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

Title: Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH 3NH 3PbI 3

Abstract

There has been considerable speculation over the nature of charge carriers in organic–inorganic hybrid perovskites, i.e., whether they are free and band-like, or they are prone to self-trapping via short range deformation potentials. Unusually long minority-carrier diffusion lengths and moderate-to-low mobilities, together with relatively few deep defects add to their intrigue. Here we implement density functional methods to investigate the room-temperature, tetragonal phase of CH 3NH 3PbI 3. We compare charge localization behavior at shallow levels and associated lattice relaxation versus those at deep polaronic states. The shallow level originates from screened Coulomb interaction between the perturbed host and an excited electron or hole. The host lattice has a tendency towards forming these shallow traps where the electron or hole is localized not too far from the band edge. In contrast, there is a considerable potential barrier that must be overcome in order to initiate polaronic hole trapping. The formation of a hole polaron (I 2 - center) involves strong lattice relaxation, including large off-center displacement of the organic cation, CH 3NH 3 +. This type of deep polaron is energetically unfavorable, and active shallow traps are expected to shape the carrier dynamics in this material.

Authors:
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1492431
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 19; Journal Issue: 40; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

None, None. Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3. United States: N. p., 2017. Web. doi:10.1039/c7cp04417h.
None, None. Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3. United States. doi:10.1039/c7cp04417h.
None, None. Sun . "Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3". United States. doi:10.1039/c7cp04417h.
@article{osti_1492431,
title = {Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3},
author = {None, None},
abstractNote = {There has been considerable speculation over the nature of charge carriers in organic–inorganic hybrid perovskites, i.e., whether they are free and band-like, or they are prone to self-trapping via short range deformation potentials. Unusually long minority-carrier diffusion lengths and moderate-to-low mobilities, together with relatively few deep defects add to their intrigue. Here we implement density functional methods to investigate the room-temperature, tetragonal phase of CH3NH3PbI3. We compare charge localization behavior at shallow levels and associated lattice relaxation versus those at deep polaronic states. The shallow level originates from screened Coulomb interaction between the perturbed host and an excited electron or hole. The host lattice has a tendency towards forming these shallow traps where the electron or hole is localized not too far from the band edge. In contrast, there is a considerable potential barrier that must be overcome in order to initiate polaronic hole trapping. The formation of a hole polaron (I2- center) involves strong lattice relaxation, including large off-center displacement of the organic cation, CH3NH3+. This type of deep polaron is energetically unfavorable, and active shallow traps are expected to shape the carrier dynamics in this material.},
doi = {10.1039/c7cp04417h},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 40,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

Works referenced in this record:

Intriguing Optoelectronic Properties of Metal Halide Perovskites
journal, June 2016


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

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

Formation, stability, and mobility of self-trapped excitations in NaI and NaI 1 x Tl x from first principles
journal, March 2013


DX-like centers in NaI:Tl upon aliovalent codoping
journal, December 2014

  • Adhikari, Rajendra; Li, Qi; Williams, Richard T.
  • Journal of Applied Physics, Vol. 116, Issue 22
  • DOI: 10.1063/1.4903766

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


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

Projector augmented-wave method
journal, December 1994


Room-temperature dynamic correlation between methylammonium molecules in lead-iodine based perovskites: An ab initio molecular dynamics perspective
journal, December 2016


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

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

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

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

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics
journal, January 2015

  • Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 14
  • DOI: 10.1039/C5CP00599J

Hybrid Organic–Inorganic Perovskites on the Move
journal, February 2016


Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite
journal, October 2016


Structural and electronic properties of organo-halide lead perovskites: a combined IR-spectroscopy and ab initio molecular dynamics investigation
journal, January 2014

  • Mosconi, Edoardo; Quarti, Claudio; Ivanovska, Tanja
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 30
  • DOI: 10.1039/C4CP00569D

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

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

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

High Defect Tolerance in Lead Halide Perovskite CsPbBr 3
journal, January 2017


Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs
journal, December 2008


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


Interplay of Orientational Order and Electronic Structure in Methylammonium Lead Iodide: Implications for Solar Cell Operation
journal, November 2014

  • Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo
  • Chemistry of Materials, Vol. 26, Issue 22
  • DOI: 10.1021/cm5032046

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

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

How Important Is the Organic Part of Lead Halide Perovskite Photovoltaic Cells? Efficient CsPbBr 3 Cells
journal, June 2015

  • Kulbak, Michael; Cahen, David; Hodes, Gary
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 13
  • DOI: 10.1021/acs.jpclett.5b00968

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


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


Suppression of nonradiative recombination in ionic insulators by defects: Role of fast electron trapping in Tl-doped CsI
journal, May 2013


Phonon–Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites
journal, December 2015

  • Karakus, Melike; Jensen, Søren A.; D’Angelo, Francesco
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 24
  • DOI: 10.1021/acs.jpclett.5b02485

Inorganic caesium lead iodide perovskite solar cells
journal, January 2015

  • Eperon, Giles E.; Paternò, Giuseppe M.; Sutton, Rebecca J.
  • Journal of Materials Chemistry A, Vol. 3, Issue 39
  • DOI: 10.1039/C5TA06398A

Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements
journal, August 2016


Energy Landscape of Molecular Motion in Cubic Methylammonium Lead Iodide from First-Principles
journal, June 2016

  • Bechtel, Jonathon S.; Seshadri, Ram; Van der Ven, Anton
  • The Journal of Physical Chemistry C, Vol. 120, Issue 23
  • DOI: 10.1021/acs.jpcc.6b03570

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

Improved Understanding of the Electronic and Energetic Landscapes of Perovskite Solar Cells: High Local Charge Carrier Mobility, Reduced Recombination, and Extremely Shallow Traps
journal, September 2014

  • Oga, Hikaru; Saeki, Akinori; Ogomi, Yuhei
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja506936f

Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance
journal, March 2014

  • De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 6
  • DOI: 10.1021/jz500279b

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Excitons versus free charges in organo-lead tri-halide perovskites
journal, April 2014

  • D’Innocenzo, Valerio; Grancini, Giulia; Alcocer, Marcelo J. P.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4586

Dual nature of the excited state in organic–inorganic lead halide perovskites
journal, January 2015

  • Stamplecoskie, Kevin G.; Manser, Joseph S.; Kamat, Prashant V.
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE02988G

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


First-principles calculations for point defects in solids
journal, March 2014

  • Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann
  • Reviews of Modern Physics, Vol. 86, Issue 1
  • DOI: 10.1103/RevModPhys.86.253

Anion vacancies as a source of persistent photoconductivity in II-VI and chalcopyrite semiconductors
journal, July 2005


Role of hydrogen-bonding and its interplay with octahedral tilting in CH 3 NH 3 PbI 3
journal, January 2015

  • Lee, Jung-Hoon; Bristowe, Nicholas C.; Bristowe, Paul D.
  • Chemical Communications, Vol. 51, Issue 29
  • DOI: 10.1039/C5CC00979K

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


Cesium Lead Halide Perovskites with Improved Stability for Tandem Solar Cells
journal, February 2016

  • Beal, Rachel E.; Slotcavage, Daniel J.; Leijtens, Tomas
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
  • DOI: 10.1021/acs.jpclett.6b00002

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

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

First-principles theory of nonradiative carrier capture via multiphonon emission
journal, August 2014


Experimental Evidence of Localized Shallow States in Orthorhombic Phase of CH 3 NH 3 PbI 3 Perovskite Thin Films Revealed by Photocurrent Beat Spectroscopy
journal, January 2016

  • Tahara, Hirokazu; Endo, Masaru; Wakamiya, Atsushi
  • The Journal of Physical Chemistry C, Vol. 120, Issue 10
  • DOI: 10.1021/acs.jpcc.6b01283

Carrier Self-trapping and Luminescence in Intrinsically Activated Scintillator: Cesium Hafnium Chloride (Cs 2 HfCl 6 )
journal, May 2016


Detection of gamma photons using solution-grown single crystals of hybrid lead halide perovskites
journal, July 2016

  • Yakunin, Sergii; Dirin, Dmitry N.; Shynkarenko, Yevhen
  • Nature Photonics, Vol. 10, Issue 9
  • DOI: 10.1038/nphoton.2016.139

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


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

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

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

Efficient carrier transport in halide perovskites: theoretical perspectives
journal, January 2014


Ferroelectricity of CH 3 NH 3 PbI 3 Perovskite
journal, March 2015


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