Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Ultrafast correlated charge and lattice motion in a hybrid metal halide perovskite

Journal Article · · Science Advances

Hybrid organic-inorganic halide perovskites have shown remarkable optoelectronic properties, exhibiting an impressive tolerance to defects believed to originate from correlated motion of charge carriers and the polar lattice forming large polarons. Few experimental techniques are capable of directly probing these correlations, requiring simultaneous sub–millielectron volt energy and femtosecond temporal resolution after absorption of a photon. Here, we use time-resolved multi-THz spectroscopy, sensitive to the internal excitations of the polaron, to temporally and energetically resolve the coherent coupling of charges to longitudinal optical phonons in single-crystal CH3NH3PbI3(MAPI). We observe room temperature intraband quantum beats arising from the coherent displacement of charge from the coupled phonon cloud. Our measurements provide strong evidence for the existence of polarons in MAPI at room temperature, suggesting that electron/hole-phonon coupling is a defining aspect of the hybrid metal-halide perovskites contributing to the protection from scattering and enhanced carrier lifetimes that define their usefulness in devices.

Research Organization:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0012541
OSTI ID:
1611842
Journal Information:
Science Advances, Journal Name: Science Advances Journal Issue: 5 Vol. 5; ISSN 2375-2548
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English

References (50)

The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors journal September 2015
Phonon Mode Transformation Across the Orthohombic–Tetragonal Phase Transition in a Lead Iodide Perovskite CH 3 NH 3 PbI 3 : A Terahertz Time-Domain Spectroscopy Approach journal December 2015
Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons journal November 2015
Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination journal February 2014
Free Carrier Emergence and Onset of Electron–Phonon Coupling in Methylammonium Lead Halide Perovskite Films journal December 2017
How many-particle interactions develop after ultrafast excitation of an electron–hole plasma journal November 2001
Internal motions of a quasiparticle governing its ultrafast nonlinear response journal December 2007
Metal-halide perovskites for photovoltaic and light-emitting devices journal May 2015
The Motion of Slow Electrons in a Polar Crystal journal April 1953
Slow Electrons in a Polar Crystal journal February 1955
Quantum dynamics of polaron formation journal January 2007
Longitudinal Optical Phonons Modified by Organic Molecular Cation Motions in Organic-Inorganic Hybrid Perovskites journal October 2018
Subthreshold Carrier-LO Phonon Dynamics in Semiconductors with Intermediate Polaron Coupling: A Purely Quantum Kinetic Relaxation Channel journal May 2001
Detection of Broadband Terahertz Waves with a Laser-Induced Plasma in Gases journal September 2006
Large polarons in lead halide perovskites journal August 2017
How hybrid perovskites get their groove journal September 2016
Local polar fluctuations in lead halide perovskite crystals text January 2016
Probing Femtosecond Lattice Displacement upon Photo-carrier generation in Lead Halide Perovskite text January 2017
Carrier Lifetimes and Polaronic Mass Enhancement in the Hybrid Halide Perovskite CH$_3$NH$_3$PbI$_3$ from Multiphonon Fröhlich Coupling text January 2018
Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling journal January 2018
Quantifying Polaron Formation and Charge Carrier Cooling in Lead-Iodide Perovskites journal May 2018
Room-Temperature Coherent Optical Phonon in 2D Electronic Spectra of CH 3 NH 3 PbI 3 Perovskite as a Possible Cooling Bottleneck journal June 2017
How Lattice Dynamics Moderate the Electronic Properties of Metal-Halide Perovskites journal November 2018
Defect Tolerance in Methylammonium Lead Triiodide Perovskite journal July 2016
Perovskite Solar Cells: The Birth of a New Era in Photovoltaics journal March 2017
Role of Dielectric Drag in Polaron Mobility in Lead Halide Perovskites journal October 2017
Resolving the Energy of γ-Ray Photons with MAPbI 3 Single Crystals journal September 2018
Small Photocarrier Effective Masses Featuring Ambipolar Transport in Methylammonium Lead Iodide Perovskite: A Density Functional Analysis journal November 2013
Probing femtosecond lattice displacement upon photo-carrier generation in lead halide perovskite journal May 2018
Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites journal January 2019
Author Correction: Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites journal February 2019
Intrinsic femtosecond charge generation dynamics in single crystal CH 3 NH 3 PbI 3 journal January 2015
Optical phonons in methylammonium lead halide perovskites and implications for charge transport journal January 2016
Origin of low electron–hole recombination rate in metal halide perovskites journal January 2018
Polarons
  • Devreese, J. T.
  • LECTURE ON THE PHYSICS OF HIGHLY CORRELATED ELECTRON SYSTEMS VII: Seventh Training Course in the Physics of Correlated Electron Systems and High-Tc Superconductors, AIP Conference Proceedings https://doi.org/10.1063/1.1612391
conference January 2003
Electrons in lattice fields journal July 1954
The Motion of Slow Electrons in a Polar Crystal journal April 1953
Slow Electrons in a Polar Crystal journal February 1955
Quantum dynamics of polaron formation journal January 2007
Local Polar Fluctuations in Lead Halide Perovskite Crystals journal March 2017
Carrier Lifetimes and Polaronic Mass Enhancement in the Hybrid Halide Perovskite CH 3 NH 3 PbI 3 from Multiphonon Fröhlich Coupling journal August 2018
Longitudinal Optical Phonons Modified by Organic Molecular Cation Motions in Organic-Inorganic Hybrid Perovskites journal October 2018
Femtosecond Charge Transport in Polar Semiconductors journal June 1999
Subthreshold Carrier-LO Phonon Dynamics in Semiconductors with Intermediate Polaron Coupling: A Purely Quantum Kinetic Relaxation Channel journal May 2001
Detection of Broadband Terahertz Waves with a Laser-Induced Plasma in Gases journal September 2006
Coherent Structural Dynamics and Electronic Correlations during an Ultrafast Insulator-to-Metal Phase Transition in VO 2 journal September 2007
Lead halide perovskites: Crystal-liquid duality, phonon glass electron crystals, and large polaron formation journal October 2017
Screening in crystalline liquids protects energetic carriers in hybrid perovskites journal September 2016
Optical Phonons in Methylammonium Lead Halide Perovskites and Implications for Charge Transport text January 2016
Lead halide perovskites: Crystal-liquid duality, phonon glass electron crystals, and large polaron formation text January 2017

Cited By (3)

Coherent charge-phonon correlations and exciton dynamics in orthorhombic CH 3 NH 3 PbI 3 measured by ultrafast multi-THz spectroscopy journal December 2019
Time- and momentum-resolved phonon population dynamics with ultrafast electron diffuse scattering journal December 2019
Time- and momentum-resolved phonon population dynamics with ultrafast electron diffuse scattering text January 2019

Similar Records

Coherent charge-phonon correlations and exciton dynamics in orthorhombic CH3NH3PbI3 measured by ultrafast multi-THz spectroscopy
Journal Article · Tue Dec 03 19:00:00 EST 2019 · Journal of Chemical Physics · OSTI ID:1802377