Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3

doi:https://doi.org/10.1039/c7cp04417h

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.

Publication Date:: 2017-01-01

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.

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                    None, None. Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3.  United States.  https://doi.org/10.1039/c7cp04417h

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                    None, None. Sun .  
        "Shallow trapping vs. deep polarons in a hybrid lead halide perovskite, CH3NH3PbI3".  United States.  https://doi.org/10.1039/c7cp04417h.

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@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},

  url          = {https://www.osti.gov/biblio/1492431},
  journal      = {Physical Chemistry Chemical Physics. PCCP (Print)},

  issn         = {1463-9076},

  number       = 40,

  volume       = 19,

  place        = {United States},

  year         = {2017},

  month        = {1}

}

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

Abstract

Citation Formats

Intriguing Optoelectronic Properties of Metal Halide Perovskites journal, June 2016

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

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Generalized Gradient Approximation Made Simple journal, October 1996

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

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

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

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

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

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

Atomic structure of metal-halide perovskites from first principles: The chicken-and-egg paradox of the organic-inorganic interaction journal, July 2016

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

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

Electro-optics of perovskite solar cells journal, December 2014

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

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

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

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

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

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

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

Energy transport and scintillation of cerium-doped elpasolite Cs 2 LiYCl 6 : Hybrid density functional calculations journal, July 2012

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

Inorganic caesium lead iodide perovskite solar cells journal, January 2015

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

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

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

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

Special points for Brillouin-zone integrations journal, June 1976

Nanoscale Charge Localization Induced by Random Orientations of Organic Molecules in Hybrid Perovskite CH 3 NH 3 PbI 3 journal, December 2014

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Intriguing Optoelectronic Properties of Metal Halide Perovskites
journal, June 2016

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

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

Generalized Gradient Approximation Made Simple
journal, October 1996

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

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

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

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

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

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

Atomic structure of metal-halide perovskites from first principles: The chicken-and-egg paradox of the organic-inorganic interaction
journal, July 2016

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

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

Electro-optics of perovskite solar cells
journal, December 2014

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

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

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

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

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

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

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

Energy transport and scintillation of cerium-doped elpasolite Cs $_{2}$ LiYCl $_{6}$ : Hybrid density functional calculations
journal, July 2012

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

Inorganic caesium lead iodide perovskite solar cells
journal, January 2015

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

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

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

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

Special points for Brillouin-zone integrations
journal, June 1976

Nanoscale Charge Localization Induced by Random Orientations of Organic Molecules in Hybrid Perovskite CH ₃ NH ₃ PbI ₃
journal, December 2014

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

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

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

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

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

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

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

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

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

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

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

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

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

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