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Title: Excitations Partition into Two Distinct Populations in Bulk Perovskites

Abstract

Organolead halide perovskites convert optical excitations to charge carriers with remarkable efficiency in optoelectronic devices. Previous research predominantly documents dynamics in perovskite thin films; however, extensive disorder in this platform may obscure the observed carrier dynamics. Here in this study, carrier dynamics in perovskite single-domain single crystals is examined by performing transient absorption spectroscopy in a transmissive geometry. Two distinct sets of carrier populations that coexist at the same radiation fluence, but display different decay dynamics, are observed: one dominated by second-order recombination and the other by third-order recombination. Based on ab initio simulations, this observation is found to be most consistent with the hypothesis that free carriers and localized carriers coexist due to polaron formation. Lastly, the calculations suggest that polarons will form in both CH 3NH 3PbBr 3 and CH 3NH 3PbI 3 crystals, but that they are more pronounced in CH 3NH 3PbBr 3. Single-crystal CH 3NH 3PbBr 3 could represent the key to understanding the impact of polarons on the transport properties of perovskite optoelectronic devices.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [4];  [5]; ORCiD logo [1]
  1. Univ. of Chicago, IL (United States). James Franck Inst., and Inst. for Biophysical Dynamics
  2. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States).Chemical Sciences and Engineering Division
  5. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Alfred P. Sloan Foundation; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); U.S. Department of Defense (DOD). National Security Science and Engineering Faculty Fellowship (NSSEFF)
OSTI Identifier:
1427475
Alternate Identifier(s):
OSTI ID: 1416406
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Optical Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 5; Journal ID: ISSN 2195-1071
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; organolead halide perovskites; bulk carrier dynamics; transient absorption; polaron formation

Citation Formats

Wang, Lili, Brawand, Nicholas P., Voros, Marton, Dahlberg, Peter D., Otto, John P., Williams, Nicholas E., Tiede, David M., Galli, Giulia, and Engel, Gregory S. Excitations Partition into Two Distinct Populations in Bulk Perovskites. United States: N. p., 2018. Web. doi:10.1002/adom.201700975.
Wang, Lili, Brawand, Nicholas P., Voros, Marton, Dahlberg, Peter D., Otto, John P., Williams, Nicholas E., Tiede, David M., Galli, Giulia, & Engel, Gregory S. Excitations Partition into Two Distinct Populations in Bulk Perovskites. United States. doi:10.1002/adom.201700975.
Wang, Lili, Brawand, Nicholas P., Voros, Marton, Dahlberg, Peter D., Otto, John P., Williams, Nicholas E., Tiede, David M., Galli, Giulia, and Engel, Gregory S. Tue . "Excitations Partition into Two Distinct Populations in Bulk Perovskites". United States. doi:10.1002/adom.201700975. https://www.osti.gov/servlets/purl/1427475.
@article{osti_1427475,
title = {Excitations Partition into Two Distinct Populations in Bulk Perovskites},
author = {Wang, Lili and Brawand, Nicholas P. and Voros, Marton and Dahlberg, Peter D. and Otto, John P. and Williams, Nicholas E. and Tiede, David M. and Galli, Giulia and Engel, Gregory S.},
abstractNote = {Organolead halide perovskites convert optical excitations to charge carriers with remarkable efficiency in optoelectronic devices. Previous research predominantly documents dynamics in perovskite thin films; however, extensive disorder in this platform may obscure the observed carrier dynamics. Here in this study, carrier dynamics in perovskite single-domain single crystals is examined by performing transient absorption spectroscopy in a transmissive geometry. Two distinct sets of carrier populations that coexist at the same radiation fluence, but display different decay dynamics, are observed: one dominated by second-order recombination and the other by third-order recombination. Based on ab initio simulations, this observation is found to be most consistent with the hypothesis that free carriers and localized carriers coexist due to polaron formation. Lastly, the calculations suggest that polarons will form in both CH3NH3PbBr3 and CH3NH3PbI3 crystals, but that they are more pronounced in CH3NH3PbBr3. Single-crystal CH3NH3PbBr3 could represent the key to understanding the impact of polarons on the transport properties of perovskite optoelectronic devices.},
doi = {10.1002/adom.201700975},
journal = {Advanced Optical Materials},
issn = {2195-1071},
number = 5,
volume = 6,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Characterization of CH3NH3PbBr3 single crystals. a, Linear absorption spectrum of CH3NH3PbBr3 single-domain single crystal. Inset: Micrograph of a polished single-domain single crystal with 500 μm scale bar. b, Upper: Experimental powder X-ray diffraction (XRD) pattern of the ground powder of several crystals. Lower: Simulated powder XRD pattern basedmore » on single crystal XRD measurement (Table S1 in the SI). c, Photoluminescence (PL) spectra of a perovskite single-domain single crystal measured in a reflective geometry with 532 nm excitation (gray) and a transmissive geometry with 535 nm excitation (black). The spectral dip at 532 nm in the reflective PL data is caused by a 532 nm notch filter.« less

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Works referenced in this record:

Rashba and Dresselhaus Effects in Hybrid Organic–Inorganic Perovskites: From Basics to Devices
journal, September 2015


Predictive Determination of Band Gaps of Inorganic Halide Perovskites
journal, October 2017

  • Wiktor, Julia; Rothlisberger, Ursula; Pasquarello, Alfredo
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 22
  • DOI: 10.1021/acs.jpclett.7b02648

Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites
journal, September 2015

  • Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9420

Preferential CH 3 NH 3 + Alignment and Octahedral Tilting Affect Charge Localization in Cubic Phase CH 3 NH 3 PbI 3
journal, April 2017

  • Kang, Byungkyun; Biswas, Koushik
  • The Journal of Physical Chemistry C, Vol. 121, Issue 15
  • DOI: 10.1021/acs.jpcc.7b01184

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

Local Polar Fluctuations in Lead Halide Perovskite Crystals
journal, March 2017


Band filling with free charge carriers in organometal halide perovskites
journal, August 2014


Long-Lived Photoinduced Polarons in Organohalide Perovskites
journal, June 2017

  • Ivanovska, Tanja; Dionigi, Chiara; Mosconi, Edoardo
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 13
  • DOI: 10.1021/acs.jpclett.7b01156

Charge-Carrier Mobilities in Metal Halide Perovskites: Fundamental Mechanisms and Limits
journal, June 2017


Temperature-Dependent Charge-Carrier Dynamics in CH 3 NH 3 PbI 3 Perovskite Thin Films
journal, September 2015

  • Milot, Rebecca L.; Eperon, Giles E.; Snaith, Henry J.
  • Advanced Functional Materials, Vol. 25, Issue 39
  • DOI: 10.1002/adfm.201502340

Top and bottom surfaces limit carrier lifetime in lead iodide perovskite films
journal, January 2017


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


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

Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination
journal, February 2014

  • Ponseca, Carlito S.; Savenije, Tom J.; Abdellah, Mohamed
  • Journal of the American Chemical Society, Vol. 136, Issue 14
  • DOI: 10.1021/ja412583t

Interface engineering of highly efficient perovskite solar cells
journal, July 2014


High-performance photovoltaic perovskite layers fabricated through intramolecular exchange
journal, May 2015


Self-consistent relativistic band structure of the CH 3 NH 3 PbI 3 perovskite
journal, July 2014


Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors
journal, April 2015

  • Zhu, Haiming; Fu, Yongping; Meng, Fei
  • Nature Materials, Vol. 14, Issue 6
  • DOI: 10.1038/nmat4271

Unravelling the mechanism of photoinduced charge transfer processes in lead iodide perovskite solar cells
journal, January 2014

  • Marchioro, Arianna; Teuscher, Joël; Friedrich, Dennis
  • Nature Photonics, Vol. 8, Issue 3
  • DOI: 10.1038/nphoton.2013.374

Electron–Rotor Interaction in Organic–Inorganic Lead Iodide Perovskites Discovered by Isotope Effects
journal, July 2016


High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization
journal, July 2015

  • Saidaminov, Makhsud I.; Abdelhady, Ahmed L.; Murali, Banavoth
  • Nature Communications, Vol. 6, Article No. 7586
  • DOI: 10.1038/ncomms8586

Bright light-emitting diodes based on organometal halide perovskite
journal, August 2014

  • Tan, Zhi-Kuang; Moghaddam, Reza Saberi; Lai, May Ling
  • Nature Nanotechnology, Vol. 9, Issue 9
  • DOI: 10.1038/nnano.2014.149

Charge Trapping in Photovoltaically Active Perovskites and Related Halogenoplumbate Compounds
journal, March 2014

  • Shkrob, Ilya A.; Marin, Timothy W.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 7
  • DOI: 10.1021/jz5004022

Screening in crystalline liquids protects energetic carriers in hybrid perovskites
journal, September 2016


Elucidating the role of disorder and free-carrier recombination kinetics in CH3NH3PbI3 perovskite films
journal, July 2015

  • La-o-vorakiat, Chan; Salim, Teddy; Kadro, Jeannette
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8903

Role of microstructure in the electron–hole interaction of hybrid lead halide perovskites
journal, August 2015

  • Grancini, Giulia; Srimath Kandada, Ajay Ram; Frost, Jarvist M.
  • Nature Photonics, Vol. 9, Issue 10
  • DOI: 10.1038/nphoton.2015.151

Hidden spin polarization in inversion-symmetric bulk crystals
journal, April 2014

  • Zhang, Xiuwen; Liu, Qihang; Luo, Jun-Wei
  • Nature Physics, Vol. 10, Issue 5
  • DOI: 10.1038/nphys2933

Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015


Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials
journal, May 2016


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


First-Principles Modeling of Mixed Halide Organometal Perovskites for Photovoltaic Applications
journal, July 2013

  • Mosconi, Edoardo; Amat, Anna; Nazeeruddin, Md. K.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 27
  • DOI: 10.1021/jp4048659

What Is Moving in Hybrid Halide Perovskite Solar Cells?
journal, February 2016


Low-temperature solution-processed wavelength-tunable perovskites for lasing
journal, March 2014

  • Xing, Guichuan; Mathews, Nripan; Lim, Swee Sien
  • Nature Materials, Vol. 13, Issue 5
  • DOI: 10.1038/nmat3911

High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors
journal, March 2014

  • Deschler, Felix; Price, Michael; Pathak, Sandeep
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
  • DOI: 10.1021/jz5005285

Cation Dynamics in Mixed-Cation (MA) x (FA) 1– x PbI 3 Hybrid Perovskites from Solid-State NMR
journal, July 2017

  • Kubicki, Dominik J.; Prochowicz, Daniel; Hofstetter, Albert
  • Journal of the American Chemical Society, Vol. 139, Issue 29
  • DOI: 10.1021/jacs.7b04930

Exciton and Free Charge Dynamics of Methylammonium Lead Iodide Perovskites Are Different in the Tetragonal and Orthorhombic Phases
journal, August 2015

  • Wang, He; Whittaker-Brooks, Luisa; Fleming, Graham R.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 34
  • DOI: 10.1021/acs.jpcc.5b04403

Discerning the Surface and Bulk Recombination Kinetics of Organic-Inorganic Halide Perovskite Single Crystals
journal, May 2016

  • Wu, Bo; Nguyen, Huy Tiep; Ku, Zhiliang
  • Advanced Energy Materials, Vol. 6, Issue 14
  • DOI: 10.1002/aenm.201600551

Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%
journal, September 2016


Comparative study on the excitons in lead-halide-based perovskite-type crystals CH3NH3PbBr3 CH3NH3PbI3
journal, September 2003

  • Tanaka, Kenichiro; Takahashi, Takayuki; Ban, Takuma
  • Solid State Communications, Vol. 127, Issue 9-10, p. 619-623
  • DOI: 10.1016/S0038-1098(03)00566-0

Enhancing photoluminescence yields in lead halide perovskites by photon recycling and light out-coupling
journal, December 2016

  • Richter, Johannes M.; Abdi-Jalebi, Mojtaba; Sadhanala, Aditya
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13941

Impact of microstructure on local carrier lifetime in perovskite solar cells
journal, April 2015


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


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

Enhanced Photoluminescence and Solar Cell Performance via Lewis Base Passivation of Organic–Inorganic Lead Halide Perovskites
journal, September 2014

  • Noel, Nakita K.; Abate, Antonio; Stranks, Samuel D.
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn5036476

The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells
journal, May 2015

  • Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8124

Low surface recombination velocity in solution-grown CH3NH3PbBr3 perovskite single crystal
journal, August 2015

  • Yang, Ye; Yan, Yong; Yang, Mengjin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8961

Inverting Transient Absorption Data to Determine Transfer Rates in Quantum Dot–TiO 2 Heterostructures
journal, March 2015

  • Senty, Tess R.; Cushing, Scott K.; Wang, Congjun
  • The Journal of Physical Chemistry C, Vol. 119, Issue 11
  • DOI: 10.1021/jp512500g

Conformal Organohalide Perovskites Enable Lasing on Spherical Resonators
journal, October 2014

  • Sutherland, Brandon R.; Hoogland, Sjoerd; Adachi, Michael M.
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn504856g

Comparison of Recombination Dynamics in CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3 Perovskite Films: Influence of Exciton Binding Energy
journal, November 2015


Organic Cations Might Not Be Essential to the Remarkable Properties of Band Edge Carriers in Lead Halide Perovskites
journal, October 2016


Implementation and Validation of Fully Relativistic GW Calculations: Spin–Orbit Coupling in Molecules, Nanocrystals, and Solids
journal, July 2016

  • Scherpelz, Peter; Govoni, Marco; Hamada, Ikutaro
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00114

Polaronic exciton binding energy in iodide and bromide organic-inorganic lead halide perovskites
journal, December 2015

  • Soufiani, Arman Mahboubi; Huang, Fuzhi; Reece, Peter
  • Applied Physics Letters, Vol. 107, Issue 23
  • DOI: 10.1063/1.4936418

Dynamic Optical Properties of CH 3 NH 3 PbI 3 Single Crystals As Revealed by One- and Two-Photon Excited Photoluminescence Measurements
journal, August 2015

  • Yamada, Yasuhiro; Yamada, Takumi; Phuong, Le Quang
  • Journal of the American Chemical Society, Vol. 137, Issue 33
  • DOI: 10.1021/jacs.5b04503

Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells
journal, June 2014

  • Juarez-Perez, Emilio J.; Sanchez, Rafael S.; Badia, Laura
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz5011169

Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites
journal, August 2015

  • Bakulin, Artem A.; Selig, Oleg; Bakker, Huib J.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
  • DOI: 10.1021/acs.jpclett.5b01555

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.