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Title: Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling

Abstract

Unusual photophysical properties of organic–inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH 3NH 3PbI 3) following photoexcitation, enabling an ultrafast probe of charge separation, hot–carrier transport, and carrier–lattice coupling under 1–sun–equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hot and band–edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot–carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz–frequency lattice distortions, associated with reorganizations of the lead–iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier–lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far–above–gap photoexcitation. As a result, this study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport.

Authors:
 [1];  [2];  [2];  [1];  [2];  [3];  [3];  [1];  [2];  [2];  [4]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Stanford Univ., Stanford, CA (United States)
  3. Pennsylvania State Univ., University Park, PA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1457108
Alternate Identifier(s):
OSTI ID: 1417766
Grant/Contract Number:  
DGE-114747; SC0012375; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 11; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; carrier-lattice coupling; charge separation; hybrid organic-inorganic perovskites; MAPbl3; THz emission; ultrafast structural dynamics

Citation Formats

Guzelturk, Burak, Belisle, Rebecca A., Smith, Matthew D., Bruening, Karsten, Prasanna, Rohit, Yuan, Yakun, Gopalan, Venkatraman, Tassone, Christopher J., Karunadasa, Hemamala I., McGehee, Michael D., and Lindenberg, Aaron M. Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling. United States: N. p., 2018. Web. doi:10.1002/adma.201704737.
Guzelturk, Burak, Belisle, Rebecca A., Smith, Matthew D., Bruening, Karsten, Prasanna, Rohit, Yuan, Yakun, Gopalan, Venkatraman, Tassone, Christopher J., Karunadasa, Hemamala I., McGehee, Michael D., & Lindenberg, Aaron M. Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling. United States. doi:10.1002/adma.201704737.
Guzelturk, Burak, Belisle, Rebecca A., Smith, Matthew D., Bruening, Karsten, Prasanna, Rohit, Yuan, Yakun, Gopalan, Venkatraman, Tassone, Christopher J., Karunadasa, Hemamala I., McGehee, Michael D., and Lindenberg, Aaron M. Tue . "Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling". United States. doi:10.1002/adma.201704737. https://www.osti.gov/servlets/purl/1457108.
@article{osti_1457108,
title = {Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling},
author = {Guzelturk, Burak and Belisle, Rebecca A. and Smith, Matthew D. and Bruening, Karsten and Prasanna, Rohit and Yuan, Yakun and Gopalan, Venkatraman and Tassone, Christopher J. and Karunadasa, Hemamala I. and McGehee, Michael D. and Lindenberg, Aaron M.},
abstractNote = {Unusual photophysical properties of organic–inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH3NH3PbI3) following photoexcitation, enabling an ultrafast probe of charge separation, hot–carrier transport, and carrier–lattice coupling under 1–sun–equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hot and band–edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot–carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz–frequency lattice distortions, associated with reorganizations of the lead–iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier–lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far–above–gap photoexcitation. As a result, this study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport.},
doi = {10.1002/adma.201704737},
journal = {Advanced Materials},
number = 11,
volume = 30,
place = {United States},
year = {2018},
month = {1}
}

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Cited by: 18 works
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Figures / Tables:

Figure 1 Figure 1: (a) Schematic illustration of the THz emission from CH3NH3PbI3 (MAPI). Following photo-excitation, a burst of THz radiation is detected in a reflection geometry encoding the time-dependent currents and charge - lattice coupling processes that occur following photo-excitation. (b) Time-domain THz electric field emitted by MAPI thin-film upon excitationmore » with 400 nm fs light pulse at a fluence of 2 μJ/cm2. Inset shows the THz signal amplitude as a function of pump fluence and the corresponding sun-equivalent intensity. (c) Amplitude spectrum of the emitted THz field exhibiting three distinct peaks at 0.65, 1.2 and 2.8 THz.« less

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Works referenced in this record:

Intriguing Optoelectronic Properties of Metal Halide Perovskites
journal, June 2016


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


Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites
journal, September 2015

  • Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9420

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

Charge-Carrier Mobilities in Metal Halide Perovskites: Fundamental Mechanisms and Limits
journal, June 2017


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

  • Monahan, Daniele M.; Guo, Liang; Lin, Jia
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 14
  • DOI: 10.1021/acs.jpclett.7b01357

The emergence of perovskite solar cells
journal, July 2014

  • Green, Martin A.; Ho-Baillie, Anita; Snaith, Henry J.
  • Nature Photonics, Vol. 8, Issue 7, p. 506-514
  • DOI: 10.1038/nphoton.2014.134

Few-Cycle THz Emission from Cold Plasma Oscillations
journal, October 1997


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

  • Ponseca, Carlito S.; Savenije, Tom J.; Abdellah, Mohamed
  • Journal of the American Chemical Society, Vol. 136, Issue 14
  • DOI: 10.1021/ja412583t

Substrate-dependent electronic structure and film formation of MAPbI3 perovskites
journal, January 2017

  • Olthof, Selina; Meerholz, Klaus
  • Scientific Reports, Vol. 7, Issue 1
  • DOI: 10.1038/srep40267

Terahertz radiation from coherent phonons excited in semiconductors
journal, March 1998

  • Tani, M.; Fukasawa, R.; Abe, H.
  • Journal of Applied Physics, Vol. 83, Issue 5
  • DOI: 10.1063/1.367007

Hybrid Organic–Inorganic Perovskites on the Move
journal, February 2016


Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites
journal, January 2017


Carrier separation and transport in perovskite solar cells studied by nanometre-scale profiling of electrical potential
journal, September 2015

  • Jiang, Chun-Sheng; Yang, Mengjin; Zhou, Yuanyuan
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9397

Bright light-emitting diodes based on organometal halide perovskite
journal, August 2014

  • Tan, Zhi-Kuang; Moghaddam, Reza Saberi; Lai, May Ling
  • Nature Nanotechnology, Vol. 9, Issue 9
  • DOI: 10.1038/nnano.2014.149

Revealing the Dynamics of Charge Carriers in Polymer:Fullerene Blends Using Photoinduced Time-Resolved Microwave Conductivity
journal, October 2013

  • Savenije, Tom J.; Ferguson, Andrew J.; Kopidakis, Nikos
  • The Journal of Physical Chemistry C, Vol. 117, Issue 46
  • DOI: 10.1021/jp406706u

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

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


Intense ultrashort terahertz pulses: generation and applications
journal, February 2011


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

  • Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500390f

Study of terahertz radiation from InAs and InSb
journal, May 2002

  • Gu, Ping; Tani, Masahiko; Kono, Shunsuke
  • Journal of Applied Physics, Vol. 91, Issue 9
  • DOI: 10.1063/1.1465507

Terahertz emission from lateral
photo-Dember currents
journal, January 2010


Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015


Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites
journal, July 2017


Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials
journal, May 2016


Femtosecond Charge Transport in Polar Semiconductors
journal, June 1999


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

  • Xing, Guichuan; Mathews, Nripan; Lim, Swee Sien
  • Nature Materials, Vol. 13, Issue 5
  • DOI: 10.1038/nmat3911

Phonon–Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites
journal, December 2015

  • Karakus, Melike; Jensen, Søren A.; D’Angelo, Francesco
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 24
  • DOI: 10.1021/acs.jpclett.5b02485

THz emission from semiconductor surfaces
journal, March 2008

  • Malevich, Vitalij L.; Adomavičius, Ramūnas; Krotkus, Arūnas
  • Comptes Rendus Physique, Vol. 9, Issue 2
  • DOI: 10.1016/j.crhy.2007.09.014

Screened Charge Carrier Transport in Methylammonium Lead Iodide Perovskite Thin Films
journal, February 2017

  • Hill, Andrew H.; Smyser, Kori E.; Kennedy, Casey L.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 5
  • DOI: 10.1021/acs.jpclett.7b00046

Monitoring a Silent Phase Transition in CH 3 NH 3 PbI 3 Solar Cells via Operando X-ray Diffraction
journal, October 2016


Small Photocarrier Effective Masses Featuring Ambipolar Transport in Methylammonium Lead Iodide Perovskite: A Density Functional Analysis
journal, November 2013

  • Giorgi, Giacomo; Fujisawa, Jun-Ichi; Segawa, Hiroshi
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 24
  • DOI: 10.1021/jz4023865

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


Table-top sources of ultrashort THz pulses
journal, September 2007


Emission of Submillimeter Electromagnetic Waves by Coherent Phonons
journal, January 1995


Persistent Energetic Electrons in Methylammonium Lead Iodide Perovskite Thin Films
journal, November 2016

  • Niesner, Daniel; Zhu, Haiming; Miyata, Kiyoshi
  • Journal of the American Chemical Society, Vol. 138, Issue 48
  • DOI: 10.1021/jacs.6b08880

Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


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

  • Stranks, S. D.; Eperon, G. E.; Grancini, G.
  • Science, Vol. 342, Issue 6156, p. 341-344
  • DOI: 10.1126/science.1243982

Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies
journal, December 2015


Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012


Numerical studies on the electro-optic detection of femtosecond electron bunches
journal, July 2008

  • Casalbuoni, S.; Schlarb, H.; Schmidt, B.
  • Physical Review Special Topics - Accelerators and Beams, Vol. 11, Issue 7
  • DOI: 10.1103/PhysRevSTAB.11.072802

Detection of terahertz radiation from longitudinal optical phonon–plasmon coupling modes in InSb film using an ultrabroadband photoconductive antenna
journal, January 2000

  • Gu, Ping; Tani, Masahiko; Sakai, Kiyomi
  • Applied Physics Letters, Vol. 77, Issue 12
  • DOI: 10.1063/1.1311609

High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
journal, December 2013

  • Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
  • Advanced Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adma.201305172

Generation of femtosecond electromagnetic pulses from semiconductor surfaces
journal, March 1990

  • Zhang, X. ‐C.; Hu, B. B.; Darrow, J. T.
  • Applied Physics Letters, Vol. 56, Issue 11
  • DOI: 10.1063/1.102601

Simulation of terahertz generation at semiconductor surfaces
journal, March 2002


Influence of surface passivation on ultrafast carrier dynamics and terahertz radiation generation in GaAs
journal, December 2006

  • Lloyd-Hughes, J.; Merchant, S. K. E.; Fu, L.
  • Applied Physics Letters, Vol. 89, Issue 23
  • DOI: 10.1063/1.2398915

Photoluminescence Lifetimes Exceeding 8 μs and Quantum Yields Exceeding 30% in Hybrid Perovskite Thin Films by Ligand Passivation
journal, July 2016


Shift current bulk photovoltaic effect in polar materials—hybrid and oxide perovskites and beyond
journal, August 2016


The In-Gap Electronic State Spectrum of Methylammonium Lead Iodide Single-Crystal Perovskites
journal, March 2016

  • Adinolfi, Valerio; Yuan, Mingjian; Comin, Riccardo
  • Advanced Materials, Vol. 28, Issue 17
  • DOI: 10.1002/adma.201505162

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


Observation of a hot-phonon bottleneck in lead-iodide perovskites
journal, October 2015


Electron–phonon coupling in hybrid lead halide perovskites
journal, May 2016

  • Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11755

    Works referencing / citing this record:

    Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite
    journal, June 2018

    • Park, Myeongkee; Neukirch, Amanda J.; Reyes-Lillo, Sebastian E.
    • Nature Communications, Vol. 9, Issue 1
    • DOI: 10.1038/s41467-018-04946-7

    Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite
    journal, June 2018

    • Park, Myeongkee; Neukirch, Amanda J.; Reyes-Lillo, Sebastian E.
    • Nature Communications, Vol. 9, Issue 1
    • DOI: 10.1038/s41467-018-04946-7

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