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

Title: Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies

Abstract

Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures. Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [3];  [1];  [1];  [1];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [4]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Northern Illinois Univ., DeKalb, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division
OSTI Identifier:
1402074
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 2; Journal Issue: 10; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Guo, Peijun, Xia, Yi, Gong, Jue, Stoumpos, Constantinos C., McCall, Kyle M., Alexander, Grant C. B., Ma, Zhiyuan, Zhou, Hua, Gosztola, David J., Ketterson, John B., Kanatzidis, Mercouri G., Xu, Tao, Chan, Maria K. Y., and Schaller, Richard D. Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.7b00790.
Guo, Peijun, Xia, Yi, Gong, Jue, Stoumpos, Constantinos C., McCall, Kyle M., Alexander, Grant C. B., Ma, Zhiyuan, Zhou, Hua, Gosztola, David J., Ketterson, John B., Kanatzidis, Mercouri G., Xu, Tao, Chan, Maria K. Y., & Schaller, Richard D. Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies. United States. https://doi.org/10.1021/acsenergylett.7b00790
Guo, Peijun, Xia, Yi, Gong, Jue, Stoumpos, Constantinos C., McCall, Kyle M., Alexander, Grant C. B., Ma, Zhiyuan, Zhou, Hua, Gosztola, David J., Ketterson, John B., Kanatzidis, Mercouri G., Xu, Tao, Chan, Maria K. Y., and Schaller, Richard D. 2017. "Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies". United States. https://doi.org/10.1021/acsenergylett.7b00790. https://www.osti.gov/servlets/purl/1402074.
@article{osti_1402074,
title = {Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies},
author = {Guo, Peijun and Xia, Yi and Gong, Jue and Stoumpos, Constantinos C. and McCall, Kyle M. and Alexander, Grant C. B. and Ma, Zhiyuan and Zhou, Hua and Gosztola, David J. and Ketterson, John B. and Kanatzidis, Mercouri G. and Xu, Tao and Chan, Maria K. Y. and Schaller, Richard D.},
abstractNote = {Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures. Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.},
doi = {10.1021/acsenergylett.7b00790},
url = {https://www.osti.gov/biblio/1402074}, journal = {ACS Energy Letters},
issn = {2380-8195},
number = 10,
volume = 2,
place = {United States},
year = {Thu Sep 28 00:00:00 EDT 2017},
month = {Thu Sep 28 00:00:00 EDT 2017}
}

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

Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

From soft harmonic phonons to fast relaxational dynamics in CH 3 NH 3 PbBr 3
journal, September 2015


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


Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide
journal, October 2016


Metal halide perovskites for energy applications
journal, May 2016


Switchable S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide perovskites
journal, April 2014


Role of Ferroelectric Nanodomains in the Transport Properties of Perovskite Solar Cells
journal, January 2016


Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites
journal, February 2015


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


Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH 3 NH 3 PbI 3
journal, November 2015


Direct Observation of Ferroelectric Domains in Solution-Processed CH 3 NH 3 PbI 3 Perovskite Thin Films
journal, September 2014


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


Crystal Growth of the Perovskite Semiconductor CsPbBr 3 : A New Material for High-Energy Radiation Detection
journal, June 2013


Photoexcitation dynamics in solution-processed formamidinium lead iodide perovskite thin films for solar cell applications
journal, December 2015


Experimental and theoretical optical properties of methylammonium lead halide perovskites
journal, January 2016


Chemical tuning of dynamic cation off-centering in the cubic phases of hybrid tin and lead halide perovskites
journal, January 2017


Phonon modes and central peaks in an A -site relaxor: A low-frequency Raman study of sodium bismuth titanate
journal, August 2014


Surface generation and detection of phonons by picosecond light pulses
journal, September 1986


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


Two-Inch-Sized Perovskite CH 3 NH 3 PbX 3 (X = Cl, Br, I) Crystals: Growth and Characterization
journal, August 2015


Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite
journal, October 2016


Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination
journal, August 2015


Elastic softening and central peaks in BaTiO3 single crystals above the cubic-tetragonal phase-transition temperature
journal, September 2008


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


Direct–indirect character of the bandgap in methylammonium lead iodide perovskite
journal, October 2016


Elastic Constants and Thermal Expansion of CsPbCl 3
journal, May 1978


Low-Temperature Solution-Grown CsPbBr 3 Single Crystals and Their Characterization
journal, September 2016


Electron–acoustic phonon coupling in single crystal CH3NH3PbI3 perovskites revealed by coherent acoustic phonons
journal, February 2017


Research Update: Relativistic origin of slow electron-hole recombination in hybrid halide perovskite solar cells
journal, September 2016


Formamidinium Lead Halide Perovskite Crystals with Unprecedented Long Carrier Dynamics and Diffusion Length
journal, April 2016


Dielectric Response: Answer to Many Questions in the Methylammonium Lead Halide Solar Cell Absorbers
journal, May 2017


CH 3 NH 3 PbCl 3 Single Crystals: Inverse Temperature Crystallization and Visible-Blind UV-Photodetector
journal, September 2015


Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†
journal, January 1990


Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH 3 NH 3 PbI 3
journal, July 2014


Ferroelectric Polarization in CH 3 NH 3 PbI 3 Perovskite
journal, April 2015


Tetragonal CH 3 NH 3 PbI 3 is ferroelectric
journal, June 2017


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


Photon recycling in lead iodide perovskite solar cells
journal, March 2016


Relaxing with relaxors: a review of relaxor ferroelectrics
journal, April 2011


The study of structural phase transitions by means of ultrasonic experiments
journal, November 1973


Ferroelectric domains in methylammonium lead iodide perovskite thin-films
journal, January 2017


CH 3 NH 3 PbI 3 perovskites: Ferroelasticity revealed
journal, April 2017


CH3NH3PbBr3 is not pyroelectric, excluding ferroelectric-enhanced photovoltaic performance
journal, May 2016


Lattice dynamics and the nature of structural transitions in organolead halide perovskites
journal, September 2016


Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy
journal, April 2017


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


Works referencing / citing this record:

Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites
journal, May 2018


Dynamic shortening of disorder potentials in anharmonic halide perovskites
journal, July 2019


Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals
journal, January 2019


Dynamic emission Stokes shift and liquid-like dielectric solvation of band edge carriers in lead-halide perovskites
journal, March 2019


Self-Healing Inside APbBr 3 Halide Perovskite Crystals
journal, January 2018


Unraveling exciton–phonon coupling in individual FAPbI3 nanocrystals emitting near-infrared single photons
journal, August 2018


Compressive sensing lattice dynamics. I. General formalism
journal, November 2019


Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics
journal, August 2018


Carrier recombination mechanism in CsPbB r 3 revealed by time-resolved photoluminescence spectroscopy
journal, December 2019


Dynamic symmetry breaking and spin splitting in metal halide perovskites
journal, August 2018


Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics.
text, January 2018


Dynamic Symmetry Breaking and Spin Splitting in Metal Halide Perovskites
text, January 2017


Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites
journal, May 2018


Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals
journal, January 2019


Dynamic shortening of disorder potentials in anharmonic halide perovskites
journal, July 2019


Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics.
text, January 2018