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Title: Pressure-Induced Bandgap Optimization in Lead-Based Perovskites with Prolonged Carrier Lifetime and Ambient Retainability

Abstract

Bond length and bond angle exhibited by valence electrons is essential to the core of chemistry. Using lead-based organic–inorganic perovskite compounds as an exploratory platform, it is demonstrated that the modulation of valence electrons by compression can lead to discovery of new properties of known compounds. Yet, despite its unprecedented progress, further efficiency boost of lead-based organic–inorganic perovskite solar cells is hampered by their wider bandgap than the optimum value according to the Shockley–Queisser limit. By modulating the valence electron wavefunction with modest hydraulic pressure up to 2.1 GPa, the optimized bandgap for single-junction solar cells in lead-based perovskites, for the first time, is achieved by narrowing the bandgap of formamidinium lead triiodide (HC(NH2)2PbI3) from 1.489 to 1.337 eV. Strikingly, such bandgap narrowing is partially retained after the release of pressure to ambient, and the bandgap narrowing is also accompanied with double-prolonged carrier lifetime. With First-principles simulation, this work opens a new dimension in basic chemical understanding of structural photonics and electronics and paves an alternative pathway toward better photovoltaic materials-by-design.

Authors:
 [1];  [1];  [2];  [1];  [1];  [3];  [3];  [4];  [5];  [2]
  1. Center for High Pressure Science and Technology Advanced Research, Shanghai 201203 China; Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA
  2. Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb IL 60115 USA
  3. Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA
  4. Center for Nanoscale Materials, Argonne National Laboratory, Argonne IL 60439 USA
  5. Hawai'i Institute of Geophysics and Planetology, School of Ocean and Earth Science and Technology, University of Hawai'i at Manoa, Honolulu HI 96822 USA
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1409585
Report Number(s):
BNL-114637-2017-JA¿¿¿
Journal ID: ISSN 1616-301X
DOE Contract Number:  
SC0012704
Resource Type:
Journal Article
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 3; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Gang, Kong, Lingping, Gong, Jue, Yang, Wenge, Mao, Ho-kwang, Hu, Qingyang, Liu, Zhenxian, Schaller, Richard D., Zhang, Dongzhou, and Xu, Tao. Pressure-Induced Bandgap Optimization in Lead-Based Perovskites with Prolonged Carrier Lifetime and Ambient Retainability. United States: N. p., 2016. Web. doi:10.1002/adfm.201604208.
Liu, Gang, Kong, Lingping, Gong, Jue, Yang, Wenge, Mao, Ho-kwang, Hu, Qingyang, Liu, Zhenxian, Schaller, Richard D., Zhang, Dongzhou, & Xu, Tao. Pressure-Induced Bandgap Optimization in Lead-Based Perovskites with Prolonged Carrier Lifetime and Ambient Retainability. United States. doi:10.1002/adfm.201604208.
Liu, Gang, Kong, Lingping, Gong, Jue, Yang, Wenge, Mao, Ho-kwang, Hu, Qingyang, Liu, Zhenxian, Schaller, Richard D., Zhang, Dongzhou, and Xu, Tao. Mon . "Pressure-Induced Bandgap Optimization in Lead-Based Perovskites with Prolonged Carrier Lifetime and Ambient Retainability". United States. doi:10.1002/adfm.201604208.
@article{osti_1409585,
title = {Pressure-Induced Bandgap Optimization in Lead-Based Perovskites with Prolonged Carrier Lifetime and Ambient Retainability},
author = {Liu, Gang and Kong, Lingping and Gong, Jue and Yang, Wenge and Mao, Ho-kwang and Hu, Qingyang and Liu, Zhenxian and Schaller, Richard D. and Zhang, Dongzhou and Xu, Tao},
abstractNote = {Bond length and bond angle exhibited by valence electrons is essential to the core of chemistry. Using lead-based organic–inorganic perovskite compounds as an exploratory platform, it is demonstrated that the modulation of valence electrons by compression can lead to discovery of new properties of known compounds. Yet, despite its unprecedented progress, further efficiency boost of lead-based organic–inorganic perovskite solar cells is hampered by their wider bandgap than the optimum value according to the Shockley–Queisser limit. By modulating the valence electron wavefunction with modest hydraulic pressure up to 2.1 GPa, the optimized bandgap for single-junction solar cells in lead-based perovskites, for the first time, is achieved by narrowing the bandgap of formamidinium lead triiodide (HC(NH2)2PbI3) from 1.489 to 1.337 eV. Strikingly, such bandgap narrowing is partially retained after the release of pressure to ambient, and the bandgap narrowing is also accompanied with double-prolonged carrier lifetime. With First-principles simulation, this work opens a new dimension in basic chemical understanding of structural photonics and electronics and paves an alternative pathway toward better photovoltaic materials-by-design.},
doi = {10.1002/adfm.201604208},
journal = {Advanced Functional Materials},
issn = {1616-301X},
number = 3,
volume = 27,
place = {United States},
year = {2016},
month = {12}
}

Works referenced in this record:

The laser micro-machining system for diamond anvil cell experiments and general precision machining applications at the High Pressure Collaborative Access Team
journal, July 2015

  • Hrubiak, Rostislav; Sinogeikin, Stanislav; Rod, Eric
  • Review of Scientific Instruments, Vol. 86, Issue 7
  • DOI: 10.1063/1.4926889

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Flexible high power-per-weight perovskite solar cells with chromium oxide–metal contacts for improved stability in air
journal, August 2015

  • Kaltenbrunner, Martin; Adam, Getachew; Głowacki, Eric Daniel
  • Nature Materials, Vol. 14, Issue 10
  • DOI: 10.1038/nmat4388

The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors
journal, September 2015


Hybrid organic—inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties
journal, January 2016

  • Brenner, Thomas M.; Egger, David A.; Kronik, Leeor
  • Nature Reviews Materials, Vol. 1, Issue 1
  • DOI: 10.1038/natrevmats.2015.7

High-Efficiency Perovskite Solar Cells Based on the Black Polymorph of HC(NH 2 ) 2 PbI 3
journal, June 2014


Cation-Induced Band-Gap Tuning in Organohalide Perovskites: Interplay of Spin–Orbit Coupling and Octahedra Tilting
journal, May 2014

  • Amat, Anna; Mosconi, Edoardo; Ronca, Enrico
  • Nano Letters, Vol. 14, Issue 6
  • DOI: 10.1021/nl5012992

The emergence of perovskite solar cells
journal, July 2014

  • Green, Martin A.; Ho-Baillie, Anita; Snaith, Henry J.
  • Nature Photonics, Vol. 8, Issue 7, p. 506-514
  • DOI: 10.1038/nphoton.2014.134

Retrograde solubility of formamidinium and methylammonium lead halide perovskites enabling rapid single crystal growth
journal, January 2015

  • Saidaminov, Makhsud I.; Abdelhady, Ahmed L.; Maculan, Giacomo
  • Chemical Communications, Vol. 51, Issue 100
  • DOI: 10.1039/C5CC06916E

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals
journal, January 2015


Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009

  • Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
  • Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
  • DOI: 10.1021/ja809598r

Efficient and stable large-area perovskite solar cells with inorganic charge extraction layers
journal, October 2015


Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells
journal, August 2014

  • Im, Jeong-Hyeok; Jang, In-Hyuk; Pellet, Norman
  • Nature Nanotechnology, Vol. 9, Issue 11
  • DOI: 10.1038/nnano.2014.181

Atomically thin two-dimensional organic-inorganic hybrid perovskites
journal, September 2015


Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells
journal, January 2014

  • Eperon, Giles E.; Stranks, Samuel D.; Menelaou, Christopher
  • Energy & Environmental Science, Vol. 7, Issue 3
  • DOI: 10.1039/c3ee43822h

Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
journal, July 2014

  • Jeon, Nam Joong; Noh, Jun Hong; Kim, Young Chan
  • Nature Materials, Vol. 13, Issue 9, p. 897-903
  • DOI: 10.1038/nmat4014

The large-volume high-pressure facility at GSECARS: A “Swiss-army-knife” approach to synchrotron-based experimental studies
journal, May 2009

  • Wang, Yanbin; Rivers, Mark; Sutton, Steve
  • Physics of the Earth and Planetary Interiors, Vol. 174, Issue 1-4
  • DOI: 10.1016/j.pepi.2008.06.017

Simultaneous band-gap narrowing and carrier-lifetime prolongation of organic–inorganic trihalide perovskites
journal, July 2016

  • Kong, Lingping; Liu, Gang; Gong, Jue
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 32
  • DOI: 10.1073/pnas.1609030113

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013

  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

Halide perovskite materials for solar cells: a theoretical review
journal, January 2015

  • Yin, Wan-Jian; Yang, Ji-Hui; Kang, Joongoo
  • Journal of Materials Chemistry A, Vol. 3, Issue 17
  • DOI: 10.1039/C4TA05033A

High-efficiency solution-processed perovskite solar cells with millimeter-scale grains
journal, January 2015


Pressure-Induced Phase Transformation, Reversible Amorphization, and Anomalous Visible Light Response in Organolead Bromide Perovskite
journal, August 2015

  • Wang, Yonggang; Lü, Xujie; Yang, Wenge
  • Journal of the American Chemical Society, Vol. 137, Issue 34
  • DOI: 10.1021/jacs.5b06346

High-pressure behavior of methylammonium lead iodide (MAPbI 3 ) hybrid perovskite
journal, May 2016

  • Capitani, Francesco; Marini, Carlo; Caramazza, Simone
  • Journal of Applied Physics, Vol. 119, Issue 18
  • DOI: 10.1063/1.4948577

Pressure-Induced Conductivity and Yellow-to-Black Piezochromism in a Layered Cu–Cl Hybrid Perovskite
journal, January 2015

  • Jaffe, Adam; Lin, Yu; Mao, Wendy L.
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja512396m

Determination of crystallite size and lattice distortions through X-ray diffraction line profile analysis: Vorschriften, Methoden und Bemerkungen
journal, January 1982

  • Delhez, R.; de Keijser, Th. H.; Mittemeijer, E. J.
  • Fresenius' Zeitschrift für analytische Chemie, Vol. 312, Issue 1
  • DOI: 10.1007/BF00482725

Growth and Anion Exchange Conversion of CH 3 NH 3 PbX 3 Nanorod Arrays for Light-Emitting Diodes
journal, July 2015


Pressure-Induced Structural and Optical Properties of Organometal Halide Perovskite-Based Formamidinium Lead Bromide
journal, June 2016


Pressure-induced phase transitions and templating effect in three-dimensional organic-inorganic hybrid perovskites
journal, July 2003


Unusual defect physics in CH 3 NH 3 PbI 3 perovskite solar cell absorber
journal, February 2014

  • Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa
  • Applied Physics Letters, Vol. 104, Issue 6
  • DOI: 10.1063/1.4864778

NH 2 CH═NH 2 PbI 3 : An Alternative Organolead Iodide Perovskite Sensitizer for Mesoscopic Solar Cells
journal, January 2014

  • Pang, Shuping; Hu, Hao; Zhang, Jiliang
  • Chemistry of Materials, Vol. 26, Issue 3
  • DOI: 10.1021/cm404006p

Formamidinium Lead Halide Perovskite Crystals with Unprecedented Long Carrier Dynamics and Diffusion Length
journal, April 2016


Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite
journal, April 2016

  • Jiang, Shaojie; Fang, Yanan; Li, Ruipeng
  • Angewandte Chemie International Edition, Vol. 55, Issue 22
  • DOI: 10.1002/anie.201601788

The efficiency limit of CH 3 NH 3 PbI 3 perovskite solar cells
journal, June 2015

  • Sha, Wei E. I.; Ren, Xingang; Chen, Luzhou
  • Applied Physics Letters, Vol. 106, Issue 22
  • DOI: 10.1063/1.4922150

Red-to-Black Piezochromism in a Compressible Pb–I–SCN Layered Perovskite
journal, May 2016


Pressure Response of an Organic−Inorganic Perovskite:  Methylammonium Lead Bromide
journal, May 2007

  • Swainson, I. P.; Tucker, M. G.; Wilson, D. J.
  • Chemistry of Materials, Vol. 19, Issue 10
  • DOI: 10.1021/cm0621601

Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires
journal, July 2015

  • Zhang, Dandan; Eaton, Samuel W.; Yu, Yi
  • Journal of the American Chemical Society, Vol. 137, Issue 29
  • DOI: 10.1021/jacs.5b05404

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013

  • Stranks, S. D.; Eperon, G. E.; Grancini, G.
  • Science, Vol. 342, Issue 6156, p. 341-344
  • DOI: 10.1126/science.1243982

Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


The nature of hydrogen-bonding interaction in the prototypic hybrid halide perovskite, tetragonal CH3NH3PbI3
journal, February 2016

  • Lee, June Ho; Lee, Jung-Hoon; Kong, Eui-Hyun
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep21687

Effect of Structural Phase Transition on Charge-Carrier Lifetimes and Defects in CH 3 NH 3 SnI 3 Perovskite
journal, March 2016

  • Parrott, Elizabeth S.; Milot, Rebecca L.; Stergiopoulos, Thomas
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
  • DOI: 10.1021/acs.jpclett.6b00322

Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies
journal, December 2015


Organolead Halide Perovskite Nanocrystals: Branched Capping Ligands Control Crystal Size and Stability
journal, June 2016

  • Luo, Binbin; Pu, Ying-Chih; Lindley, Sarah A.
  • Angewandte Chemie International Edition, Vol. 55, Issue 31
  • DOI: 10.1002/anie.201602236

Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells
journal, March 1961

  • Shockley, William; Queisser, Hans J.
  • Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519
  • DOI: 10.1063/1.1736034

Lead-free solid-state organic–inorganic halide perovskite solar cells
journal, May 2014

  • Hao, Feng; Stoumpos, Constantinos C.; Cao, Duyen Hanh
  • Nature Photonics, Vol. 8, Issue 6
  • DOI: 10.1038/nphoton.2014.82

High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
journal, December 2013

  • Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
  • Advanced Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adma.201305172

Steric engineering of metal-halide perovskites with tunable optical band gaps
journal, December 2014

  • Filip, Marina R.; Eperon, Giles E.; Snaith, Henry J.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6757

Microstructural parameters from X-ray diffraction peak broadening
journal, October 2004


Single Crystal Formamidinium Lead Iodide (FAPbI 3 ): Insight into the Structural, Optical, and Electrical Properties
journal, January 2016