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

Title: Coherent band-edge oscillations and dynamic longitudinal-optical phonon mode splitting as evidence for polarons in perovskites

Abstract

The coherence of collective modes, such as phonons and polarons, and their modulation of electronic states is long sought in complex systems, which is a crosscutting issue in photovoltaics and quantum electronics. In photovoltaic cells and lasers based on metal halide perovskites, the presence of polarons, i.e., photocarriers dressed by the macroscopic motion of charged lattice, assisted by terahertz (THz) longitudinal-optical (LO) phonons, has been intensely studied yet is still debated. This may be key for explaining the remarkable properties of the perovskite materials, e.g., defect tolerance, long charge lifetimes, and diffusion lengths. In this work we use the intense single-cycle THz pulse with peak electric field up to E THz = 1000 kV/cm to drive coherent polaronic band-edge oscillations at room temperature in CH3NH3PbI3 (MAPbI3). We reveal the oscillatory behavior is dominated by a specific quantized lattice vibration mode at $ω$LO ~ 4 THz, which is both dipole and momentum forbidden. THz-driven coherent polaron dynamics exhibits distinguishing features: room temperature coherent oscillations at ω LO longer than 1 ps in both single crystals and thin films, mode-selective modulation of different band-edge states assisted by electron-phonon interaction, and dynamic mode splitting at low temperature due to entropy and anharmonicity of organic cations. Our results demonstrate intense THz-driven coherent band-edge modulation is a powerful probe of electron-lattice coupling phenomena and polaronic quantum control in perovskites.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [1];  [3];  [3];  [2];  [1]; ORCiD logo [1]
  1. Ames Lab., and Iowa State Univ., Ames, IA (United States)
  2. Univ. of Toledo, OH (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF)
OSTI Identifier:
1607928
Alternate Identifier(s):
OSTI ID: 1604859
Report Number(s):
IS-J-10184
Journal ID: ISSN 2469-9950; PRBMDO
Grant/Contract Number:  
AC02-07CH11358; DMR 1807818; 1122374; EECS 1611454
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 101; Journal Issue: 11; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE

Citation Formats

Liu, Z., Vaswani, C., Luo, L., Cheng, D., Yang, X., Zhao, X., Yao, Y., Song, Z., Brenes, R., Kim, R. J. H., Jean, J., Bulović, V., Yan, Y., Ho, K.-M., and Wang, J. Coherent band-edge oscillations and dynamic longitudinal-optical phonon mode splitting as evidence for polarons in perovskites. United States: N. p., 2020. Web. doi:10.1103/PhysRevB.101.115125.
Liu, Z., Vaswani, C., Luo, L., Cheng, D., Yang, X., Zhao, X., Yao, Y., Song, Z., Brenes, R., Kim, R. J. H., Jean, J., Bulović, V., Yan, Y., Ho, K.-M., & Wang, J. Coherent band-edge oscillations and dynamic longitudinal-optical phonon mode splitting as evidence for polarons in perovskites. United States. doi:https://doi.org/10.1103/PhysRevB.101.115125
Liu, Z., Vaswani, C., Luo, L., Cheng, D., Yang, X., Zhao, X., Yao, Y., Song, Z., Brenes, R., Kim, R. J. H., Jean, J., Bulović, V., Yan, Y., Ho, K.-M., and Wang, J. Mon . "Coherent band-edge oscillations and dynamic longitudinal-optical phonon mode splitting as evidence for polarons in perovskites". United States. doi:https://doi.org/10.1103/PhysRevB.101.115125. https://www.osti.gov/servlets/purl/1607928.
@article{osti_1607928,
title = {Coherent band-edge oscillations and dynamic longitudinal-optical phonon mode splitting as evidence for polarons in perovskites},
author = {Liu, Z. and Vaswani, C. and Luo, L. and Cheng, D. and Yang, X. and Zhao, X. and Yao, Y. and Song, Z. and Brenes, R. and Kim, R. J. H. and Jean, J. and Bulović, V. and Yan, Y. and Ho, K.-M. and Wang, J.},
abstractNote = {The coherence of collective modes, such as phonons and polarons, and their modulation of electronic states is long sought in complex systems, which is a crosscutting issue in photovoltaics and quantum electronics. In photovoltaic cells and lasers based on metal halide perovskites, the presence of polarons, i.e., photocarriers dressed by the macroscopic motion of charged lattice, assisted by terahertz (THz) longitudinal-optical (LO) phonons, has been intensely studied yet is still debated. This may be key for explaining the remarkable properties of the perovskite materials, e.g., defect tolerance, long charge lifetimes, and diffusion lengths. In this work we use the intense single-cycle THz pulse with peak electric field up to ETHz=1000 kV/cm to drive coherent polaronic band-edge oscillations at room temperature in CH3NH3PbI3 (MAPbI3). We reveal the oscillatory behavior is dominated by a specific quantized lattice vibration mode at $ω$LO ~ 4 THz, which is both dipole and momentum forbidden. THz-driven coherent polaron dynamics exhibits distinguishing features: room temperature coherent oscillations at ωLO longer than 1 ps in both single crystals and thin films, mode-selective modulation of different band-edge states assisted by electron-phonon interaction, and dynamic mode splitting at low temperature due to entropy and anharmonicity of organic cations. Our results demonstrate intense THz-driven coherent band-edge modulation is a powerful probe of electron-lattice coupling phenomena and polaronic quantum control in perovskites.},
doi = {10.1103/PhysRevB.101.115125},
journal = {Physical Review B},
number = 11,
volume = 101,
place = {United States},
year = {2020},
month = {3}
}

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

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons
journal, November 2015


Large polaron formation and its effect on electron transport in hybrid perovskites
journal, January 2019

  • Zheng, Fan; Wang, Lin-wang
  • Energy & Environmental Science, Vol. 12, Issue 4
  • DOI: 10.1039/C8EE03369B

Local Polar Fluctuations in Lead Halide Perovskite Crystals
journal, March 2017


Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites
journal, January 2016

  • Leguy, Aurélien M. A.; Goñi, Alejandro R.; Frost, Jarvist M.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 39
  • DOI: 10.1039/C6CP03474H

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

Probing femtosecond lattice displacement upon photo-carrier generation in lead halide perovskite
journal, May 2018

  • Batignani, Giovanni; Fumero, Giuseppe; Srimath Kandada, Ajay Ram
  • Nature Communications, Vol. 9, Issue 1
  • DOI: 10.1038/s41467-018-04367-6

Light control of surface–bulk coupling by terahertz vibrational coherence in a topological insulator
journal, February 2020


Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites
journal, January 2019

  • Thouin, Félix; Valverde-Chávez, David A.; Quarti, Claudio
  • Nature Materials, Vol. 18, Issue 4
  • DOI: 10.1038/s41563-018-0262-7

Grain boundary dominated ion migration in polycrystalline organic–inorganic halide perovskite films
journal, January 2016

  • Shao, Yuchuan; Fang, Yanjun; Li, Tao
  • Energy & Environmental Science, Vol. 9, Issue 5
  • DOI: 10.1039/C6EE00413J

Reversible modulation and ultrafast dynamics of terahertz resonances in strongly photoexcited metamaterials
journal, September 2012


Ultrafast manipulation of topologically enhanced surface transport driven by mid-infrared and terahertz pulses in Bi2Se3
journal, February 2019


Dynamic Screening and Slow Cooling of Hot Carriers in Lead Halide Perovskites
journal, September 2018

  • Joshi, Prakriti Pradhan; Maehrlein, Sebastian F.; Zhu, Xiaoyang
  • Advanced Materials, Vol. 31, Issue 47
  • DOI: 10.1002/adma.201803054

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

  • Saidaminov, Makhsud I.; Abdelhady, Ahmed L.; Murali, Banavoth
  • Nature Communications, Vol. 6, Article No. 7586
  • DOI: 10.1038/ncomms8586

Optical phonons in methylammonium lead halide perovskites and implications for charge transport
journal, January 2016

  • Sendner, Michael; Nayak, Pabitra K.; Egger, David A.
  • Materials Horizons, Vol. 3, Issue 6
  • DOI: 10.1039/C6MH00275G

Rotational Cation Dynamics in Metal Halide Perovskites: Effect on Phonons and Material Properties
journal, September 2018

  • Gallop, Nathaniel P.; Selig, Oleg; Giubertoni, Giulia
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 20
  • DOI: 10.1021/acs.jpclett.8b02227

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


Helicity-dependent terahertz photocurrent and phonon dynamics in hybrid metal halide perovskites
journal, December 2019

  • Cheng, D.; Liu, Z.; Luo, L.
  • The Journal of Chemical Physics, Vol. 151, Issue 24
  • DOI: 10.1063/1.5127767

Ultrafast nonthermal terahertz electrodynamics and possible quantum energy transfer in the Nb 3 Sn superconductor
journal, March 2019


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

Longitudinal Optical Phonons Modified by Organic Molecular Cation Motions in Organic-Inorganic Hybrid Perovskites
journal, October 2018


Direct observation of mode-specific phonon-band gap coupling in methylammonium lead halide perovskites
journal, September 2017


Lightwave-driven gapless superconductivity and forbidden quantum beats by terahertz symmetry breaking
journal, July 2019


Terahertz-induced interband tunneling of electrons in GaAs
journal, August 2010


Ultrafast probes of nonequilibrium hole spin relaxation in the ferromagnetic semiconductor GaMnAs
journal, April 2015


Photovoltaic concepts inspired by coherence effects in photosynthetic systems
journal, December 2016

  • Brédas, Jean-Luc; Sargent, Edward H.; Scholes, Gregory D.
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4767

Quantifying Polaron Formation and Charge Carrier Cooling in Lead-Iodide Perovskites
journal, May 2018

  • Bretschneider, Simon A.; Ivanov, Ivan; Wang, Hai I.
  • Advanced Materials, Vol. 30, Issue 29
  • DOI: 10.1002/adma.201707312

Ultrafast terahertz snapshots of excitonic Rydberg states and electronic coherence in an organometal halide perovskite
journal, June 2017

  • Luo, Liang; Men, Long; Liu, Zhaoyu
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15565

Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells
journal, November 2015

  • Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms10030

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


Free Carrier Emergence and Onset of Electron–Phonon Coupling in Methylammonium Lead Halide Perovskite Films
journal, December 2017

  • Ghosh, Tufan; Aharon, Sigalit; Etgar, Lioz
  • Journal of the American Chemical Society, Vol. 139, Issue 50
  • DOI: 10.1021/jacs.7b09508

Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal, and cubic phases of methylammonium lead iodide
journal, October 2015


Grain-Size-Limited Mobility in Methylammonium Lead Iodide Perovskite Thin Films
journal, August 2016


Ultrafast observation of critical nematic fluctuations and giant magnetoelastic coupling in iron pnictides
journal, February 2014

  • Patz, Aaron; Li, Tianqi; Ran, Sheng
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4229

Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals
journal, May 2018


Ultrafast correlated charge and lattice motion in a hybrid metal halide perovskite
journal, May 2019

  • Lan, Yang; Dringoli, Benjamin J.; Valverde-Chávez, David A.
  • Science Advances, Vol. 5, Issue 5
  • DOI: 10.1126/sciadv.aaw5558

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

  • Rakita, Yevgeny; Bar-Elli, Omri; Meirzadeh, Elena
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 28
  • DOI: 10.1073/pnas.1702429114

Terahertz-light quantum tuning of a metastable emergent phase hidden by superconductivity
journal, June 2018


Femtosecond switching of magnetism via strongly correlated spin–charge quantum excitations
journal, April 2013

  • Li, Tianqi; Patz, Aaron; Mouchliadis, Leonidas
  • Nature, Vol. 496, Issue 7443
  • DOI: 10.1038/nature11934

Generation of Coherent Optical Phonons in Methylammonium Lead Iodide Thin Films
journal, March 2018

  • Fei, Chengbin; Sarmiento, Julio S.; Wang, He
  • The Journal of Physical Chemistry C, Vol. 122, Issue 30
  • DOI: 10.1021/acs.jpcc.8b03529

Is CH 3 NH 3 PbI 3 Polar?
journal, June 2016

  • G., Sharada; Mahale, Pratibha; Kore, Bhushan P.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
  • DOI: 10.1021/acs.jpclett.6b00803

Ferroelectric large polarons
journal, April 2018


Ultrafast Terahertz Probes of Interacting Dark Excitons in Chirality-Specific Semiconducting Single-Walled Carbon Nanotubes
journal, March 2015


Methylammonium Cation Dynamics in Methylammonium Lead Halide Perovskites: A Solid-State NMR Perspective
journal, February 2018

  • Bernard, Guy M.; Wasylishen, Roderick E.; Ratcliffe, Christopher I.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 6
  • DOI: 10.1021/acs.jpca.7b11558

Spatial–temporal spectroscopy characterizations and electronic structure of methylammonium perovskites
journal, July 2018

  • Liu, Zhaoyu; Bhamu, K. C.; Luo, Liang
  • MRS Communications, Vol. 8, Issue 03
  • DOI: 10.1557/mrc.2018.114

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