skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The effects of electronic impurities and electron-hole recombination dynamics on large-grain organic-inorganic perovskite photovoltaic efficiencies

Abstract

Hybrid organic-inorganic perovskites have attracted considerable attention after promising developments in energy harvesting and other optoelectronic applications. However, further optimization will require a deeper understanding of the intrinsic photophysics of materials with relevant structural characteristics. Here, the dynamics of photoexcited charge carriers in large-area grain organic-inorganic perovskite thin films is investigated via confocal time-resolved photoluminescence spectroscopy. It is found that the bimolecular recombination of free charges is the dominant decay mechanism at excitation densities relevant for photovoltaic applications. Bimolecular coefficients are found to be on the order of 10–9 cm3 s–1, comparable to typical direct-gap semiconductors, yet significantly smaller than theoretically expected. It is also demonstrated that there is no degradation in carrier transport in these thin films due to electronic impurities. Here, suppressed electron–hole recombination and transport that is not limited by deep level defects provide a microscopic model for the superior performance of large-area grain hybrid perovskites for photovoltaic applications.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. de Bordeaux, Talence (France); Institut d'Optique & CNRS, Talence (France)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1364557
Report Number(s):
LA-UR-17-23970
Journal ID: ISSN 1616-301X
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 26; Journal Issue: 24; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; material science; perovskites; electronic impurities; carrier dynamics; organic-inorganic perovskite; photovoltaic

Citation Formats

Blancon, Jean-Christophe Robert, Nie, Wanyi, Neukirch, Amanda J., Gupta, Gautam, Tretiak, Sergei, Cognet, Laurent, Mohite, Aditya, and Crochet, Jared John. The effects of electronic impurities and electron-hole recombination dynamics on large-grain organic-inorganic perovskite photovoltaic efficiencies. United States: N. p., 2016. Web. doi:10.1002/adfm.201505324.
Blancon, Jean-Christophe Robert, Nie, Wanyi, Neukirch, Amanda J., Gupta, Gautam, Tretiak, Sergei, Cognet, Laurent, Mohite, Aditya, & Crochet, Jared John. The effects of electronic impurities and electron-hole recombination dynamics on large-grain organic-inorganic perovskite photovoltaic efficiencies. United States. doi:10.1002/adfm.201505324.
Blancon, Jean-Christophe Robert, Nie, Wanyi, Neukirch, Amanda J., Gupta, Gautam, Tretiak, Sergei, Cognet, Laurent, Mohite, Aditya, and Crochet, Jared John. Wed . "The effects of electronic impurities and electron-hole recombination dynamics on large-grain organic-inorganic perovskite photovoltaic efficiencies". United States. doi:10.1002/adfm.201505324. https://www.osti.gov/servlets/purl/1364557.
@article{osti_1364557,
title = {The effects of electronic impurities and electron-hole recombination dynamics on large-grain organic-inorganic perovskite photovoltaic efficiencies},
author = {Blancon, Jean-Christophe Robert and Nie, Wanyi and Neukirch, Amanda J. and Gupta, Gautam and Tretiak, Sergei and Cognet, Laurent and Mohite, Aditya and Crochet, Jared John},
abstractNote = {Hybrid organic-inorganic perovskites have attracted considerable attention after promising developments in energy harvesting and other optoelectronic applications. However, further optimization will require a deeper understanding of the intrinsic photophysics of materials with relevant structural characteristics. Here, the dynamics of photoexcited charge carriers in large-area grain organic-inorganic perovskite thin films is investigated via confocal time-resolved photoluminescence spectroscopy. It is found that the bimolecular recombination of free charges is the dominant decay mechanism at excitation densities relevant for photovoltaic applications. Bimolecular coefficients are found to be on the order of 10–9 cm3 s–1, comparable to typical direct-gap semiconductors, yet significantly smaller than theoretically expected. It is also demonstrated that there is no degradation in carrier transport in these thin films due to electronic impurities. Here, suppressed electron–hole recombination and transport that is not limited by deep level defects provide a microscopic model for the superior performance of large-area grain hybrid perovskites for photovoltaic applications.},
doi = {10.1002/adfm.201505324},
journal = {Advanced Functional Materials},
number = 24,
volume = 26,
place = {United States},
year = {2016},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Metal-halide perovskites for photovoltaic and light-emitting devices
journal, May 2015

  • Stranks, Samuel D.; Snaith, Henry J.
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.90

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


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

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

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

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

Role of the crystallization substrate on the photoluminescence properties of organo-lead mixed halides perovskites
journal, August 2014

  • De Bastiani, Michele; D’Innocenzo, Valerio; Stranks, Samuel D.
  • APL Materials, Vol. 2, Issue 8
  • DOI: 10.1063/1.4889845

Tuning the Light Emission Properties by Band Gap Engineering in Hybrid Lead Halide Perovskite
journal, December 2014

  • D’Innocenzo, Valerio; Srimath Kandada, Ajay Ram; De Bastiani, Michele
  • Journal of the American Chemical Society, Vol. 136, Issue 51
  • DOI: 10.1021/ja511198f

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


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


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

Homogeneous Emission Line Broadening in the Organo Lead Halide Perovskite CH 3 NH 3 PbI 3– x Cl x
journal, March 2014

  • Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
  • DOI: 10.1021/jz500434p

Photocarrier Recombination Dynamics in Perovskite CH 3 NH 3 PbI 3 for Solar Cell Applications
journal, August 2014

  • Yamada, Yasuhiro; Nakamura, Toru; Endo, Masaru
  • Journal of the American Chemical Society, Vol. 136, Issue 33
  • DOI: 10.1021/ja506624n

Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free Charge, and Subgap States
journal, September 2014


Advancements in perovskite solar cells: photophysics behind the photovoltaics
journal, January 2014

  • Sum, Tze Chien; Mathews, Nripan
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE00673A

Multifaceted Excited State of CH 3 NH 3 PbI 3 . Charge Separation, Recombination, and Trapping
journal, May 2015

  • Christians, Jeffrey A.; Manser, Joseph S.; Kamat, Prashant V.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 11
  • DOI: 10.1021/acs.jpclett.5b00594

Correlated electron–hole plasma in organometal perovskites
journal, September 2014

  • Saba, Michele; Cadelano, Michele; Marongiu, Daniela
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6049

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

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


Electro-optics of perovskite solar cells
journal, December 2014

  • Lin, Qianqian; Armin, Ardalan; Nagiri, Ravi Chandra Raju
  • Nature Photonics, Vol. 9, Issue 2
  • DOI: 10.1038/nphoton.2014.284

Optical Description of Mesostructured Organic–Inorganic Halide Perovskite Solar Cells
journal, December 2014

  • Anaya, Miguel; Lozano, Gabriel; Calvo, Mauricio E.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
  • DOI: 10.1021/jz502351s

Complex Refractive Index Spectra of CH 3 NH 3 PbI 3 Perovskite Thin Films Determined by Spectroscopic Ellipsometry and Spectrophotometry
journal, December 2014

  • Löper, Philipp; Stuckelberger, Michael; Niesen, Bjoern
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
  • DOI: 10.1021/jz502471h

Spontaneous and Stimulated Recombination Radiation in Semiconductors
journal, January 1964


Inhibited Spontaneous Emission in Solid-State Physics and Electronics
journal, May 1987


Chlorine Doping Reduces Electron–Hole Recombination in Lead Iodide Perovskites: Time-Domain Ab Initio Analysis
journal, October 2015


Room temperature optical properties of organic–inorganic lead halide perovskites
journal, June 2015


The rate of radiative recombination in the nitride semiconductors and alloys
journal, September 1999

  • Dmitriev, Alexey; Oruzheinikov, Alexander
  • Journal of Applied Physics, Vol. 86, Issue 6
  • DOI: 10.1063/1.371196

Band-to-Band Radiative Recombination in Groups IV, VI, and III-V Semiconductors (I)
journal, January 1967


Self‐absorption effects on the radiative lifetime in GaAs‐GaAlAs double heterostructures
journal, February 1977


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

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

Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites
journal, June 2015

  • Miyata, Atsuhiko; Mitioglu, Anatolie; Plochocka, Paulina
  • Nature Physics, Vol. 11, Issue 7
  • DOI: 10.1038/nphys3357

Analysis of Multivalley and Multibandgap Absorption and Enhancement of Free Carriers Related to Exciton Screening in Hybrid Perovskites
journal, May 2014

  • Even, Jacky; Pedesseau, Laurent; Katan, Claudine
  • The Journal of Physical Chemistry C, Vol. 118, Issue 22
  • DOI: 10.1021/jp503337a

The Role of Intrinsic Defects in Methylammonium Lead Iodide Perovskite
journal, March 2014

  • Kim, Jongseob; Lee, Sung-Hoon; Lee, Jung Hoon
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
  • DOI: 10.1021/jz500370k

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

Charge Carriers in Planar and Meso-Structured Organic–Inorganic Perovskites: Mobilities, Lifetimes, and Concentrations of Trap States
journal, July 2015

  • Hutter, Eline M.; Eperon, Giles E.; Stranks, Samuel D.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 15
  • DOI: 10.1021/acs.jpclett.5b01361

Pedestrian Guide to Symmetry Properties of the Reference Cubic Structure of 3D All-Inorganic and Hybrid Perovskites
journal, June 2015


Solid-State Physics Perspective on Hybrid Perovskite Semiconductors
journal, April 2015

  • Even, Jacky; Pedesseau, Laurent; Katan, Claudine
  • The Journal of Physical Chemistry C, Vol. 119, Issue 19
  • DOI: 10.1021/acs.jpcc.5b00695

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

Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications
journal, March 2014

  • Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep04467

GW Band Structures and Carrier Effective Masses of CH 3 NH 3 PbI 3 and Hypothetical Perovskites of the Type APbI 3 : A = NH 4 , PH 4 , AsH 4 , and SbH 4
journal, October 2015

  • Filip, Marina R.; Verdi, Carla; Giustino, Feliciano
  • The Journal of Physical Chemistry C, Vol. 119, Issue 45
  • DOI: 10.1021/acs.jpcc.5b07891

Trap States in Lead Iodide Perovskites
journal, January 2015

  • Wu, Xiaoxi; Trinh, M. Tuan; Niesner, Daniel
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja512833n

Light intensity dependence of open-circuit voltage of polymer:fullerene solar cells
journal, March 2005

  • Koster, L. J. A.; Mihailetchi, V. D.; Ramaker, R.
  • Applied Physics Letters, Vol. 86, Issue 12
  • DOI: 10.1063/1.1889240

Optical properties and limiting photocurrent of thin-film perovskite solar cells
journal, January 2015

  • Ball, James M.; Stranks, Samuel D.; Hörantner, Maximilian T.
  • Energy & Environmental Science, Vol. 8, Issue 2
  • DOI: 10.1039/C4EE03224A

Perovskite Solar Cells with Near 100% Internal Quantum Efficiency Based on Large Single Crystalline Grains and Vertical Bulk Heterojunctions
journal, July 2015

  • Yang, Bin; Dyck, Ondrej; Poplawsky, Jonathan
  • Journal of the American Chemical Society, Vol. 137, Issue 29
  • DOI: 10.1021/jacs.5b03144

Dielectric study of CH3NH3PbX3 (X = Cl, Br, I)
journal, July 1992

  • Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi
  • Journal of Physics and Chemistry of Solids, Vol. 53, Issue 7
  • DOI: 10.1016/0022-3697(92)90121-S

Lead iodide perovskite light-emitting field-effect transistor
journal, June 2015

  • Chin, Xin Yu; Cortecchia, Daniele; Yin, Jun
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8383

Ambipolar solution-processed hybrid perovskite phototransistors
journal, September 2015

  • Li, Feng; Ma, Chun; Wang, Hong
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9238

Perovskites for Solar Thermoelectric Applications: A First Principle Study of CH 3 NH 3 AI 3 (A = Pb and Sn)
journal, August 2014

  • He, Yuping; Galli, Giulia
  • Chemistry of Materials, Vol. 26, Issue 18
  • DOI: 10.1021/cm5026766

Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells
journal, August 2014

  • Frost, Jarvist M.; Butler, Keith T.; Walsh, Aron
  • APL Materials, Vol. 2, Issue 8
  • DOI: 10.1063/1.4890246

Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons
journal, November 2015


Are Mobilities in Hybrid Organic–Inorganic Halide Perovskites Actually “High”?
journal, November 2015

  • Brenner, Thomas M.; Egger, David A.; Rappe, Andrew M.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
  • DOI: 10.1021/acs.jpclett.5b02390

First-Principles Calculation of the Bulk Photovoltaic Effect in CH 3 NH 3 PbI 3 and CH 3 NH 3 PbI 3– x Cl x
journal, December 2014

  • Zheng, Fan; Takenaka, Hiroyuki; Wang, Fenggong
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
  • DOI: 10.1021/jz502109e

Revealing the role of organic cations in hybrid halide perovskite CH3NH3PbI3
journal, April 2015

  • Motta, Carlo; El-Mellouhi, Fedwa; Kais, Sabre
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8026

Erratum: Corrigendum: The mitochondrial uniporter controls fight or flight heart rate increases
journal, June 2015

  • Wu, Yuejin; Rasmussen, Tyler P.; Koval, Olha M.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8241

The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors
journal, February 2012


Optimizing Composition and Morphology for Large-Grain Perovskite Solar Cells via Chemical Control
journal, August 2015


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

Bimolecular Recombination Coefficient as a Sensitive Testing Parameter for Low-Mobility Solar-Cell Materials
journal, May 2005


A Physics-Based Analytical Model for Perovskite Solar Cells
journal, September 2015


Trap-Assisted Non-Radiative Recombination in Organic-Inorganic Perovskite Solar Cells
journal, February 2015

  • Wetzelaer, Gert-Jan A. H.; Scheepers, Max; Sempere, Araceli Miquel
  • Advanced Materials, Vol. 27, Issue 11
  • DOI: 10.1002/adma.201405372

Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
journal, April 2014

  • Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500390f

    Works referencing / citing this record:

    Single-crystalline layered metal-halide perovskite nanowires for ultrasensitive photodetectors
    journal, July 2018


    Single-crystalline layered metal-halide perovskite nanowires for ultrasensitive photodetectors
    journal, July 2018