Zhao, Yanan; Ma, Yinxing
  • Journal of Materials Chemistry A, Vol. 7, Issue 31
  • DOI: 10.1039/c9ta06084g

Encapsulation of methylammonium lead bromide perovskite in nanoporous GaN
journal, February 2019

  • Lim, Kevin T. P.; Deakin, Callum; Ding, Boning
  • APL Materials, Vol. 7, Issue 2
  • DOI: 10.1063/1.5083037

Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation
journal, July 2017


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