Temperature-driven anion migration in gradient halide perovskites

Scheidt, Rebecca A.; Kamat, Prashant V.

doi:10.1063/1.5120270

Title: Temperature-driven anion migration in gradient halide perovskites

Abstract

Cesium lead halide perovskite films with a systematic change in the halide composition of CsPbBr_3-xI_x, in which iodide concentration varies from x = 0 to x = 3, provide a built-in gradient band structure. Such a gradient structure allows for the integrated capture of visible photons and directs them to the energetically low-lying iodide rich region. Annealing gradient halide perovskite films at temperatures ranging from 50 °C to 90 °C causes the films to homogenize into mixed halide perovskites. The movement of halide ions during the homogenization process was elucidated using UV-Visible absorbance and X-ray photoelectron spectroscopy. The halide ion movement in CsPbBr_3-xI_x gradient films was tracked via absorbance changes in the visible region of the spectrum that enabled us to measure the temperature dependent rate constant and energy of activation (74.5 kJ/mol) of halide ion homogenization. Excited state processes of both gradient and homogenized films probed through transient absorption spectroscopy showed the direct flow of charge carriers and charge recombination in both films.

Authors:

Scheidt, Rebecca A. ^[1];

^[1]

Univ. of Notre Dame, IN (United States). Radiation Research Lab. Dept. of Chemistry and Biochemistry

Publication Date:: Tue Oct 01 00:00:00 EDT 2019

Research Org.:: University of Notre Dame, IN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1799643

Alternate Identifier(s):: OSTI ID: 1567923

Grant/Contract Number:: FC02-04ER15533

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 151; Journal Issue: 13; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Scheidt, Rebecca A., and Kamat, Prashant V. Temperature-driven anion migration in gradient halide perovskites.  United States: N. p., 2019. 
Web.  doi:10.1063/1.5120270.

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                    Scheidt, Rebecca A., & Kamat, Prashant V. Temperature-driven anion migration in gradient halide perovskites.  United States.  https://doi.org/10.1063/1.5120270

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                    Scheidt, Rebecca A., and Kamat, Prashant V. Tue .  
"Temperature-driven anion migration in gradient halide perovskites".  United States.  https://doi.org/10.1063/1.5120270.  https://www.osti.gov/servlets/purl/1799643.

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@article{osti_1799643,

  title        = {Temperature-driven anion migration in gradient halide perovskites},

  author       = {Scheidt, Rebecca A. and Kamat, Prashant V.},

  abstractNote = {Cesium lead halide perovskite films with a systematic change in the halide composition of CsPbBr3-xIx, in which iodide concentration varies from x = 0 to x = 3, provide a built-in gradient band structure. Such a gradient structure allows for the integrated capture of visible photons and directs them to the energetically low-lying iodide rich region. Annealing gradient halide perovskite films at temperatures ranging from 50 °C to 90 °C causes the films to homogenize into mixed halide perovskites. The movement of halide ions during the homogenization process was elucidated using UV-Visible absorbance and X-ray photoelectron spectroscopy. The halide ion movement in CsPbBr3-xIx gradient films was tracked via absorbance changes in the visible region of the spectrum that enabled us to measure the temperature dependent rate constant and energy of activation (74.5 kJ/mol) of halide ion homogenization. Excited state processes of both gradient and homogenized films probed through transient absorption spectroscopy showed the direct flow of charge carriers and charge recombination in both films.},

  doi          = {10.1063/1.5120270},

  journal      = {Journal of Chemical Physics},

  number       = 13,

  volume       = 151,

  place        = {United States},

  year         = {Tue Oct 01 00:00:00 EDT 2019},

  month        = {Tue Oct 01 00:00:00 EDT 2019}

}

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Title: Temperature-driven anion migration in gradient halide perovskites

Abstract

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Modulation of Charge Recombination in CsPbBr ₃ Perovskite Films with Electrochemical Bias
journal, November 2017

Electronic band structure, phonons, and exciton binding energies of halide perovskites CsSnCl $_{3}$ , CsSnBr $_{3}$ , and CsSnI $_{3}$
journal, October 2013

Quantification of Ionic Diffusion in Lead Halide Perovskite Single Crystals
journal, May 2018

Band Edge Energies and Excitonic Transition Probabilities of Colloidal CsPbX ₃ (X = Cl, Br, I) Perovskite Nanocrystals
journal, September 2016

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics
journal, January 2015

Shift Happens . How Halide Ion Defects Influence Photoinduced Segregation in Mixed Halide Perovskites
journal, June 2017

A Victim of Halide Ion Segregation. How Light Soaking Affects Solar Cell Performance of Mixed Halide Lead Perovskites
journal, July 2017

CsPbBr ₃ Solar Cells: Controlled Film Growth through Layer-by-Layer Quantum Dot Deposition
journal, November 2017

The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers
journal, May 2015

Transformation of Sintered CsPbBr ₃ Nanocrystals to Cubic CsPbI ₃ and Gradient CsPbBr _x I _{3– x} through Halide Exchange
journal, June 2016

Perspective: Theory and simulation of hybrid halide perovskites
journal, June 2017

Relationships between Lead Halide Perovskite Thin-Film Fabrication, Morphology, and Performance in Solar Cells
journal, November 2015

Impact of Surfaces on Photoinduced Halide Segregation in Mixed-Halide Perovskites
journal, October 2018

Light-Induced Phase Segregation in Halide-Perovskite Absorbers
journal, November 2016

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

Controlling the Phase Segregation in Mixed Halide Perovskites through Nanocrystal Size
journal, November 2018

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

Taking Control of Ion Transport in Halide Perovskite Solar Cells
text, January 2018

To Exchange or Not to Exchange . Suppressing Anion Exchange in Cesium Lead Halide Perovskites with PbSO ₄ –Oleate Capping
journal, March 2018

Bidirectional Halide Ion Exchange in Paired Lead Halide Perovskite Films with Thermal Activation
journal, July 2019

Intrinsic anion diffusivity in lead halide perovskites is facilitated by a soft lattice
journal, November 2018

Transforming Hybrid Organic Inorganic Perovskites by Rapid Halide Exchange
journal, March 2015

Perspective: Theory and simulation of hybrid halide perovskites
text, January 2017

Reversible Halide Exchange Reaction of Organometal Trihalide Perovskite Colloidal Nanocrystals for Full-Range Band Gap Tuning
journal, July 2015

First principle study of the structural and optoelectronic properties of cubic perovskites CsPbM3 (M=Cl, Br, I)
journal, September 2011

Recent insights for achieving mixed halide perovskites without halide segregation
journal, October 2018

Understanding Degradation Mechanisms and Improving Stability of Perovskite Photovoltaics
journal, November 2018

Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions
journal, August 2015

First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions
journal, April 2018

Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX ₃ , X = Cl, Br, I)
journal, July 2015

Cesium Enhances Long-Term Stability of Lead Bromide Perovskite-Based Solar Cells
journal, December 2015

Halide Perovskite Photovoltaics: Background, Status, and Future Prospects
journal, March 2019

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites
journal, August 2017

Making and Breaking of Lead Halide Perovskites
journal, January 2016

Visualization and Studies of Ion-Diffusion Kinetics in Cesium Lead Bromide Perovskite Nanowires
journal, February 2018

Light-Induced Anion Phase Segregation in Mixed Halide Perovskites
journal, November 2017

Tracking Transformative Transitions: From CsPbBr ₃ Nanocrystals to Bulk Perovskite Films
journal, March 2019

Study on the stability of CH ₃ NH ₃ PbI ₃ films and the effect of post-modification by aluminum oxide in all-solid-state hybrid solar cells
journal, January 2014

Phase Stability and Diffusion in Lateral Heterostructures of Methyl Ammonium Lead Halide Perovskites
journal, June 2019

Lead Halide Perovskites: Challenges and Opportunities in Advanced Synthesis and Spectroscopy
journal, March 2017

Taking Control of Ion Transport in Halide Perovskite Solar Cells
journal, July 2018

Tracking Iodide and Bromide Ion Segregation in Mixed Halide Lead Perovskites during Photoirradiation
journal, June 2016

Surface- vs Diffusion-Limited Mechanisms of Anion Exchange in CsPbBr ₃ Nanocrystal Cubes Revealed through Kinetic Studies
journal, September 2016

Nanocrystals of Cesium Lead Halide Perovskites (CsPbX ₃ , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015